Liquid dishwashing detergent

Abstract

The present invention relates to a liquid dishwashing detergent, a detergent formulation of this dishwashing detergent, the use of this dishwashing detergent and a method for machine dishwashing using this dishwashing detergent.

Description

The present invention relates to a liquid dishwasher detergent, a detergent supply form of this dishwasher detergent, the use of this dishwasher detergent and a machine dishwashing method using this dishwasher detergent.The most important criterion in automatic dishwashing is the cleaning performance on a wide variety of stains which are introduced into the dishwasher in the form of food residue. In this respect, there is generally a need for dishwashing agents with increased cleaning performance.The problem thus arises of providing liquid automatic dishwashing agents without adversely affecting the cleaning performance or stability.The stability of liquid detergent compositions and hence the cleaning performance (even after prolonged storage) can be improved by spatially separating incompatible ingredients from one another. However, it is decisive that the desired amounts of the different compositions are metered in exactly the correct ratio to one another. In addition, it is also important that the consumer perceives that a uniform dosing has taken place; otherwise, he is guided to carry out overdosage without this being necessary. Such overdosage is to be avoided with regard to the economy and the ecology of dishwashing.WO 2015 / 091147 A1 discloses a combination of compositions in separate chambers with an optimized viscosity (measured with Brookfield LVDV II+ viscometer at 20° C., spindle no. 31 and 1 rpm (revolution per minute). The viscosity should be above 230 mPa*s-1, in particular between 240 and 1000 mPa*s-1.It is an object of the present invention to provide a liquid dishwashing detergent which is more environmentally compatible, in particular more biodegradable, can be easily metered and at the same time has good cleaning performance.It has now been found that the compositions according to the invention are stable and optically appealing dishwashing detergent formulations which are at the same time readily biodegradable, have a good cleaning performance and a good final rinse performance, and which can be metered uniformly and without difficulty from the storage vessel.A first subject of the present invention is therefore a liquid automatic dishwashing agent, characterized in that the automatic dishwashing agent has two liquid compositions A and B which are spatially separated from one another, wherein (a) the composition has a pH of less than 8.5, preferably of 8 or less, more preferably of 7 to 8, in particular of 7.3 to 7.8, and comprises: (i) at least one enzyme, preferably a protease and / or amylase; (ii) at least one builder, wherein the at least one builder is preferably selected from soda, citrate, aminocarboxylic acids and their salts, and mixtures thereof, wherein the aminocarboxylic acids are in particular selected from the group consisting of methylglycinediacetic acid (MGDA), glutaminediacetic acid (GLDA) and ethylenediaminedisuccinic acid (EDDS) and their salts, and (iii) at least one biodegradable thickener, preferably a thickening polysaccharide, in particular xanthan, preferably in an amount of 0.01 to 1.2 wt %, preferably 0.05 to 1.0 wt %, in particular 0.1 to 0.6 wt %, in each case based on the total weight of the composition A, (iv) wherein the composition A has a density of 0.9 to 1.5 g / cm 3, preferably 1.0 to 1.4 g / cm 3, in particular of 1.15 to 1.3 g / cm 3 and / or a viscosity of more than 1000 mPas, preferably more than 1200 mPas, in particular more than 1500 mPas, particularly preferably more than 1800 mPas, measured at 20° C.; (b) the composition B has a pH greater than 9, preferably greater than 10, in particular from greater than 10 to less than 11.5, and comprises: (i) at least one builder, wherein the at least one builder is preferably selected from soda, citrate, aminocarboxylic acids and their salts, and mixtures thereof, wherein the aminocarboxylic acids are in particular selected from the group consisting of methylglycinediacetic acid (MGDA), glutaminediacetic acid (GLDA) and ethylenediaminedisuccinic acid (EDDS) and their salts; and (ii) at least one biodegradable thickener, preferably a thickening polysaccharide, in particular xanthan, preferably in an amount of 0.01 to 1.2% by weight, preferably 0.05 to 1.0% by weight, in particular 0.1 to 0.5% by weight, in each case based on the total weight of composition B, and (iii) wherein composition B has a density of 1.0 to 1.5 g / cm 3, preferably 1.1 to 1.4 g / cm 3, in particular of 1.15 to 1.35 g / cm 3 and / or a viscosity of more than 1000 mPas, preferably more than 1100 mPas, in particular more than 1200 mPas, particularly preferably more than 1500 mPas, measured at 20° C.The viscosity is measured at 20° C., for example using a Brookfield LVDV II+Pro, spindle 31 using a standard small sample adapter. The number of revolutions of the spindle used for the measurement is preferably 12 revolutions per minute.The thickener used is at least one biodegradable thickener, preferably a thickening polysaccharide, in particular xanthan. The polysaccharide is preferred, in particular in an amount sufficient to set the desired viscosity, for example in an amount of 0.01 to 1.2% by weight, preferably 0.05 to 1.0% by weight, in particular 0.1 to 0.6% by weight, based on the total weight of the respective composition. Composition A preferably comprises in particular 0.1 to 0.6% by weight xanthan and composition B preferably comprises 0.1 to 0.5% by weight, in each case based on the total weight of the respective composition.The present invention likewise relates to a detergent supply form comprising a dishwasher detergent according to the invention, an automatic dishwashing method in which a dishwasher detergent is used, and the use of a dishwasher detergent according to the invention in an automatic dishwashing method.These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be used in any other aspect of the invention. Further, it is to be understood that the examples herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples. All percentages are % by weight unless otherwise stated. Numerical ranges indicated in the format "from x to y" include the above values. When several preferred numerical ranges are specified in this format, it is understood that all ranges arising from the combination of the various endpoints are also detected. Unless specified further, all data refer to 20° C. and atmospheric pressure."At least one" as used herein includes, but is not limited to, 1, 2, 3, 4, 5, 6, and more. In relation to an ingredient, the specification refers to the type of ingredient and not to the absolute number of molecules. "At least one builder" thus means, for example, at least one type of builder, i.e. that one type of builder or a mixture of several different builders can be meant. Together with weight data, the data refer to all compounds of the stated type which are contained in the composition / mixture, i.e. the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.Where molecular weights are referred to herein, these figures always refer to the number-average molecular weight M n, unless explicitly stated otherwise. The number average molar mass can be determined, for example, by means of gel permeation chromatography (GPC) in accordance with DIN 55672-1:2007-08 using THF as eluent. The mass average molar mass M w can likewise be determined by means of GPC, as described for M n.The present automatic dishwashing agents are preferably phosphate-free, i.e. the respective compositions contain phosphates in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the respective composition."NaOH-free" as used herein means that substantially no sodium hydroxide (NaOH) has been added to the composition in question. In certain embodiments, the composition contains NaOH in amounts of less than 0.5 wt %, preferably less than 0.1 wt, based on the respective composition. However, it is understood that these quantities do not relate to agents or compositions in which sodium and hydroxide ions are present dissociated and in which the corresponding ions can also originate, for example, from KOH and sodium citrate."Liquid" as used herein includes compositions that are liquid or flowable at 20°C, such as liquids and gels.The pH of the particular composition reported in the various embodiments refers to the pH measured at 20° C. with a standard electrode in the neat state.The term "spatially separated" with respect to the compositions as used herein means that the compositions cannot come into contact with each other prior to use. For this purpose, the dishwashing agent is usually provided in a multi-chamber packaging, such as a bottle or pouch, in particular a two-chamber bottle or a two-chamber pouch, wherein the respective composition is located in a separate chamber separately from the other composition(s).The automatic dishwashing agent has a plurality of spatially separated compositions, whereby it is possible on the one hand to separate incompatible ingredients from one another and on the other hand to offer compositions in combination which are used at different times in the dishwasher.It is particularly preferred for the spatially separated compositions to be present in a multi-chamber bottle, in particular a two-chamber bottle, wherein the respective composition is located separately from the other composition(s) in a separate chamber.Preferably, composition A contains at least one amylase and at least one protease. In further embodiments, composition A further additionally comprises at least one further enzyme. Suitable enzymes include, but are not limited to, proteases, lipases, hemicellulases, especially pectinases and / or mannanases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.These enzymes and the amylases and proteases used are in principle of natural origin; starting from the natural molecules, improved variants are available for use in dishwashing agents, which are correspondingly preferably used. Dishwashing detergents according to the invention preferably comprise the respective enzymes in total amounts of 1×10 -6 to 5% by weight, in each case based on active protein and the total weight of the respective composition. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.Proteases are among the technically most important enzymes at all. For washing and dishwashing agents, they are the enzymes that are the longest-established and contained in virtually all modern, efficient washing and dishwashing agents. They cause the degradation of protein-containing stains on the washware. Among these, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are in turn particularly important, which are serine proteases on account of the catalytically active amino acids. They act as non-specific endopeptidases and hydrolyze any acid amide bonds that are internal to peptides or proteins. Their pH optimum is usually in the substantially alkaline range. An overview of this family is provided, for example, by the article "Subtilases: Subtilisin-like Proteases" by R. Siezen, pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996. Subtilases are naturally formed by microorganisms. Among these, the subtilisins formed and secreted by Bacillus species are to be mentioned in particular as the most important group within the subtilases.Examples of the proteases of the subtilisin type preferably used in washing and dishwashing 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 enzymes thermitase, proteinase K and the proteases TW3 and TW7 which are assigned to the subtilases but no longer to the subtilisins in the narrower sense, and variants of the proteases mentioned which have an amino acid sequence which is altered in relation to the starting protease. Proteases are changed in a targeted or random-based manner by methods known from the prior art and are thus optimized, for example, for use in washing and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, for most proteases known from the prior art, correspondingly optimized variants are known.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 dishwashing detergents. Furthermore, the α-amylase from Bacillussp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens(DSM 9948) should be emphasized.Lipases or cutinases can furthermore be used according to the invention, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally available or further developed from Humicola lanuginosa(Thermomyces lanuginosus), in particular those with one or more of the following amino acid exchanges starting from the lipase mentioned in positions D96L, T213R and / or N233R., particularly preferably T213R and N233R.Enzymes can furthermore be used which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (=tunginases), pectin esterases, pectate lyases, xyloglucanases (=tungen), pullulanases and β-glucanases.To increase the bleaching action, it is possible according to the invention to use oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin-, glucose- or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally preferably added in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the electron flow (mediators) at greatly different redox potentials between the oxidizing enzymes and the stains.Detergent-active proteases and amylases are generally provided not 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, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers or further auxiliaries.Alternatively, the enzymes can be encapsulated for both the solid and 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 water-impermeable, air-impermeable and / or chemical-impermeable protective layer. In superimposed layers, further active compounds, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can additionally be applied. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid bed processes. Advantageously, such granules are low in dust, for example by applying polymeric film formers, and are stable on storage because of the coating.Furthermore, it is possible to make up two or more enzymes together, so that a single granulate has a plurality of enzyme activities.As can be seen from the previous embodiments, the enzyme protein constitutes only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention each contain between 0.1 and 40 wt %, preferably between 0.2 and 30 wt %, particularly preferably between 0.4 and 20 wt %, and in particular between 0.8 and 10 wt %, of the enzyme protein.Preference is given in particular to those dishwashing agent compositions, in particular composition A, which comprise, based in each case on their total weight, 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of the respective enzyme preparation.Enzyme amounts preferably used according to the invention, based on the active enzyme protein, are 0.01 to 1.2% by weight of protease and / or 0.001 to 0.05% by weight of amylase, based in each case on the total weight of the cleaning agent A. Particular preference is given in particular to those cleaning agents A which, based in each case on their total weight, comprise 0.15 to 0.8% by weight of protease and / or 0.015 to 0.03% by weight of amylase as active enzyme protein, preferably protease and amylase, in the amounts mentioned.A protein and / or enzyme can be protected, especially during storage, against damage such as, for example, inactivation, denaturation or decomposition, for example, by physical influences, oxidation or proteolytic cleavage. In the case of microbial recovery of the proteins and / or enzymes, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.Formulations according to the invention may contain one or more enzyme stabilizers. Enzyme stabilizers serve to protect enzymes--especially during storage--from damage, such as, for example, inactivation, denaturation or decomposition, for example, due to physical influences, oxidation or proteolytic cleavage.Examples of enzyme stabilizers are reversible protease inhibitors, e.g. benzamidine hydrochloride, borax, boric acid, boronic acids or salts or esters thereof, including in particular derivatives with aromatic groups, e.g. ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or esters of the abovementioned compounds. Peptide aldehydes, i.e. oligopeptides with reduced carbon terminus, in particular those of 2 to 50 monomers, are also used for this purpose. Peptidic reversible protease inhibitors include ovomucoid and leupeptin. Specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins of proteases and specific peptide inhibitors are likewise suitable for this purpose. Further examples of enzyme stabilizers are amino alcohols, such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic mono- and dicarboxylic acids up to C12-carboxylic acids, such as succinic acid, for example. Terminally capped fatty acid amide alkoxylates are also suitable as enzyme stabilizers. A good stabilizer for proteases is also calcium chloride.For this purpose, the dishwashing agents can contain, for example, calcium salts as stabilizers. Water soluble calcium salts suitable as enzyme stabilizers include, but are not limited to, calcium chloride (CaCl 2), calcium lactate or calcium acetate. Other salts of calcium with alpha-hydroxycarboxylic acids or alpha-amino acids are likewise suitable.In various embodiments, calcium salts suitable for stabilizing enzymes are present in composition A in an amount of from 0.05 to 2% by weight, in particular from 0.1 to 0.6% by weight, based on the total weight of composition A.Generally, all phosphonates suitable as complexing agents for dishwashing agents can be used as phosphonate. Preferably, a hydroxyalkane phosphonate and / or aminoalkane phosphonate is used as phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Suitable aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and higher homologs thereof. In particular, the alkali metal salts of phosphonates are used. Phosphonates are contained in the agents preferably in amounts of 0.5 to 7 wt %, in particular in amounts of 1 to 6 wt %, in each case based on the total weight of composition B, in particular in the form of the HEDP sodium salt. In preferred embodiments, the amount is no more than 300 mg phosphor / job.The present automatic dishwashing agents are in another embodiment preferably phosphonate-free. "phosphonate-free", as used herein, means that the composition in question is substantially free of phosphonates, i.e. contains phosphonates in particular in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the respective composition.The dishwashing detergents furthermore comprise at least one builder, namely in the form that composition A and B each comprises at least one builder (builder), the at least one builder preferably being selected from soda, citrate, aminocarboxylic acids and their salts, and mixtures thereof, the aminocarboxylic acids being selected in particular from the group consisting of methylglycinediacetic acid (MGDA), glutaminediacetic acid (GLDA) and ethylenediaminedisuccinic acid (EDDS) and their salts.In addition to their builder effect, the free acids typically also have the property of an acidifying component and can thus also serve to adjust the pH. Particular mention may be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these.Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) usable in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four or five, acid functions in the entire molecule. Dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids, are thus preferred as polycarboxylic acids. The polycarboxylic acids may also carry further functional groups, such as hydroxyl or amino groups, for example. Examples of these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids (preferably aldaric acids, for example galactoaric acid and gluconic acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, such as nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediaminedisuccinic acid (ethylenediaminedisuccinate, EDDS), and derivatives thereof and mixtures thereof, wherein glutamine-N,N-diacetic acid (also referred to as N,N-bis(carboxymethyl)-L-glutamic acid or GLDA) as described above is preferably excluded. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, MGDA and mixtures thereof. Particularly preferably, the aminocarboxylic acids are selected in particular from the group consisting of methylglycinediacetic acid (MGDA), glutaminediacetic acid (GLDA) and ethylenediaminedisuccinic acid (EDDS) and their salts.In a particularly preferred embodiment, the at least one builder in composition A and / or B is methyl glycine diacetic acid (MGDA). In preferred embodiments, composition B contains two or more builders, such as soda and / or citrate, optionally in combination with MGDA. Generally, the term MGDA as used herein includes both the free acid and the corresponding salts.Preferably, compositions A and / or B, based in each case on the total weight of the cleaning agent A or B, comprise methyl glycine diacetic acid and / or its salt in an amount of 6.0 to 25.0% by weight, preferably 8.0 to 20.0% by weight, in particular 9.0 to 15.0% by weight.In various embodiments, dishwashing agents according to the invention (cleaning agents A and / or B) contain, as one of their essential builders, one or more salts of citric acid, i.e. citrates, for example sodium citrate or potassium citrate. These are preferably in a proportion of from 1 to 30% by weight, in particular from 2 to 25% by weight, particularly from 3 to 20% by weight, in each case based on the total weight of the respective composition A or B.Preference is likewise given to the use of carbonate(s) and / or bicarbonate(s), preferably alkali carbonate(s), particularly preferably sodium carbonate (soda), preferably in detergent composition B, in amounts of from 2 to 30% by weight, preferably from 4 to 20% by weight and in particular from 5 to 15% by weight, in each case based on the weight of composition A or B. In various embodiments composition A comprises no carbonate / bicarbonate. In various other embodiments, composition B comprises carbonates / hydrogen carbonates, in particular soda, preferably in an amount of 6 to 15 wt %, in particular 7 to 12 wt %.Most particularly, the composition B comprises MGDA, trisodium salt in an amount of up to 15.0 wt %, up to 20 wt % citrate and up to 15 wt % soda, in each case based on the total weight of the composition B.Particularly preferred dishwashing agents according to the invention, preferably automatic dishwashing agents, are characterized in that composition B comprises at least two builders from the group of carbonates, MGDA and citrates, wherein the proportion by weight of these builders, based on the total weight of the composition, is preferably 5 to 40 wt %, preferably 8 to 30 wt % and in particular 10 to 25 wt %.Composition A in various embodiments comprises at least one builder, this builder preferably being MGDA. Composition A may contain additional builders, especially citrate, but in various embodiments no further builder is present. The amount of MGDA in composition A is preferably up to 25% by weight, more preferably 2 to 20% by weight, in particular 8-15% by weight. In certain embodiments, composition A contains up to 13 wt% MGDA.Polymeric polycarboxylates (organic polymers having a large number of (in particular greater than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins can furthermore be used. Biodegradable polymers are particularly preferred.In a particularly preferred embodiment, the compositions are free of homopolymers of acrylic acid, since these compounds are not biodegradable and are not preferred for ecological reasons. Free of homopolymers of acrylic acid as used herein means that the composition in question is substantially free of acrylic acid homopolymers, i.e. contains in particular acrylic acid homopolymers in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the respective composition.In a further particularly preferred embodiment, the compositions are free of co- and terpolymers of acrylic acid with monomers which have sulphonic acid-containing groups, since these compounds have not been biodegradable up to now and are therefore not preferred for ecological reasons. Free of the polymers mentioned as used herein means that the composition in question is substantially free of such polymers, i.e. contains in particular such polymers in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the respective composition.In a particularly preferred embodiment, the compositions A and B each comprise less than 1% by weight of polymers which, as a monomer which is present in an amount of more than 40 mol %, comprise acrylic acid or methacrylic acid and also, if appropriate, additionally comprise sulphonic acid-containing groupsIn preferred inventive cleaning agents, in particular dishwashing agents, preferably automatic dishwashing agents, the content of silicates, based on the total weight of the cleaning agent, is limited to amounts below 10 wt %, preferably below 5 wt % and in particular below 2 wt %. It is particularly preferred that the agents are free of silicates, wherein "free" in this context means that the amount is limited to less than 0.1 wt %.In addition to the above-mentioned builders, the dishwashing detergents according to the invention, in particular composition B, can furthermore contain alkali metal hydroxides as alkali source. These alkali carriers are used in the compositions and in particular in the second phases (composition B) preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 8% by weight, particularly preferably between 0.1 and 9% by weight and in particular between 0.5 and 7.5% by weight, in each case based on the total weight of the composition. In various further embodiments, composition B comprises less than 1.71 wt %, based on the total weight of composition B, of NaOH, preferably less than 1.0 wt % of NaOH, more preferably composition B is free of NaOH, in particular free of added NaOH. In preferred embodiments, composition B therefore comprises potassium hydroxide (KOH) as alkali source instead of NaOH, preferably in the amounts stated above, in particular from 0.5 to 7.5% by weight.The dishwashing detergents preferably also comprise at least one surfactant. The surfactants can be present both in composition A and in composition B or both. Preferably, however, the at least one surfactant is present in composition A, very particularly preferably in amounts of up to 5% by weight, based on the total weight of composition A.The surfactants present are preferably nonionic surfactants. As nonionic surfactants, it is possible to use any nonionic surfactants known to the skilled worker. Preference is given to using low-foaming nonionic surfactants, especially alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. The automatic dishwashing detergents particularly preferably comprise nonionic surfactants from the group of alkoxylated alcohols.Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant(s) having 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.Surfactants preferably to be used originate from the groups of alkoxylated non-ionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are furthermore distinguished by good foam control.Low-foaming nonionic surfactants have proven to be particularly preferred in the context of the present invention, which nonionic surfactants have alternating ethylene oxide and alkylene oxide units. Among these, surfactants having EO-AO-EO-AO blocks are again preferred, one to ten EO or AO groups each being bonded to one another before a block of the other groups follows. Preference is given here to nonionic surfactants of the general formula in which R 1 is 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 are independently integers from 1 to 6.Thus, especially preferred are nonionic surfactants having a C 9-15- alkyl group with 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.Preferred nonionic surfactants here are those of the general formula R 1- CH(OH)CH 2 O-(AO) w-( A'O) x-( A"O) y-( A"'O) z- R 2, in whichR 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24- alkyl or alkenyl radical;R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;A, A', A" and A"' independently of one another represent 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- CH2, -CH2-CH(CH3)-CH2-, -CH2-CH(CH2-CH3),w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.By adding the abovementioned nonionic surfactants of the general formula R 1- CH(OH)CH 2 O-(AO) w-( A'O) x-( A"O) y-( A"'O) z- R 2, also referred to below as "mixed hydroxy ethers", the cleaning performance of the preparations according to the invention can be significantly improved, both in comparison with surfactant-free systems and in comparison with systems which comprise alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.Preference is given to 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 having 4 to 18 carbon atoms or mixtures thereof, R_NER70is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is 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 ethers.Particularly preferred end group-capped, poly(oxyalkylated) nonionic surfactants are those which, according to the formula R 1 O[CH 2 CH 2 O] x CH 2 CH(OH)R 2, have, in addition to a radical R 1, which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, where x is values between 1 and 90, preferably values between 30 and 80 and in particular values between 30 and 60.Further preferred non-ionic surfactants are the end group-capped poly(oxyalkylated) non-ionic 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 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is a value between 1 and 30, k and j is a value 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, particular preference being given to radicals having 8 to 18 carbon atoms. For the radical R 3 particular preference is given to H, -CH 3 or -CH 2 CH 3. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.As described above, each R 3 in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can 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 can be quite larger, wherein the range of variation increases with increasing x values and includes, for example, a large number of (EO) groups, combined with a small number of (PO) groups, or vice versa.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 simplified to R 1 O[CH 2 CH(R 3) O] x CH 2 CH(OH)CH 2 OR 2. In the latter formula, R 1, R 2 and R 3 are as defined above and x is numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.Finally, the nonionic surfactants of the general formula R 1- CH(OH)CH 2 O-(AO) w- R 2 in whichR 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24- alkyl or alkenyl radical;R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;a is a radical from the group consisting of CH 2 CH 2, CH 2 CH 2 CH 2, CH 2 CH(CH 3), preferably CH 2 CH 2 andw is a value between 1 and 120, preferably 10 to 80, in particular 20 to 40The 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 ethers and the C 4-22 fatty alcohol (EO) 40-80-2- hydroxyalkyl ethers.In various embodiments of the invention, instead of the end group-capped hydroxy mixed ethers defined above, it is also possible to use the corresponding non-end group-capped hydroxy mixed ethers. These may satisfy the above formulae wherein R is 2 but hydrogen and R is 1, R is 3, A, A', A", A"', w, x, y and z are as defined above.Preferred dishwashing agents are characterized in that the dishwashing agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of the hydroxy mixed ethers, wherein the proportion by weight of the nonionic surfactant based on the total weight of the dishwashing agent is preferably 0.1 to 5 wt %, preferably 0.5 to 4.5 wt % and in particular 1.0 to 4.0 wt %.According to a preferred embodiment, the cleaning agents B comprise at least one anionic surfactant, preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol sulfonates and / or alkylbenzenesulfonates, which are preferably used as sodium salts, but can also be present as other alkali metal or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts. Linear alkyl sulfates or alkyl sulfonates having at least 14 carbon atoms in the alkyl radical or alkyl benzyl sulfonates having at least 12, preferably 14 carbon atoms in the alkyl radical are preferred. Linear alkyl sulfates having at least 14 carbon atoms, preferably at least 16 carbon atoms, in the alkyl radical are particularly preferred.The anionic surfactants are particularly preferably used in an amount of 0.01 to 5% by weight in composition B, based on the total weight of composition B.Very particularly preferably, the at least one anionic surfactant is present as distinct, distinguishable particles in composition B. The particles preferably have an average particle size, determinable by a sieve of corresponding size, of 0.1 to 4 mm, preferably 0.25 to 3 mm. These particles are visible to the consumable and are preferably uniformly distributed in composition B. These particle sizes are stabilized particularly well in the formulation by the biodegradable thickener, in particular xanthan, without these particles also falling to the bottom after a relatively long storage time and thus being able to be poured out of the double-chamber bottle only in an uneven manner. Particularly suitable is, for example, Lanette® E ex BASF.Particularly preferably, these particles are present in the composition B in an amount of 0.05 to 5 wt %, preferably 0.1 to 3.5 wt %, in particular 0.2 to 2 wt %, based on the total weight of the composition B. The anionic surfactants mentioned thus promote cleaning performance without greatly adversely affecting the foaming behavior. Particularly suitable is, for example, Lanette® E ex BASF.According to a particularly preferred embodiment, the cleaning agent composition A comprises at least one amylase and at least one protease and optionally at least one further enzyme selected from the group consisting of lipases, hemicellulases, in particular pectinases and / or mannanases, cellulases, perhydrolases and oxidoreductases, at least one calcium salt, in particular calcium chloride (CaCl 2), in an amount of 0.05 to 2 wt %, in particular 0.1 to 0.6 wt %, based on composition A, and at least one surfactant, preferably nonionic surfactant, preferably in an amount of up to 5 wt %, based on the total weight of composition A; based on the total weight of composition A.In general, the pH of the dishwashing detergent can be adjusted by means of customary pH regulators. In various embodiments, the pH (neat, measured at 25° C.) of composition A is in a range from 5.5 to 8.5, preferably 6.5 to 8.0, more preferably from 7.0 to 8.0, in particular from 7.3 to 7.8, and the pH of composition B is in a range from 9.0 to 12, preferably 10.0 to 11.5, preferably greater than 10, in particular 10.5 to 11.5. 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 else amidosulfonic acid. In addition, however, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Suitable bases are from the group of the alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide is preferred. Particularly preferably, the alkali source described above is used for adjusting the pH. Even if volatile alkali, for example in the form of ammonia and / or alkanolamines which may contain up to 9 carbon atoms in the molecule, can be used for adjusting the pH, it being possible here for the alkanolamine to be selected from the group consisting of mono-, di-, triethanol- and propanolamine and mixtures thereof, it is preferable to dispense with such volatile alkali sources, in particular ethanolamines. In various embodiments, the compositions therefore comprise less than 1.75% by weight of alkanolamine, in particular monoethanolamine, very particularly preferably they are free thereof. It has been found that the omission of such alkanolamines enhances the stability of the compositions."About" as used herein in connection with a numerical value means ± 5% "about 7.5", thus means 7.125 to 7.875.To adjust and / or stabilize the pH, the agent according to the invention may contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5 wt %. Buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate2H 2 O and tricalum citrate H 2 O.The agents according to the invention preferably contain at least one further constituent, preferably selected from the group consisting of sequestrants, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitter substances and antimicrobial active ingredients.Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also the irritation of the glass surface of mechanically cleaned glasses. Preferred glass corrosion inhibitors originate from the group of the bismuth, magnesium and zinc salts and the magnesium and zinc complexes. In the context of the present invention, the content of zinc salt in dishwashing detergents is preferably between 0.1 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+) is between 0.01 to 1% by weight, preferably between 0.02 to 0.5% by weight and in particular between 0.04 to 0.2% by weight, based in each case on the total weight of the glass corrosion inhibitor-containing agent. In particular, zinc acetate, for example, can be used. Additionally or alternatively to the above-mentioned. Salts (in particular the zinc salts) can be used as glass corrosion inhibitors, polyethyleneimines, as are obtainable, 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.Within the scope of the present invention, individual perfume compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or perfumes. However, mixtures of different fragrances are preferably used which together produce an appealing scent note. Perfume oils of this kind may also comprise natural perfume mixtures, as are obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.The formulation of dishwashing detergents described herein can be carried out in various ways. The liquid supply forms based on water and / or organic solvents can be thickened, in the form of gels.The dishwashing agents described herein are preferably packaged in a multi-chamber bottle, in particular in a two-chamber bottle, and metered from the latter, preferably into the metering chamber of the dishwasher.According to a further embodiment, the present invention relates to a detergent supply form comprising a dishwashing detergent as described above in a multi-chamber package, characterized in that the compositions A and B are each present in a separate chamber of the package, wherein each of the chambers of the package has its own outlet opening having an outlet diameter of 3.0 to 6.0 mm, preferably of 3.5 to 5.5 mm, in particular of 4.0 to 5.0 mm.The corresponding use of the automatic dishwashing agents according to the invention is likewise the subject matter of the invention. The invention also relates to a dishwashing method, in particular an automatic dishwashing method, in which a dishwashing agent according to the invention is used. The present application therefore furthermore relates to 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 agent according to the invention can be introduced or introduced manually into the interior of the dishwasher, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber.ExamplesExample 1:Table 1: Composition of automatic dishwashing detergent (% by weight of active substance) Table 1: Composition of automatic dishwashing detergent (% by weight of active substance)C chloride0,270,27Xanthan gum00,45Polyacrylate-Based Thickener0,90,0Polymer (biodegradable)4,04,0Na citrate×2H2O4,04,0MGDA, trisodium salt1010Citric acid anhydrous2,82,8Nonionic Surfactant3,53,5Protease (Active Enzyme Protein)0,260,26Stainzyme 12L (telqel)1,61,6Perfume, colorants, preservatives, further auxiliaries1,01,0WaterAdd 100Add 100Density (g / cm 3)1,141,13pH7,57,5Viscosity, Brookfield LVDV II+Pro, spindle 31160 (30 rpm)2300 (12 rpm)Xanthan gum0,00,375Polyacrylate-Based Thickener0,90,0HEDP, sodium salt7,657,65KOH5,05,0MGDA, trisodium salt1010Citric acid anhydrous0,82,8Lanette E Granules0,250,25Soda Soda Soda9,009,00Perfume, dye, preservative, pH adjusting agents, adjuvants1,01,0WaterAdd 100Add 100pH11,211,2Viscosity, Brookfield LVDV II+Pro, spindle 31650 (30 rpm)1902 (12 rpm)The viscosity was measured at 20° C. using a Brookfield LVDV II+Pro, spindle 31 using a standard small sample adapter. The rotational speed of the spindle used for the measurement is noted after the respective value.The enzyme phase (16 g each) and the alkali phase (17 g each) are each metered into the dishwasher chamber from a double chamber bottle. The composition E1 has improved cleaning performance and improved staining, in particular on glass, porcelain, plastic and stainless steel. In addition, an improvement in deposit inhibition could be found.If the comparative mixture is metered from the double chamber bottle (held vertically) into the metering chamber of a commercially available dishwasher, the enzyme phase completely coats the alkali phase, so that the consumer only perceives the enzyme phase in the chamber. Under certain circumstances, this leads to an overdosage or erroneous assessment by the consumer. If the formulation according to the invention is introduced into the metering chamber accordingly, the two phases are present visibly next to one another. The outlet opening of the dual-chamber bottle was additionally enlarged to 4.9 mm for each of the two chambers, so that with the viscosity or density according to the invention both gels could flow out uniformly and also be present optically in the dishwasher chamber with an equal extension next to one another. The risk of an overdosage or incorrect assessment of the dosage by the consumer is thus reduced.References included in the specificationThis list of documents cited by the applicant has been produced in an automated manner and is only included for the better information of the reader. The list is not part of the German patent application or utility model application. The DPMA does not take any adhesion for any faults or omissions.Cited Non-Patent LiteratureDIN 55672-1:2007-08

[0014] Subtilases: Subtilisin-like proteases" by R. Siezen, pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996

[0024]

Claims

Liquid automatic dishwashing agent, characterized in that the automatic dishwashing agent has two liquid compositions A and B which are spatially separated from one another, wherein (c) the composition has a pH of less than 8.5, preferably of 8 or less, more preferably of 7 to 8, in particular of 7.3 to 7.8, and comprises: (i) at least one enzyme, preferably a protease and / or amylase; (ii) at least one builder, wherein the at least one builder is preferably selected from soda, citrate, aminocarboxylic acids and their salts, and mixtures thereof, wherein the aminocarboxylic acids are in particular selected from the group consisting of methylglycinediacetic acid (MGDA), glutaminediacetic acid (GLDA) and ethylenediaminedisuccinic acid (EDDS) and their salts, and (iii) at least one biodegradable thickener, preferably a thickening polysaccharide, in particular xanthan, preferably in an amount of 0.01 to 1.2% by weight, preferably 0.05 to 1.0% by weight, in particular 0.1 to 0.6% by weight, in each case based on the total weight of the composition A, (iv), wherein the composition A has a density of 0.9 to 1.5 g / cm 3, preferably 1.0 to 1.4 g / cm 3, in particular of 1.15 to 1.3 g / cm 3 and / or a viscosity of more than 1000 mPas, preferably more than 1200 mPas, in particular more than 1500 mPas, particularly preferably more than 1800 mPas, measured at 20° C.; (d) the composition B has a pH greater than 9, preferably greater than 10, in particular from greater than 10 to less than 11.5, and comprises: (i) at least one builder, wherein the at least one builder is preferably selected from soda, citrate, aminocarboxylic acids and their salts, and mixtures thereof, wherein the aminocarboxylic acids are in particular selected from the group consisting of methylglycinediacetic acid (MGDA), glutaminediacetic acid (GLDA) and ethylenediaminedisuccinic acid (EDDS) and their salts; and (ii) at least one biodegradable thickener, preferably a thickening polysaccharide, in particular xanthan, preferably in an amount of 0.01 to 1.2% by weight, preferably 0.05 to 1.0% by weight, in particular 0.1 to 0.5% by weight, in each case based on the total weight of composition B, and (iii) wherein composition B has a density of 1.0 to 1.5 g / cm 3, preferably 1.1 to 1.4 g / cm 3, in particular of 1.15 to 1.35 g / cm 3 and / or a viscosity of more than 1000 mPas, preferably more than 1100 mPas, in particular more than 1200 mPas, particularly preferably more than 1500 mPas, measured at 20° C.Dishwashing agent according to claim 1, characterized in that composition A contains at least one amylase and at least one protease and optionally at least one further enzyme selected from the group consisting of lipases, hemicellulases, in particular pectinases and / or mannanases, cellulases, perhydrolases and oxidoreductases, preferably 0.01 to 1.2 wt.% protease, preferably 0.15 to 0.8 wt.% protease as active enzyme protein, and / or 0.001 to 0.05 wt.% amylase, preferably 0.015 to 0.03 wt.% amylase as active enzyme protein.Dishwashing agent according to claim 1 or 2, characterised in that composition A and / or B, in each case based on the total weight of the respective cleaning agent, methyl glycine diacetic acid and / or its salt in an amount of 6.0 to 25.0 wt.%, preferably 8.0 to 20.0 wt.%, in particular 9.0 to 15.0 wt.%.Dishwashing detergent according to one of the preceding claims, characterized in that the compositions A and B each comprise less than 1% by weight of homopolymers of acrylic acid and / or co- and terpolymers of acrylic acid with monomers which comprise sulphonic acid-containing groups.Dishwashing detergent according to one of the preceding claims, characterized in that composition A comprises (i) at least one amylase and at least one protease and optionally at least one further enzyme selected from the group consisting of lipases, hemicellulases, in particular pectinases and / or mannanases, cellulases, perhydrolases and oxidoreductases, (ii) at least one calcium salt, in particular calcium chloride (CaCl 2), in an amount of 0.05 to 2% by weight, in particular 0.1 to 0.6% by weight, based on composition A, and (iii) at least one surfactant, preferably in an amount of up to 5% by weight, based on the total weight of composition A; based on the total weight of composition A.Dishwashing detergent according to any of the preceding claims, characterized in that composition B (i) comprises at least one alkali source, the alkali source comprising less than 1.7% by weight of NaOH, preferably free of added NaOH, and preferably comprising KOH, based on the total weight of composition B; and / or (ii) the at least one builder MGDA, trisodium salt in an amount of up to 15.0% by weight, up to 20% by weight of citrate and up to 15% by weight of soda, in each case based on the total weight of composition B, and / or (iii) optionally comprises at least one phosphonate, in particular 1-hydroxyethane-(1,1-diphosphonic acid) (HEDP), the at least one phosphonate, in particular HEDP, in an amount of 0.5 to 7% by weight, preferably 1 to 6% by weight, based on composition B, in particular in an amount of not more than 300 mg phosphorus / job.Dishwashing agent according to one of the preceding claims, characterized in that the dishwashing agent contains at least one further constituent, preferably at least two further constituents, selected from the group consisting of polymers, corrosion inhibitors, glass corrosion inhibitors, fragrances and perfume carriers.A detergent supply form comprising a dishwashing detergent according to any of the preceding claims 1 to 7 in a multi-chamber package, characterized in that the compositions A and B are each present in a separate chamber of the package, wherein each of the chambers of the package has its own outlet opening having an outlet diameter of 3.0 to 6.0 mm, preferably of 3.5 to 5.5 mm, in particular of 4.0 to 5.0 mm.Automatic dishwashing method, characterized in that a dishwashing agent according to one of Claims 1 to 8 is used.