Liquid cleaning agent

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

The invention relates to cleaning agents which are liquid at 20° C. and which contain 0.2 to 6.0% by weight of phosphonates, but neither homopolymers of acrylic acid and methacrylic acid nor co- or terpolymers of acrylic acid or methacrylic acid with monomers containing sulfonic acid groups.The use of phosphonates in liquid detergent compositions having a pH in the neutral range results in reduced shelf life of the formulations, as crystals form over extended storage periods.The object of the present invention is therefore to provide liquid detergents which exhibit good cleaning performance on ground meat and at the same time have good storage stability at 4 weeks and 40° C.Surprisingly, it has been found that liquid detergent formulations in the neutral range which comprise phosphonates lead to an improvement in the cleaning performance of ground meat without a reduction in storage stability if the content of homopolymers of acrylic acid and methacrylic acid and of co- and terpolymers of acrylic acid or methacrylic acid with monomers which have sulphonic acid-containing groups is kept low.A first subject 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 sulphonic acid groups;0,15 up to 0.8% by weight of xanthan,0,2 up to 6.0% by weight phosphonate(s),2,0 up to 15.0% by weight of complexing agents from the group of methyl glycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and / or salts thereof.Automatic dishwashing agents according to the invention are free from homopolymers of acrylic acid and methacrylic acid, since these compounds are not biodegradable and are not preferred for ecological reasons. "Free from homopolymers" of acrylic acid and methacrylic acid, as used herein, means that the composition in question is substantially free from homopolymers of acrylic acid and methacrylic acid, i.e. contains in particular such polymers in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the composition in question.Automatic dishwashing agents according to the invention are free of co- and terpolymers of acrylic acid or methacrylic acid with monomers which have sulphonic acid-containing groups, since these compounds have not been biodegradable up to now and are therefore not preferred for ecological reasons. Free of the polymers mentioned as used herein means that the composition in question is substantially free of such polymers, i.e. contains such polymers in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the respective composition.The detergent according to the invention is characterized in that the composition has a pH of 6.5 to 8.5 at 20° C. The pH is measured in the product itself, i.e. neat. A suitable measuring device is, for example, a conventional pH electrode.In the further description, the term "at least one" is synonymous with the term "one or more", and both terms may be used interchangeably."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 foregoing 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 relates to the type of ingredient and not to the absolute number of molecules. "At least one surfactant" thus means, for example, at least one type of surfactant, i.e. it may mean one type of surfactant or a mixture of several different surfactants. Together with the weight data, the data refer to all compounds of the stated type present in the composition / mixture, i.e. the composition does not comprise any further compounds of this type beyond the stated amount of the corresponding compounds.The cleaning composition of the present 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 that are flowable and pourable at 20°C (1 bar).The inventive cleaning agents or automatic dishwashing agents are water-based. Based on the total weight of the composition, they preferably contain from 30 to 85% by weight of water. It is particularly preferred if the automatic dishwashing agent contains, based on its total weight, 40 to 80 wt %, preferably 50 to 79 wt %, of water.As an essential constituent, the inventive cleaning agent or automatic dishwashing agent contains, based on its total weight, 0.15 to 0.8% by weight xanthan.Xanthan is a microbial anionic heteropolysaccharide produced by Xanthomonas campestrisand some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan. Xanthan may alternatively also be referred to as xanthan gum, E 414 or xantan and has CAS number 11138-66-2.Thickening with xanthan 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 over 85% of the weight of the composition. This means that 85 weight percent of the composition ingredients are biodegradable. Preferably, more than 90% by weight of the composition is biodegradable, more preferably more than 98% of the composition is biodegradable. The biodegradability of the components is defined according to OECD 301.In the range of 0.15 to 0.8% by weight, the xanthan can be completely dissolved and is capable of stabilizing the liquid detergent and of minimizing disintegration of the mixture. In particular, the sedimentation of all further constituents present in the cleaning agent can also be reduced.Particularly stable and homogeneous detergents were obtained when the xanthan, based on the total weight of the automatic dishwashing detergent or detergent, was used in a quantity range from 0.20 to 0.7% by weight, preferably 0.30 to 0.65% by weight.The best results could be obtained when the detergent contained 0.35 to 0.60% by weight xanthan. In this most preferred embodiment, the amount of water could be maximally reduced, the xanthan could nevertheless be completely dissolved and sedimentation of all further constituents prevented.As a further constituent essential to the invention, the automatic dishwashing detergent or cleaning agent according to the invention contains, based on its total weight, from 2.0 to 15% by weight of complexing agents from the group consisting of methylglycinediacetic acid (MGDA), glutamic aciddiacetic acid (GLDA) and / or salts thereof.Suitable salts of MGDA are, for example, the sodium, potassium, magnesium, calcium, zinc or ammonium ion (NH 4+)- salts. Very particular preference is given to using MGDA in the form of its trisodium salt in the cleaning agent.Another very particularly suitable complexing agent is glutamic acid diacetic acid (GLDA). GLDA has a stereogenic center. Both the (S) form and the (R) form (or both the L form and the D form) are according to the invention. Very particular preference is given to using GLDA in the form of its tetrasodium salt in the cleaning agent.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). In particular, if the cleaning agent contains the complexing agent or agents MGDA and / or GLDA in the form of trisodium or tetrasodium salts, the ionic strength in the cleaning agent is increased as a result.It has been found that, in particular, the viscosity could be adjusted well to the desired range and also did not change adversely in the course of storage if the cleaning agent contained the complexing agent or agents, in particular the salts of methyl glycine diacetic acid (MGDA) and / or glutamic acid diacetic acid (GLDA), in a quantity range of 2.0 to 15 wt %.Very particularly preferably, the complexing agent or agents, in particular the sodium salts of MGDA and / or GLDA, are contained in the cleaning agent in a quantity range of 2.5 to 10 wt %, preferably 3.0 to 8.0 wt %, particularly preferably 4.0 to 6.0 wt %.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 % complexing agents from the group of methyl glycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and / or salts thereof.A further group of ingredients according to the invention are the phosphonates. The complexing phosphonates include, in addition to 1-hydroxyethane-1,1-diphosphonic acid, a number of different compounds such as diethylenetriaminepenta(methylenephosphonic acid) (DTPMP). In this application, hydroxyalkane phosphonates or aminoalkane phosphonates are particularly preferred. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as sodium salt, the disodium salt reacting neutral and the tetrasodium salt alkaline (pH 9). Suitable aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and higher homologs thereof. They are preferably used in the form of the neutrally reacting sodium salts, for example as hexasodium salt of EDTMP or as hepta- and octasodium salt of DTPMP. From the class of phosphonates, HEDP is preferably used as builder. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferred, especially if the compositions also comprise bleaches, to use aminoalkanephosphonates, especially DTPMP, or to use mixtures of the phosphonates mentioned.A preferred detergent composition in the context of this application comprises one or more phosphonate(s) from the group a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof; b) ethylenediaminetetra(methylenephosphonic acid) (EDTMP) and / or salts thereof; c) diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and / or salts thereof; d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or salts thereof; e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof; f) hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP) and / or salts thereof; g) nitrilotri(methylenephosphonic acid) (NTMP) and / or salts thereof.Particularly preferred are detergent compositions containing as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriamine penta(methylene phosphonic acid) (DTPMP).The automatic dishwashing agents according to the invention can of course comprise two or more different phosphonates. The proportion by weight of phosphonates relative to the total weight of detergent composition according to the invention is preferably 0.2 to 6.0% by weight, preferably 1.0 to 4.5% by weight, in particular 2.0 to 4.0% by weight, of phosphonate(s). In particular, HEDP is used in the amounts mentioned, in particular as sodium salt.In addition to the complexing agents as described above, the cleaning agent according to the invention particularly preferably contains citric acid and / or the salts of citric acid. A particularly suitable salt of citric acid is sodium citrate, in particular trisodium citrate, anhydrous trisodium citrate or trisodium citrate dihydrate.Combinations of citric acid or salts thereof with methyl glycine diacetic acid (MGDA) or salts thereof are also preferably used. The combination of trisodium salt of methylglycinediacetic acid (MGDA) and trisodium citrate is particularly preferred.In a particularly preferred embodiment, a detergent detergent according to the invention is characterized in that it comprises - based on the total weight of the detergent - 0.5 to 10% by weight, preferably 1.0 to 8.0% by weight, more preferably 2.0 to 6.0% by weight, of citric acid and / or salts thereof.In a particularly preferred embodiment, a detergent detergent according to the invention is characterized in that it comprises - based on the total weight of the detergent - from 0.5 to 10% by weight, preferably from 1.0 to 8.0% by weight, more preferably from 2.0 to 6.0% by weight, of sodium citrate.The inventive cleaning agent or machine dishwashing agent contains at least one protease and / or at least one amylase (e).Enzymes are added to increase cleaning performance or to provide equal quality cleaning performance under milder conditions (e.g., at lower temperatures). The enzymes may be used in free form or in chemically or physically immobilized form on a support or in encapsulated form.Cleaning agents according to the invention preferably contain enzymes in total amounts of 1×10 -6 wt. % to 5 wt. %, based on active protein. The protein purification function can be determined by known methods, for example the BCA method or the biuret method.Among the proteases, the subtilisin type proteases are preferred. Examples of these are the subtilisins BPN' and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, the subtilisin DY, and the enzymes thermitase, proteinase K and the proteases TW3 and TW7 which belong to the subtilases but no longer to the subtilisins in the narrower sense.Examples of amylases which can be used according to the invention are α-amylases from Bacillus licheniformis, from B. amyloliquefaciens from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the further developments of the aforementioned amylases which have been improved for use in cleaning agents. In this connection, the α-amylases from Bacillussp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens(DSM 9948).Detergent-active proteases and amylases are generally not provided in the form of the pure protein, but in the form of stabilized, storable and transportable preparations. These finished preparations include, for example, the solid preparations obtained by granulation, extrusion or freeze drying or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously concentrated to the maximum, low-water and / or supplemented with stabilizers or other auxiliaries.Alternatively, the enzymes can also be encapsulated, 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 in a solid gel, or in those of the core-shell type in which an enzyme-containing core is coated with a water-impermeable, air-impermeable and / or chemical-impermeable protective layer. In the case of outer layers, it is additionally possible to apply other active compounds such as stabilizers, emulsifiers, pigments or dyes. Such capsules are applied by methods known per se, for example by shaking or roll granulation or by fluidized bed methods. Such granules are advantageously low in dust, for example by the use of polymeric film formers, and are stable in storage by the coating.As can be seen from the foregoing, the enzyme protein constitutes 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% by weight, preferably between 2 and 30% by weight, particularly preferably between 3 and 25% by weight, of the enzyme protein. In particular, preferred cleaning agents are those which, based on their total weight, contain from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and especially from 0.5 to 8% by weight of the respective enzyme preparations.If the dishwashing detergent formulations contain enzymes, they preferably contain these in amounts of from 0.001 to 3.0% of the active enzyme protein, based on the weight of the total composition. The percentage of enzymes is calculated from the mass of active enzyme protein per weight of total composition.Enzyme amounts preferably used according to the invention, based on the active enzyme protein, are 0.01 to 1.2% by weight protease and / or 0.001 to 0.05% by weight amylase, based in each case on the total weight of the cleaning agent. Particular preference is given in particular to those cleaning agents which, based in each case on their total weight, comprise from 0.05 to 0.5% by weight of protease and / or from 0.005 to 0.03% by weight of amylase as active enzyme protein, preferably protease and amylase in the amounts mentioned.In accordance with the invention, amylases and proteases (e) are preferably used.Formulations according to the invention may contain one or more enzyme stabilizers. Enzyme stabilizers serve to protect enzymes--especially during storage--from damage, such as, for example, inactivation, denaturation or decomposition, for example, due to physical influences, oxidation or proteolytic cleavage.Examples of enzyme stabilizers are reversible protease inhibitors, e.g. benzamidine hydrochloride, borax, boric acid, boronic acids or salts or esters thereof, including in particular derivatives with aromatic groups, e.g. ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or esters of the abovementioned compounds. Peptide aldehydes, i.e. oligopeptides with reduced carbon terminus, in particular those of 2 to 50 monomers, are also used for this purpose. Peptidic reversible protease inhibitors include ovomucoid and leupeptin. Specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins of proteases and specific peptide inhibitors are likewise suitable for this purpose. Further examples of enzyme stabilizers are amino alcohols, such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic mono- and dicarboxylic acids up to C12-carboxylic acids, such as succinic acid, for example. Terminally capped fatty acid amide alkoxylates are also suitable as enzyme stabilizers. A good stabilizer for proteases is also calcium chloride.With regard to the rheological properties of the cleaning agent, it has been found to be particularly advantageous in particular if the cleaning agent contained calcium chloride for stabilizing the protease (e).For this reason, calcium chloride is also preferably used in certain quantity ranges in the cleaning agent. Particularly suitable amounts of calcium chloride used are 0.05 to 0.60% by weight, preferably 0.10 to 0.50% by weight, particularly preferably 0.15 to 0.35% by weight, these amounts being based on the total weight of the cleaning agent.The cleaning agent according to the invention is particularly preferably substantially phosphate-free. By "phosphate free" is meant herein that the detergent is substantially free of phosphate (including orthophosphate, polyphosphate and / or pyrophosphate), especially with phosphates in an amount of less than 0.1 wt %, preferably less than 0.01 wt %, based on the total weight of the composition.The expression "substantially free of" means that the respective compound may in principle be present, but is then present in an amount which does not impair a function of the other constituents. In the context of the present invention, the property "substantially free of" a particular compound is therefore preferably understood to mean a total weight of less than 0.1% by weight, more preferably less than 0.001% by weight, in particular free of this, based on the total weight of the composition.According to a preferred embodiment, the inventive cleaning agent or the automatic dishwashing agent contains, based on its total weight, 1.0 to 4.0% by weight of nonionic surfactants.As nonionic surfactants, any nonionic surfactants known to the skilled person can be used. Preferably, low foaming nonionic surfactants are used, in particular alkoxylated, in particular 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.Preferred alcohol ethoxylates have a restricted homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols having more than 12 EO may also be used. Examples of these are tallow fatty alcohols with 14 EO, 25 EO, 30 EO or 40 EO.Particular preference is given to using ethoxylated nonionic surfactants which have been obtained from C 6- C 20- monohydroxyalkanols or C 6- C 20- alkyl phenols or C 16- C 20- fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol ethylene oxide per mol alcohol. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C16-20 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. Particular preference is given here to the so-called narrow range ethoxylates.Surfactants preferably used originate from the group of alkoxylated nonionic surfactants, in particular 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 distinguished by good foam control.Within the scope of the present invention, low-foaming nonionic surfactants which alternately have ethylene oxide and alkylene oxide units have proven to be particularly preferred. Among these, surfactants having EO-AO-EO-AO blocks, in which one to ten EO groups or AO groups are bonded to one another before one block follows the respective other group, are preferred. Preference is given here to nonionic surfactants of the general formula in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated functional C 6- C 24- alkyl or alkenyl group; each R2and R3group is independently selected from -CH 3, - CH 2 CH 3, - CH(CH 3)2; and the indices w, x, y and z are independently integers from 1 to 6.Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1- OH and ethylene oxide or alkylene oxide. The functional group R 1 in whichThe above formula may vary depending on the origin of the alcohol. When 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 being preferred from alcohols of native origin having 12 to 18 carbon atoms, such as coconut, palm, tallow or oleyl alcohol. Some examples of alcohols obtainable from synthetic sources are the Guerbet alcohols or functional groups which are methyl-branched or linear and methyl-branched in the 2-position, as are usually present in functional groups of oxo alcohols, in a mixture. Regardless of the type of alcohol used to prepare 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, more preferably 9 to 15, especially 9 to 11, carbon atoms in the above formula.Suitable alkylene oxide unit, which is present in the preferred nonionic surfactants alternately with the ethylene oxide unit, is, in addition to propylene oxide, in particular butylene oxide. 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. Preferably, nonionic surfactants of the above formula are used, wherein R 2 and R 3 are 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.Further preferably used nonionic surfactants of the solid phase are nonionic surfactants of the general formula R 1 O(AlkO)xM(OAlk)yOR 2,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 from the group consisting of 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.Preference is given in this case to 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 2in 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.In this case, preference is given in particular to 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 2in 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 are values from 20 to 30. Such compounds can be obtained, for example, by reacting alkyl diols HO-CHR-CH 2- OH with ethylene oxide, followed by reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.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 whichR 1 represents a linear or branched, saturated or mono- or polyunsaturated C6-24alkyl or alkenyl functional group;R 2 represents hydrogen or a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms;A, A', A" and A"' are independently of one another 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- CH2, -CH2-CH(CH3)-CH2-, -CH2-CH(CH2-CH3);w, x, y and z are values between 0.5 and 120, where x, y and / or z may also be 0.By adding the abovementioned nonionic surfactants of the general formula R 1- CH(OH)CH2O-(AO)w-(A'O)x-(A"O)y-(A"'O)z-R 2, also referred to below as "mixed hydroxy ethers", the cleaning performance of preparations according to the invention can be improved significantly both in comparison with surfactant-free systems and in comparison with systems having alternative nonionic surfactants, for example from the group of polyalkoxylated fatty substances.By using these nonionic surfactants which have one or more free hydroxyl groups on one or both terminal alkyl functional groups, the stability of the enzymes present in the detergent formulations of the invention can be substantially improved.In particular, preferred are those end-capped poly(oxyalkylated) nonionic surfactants corresponding to the following formula, R 1- O-(CH 2 CH 2 O)n-CH 2 CH(OH)-R 2 besides 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.Particularly preferred are surfactants of the above formula wherein 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.Preference is given to surfactants of the formula R 1 O[CH 2 CH(CH 3) O] x[ CH 2 CH 2 O] y CH 2 CH(OH)R 2, in which R 1 represents a linear or branched aliphatic hydrocarbon function having 4 to 18 carbon atoms or mixtures thereof, R_NER121 denotes 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 nonionic surfactants comprises, 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.In particular, preference is given to 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 in which R 1 and R2independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon function having 2 to 26 carbon atoms, R3independently of one another is selected from -CH3, -CH2CH3, -ch_ner137_ch_ner138_-ch_ner139_, -ch(ch_ner140_)_ner141_, but preferably -CH 3 and x and y independently of one another are 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 and 1.5 being very particularly preferred.Further nonionic surfactants which can preferably be used are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 O[CH 2 CH(R 3) O] x[ CH 2]k CH(OH)[CH 2]j OR 2, in which R 1 and R 2 represent linear or branched, saturated or unsaturated, saturated or unsaturated, aliphatic or aromatic hydrocarbon functions having 1 to 30 carbon atoms, R 3 H or a methyl, ethyl, n-propyl, isopropyl, 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. When the value x>2, each R 3 in the above formula may be R 1 O[CH 2 CH(R 3) O] x[ CH 2]k CH(OH)[CH 2]j OR 2 different. R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional 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.As described above, each R 3 in the above formula may be different when x>2. If x is 3, for example, the functional group R 3 can be chosen such that ethylene oxide (R 3= H) or propylene oxide units (R 3= CH3) are formed, which can be joined to one another in any desired sequence, 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 be quite larger, wherein the range of variation increases with the size of the values for x and, for example, a large number of (EO) groups is 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 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 last-mentioned formula, R 1, R 2 and R 3 are as defined above and x is numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Finally, the nonionic surfactants of the general formula R 1- CH(OH)CH2O-(AO)w-R 2 have proven to be particularly effective in whichR 1 represents a linear or branched, saturated or mono- or polyunsaturated C6-24alkyl or alkenyl functional group;R 2 represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms;a is a functional group from the group consisting of CH2 CH2, CH2 CH2 CH2, CH2 CH(CH3), preferably CH2 CH2, andw is a value between 1 and 120, preferably 10 to 80, in particular 20 to 40.The group of these nonionic surfactants includes, for example, the C4-22fatty alcohol (EO)10-80-2-hydroxyalkyl ethers, in particular also the C8-12fatty alcohol (EO)22-2-hydroxydecyl ethers and the C4-22fatty alcohol (EO)40-80-2-hydroxyalkyl ethers.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 O-R 2, in which R 1 and R2independently of one another represent an alkyl-functional group or alkenyl-functional group having 4 to 22 carbon atoms; R 3 and R 4 independently of one another represent H or an alkyl-functional group or alkenyl-functional group having 1 to 18 carbon atoms, and x and y independently of one another represent values between 1 and 40.In 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 O-R 2 in which R 3 and R4represent H and the indices x and y independently of one another assume values from 1 to 40, preferably from 1 to 15.In 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 O-R 2 where the functional groups R 1 and R2each independently represent saturated alkyl-functional groups having 4 to 14 carbon atoms and the indices x and y each independently assume values from 1 to 15 and in particular from 1 to 12.Furthermore, preference is given to those compounds of the general formula R 1- O(CH 2 CH 2 O) x CR 3 R 4( OCH 2 CH 2)y O-R 2 in which one of the functional groups R 1 and R2branched.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 O-R 2, where the indices x and y, independently of one another, assume values from 8 to 12.The indicated C chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical averages which can be an integer or a fraction for a specific product. On account of the preparation processes, the commercial products of the formulae mentioned above generally consist not of a single representative but of mixtures, and therefore averages and fractional numbers resulting therefrom can be obtained both for the C chain lengths and for the degrees of ethoxylation and alkoxylation.Of course, the above nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants.Particular preference is given to nonionic surfactants having a melting point above room temperature. Particular preference is / are given to nonionic surfactants having a melting point above 20° C., preferably above 25° C., particularly preferably between 25 and 60° C., and in particular between 26.6 and 43.3° C.The room temperature solid nonionic surfactant preferably has propylene oxide (PO) units in the molecule. Preferably, such PO units constitute up to 25 wt.%, more preferably up to 20 wt.% and most preferably up to 15 wt.% of the total molar mass of the non-ionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkyl phenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol content of such nonionic surfactant molecules preferably constitutes 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 nonionic surfactants. Preferred compositions are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule make up up up to 25 wt %, preferably up to 20 wt % and in particular up to 15 wt % of the total molar mass of the nonionic surfactant.Where molecular weights are referred to herein, these data are always based on the number average molecular weight Mn, unless expressly stated otherwise. The number average molar mass can be determined, for example, by gel permeation chromatography (GPC) to DIN 55672-1:2007-08 using THF as eluent. The weight average molecular weight Mwcan also be determined by GPC as described for Mn.The use of the nonionic surfactant or surfactants in the quantitative range from 1.0 to 4.0% by weight ensures the formulation of stable and homogeneous cleaning agents without sedimentation and without phase separation.This was possible above all over longer storage periods and relatively large temperature ranges if the cleaning agent contained the surfactant or surfactants in a total amount of 1.5 to 3.0% by weight, based on the total weight of the cleaning agent.In a particularly preferred embodiment, a cleaning agent according to the invention is characterized in that it is substantially free of phosphates.The cleaning composition of the present invention is substantially free of bleaches. In the context of the invention, this means that the compositions contain less than 0.1% by weight of percarbonate salts, alkali hypochlorite, H2O2and precursors thereof, based on the total weight of the composition. Preferably, the compositions contain less than 0.01 wt%, more preferably less than 0.001 wt%, of these components, based on the total weight of the composition.By "bleach-free" is meant herein that the detergent is substantially free of active ingredients capable of delivering bleaches, especially peroxide-containing compounds, hypohalogenated compounds or H2O2, to the wash liquor in an automatic dishwasher. In a preferred embodiment, "bleach-free" means that the composition contains bleach compounds (bleach-releasing compounds) in an amount of less than 0.1 wt %, preferably less than 0.01 wt %, based on the total weight of the composition.In a particularly preferred embodiment, a cleaning agent according to the invention is characterized in that it is substantially free of bleaches.According to one embodiment preferred according to the invention, the automatic dishwashing detergents are likewise free of polyacrylate-containing thickeners. Free of the polyacrylate-containing thickeners mentioned as used herein means that the relevant composition is substantially 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.Particularly preferred dishwashing agents according to the invention, preferably automatic dishwashing agents, are characterized in that the composition contains at least two builders from the group of MGDA and citrates, wherein the proportion by weight of these builders, based on the total weight of the composition, is preferably 4 to 40 wt %, preferably 6 to 30 wt % and in particular 8 to 20 wt %.Polymeric polycarboxylates (organic polymers having a large number of (in particular greater than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins can furthermore be used. Biodegradable polymers are particularly preferred.In a particularly preferred embodiment, the compositions each comprise less than 1% by weight of polymers which comprise acrylic acid or methacrylic acid and also optionally additionally sulphonic acid-containing groups as a monomer which is present to an extent of more than 40 mol %, preferably more than 60 mol %Machine dishwashing detergents optionally also comprise one or more further ingredients which may be selected, for example, from the group of builders, builders, pH adjusters, corrosion inhibitors, fragrances, foam inhibitors and dyes.Suitable builders and / or cobuilders which can be used are in particular water-soluble or water-insoluble substances, the main function of which is to bind calcium and magnesium ions. The terms "builder" and "cobuilder" of the present invention do not include citric acid, methyl glycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), and / or salts thereof. Builders and / or cobuilders may 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 a-hydroxypropionic acid.Further builders that can be used in connection with the dishwashing formulations according to the invention are carbonates and hydrocarbons, of which the alkali salts, in particular sodium salts, are preferred.The detergent formulations contemplated herein may contain, in addition to the above surfactants, one or more different surfactants selected from the group consisting of anionic surfactants, cationic, zwitterionic and amphoteric surfactants. Combinations of the above-mentioned types of surfactants are also conceivable.To prevent glass corrosion, which is manifested by haze, schillers, schlieren and lines on the glasses, glass corrosion inhibitors are preferably used. Preferred glass corrosion inhibitors are, for example, magnesium, zinc and bismuth salts and complexes and also polyethyleneimine.Corrosion inhibitors which can be used are, inter alia, silver stabilizers from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes, provided they are ecologically compatible.Other examples of enzyme stabilizers are sodium sulfite, reducing sugars and potassium sulfate. Another example of a suitable enzyme stabilizer is sorbitol.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, glycerol and / or sorbitol. These amounts of organic solvents contribute to flowability and to stabilization of the active ingredients.In a preferred embodiment of the present invention, the dishwashing composition comprises one or more organic solvents selected from the group of sorbitol, glycerol and / or propanediol. The composition preferably comprises 1 to 25% by weight, preferably 2 to 12% by weight, of the total composition from the group of sorbitol, glycerol and / or propanediol.Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also the irritation of the glass surface of mechanically cleaned glasses. Preferred glass corrosion inhibitors originate from the group of the magnesium and zinc salts and the magnesium and zinc complexes. In the context of the present invention, the content of zinc salt in liquid dishwashing detergents is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight, or the content of zinc 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, based in each case on the total weight of the glass corrosion inhibitor-containing agent.Within the scope of the present invention, individual perfume compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or perfumes. However, mixtures of different fragrances are preferably used which together produce an appealing scent note. Perfume oils of this kind may also comprise natural perfume mixtures, as are obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.The liquid dishwashing agent can comprise at least one alcohol, in particular a polyhydric alcohol. Such polyhydric alcohols can allow incorporation of other ingredients into a liquid dishwashing formulation at a low water level, especially when the water level is limited to 20% by weight.The polyhydric alcohol is preferably selected from glycerol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, and mixtures thereof. Another well-suited alcohol, which also possesses antimicrobial properties, is phenoxyethanol.According to the invention, it was possible to develop a cleaning agent which, despite the presence of phosphonates, could be adjusted stably to the desired viscosity range and was present in a particularly homogeneous form without phase separations or sedimentations occurring. Portioning and homogenization was particularly possible when the cleaning agent had a viscosity of 2000 to 6000 mPas, preferably of 2200 to 5500 mPas, more preferably of 2400 to 5000 mPas, even more preferably of 2600 to 4500 mPas and very preferably of 3000 to 4000 mPas (measured with a Brookfield LVDV II+ viscometer at 20° C., spindle no. 31, 6 revolutions per minute).The present application further relates to the use of a cleaning agent which is liquid at 20° C. for cleaning dishes. The compositions are preferably used in dishwashers and / or dishwashers. In the context of the present invention, "dishes" are understood to mean plates, cups, cutlery, glasses, storage containers, cookware (cookware) and the like.The present application further relates to the use of a detergent detergent as disclosed in detail in the description of the first subject matter of the invention for automatic dishwashing.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 it appears 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 a dishwasher, in which the agent is introduced into the interior of a dishwasher during the execution of a wash program, before the start of the main wash cycle or in the course of the main wash cycle. The dispensing or introduction of the agent into the interior of the dishwasher can be effected manually, but preferably the agent is dispensed into the interior of the dishwasher by means of the metering chamber. The metering is effected here by the user pouring the cleaning agent into this metering chamber from a storage bottle or a storage vessel designed for multiple use.The present application further relates to a method for automatic dishwashing, in which a liquid cleaning agent, as has been disclosed in detail in the description of the first subject matter of the invention, is metered from a storage container suitable for multiple use, preferably a storage bottle, into the device of a dishwasher provided for this purpose.In various embodiments of the disclosure, the (washing) temperature in such dishwashing methods is preferably 50° C. or less, particularly preferably 45° C. or less, even more preferably 40° C. or less.For the description of the use and method according to the invention, what has been stated in relation to the cleaning agent according to the invention applies mutatismutatically.Examples:Example 1:Exemplary compositions 1 to 3 were prepared using the components summarized in Table 1, wherein the amounts of the actives in wt % are based on the total weight of the composition, unless otherwise stated. Table 1: Table 1:Dye, preservative0,50,50,50,5Xanthan Gum0,520,50,50Polyacrylate-based thickeners0000,8Calcium chloride0,20,20,20,2HEDP, sodium salt3,71,81,71,8MGDA trisodium salt, (methylglycinediacetic acid, trisodium salt)5,04,04,34,0Sodium citrate dihydrate5,05,05,05,0Homopolymer of acrylic acid0002Low foaming nonionic surfactant (hydroxy mixed ether)1,71,71,71,7Amylase (based on the amount of active protein)0,040,040,040,04Protease (based on the amount of active protein)0,140,140,140,14WaterAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAppearance of the gel at 20°C after one week of storage at 40°CNo phase separation; no marked post-thickeningNo phase separation; no marked post-thickeningNo phase separation; no marked post-thickeningStrong post-thickening; sedimentation of individual constituentsThe pH of the neat liquid concentrates was adjusted to 7.8 (at 20°C) by addition of formic acid.Example 2:The cleaning performance was determined according to IKW 2016 in a Miele GSL 2 dishwasher in the program 45-8-55. The water hardness was 21° dH. Ballast soil according to IKW 2016 was used. The cleaners used were in each case 30 g of the formulation E2 and V1. After completion of each rinse cycle, the tableware were visually inspected on a scale of 1-10. The higher the value, the better the cleaning performance. Table 2: Cleaning performance Table 2: Cleaning performanceE23,8V11,9It was observed that the omission of acrylic-based thickeners and high-acrylate-containing active substances led to better stabilization of the gels (cf. Table 1) and at the same time it was possible to improve the cleaning performance (cf. Table 2). In addition, the final rinse performance was also positively influenced.

Claims

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, in particular less than 0.1% by weight, homopolymers of acrylic acid and methacrylic acid; less than 1% by weight, in particular less than 0.1% by weight, co- or terpolymers of acrylic acid or methacrylic acid with monomers containing sulphonic acid groups; 0.15 to 0.8% by weight xanthan, 0.2 to 6.0% by weight phosphonate(s), 2.0 to 15.0% by weight complexing agents from the group of methyl glycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and / or salts thereof.Liquid cleaning agent according to claim 1, characterised 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).Liquid cleaning agent according to claim 1 or 2, characterised in that it contains 0.2 to 0.7 wt.%, preferably 0.3 to 0.65 wt.% xanthan.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.%, complex images, in particular methyl glycine diacetic acid (MGDA) and / or salts thereof.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 protease and / or of 0.001 to 0.05% by weight amylase, particularly preferably of 0.05 to 0.5% by weight protease and / or 0.005 to 0.03% by weight amylase.Liquid cleaning agent according to one of the preceding claims, characterized in that it contains 1.0 to 4.0% by weight, preferably 1.5 to 3.0% by weight, of nonionic surfactants.Liquid cleaning agent according to one of the preceding claims, characterized in that it contains - based on the total weight of the cleaning agent - 0.5 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 salts thereof.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% by weight, preferably 0.1 to 0.5% by weight, more preferably 0.15 to 0.35% by weight calcium chloride.Liquid detergent according to any one of the preceding claims according to any one of claims 1 to 8, characterized in that it is substantially free from phosphates and / or bleaches.Use of the detergent according to any of claims 1 to 9 as an automatic dishwashing detergent.Method for automatic dishwashing, characterized in that a cleaning agent according to one of Claims 1 to 9 is metered into the dishwasher.