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

Machine dishwashing detergent with bleaching agents, builders and enzymes Download PDF

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Publication number
EP3325597B1
EP3325597B1 EP16741307.9A EP16741307A EP3325597B1 EP 3325597 B1 EP3325597 B1 EP 3325597B1 EP 16741307 A EP16741307 A EP 16741307A EP 3325597 B1 EP3325597 B1 EP 3325597B1
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EP
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Prior art keywords
acid
dishwasher detergent
automatic dishwasher
weight
enzyme
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German (de)
French (fr)
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EP3325597A1 (en
Inventor
Inga Kerstin Vockenroth
Johannes Zipfel
Silke Menke
Thomas Weber
Noelle Wrubbel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3907Organic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • C11D17/0078Multilayered tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045Multi-compartment
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase

Definitions

  • 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.
  • 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.
  • a builder is also contained in the enzyme area, the builder comprising methylglycinediacetic acid (MGDA).
  • MGDA methylglycinediacetic acid
  • Other multi-phase dishwashing detergents containing MGDA are from US 2014/0018278 A1 , DE 102013225485 A1 and US 2013/0199569 A1 known.
  • the object of the present invention was to provide a, preferably phosphate-free, machine dishwashing detergent which has a further increased cleaning performance.
  • 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.
  • MGDA methylglycinediacetic acid
  • 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.
  • 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.
  • At least one as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • 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.
  • 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.
  • 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.
  • GPC gel permeation chromatography
  • the mass average molecular weight M w can also be determined by means of GPC, as described for M n .
  • 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".
  • 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”.
  • 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.
  • 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.
  • the oxo alcohols or their derivatives obtainable, for example, according to RoELEN's oxo synthesis can also be used accordingly.
  • 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.
  • 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.
  • 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.
  • 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.
  • amylases which can be used according to the invention are the ⁇ -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 ⁇ -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.
  • suitable precursors 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.
  • 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.
  • 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.
  • 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.
  • damage such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • 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.
  • 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.
  • 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.
  • 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.
  • the weight information on enzymes means the amount of active enzyme protein based on the total mass of the entire composition.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • Suitable manganese complexes are, for example, [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 2 ( ⁇ -OAc) 1 (TACN ) 2 ] (BPh 4 ) 2 , [Mn IV 4 ( ⁇ -O) 6 (TACN) 4 ] (ClO 4 ) 4 , [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN ) 2 ] (ClO 4 ) 2 , [Mn III M n IV ( ⁇ -O) 1 (g-OAc) 2 (Me-TACN) 2 ] (ClO 4 ) 3 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 and [Mn IV 2 ( ⁇ -O) 3 (Me / Me-TACN) 2 ] (PF 6 ) 2 (OAc
  • 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.
  • 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
  • the aforementioned bleach-enhancing transition metal complexes 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.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • 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.
  • dishwashing detergents 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 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
  • 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 ( ⁇ -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.
  • the bleaching catalyst and the hydrogen peroxide source are preferably present in the above-mentioned amounts.
  • 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.
  • 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 tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • Glycolurils especially tetraacetyl
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the agents are preferably phosphate-free.
  • 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.
  • silicates 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).
  • crystalline sheet silicates of the formula NaMSi x O 2x + 1 .yH 2 O, in which x represents 2 are particularly suitable.
  • both are ⁇ -sodium disitikate Na 2 Si 2 O 5 .y H 2 O and, above all, Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -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 ( ⁇ -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.
  • 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.
  • 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.
  • 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.
  • 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.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • 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.
  • 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.
  • 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.
  • alkali carriers mentioned are also preferably made up separately from the enzyme phase and can be contained, for example, in the bleaching phase.
  • 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.
  • polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • NTA nitrilotriacetic acid
  • 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.
  • 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.
  • the agents according to the invention can contain surfactants, the group of surfactants including nonionic, anionic, cationic and amphoteric surfactants.
  • 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.
  • Suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • 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.
  • 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.
  • Suitable nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units.
  • 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.
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • each R 3 in the above formula can be different if x ⁇ 2.
  • 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 .
  • 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.
  • 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.
  • the corresponding non-end-capped hydroxy mixed ethers can also be used instead of the end group-capped hydroxy mixed ethers.
  • R 2 is hydrogen and R 1 , R 3 , A, A ', A ", A"', w, x, y and z are as defined above.
  • 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.
  • 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.
  • anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms.
  • 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.
  • 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 agents described herein may also contain various polymers.
  • Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -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.
  • 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.
  • metal ions preferably alkali metal ions and in particular by sodium ions.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • 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.
  • 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.
  • Particularly preferred unsaturated carboxylic acid esters are alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -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
  • 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.
  • 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.
  • the pH of the dishwashing detergent can be adjusted using conventional pH regulators, the pH being selected depending on the intended use.
  • 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.
  • 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.
  • 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.
  • alkali metal hydroxides of which potassium hydroxide and especially sodium hydroxide is preferred.
  • 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.
  • 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.
  • 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.
  • 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.
  • fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • mixtures of different fragrances are preferably used, which together produce an appealing fragrance.
  • 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
  • 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.
  • 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.
  • 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.
  • disintegration aids so-called tablet disintegrants
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m to 100 ⁇ m, in particular from 12 ⁇ m to 60 ⁇ m, particularly preferably from 15 ⁇ m to 50 ⁇ m, especially from 20 ⁇ m to 40 ⁇ m, in particular from 22 ⁇ m to 35 ⁇ m is used.
  • 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 ⁇ m, preferably 0.5 to 500 ⁇ m, particularly preferably 1 to 250 ⁇ m and in particular 2.5 to 100 ⁇ m.
  • 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.
  • disposable detergent or cleaning agent portions according to the invention are characterized in that the wrapper is a film packaging shrunk onto it.
  • 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),
  • 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.
  • 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.
  • 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 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

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Description

Maschinelles Geschirrspülmittel enthaltend Bleichmittel, Builder und EnzymeAutomatic dishwashing detergent containing bleach, builders and enzymes

Die vorliegende Erfindung betrifft ein maschinelles Geschirrspülmittel, das eine verbesserte Reinigungsleistung, insbesondere an enzymsensitiven Anschmutzungen zeigt, die Verwendung dieses Geschirrspülmittels sowie ein Verfahren zum maschinellen Geschirrspülen unter Verwendung dieses Geschirrspülmittels.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.

Das wichtigste Kriterium beim maschinellen Geschirrspülen ist die Reinigungsleistung an verschiedensten Anschmutzungen, welche in Form von Lebensmittelresten in die Geschirrspülmaschine eingebracht werden. Insofern besteht generell Bedarf an Geschirrspülmitteln mit gesteigerter Reinigungsleistung. Zusätzlich ist ein genereller Trend aus Umweltschutzgründen beim maschinellen Geschirrspülen auf Phosphate zu verzichten zu beobachten. Es stellt sich somit das Problem, phosphatfreie maschinelle Geschirrspülmittel bereitzustellen, ohne das die Reinigungsleistung beeinträchtigt wird.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 der EP 2 217 690 A1 wird eine Zusammensetzung beschrieben, die ein Enzym und eine bleichende Verbindung umfasst, wobei das Enzym und die bleichende Verbindung jeweils in eigenständigen Bereichen, d.h. räumlich voneinander getrennt formuliert werden, da diese Trennung die Enzymstabilität positiv beeinflusst. In den beschriebenen Formulierungen ist in dem Enzymbereich ferner ein Builder enthalten, wobei der Builder Methylglycindiessigsäure (MGDA) umfasst. Weitere mehrphasige Geschirrspülmittel, enthaltend MGDA sind aus US 2014/0018278 A1 , DE 102013225485 A1 und US 2013/0199569 A1 bekannt.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.

Ausgehend von dem bekannten Stand der Technik bestand die Aufgabe der vorliegenden Erfindung darin, ein, vorzugsweise phosphatfreies, maschinelles Geschirrspülmittel zur Verfügung zu stellen, das eine weiter gesteigerte Reinigungsleistung aufweist.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.

Es wurde nun überraschenderweise gefunden, dass es vorteilhaft für die Reinigungsleistung, speziell an enzymsensitiven Anschmutzungen, insbesondere protease-sensitiven Anschmutzungen, sowie hinsichtlich der Lagerungsstabilität der Enzyme ist, wenn die Enzymphase weitgehend frei von organischen Buildern, insbesondere MGDA, ist und die organischen Builder, insbesondere MGDA, in der Bleichephase des Mittels enthalten sind.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.

Ein erster Gegenstand der vorliegenden Erfindung ist daher ein maschinelles Geschirrspülmittel, umfassend (A) eine Enzymphase, wobei die Enzymphase mindestens ein Enzym enthält und im Wesentlichen frei ist von Bleichmitteln und organischen Buildern aus der Klasse der Aminocarbonsäuren und deren Salzen; und (B) eine Bleichephase, wobei die Bleichephase mindestens ein Bleichmittel, mindestens einen Bleichkatalysator, und mindestens einen organischen Builder aus der Klasse der Aminocarbonsäuren und deren Salzen, insbesondere Methylglycindiessigsäure (MGDA) oder ihre Salze, enthält.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.

Ebenfalls Gegenstand der vorliegenden Erfindung ist die Verwendung eines erfindungsgemäßen maschinellen Geschirrspülmittels in einem maschinellen Geschirrspülverfahren, insbesondere die Verwendung zur Verbesserung der Reinigungsleistung an enzymsensitiven Anschmutzungen auf Geschirr bei dessen Reinigung in einer automatischen Geschirrspülmaschine.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.

Schließlich richtet sich die vorliegende Erfindung auch auf ein maschinelles Geschirrspülverfahren, bei dem ein erfindungsgemäßes maschinelles Geschirrspülmittel insbesondere zu dem Zweck, die Reinigungsleistung an enzymsensitiven Anschmutzungen zu verbessern, zum Einsatz kommt.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.

Diese und weitere Aspekte, Merkmale und Vorteile der Erfindung werden für den Fachmann aus dem Studium der folgenden detaillierten Beschreibung und Ansprüche ersichtlich. Dabei kann jedes Merkmal aus einem Aspekt der Erfindung in jedem anderen Aspekt der Erfindung eingesetzt werden. Ferner ist es selbstverständlich, dass die hierin enthaltenen Beispiele die Erfindung beschreiben und veranschaulichen sollen, diese aber nicht einschränken und insbesondere die Erfindung nicht auf diese Beispiele beschränkt ist. Alle Prozentangaben sind, sofern nicht anders angegeben, Gewichts-%. Numerische Bereiche, die in dem Format "von x bis y" angegeben sind, schließen die genannten Werte ein. Wenn mehrere bevorzugte numerische Bereiche in diesem Format angegeben sind, ist es selbstverständlich, dass alle Bereiche, die durch die Kombination der verschiedenen Endpunkte entstehen, ebenfalls erfasst werden.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.

"Mindestens ein", wie hierin verwendet, bedeutet 1 oder mehr, d.h. 1, 2, 3, 4, 5, 6, 7, 8, 9 oder mehr. Bezogen auf einen Inhaltsstoff bezieht sich die Angabe auf die Art des Inhaltsstoffs und nicht auf die absolute Zahl der Moleküle. "Mindestens ein Bleichkatalysator" bedeutet somit beispielsweise mindestens eine Art von Bleichkatalysator, d.h. dass eine Art von Bleichkatalysator oder eine Mischung mehrerer verschiedener Bleichkatalysatoren gemeint sein kann. Zusammen mit Gewichtsangaben bezieht sich die Angabe auf alle Verbindungen der angegebenen Art, die in der Zusammensetzung/Mischung enthalten sind, d.h. dass die Zusammensetzung über die angegebene Menge der entsprechenden Verbindungen hinaus keine weiteren Verbindungen dieser Art enthält."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.

Wenn hierin auf Molmassen Bezug genommen wird, beziehen sich diese Angaben immer auf die zahlenmittlere Molmasse Mn, sofern nicht explizit anders angeben. Das Zahlenmittel der Molmasse kann beispielsweise mittels Gel-Permeations-Chromatographie (GPC) gemäß DIN 55672-1:2007-08 mit THF als Eluent bestimmt werden. Die massenmittlere Molmasse Mw kann ebenfalls mittels GPC bestimmt werden, wie für Mn beschrieben.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 .

Alle Prozentangaben, die im Zusammenhang mit den hierin beschriebenen Zusammensetzungen gemacht werden, beziehen sich, sofern nicht explizit anders angegeben auf Gew.-%, jeweils bezogen auf die betreffende Mischung.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.

"Im Wesentlichen frei von" oder "Frei von", wie hierin verwendet, bedeutet, dass der betreffende Inhaltsstoff in der entsprechende Phase oder dem entsprechenden Mittel in vernachlässigbarer Menge enthalten ist, insbesondere in einer Menge, die für die typische Funktionalität des Inhaltsstoffs nicht ausreichend ist."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.

Bevorzugt ist die Enzymphase "im Wesentlichen frei von MGDA oder ihren Salzen". Insbesondere bezieht sich diese Angabe auf Mengen von 1 Gew.-% oder weniger, vorzugsweise 0,5 Gew.-% oder weniger, noch bevorzugter 0,1 Gew.-% oder weniger, weiter bevorzugt 0,01 Gew.-% oder weniger, am meisten bevorzugt 0,001 Gew.-% oder weniger oder 0,0001 Gew.-% oder weniger, jeweils bezogen auf das Gewicht der Enzymphase. Entsprechende Mengen gelten ebenfalls für den Ausdruck "phosphatfrei", dabei sind die vorstehend genannten Gewichtsanteile jeweils bezogen auf das gesamte Reinigungsmittel.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.

Bevorzugt ist die Bleichephase "im Wesentlichen frei von Enzymen". Insbesondere bezieht sich diese Angabe auf Mengen an Enzymprotein von 0,1 Gew.-% oder weniger, vorzugsweise 0,05 Gew.-% oder weniger, noch bevorzugter 0,01 Gew.-% oder weniger, weiter bevorzugt 0,001 Gew.-% oder weniger, am meisten bevorzugt 0,0005 Gew.-% oder weniger oder 0,0001 Gew.-% oder weniger, jeweils bezogen auf das Gewicht der Bleichephase.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.

Im Rahmen der vorliegenden Erfindung stehen Fettsäuren bzw. Fettalkohole bzw. deren Derivate - soweit nicht anders angegeben - stellvertretend für verzweigte oder unverzweigte Carbonsäuren bzw. Alkohole bzw. deren Derivate mit vorzugsweise 6 bis 22 Kohlenstoffatomen. Insbesondere sind auch die beispielsweise nach der RoELENschen Oxo-Synthese erhältlichen Oxo-Alkohole bzw. deren Derivate entsprechend einsetzbar.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.

Wann immer im Folgenden Erdalkalimetalle als Gegenionen für einwertige Anionen genannt sind, so bedeutet das, dass das Erdalkalimetall natürlich nur in der halben - zum Ladungsausgleich ausreichenden - Stoffmenge wie das Anion vorliegt.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.

Die Mittel der vorliegenden Erfindung enthalten mindestens ein Enzym, vorzugsweise in Form einer Enzymzubereitung oder Enzymzusammensetzung, die ein oder mehrere Enzyme enthalten kann. Geeignete Enzyme umfassen, ohne darauf beschränkt zu sein, Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen, Perhydrolasen oder Oxidoreduktasen, sowie vorzugsweise deren Gemische. Diese Enzyme sind im Prinzip natürlichen Ursprungs; ausgehend von den natürlichen Molekülen stehen für den Einsatz in Reinigungsmitteln verbesserte Varianten zur Verfügung, die entsprechend bevorzugt eingesetzt werden. Erfindungsgemäße Reinigungsmittel enthalten Enzyme vorzugsweise in Gesamtmengen von 1 x 10-6 bis 5 Gew.-% bezogen auf aktives Protein. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren oder dem Biuret-Verfahren bestimmt werden.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.

Proteasen gehören zu den technisch bedeutendsten Enzymen überhaupt. Für Wasch- und Reinigungsmittel sind sie die am längsten etablierten und in praktisch allen modernen, leistungsfähigen Wasch- und Reinigungsmitteln enthaltenen Enzyme. Sie bewirken den Abbau proteinhaltiger Anschmutzungen auf dem Reinigungsgut. Hierunter sind wiederum Proteasen vom Subtilisin-Typ (Subtilasen, Subtilopeptidasen, EC 3.4.21.62) besonders wichtig, welche aufgrund der katalytisch wirksamen Aminosäuren Serin-Proteasen sind. Sie wirken als unspezifische Endopeptidasen und hydrolysieren beliebige Säureamidbindungen, die im Inneren von Peptiden oder Proteinen liegen. Ihr pH-Optimum liegt meist im deutlich alkalischen Bereich. Einen Überblick über diese Familie bietet beispielsweise der Artikel " Subtilases: Subtilisin-like Proteases" von R. Siezen, Seite 75-95 in " Subtilisin enzymes", herausgegeben von R. Bott und C. Betzel, New York, 1996 . Subtilasen werden natürlicherweise von Mikroorganismen gebildet. Hierunter sind insbesondere die von Bacillus-Spezies gebildeten und sezernierten Subtilisine als bedeutendste Gruppe innerhalb der Subtilasen zu erwähnen.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.

Beispiele für die in Wasch- und Reinigungsmitteln bevorzugt eingesetzten Proteasen vom Subtilisin-Typ sind die Subtilisine BPN' und Carlsberg, die Protease PB92, die Subtilisine 147 und 309, die Protease aus Bacillus lentus, insbesondere aus Bacillus lentus DSM 5483, Subtilisin DY und die den Subtilasen, nicht mehr jedoch den Subtilisinen im engeren Sinne zuzuordnenden Enzyme Thermitase, Proteinase K und die Proteasen TW3 und TW7, sowie Varianten der genannten Proteasen, die eine gegenüber der Ausgangsprotease veränderte Aminosäuresequenz aufweisen. Proteasen werden durch aus dem Stand der Technik bekannte Verfahren gezielt oder zufallsbasiert verändert und so beispielsweise für den Einsatz in Wasch- und Reinigungsmitteln optimiert. Dazu gehören Punktmutagenese, Deletions- oder Insertionsmutagenese oder Fusion mit anderen Proteinen oder Proteinteilen. So sind für die meisten aus dem Stand der Technik bekannten Proteasen entsprechend optimierte Varianten bekannt.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.

Beispiele für erfindungsgemäß einsetzbare Amylasen sind die α-Amylasen aus Bacillus licheniformis, aus B. amyloliquefaciens, aus B. stearothermophilus, aus Aspergillus niger und A. oryzae sowie die für den Einsatz in Reinigungsmitteln verbesserten Weiterentwicklungen der vorgenannten Amylasen. Des Weiteren sind für diesen Zweck die α-Amylase aus Bacillus sp. A 7-7 (DSM 12368) und die Cyclodextrin-Glucanotransferase (CGTase) aus B. agaradherens (DSM 9948) hervorzuheben.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).

Erfindungsgemäß einsetzbar sind weiterhin Lipasen oder Cutinasen, insbesondere wegen ihrer Triglycerid-spaltenden Aktivitäten, aber auch, um aus geeigneten Vorstufen in situ Persäuren zu erzeugen. Hierzu gehören beispielsweise die ursprünglich aus Humicola lanuginosa (Thermomyces lanuginosus) erhältlichen, beziehungsweise weiterentwickelten Lipasen, insbesondere solche mit dem Aminosäureaustausch D96L, T213R und/oder N233R, besonders bevorzugt alle der Austausche D96L, T213R und N233R.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.

Weiterhin können Enzyme eingesetzt werden, die unter dem Begriff Hemicellulasen zusammengefasst werden. Hierzu gehören beispielsweise Mannanasen, Xanthanlyasen, Pektinlyasen (=Pektinasen), Pektinesterasen, Pektatlyasen, Xyloglucanasen (=Xylanasen), Pullulanasen und β-Glucanasen.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.

Zur Erhöhung der bleichenden Wirkung können erfindungsgemäß Oxidoreduktasen, beispielsweise Oxidasen, Oxygenasen, Katalasen, Peroxidasen, wie Halo-, Chloro-, Bromo-, Lignin-, Glucose- oder Mangan-peroxidasen, Dioxygenasen oder Laccasen (Phenoloxidasen, Polyphenoloxidasen) eingesetzt werden. Vorteilhafterweise werden zusätzlich vorzugsweise organische, besonders bevorzugt aromatische, mit den Enzymen wechselwirkende Verbindungen zugegeben, um die Aktivität der betreffenden Oxidoreduktasen zu verstärken (Enhancer) oder um bei stark unterschiedlichen Redoxpotentialen zwischen den oxidierenden Enzymen und den Anschmutzungen den Elektronenfluss zu gewährleisten (Mediatoren).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 verschiedenen Ausführungsformen der Erfindung enthält das Mittel mindestens eine Protease und, vorzugsweise, auch mindestens eine Amylase.In various embodiments of the invention, the agent contains at least one protease and, preferably, also at least one amylase.

Ein Protein und/oder Enzym kann besonders während der Lagerung gegen Schädigungen wie beispielsweise Inaktivierung, Denaturierung oder Zerfall etwa durch physikalische Einflüsse, Oxidation oder proteolytische Spaltung geschützt werden. Bei mikrobieller Gewinnung der Proteine und/oder Enzyme ist eine Inhibierung der Proteolyse besonders bevorzugt, insbesondere wenn auch die Mittel Proteasen enthalten. Reinigungsmittel können zu diesem Zweck Stabilisatoren enthalten; die Bereitstellung derartiger Mittel stellt eine bevorzugte Ausführungsform der vorliegenden Erfindung dar.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.

Reinigungsaktive Proteasen und Amylasen werden in der Regel nicht in Form des reinen Proteins sondern vielmehr in Form stabilisierter, lager- und transportfähiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zählen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt.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.

Alternativ können die Enzyme sowohl für die feste als auch für die flüssige Darreichungsform verkapselt werden, beispielsweise durch Sprühtrocknung oder Extrusion der Enzymlösung zusammen mit einem vorzugsweise natürlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale-Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalien-undurchlässigen Schutzschicht überzogen ist. In aufgelagerten Schichten können zusätzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch Schüttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staubarm und aufgrund der Beschichtung lagerstabil.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.

Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

Wie aus der vorherigen Ausführungen ersichtlich, bildet das Enzym-Protein nur einen Bruchteil des Gesamtgewichts üblicher Enzym-Zubereitungen. Erfindungsgemäß bevorzugt eingesetzte Protease- und Amylase-Zubereitungen enthalten zwischen 0,1 und 40 Gew.-%, bevorzugt zwischen 0,2 und 30 Gew.-%, besonders bevorzugt zwischen 0,4 und 20 Gew.-% und insbesondere zwischen 0,8 und 10 Gew.-% des Enzymproteins.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.

Bevorzugt werden insbesondere solche Mittel, die, jeweils bezogen auf ihr Gesamtgewicht, 0,1 bis 12 Gew.-%, vorzugsweise 0,2 bis 10 Gew.-% und insbesondere 0,5 bis 8 Gew.-% Enzym-Zubereitungen enthalten.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.

Sofern nicht anders angegeben ist mit den Gewichtsangaben zu Enzymen jeweils die Menge an aktivem Enzymprotein bezogen auf die Gesamtmasse der gesamten Zusammensetzung gemeint. In einer bevorzugten Ausführungsform enthält die Enzymphase mindestens 0,0001 Gew.-%, bevorzugt mindestens 0,001 Gew.-%, insbesondere mindestens 0,01 Gew.-%, besonders bevorzugt mindestens 0,05 Gew.-%, ganz besonders bevorzugt mindestens 0,1 Gew.-% Protease pro Gramm der Gesamtzusammensetzung. In einer weiteren bevorzugten Ausführungsform enthält die Enzymphase mindestens 0,0001 Gew.-%, bevorzugt mindestens 0,0005 Gew.-%, insbesondere mindestens 0,001 Gew.-% besonders bevorzugt mindestens 0,005 Gew.-%, ganz besonders bevorzugt mindestens 0,01 Gew.-% Amylase pro Gramm der Gesamtzusammensetzung.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.

Gemäß einer besonders bevorzugten Ausführungsform enthält die Enzymphase mindestens 0,0005 Gew.-%, insbesondere mindestens 0,001 Gew.-% besonders bevorzugt mindestens 0,005 Gew.-%, ganz besonders bevorzugt mindestens 0,01 Gew.-% Amylase pro Gramm der Gesamtzusammensetzung und mindestens 0,001 Gew.-%, insbesondere mindestens 0,01 Gew.-%, besonders bevorzugt mindestens 0,05 Gew.-%, ganz besonders bevorzugt mindestens 0,1 Gew.-% Protease pro Gramm der Gesamtzusammensetzung.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.

Die hierin beschriebenen Zusammensetzungen können auch Enzymstabilisatoren beinhalten. Eine Gruppe von Stabilisatoren sind reversible Proteaseinhibitoren. Häufig werden hierfür Benzamidin-Hydrochlorid, Borax, Borsäuren, Boronsäuren oder deren Salze oder Ester eingesetzt, darunter vor allem Derivate mit aromatischen Gruppen, etwa ortho-, meta- oder para-substituierte Phenylboronsäuren, insbesondere 4-Formylphenyl-Boronsäure, beziehungsweise die Salze oder Ester der genannten Verbindungen. Auch Peptidaldehyde, das heißt Oligopeptide mit reduziertem C-Terminus, insbesondere solche aus 2 bis 50 Monomeren, oder deren Hydrogensulfitaddukte werden zu diesem Zweck eingesetzt. Zu den peptidischen reversiblen Proteaseinhibitoren gehören unter anderem Ovomucoid und Leupeptin. Auch spezifische, reversible Peptid-Inhibitoren für die Protease Subtilisin sowie Fusionsproteine aus Proteasen und spezifischen Peptid-Inhibitoren sind hierfür geeignet.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.

Weitere Enzymstabilisatoren sind Aminoalkohole wie Mono-, Di-, Triethanol- und -Propanolamin und deren Mischungen, aliphatische Carbonsäuren bis zu C12, wie beispielsweise Bernsteinsäure, andere Dicarbonsäuren oder Salze der genannten Säuren. Auch endgruppenverschlossene Fettsäureamidalkoxylate sind für diesen Zweck geeignet. Weitere Enzymstabilisatoren sind dem Fachmann aus dem Stand der Technik bekannt.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.

Die erfindungsgemäß einsetzbaren Bleichkatalysatoren schließen ein, sind aber nicht beschränkt auf die Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe, vorzugsweise der Mn-, Fe-, Co-, Ru - oder Mo-Salenkomplexe oder -carbonylkomplexe. Auch Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- und Cu-Komplexe mit N-haltigen Tripod-Liganden sowie Co-, Fe-, Cu- und Ru-Amminkomplexe sind als Bleichkatalysatoren verwendbar.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.

Mit besonderem Vorzug werden Komplexe des Mangans in der Oxidationsstufe II, III, IV oder IV eingesetzt, die vorzugsweise einen oder mehrere makrocyclische(n) Ligand(en) mit den Donorfunktionen N, NR, PR, O und/oder S enthalten. Vorzugsweise werden Liganden eingesetzt, die Stickstoff-Donorfunktionen aufweisen. Dabei ist es besonders bevorzugt, Bleichkatalysator(en) in den erfindungsgemäßen Mitteln einzusetzen, welche als makromolekularen Liganden 1,4,7-Trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-Triazacyclononan (TACN), 1,5,9-Trimethyl-1,5,9-triazacyclododecan (Me-TACD), 2-Methyl-1,4,7-trimethyl-1,4,7-triazacyclononan (Me/Me-TACN) und/oder 2-Methyl-1,4,7-triazacyclononan (Me/TACN) enthalten. Geeignete Mangankomplexe sind beispielsweise [MnIII 2(µ-O)1(µ-OAc)2(TACN)2](ClO4)2, [MnIIIMnIV(µ-O)2(µ-OAc)1(TACN)2](BPh4)2, [MnIV 4(µ-O)6(TACN)4](ClO4)4, [MnIII 2(µ-O)1(µ-OAc)2(Me-TACN)2](ClO4)2, [MnIIIMn IV(µ-O)1(g-OAc)2(Me-TACN)2](ClO4)3, [MnIV 2(µ-O)3(Me-TACN)2](PF6)2 und [MnIV 2(µ-O)3(Me/Me-TACN)2](PF6)2 (OAc = OC(O)CH3).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 ).

Maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass sie einen Bleichkatalysator ausgewählt aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe, vorzugsweise aus der Gruppe der Komplexe des Mangans mit 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN) oder 1,2,4,7-tetramethyl-1,4,7-triazacyclononan (Me/Me-TACN) enthalten, werden erfindungsgemäß bevorzugt, da durch die vorgenannten Bleichkatalysatoren insbesondere das Reinigungsergebnis signifikant verbessert werden kann.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.

Die vorgenannten bleichverstärkenden Übergangsmetallkomplexe, insbesondere mit den Zentralatomen Mn und Co werden vorzugsweise in einer Menge bis zu 1 Gew.-%, insbesondere von 0,001 Gew.-% bis 0,1 Gew.-% und besonders bevorzugt von 0,01 Gew.-% bis 0,05 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Mittel, eingesetzt. In speziellen Fällen kann jedoch auch mehr Bleichkatalysator eingesetzt werden.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.

Die erfindungsgemäß einsetzbaren Bleichmittel sind wasch- oder reinigungsaktive Substanzen. Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumpercarbonat, das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure. Weiterhin können auch Bleichmittel aus der Gruppe der organischen Bleichmittel eingesetzt werden. Typische organische Bleichmittel sind die Diacylperoxide, wie z.B. Dibenzoylperoxid. Weitere typische organische Bleichmittel sind die Peroxysäuren, wobei als Beispiele besonders die Alkylperoxysäuren und die Arylperoxysäuren genannt werden. Einsetzbar sind außerdem alle weiteren dem Fachmann aus dem Stand der Technik bekannten anorganischen oder organischen Peroxybleichmittel.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.

Als Bleichmittel können auch Chlor oder Brom freisetzende Substanzen eingesetzt werden. Unter den geeigneten Chlor oder Brom freisetzenden Materialien kommen beispielsweise heterozyklische N-Brom- und N-Chloramide, beispielsweise Trichlorisocyanursäure, Tribromisocyanursäure, Dibromisocyanursäure und/oder Dichlorisocyanursäure (DICA) und/oder deren Salze mit Kationen wie Kalium und Natrium in Betracht. Hydantoinverbindungen, wie 1,3-Dichlor-5,5-dimethylhydanthoin sind ebenfalls geeignet.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.

Vorzugsweise ist das Bleichmittel in einer Menge von 1-35 Gew.-% und zunehmend bevorzugt von 2-30 Gew.-%, 3,5-25 Gew.-%, von 4-20 Gew.-% und besonders bevorzugt von 5-15 Gew.-% in dem erfindungsgemäßen Geschirrspülmittel enthalten, jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels. Bevorzugte Geschirrspülmittel sind ferner dadurch gekennzeichnet, dass das Geschirrspülmittel, jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels, 2 bis 20 Gew.-%, vorzugsweise 3 bis 18 Gew.-% und insbesondere 4 bis 15 Gew.-% Natriumpercarbonat enthält.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.

Besonders bevorzugte Ausführungsformen erfindungsgemäßer Geschirrspülmittel sind dadurch gekennzeichnet, dass der Bleichkatalysator ausgewählt ist aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe, vorzugsweise aus der Gruppe der Komplexe des Mangans mit 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN) oder 1,2,4,7-tetramethyl-1,4,7-triazacyclononan (Me/Me-TACN), und/oder
die Wasserstoffperoxidquelle Natriumpercarbonat, Natriumperborattetrahydrat oder Natriumperboratmonohydrat oder eine Kombination hiervon ist. Ganz besonders bevorzugt ist der Bleichkatalysator ein Komplex des Mangans mit 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), insbesondere [MnIV 2(µ-O)3(Me-TACN)2](PF6)2, oder 1,2,4,7-tetramethyl-1,4,7-triazacyclononan (Me/Me-TACN) oder eine Mischung davon, und die Wasserstoffperoxidquelle Natriumpercarbonat. In den genannten Kombinationen liegen der Bleichkatalysator und die Wasserstoffperoxidquelle vorzugsweise in den vorstehend jeweils genannten Mengen vor.
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 verschiedenen Ausführungsformen der Erfindung enthalten die maschinellen Geschirrspülmittel zusätzlich mindestens einen Bleichaktivator. Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Von allen dem Fachmann aus dem Stand der Technik bekannten Bleichaktivatoren werden mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS) besonders bevorzugt eingesetzt. Ganz besonders bevorzugt ist TAED. Auch Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Diese Bleichaktivatoren werden vorzugsweise in Mengen bis 10 Gew.-%, insbesondere 0,1 Gew.-% bis 8 Gew.-%, besonders 2 bis 8 Gew.-% und besonders bevorzugt 2 bis 6 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Mittels, eingesetzt. Die Bleichaktivatoren können, im Gegensatz zu dem Bleichmittel und dem Bleichkatalysator, in der Enzymphase des Mittels formuliert sein. In verschiedenen Ausführungsformen ist dies eine bevorzugte Ausführungsform, die dazu dient in dem Mittel Bleichmittel und Bleichaktivator voneinander zu trennen.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.

Schließlich enthalten die erfindungsgemäßen Mittel mindestens einen Builder aus der Klasse der Aminocarbonsäuren und deren Salzen. Ein besonders bevorzugter Vertreter dieser Klasse ist Methylglycindiessigsäure (MGDA) oder Salze davon, aber auch Glutamindiessigsäure (GLDA) oder ihre Salze oder Ethylendiamindiessigsäure oder ihre Salze (EDDS) können eingesetzt werden. Der Gehalt an diesen Aminocarbonsäuren, insbesondere von MGDA, bzw. ihren Salzen kann beispielsweise zwischen 5 und 35 Gew.-% bevorzugt zwischen 10 und 25 Gew.-% und insbesondere zwischen 10 und 20 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Mittels, ausmachen. Aminocarbonsäuren und ihre Salze können zusammen mit anderen Gerüststoffen, insbesondere auch mit den phosphatfreien Gerüststoffen eingesetzt werden, die weiter unten beschrieben werden.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.

Die hierin beschriebenen Mittel umfassen mindestens zwei voneinander getrennte Phasen, nämlich mindestens eine Enzym-haltige Phase oder mindestens eine Bleiche-haltige Phase.The agents described herein comprise at least two separate phases, namely at least one enzyme-containing phase or at least one bleach-containing phase.

Eine Phase im Sinne der vorliegenden Erfindung ist ein räumlicher Bereich, in dem physikalische Parameter und die chemische Zusammensetzung homogen sind. Eine Phase unterscheidet sich von einer anderen Phase durch verschiedene Merkmale, beispielsweise Inhaltsstoffe, physikalische Eigenschaften, äußeres Erscheinungsbild etc. Bevorzugt können verschiedene Phasen optisch unterschieden werden. So ist für den Verbraucher die wenigstens eine erste Phase eindeutig von der wenigstens einen zweiten Phase zu unterschieden. Weist das erfindungsgemäße Wasch- oder Reinigungsmittel mehr als eine erste Phase auf, so können diese ebenfalls jeweils mit dem bloßen Auge voneinander unterschieden werden, weil sie sich beispielsweise in der Farbgebung voneinander unterscheiden. Gleiches gilt, wenn zwei oder mehr zweite Phasen vorliegen. Auch in diesem Fall ist eine optische Unterscheidung der Phasen, beispielsweise auf Grund eines Farb- oder Transparenzunterschiedes möglich. Phasen im Sinne der vorliegenden Erfindung sind somit in sich abgeschlossene Bereiche, die vom Verbraucher optisch mit dem bloßen Auge voneinander unterschieden werden können. Die einzelnen Phasen können bei der Verwendung unterschiedliche Eigenschaften aufweisen, wie beispielsweise die Geschwindigkeit, mit der sich die Phase in Wasser löst und somit die Geschwindigkeit und die Reihenfolge der Freisetzung der in der jeweiligen Phase enthaltenen Inhaltsstoffe.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.

Die Phasen sind typischerweise räumlich voneinander getrennt. Das kann in verschiedenen Ausführungsformen derart erfolgen, dass sie, wenn eine oder beide der Phasen flüssige Phasen sind, die flüssige Phase in einem separaten, abgeschlossenen Bereich, beispielsweise der Kammer eines Pouches, von der anderen Phase getrennt vorliegt. Derartige Konfektionsformen sind im Stand der Technik bekannt. Bei festen Mitteln, d.h. Mitteln in denen beide Phasen Feststoffe sind, werden die beiden Phasen ebenfalls räumlich getrennt voneinander konfektioniert, beispielsweise in Form eines Mehrkammer-Pouches, wobei jede der Phasen in einer separaten Kammer vorliegt. Alternativ können die beiden Phasen im Fall von kompaktierten Mitteln, wie beispielsweise Tabs oder Tabletten, insbesondere mehrphasigen Tabs wie sie im Stand der Technik bekannt sind, räumlich direkt benachbart angeordnet seien und zwar in der Art, dass die Phasen separat formuliert sind und sich kontaktieren, aber nicht vermischen können.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.

Vorzugsweise enthalten die erfindungsgemäßen Mittel mindestens einen weiteren Bestandteil, insbesondere mindestens zwei weitere Bestandteile, ausgewählt aus der Gruppe bestehend aus weiteren Gerüststoffen, Tensiden, Polymeren, Korrosionsinhibitoren und Glaskorrosionsinhibitoren, Desintegrationshilfsmitteln, Duftstoffen und Parfümträgern.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.

Nachfolgend werden mögliche Inhaltsstoffe beschrieben, welche vorteilhafterweise in den erfindungsgemäßen maschinellen Geschirrspülmitteln eingesetzt werden können.Possible ingredients are described below, which can advantageously be used in the automatic dishwashing detergents according to the invention.

Vorteilhafterweise können zusätzliche Gerüststoffe eingesetzt werden. Zu den zusätzlich einsetzbaren Gerüststoffen zählen insbesondere die Zeolithe, Silikate, Carbonate, organische Cobuilder und - wo keine ökologischen Vorurteile gegen ihren Einsatz bestehen - auch die Phosphate. Vorzugsweise sind die Mittel aber phosphatfrei.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.

Vorzugsweise können kristalline schichtförmige Silikate der allgemeinen Formel NaMSixO2x+1 · y H2O eingesetzt werden, worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4, wobei besonders bevorzugte Werte für x 2, 3 oder 4 sind, und y für eine Zahl von 0 bis 33, vorzugsweise von 0 bis 20 steht. Die kristallinen schichtförmigen Silikate der Formel NaMSixO2x+1 · y H2O werden beispielsweise von der Firma Clariant GmbH (Deutschland) unter dem Handelsnamen Na-SKS vertrieben. Beispiele für diese Silikate sind Na-SKS-1 (Na2Si22O45 · x H2O, Kenyait), Na-SKS-2 (Na2Si14O29 · x H2O, Magadiit), Na-SKS-3 (Na2Si8O17 · x H2O) oder Na-SKS-4 (Na2Si4O9 · x H2O, Makatit). Für die Zwecke der vorliegenden Erfindung besonders geeignet sind kristalline Schichtsilikate der Formel NaMSixO2x+1 · y H2O, in denen x für 2 steht. Insbesondere sind sowohl β- als auch δ-Natriumdisitikate Na2Si2O5 · y H2O sowie weiterhin vor allem Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (β-Na2Si2O5, Natrosilit), Na-SKS-9 (NaHSi2O5 · H2O), Na-SKS-10 (NaHSi2O5 · 3 H2O, Kanemit), Na-SKS-11 (t-Na2Si2O5) und Na-SKS-13 (NaHSi2O5), insbesondere aber Na-SKS-6 (δ-Na2Si2O5) bevorzugt.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.

Maschinelle Geschirrspülmittel enthalten vorzugsweise einen Gewichtsanteil des kristallinen schichtförmigen Silikats der Formel NaMSixO2x+1 · y H2O von 0,1 bis 20 Gew.-%, bevorzugt von 0,2 bis 15 Gew.-% und insbesondere von 0,4 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht dieser Mittel.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.

Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O:SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche vorzugsweise löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/Verdichtung oder durch Übertrocknung hervorgerufen worden sein. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" verstanden, dass die Silikate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen, hervorrufen.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.

Im Rahmen der vorliegenden Erfindung ist es bevorzugt, dass diese(s) Silikat(e), vorzugsweise Alkalisilikate, besonders bevorzugt kristalline oder amorphe Alkalidisilikate, in den Mitteln in Mengen von 3 bis 60 Gew.-%, vorzugsweise von 8 bis 50 Gew.-% und insbesondere von 20 bis 40 Gew.-%, jeweils bezogen auf das Gewicht des maschinellen Geschirrspülmittels, enthalten sind. Die Silikate sind vorzugsweise getrennt von der Enzymphase und, optional, auch der Bleichephase formuliert und können beispielsweise in einer dritten Phase des Mittels enthalten sein. Beispiele für eine solche Konfektionierung sind die bekannten festen Geschirrspülmitteltabs mit 2 Phasen und einem Kern, wobei hier beispielsweise der Kern das Silikat enthalten kann.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.

Obwohl auch ein Einsatz der allgemein bekannten Phosphate als Buildersubstanzen möglich ist, sind die hierin beschriebenen Mittel vorzugsweise phosphatfrei.Although it is also possible to use the generally known phosphates as builders, the agents described here are preferably phosphate-free.

Die Geschirrspülmittel können als weiteren Gerüststoff insbesondere auch Phosphonate enthalten, die erfindungsgemäß nicht unter die Phosphate subsummiert werden. Als Phosphonat-Verbindung wird vorzugsweise ein Hydroxyalkan- und/oder Aminoalkanphosphonat eingesetzt. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Phosphonate sind in den Mitteln vorzugsweise in Mengen von 0,1 bis 10 Gew.-%, insbesondere in Mengen von 0,5 bis 8 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels, enthalten. Die Phosphonate werden vorzugsweise ebenfalls separat von der Enzymphase formuliert, so dass die Enzymphase in verschiedenen Ausführungsformen keine Phosphonate enthält. Die Phosphonate können beispielsweise in der Bleichephase formuliert werden.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.

Weitere Gerüststoffe sind die Alkaliträger. Als Alkaliträger gelten beispielsweise Alkalimetallhydroxide, Alkalimetallcarbonate, Alkalimetallhydrogencarbonate, Alkalimetallsesquicarbonate, die genannten Alkalisilikate, Alkalimetasilikate, und Mischungen der vorgenannten Stoffe, wobei im Sinne dieser Erfindung bevorzugt die Alkalicarbonate, insbesondere Natriumcarbonat, Natriumhydrogencarbonat oder Natriumsesquicarbonat eingesetzt werden können. Besonders bevorzugt ist ein Buildersystem enthaltend eine Mischung aus Tripolyphosphat und Natriumcarbonat. Ebenfalls besonders bevorzugt ist ein Buildersystem enthaltend eine Mischung aus Tripolyphosphat und Natriumcarbonat und Natriumdisilikat. Aufgrund ihrer im Vergleich mit anderen Buildersubstanzen geringen chemischen Kompatibilität mit den übrigen Inhaltsstoffen von maschinellen Geschirrspülmitteln, werden die optionalen Alkalimetallhydroxide bevorzugt nur in geringen Mengen, vorzugsweise in Mengen unterhalb 10 Gew.-%, bevorzugt unterhalb 6 Gew.-%, besonders bevorzugt unterhalb 4 Gew.-% und insbesondere unterhalb 2 Gew.-%, jeweils bezogen auf das Gesamtgewicht des maschinellen Geschirrspülmittels, eingesetzt. Besonders bevorzugt werden Mittel, welche bezogen auf ihr Gesamtgewicht weniger als 0,5 Gew.-% und insbesondere keine Alkalimetallhydroxide enthalten.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.

Besonders bevorzugt ist der Einsatz von Carbonat(en) und/oder Hydrogencarbonat(en), vorzugsweise Alkalicarbonat(en), besonders bevorzugt Natriumcarbonat, in Mengen von 2 bis 50 Gew.-%, vorzugsweise von 5 bis 40 Gew.-% und insbesondere von 7,5 bis 30 Gew.-%, jeweils bezogen auf das Gewicht des maschinellen Geschirrspülmittels. Auch die genannten Alkaliträger werden vorzugsweise separat von der Enzymphase konfektioniert und können beispielsweise in der Bleichephase enthalten sein.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.

Als weitere organische Cobuilder sind insbesondere Polycarboxylate / Polycarbonsäuren, Asparaginsäure, Polyacetale, Dextrine, weitere organische Cobuilder sowie Phosphonate zu nennen. Diese Stoffklassen werden nachfolgend beschrieben.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.

Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form der freien Säure und/oder ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Die freien Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes der maschinellen Geschirrspülmittel. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.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.

Als besonders vorteilhaft für die Reinigungs- und Klarspülleistung erfindungsgemäßer Mittel hat sich der Einsatz von Citronensäure und/oder Citraten in diesen Mitteln erwiesen. Erfindungsgemäß bevorzugt werden daher maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass das maschinelle Geschirrspülmittel Citronensäure oder ein Salz der Citronensäure enthält und dass der Gewichtsanteil der Citronensäure oder des Salzes der Citronensäure vorzugsweise mehr als 5 Gew.-%, insbesondere zwischen 10 und 40 Gew.-% beträgt. Citronensäure und Citrate können auch in der Enzymphase formuliert werden.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.

Darüber hinaus können alle Verbindungen, die in der Lage sind, Komplexe mit Erdalkaliionen auszubilden, als Gerüststoffe eingesetzt werden.In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as builders.

Die erfindungsgemäßen Mittel können Tenside enthalten, wobei zur Gruppe der Tenside die nichtionischen, die anionischen, die kationischen und die amphoteren Tenside gezählt werden.The agents according to the invention can contain surfactants, the group of surfactants including nonionic, anionic, cationic and amphoteric surfactants.

Als nichtionische Tenside können alle dem Fachmann bekannten nichtionischen Tenside eingesetzt werden. Als nichtionische Tenside eignen sich beispielsweise Alkylglykoside der allgemeinen Formel RO(G)x, in der R einem primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen entspricht und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.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.

Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.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.

Weitere geeignete Tenside sind die als PHFA bekannten Polyhydroxyfettsäureamide.Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

Bevorzugt werden allerdings schwachschäumende nichtionische Tenside eingesetzt, insbesondere alkoxylierte, vor allem ethoxylierte, schwachschäumende nichtionische Tenside. Mit besonderem Vorzug enthalten die maschinellen Geschirrspülmittel nichtionische Tenside aus der Gruppe der alkoxylierten Alkohole.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.

Eine Klasse einsetzbarer nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden können, sind demnach alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette.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.

Bevorzugt einzusetzende Tenside stammen aus den Gruppen der ethoxylierten primären Alkohole und Mischungen dieser Tenside mit strukturell komplizierter aufgebauten Tensiden wie Polyoxypropylen/Polyoxyethylen/Polyoxypropylen ((PO/EO/PO)-Tenside). Solche (PO/EO/PO)-Niotenside zeichnen sich durch gute Schaumkontrolle aus.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.

Geeignete Niotenside sind solche, welche alternierende Ethylenoxid- und Alkylenoxideinheiten aufweisen. Unter diesen sind wiederum Tenside mit EO-AO-EO-AO-Blöcken bevorzugt, wobei jeweils eine bis zehn EO- bzw. AO-Gruppen aneinander gebunden sind, bevor ein Block aus den jeweils anderen Gruppen folgt. Hier sind nichtionische Tenside der allgemeinen Formel

Figure imgb0001
bevorzugt, in der R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-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 C9-15-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
Figure imgb0001
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.

Bevorzugte nichtionische Tenside sind hierbei solche der allgemeinen Formel

        R1-CH(OH)CH2O-(AO)w-(A'O)x-(A"O)y-(A"'O)z-R2,

in der

  • R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-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.

Bevorzugt werden insbesondere solche endgruppenverschlossene, poly(oxyalkylierten) Niotenside, die, gemäß der Formel R1O[CH2CH2O]xCH2CH(OH)R2, neben einem Rest R1, welcher für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 2 bis 30 Kohlenstoffatomen, vorzugsweise mit 4 bis 22 Kohlenstoffatomen steht, weiterhin einen linearen oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen Kohlenwasserstoffrest R2 mit 1 bis 30 Kohlenstoffatomen aufweisen, wobei x für Werte zwischen 1 und 90, vorzugsweise für Werte zwischen 10 und 80 und insbesondere für Werte zwischen 20 und 60 steht. Insbesondere bevorzugt sind Tenside der vorstehenden Formel, in denen R1 für C7 bis C13, x für eine ganze natürliche Zahl von 16 bis 28 und R2 für C8 bis C12 steht.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 .

Weiterhin bevorzugt sind Tenside der Formel R1O[CH2CH(CH3)O]x[CH2CH2O]yCH2CH(OH)R2, in der R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 18 Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x für Werte zwischen 0,5 und 1,5 sowie y für einen Wert von mindestens 15 steht.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.

Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C2-26 Fettalkohol-(PO)1-(EO)15-40-2-hydroxyalkylether, insbesondere auch die C8-10 Fettalkohol-(PO)1-(EO)22-2-hydroxydecylether. Besonders bevorzugt werden weiterhin solche endgruppenverschlossenen poly(oxyalkylierten) Niotenside der Formel R1O[CH2CH2O]x[CH2CH(R3)O]yCH2CH(OH)R2, in der R1 und R2 unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht, R3 unabhängig voneinander ausgewählt ist aus -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2, vorzugsweise jedoch für -CH3 steht, und x und y unabhängig voneinander für Werte zwischen 1 und 32 stehen, wobei Niotenside mit R3 = -CH3 und Werten für x von 15 bis 32 und y von 0,5 und 1,5 ganz besonders bevorzugt sind.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.

Weitere bevorzugt einsetzbare Niotenside sind die endgruppenverschlossenen poly(oxyalkylierten) Niotenside der Formel R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2, in der R1 und R2 für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen stehen, R3 für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht, x für Werte zwischen 1 und 30, k und j für Werte zwischen 1 und 12, vorzugsweise zwischen 1 und 5 stehen. Wenn der Wert x ≥ 2 ist, kann jedes R3 in der oben stehenden Formel R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2 unterschiedlich sein. R1 und R2 sind vorzugsweise lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 Kohlenstoffatomen, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind. Für den Rest R3 sind H, -CH3 oder -CH2CH3 besonders bevorzugt. Besonders bevorzugte Werte für x liegen im Bereich von 1 bis 20, insbesondere von 6 bis 15.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.

Wie vorstehend beschrieben, kann jedes R3 in der oben stehenden Formel unterschiedlich sein, falls x ≥ 2 ist. Hierdurch kann die Alkylenoxideinheit in der eckigen Klammer variiert werden. Steht x beispielsweise für 3, kann der Rest R3 ausgewählt werden, um Ethylenoxid- (R3 = H) oder Propylenoxid- (R3 = CH3) Einheiten zu bilden, die in jedweder Reihenfolge aneinandergefügt sein können, beispielsweise (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) und (PO)(PO)(PO). Der Wert 3 für x ist hierbei beispielhaft gewählt worden und kann durchaus größer sein, wobei die Variationsbreite mit steigenden x-Werten zunimmt und beispielsweise eine große Anzahl (EO)-Gruppen, kombiniert mit einer geringen Anzahl (PO)-Gruppen einschließt, oder umgekehrt.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 .

Besonders bevorzugte endgruppenverschlossene poly(oxyalkylierte) Alkohole der oben stehenden Formel weisen Werte von k = 1 und j = 1 auf, so dass sich die vorstehende Formel zu R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR2 vereinfacht. In der letztgenannten Formel sind R1, R2 und R3 wie oben definiert und x steht für Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesondere von 6 bis 18. Besonders bevorzugt sind Tenside, bei denen die Reste R1 und R2 9 bis 14 C-Atome aufweisen, R3 für H steht und x Werte von 6 bis 15 annimmt.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.

Als besonders wirkungsvoll haben sich schließlich die nichtionischen Tenside der allgemeinen Formel R1-CH(OH)CH2O-(AO)w-R2 erwiesen, in der

  • R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-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

Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C4-22 Fettalkohol-(EO)10-80-2-hydroxyalkylether, insbesondere auch die C8-12 Fettalkohol-(EO)22-2-hydroxydecylether und die C4-22 Fettalkohol-(EO)40-80-2-hydroxyalkylether.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 verschiedenen Ausführungsformen der Erfindung können anstelle der oben definierten endgruppenverschlossenen Hydroxymischether auch die entsprechenden nicht endgruppenverschlossenen Hydroxymischether eingesetzt werden. Diese können den obigen Formeln genügen, wobei R2 aber Wasserstoff ist und R1, R3, A, A', A", A"', w, x, y und z wie oben definiert sind.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.

Die hierin beschriebenen Mittel, die mindestens ein nichtionisches Tensid, vorzugsweise ein nichtionisches Tensid aus der Gruppe der Hydroxymischether, umfassen, enthalten das Tensid in verschiedenen Ausführungsformen in einer Menge bezogen auf das Gesamtgewicht des Mittels von mindestens 2 Gew.%, vorzugsweise mindestens 5 Gew.%. Die absolut pro Anwendung eingesetzten Mengen können beispielsweise im Bereich von 0,5-10 g/job, vorzugsweise im Bereich von 0,5-5 g/job liegen.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.

Insbesondere bevorzugt sind nichtionische Tenside, die einen Schmelzpunkt oberhalb Raumtemperatur aufweisen. Nichtionische(s) Tensid(e) mit einem Schmelzpunkt oberhalb von 20°C, vorzugsweise oberhalb von 25°C, besonders bevorzugt zwischen 25 und 60°C und insbesondere zwischen 26,6 und 43,3°C, ist/sind besonders bevorzugt.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 .

Als anionische Tenside eignen sich in den Geschirrspülmitteln alle anionischen oberflächenaktiven Stoffe. Diese sind gekennzeichnet durch eine wasserlöslich machende, anionische Gruppe wie z. B. eine Carboxylat-, Sulfat-, Sulfonat- oder Phosphat-Gruppe und eine lipophile Alkylgruppe mit etwa 8 bis 30 C-Atomen. Zusätzlich können im Molekül Glykol- oder Polyglykolether-Gruppen, Ester-, Ether- und Amidgruppen sowie Hydroxylgruppen enthalten sein. Geeignete anionische Tenside liegen vorzugsweise in Form der Natrium-, Kalium- und Ammonium- sowie der Mono-, Di- und Trialkanolammoniumsalze mit 2 bis 4 C-Atomen in der Alkanolgruppe vor, aber auch Zink, Mangan(II), Magnesium, Calcium oder Mischungen hieraus können als Gegenionen dienen.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.

Bevorzugte anionische Tenside sind Alkylsulfate, Alkylpolyglykolethersulfate und Ethercarbonsäuren mit 10 bis 18 C-Atomen in der Alkylgruppe und bis zu 12 Glykolethergruppen im Molekül.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.

An Stelle der genannten Tenside oder in Verbindung mit ihnen können auch kationische und/oder amphotere Tenside, wie Betaine oder quartäre Ammoniumverbindungen, eingesetzt werden. Es ist allerdings bevorzugt, dass keine kationischen und/oder amphoteren Tenside eingesetzt werden.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.

Die vorstehend für die beschriebenen Tenside und weiteren Gerüststoffe angegebenen Mengen beziehen sich üblicherweise auf die Mengen, die eingesetzt werden, wenn das jeweilige Tensid oder der jeweilige Gerüststoffe allein eingesetzt wird, sofern nicht explizit anders angegeben. Es ist daher selbstverständlich, dass beim Einsatz mehrerer Tenside oder Gerüststoffe, die Mengenangaben entsprechend anzupassen sind.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.

Die hierin beschriebenen Mittel können ferner verschiedenen Polymere enthalten.The agents described herein may also contain various polymers.

Erfindungsgemäß können in verschiedenen Ausführungsformen beispielsweise Homopolymere von α,β ethylenisch ungesättigten Carbonsäuren eingesetzt werden. Als ungesättigte Carbonsäure(n) wird/werden mit besonderem Vorzug ungesättigte Carbonsäuren der Formel R1(R2)C=C(R3)COOH eingesetzt, in der R1 bis R3 unabhängig voneinander für -H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist.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.

Besonders bevorzugte ungesättigte Carbonsäuren sind Acrylsäure, Methacrylsäure, Ethacrylsäure, α-Chloroacrylsäure, α-Cyanoacrylsäure, Crotonsäure, α-Phenyl-Acrylsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure, Citraconsäure (Methylmaleinsäure), Methylenmalonsäure, Sorbinsäure, Zimtsäure oder deren Mischungen. Ganz besonders bevorzugt ist Acrylsäure. In verschiedenen Ausführungsformen der Erfindung ist das Homopolymer daher eine Polyacrylsäure.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.

In den Polymeren können die Carbonsäuregruppen ganz oder teilweise in neutralisierter Form vorliegen, d.h. dass das acide Wasserstoffatom der Carbonsäuregruppe in einigen oder allen Carbonsäuregruppen gegen Metallionen, vorzugsweise Alkalimetallionen und insbesondere gegen Natriumionen, ausgetauscht sein kann. Der Einsatz von teil- oder vollneutralisierten Polymeren ist erfindungsgemäß bevorzugt.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.

Die Molmasse der eingesetzten Homopolymere kann variiert werden, um die Eigenschaften der Polymere dem gewünschten Verwendungszweck anzupassen. Bevorzugte Geschirrspülmittel sind dadurch gekennzeichnet, dass die Homopolymere, insbesondere die Polyacrylsäuren, Molmassen Mn von 1000 bis 20.000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 1100 bis 10000 g/mol, und besonders bevorzugt von 1200 bis 5000 g/mol, aufweisen, bevorzugt sein.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 verschiedenen bevorzugten Ausführungsformen der Erfindung enthalten die Mittel ferner mindestens ein Sulfopolymer. Die in diesem Zusammenhang verwendbaren Polymere sind insbesondere Copolymere, die zwei, drei, vier oder mehr unterschiedliche Monomereinheiten aufweisen können, wobei mindestens eine Monomereinheit eine Sulfonsäuregruppe trägt. Bevorzugte Copolymere enthalten neben Sulfonsäuregruppen-haltigem(n) Monomer(en) wenigstens ein Monomer aus der Gruppe der ungesättigten Carbonsäuren.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.

Als ungesättigte Carbonsäure(n) wird/werden mit besonderem Vorzug die oben beschriebenen ungesättigten Carbonsäuren eingesetzt. Ganz besonders bevorzugt ist dabei Acrylsäure.The unsaturated carboxylic acids described above are used with particular preference as unsaturated carboxylic acid (s). Acrylic acid is very particularly preferred.

Bei den Sulfonsäuregruppen-haltigen Monomeren sind solche der Formel

        R5(R6)C=C(R1)-X-SO3H

bevorzugt, in der R5 bis R7 unabhängig voneinander für-H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit-NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste oder für -COOH oder -COOR4 stehen, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.
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 -.

Unter diesen Monomeren bevorzugt sind solche der Formeln

        H2C=CH-X-SO3H

        H2C=C(CH3)-X-SO3H

        HO3S-X-(R6)C=C(R7)-X-SO3H,

in denen R6 und R7 unabhängig voneinander ausgewählt sind aus -H, -CH3, -CH2CH3,-CH2CH2CH3 und -CH(CH3)2 und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.
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 -.

Besonders bevorzugte Sulfonsäuregruppen-haltige Monomere sind dabei 1-Acrylamido-1-propansulfonsäure, 2-Acrylamido-2-propansulfonsäure, 2-Acrylamido-2-methyl-1-propansulfonsäure, 2-Methacrylamido-2-methyl-1-propansulfonsäure, 3-Methacrylamido-2-hydroxy-propansulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Allyloxybenzolsulfonsäure, Methallyloxybenzolsulfonsäure, 2-Hydroxy-3-(2-propenyloxy)propansulfonsäure, 2-Methyl-2-propen1-sulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 3-Sulfopropylacrylat, 3-Sulfopropylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Mischungen der genannten Säuren oder deren wasserlösliche Salze.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.

Auch in den Copolymeren können die Säuregruppen ganz oder teilweise in neutralisierter Form vorliegen, d.h. dass das acide Wasserstoffatom der Sulfon- und/oder Carbonsäuregruppe in einigen oder allen Säuregruppen gegen Metallionen, vorzugsweise Alkalimetallionen und insbesondere gegen Natriumionen, ausgetauscht sein kann. Der Einsatz von teil- oder vollneutralisierten Copolymeren ist erfindungsgemäß bevorzugt.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.

Die Monomerenverteilung der bevorzugt eingesetzten Copolymere beträgt bei Copolymeren, die nur Carbonsäuregruppen-haltige Monomere und Sulfonsäuregruppen-haltige Monomere enthalten, vorzugsweise jeweils 5 bis 95 Gew.-%, besonders bevorzugt beträgt der Anteil des Sulfonsäuregruppen-haltigen Monomers 50 bis 90 Gew.-% und der Anteil des Carbonsäuregruppen-haltigen Monomers 10 bis 50 Gew.-%, die Monomere sind hierbei vorzugsweise ausgewählt aus den zuvor genannten.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 verschiedenen Ausführungsformen können die Copolymere neben den oben beschriebenen Carbonsäuregruppen-haltigen Monomeren und Sulfonsäuregruppen-haltigen Monomeren weitere Monomere enthalten, insbesondere ungesättigte Carbonsäureestergruppen-haltige Monomere. In solchen Terpolymeren sind die Carbonsäureestergruppen-haltigen Monomere beispielsweise solche der Formel R1(R2)C=C(R3)COOR4, in der R1 bis R3 wie oben definiert sind und R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist.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.

Besonders bevorzugte ungesättigte Carbonsäureester sind Alkylester von Monocarbonsäuren wie der Acrylsäure, Methacrylsäure, Ethacrylsäure, α-Chloroacrylsäure, α-Cyanoacrylsäure, Crotonsäure, α-Phenyl-Acrylsäure, Sorbinsäure, Zimtsäure oder deren Mischungen. Ganz besonders bevorzugt sind C1-8 Alkylester von Acrylsäure, wie Methylacrylat, Ethylacrylat, Propylacrylat, Butylacrylat. Ganz besonders bevorzugt ist Ethylacrylat.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.

Die Molmasse der eingesetzten Copolymere kann variiert werden, um die Eigenschaften der Polymere dem gewünschten Verwendungszweck anzupassen. Bevorzugte Geschirrspülmittel sind dadurch gekennzeichnet, dass die Copolymere Molmassen Mn von 2000 bis 200.000 g/mol, vorzugsweise von 4000 bis 25.000 g/mol und insbesondere von 5000 bis 15.000 g/mol aufweisen.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.

Die oben beschriebenen Homopolymere und Copolymere können jeweils in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise 1 bis 5 Gew.-%, bezogen auf das Gesamtgewicht des Mittels eingesetzt werden. Absolute Mengen liegen typischerweise im Bereich von 0,1 bis 2 g/job, vorzugsweise im Bereich von 0,2 bis 1,0 g/job. Das Massenverhältnis der Polymere zueinander, d.h. Homopolymer zu Copolymer, beträgt dabei in verschiedenen Ausführungsformen 5:1 bis 1:5, vorzugsweise 2:1 bis 1:2.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.

Die Geschirrspülmittel können alternativ oder zusätzlich weitere Polymere enthalten. Zur Gruppe geeigneter Polymere zählen insbesondere die reinigungsaktiven amphoteren, zwitterionischen oder kationischen Polymere, beispielsweise die Klarspülpolymere und/oder als Enthärter wirksame Polymere.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.

Bevorzugte einsetzbare amphotere Polymere stammen aus der Gruppe der Alkylacrylamid/Acrylsäure-Copolymere, der Alkylacrylamid/Methacrylsäure-Copolymere, der Alkylacrylamid/Methylmethacrylsäure-Copolymere, der Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere, der Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)-acrylsäure-Copolymere, der Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere, der Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere sowie der Copolymere aus ungesättigten Carbonsäuren, kationisch derivatisierten ungesättigten Carbonsäuren und gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.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.

Weitere einsetzbare zwitterionische Polymere stammen aus der Gruppe der Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze, der Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze und der Methacroylethylbetain/Methacrylat-Copolymere.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.

Einsetzbare kationische Polymere stammen aus den Gruppen der quaternierten Cellulose-Derivate, der Polysiloxane mit quaternären Gruppen, der kationischen Guar-Derivate, der polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Acrylsäure und Methacrylsäure und deren Estern und Amiden, der Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, der Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, der quaternierter Polyvinylalkohole oder der unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.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.

In einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung liegen die vorgenannten amphoteren, zwitterionischen oder kationischen Polymere in vorkonfektionierter Form vor. Zur Konfektionierung der Polymere eignet sich dabei u.a.

  • 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.

Maschinelle Geschirrspülmittel enthalten die vorgenannten kationischen und/oder amphoteren Polymere vorzugsweise in Mengen zwischen 0,01 und 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht des maschinellen Geschirrspülmittels. Bevorzugt werden im Rahmen der vorliegenden Anmeldung jedoch solche maschinelle Geschirrspülmittel, bei denen der Gewichtsanteil der kationischen und/oder amphoteren Polymere zwischen 0,01 und 8 Gew.-%, vorzugsweise zwischen 0,01 und 6 Gew.-%, bevorzugt zwischen 0,01 und 4 Gew.-%, besonders bevorzugt zwischen 0,01 und 2 Gew.-% und insbesondere zwischen 0,01 und 1 Gew.-%, jeweils bezogen auf das Gesamtgewicht des maschinellen Geschirrspülmittels, beträgt.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.

Generell kann der pH-Wert des Geschirrspülmittels mittels üblicher pH-Regulatoren eingestellt werden, wobei der pH-Wert abhängig von dem gewünschten Einsatzzweck gewählt wird. In verschiedenen Ausführungsformen liegt der pH-Wert in einem Bereich von 5,5 bis 11, vorzugsweise 5,5 bis 10,5, noch bevorzugter 7 bis 10,5, insbesondere größer 7, vor allem im Bereich 8 bis 10. Als pH-Stellmittel dienen Säuren und/oder Alkalien, vorzugsweise Alkalien. Geeignete Säuren sind insbesondere organische Säuren wie die Essigsäure, Zitronensäure, Glycolsäure, Milchsäure, Bernsteinsäure, Adipinsäure, Äpfelsäure, Weinsäure und Gluconsäure oder auch Amidosulfonsäure. Daneben können aber auch die Mineralsäuren Salzsäure, Schwefelsäure und Salpetersäure bzw. deren Mischungen eingesetzt werden. Geeignete Basen stammen aus der Gruppe der Alkali- und Erdalkalimetallhydroxide und -carbonate, insbesondere der Alkalimetallhydroxide, von denen Kaliumhydroxid und vor allem Natriumhydroxid bevorzugt ist. Besonders bevorzugt ist allerdings flüchtiges Alkali, beispielsweise in Form von Ammoniak und/oder Alkanolaminen, die bis zu 9 C-Atome im Molekül enthalten können. Das Alkanolamin ist hierbei vorzugsweise ausgewählt aus der Gruppe bestehend aus Mono-, Di-, Triethanol- und -Propanolamin und deren Mischungen.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.

Zur Einstellung und/oder Stabilisierung des pH-Werts kann das erfindungsgemäße Mittel auch ein oder mehrere Puffersubstanzen (INCI Buffering Agents) enthalten, üblicherweise in Mengen von 0,001 bis 5 Gew.-%. Bevorzugt sind Puffersubstanzen, die zugleich Komplexbildner oder sogar Chelatbildner (Chelatoren, INCI Chelating Agents) sind. Besonders bevorzugte Puffersubstanzen sind die Citronensäure bzw. die Citrate, insbesondere die Natrium- und Kaliumcitrate, beispielsweise Trinatriumcitrat·2H2O und Trikaliumcitrat·H2O.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.

Glaskorrosionsinhibitoren verhindern das Auftreten von Trübungen, Schlieren und Kratzern aber auch das Irisieren der Glasoberfläche von maschinell gereinigten Gläsern. Bevorzugte Glaskorrosionsinhibitoren stammen aus der Gruppe der Magnesium- und Zinksalze sowie der Magnesium- und Zinkkomplexe. Im Rahmen der vorliegenden Erfindung beträgt der Gehalt an Zinksalz in maschinellen Geschirrspülmitteln vorzugsweise zwischen 0,1 bis 5 Gew.-%, bevorzugt zwischen 0,2 bis 4 Gew.-% und insbesondere zwischen 0,4 bis 3 Gew.-%, bzw. der Gehalt an Zink in oxidierter Form (berechnet als Zn2+) zwischen 0,01 bis 1 Gew.-%, vorzugsweise zwischen 0,02 bis 0,5 Gew.-% und insbesondere zwischen 0,04 bis 0,2 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Glaskorrosionsinhibitor-haltigen Mittels. Zusätzlich oder alternativ zu den o.g. Salzen (insbesondere den Zinksalzen) können Polyethylenimine, wie sie beispielsweise unter dem Namen Lupasol® (BASF) erhältlich sind, vorzugsweise in einer Menge von 0 bis 5 Gew.-%, insbesondere 0,01 bis 2 Gew.-%, als Glaskorrosionsinhibitoren eingesetzt werden.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.

Als Parfümöle bzw. Duftstoffe können im Rahmen der vorliegenden Erfindung einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, z.B. Pinien-, Citrus-, Jasmin-, Patchouli-, Rosen- oder Ylang-Ylang-Öl.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.

Weiterhin können Konservierungsmittel in den Mitteln enthalten sein. Geeignet sind beispielsweise Konservierungsmittel aus den Gruppen der Alkohole, Aldehyde, antimikrobiellen Säuren und/oder deren Salze, Carbonsäureester, Säureamide, Phenole, Phenolderivate, Diphenyle, Diphenylalkane, Harnstoffderivate, Sauerstoff-, Stickstoff-Acetale sowie -Formale, Benzamidine, Isothiazole und deren Derivate wie Isothiazoline und Isothiazolinone, Phthalimidderivate, Pyridinderivate, antimikrobiellen oberflächenaktiven Verbindungen, Guanidine, antimikrobiellen amphoteren Verbindungen, Chinoline, 1,2-Dibrom-2,4-dicyanobutan, lodo-2-propynyl-butyl-carbamat, Iod, lodophore und Peroxide. Bevorzugte antimikrobielle Wirkstoffe werden vorzugsweise ausgewählt aus der Gruppe umfassend Ethanol, n-Propanol, i-Propanol, 1,3-Butandiol, Phenoxyethanol, 1,2-Propylenglykol, Glycerin, Undecylensäure, Zitronensäure, Milchsäure, Benzoesäure, Salicylsäure, Thymol, 2-Benzyl-4-chlorphenol, 2,2'-Methylen-bis-(6-brom-4-chlorphenol), 2,4,4'-Trichlor-2'-hydroxydiphenylether, N-(4-Chlorphenyl)-N-(3,4-dichlorphenyl)-harnstoff, N,N'-(1,10-decandiyldi-1-pyridinyl-4-yliden)-bis-(1-octanamin)-dihydrochlorid, N,N'-Bis-(4-Chlorphenyl)-3,12-diimino-2,4,11,13-tetraazatetradecandiimidamid, antimikrobielle quaternäre oberflächenaktive Verbindungen, Guanidine. Besonders bevorzugte Konservierungsmittel sind jedoch ausgewählt aus der Gruppe umfassend Salicylsäure, quaternäre Tenside, insbesondere Benzalkoniumchlorid und Isothiazole und deren Derivate wie Isothiazoline und Isothiazolinone.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.

Generell kann die Konfektionierung hierin beschriebener maschineller Geschirrspülmittel in unterschiedlicher Weise erfolgen. Die Mittel können in fester oder flüssiger sowie als Kombination fester und flüssiger Angebotsformen vorliegen. Als feste Angebotsformen eignen sich insbesondere Pulver, Granulate, Extrudate, Kompaktate, insbesondere Tabletten. Die flüssigen Angebotsformen auf Basis von Wasser und/oder organischen Lösungsmitteln können verdickt, in Form von Gelen vorliegen. Die Mittel werden in Form mehrphasiger Produkte konfektioniert. Die einzelnen Phasen solcher mehrphasiger Mittel können gleiche oder unterschiedliche Aggregatzustände aufweisen.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.

Die Geschirrspülmittel können als Formkörper vorliegen. Um den Zerfall solcher vorgefertigter Formkörper zu erleichtern, ist es möglich, Desintegrationshilfsmittel, so genannte Tablettensprengmittel, in diese Mittel einzuarbeiten, um die Zerfallszeiten zu verkürzen. Unter Tablettensprengmitteln bzw. Zerfallsbeschleunigern werden Hilfsstoffe verstanden, die für den raschen Zerfall von Tabletten in Wasser oder anderen Medien und für die zügige Freisetzung der Wirkstoffe sorgen. Bevorzugt können Desintegrationshilfsmittel in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise 3 bis 7 Gew.-% und insbesondere 4 bis 6 Gew.-%, jeweils bezogen auf das Gesamtgewicht des desintegrationshilfsmittelhaltigen Mittels, eingesetzt werden.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.

Die hierin beschriebenen maschinellen Geschirrspülmittel werden vorzugsweise zu Dosiereinheiten vorkonfektioniert. Diese Dosiereinheiten sind dann ebenfalls als mehrphasige Produkte konfektioniert und umfassen vorzugsweise die für einen Reinigungsgang notwendige Menge an reinigungsaktiven Substanzen. Bevorzugte Dosiereinheiten weisen ein Gewicht zwischen 12 und 30 g, bevorzugt zwischen 14 und 26 g und insbesondere zwischen 15 und 22 g auf. Das Volumen der vorgenannten Dosiereinheiten sowie deren Raumform sind mit besonderem Vorzug so gewählt, dass eine Dosierbarkeit der vorkonfektionierten Einheiten über die Dosierkammer einer Geschirrspülmaschine gewährleistet ist. Das Volumen der Dosiereinheit beträgt daher bevorzugt zwischen 10 und 35 ml, vorzugsweise zwischen 12 und 30 ml.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.

Die maschinellen Geschirrspülmittel, insbesondere die vorgefertigten Dosiereinheiten weisen mit besonderem Vorzug eine wasserlösliche Umhüllung auf.The machine dishwashing detergents, in particular the prefabricated metering units, particularly preferably have a water-soluble coating.

Die wasserlösliche Umhüllung wird vorzugsweise aus einem wasserlöslichen Folienmaterial, welches ausgewählt ist aus der Gruppe, bestehend aus Polymeren oder Polymergemischen, gebildet. Die Umhüllung kann aus einer oder aus zwei oder mehr Lagen aus dem wasserlöslichen Folienmaterial gebildet werden. Das wasserlösliche Folienmaterial der ersten Lage und der weiteren Lagen, falls vorhanden, kann gleich oder unterschiedlich sein. Besonders bevorzugt sind Folien, die beispielsweise zu Verpackungen wie Schläuchen oder Kissen verklebt und/oder versiegelt werden können, nachdem sie mit einem Mittel befüllt wurden.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.

Die wasserlösliche Verpackung kann eine oder mehr Kammern aufweisen. Das Mittel kann in einer oder mehreren Kammern, falls vorhanden, der wasserlöslichen Umhüllung enthalten sein. Die Menge an Mittel entspricht vorzugsweise der vollen oder halben Dosis, die für einen Spülgang benötigt wird.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.

Es ist bevorzugt, dass die wasserlösliche Umhüllung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthält. Wasserlösliche Umhüllungen, die Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthalten, weisen eine gute Stabilität bei einer ausreichend hohen Wasserlöslichkeit, insbesondere Kaltwasserlöslichkeit, auf.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.

Geeignete wasserlösliche Folien zur Herstellung der wasserlöslichen Umhüllung basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer, dessen Molekulargewicht im Bereich von 5.000 bis 1.000.000 gmol-1, vorzugsweise von 20.000 bis 500.000 gmol-1, besonders bevorzugt von 30.000 bis 100.000 gmol-1 und insbesondere von 40.000 bis 80.000 gmol-1 liegt.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 .

Die Herstellung von Polyvinylalkohol geschieht üblicherweise durch Hydrolyse von Polyvinylacetat, da der direkte Syntheseweg nicht möglich ist. Ähnliches gilt für Polyvinylalkoholcopolymere, die aus entsprechend aus Polyvinylacetatcopolymeren hergestellt werden. Bevorzugt ist, wenn wenigstens eine Lage der wasserlöslichen Umhüllung einen Polyvinylalkohol umfasst, dessen Hydrolysegrad 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-% ausmacht.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%.

Einem zur Herstellung der wasserlöslichen Umhüllung geeignetem Polyvinylalkohol-enthaltendem Folienmaterial kann zusätzlich ein Polymer ausgewählt aus der Gruppe umfassend (Meth)Acrylsäure-haltige (Co)Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester, Polyether, Polymilchsäure oder Mischungen der vorstehenden Polymere zugesetzt sein. Ein bevorzugtes zusätzliches Polymer sind Polymilchsäuren.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.

Bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol Dicarbonsäuren als weitere Monomere. Geeignete Dicarbonsäuren sind Itaconsäure, Malonsäure, Bernsteinsäure und Mischungen daraus, wobei Itaconsäure bevorzugt ist.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.

Ebenfalls bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol eine ethylenisch ungesättige Carbonsäure, deren Salz oder deren Ester. Besonders bevorzugt enthalten solche Polyvinylalkoholcopolymere neben Vinylalkohol Acrylsäure, Methacrylsäure, Acrylsäureester, Methacrylsäureester oder Mischungen daraus.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.

Es kann bevorzugt sein, dass das Folienmaterial weitere Zusatzstoffe enthält. Das Folienmaterial kann beispielsweise Weichmacher wie Dipropylenglycol, Ethylenglycol, Diethylenglycol, Propylenglycol, Glycerin, Sorbitol, Mannitol oder Mischungen daraus enthalten. Weitere Zusatzstoffe umfassen beispielsweise Freisetzungshilfen, Füllmittel, Vernetzungsmittel, Tenside, Antioxidationsmittel, UV-Absorber, Antiblockmittel, Antiklebemittel oder Mischungen daraus.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.

Geeignete wasserlösliche Folien zum Einsatz in den wasserlöslichen Umhüllungen der wasserlöslichen Verpackungen gemäß der Erfindung sind Folien, die von der Firma MonoSol LLC beispielsweise unter der Bezeichnung M8630, C8400 oder M8900 vertrieben werden. Andere geeignete Folien umfassen Folien mit der Bezeichnung Solublon® PT, Solublon® GA, Solublon® KC oder Solublon® KL von der Aicello Chemical Europe GmbH oder die Folien VF-HP von Kuraray.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.

Gemäß einer bevorzugten Ausführungsform ist das mehrphasige Geschirrspülmittel von einer wasserlöslichen Folie eng umhüllt
Die wasserlösliche Folie, welche bei der engen Umhüllung bevorzugt eingesetzt wird, umfasst besonders bevorzugt Polyvinylalkohol, wie oben beschrieben, wobei als Ausgangsdicke vorzugsweise eine Dicke von 10 µm bis 100 µm, insbesondere von 12 µm bis 60 µm, besonders bevorzugt von 15 µm bis 50 µm, vor allem von 20 µm bis 40 µm, insbesondere von 22 µm bis 35 µm verwendet wird.
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.

Im Falle einer engen Umhüllung, ist jeweils eine Einmalportion des Wasch- oder Reinigungsmittels umhüllt. Für die erfindungsgemäßen umhüllten Wasch- oder Reinigungsmitteleinmalportion ist es wichtig, dass die Umhüllung an jeder Stelle der Tabletten dicht an deren Oberfläche anliegt. Idealerweise steht die Umhüllung sogar unter Spannung, was jedoch nicht zwingend erforderlich ist. Dieses dichte Anliegen der Umhüllung ist förderlich für den Zerfall: Beim ersten Kontakt mit Wasser wird die Umhüllung an irgendeiner Stelle eine geringe Menge Wasser durchlassen, wobei sie sich zunächst überhaupt nicht zu lösen braucht. An dieser Stelle beginnt das in der Tablette enthaltene Sprengmittel zu quellen. Dies führt dazu, dass die Umhüllung nun infolge der Volumenzunahme der Tablette schlagartig aufreißt und die Tablette freigibt. Bei einer nicht eng anliegenden Umhüllung funktioniert der hier beschrieben Mechanismus nicht, da die Tablette quellen kann, ohne dass die Umhüllung dadurch gesprengt würde. Dabei ist der Einsatz eines quellbaren Desintegrationsmittels einem gasentwickelnden System überlegen, da dessen sprengende Wirkung in jedem Fall zu einem Aufreißen der Umhüllung führt. Bei einem gasentwickelnden System kann die Sprengwirkung durch Entweichen des Gases aus einer Leckstelle der Umhüllung "verpuffen".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.

Erfindungsgemäße bevorzugte Wasch- oder Reinigungsmitteleinmalportionen sind dadurch gekennzeichnet, dass der Abstand zwischen der Einmalportion und wasserlöslicher Umhüllung über die gesamte Fläche 0,1 bis 1000 µm, vorzugsweise 0,5 bis 500 µm, besonders bevorzugt 1 bis 250 µm und insbesondere 2,5 bis 100 µm, beträgt.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 einer bevorzugten Ausführungsform wird die Folienumhüllung zunächst lose um eine Wasch- oder Reinigungsmitteleinmalportion gelegt und verschweißt und dann auf diese aufgeschrumpft, so dass ein enger Kontakt zwischen der Folienverpackung und dem Reinigungsmittelkonzentrat gegeben ist. Demzufolge sind erfindungsgemäße Wasch- oder Reinigungsmitteleinmalportionen dadurch gekennzeichnet, dass die Umhüllung eine auf diese aufgeschrumpfte Folienverpackung ist.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.

Beispielsweise kann diese Umhüllung erfolgen, indem eine wasserlösliche Unterfolie auf eine Transportkette oder ein Form(en)werkzeug aufgelegt wird, dann eine oder mehrerer Wasch- oder Reinigungsmittelportion(en) auf die Unterfolie aufgelegt werden; anschließend eine wasserlösliche Oberfolie auf die Wasch- oder Reinigungsmittelportion(en) auf der Unterfolie aufgelegt und diese dann auf der Unterfolie unter Einschluss der Wasch- oder Reinigungsmittelportion(en) fixiert wird,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),

Alternativ kann dieser Schritt auch durch eine einsträngige Folie erfolgen, die dann als Schlauch um die Einmalportionen gelegt wird. Anschließend erfolgt ein Versiegeln und optionales Schneiden der Folien. Anschließend kann dann das Aufschrumpfen der Folie durch die Verwendung von Heißluft oder Infrarot-Strahlung, optional mit Andrücken, erfolgen.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.

Solche wasserlöslichen Umhüllungen sind auch in den Patentanmeldungen WO 2004/031338 A sowie WO 2003/099985 A , auf deren Offenbarung hiermit in vollem Umfang Bezug genommen wird, bereits beschrieben.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.

Beispielhafte Formulierungen der erfindungsgemäßen Mittel schließen insbesondere auch phosphatfreie Geschirrspülmittel ein. Eine beispielhafte Rezeptur, in der die hierin beschriebenen Polymere in den angegebenen Mengen als zusätzlicher Bestandteil eingesetzt werden können, ist die folgende: Phosphatfreie, feste Geschirrspülmittelformulierung (Tab): Rohstoff Menge (Gew.-%) Na-Citrat 15,00-20,00 Phosphonat (z.B. HEDP) 2,50-7,50 MGDA 0,00-25,00 Silikat (Na-Disilikat) 5,00-35,00 Soda 12,50-25,00 Na-Percarbonat 10,00-15,00 Bleichkatalysator (Mn-basiert) 0,02-0,50 TAED 2,00-3,00 Niotensid 2,50-10,00 Polycarboxylat 5,00-10,00 Kationisches Copolymer 0,25-0,75 PVP (quervernetzt) 0,00-1,50 Protease 1,50-5,00 Amylase 0,50-3,00 Benzotriazol (Silberschutz) 0,00-0,50 Parfüm 0,05-0,15 Farbstofflösung 0,00-1,00 Zn-Acetat wasserfrei 0,10-0,30 Na-Sulfat 0,00-25,00 Wasser 0,00-1,50 pH-Stellmittel (Citronensäure) 1,00-1,50 Prozesshilfsmittel 0,00-5,00 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

Die entsprechende Verwendung der erfindungsgemäßen maschinellen Geschirrspülmittel ist ebenfalls Gegenstand der Erfindung. Ebenso betrifft die Erfindung ein Geschirrspülverfahren, insbesondere maschinelles Geschirrspülverfahren, bei welchem ein Geschirrspülmittel gemäß der Erfindung eingesetzt wird. Gegenstand der vorliegenden Anmeldung ist daher weiterhin ein Verfahren zur Reinigung von Geschirr in einer Geschirrspülmaschine, bei welchem das erfindungsgemäße Mittel während des Durchlaufens eines Geschirrspülprogramms vor Beginn des Hauptspülgangs oder im Verlaufe des Hauptspülgangs in den Innenraum einer Geschirrspülmaschine eindosiert wird. Die Eindosierung bzw. der Eintrag des erfindungsgemäßen Mittels in den Innenraum der Geschirrspülmaschine kann manuell erfolgen, vorzugsweise wird das Mittel jedoch mittels der Dosierkammer in den Innenraum der Geschirrspülmaschine dosiert.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.

Die im Kontext mit den erfindungsgemäßen Mitteln beschriebenen Ausführungsformen sind ohne Weiteres auch auf die erfindungsgemäßen Verfahren und Verwendungen übertragbar und umgekehrt.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.

BeispieleExamples Beispiel 1: ReinigungsleistungExample 1: Cleaning performance

Tabelle 1: Zusammensetzung des maschinellen Geschirrspülmittels (Angaben in Gew.-% jeweils bezogen auf das gesamte Reinigungsmittel)Table 1: Composition of the automatic dishwashing detergent (data in% by weight based on the total detergent) Rohstofferaw materials E1E1 V1V1 %% %% BleichephaseBleaching phase Na-CitratNa citrate 3,53.5 3,53.5 HEDPHEDP 4,54.5 4,54.5 MGDAMGDA 1212th -- Sodasoda 15,7515.75 15,7515.75 Na-PercarbonatNa percarbonate 14,514.5 14,514.5 BleichkatalysatorBleaching catalyst 0,030.03 0,030.03 NiotensideNonionic surfactants 5,15.1 5,15.1 SulfopolymerSulfopolymer 55 55 Acrylat-HomopolymerAcrylate homopolymer 0,50.5 0,50.5 FarbstoffeDyes 0,350.35 0,350.35 EnzymphaseEnzyme phase Na-CitratNa citrate 1111 1111 MGDAMGDA -- 1212th TAEDTAED 33rd 33rd NiotensideNonionic surfactants 1,51.5 1,51.5 SulfopolymerSulfopolymer 2,52.5 2,52.5 PEG 4000PEG 4000 11 11 Enzyme (tq, Proteasen und Amylasen)Enzymes (tq, proteases and amylases) 66 66 Farbstoffe, ParfümDyes, perfume 0,60.6 0,60.6 Zn-AcetatZn acetate 0,20.2 0,20.2 3. Phase3rd phase Na-CitratNa citrate 1,51.5 1,51.5 HEDPHEDP 1,51.5 1,51.5 MGDAMGDA 22nd 22nd Silikatsilicate 44th 44th Sodasoda 2,32.3 2,32.3 NiotensidNonionic surfactant 0,20.2 0,20.2 SulfopolymerSulfopolymer 11 11 FarbstoffeDyes 0,20.2 0,20.2 Wasserwater Ad 100Ad 100 Ad 100Ad 100

Die Reinigungsleistung wurde in Miele GSL Geschirrspülmaschinen im 45°C Programm bestimmt. Wasserhärte 21 °dH. Dazu wurden 20g der obigen Rezepturen (Tab) verwendet. Nach Beendigung des Spülzyklus wurde das Geschirr visuell abgemustert anhand einer Skala von 1-10. Je höher der Wert, desto besser die Reinigungsleistung. Man erkennt, dass die erfindungsgemäße Rezeptur E1, die MGDA in der Bleichephase enthält, gegenüber der Vergleichsrezeptur V1, die MGDA in der Enzymphase enthält, eine bessere Reinigungsleistung an enzymsensitiven Anschmutzungen, wie Hackfleisch, zeigt (Tabelle 2). Tabelle 2: Reinigungsleistung ADW Produkt (frisch) Hackfleisch E1 6,3 V1 5,9 ADW Produkt Nach 1 Woche Lagerung bei 40 °C E1 6,6 V1 5,9 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.
EP16741307.9A 2015-07-23 2016-07-20 Machine dishwashing detergent with bleaching agents, builders and enzymes Active EP3325597B1 (en)

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DE102015213940.9A DE102015213940A1 (en) 2015-07-23 2015-07-23 Machine dishwashing detergent containing bleach, builder and enzymes
PCT/EP2016/067263 WO2017013159A1 (en) 2015-07-23 2016-07-20 Machine dishwashing detergent with bleaching agents, builders and enzymes

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EP4379028A1 (en) * 2022-11-30 2024-06-05 Henkel AG & Co. KGaA Builder system for effect on boosting protein soil removal

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DE102017212561A1 (en) * 2017-07-21 2019-01-24 Henkel Ag & Co. Kgaa Dishwashing detergent containing citrate dihydrate and anhydrate
CA3081788C (en) 2017-11-14 2022-08-09 Ecolab Usa Inc. Solid controlled release caustic detergent compositions
CN114222808A (en) 2019-09-27 2022-03-22 埃科莱布美国股份有限公司 Concentrated two-in-one dishwasher detergent and rinse aid

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WO2012025740A1 (en) 2010-08-27 2012-03-01 Reckitt Benckiser N.V. Detergent composition comprising manganese-oxalate
US20140018278A1 (en) 2012-07-11 2014-01-16 Xinbei Song Dishwashing composition with improved protection against aluminum corrosion
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ES2810750T3 (en) 2021-03-09
PL3325597T3 (en) 2020-12-28
WO2017013159A1 (en) 2017-01-26
EP3325597A1 (en) 2018-05-30

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