WO2025131707A1 - Liquid dishwashing product - Google Patents

Abstract

The present invention relates to a liquid dishwashing product, to a cleaning product form of the dishwashing product, to the use of said dishwashing product and to a method for washing dishes in a dishwasher using said dishwashing product.

Description

Liquid dishwashing detergent

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.

The most important criterion in automatic dishwashing is the cleaning performance of various types of soiling, which are introduced into the dishwasher in the form of food residue. Therefore, there is a general need for dishwashing detergents with increased cleaning performance.

The problem therefore arises of providing liquid automatic dishwashing detergents without compromising cleaning performance or stability.

The stability of liquid detergent compositions and thus their cleaning performance (even after extended storage) can be improved by spatially separating incompatible ingredients. However, it is crucial that the desired amounts of the various components are dosed in precisely the correct ratio. Furthermore, it is also important that the consumer perceives that consistent dosing has occurred; otherwise, they will be tempted to overdose unnecessarily. Such overdosing should be avoided for both economic and ecological reasons.

WÖ2015/091147 A1 discloses a combination of compositions in separate chambers with an optimized viscosity (measured with a Brookfield LVDV II+ viscometer at 20 °C, spindle no. 31 and 1 rpm). The viscosity should be above 230 mPa*s-1, in particular between 240 and 1000 mPa*s-1.

The object of the present invention was therefore to provide a liquid dishwashing detergent which is more ecologically compatible, in particular more biodegradable, can be easily dosed and at the same time has good cleaning performance.

It has now been found that the compositions according to the invention represent stable and visually appealing dishwashing detergent formulations which are at the same time readily biodegradable, have good cleaning performance and good rinsing performance, and which can be dosed evenly and without difficulty from the storage container. A first subject of the present invention is therefore a liquid automatic dishwashing detergent, characterized in that the automatic dishwashing detergent has two spatially separated liquid compositions A and B, wherein

(a) the composition has a pH of less than 8.5, preferably 8 or less, more preferably from 7 to 8, in particular from 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 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 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; and

(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 wt.%, preferably 0.05 to 1.0 wt.%, in particular 0.1 to 0.5 wt.%, in each case based on the total weight of composition B, and (iii) wherein the 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 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 with a standard small sample adapter. The spindle speed used for the measurement is preferably 12 revolutions per minute.

At least one biodegradable thickener, preferably a thickening polysaccharide, in particular xanthan, is used as the thickener. The polysaccharide is preferably used in an amount sufficient to adjust 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 particularly preferably contains 0.1 to 0.6% by weight of xanthan, and composition B preferably contains 0.1 to 0.5% by weight, in each case based on the total weight of the respective composition.

The present invention also relates to a cleaning agent package containing a dishwashing agent according to the invention, a machine dishwashing process in which a dishwashing agent is used and the use of a dishwashing agent according to the invention in a machine dishwashing process.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. It is further understood 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 limited to these examples. All percentages are by weight unless otherwise stated. Numerical ranges given in the format "from x to y" include the stated values. Where multiple preferred numerical ranges are given in this format, it is to be understood that all ranges resulting from the combination of the various endpoints are also included. Unless otherwise specified, 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. When referring to an ingredient, the statement 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, meaning that it can refer to one type of builder or a mixture of several different builders. Together with weight specifications, the statement refers to all compounds of the specified type contained in the composition/mixture, meaning that the composition contains no further compounds of this type beyond the specified amount of the corresponding compounds.

Whenever reference is made to molar masses herein, these data always refer to the number-average molar mass M _n , unless explicitly stated otherwise. The number-average molar mass can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 using THF as the eluent. The mass-average molar mass Mw can also be determined by GPC, as described for M _n .

The present automatic dishwashing detergents 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 essentially 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% by weight, preferably less than 0.1% by weight, based on the respective composition. However, it is understood that these amounts do not refer to agents or compositions in which sodium and hydroxide ions are present in dissociated form 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 stated pH value of the respective composition in the various embodiments refers to the pH value measured with a standard electrode in the undiluted state at 20°C.

The term "spatially separated" in relation to the compositions, as used herein, means that the compositions cannot come into contact with each other prior to use. Typically, the dishwashing detergent is provided in a multi-compartment package, such as a bottle or pouch, particularly a dual-compartment bottle or pouch, with each composition separated from the other composition(s) in a separate compartment. The automatic dishwashing detergent has several spatially separated compositions, which makes it possible, on the one hand, to separate incompatible ingredients from one another and, on the other hand, to offer compositions in combination which are used at different times in the dishwasher.

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 in a separate chamber separate from the other composition(s).

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

These enzymes, as well as the amylases and proteases used, are essentially of natural origin; improved variants based on the natural molecules are available for use in dishwashing detergents and are therefore preferred. Dishwashing detergents according to the invention preferably contain the respective enzymes in total amounts of 1 x 10 ^-6 to 5 wt.%, based on the active protein and the total weight of the respective composition. The protein concentration can be determined using known methods, for example, the BCA method or the biuret method.

Proteases are among the most technically important enzymes of all. They are the longest-established enzymes in detergents and dishwashing detergents and are contained in virtually all modern, high-performance detergents and dishwashing detergents. They break down protein-containing soils on the items being cleaned. Among these, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important. These are serine proteases due to the catalytically active amino acids. They act as nonspecific endopeptidases and hydrolyze any acid amide bonds found within peptides or proteins. Their pH optimum is usually in the significantly alkaline range. An overview of this family is provided, for example, in 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 produced by microorganisms. Among them, the subtilisins, produced and secreted by Bacillus species, are particularly noteworthy as the most important group within the subtilases. Examples of the subtilisin-type proteases preferably used in detergents and dishwashing detergents are the subtilisins BPN' and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY, and the enzymes thermitase, proteinase K, and the proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense, as well as variants of the aforementioned proteases that have an amino acid sequence that is altered compared to the parent protease. Proteases are modified in a targeted or random manner using methods known from the state of the art and thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis, or fusion with other proteins or protein fragments. For most of the proteases known from the state of the art, optimized variants are known.

Examples of amylases that can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger, and A. oryzae, as well as the improved versions of the aforementioned amylases for use in dishwashing detergents. Also particularly suitable for this purpose are the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Lipases or cutinases can also be used according to the invention, particularly for 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 one or more of the following amino acid substitutions starting from the aforementioned lipase at positions D96L, T213R, and/or N233R, particularly preferably T213R and N233R.

Enzymes that fall under the term hemicellulases can also be used. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases, and ß-glucanases.

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

Cleaning-active proteases and amylases are generally not supplied in the form of pure proteins, but rather in the form of stabilized, storable, and transportable preparations. These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel-like products, solutions of the enzymes, preferably as concentrated as possible, with little water content, and/or containing stabilizers or other additives.

Alternatively, the enzymes can be encapsulated for both solid and liquid dosage forms, 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 if in a solidified gel, or in core-shell capsules in which an enzyme-containing core is coated with a water-, air-, and/or chemical-impermeable protective layer. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shake or roll granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film formers, are low in dust and, due to the coating, are stable in storage.

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

As can be seen from the above, 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.

Particularly preferred dishwashing detergent compositions, in particular composition A, contain, in each case based 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.

The enzyme amounts preferably used according to the invention, based on the active enzyme protein, are 0.01 to 1.2 wt.% protease and/or 0.001 to 0.05 wt.% amylase, each based on the total weight of the cleaning agent A. Particularly preferred are those cleaning agents A which, in each case based on their total weight, contain 0.15 to 0.8 wt.% protease and/or 0.015 to 0.03 wt.% amylase as active enzyme protein, preferably protease and amylase in the stated amounts.

A protein and/or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation, or degradation due to physical influences, oxidation, or proteolytic cleavage. Inhibition of proteolysis is particularly preferred for microbial production of proteins and/or enzymes, especially 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 inactivation, denaturation, or decomposition, e.g., 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 their salts or esters, 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 aforementioned compounds. Peptide aldehydes, i.e., oligopeptides with a reduced carbon terminus, particularly those consisting of 2 to 50 monomers, are also used for this purpose. Peptide reversible protease inhibitors include, among others, ovomucoid and leupeptin. Specific, reversible peptide inhibitors for the protease subtilisin, as well as fusion proteins of proteases and specific peptide inhibitors, are also suitable for this purpose. Other examples of enzyme stabilizers include amino alcohols such as mono-, di-, triethanolamine, and propanolamine, and their mixtures, aliphatic mono- and dicarboxylic acids, and even C12 carboxylic acids such as succinic acid. Terminally capped fatty acid amide alkoxylates are also suitable as enzyme stabilizers. Calcium chloride is also a good stabilizer for proteases.

For this purpose, the dishwashing detergents 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), calcium lactate, or calcium acetate. Other calcium salts with alpha-hydroxycarboxylic acids or alpha-amino acids are also suitable. Calcium salts suitable for stabilizing enzymes are contained in various embodiments in composition A in an amount of 0.05 to 2 wt.%, in particular 0.1 to 0.6 wt.%, based on the total weight of composition A.

In general, all phosphonates suitable as complexing agents for dishwashing detergents can be used as the phosphonate compound. A hydroxyalkane and/or aminoalkanephosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates. In particular, the alkali metal salts of the phosphonates are used. Phosphonates are preferably present in the detergents in amounts of 0.5 to 7% by weight, in particular in amounts of 1 to 6% by weight, based in each case on the total weight of composition B, in particular in the form of the HEDP sodium salt. In preferred embodiments, the amount is not more than 300 mg phosphorus/job.

In another embodiment, the present automatic dishwashing detergents are preferably phosphonate-free. "Phosphonate-free," as used herein, means that the composition in question is substantially free of phosphonates, i.e., in particular, contains phosphonates in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the respective composition.

The dishwashing detergents further contain at least one builder in the form that compositions A and B each contain at least one builder (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.

In addition to their builder effect, free acids typically also have the property of an acidifying component and can therefore also be used to adjust the pH value. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof are particularly worth mentioning.

Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, whereby polycarboxylic acids are understood to be carboxylic acids which have more than one, in particular two to eight acid functions, preferably two to six, in particular two, three, four or five Acid functions are present throughout the molecule. Preferred polycarboxylic acids are therefore dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and pentacarboxylic acids, especially di-, tri-, and tetracarboxylic acids. The polycarboxylic acids may also contain additional functional groups, such as hydroxyl or amino groups. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, such as nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediaminedisuccinate (ethylenediamine disuccinate, EDDS), and their derivatives and mixtures thereof, with glutamic N,N-diacetic acid (also referred to as N,N-bis(carboxymethyl)-L-glutamic acid or GLDA) preferably being excluded as described above. 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 preferred are the aminocarboxylic acids selected from the group consisting of methylglycinediacetic acid (MGDA), glutamic diacetic acid (GLDA), and ethylenediamine disuccinic acid (EDDS) and their salts.

In a particularly preferred embodiment, the at least one builder in Composition A and/or B is methylglycinediacetic 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, encompasses both the free acid and the corresponding salts.

Composition A and/or B preferably contain, in each case based on the total weight of the cleaning agent A or B, methylglycinediacetic 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.%.

In various embodiments, dishwashing detergents according to the invention (cleaning agents A and/or B) contain one or more salts of citric acid, i.e., citrates, for example sodium or potassium citrate, as one of their essential builders. These are preferably present in a proportion of 1 to 30 wt.%, in particular 2 to 25 wt.%, especially 3 to 20 wt.%, based in each case on the total weight of the respective composition A or B.

Preference is also given to the use of carbonate(s) and/or hydrogencarbonate(s), preferably alkali carbonate(s), particularly preferably sodium carbonate (soda), preferably in cleaning agent composition B, in amounts of 2 to 30 wt.%, preferably 4 to 20 Wt.% and in particular from 5 to 15 wt.%, in each case based on the weight of composition A or B. In various embodiments, composition A contains no carbonate/hydrogen carbonate. In various other embodiments, composition B contains carbonates/hydrocarbonates, in particular soda, preferably in an amount of 6 to 15 wt.%, in particular 7 to 12 wt.%.

More particularly, 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, each based on the total weight of Composition B.

Particularly preferred dishwashing detergents according to the invention, preferably automatic dishwashing detergents, are characterized in that composition B contains at least two builders from the group of carbonates, MGDA and citrates, the weight fraction of these builders, based on the total weight of the composition, preferably being 5 to 40 wt.%, preferably 8 to 30 wt.% and in particular 10 to 25 wt.%.

In various embodiments, Composition A contains at least one builder, this builder preferably being MGDA. Composition A may contain additional builders, in particular citrate, but in various embodiments, no further builder is contained. The amount of MGDA in Composition A is preferably up to 25 wt.%, more preferably 2 to 20 wt.%, especially 8-15 wt.%. In certain embodiments, Composition A contains up to 13 wt.% MGDA.

Also suitable are polymeric polycarboxylates (organic polymers with a large number of carboxylate functions (especially more than ten) in the macromolecule), polyaspartates, polyacetals, and dextrins. Biodegradable polymers are particularly preferred.

In a particularly preferred embodiment, the compositions are free of acrylic acid homopolymers, since these compounds are not biodegradable and are not preferred for ecological reasons. Free of acrylic acid homopolymers, as used herein, means that the composition in question is essentially free of acrylic acid homopolymers, i.e., in particular, contains acrylic acid homopolymers in amounts of less than 0.1 wt.%, preferably less than 0.01 wt.%, based on the respective composition.

In another particularly preferred embodiment, the compositions are free of copolymers and terpolymers of acrylic acid with monomers containing sulfonic acid-containing groups, since these compounds are not yet biodegradable 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, ie in particular contains 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, compositions A and B each contain less than 1 wt.% of polymers which, as a monomer present at more than 40 mol.%, contain acrylic acid or methacrylic acid and optionally additionally sulfonic acid-containing groups

In preferred cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, the silicate content, 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 be free of silicates, where "free" in this context means that the amount is limited to less than 0.1 wt.%.

In addition to the aforementioned builders, the dishwashing detergents according to the invention, in particular composition B, can further contain alkali metal hydroxides as an alkali source. These alkali carriers are used in the detergents 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 contains less than 1.71% by weight, based on the total weight of composition B, of NaOH, preferably less than 1.0% by weight of NaOH, even more preferably composition B is free of NaOH, in particular free of added NaOH. In preferred embodiments, composition B therefore contains potassium hydroxide (KOH) as an alkali source instead of NaOH, preferably in the amounts indicated above, in particular between 0.5 and 7.5% by weight. In particular, the alkali metal hydroxides, especially KOH, are used in amounts such that the pH values of the compositions according to the invention are achieved.

The dishwashing detergents preferably also contain at least one surfactant. The surfactants can be present in either composition A or composition B, or both. However, the at least one surfactant is preferably present in composition A, most preferably in amounts of up to 5% by weight based on the total weight of composition A. The surfactants contained are preferably nonionic surfactants. All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. Low-foaming nonionic surfactants are preferred, particularly alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. The dishwasher detergents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.

Particularly preferred are nonionic surfactants having a melting point above room temperature. Nonionic surfactants with a melting point above 20°C, preferably above 25°C, particularly preferably between 25 and 60°C, and especially between 26.6 and 43.3°C, are particularly preferred.

Preferred surfactants come from the group of alkoxylated nonionic surfactants, especially 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 also characterized by good foam control.

Particularly preferred nonionic surfactants in the context of the present invention are low-foaming nonionic surfactants containing alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups bonded to one another before a block of the other groups follows. These are nonionic surfactants of the general formula

R1-O-(CH ₂ -CH ₂ -O)— (CH ₂ -C HO)— (CH ₂ -CH ₂ -O)— (CH ₂ — C HO)— H

R2 R3 is preferred, in which R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24 alkyl or alkenyl radical; each group R ² or R ³ is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, CH(CH3)2 and the indices w, x, y, z independently represent integers from 1 to 6.

Thus, nonionic surfactants which have a Cg-15 alkyl radical 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 are particularly preferred.

Preferred nonionic surfactants are those of the general formula R ¹ -CH(OH)CH2O- (AO)w-(A'O)x-(A”O) _y -(A'”O)zR ² , in which R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated Ce-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 represent a radical from the group -CH2CH2, -CH2CH2-CH2, -CH ₂ -CH(CH ₃ ), -CH2-CH2-CH2-CH2, -CH ₂ -CH(CH ₃ )- CH ₂ -, -CH ₂ -CH(CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 120, where x, y and/or z can also be 0.

By adding the above-mentioned non-ionic surfactants of the general formula R ¹ - CH(OH)CH2O-(AO)w-(A'O)x-(A”O)y-(A'”O)zR ² , hereinafter also referred to as

“Hydroxy mixed ethers”, the cleaning performance of the preparations according to the invention can be significantly improved, both in comparison to surfactant-free systems and in comparison to systems containing alternative non-ionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

Preferred surfactants are those of the formula R ¹ O[CH2CH(CH ₃ )O]x[CH2CH2O] _y CH2CH(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 ² is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15.

The group of these non-ionic surfactants includes, for example, the C2-26 fatty alcohol (PO)i-(EO)i5-4o-2-hydroxyalkyl ethers, in particular the Cs-io fatty alcohol (PO)i-(EO)22-2-hydroxydecyl ethers.

Particularly preferred are those end-capped, poly(oxyalkylated) nonionic surfactants which, according to the formula R ¹ O[CH2CH2O] _X CH2CH(OH)R ² , in addition to a radical R ¹ which stands for 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 have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where x stands for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Further preferred nonionic surfactants are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R ¹ O[CH2CH(R ³ )O]x[CH2]kCH(OH)[CH2]jOR ² , in which R ¹ and R ² are linear or branched, saturated or unsaturated, aliphatic or aromatic

hydrocarbon radicals with 1 to 30 carbon atoms, R ³ is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5. If the value x > 2, each R ³ in the above formula R ¹ O[CH ₂ CH(R ³ )O]x[CH ₂ ]kCH(OH)[CH ₂ ]jOR ² can 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, with radicals having 8 to 18 C atoms being particularly preferred. For the radical R ³ , H, -CH 3 or -CH ₂ CH3 are particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula 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)(PO)(EO) and (PO)(PO)(PO). The value 3 for x has been chosen here as an example and can certainly be larger, whereby 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-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]XCH ₂ CH(OH)CH ₂ OR ^2. In the latter formula, R ¹ , R ² and R ³ are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particular preference is given to surfactants in which the radicals R ¹ and R ² have 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15.

Finally, the non-ionic 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 Ce- _2-4 -alkyl or alkenyl radical;

R ² represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A represents a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH(CH3), preferably CH ₂ CH ₂ , and w represents values between 1 and 120, preferably 10 to 80, in particular 20 to 40 The group of these non-ionic surfactants includes, for example, the C4-22 fatty alcohol (EO)io-ao-2-hydroxyalkyl ethers, in particular the C8-12 fatty alcohol (EO)22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO)4o-so-2-hydroxyalkyl ethers.

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

Preferred dishwashing detergents are characterized in that the dishwashing detergent contains at least one non-ionic surfactant, preferably a non-ionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the non-ionic surfactant in the total weight of the dishwashing detergent 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 contain 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 or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri-, or tetraalkylammonium salts. Preference is given to linear alkyl sulfates or alkylsulfonates having at least 14 carbon atoms in the alkyl radical or alkylbenzylsulfonates having at least 12, preferably 14, carbon atoms in the alkyl radical. 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 wt.% in composition B, based on the total weight of composition B.

Most 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 using a sieve of appropriate size, of 0.1 to 4 mm, preferably 0.25 to 3 mm. These particles are visible to the consumer and are preferably evenly distributed in composition B. These particle sizes are particularly well stabilized in the formulation by the biodegradable thickener, in particular xanthan gum, without these particles sinking to the bottom even after extended storage times and thus only being poured unevenly from the double-chamber bottle. Lanette® E ex BASF, for example, is particularly suitable. These particles are particularly preferably present in 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 composition B. Thus, the anionic surfactants mentioned enhance cleaning performance without significantly negatively affecting foaming behavior. Lanette® E ex BASF, for example, is particularly suitable.

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), 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 non-ionic 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 using conventional pH regulators. In various embodiments, the pH (undiluted, measured at 25°C) of composition A is in a range from 5.5 to 8.5, preferably 6.5 to 8.0, particularly preferably from 7.0 to 8.0, in particular 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. Acids and/or alkalis, preferably alkalis, serve as pH adjusters. 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 also 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 is preferred. The alkali source described above is particularly preferably used to adjust the pH. Even if volatile alkali, for example in the form of ammonia and/or alkanolamines, which can contain up to 9 carbon atoms in the molecule, can be used to adjust the pH, wherein the alkanolamine can be selected from the group consisting of mono-, di-, triethanolamine, and propanolamine and mixtures thereof, such volatile alkali sources, in particular ethanolamines, are preferably omitted. In various embodiments, the compositions therefore contain less than 1.75% by weight of alkanolamine, in particular monoethanolamine; very particularly preferably, they are free of It has been found that the omission of such alkanolamines increases the stability of the compositions.

"Approximately," as used herein in connection with a numerical value, means the numerical value ±5%. "Approximately 7.5" therefore 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), typically in amounts of 0.001 to 5 wt.%. Buffer substances that are also complexing agents or even chelating agents (INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, especially sodium and potassium citrates, for example trisodium citrate 2H2O and tripotassium citrate H2O.

The agents according to the invention preferably contain at least one further component, preferably selected from the group consisting of sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bittering agents and antimicrobial agents.

Glass corrosion inhibitors prevent the occurrence of cloudiness, streaks, and scratches, as well as iridescence on the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of bismuth, magnesium, and zinc salts, as well as magnesium and zinc complexes. In the context of the present invention, the zinc salt content in dishwashing detergents is preferably between 0.1 and 5% by weight, more preferably between 0.2 and 4% by weight, and in particular between 0.4 and 3% by weight, or the zinc content in oxidized form (calculated as Zn ²⁺ ) is 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, in each case based on the total weight of the agent containing the glass corrosion inhibitor. In particular, zinc acetate, for example, can be used. In addition to or as an alternative to the above-mentioned salts (in particular the zinc salts), polyethyleneimines, such as those available, for example, under the name Lupasol® (BASF), can be used as glass corrosion inhibitors, 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 fragrance compounds, e.g., synthetic products of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type, can be used as perfume oils or fragrances. However, mixtures of different fragrances are preferred, which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources, e.g., pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil. The dishwashing detergents described herein can be packaged in various ways. The liquid forms based on water and/or organic solvents can be thickened or in gel form.

The dishwashing detergents described herein are preferably packaged in a multi-chamber bottle, in particular in a two-chamber bottle, and are dosed from this, preferably into the dosing chamber of the dishwasher.

According to a further embodiment, the present invention relates to a cleaning agent packaging comprising a dishwashing agent 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, each of the chambers of the package having its own outlet opening with 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 detergents according to the invention is also the subject of the invention. The invention likewise relates to a dishwashing method, in particular an automatic dishwashing method, in which a dishwashing detergent according to the invention is used. The present application therefore further relates to a method for cleaning dishes in a dishwasher, in which the detergent according to the invention is metered into the interior of a dishwasher during the course of a dishwashing program, before the start of the main wash cycle or during the main wash cycle. The dosing or introduction of the detergent according to the invention into the interior of the dishwasher can be carried out manually, but the detergent is preferably metered into the interior of the dishwasher by means of the metering chamber.

Examples

Example 1:

Table 1 : Composition of the automatic dishwashing detergent (wt% active substance)

Viscosity measurements were performed at 20 °C using a Brookfield LVDV II+Pro, spindle 31, and a standard small sample adapter. The spindle speed used for the measurement is indicated after the respective value.

The enzyme phase (16 g ^each ) and the alkaline phase (17 g each) are each dispensed into the dishwasher compartment from a dual-chamber bottle. Composition E1 demonstrates improved cleaning performance and improved stain removal, particularly on glass, porcelain, plastic, and stainless steel. Improvement in scale inhibition was also observed.

If the comparison mixture is dosed from the double-chamber bottle (held vertically) into the dosing chamber of a standard dishwasher, the enzyme phase completely covers the alkali phase, so that the consumer only perceives the enzyme phase in the chamber. This may lead to overdosing or misjudgment by the consumer. If the formulation according to the invention is poured into the dosing chamber accordingly, both phases are visibly present next to each other. The outlet opening of the double-chamber bottle was additionally enlarged to 4.9 mm for each of the two chambers so that, with the viscosity and density according to the invention, both gels could flow out evenly and also visually appear to be present next to each other in the dishwasher chamber with the same extent. The risk of overdosing or misjudgment of the dosage by the consumer is thus reduced.

Claims

Patent claims 1 . Liquid automatic dishwashing detergent, characterized in that the automatic dishwashing detergent has two spatially separated liquid compositions A and B, wherein (c) the composition has a pH of less than 8.5, preferably 8 or less, more preferably from 7 to 8, in particular from 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 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 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; and (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 wt.%, in each case based on the total weight of composition B, and (iii) wherein the 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 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. 2. Dishwashing detergent 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% by weight of protease, preferably 0.15 to 0.8% by weight of protease as active enzyme protein, and/or 0.001 to 0.05% by weight of amylase, preferably 0.015 to 0.03% by weight of amylase as active enzyme protein. 3. Dishwashing detergent according to claim 1 or 2, characterized in that composition A and/or B, in each case based on the total weight of the respective cleaning agent, methylglycinediacetic 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.%. 4. Dishwashing detergent according to one of the preceding claims, characterized in that compositions A and B each contain less than 1% by weight of homopolymers of acrylic acid and/or copolymers and terpolymers of acrylic acid with monomers containing sulfonic acid-containing groups. 5. Dishwashing detergent according to one of the preceding claims, characterized in that composition A contains (i) at least one amylase and at least one protease and optionally at least one further enzyme selected from the group consisting of lipases, hemicellulases, in particular pectinases and/or mannanases, cellulases, perhydrolases and oxidoreductases, (ii) at least one calcium salt, in particular calcium chloride (CaCh), in an amount of 0.05 to 2 wt.%, in particular 0.1 to 0.6 wt.% 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. 6. Dishwashing detergent according to one of the preceding claims, characterized in that composition B (i) contains at least one alkali source, wherein the alkali source contains less than 1.7 wt.% NaOH based on the total weight of composition B, is preferably free of added NaOH, and preferably comprises KOH; and/or (ii) the at least one builder MGDA, trisodium salt in an amount of up to 15.0 wt.%, up to 20 wt.% citrate and up to 15 wt.% soda, each 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), which contains at least one phosphonate, in particular HEDP, in an amount of 0.5 to 7 wt.%, preferably 1 to 6 wt.% based on composition B, in particular in an amount of not more than 300 mg phosphorus/job. 7. Dishwashing detergent according to one of the preceding claims, characterized in that the dishwashing detergent contains at least one further component, preferably at least two further components, selected from the group consisting of polymers, corrosion inhibitors, glass corrosion inhibitors, fragrances and perfume carriers. 8. A cleaning agent packaging comprising a dishwashing detergent according to any one 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, each of the chambers of the package having its own outlet opening with 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. 9. A machine dishwashing process, characterized in that a dishwashing detergent according to one of claims 1 to 8 is used.