Dishwashing detergent with innovative bleaching system

Abstract

The bleaching performance of citrate-based automatic dishwashing detergents was to be improved. This was achieved without the use of transition-metal-containing catalysts by using organic peroxoacids with cationic group-forming compounds in which a quaternary nitrogen atom is part of a heterocyclic 6-membered residue.

Description

The invention relates to automatic dishwashing compositions comprising a novel bleaching system and to the methods using said compositions.In contrast to automatic dishwashing detergents in tablet form, single doses which are not tableted, such as more or less compacted powder formulations enclosed in PVA film, for example, do not require tableting auxiliaries such as cellulose / derivatives, polyacrylates (if these do not contribute to chalk control), starch, etc. In this respect, these are usually more compact formulations.These formulations sometimes exhibit other sensitivities during storage, which may be attributed, for example, but not limited to, easier diffusion of gases between the particles in the looser form, the larger freely accessible surface area, or most often also to the presence of a single phase, while tablets have relatively small particle interstices, small freely accessible surfaces dictated by the tablet outer form, and may also be easily constructed from separate phases, so that contact areas of incompatible ingredients may be restricted. Visual changes may be indicative of such instability. A very prominent optical change is the discoloration of the manganese-containing bleach catalyst in such dishwashing detergents. Tableted machine dishwashing detergents can also exhibit such discolorations on the surface by the catalyst.In addition to a low sensitivity of the composition, which improves, inter alia, the shelf life, there is a further focus on the sustainability of the raw materials which are used in relatively large amounts, for example the main builder component.In all the desired changes and improvements in the individual areas, it remains of greatest importance that the cleaning performance on the different stains is at least satisfactory and does not deteriorate compared to the established products.The use of MGDA as builder enables a performance compact formulation which can also contribute to the removal of tea stains. A first step for introducing a major builder based on renewable raw materials may be the switching from MGDA to citrate. This change, however, is associated with a drastic decrease in tea removal.It is an object of the present application to provide a compact automatic dishwashing formulation whose main builder component can be provided from renewable resources, which provides good overall cleaning performance including good tea removal and which does not show discolorations on storage.Surprisingly, it has been found that bleach activators, as described below, lead to good cleaning performance in automatic dishwashing detergents based on citrate without the presence of transition metal-containing bleach catalysts in the presence of bleaches.The present invention therefore relates first to an automatic dishwashing detergent comprising citrate, bleach, at least one bleach activator, where the detergent does not comprise a transition metal-based bleach catalyst and where at least one bleach activator is selected from one or more compounds of the general formula (I), in whichA for O, S, Se;Z is an optionally substituted C 1-30 alkylene, C 3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene radical;X is - for an anion, in particular chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate and / or phosphate;Y for NR 6, O, S, Se;R, R 1, R 2, R 3, R 4, R 5 and R 6 independently of one another represent H, a C 1-30 alkyl, C 3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical; andn is a number in the range from 1 to 12,wherein 1 or more non-adjacent carbon atoms not bonded to a heteroatom in the hydrocarbon radicals may be replaced by a heteroatom, in particular N, O, S and / or Se.The agent can be used in machine dishwashing methods. Therefore, a further subject matter of this application is a method for cleaning dishes in a dishwasher.These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be used in any other aspect of the invention. Further, it is to be understood that the examples herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples. Unless otherwise stated, all percentages are % by weight, based on the total weight of the agent / composition. Numerical ranges indicated in the format "from x to y" include the above values. When several preferred numerical ranges are specified in this format, it is understood that all ranges arising from the combination of the various endpoints are also detected."At least one" as used herein refers to 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. In the context of ingredients of the compositions described herein, this indication does not refer to the absolute amount of molecules but to the type of ingredient. "At least one anionic surfactant" therefore means, for example, one or more different anionic surfactants, i.e. one or more different types of anionic surfactants. Together with quantities, the quantities refer to the total quantity of the correspondingly designated type of constituent. For compositions which are present in packaged form as a single dose, among other things, amounts of individual ingredients or groups of ingredients can be specified both as weight % as described above and by way of the mass of the respectively named ingredient per single dose (g / job). Amounts or ranges of amounts described in this way can relate both to ready-made individual doses and to the amount obtained in accordance with the dosing recommendation. When used in automatic dishwashing methods, the concentration of the individual ingredients or groups of ingredients in the wash liquor may also be relevant to the performance of the agent. The concentration can be expressed in ppm (parts per millon), which corresponds to the amount in grams (active material) per kilogram (rinse liquor).The composition according to the invention contains citrate as the main builder. The term citrate includes the salts of citric acid, preference being given to the alkali metal salts, in particular sodium citrate. Preferred dishwashing agents according to the invention contain citrate in an amount of 10 to 40 wt %, preferably in an amount of 15 to 35 wt %, based on the total amount of the agent. Preferred dishwashing agents according to the invention contain citrate in an amount of 2.0 to 6.0 g / job, preferably of 3 to 4.5 g / job. This amount, both percent and mass, refers to citrate anhydrate, for example. Sodium citrate anhydrate. It can be completely or partially replaced by molar exchange with citrate dihydrate, for example. Sodium citrate dihydrate.Automatic dishwashing agents according to the invention additionally comprise at least one bleach. Oxygen bleaches are preferred bleachers. Among the compounds which serve as bleaching agents and which deliver in water H 2 O 2 sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further usable bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 yielding peroxyacid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peroxyacid or diperdodecanedioic acid. Furthermore, it is also possible to use bleaches from the group of the organic bleaches. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, examples of which include particularly the alkyl peroxyacids and the aryl peroxyacids.Sodium percarbonate is preferably used as bleach in the compositions according to the invention. Agents according to the invention are preferred which comprise bleaches in an amount of 5 to 25 wt %, particularly preferably in an amount of 10 to 20 wt %, based on the total amount of agent.The dishwasher detergents according to the invention further comprise at least one bleach activator of the general formula (I) as described above. It has been found that under perhydrolysis conditions organic peroxo acids with cationic group-forming compounds in which a quaternary N atom is part of a heterocyclic 6-membered radical are particularly suitable for enhancing the bleaching action of citrate-based automatic dishwashing agents containing a bleaching agent.The bleach-activating compound of the general formula (I), in whichA for O, S, Se;Z is an optionally substituted C 1-30 alkylene, C 3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene radical;X is - for an anion, in particular chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate and / or phosphate;Y for NR 6, O, S, Se;R, R 1, R 2, R 3, R 4, R 5 and R 6 independently of one another represent H, a C 1-30 alkyl, C 3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical; andn is a number in the range from 1 to 12.In the hydrocarbon radicals indicated, 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by a heteroatom, in particular N, O, S and / or Se. If X - is a polyvalent anion, a plurality of the cationic heterocycle-containing units forming the remaining part of the compound of the formula (I) are accordingly present per anion X -. R, R 1, R 2, R 3, R 4, R 5 and / or R 6 are preferably H, and / or A is preferably O, and / or n is preferably at least 2 and in particular a number in the range from 2 to 4. As is represented in the formula (II) BELOW, Z is preferably derived from an optionally substituted alkylbenzene unit in which a carbon atom of the aromatic ring is bonded to the unit C=A, a carbon atom of the alkyl radical is bonded to the shown carbon atom of the six-membered heterocycle, and the methyl group is the preferred alkyl radical: For the compounds of the formula (II), the definitions given for formula (I) apply for A, n, R and R 1 to R 5 and X- likewise; R', R 9 and R 10 independently of one another stand for H, a C 1-30 alkyl, C 3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical, it also being possible for 1 or more non-adjacent carbon atoms not bonded to a heteroatom to be replaced in these by a heteroatom, in particular N, O, S and / or Se. Preferably, R', R are 9 and / or R are 10 H.Preferred compositions are those which contain the bleach-activating compound of the formula (I) when Y and A are O, R, R 1, R 2, R 3, R 4 and R 5 independently of one another are H or a C 1- alkyl radical.The agents according to the invention can be designed in such a way that they comprise a further bleach activator which is not described by formula (I). Bleach activators of this type are peroxocarboxylic acid-yielding compounds under perhydrolysis conditions, in particular compounds which under perhydrolysis conditions yield optionally substituted perbenzoic acid and / or aliphatic peroxocarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms. Of these, individual substances or mixtures can be used. Suitable bleach activators are those mentioned at the beginning which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted Ben zoyl ¬ groups. Preference is given to polyacylated Alkylen¬di¬ami¬ne insbesonddere Tetra¬ace¬tyl¬ethylen¬di¬amin (TAED), acylated glycolurils, insbesonddere Tetra¬ace¬tyl¬glykol¬uril (TAGU), acylated triazine derivatives, ins¬be¬son¬dere 1,5-Di ace tyl ¬ 2,4-di oxo ¬ hexahydro ¬ 1,3,5-triazine (DADHT), N-acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of the diene type, respectively, In particular, No mannoyl- or Iso mannanoyl- or Lauroyloxy¬ben¬zol¬sulfonat (NOBS); Nonrably iso-NOBS or LOBS, respectively), 4-(2-decanoyloxyethoxycarbonyloxy)benzene sul-fonate (DECOBS) or Decanoyloxyben¬zoat (DOBA), acylated polyhydric alcohols, ins¬be¬son¬de¬re triacetin, Ethylen¬gly¬kol¬di¬acetat and 2,5-di acetoxy 2,5-di hydroformylation xanthine and its mixtures (SORMAN), acy- retin and 2,5-di hydroformylation and its mixtures (SORMAN), acy- , ins¬be¬son¬dere pentaacetylglucose (PAG), Penta¬acetyl¬fruktose tetraacetyl-xylose and octaacetyllactose, acetylating nt, optionally N-alkylated gluca tetramine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam.In one embodiment, the agent according to the invention comprises tetraacetylethylenediamine (TAED) as a further bleach activator. In these agents, TAED is preferably in amounts of from 0.5 to 5 wt %, particularly preferably from 1.0 to 3.5 wt %, particularly preferably from 1.5 to 2.5 wt %, based on the total amount of the agent. In one embodiment, the agent according to the invention comprises TAED and the at least one bleach activator of formula (I) in a mass ratio of 1:1 to 1:10, preferably of 1:2 to 1:3.In another preferred embodiment, the agent according to the invention does not comprise tetraacetylethylenediamine (TAED) as a further bleach activator. In an even more preferred further embodiment, the agent according to the invention does not comprise any further bleach activator in addition to the at least one bleach activator of formula (I). This means that the automatic dishwashing detergent according to the invention is preferably free from further Perhydro¬Iyse¬be¬ding¬ung¬en peroxo chrysant ary characterization.Both for compositions which exclusively comprise one or more bleach activators of formula (I) and for compositions which comprise further bleach activators in addition to the bleach activators of formula (I), as described above, it is preferred that the composition of the invention comprises the at least one bleach activator in a total amount of from 1.0 to 10% by weight, based on the total amount of the composition, and / or from 0.4 to 1.0 g / job.It is also preferred according to the invention that the bleach activator of formula (I) is present in the composition in a total amount of from 0.4 to 1.0 g / job, preferably from 0.5 to 0.8 g / job, in particular at least 0.6 g / job. Furthermore, it is preferred according to the invention that the bleach activator of formula (I) is present in the composition in a total amount of 1.1 to 2.8 mmol / job, preferably 1.4 to 2.2 mmol / job, in particular at least 1.6 mmol / job.In known machine dishwashing agents based on citrate, a transition metal-containing or transition metal-based bleach catalyst is usually used in addition to sodium percarbonate as bleach and TAED as bleach activator in order to achieve the desired bleaching performance. The compositions claimed and according to the invention here do not comprise a transition metal-based bleach catalyst. This means in particular that none / r of the customary bleach-enhancing transition metal salts or transition metal complexes, for example Mn-, Fe-, Co-, Ru- or Mo-salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and also Co, Fe, Cu and Ru-ammine complexes are also used. This applies correspondingly to the complexes of manganese in the oxidation state II, III, IV or V which contain one or more macrocyclic ligand(s) with the donor functions N, NR, PR, O and / or S, for example these which contain, as macromolecular ligands, 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Corresponding manganese complexes are, for example, [Mn III2( μ-O) 1( μ-OAc) 2( TACN) 2]( ClO 4)2, [ Mn III Mn IV( μ-O) 2( μ-OAc) 1( TACN) 2]( BPh4)2, [MnIVNER69_(μ-O)6(TACN)4](ClO4)4, [Mn III2( μ-O) 1( μ-OAc) 2( Me-TACN) 2]( ClO4) 2, [ Mn III Mn IV( μ-O) 1( μ-OAc) 2( Me-TACN) 2]( ClO4)3, [Mn IV2( μ-O) 3( Me-TACN) 2]( PF 6)2 and [Mn IV2( μ-O) 3( Me / Me-TACN) 2]( PF 6)2( OAc=OC(O)CH 3).In addition to the active substances already described in more detail, the agent according to the invention can have one or more further ingredients from the group of builders, surfactants, polymers, enzymes, glass corrosion inhibitors, corrosion inhibitors, fragrances, dyes.The group of surfactants includes the nonionic, anionic, cationic and amphoteric surfactants. It is preferred that the agent according to the invention comprises at least one nonionic surfactant. Automatic dishwashing agents which contain nonionic surfactant(s) in amounts of 1 to 10 wt %, preferably 2 to 8 wt % and in particular 3 to 6 wt %, are preferred according to the invention.As nonionic surfactants, it is possible to use any nonionic surfactants known to the skilled worker. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO(G)x in which R corresponds to a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any desired number between 1 and 1 O; preferably x is 1.2 to 1.4.Also suitable are non-ionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and of the fatty acid alkanolamides. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.A further class of nonionic surfactants preferably used, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.Preferred surfactants are low-foaming nonionic surfactants. With particular preference, detergents or cleaners, in particular automatic dishwashing cleaners, comprise nonionic surfactants from the group of alkoxylated alcohols. Nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 mol of ethylene oxide (EO) per mol of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in a mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear radicals from alcohols of native origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow fatty or oleyl alcohol, and on average 2 to 8 mol of EO per mol of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11- alcohol with 7 EO, C 13-15- alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18- alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14- alcohol with 3 EO and C 12-8- alcohol with 5 EO. The degrees of ethoxylation indicated represent statistical averages which can correspond to a whole or a broken number for a specific product. Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols having more than 12 EO can also be used. Examples thereof are tallow fatty alcohol having 14 EO, 25 EO, 30 EO or 40 EO.It is therefore particularly preferred to use ethoxylated nonionic surfactants which have been obtained from C 6-20- monohydroxyalkanols or C 6-20- alkyl phenols or C 16-20- 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 (C 16-20- alcohol), preferably a C18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide. Of these, the so-called narrow range ethoxylates are particularly preferred.It is also particularly preferable to use combinations of one or more tallow fatty alcohols having from 20 to 30 EO and silicone defoamers.Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant(s) having a melting point above 20° C., preferably above 25° C., particularly preferably between 25 and 60° C., and in particular between 26.6 and 43.3° C., is / are particularly preferred. Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pa·s, preferably above 35 Pa·s and in particular above 40 Pa·s. Non-ionic surfactants which have a wax-like consistency at room temperature are also preferred depending on their intended application.Non-ionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO non-ionic surfactants, are likewise used with particular preference.The nonionic surfactant which is solid at room temperature preferably has propylene oxide 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 agents 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.Surfactants preferably to be used originate from the groups of alkoxylated non-ionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are furthermore distinguished by good foam control. Further particularly preferably used nonionic surfactants having melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 mol of ethylene oxide and 99 mol of propylene oxide per mol of trimethylolpropane.Low-foaming nonionic surfactants have proven to be particularly preferred in the context of the present invention, which nonionic surfactants have alternating ethylene oxide and alkylene oxide units. Among these, surfactants having EO-AO-EO-AO blocks are again preferred, one to ten EO or AO groups each being bonded to one another before a block of the other groups follows. Nonionic surfactants of the general formulaR 1- is O-(CH 2- CH 2- O) w-( CH 2- CHR 2- O) x-( CH 2- CH 2- O) y-( CH2-CHR3-O)z-H, in which R1 is a straight-chain or branched, saturated or mono- or polyunsaturated C_NER12-alkyl or alkenyl radical; each group R2or R3is independently selected from -CH 3, - CH 2 CH 3, - CH 2 CH 2 CH 3, CH(CH 3)2 and the indices w, x, y, z are independently integers from 1 to 6.The 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 radical R 1 in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is generally unbranched, with the linear radicals being preferred from alcohols of native origin having 12 to 18 C atoms, for example from coconut, palm, tallow fat or oleyl alcohol. Alcohols obtainable from synthetic sources are, for example, the Guerbet alcohols or 2-methyl-branched or linear and methyl-branched radicals in a mixture, as are usually present in oxo alcohol radicals. Regardless of the type of alcohol used to prepare the nonionic surfactants present in the compositions, nonionic surfactants are preferred in which R 1 in the above formula represents an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.Suitable alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit is, in addition to propylene oxide, in particular butylene oxide. However, other alkylene oxides in which R is 2 or. R 3 independently of one another are selected from -CH 2 CH 2 CH 3 and -CH(CH 3)2 are suitable. Preference is given to using nonionic surfactants of the above formula in which R is 2 or. R 3 is a radical -CH 3, w and x are each independently of the other values of 3 or 4, and y and z are each independently of the other values of 1 or 2. In summary, preference is given in particular to nonionic surfactants which have a C 9-15- alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.surfactants of the general formula R 1- CH(OH)CH 2 O-(AO) w-( A'O) x-( A"O) y-( A""O) z- R 2, in which R 1 and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40- alkyl or alkenyl radical; A, A', A" and A"' independently of one another represent a radical from the group -CH 2 CH 2, - CH 2 CH 2 CH 2, - CH 2 CH(CH 3), - CH 2 CH 2 CH 2 CH2, -CH2CH(CH3)-CH2, -CH2CH(CH2CH3); and w, x, y and z represent values between 0.5 and 90, where x, y and / or z may also be O, are preferred according to the invention.Preference is given in particular to those end group-terminated poly(oxyalkylated) nonionic surfactants which, according to the formula R 1 O[CH 2 CH 2 O] x CH 2 CH(OH)R 2, have, in addition to a radical R 1, which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, also a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, where x is values between 1 and 90, preferably values between 30 and 80 and in particular values between 30 and 60.Particularly 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 radical having 4 to 18 carbon atoms or mixtures thereof, R_NER3-denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x represents values between 0.5 and 1.5 and y represents a value of at least 15.By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits during machine dishwashing can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.Particular preference is furthermore given to those end group-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 O[CH 2 CH 2 O] x[ CH 2 CH(R 3) O] y CH 2 CH(OH)R 2, in which R 1 and R2each independently represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R3each independently is selected from -CH3, -CH2CH3, -ch_ner208_ch_ner209_ch_ner210_ -ch(ch_ner211_)_ner212_, but preferably -CH 3 and x and y independently of one another are values between 1 and 32, with nonionic surfactants with R 3= - CH 3 and values for x from 15 to 32 and y from 0.5 and 1.5 being very particularly preferred.Further preferred non-ionic surfactants that can be used are the end group-capped poly(oxyalkylated) non-ionic surfactants of the formula R 1 O[CH 2 CH(R 3) O] x[ CH 2]k CH(OH)[CH 2]j OR 2, in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are 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 radicals having 6 to 22 carbon atoms, particular preference being given to radicals having 8 to 18 carbon atoms. For the radical R 3 particular preference is given to H, -CH 3 or -CH 2 CH 3. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.As described above, each R3in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, if x is 3, the R3radical may be selected to form ethylene oxide (R 3= H) or propylene oxide (R 3= CH 3) units which may be joined together in any order, for example (EO)(PO)(EO ), (EO)(EO)(PO ), (EO)(EO)(EO ), (PO)(EO)(PO ), (PO)(PO)(EO ) and (PO)(PO)(PO ). The value 3 for x has been chosen here as an example and can be quite larger, wherein the range of variation increases with increasing x values and includes, for example, a large number of (EO) groups, combined with a small number of (PO) groups, or vice versa. Particularly preferred end group-capped poly(oxyalkylated) alcohols of the above formula have values of k=1 and j=1 so that the above formula is simplified to R 1 O[CH 2 CH(R 3) O] x CH 2 CH(OH)CH 2 OR 2. In the latter formula, R 1, R 2 and R 3 are as defined above and x is numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.The indicated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the above-mentioned non-ionic surfactants represent statistical mean values, which can be an integer or a fractional number for a specific product. On account of the preparation processes, commercial products of the formulae mentioned usually consist not of an individual representative but of mixtures, as a result of which averages and numbers fractional as a result can be obtained both for the C chain lengths and for the degrees of ethoxylation or alkoxylation. Of course, the aforementioned nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants. Surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the above-mentioned general formulae, but rather mixtures which comprise two, three, four or more nonionic surfactants which can be described by different ones of the above-mentioned general formulae.Agents according to the invention can of course also contain further builders in addition to citrate. These builders include, in particular, silicates, carbonates and organic cobuilders. Organic cobuilders which may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, polyaspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.Usable organic builder substances are, for example, the polycarboxylic acids usable in the form of the free acid and / or its sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. Examples of these are adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures thereof. In addition to their builder action, the free acids typically also have the property of an acidifying component and thus also serve to establish a lower and milder pH of detergents or cleaners. Particular mention may be made here of succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these.Automatic dishwashing agents according to the invention preferably contain as builder crystalline layered silicates of the general formula NaMSi x O2 x+1 · y H2O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.It is also possible to use amorphous sodium silicates having a Na 2 O:SiO 2 modulus of from 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which are preferably solution-delayed and have secondary wash properties.Automatic dishwashing agents preferred in the context of the present invention contain 1 to 10 wt %, preferably 2 to 8 wt %, and in particular 2 to 6 wt % silicate(s).Particular preference is given to the use of carbonate(s) and / or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of from 5 to 50% by weight, preferably from 10 to 40% by weight and in particular from 15 to 30% by weight, in each case based on the weight of the automatic dishwashing detergent.Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 500 to 70000 g / mol.Suitable polymers are in particular polyacrylates, which preferably have a molecular mass of 2000 to 20000 g / mol. Owing to their superior solubility, short-chain polyacrylates having molar masses of 2000 to 10000 g / mol, and particularly preferably of 3000 to 5000 g / mol, may in turn be preferred from this group.Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable. Their molecular weight based on free acids is generally 2000 to 70000 g / mol, preferably 20000 to 50000 g / mol and more preferably 30000 to 40000 g / mol.The (co)polymeric polycarboxylates can be used either as powder or as aqueous solution. The content of (co)polymeric polycarboxylates in the automatic dishwashing agents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.Further suitable builders are the phosphonates. The complexing phosphonates include a number of different compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriamine penta(methylene phosphonic 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. Automatic dishwashing agents which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred.Preferred agents according to the invention contain phosphonate, particularly preferably HEDP. Preferred dishwashing agents according to the invention contain phosphonate, preferably HEDP, in an amount of 3 to 10 wt. %, preferably in an amount of 5 to 8 wt. %, based on the total amount of the agent. Preferred dishwashing agents according to the invention contain phosphonate, preferably HEDP, in an amount of 0.5 to 2.5 g / job, preferably of 1.0 to 1.7 g / job.The group of wash- or cleaning-active polymers includes, for example, the final rinse polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can also be used in detergents or cleaning agents in addition to nonionic polymers.The agents according to the invention may contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt %, in each case based on the total weight of the washing or cleaning agent. However, those agents are preferred in the context of the present application in which the weight proportion of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, particularly preferably between 0.01 and 2% by weight and in particular between 0.01 and 1% by weight, in each case based on the total weight of the automatic dishwashing agent.Enzymes can be used to increase the cleaning performance of automatic dishwashing detergents. These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are correspondingly preferably used. Detergents or cleaning agents preferably contain enzymes in total amounts of 1 x 10-6 to 5 wt. %, based on active protein.The protein concentration can be determined by known methods, for example the BCA method or the biuret method.The enzymes can be used in any form established according to the prior art.These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers. Alternatively, the enzymes can be encapsulated for both the solid and the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water-impermeable, air-impermeable and / or chemical-impermeable protective layer.Furthermore, it is possible to make up two or more enzymes together, so that a single granulate has a plurality of enzyme activities. A protein and / or enzyme can be protected, especially during storage, against damage such as, for example, inactivation, denaturation or decomposition, for example, by physical influences, oxidation or proteolytic cleavage. In the case of microbial recovery of the proteins and / or enzymes, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Detergents or cleaning agents may contain stabilizers for this purpose; the provision of such agents represents a preferred embodiment of the present invention.Preferably, one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, are used in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 5% by weight and in particular from 0.4 to 5% by weight, in each case based on the total enzyme-containing agent.The agent according to the invention can be present in the form of a prefabricated single dose or portion unit. It is preferred according to the invention that the agent is present in a water-soluble envelope as a prefabricated single dose. In addition, agents in a water-soluble envelope as a prefabricated single dose are preferred according to the invention if the total weight of the single dose is from 8 to 30 g, in particular from 10 to 25 g, preferably from 12 to 21 g, particularly preferably from 13 to 17 g.The water-soluble coating may be formed by one or more water-soluble films. The water-soluble film may comprise one or more structurally different water-soluble polymer(s). Suitable water-soluble polymer(s) are, in particular, polymers from the group of (optionally acetalized) polyvinyl alcohols (PVAL) and copolymers thereof. Water-soluble films for producing the portion unit are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is preferably in the range from 10,000 to 1,000,000 gmol-1, preferably from 20,000 to 500,000 gmol-1, particularly preferably from 30,000 to 100,000 gmol-1 and in particular from 40,000 to 80,000 gmol-1. Preferred water soluble films comprise at least 30 wt.%, preferably at least 50 wt.% and in particular at least 70 wt.% polyvinyl alcohol or polyvinyl alcohol copolymers. The preparation of the polyvinyl alcohol and polyvinyl alcohol copolymers typically involves the hydrolysis of intermediate polyvinyl acetate. Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %. Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic esters, methacrylic esters or mixtures thereof; among the esters, C1-4-alkyl esters or hydroxyalkyl esters are preferred. Other suitable monomers are ethylenically unsaturated dicarboxylic acids, for example itaconic acid, maleic acid, fumaric acid and mixtures thereof.Suitable water-soluble films for use in the portion units according to the invention are films which are sold by the company MonoSol LLC, for example under the name M8630, M8720, M8310, C8400 or M8900. Other suitable films include Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL films from Aicello Chemical Europe GmbH, or Kuraray's VF-HP films, as well as the Hi-Selon Series from Mitsubishi Chemical Corporation.The present application also relates to a method for cleaning dishes in a dishwasher comprising the steps: a) providing a wash liquor comprising an agent according to the invention, b) bringing the wash liquor according to a) into contact with the dishes to be cleaned.It is preferred according to the invention that in the process the wash or rinse liquor according to a) has a temperature of from 15 to 75° C., preferably from 30 to 60° C., particularly preferably from 35 to 50° C.In this context, preference is given according to the invention to methods in which individual ingredients or combinations of ingredients are present in specific concentration ranges. In the case of cleaning performance as considered here, this relates in particular to the concentration of builder and bleach activator. Preference is therefore given to processes in which the wash or rinse liquor comprises the bleach activator of the formula (I) in concentrations of from 80 to 500 ppm, preferably from 120 to 400 ppm, more preferably from 140 to 300 ppm, in particular from 180 to 250 ppm. Furthermore, preference is given to processes in which the wash or rinse liquor comprises citrate in a concentration of from 500 to 2000 ppm, preferably from 700 to 1700 ppm, particularly preferably from 900 to 1500 ppm. This information also relates to citrate anhydrate, for example. Sodium citrate anhydrate. Preference is also given to processes in which the wash or rinse liquor comprises phosphonate, preferably HEDP, in a concentration of from 100 to 800 ppm, preferably from 200 to 600 ppm, more preferably from 250 to 500 ppm, more preferably from 300 to 450 ppm. In preferred processes, the concentration of the bleach activator of formula (I) is from 80 to 500 ppm, preferably from 120 to 400 ppm, particularly preferably from 140 to 300 ppm, in particular from 180 to 250 ppm, and / or the concentration of citrate, preferably sodium citrate, is from 500 to 2000 ppm, preferably from 700 to 1700 ppm, particularly preferably from 900 to 1500 ppm, and / or the concentration of phosphonate, preferably HEDP, is from 100 to 800 ppm, preferably from 200 to 600 ppm, particularly preferably from 250 to 500 ppm, in particular preferably 300 to 450 ppm, in the wash or rinse liquor.Exemplary Embodiments:Example 1:The preparation processes of the bleach-activating compounds of formula (I) are known from WO2021 / 099244A1.According to the procedure, 4-methyl-4-(4-((2-oxoazepan-1-yl)carbonyl)benzyl)morpholin-4-ium chloride was prepared, which is referred to below as Akt1. Table 1: Table 1:TAED0,386400,2670,40,533Soda Soda Soda5,155,155,155,155,15Na percarbonate2,812,812,812,812,81Na citrate*2 H2O1,541,541,541,541,54Na citrate anhydrate2,62,62,62,62,6Akt100,80,5330,40,267Rinse-Aid Surfactant0,760,760,760,760,76Protease granules0,420,420,420,420,42Mn-TACN0,00450000Sulfonated acrylate0,7650,7650,7650,7650,765Amylase granules0,190,190,190,190,19HEDP1,32891,32891,32891,32891,3289Silicate Silicate0,360,360,360,360,36Remaining substances (accompanying substances of the granules, perfume, water, anticorrosives such as zinc acetate)0,690,690,690,690,69Sum Sum1717,4117,4117,4117,41The cleaning performance of the compositions was tested by the IKW method (Miele GSL, program 45 8 55 at 21° dH; IKW 2015, sofwjournal, 142, 06 / 16), wherein two tea varieties were used to intensively test the performance in this respect. According to the IKW method, a comparison can only take place within one experiment, since, among other things, the stains are subject to batch fluctuations, which can change the absolute values from experiment to experiment. Table 2: Table 2:V15,35,16,45,75,32,59,25,75,2E14,75,96,65,953,195,85,3E2336,54,95,22,98,95,23E32,42,96,45,352,98,95,22,7E422,76,865,42,98,95,42,3avg. (tea average): Average value over the stains, wherein instead of both tea types the average value of the two tea types is included in the calculation. tea only: Average value of the two tea results.The cleaning performance of the composition E1 according to the invention on the tea stains is comparable to the performance of the bleach catalyst-containing formula V1 or exceeds it in the case of tea (BOP). By comparing the formulations according to the invention from E4 to E1, it is found that the cleaning performance on tea is improved with an increase in the proportion of bleach activator of formula (I) in the total bleach activator amount.The cleaning performance of the compositions according to the invention does not differ significantly from the cleaning performance of the comparative composition V1 with respect to the further soilings.Example 2:Table 3: Table 3: Table 3: Table 3:Na citrate*2 H2O3,142483,142483,14248Citric acid is anhydrous and anhydrous0,0260,0260,026Na citrate anhydrate0,890,890,89HEDP1,342481,342481,34248Silicate Silicate1,3651,3651,365Sodium hydrogen carbonate0,5590,5590,559Soda Soda Soda4,5174,5174,517Na percarbonate2,9712,9712,971Mn-TACN0,00483Rinse-Aid Surfactant0,98170,98170,9817Linear polyacrylate0,360,360,36Sulfonated acrylate0,82170,82170,8217Protease granules0,480,480,48Amylase granules0,0980,0980,098TAED0,3680,92Remaining (accompanying substances of the granules, perfume, dyestuff, water, anticorrosives such as zinc acetate, benzotriazole, PEG-4000)2,072812,072812,07281Akt11,61Sum Sum2020,5521,24The cleaning performance of the compositions V2, V3 and E5 was tested by the IKW method (Miele GSL, program 45 8 55 at 21° dH; IKW2015, sofwjournal, 142, 06 / 16), wherein two tea types were used to intensively test the relevant cleaning performance. According to the IKW method, a comparison can only take place within one experiment, since, among other things, the stains are subject to batch fluctuations, which can change the absolute values from experiment to experiment. Table 4: Table 4: Table 4: Table 4:V27,88,37,26,55,43,88,16,5V32,02,87,36,35,74,48,25,7E59,39,86,96,15,34,77,56,7avg. (tea average): Mean value of the stains, wherein instead of both tea types the mean value of the two tea types is included in the calculation.It has been found that the composition according to the invention provides improved cleaning performance both with respect to composition V3 and with respect to composition V2 on both tea varieties. In addition, the cleaning performance of spaghetti was also advantageous compared with V3 and V2.Example 3: Example 3:The concentration dependence of the bleaching performance was also tested. It was tested by the IKW method (Miele GSL, program 45 8 55 at 21° dH; IKW 2015, sofwjournal, 142, 06 / 16), wherein two tea types were used to test the relevant performance intensively. Only the tea stains were scraped off. According to the IKW method, a comparison can only take place within one experiment, since, among other things, the stains are subject to batch fluctuations, which can change the absolute values from experiment to experiment. For this purpose, automated dishwashing agents based on citrate without bleach activator / bleach catalyst were used, to each of which TAED or Akt1 was added in the stated amount. Table 5: Table 5: Table 5: Table 5:+ 0.8 g / job TAED (3.5 mmol / job)3,03,0+ 0.4 g / job Akt1 (1.1 mmol / job)4,03,7+ 0.5 g / job Akt1(1.4 mmol / job)4,75,3+ 0.6 g / job Akt1(1.6 mmol / job)5,65,6It was found that the cleaning performance on tea was significantly higher even at an amount of Akt1 of 1.1 mmol / job than at an amount of 3.5 mmol / job of TAED.References included in the specificationThis list of documents cited by the applicant has been produced in an automated manner and is only included for the better information of the reader. The list is not part of the German patent application or utility model application. The DPMA does not take any adhesion for any faults or omissions.Patent Literature citedWO 2021 / 099244A1

[0077]

Claims

Automatic dishwashing agent comprising a) citrate, b) bleaching agent, c) at least one bleach activator, wherein the agent does not have a transition metal-based bleach catalyst and wherein at least one bleach activator is selected from one or more compounds of the general formula (I), in which A is O, S, Se; Z is an optionally substituted C 1-30 alkylene, C 3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene radical; X - is an anion, in particular chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate and / or phosphate; Y is NR 6, O, S, Se; R, R 1, R 2, R 3, R 4, R 5 and R 6 independently of one another represent H, a C 1-30 alkyl, C 3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical; and n represents a number in the range from 1 to 12, wherein 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced in the hydrocarbon radicals by a heteroatom, in particular N, O, S and / or Se.Composition according to Claim 1, wherein tetraacetylethylenediamine (TAED) is used as further bleach activator.The agent according to claim 1, wherein the agent does not comprise tetraacetylethylenediamine (TAED) as a further bleach activator.Agent according to any one of the preceding claims, wherein the agent comprises citrate in an amount of 10 to 40 wt.%, preferably in an amount of 15 to 35 wt.%, based on the total amount of agent.Agent according to one of the preceding claims, wherein the bleaching agent is sodium percarbonate and the agent comprises sodium percarbonate preferably in an amount of 5 to 25 wt.%, particularly preferably in an amount of 10 to 20 wt.%, based on the total amount of the agent.The agent according to any one of the preceding claims, wherein Y and A are O, R, R 1, R 2, R 3, R 4 and R 5 independently of one another are H or a C1 alkyl radical.Agent according to one of the preceding claims, wherein the agent comprises the at least one bleach activator in a total amount of 1.0 to 10 wt.%, based on the total amount of the agent, and / or 0.4 to 1.0 g / job.Agent according to claim 2, wherein a mixture of tetraacetylethylenediamine and bleach activator according to formula (I) is present in a mass ratio of 1:1 to 1:10, preferably of 1:2 to 1:3.A method for cleaning dishes in a dishwasher comprising the steps: a) providing a wash liquor comprising an agent according to any of claims 1 to 8, b) contacting the wash liquor according to a) with the dishes to be cleaned.The process according to claim 9, wherein, in the process, the wash liquor of a) has a temperature of from 15 to 75°C, preferably from 30 to 60°C, more preferably from 35 to 50°C.