Liquid cleaning composition comprising phosphonate and xanthan

Abstract

The invention relates to cleaning agents which are liquid at 20 °C and which contain 0.2 to 6.0 wt.% of phosphonates, but neither homopolymers of acrylic acid and methacrylic acid nor copolymers or terpolymers of acrylic acid or methacrylic acid with monomers containing sulfonic acid groups.

Description

[0001] The invention relates to cleaning agents which are liquid at 20 °C and which contain 0.2 to 6.0 wt.% of phosphonates, but neither homopolymers of acrylic acid and methacrylic acid nor copolymers or terpolymers of acrylic acid or methacrylic acid with monomers containing sulfonic acid groups.

[0002] The use of phosphonates in liquid detergent compositions that have a pH in the neutral range leads to a reduced storage stability of the formulations, as crystals form during longer storage periods.

[0003] The object of the present invention is therefore to provide liquid cleaning agents which show good cleaning performance on minced meat and at the same time have good storage stability at 4 weeks and 40 °C.

[0004] Surprisingly, it was found that liquid detergent formulations in the neutral range containing phosphonates lead to an improvement in the cleaning performance on minced meat without a reduction in storage stability if the content of homopolymers of acrylic acid and methacrylic acid as well as co- and terpolymers of acrylic acid or methacrylic acid with monomers containing sulfonic acid-containing groups is kept low.

[0005] A first aspect of the present invention therefore relates to a liquid cleaning agent which has a pH value between 6.5 and 8.5 and contains - based on the total weight of the agent: less than 1% by weight of homopolymers of acrylic acid and methacrylic acid; less than 1% by weight of copolymers or terpolymers of acrylic acid or methacrylic acid with monomers containing sulfonic acid groups; 0.15 to 0.8% by weight of xanthan gum, 0.2 to 6.0% by weight of phosphonate(s), 2.0 to 15.0% by weight of complexing agents from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and / or their salts.

[0006] Dishwashing detergents according to the invention are free of homopolymers of acrylic acid and methacrylic acid, since these compounds are not biodegradable and are not preferred for ecological reasons. "Free of homopolymers" of acrylic acid and methacrylic acid, as used herein, means that the composition in question is essentially free of acrylic acid and methacrylic acid homopolymers, i.e., 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.

[0007] Dishwashing detergents according to the invention are free from copolymers and terpolymers of acrylic acid or methacrylic acid with monomers containing sulfonic acid-containing groups, since these compounds are not yet biodegradable and are therefore not preferred for ecological reasons. Free from the polymers mentioned as used herein means that the composition in question is essentially free of such polymers, i.e., contains such polymers in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the respective composition.

[0008] The cleaning agent according to the invention is characterized in that the composition has a pH value of 6.5 to 8.5 at 20°C. The pH value is measured in the product itself, i.e., undiluted. A suitable measuring device is, for example, a conventional pH electrode.

[0009] In the further description, the term "at least one" is synonymous with the term "one or more", and both terms can be used interchangeably.

[0010] "One or more," as used herein, refers to at least one and includes 1, 2, 3, 4, 5, 6, 7, 8, 9, or more of the named types. Similarly, "at least one," as used herein, refers to, but is not limited to, 1, 2, 3, 4, 5, 6, and more. With respect to an ingredient, it refers to the type of ingredient, not the absolute number of molecules. Thus, for example, "at least one surfactant" means at least one type of surfactant, meaning it can refer to one type of surfactant or a mixture of several different surfactants. Together with the weight data, the data refers to all compounds of the specified type contained in the composition / mixture, meaning that the composition contains no further compounds of that type beyond the specified amount of the corresponding compounds.

[0011] The cleaning composition according to the invention is provided in the form of a liquid. The term "liquid," as used herein, includes liquids and gels. The term "liquid," as used herein, refers to dishwashing detergents or cleaning agents that are flowable and pourable at 20°C (1 bar).

[0012] The cleaning agents or automatic dishwashing detergents according to the invention are water-based. They preferably contain, based on the total weight of the composition, 30 to 85% by weight of water. It is particularly preferred if the automatic dishwashing detergent contains, based on its total weight, 40 to 80% by weight, preferably 50 to 79% by weight, of water.

[0013] As an essential component, the cleaning agent or automatic dishwashing agent according to the invention contains - based on its total weight - 0.15 to 0.8 wt.% xanthan.

[0014] Xanthan gum is a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions. It has a molecular weight of 2 to 15 million Daltons. Xanthan gum is formed from a chain of ß-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate, and pyruvate, with the number of pyruvate units determining the viscosity of the xanthan gum. Xanthan gum can also be referred to as xanthan gum, E 414, or xanthan gum, and has the CAS number 11138-66-2.

[0015] Thickening with xanthan gum can improve the biodegradability of the cleaning agent. Preferably, the active ingredients of the compositions are biodegradable, resulting in a high percentage of biodegradability, preferably above 85% by weight of the composition. This means that 85% by weight of the components of the composition are biodegradable. Preferably, more than 90% by weight of the composition is biodegradable, and more preferably, more than 98% of the composition is biodegradable. The biodegradability of the components is defined according to OECD 301.

[0016] In amounts ranging from 0.15 to 0.8 wt.%, xanthan gum can be completely dissolved and is able to stabilize the liquid cleaning agent and minimize disintegration of the mixture. In particular, the sedimentation of all other components contained in the cleaning agent can also be reduced.

[0017] Particularly stable and homogeneous cleaning agents were obtained when the xanthan gum was used in an amount range of 0.20 to 0.7 wt.%, preferably 0.30 to 0.65 wt.%, based on the total weight of the automatic dishwashing detergent or cleaning agent.

[0018] The best results were obtained when the cleaning agent contained 0.35 to 0.60 wt.% xanthan gum. In this most preferred embodiment, the amount of water could be reduced to a maximum, while still allowing the xanthan gum to be completely dissolved and preventing sedimentation of all other components.

[0019] As a further component essential to the invention, the machine dishwashing detergent or cleaning agent according to the invention contains - based on its total weight - 2.0 to 15% by weight of complexing agents from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and / or their salts.

[0020] Suitable salts of MGDA include sodium, potassium, magnesium, calcium, zinc, or ammonium ion (NH 4 +< ) salts. MGDA is particularly preferably used in cleaning agents in the form of its trisodium salt.

[0021] Another particularly suitable complexing agent is glutamic acid diacetic acid (GLDA). GLDA possesses a stereogenic center. Both the (S) form and the (R) form (or both the L-form and the D-form) are within the scope of the invention. GLDA is particularly preferably used in the form of its tetrasodium salt in the cleaning agent.

[0022] Particularly preferred representatives of this class are their alkali metal salts, in particular the trisodium salt of methylglycinediacetic acid (MGDA) or the tetrasodium salt of glutamatediacetic acid (GLDA). Especially when the cleaning agent contains the complexing agent(s) MGDA and / or GLDA in the form of the trisodium or tetrasodium salts, the ionic strength in the cleaning agent is increased.

[0023] It has been found that the viscosity could be adjusted to the desired range and did not change adversely during storage, in particular when the cleaning agent contained the complexing agent(s), in particular the salts of methylglycinediacetic acid (MGDA) and / or glutamic acid diacetic acid (GLDA), in a quantity range of 2.0 to 15 wt.%.

[0024] The complexing agent(s), in particular the sodium salts of MGDA and / or GLDA, are very particularly preferably contained in the cleaning agent in an amount range of 2.5 to 10 wt.%, preferably 3.0 to 8.0 wt.%, particularly preferably 4.0 to 6.0 wt.%.

[0025] In a particularly preferred embodiment, a cleaning agent according to the invention is characterized in that it contains - based on the total weight of the cleaning agent - 2.5 to 10 wt.%, preferably 3.0 to 8.0 wt.%, particularly preferably 4.0 to 6.0 wt.% of complexing agents from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and / or their salts.

[0026] Another group of ingredients according to the invention are the phosphonates. In addition to 1-hydroxyethane-1,1-diphosphonic acid, the complex-forming phosphonates include a number of different compounds such as diethylenetriaminepenta-(methylenephosphonic acid) (DTPMP). In this application, hydroxyalkane and aminoalkanephosphonates are particularly preferred. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, with the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably used in the form of the neutrally reacting sodium salts, e.g. B. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP.HEDP, a phosphonate builder, is preferred. Aminoalkanephosphonates also possess a pronounced heavy metal binding capacity. Accordingly, it may be preferable to use aminoalkanephosphonates, especially DTPMP, or mixtures of the aforementioned phosphonates, especially if the products also contain bleach.

[0027] A preferred cleaning composition in the context of this application contains one or more phosphonate(s) from the group a) Aminotrimethylenephosphonic acid (ATMP) and / or its salts; b) Ethylenediaminetetra(methylenephosphonic acid) (EDTMP) and / or its salts; c) Diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and / or its salts; d) 1-Hydroxyethane-1,1-diphosphonic acid (HEDP) and / or its salts; e) 2-Phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or its salts; f) Hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP) and / or its salts; g) Nitrilotri(methylenephosphonic acid) (NTMP) and / or its salts.

[0028] Particularly preferred cleaning compositions are those which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates.

[0029] Of course, the automatic dishwashing detergents according to the invention can contain two or more different phosphonates. The weight fraction of the phosphonates in the total weight of the cleaning composition according to the invention is preferably 0.2 to 6.0 wt. %, more preferably 1.0 to 4.5 wt. %, in particular 2.0 to 4.0 wt. % phosphonate(s). HEDP is used in particular in the stated amounts, especially as the sodium salt.

[0030] In addition to the complexing agents as described above, the cleaning agent according to the invention particularly preferably contains citric acid and / or citric acid salts. A particularly suitable citric acid salt is sodium citrate, in particular trisodium citrate, anhydrous trisodium citrate, or trisodium citrate dihydrate.

[0031] Combinations of citric acid or its salts with methylglycinediacetic acid (MGDA) or its salts are also preferred. The combination of the trisodium salt of methylglycinediacetic acid (MGDA) and trisodium citrate is particularly preferred.

[0032] In a particularly preferred embodiment, a cleaning agent according to the invention is characterized in that it contains - based on the total weight of the cleaning agent - 0.5 to 10 wt.%, preferably 1.0 to 8.0 wt.%, more preferably 2.0 to 6.0 wt.% of citric acid and / or its salts.

[0033] In a particularly preferred embodiment, a cleaning agent according to the invention is characterized in that it contains - based on the total weight of the cleaning agent - 0.5 to 10 wt.%, preferably 1.0 to 8.0 wt.%, more preferably 2.0 to 6.0 wt.% sodium citrate.

[0034] The cleaning agent or dishwasher detergent according to the invention contains at least one protease and / or at least one amylase (e).

[0035] Enzymes are added to enhance cleaning performance or to ensure the same cleaning performance under milder conditions (e.g., at lower temperatures). The enzymes can be used in free form or in chemically or physically immobilized form on a carrier or in encapsulated form.

[0036] Detergents according to the invention preferably contain enzymes in total amounts of 1 x 10 -6 wt% to 5 wt%, based on active protein. The protein detergent ion can be determined using known methods, e.g., the BCA method or the biuret method.

[0037] Among proteases, subtilisin-type proteases are preferred. Examples include subtilisins BPN' and Carlsberg, as well as their more advanced forms, protease PB92, subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY, as well as the enzymes thermitase, proteinase K, and proteases TW3 and TW7, which belong to the subtilases but no longer to the subtilisins in the strict sense.

[0038] Examples of amylases that can be used according to the invention are α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger, and A. oryzae, as well as further developments of the aforementioned amylases that have been improved for use in cleaning agents. Particularly noteworthy in this context are the α-amylases from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

[0039] Cleaning-active proteases and amylases are generally not supplied in the form of pure proteins, but rather in stabilized, storable, and transportable preparations. These finished preparations include, for example, solid preparations obtained by granulation, extrusion, or freeze-drying, or, particularly in the case of liquid or gel-like products, solutions of the enzymes, preferably maximally concentrated, low in water, and / or supplemented with stabilizers or other excipients.

[0040] Alternatively, the enzymes can also be encapsulated, e.g. by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, e.g. those in which the enzymes are enclosed in a solid gel, or in those of the core-shell type, in which an enzyme-containing core is coated with a water-, air- and / or chemical-impermeable protective layer. In the case of cover layers, other active ingredients such as stabilizers, emulsifiers, pigments or dyes can also be applied. Such capsules are applied using methods known per se, for example by shake or roll granulation or in the fluidized bed process. Such granules are advantageously low in dust, e.g. through the use of polymeric film formers, and are storage-stable due to the coating.

[0041] As can be seen from the foregoing, the enzyme protein makes up only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used according to the invention contain between 1 and 40 wt.%, preferably between 2 and 30 wt.%, particularly preferably between 3 and 25 wt.% of the enzyme protein. Particularly preferred cleaning agents are those which, based on their total weight, contain 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and especially 0.5 to 8 wt.% of the respective enzyme preparations.

[0042] If the dishwashing detergent formulations contain enzymes, they preferably contain them in amounts of 0.001 to 3.0% of the active enzyme protein, based on the weight of the total composition. The percentage of enzymes is calculated based on the mass of the active enzyme protein per weight of the total composition.

[0043] The 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, each based on the total weight of the cleaning agent. Particularly preferred cleaning agents are those which, based on their total weight, contain 0.05 to 0.5% by weight of protease and / or 0.005 to 0.03% by weight of amylase as the active enzyme protein, preferably protease and amylase in the stated amounts.

[0044] According to the invention, amylases and proteases (e) are preferably used.

[0045] Formulations according to the invention may contain one or more enzyme stabilizers. Enzyme stabilizers serve to protect enzymes – particularly during storage – from damage such as inactivation, denaturation, or decomposition, e.g., due to physical influences, oxidation, or proteolytic cleavage.

[0046] 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, in particular 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.

[0047] With regard to the rheological properties of the cleaning agent, it has been found to be particularly advantageous if the cleaning agent contained calcium chloride to stabilize the protease (e).

[0048] For this reason, calcium chloride is also preferably used in cleaning agents in certain amounts. Particularly suitable amounts of calcium chloride are 0.05 to 0.60 wt.%, preferably 0.10 to 0.50 wt.%, and particularly preferably 0.15 to 0.35 wt.%, with these amounts being based on the total weight of the cleaning agent.

[0049] The cleaning agent according to the invention is particularly preferably substantially phosphate-free. "Phosphate-free" is understood here to mean that the cleaning agent is substantially free of phosphate (including orthophosphate, polyphosphate, and / or pyrophosphate), in particular with phosphates in an amount of less than 0.1% by weight, preferably less than 0.01% by weight, based on the total weight of the composition.

[0050] The expression "essentially free of" means that the respective compound may in principle be present, but is then present in an amount that does not impair the function of the other components. Therefore, within the context of the present invention, the property "essentially free of" a particular compound is preferably understood to mean a total weight of less than 0.1 wt.%, more preferably less than 0.001 wt.%, in particular free of the compound, based on the total weight of the composition.

[0051] According to a preferred embodiment, the cleaning agent or automatic dishwashing agent according to the invention contains - based on its total weight - 1.0 to 4.0 wt.% of non-ionic surfactants.

[0052] All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. Low-foaming nonionic surfactants are preferably used, especially alkoxylated, especially ethoxylated, low-foaming nonionic surfactants such as alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, or amine oxides. Particularly preferred nonionic surfactants are described in more detail below.

[0053] Preferred alcohol ethoxylates have a narrow range (NRE) distribution. In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohols with 14 EO, 25 EO, 30 EO, or 40 EO.

[0054] Particular preference is given to using ethoxylated nonionic surfactants obtained from C6-C20 monohydroxyalkanols or C6-C20 alkylphenols or C16-C20 fatty alcohols and more than 12 mol, preferably more than 15 mol, and in particular more than 20 mol, of ethylene oxide per mole of alcohol. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C16-C20 alcohol), preferably from a C18 alcohol, and at least 12 mol, preferably at least 15 mol, and in particular at least 20 mol, of ethylene oxide. The so-called "narrow-range ethoxylates" are particularly preferred.

[0055] Preferred surfactants come from the group of alkoxylated nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

[0056] In the context of the present invention, low-foam nonionic surfactants containing alternating ethylene oxide and alkylene oxide units have proven particularly preferred. Among these, surfactants with EO-AO-EO-AO blocks are preferred, wherein one to ten EO groups or AO groups are linked to one another before a block of the respective other group follows. Nonionic surfactants of the general formula

[0057] preferred are those in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated functional C 6 -C 24 alkyl or alkenyl group; each R 2 and R 3 group is independently selected from -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 ; and the indices w, x, y and z independently represent integers from 1 to 6.

[0058] Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1< -OH and ethylene or alkylene oxide. The functional group R 1< in the above formula can vary depending on the origin of the alcohol. If native sources are used, the functional group R 1< has an even number of carbon atoms and is generally unbranched, with the linear functional groups of alcohols of native origin with 12 to 18 C atoms, such as coconut, palm, tallow or oleyl alcohol, being preferred. Some examples of alcohols available from synthetic sources are the Guerbet alcohols or functional groups that are methyl-branched or linear and 2-methyl-branched, as are usually present in functional groups of oxo alcohols, in mixtures.Regardless of the type of alcohol used to produce the nonionic surfactants contained in the compositions, nonionic surfactants are preferred in which R 1< represents a functional alkyl group having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15, in particular 9 to 11, carbon atoms in the above formula.

[0059] As an alkylene oxide unit, which is present alternately with the ethylene oxide unit in the preferred nonionic surfactants, in addition to propylene oxide, butylene oxide is particularly suitable. However, other alkylene oxides in which R 2< and R 3< are independently selected from -CH 2 CH 2 CH 3 and -CH(CH 3 ) 2 are also suitable. Preference is given to using nonionic surfactants of the above formula in which R 2< and R 3< represent a functional group -CH 3; w and x independently represent values ​​of 3 or 4; and y and z independently represent values ​​of 1 or 2.

[0060] Other preferably used non-ionic surfactants of the solid phase are non-ionic surfactants of the general formula R 1< O(AlkO)xM(OAlk)yOR 2< ,

[0061] in which R 1< and R 2< independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl function having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl function having 2 to 4 carbon atoms; x and y independently of one another represent values ​​between 1 and 70; and M represents an alkyl function selected from the group CH 2 , CHR 3< , CRR 34< , CH2CHR 3< and CHR 3< CHR 4< , R 3< and R 4<, which independently of one another represent a branched or unbranched, saturated or unsaturated alkyl function having 1 to 18 carbon atoms.

[0062] In this case, nonionic surfactants of the general formula R 1< -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CHR(OCH 2 CH 2 ) y O-CH 2 CH(OH)-R 2< are preferred, in which R, R 1< and R 2< independently represent a functional alkyl group or a functional alkenyl group having 6 to 22 carbon atoms; x and y independently represent values ​​between 1 and 40.

[0063] In this case, compounds of the general formula R 1< -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CHR(OCH 2 CH 2 ) y O-CH 2 CH(OH)-R 2< are particularly preferred.

[0064] in which R represents a linear, saturated alkyl function having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another represent values ​​from 20 to 30. Such compounds can be obtained, for example, by reacting alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.

[0065] In this case, preferred nonionic surfactants are those of the general formula R 1< -CH(OH)CH 2 O-(AO) w -(AO) x -(A"O) y -(A‴O) z -R 2< , in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated functional C6-24 alkyl or alkenyl group; R 2< represents hydrogen or a linear or branched functional hydrocarbon group having 2 to 26 carbon atoms; A, A', A" and A‴ independently represent a functional group from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH(CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH(CH 3 )-CH 2 -, -CH 2 -CH(CH 2 -CH 3 ); w, x, y and z represent values ​​between 0.5 and 120, where x, y and / or z can also be 0.

[0066] 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 preparations according to the invention can be significantly improved both in comparison to surfactant-free systems and in comparison to systems with alternative non-ionic surfactants, for example from the group of polyalkoxylated fatty substances.

[0067] By using these non-ionic surfactants, which have one or more free hydroxyl groups on one or both terminal alkyl functional groups, the stability of the enzymes contained in the cleaning agent preparations according to the invention can be significantly improved.

[0068] In particular, those end-capped poly(oxyalkylated) nonionic surfactants are preferred which correspond to the following formula, R 1< -O-(CH 2 CH 2 O)n-CH 2 CH(OH)-R 2< in addition to a functional group R 1< which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functions having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, also have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon function R 2< having 1 to 30 carbon atoms, where n represents values ​​between 1 and 90, preferably values ​​between 10 and 80 and in particular values ​​between 20 and 60.

[0069] Particularly preferred surfactants are those of the above formula in which R 1< is C 7 to C 13 , n is an integer from 16 to 28 and R 2< is C 8 to C 12 .

[0070] Preferred surfactants are those 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< represents a linear or branched aliphatic hydrocarbon function having 4 to 18 carbon atoms or mixtures thereof, R 2< represents a linear or branched hydrocarbon function having 2 to 26 carbon atoms or mixtures thereof, x represents values ​​between 0.5 and 1.5 and y represents a value of at least 15. The group of these non-ionic surfactants includes, for example, the C2-26 fatty alcohol (PO) 1 - (EO) 15-40 2-hydroxyalkyl ethers, in particular the C8-10 fatty alcohol (PO) 1 - (EO) 22 2-hydroxydecyl ethers.

[0071] In particular, the end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1< O[CH 2 CH 2 O] x [CH 2 CH(R 3< )O] y CH 2 CH(OH)R 2< are preferred, in which R 1< and R 2< independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon function having 2 to 26 carbon atoms, R 3< is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH(CH 3 ) 2 , but preferably represents -CH 3 , and x and y independently of one another represent values ​​between 1 and 32, with nonionic surfactants with R 3< = -CH3 and with values ​​for x from 15 to 32 and for y from 0.5 to 1.5 being very particularly preferred.

[0072] Further non-ionic surfactants which can preferably be used are the end-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< represent linear or branched, saturated or unsaturated, saturated or unsaturated, aliphatic or aromatic hydrocarbon functions having 1 to 30 carbon atoms, R 3< represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl function, x represents values ​​between 1 and 30 and k and j represent 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 ] k CH(OH)[CH 2 ] j OR 2< can be different.R 1< and R 2< are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic functional hydrocarbon groups having 6 to 22 carbon atoms, with functional groups having 8 to 18 carbon atoms being particularly preferred. For the functional group R 3<, H, --CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values ​​for x are in the range from 1 to 20, in particular from 6 to 15.

[0073] As described above, each R 3< in the above formula can be different if x > 2. In this way, the alkylene oxide unit in square brackets can be varied. For example, if x is 3, the functional group R 3< can be chosen to form ethylene oxide (R 3< = H) or propylene oxide units (R 3< = CH3), which can be linked 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 was chosen here as an example and can certainly be larger, whereby the range of variation increases with the size of the values ​​for x and, for example, a large number of (EO) groups are combined with a small number of (PO) groups, or vice versa.

[0074] Particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values ​​of k = 1 and j = 1, and therefore the previous 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 stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred surfactants are those in which the functional groups 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 nonionic surfactants of the general formula R 1< -CH(OH)CH2O-(AO)wR 2< have proven particularly effective in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated functional C 6-24 alkyl or alkenyl group; R 2< represents a linear or branched functional hydrocarbon group having 2 to 26 carbon atoms; A represents a functional group selected 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, and w represents values ​​between 1 and 120, preferably 10 to 80, in particular 20 to 40.

[0075] The group of these non-ionic surfactants includes, for example, the C4-22 fatty alcohol (EO)10-80-2-hydroxyalkyl ethers, in particular the C8-12 fatty alcohol (EO)22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO)40-80-2-hydroxyalkyl ethers.

[0076] In various embodiments, the non-ionic surfactant is selected from non-ionic surfactants of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< , in which R 1< and R 2< independently represent an alkyl functional group or alkenyl functional group having 4 to 22 carbon atoms; R 3< and R 4< independently represent H or an alkyl functional group or alkenyl functional group having 1 to 18 carbon atoms and x and y independently represent values ​​between 1 and 40.

[0077] In particular, compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< are preferred, in which R 3< and R 4< are H and the indices x and y independently assume values ​​from 1 to 40, preferably from 1 to 15.

[0078] In particular, compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< are preferred, where the functional groups R 1< and R 2< independently of one another represent saturated alkyl functional groups having 4 to 14 carbon atoms and the indices x and y independently of one another assume values ​​from 1 to 15 and in particular from 1 to 12.

[0079] In addition, compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< are preferred in which one of the functional groups R 1< and R 2< is branched.

[0080] Very particular preference is given to compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< , where the indices x and y, independently of one another, assume values ​​from 8 to 12.

[0081] The stated carbon chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical averages, which can be a whole number or a fraction for a specific product. Due to the manufacturing processes, commercial products of the above-mentioned formulas generally do not consist of a single representative, but of mixtures, which is why average values ​​and resulting fractions may result for both the carbon chain lengths and the degrees of ethoxylation and alkoxylation.

[0082] Of course, the above-mentioned non-ionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.

[0083] Nonionic surfactants with a melting point above room temperature are particularly preferred. Nonionic surfactants with a melting point above 20°C, preferably above 25°C, particularly preferably between 25 and 60°C, and in particular between 26.6 and 43.3°C are particularly preferred.

[0084] The non-ionic surfactant, which is solid at room temperature, preferably has propylene oxide (PO) units in the molecule. Such PO units preferably make up to 25% by weight, more preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the non-ionic surfactant. Particularly preferred non-ionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such non-ionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such non-ionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated non-ionic surfactants in which the propylene oxide units in the molecule make up up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight.-% of the total molecular weight of the non-ionic surfactant.

[0085] Whenever reference is made to molar masses, these figures always refer to the number-average molar mass Mn, 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 weight-average molar mass Mw can also be determined by GPC as described for Mn.

[0086] The use of the non-ionic surfactant(s) in the quantity range of 1.0 to 4.0 wt.% ensures the formulation of stable and homogeneous cleaning agents without sedimentation and without phase separation.

[0087] This was particularly possible over longer storage periods and wider temperature ranges when the cleaning agent contained the surfactant(s) in a total amount of 1.5 to 3.0 wt.% based on the total weight of the cleaning agent.

[0088] In a particularly preferred embodiment, a cleaning agent according to the invention is characterized in that it is substantially free of phosphates.

[0089] The cleaning composition according to the invention is essentially free of bleaching agents. Within the context of the invention, this means that the compositions contain less than 0.1% by weight of percarbonate salts, alkali hypochlorite, H2O2, and their precursors, based on the total weight of the composition. Preferably, the compositions contain less than 0.01% by weight, more preferably less than 0.001% by weight, of these components, based on the total weight of the composition.

[0090] "Bleach-free" here means that the cleaning agent is substantially free of active ingredients capable of releasing bleaching agents, particularly peroxide-containing compounds, hypohalogenated compounds, or H2O2, into the wash liquor in an automatic dishwasher. In a preferred embodiment, "bleach-free" means that the composition contains bleaching compounds (compounds that release bleaching agents) in an amount of less than 0.1% by weight, preferably less than 0.01% by weight, based on the total weight of the composition.

[0091] In a particularly preferred embodiment, a cleaning agent according to the invention is characterized in that it is substantially free of bleaching agents.

[0092] According to a preferred embodiment of the invention, the automatic dishwashing detergents are also free of polyacrylate-containing thickeners. Free of the polyacrylate-containing thickeners mentioned as used herein means that the composition in question is essentially free of such polymers, ie, contains such polymers in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the respective composition.

[0093] Particularly preferred dishwashing detergents according to the invention, preferably automatic dishwashing detergents, are characterized in that the composition contains at least two builders from the group of MGDA and citrates, the weight proportion of these builders, based on the total weight of the composition, preferably being 4 to 40 wt.%, preferably 6 to 30 wt.% and in particular 8 to 20 wt.%.

[0094] 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.

[0095] In a particularly preferred embodiment, the compositions each contain less than 1% by weight of polymers which, as a monomer which is present at more than 40 mol%, preferably at more than 60 mol%, contain acrylic acid or methacrylic acid and optionally additionally sulfonic acid-containing groups. Machine dishwashing detergents optionally also contain one or more further ingredients which can be selected, for example, from the group of builders, builders, pH adjusters, corrosion inhibitors, fragrances, foam inhibitors and dyes.

[0096] Particularly suitable builders and / or cobuilders that can be used are water-soluble or water-insoluble substances whose primary function is to bind calcium and magnesium ions. The terms "builder" and "cobuilder" according to the invention do not include citric acid, methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA), and / or their salts. Builders and / or cobuilders can be low-molecular-weight carboxylic acids and their salts, such as alkali metal malonates, fatty acid sulfonates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monoacetate, tartrate diacetate, and α-hydroxypropionic acid.

[0097] Other builders that can be used in conjunction with the dishwashing detergent formulations according to the invention are carbonates and hydrocarbons, of which the alkali salts, in particular sodium salts, are preferred.

[0098] The detergent formulations contemplated here may contain, in addition to the surfactants mentioned above, one or more different surfactants selected from the group consisting of anionic surfactants, cationic, zwitterionic, and amphoteric surfactants. Combinations of the above-mentioned surfactant types are also conceivable.

[0099] To prevent glass corrosion, which manifests itself as cloudiness, iridescence, streaks, and lines on the glass, glass corrosion inhibitors are preferably used. Preferred glass corrosion inhibitors include magnesium, zinc, and bismuth salts and complexes, as well as polyethyleneimine.

[0100] Silver preservatives from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used as corrosion inhibitors, provided they are ecologically compatible.

[0101] Other examples of enzyme stabilizers include sodium sulfite, reducing sugars, and potassium sulfate. Another example of a suitable enzyme stabilizer is sorbitol.

[0102] Organic solvents may also be present, but are preferably limited to an amount of up to 30% by weight, based on the weight of the composition. Particularly preferred organic solvents are propanediol, glycerin, and / or sorbitol. These amounts of organic solvents contribute to the flowability and stabilization of the active ingredients.

[0103] In a preferred embodiment of the present invention, the dishwashing detergent composition contains one or more organic solvents selected from the group consisting of sorbitol, glycerin, and / or propanediol. The composition preferably contains 1 to 25% by weight, preferably 2 to 12% by weight of the total composition, of the group consisting of sorbitol, glycerin, and / or propanediol.

[0104] Glass corrosion inhibitors prevent the occurrence of clouding, streaks, and scratches, as well as iridescence on the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts, as well as magnesium and zinc complexes. In the context of the present invention, the zinc salt content in liquid dishwashing detergents is preferably between 0.1 and 5 wt. %, more preferably between 0.2 and 4 wt. %, and in particular between 0.4 and 3 wt. %, or the zinc content in oxidized form (calculated as Zn 2< +) is between 0.01 and 1 wt. %, preferably between 0.02 and 0.5 wt. % and in particular between 0.04 and 0.2 wt. %, in each case based on the total weight of the agent containing the glass corrosion inhibitor.

[0105] 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.

[0106] The liquid dishwashing detergent may contain at least one alcohol, particularly a polyhydric alcohol. Such polyhydric alcohols can allow the incorporation of other ingredients into a liquid dishwashing detergent formulation with a small amount of water, particularly when the amount of water is limited to 20% by weight.

[0107] The polyhydric alcohol is preferably selected from glycerin, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, and mixtures thereof. Another suitable alcohol that also possesses antimicrobial properties is phenoxyethanol.

[0108] According to the invention, a cleaning agent was developed that, despite the presence of phosphonates, could be stably adjusted to the desired viscosity range and was present in a particularly homogeneous form without the occurrence of phase separation or sedimentation. Portioning and homogenization were particularly easy when the cleaning agent had a viscosity of 2000 to 6000 mPas, preferably 2200 to 5500 mPas, more preferably 2400 to 5000 mPas, even more preferably 2600 to 4500 mPas, and most preferably 3000 to 4000 mPas (measured with a Brookfield LVDV II+ viscometer at 20 °C, spindle no. 31, 6 revolutions per minute).

[0109] In a preferred embodiment, the above-described cleaning agents according to the invention are provided in packaging that does not contain any other cleaning agent compositions with a pH of 9 to 11.5. Preferably, the packaging does not contain any other cleaning agent compositions with a pH of 8.6 to 12.0. The pH is determined using a standard hydrogen electrode in the undiluted state. Particularly preferably, the cleaning agents according to the invention are provided in packaging that does not contain any other cleaning agent compositions. Advantageously, the cleaning composition alone leads to good cleaning of the dishes, even without other alkaline cleaning compositions.Particularly advantageous is the sole use of the cleaning agent composition according to the invention, in particular without further alkaline cleaning agent compositions in the same rinse cycle, which leads to very low glass corrosion and therefore good glass protection as well as a clear shine, especially of the glasses.

[0110] The present application further relates to the use of a detergent that is liquid at 20°C for cleaning dishes. The compositions are preferably used in dishwashers and / or automatic dishwashers. For the purposes of the present invention, "dishes" include plates, cups, cutlery, glasses, storage containers, cooking utensils (cookware), and the like.

[0111] A further subject matter of the present application is the use of a detergent-detergent, as disclosed in detail in the description of the first subject matter of the invention, for machine dishwashing.

[0112] The present invention further relates to a method for cleaning dishes, preferably in an automatic dishwasher, characterized in that at least one cleaning agent according to the invention, as disclosed in detail in the description of the first subject matter of the invention, is used in at least one method step. In particular, the present invention relates to a method for cleaning dishes in an automatic dishwasher, in which the agent is introduced into the interior of an automatic dishwasher during the execution of a washing program, before the start of the main wash cycle, or during the course of the main wash cycle. The dispensing or introduction of the agent into the interior of the dishwasher can be done manually, but the agent is preferably dispensed into the interior of the dishwasher by means of the dosing chamber.Dosing is carried out by the user, who pours the cleaning agent from a storage bottle or container designed for multiple use into this dosing chamber.

[0113] In particular, the cleaning agents according to the invention are used in a dishwashing process according to the invention in the absence of further cleaning agents which have a pH of 9 to 11.5, preferably a pH of 8.6 to 12.0, in each case in the undiluted state.

[0114] A further subject of the present application is a method for automatic dishwashing, in which a liquid cleaning agent, as disclosed in detail in the description of the first subject of the invention, is dosed from a storage container suitable for multiple use, preferably a storage bottle, into the device of a dishwasher provided for this purpose.

[0115] In various embodiments of the disclosure, the (washing) temperature in such dishwashing methods is preferably 50°C or less, more preferably 45°C or less, even more preferably 40°C or less.

[0116] For the description of the use and method according to the invention, what has been said about the cleaning agent according to the invention applies mutatis mutandis. Examples: Example 1:

[0117] Exemplary compositions 1 to 3 were prepared using the components summarized in Table 1, wherein the amounts of active ingredients in wt% refer to the total weight of the composition, unless otherwise stated. Table 1: component E1 (wt%) E2 (wt%) E3 (wt%) V1 (wt%) Dye, preservative 0,5 0,5 0,5 0,5 Xanthan 0,52 0,5 0,5 0 Polyacrylate-based thickener 0 0 0 0,8 Calcium chloride 0,2 0,2 0,2 0,2 HEDP, sodium salt 3,7 1,8 1,7 1,8 MGDA trisodium salt, (methylglycinediacetic acid, trisodium salt) 5,0 4,0 4,3 4,0 Sodium citrate dihydrate 5,0 5,0 5,0 5,0 Homopolymer of acrylic acid 0 0 0 2 low-foaming non-ionic surfactant (hydroxy mixed ether) 1,7 1,7 1,7 1,7 Amylase (relative to the amount of active protein) 0,04 0,04 0,04 0,04 Protease (relative to the amount of active protein) 0,14 0,14 0,14 0,14 Water to 100 to 100 to 100 to 100 Appearance of the gel at 20 °C after one week of storage at 40 °C No phase separation; no significant thickening No phase separation; no significant thickening No phase separation; no significant thickening Strong thickening; sedimentation of individual components

[0118] The pH of the undiluted liquid concentrates was adjusted to a value of 7.8 (at 20 °C) by adding formic acid. Example 2:

[0119] Cleaning performance was determined according to IKW 2016 in a Miele GSL 2 dishwasher using the 45-8-55 cycle. The water hardness was 21 °dH. Ballast soil was used according to IKW 2016. 30 g of formulation E2 and V1 were used as detergent. After each wash cycle, the dishes were visually inspected on a scale of 1-10. The higher the value, the better the cleaning performance. Table 2: Cleaning performance product Minced meat soiling E2 3,8 V1 1,9

[0120] It was observed that the elimination of acrylic-based thickeners and high-acrylate active ingredients led to better gel stabilization (see Table 1) and, at the same time, improved cleaning performance (see Table 2). Furthermore, the rinse performance was also positively influenced.

Claims

1. Liquid cleaning agent which has a pH value between 6.5 and 8.5 and - based on the total weight of the agent - contains: less than 1% by weight, in particular less than 0.1% by weight of homopolymers of acrylic acid and methacrylic acid; less than 1% by weight, in particular less than 0.1% by weight of copolymers or terpolymers of acrylic acid or methacrylic acid with monomers containing sulfonic acid groups; 0.15 to 0.8% by weight of xanthan gum, 0.2 to 6.0% by weight of phosphonate(s), 2.0 to 15.0% by weight of complexing agents from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and / or salts thereof.

2. Liquid cleaning agent according to claim 1, characterized in that it contains 0.5 to 5.0 wt.%, preferably 1.0 to 4.5 wt.%, in particular 2.0 to 4.0 wt.% phosphonate(s).

3. Liquid cleaning agent according to claim 1 or 2, characterized in that it contains 0.2 to 0.7 wt.%, preferably 0.3 to 0.65 wt.% xanthan.

4. Liquid cleaning agent according to one of the preceding claims, characterized in that it contains 2.5 to 10 wt.%, preferably 3 to 8 wt.% of complexing agents, in particular methylglycinediacetic acid (MGDA) and / or its salts.

5. Liquid cleaning agent according to one of the preceding claims, characterized in that it contains at least one protease and / or at least one amylase, preferably in amounts of active enzyme protein, in each case based on the total weight of the cleaning agent, of 0.01 to 1.2% by weight of protease and / or of 0.001 to 0.05% by weight of amylase, particularly preferably of 0.05 to 0.5% by weight of protease and / or 0.005 to 0.03% by weight of amylase.

6. Liquid cleaning agent according to one of the preceding claims, characterized in that it contains 1.0 to 4.0 wt.%, preferably 1.5 to 3.0 wt.% non-ionic surfactants.

7. Liquid cleaning agent according to one of the preceding claims, characterized in thatit contains - based on the total weight of the cleaning agent - 0.5 to 10 wt.%, preferably 1 to 8 wt.%, more preferably 2 to 6 wt.% and most preferably 3 to 5 wt.% citric acid and / or its salts.

8. Liquid cleaning agent according to one of the preceding claims, characterized in that it contains - based on the total weight of the cleaning agent - 0.05 to 0.60 wt.%, preferably 0.1 to 0.5 wt.%, more preferably 0.15 to 0.35 wt.% calcium chloride.

9. Liquid cleaning agent according to one of the preceding claims according to one of claims 1 to 8, characterized in that it is essentially free from phosphates and / or bleaching agents.

10. Use of the cleaning agent according to one of claims 1 to 9 as an automatic dishwashing detergent.

11. Process for automatic dishwashing, characterized in that a cleaning agent according to one of claims 1 to 9 is dosed into the dishwasher.

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