Automatic dishwasher detergent with novel bleaching system

Abstract

The aim of the invention is to improve the bleaching power of citrate-based automatic dishwasher detergents. This property can be improved, without using transition-metal-containing catalysts, by using compounds that form organic peroxoacids having a cationic group under the conditions of perhydrolysis. In these compounds, a quaternary N atom is part of a heterocyclic 6-membered group.

Description

[0001] 'Dishwasher detergent with innovative bleaching system'

[0002] The invention relates to automatic dishwashing detergents having a novel bleaching system and to processes using these detergents.

[0003] In contrast to automatic dishwashing detergents in tablet form, non-tableted single doses, such as more or less compacted powder formulations enclosed in PVA film, do not require tableting aids such as cellulose / cellulose derivatives, polyacrylates (unless these contribute to the fight against limescale), starch, etc. In this respect, they are usually more compact formulations.

[0004] These formulations sometimes display different sensitivities during storage, which can be attributed, for example but not exclusively, to the easier diffusion of gases between the particles in the looser form, the larger freely accessible surface area, or usually also to the presence of a single phase, whereas tablets have relatively small interparticle spaces, small freely accessible surfaces, which are determined by the outer shape of the tablet, and can also be easily constructed from separate phases so that contact surfaces between incompatible ingredients can be limited. Optical changes can be signs of such instability. One easily noticeable optical change is the discoloration of the manganese-containing bleach catalyst in such dishwashing detergents. Tableted automatic dishwashing detergents can also display similar discoloration on the surface caused by the catalyst.

[0005] In addition to a low sensitivity of the composition, which improves storage capacity, among other things, another focus is on the sustainability of the raw materials that are used in larger quantities, such as the main builder component.

[0006] Despite all the changes and improvements being sought in the individual areas, it remains of utmost importance that the cleaning performance on the various types of soiling is at least satisfactory and does not deteriorate compared to established products.

[0007] The use of MGDA as a builder enables a high-performance, compact formulation that can also contribute to the removal of tea soils. A first step toward introducing a main builder based on renewable raw materials could be switching from MGDA to citrate. However, this switch is associated with a drastic reduction in tea soil removal.

[0008] The object of the present application was therefore to provide a compact formulation for an automatic dishwashing detergent, the main builder component of which can be provided from renewable resources, which provides good overall cleaning performance including good tea removal and which does not show any discoloration during storage.

[0009] Surprisingly, it was found that bleach activators as described below lead to good cleaning performance in citrate-based automatic dishwashing detergents without the presence of transition metal-containing bleach catalysts in the presence of bleaching agents.

[0010] A first aspect of the present invention is therefore an automatic dishwashing detergent comprising citrate, bleaching agent, at least one bleach activator, wherein the detergent does not comprise 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 the

[0011] A for O, S, Se;

[0012] Z represents an optionally substituted C1-30 alkylene, C3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene radical;

[0013] X' represents an anion, in particular chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate and / or phosphate;

[0014] Y for NR 6 , O, S, Se;

[0015] R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6independently of one another represent H, a C1-30 alkyl, C3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical; and n represents a number in the range from 1 to 2, where in the hydrocarbon radicals 1 or more non-adjacent carbon atoms not bonded to a heteroatom may be replaced by a heteroatom, in particular N, O, S and / or Se.

[0016] The agent can be used in automatic dishwashing processes. Therefore, a further subject of this application is a method for cleaning dishes in a dishwasher.

[0017] These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Furthermore, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples. All percentages are, unless otherwise stated, % by weight based on the total weight of the agent / composition. Numerical ranges given in the format "from x to y" include the stated values. Where multiple preferred numerical ranges are given in this format, it is to be understood that all ranges resulting from the combination of the various endpoints are also encompassed.

[0018] “At least one”, as used herein, refers to 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of components of the compositions described herein, this information does not refer to the absolute amount of molecules but to the type of component. “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 amount of the correspondingly designated type of component. For compositions that are presented as a unit dose, quantities of individual ingredients or groups of ingredients can be stated both as % by weight as described above and as the mass of the respective named ingredient per unit dose (g / job).Quantities or ranges described in this way can refer to both pre-packaged individual doses and the actual amount obtained according to the dosage recommendation. When used in automatic dishwashing processes, the concentration of individual ingredients or groups of ingredients in the wash liquor can also be relevant for the performance of the product. The concentration can be expressed in ppm (parts per million), which corresponds to the amount in grams (active ingredient) per kilogram (wash liquor).

[0019] The agent according to the invention contains citrate as the main builder. The term citrate encompasses the salts of citric acid, preferred being 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 3 to 4.5 g / job. This amount, both in percentage and by mass, refers to citrate anhydrate, e.g., sodium citrate anhydrate. It can be fully or partially replaced by an equal molar exchange with citrate dihydrate, e.g., sodium citrate dihydrate.

[0020] Dishwashing detergents according to the invention also contain at least one bleaching agent. Oxygen bleaching agents are preferred as bleaching agents. Among the compounds that yield H2O2 in water, sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate are particularly important. Other useful bleaching agents include peroxypyrophosphates, citrate perhydrates, and H2O2-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid, or diperdodecanedioic acid. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, with particular examples being alkyl peroxyacids and aryl peroxyacids.

[0021] Sodium percarbonate is preferably used as the bleaching agent in the compositions according to the invention. Preference is given to compositions according to the invention containing bleaching agent 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 composition.

[0022] The dishwashing detergents according to the invention further contain at least one bleach activator according to the general formula (I) as described above. It has been found that compounds forming organic peroxy acids with a cationic group under perhydrolysis conditions, in which a quaternary nitrogen atom is part of a heterocyclic 6-membered radical, are particularly suitable for enhancing the bleaching effect of citrate-based automatic dishwashing detergents containing a bleaching agent.

[0023] The bleach-activating compound of general formula (I), in the

[0024] A for O, S, Se;

[0025] Z represents an optionally substituted C1-30 alkylene, C3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene radical;

[0026] X- represents an anion, in particular chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate and / or phosphate;

[0027] Y for NR 6 , O, S, Se;

[0028] R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently of one another represent H, a C1-30 alkyl, C3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical; and n represents a number in the range from 1 to 12.

[0029] In the indicated hydrocarbon radicals, one or more non-adjacent carbon atoms not bonded to a heteroatom may be replaced by a heteroatom, in particular N, O, S, and / or Se. If X- is a polyvalent anion, correspondingly several of the units forming the remaining part of the compound according to formula (I) and containing the cationic heterocycle are present per anion X-. R, R 1 , R 2 , R 3 , R 4 , R 5 and / or R 6are 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 shown in the following formula (II), Z is preferably derived from an optionally substituted alkylbenzene unit in which a C atom of the aromatic ring is bonded to the unit C=A, a C atom of the alkyl radical is bonded to the shown N atom of the six-membered heterocycle and the methyl group is the preferred alkyl radical:

[0030] For the compounds of formula (II), the definitions for A, n, R and R given for formula (I) apply. 1 to R 5 and X- also; R', R 9 and R 10are independently of one another H, a C1-30 alkyl, C3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical, where in these too one or more non-adjacent carbon atoms not bonded to a heteroatom may be replaced by a heteroatom, in particular N, O, S and / or Se. Preferably, R', R 9 and / or R 10 H.

[0031] Preferred agents are those containing the bleach-activating compound according to formula (I) when Y and A are O, R, R 1 , R 2 , R 3 , R 4 and R 5 independently of one another represent H or a Ci-alkyl radical.

[0032] The agents according to the invention can be designed in such a way that they contain a further bleach activator which is not described by formula (I). Such bleach activators are compounds which, under perhydrolysis conditions, yield peroxocarboxylic acid, 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. Individual substances or mixtures of these can be used. Suitable bleach activators are the bleach activators cited at the outset, which contain O- and / or N-acyl groups, in particular of the stated number of C atoms, and / or optionally substituted benzoic acid. , zoy|- , groups. Polyacylated alkylene groups are preferred. , di- , ami- , ne, especially Tetra- , ace- , ty|- , ethylene- , di-'amine (TAED), acylated glycoburils, especially tetra-, ace- , ty|- , glycol- , uril (TAGU), acylated triazine derivatives, especially 1,5-di- , ace- , ty|- , -2.4- di- , oxo-'-'hexahydro-'-1,3,5-triazine (DADHT), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids thereof, in particular noanoyl or isonaoyl or lauroyloxy-'benzene-'sulfonate (NOBS or iso-NOBS or LOBS), 4-(2-decanoyloxyethoxycarbonyloxy)-benzenesulfonate , fonate (DECOBS) or decanoyloxybenzoate (DOBA), acylated polyhydric alcohols, in particular , be- , son- , de- , re triacetin, ethylene glycobdiacetate and 2,5- di- , acetoxy-2,5-di-'hydro-'fu-'ran as well as acetylated sorbitol and mannitol and their mixtures (SORMAN), acylic sugar derivatives, in other penta- ,acetylglucose (PAG), penta-acetyltructose, tetra- , acetyl-xylose and octaacetyllactose, acetylated, optionally N-alkylated glucarmin and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam.

[0033] In one embodiment, the agent according to the invention contains tetraacetylethylenediamine (TAED) as a further bleach activator. In these agents, TAED is preferably present in amounts of 0.5 to 5 wt. %, particularly preferably 1.0 to 3.5 wt. %, especially preferably 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 according to formula (I) in a mass ratio of 1:1 to 1:10, preferably 1:2 to 1:3.

[0034] In another preferred embodiment, the agent according to the invention does not contain tetraacetylethylenediamine (TAED) as a further bleach activator. In an even more preferred further embodiment, the agent according to the invention does not contain any further bleach activator besides the at least one bleach activator according to formula (I). This means that the automatic dishwashing agent according to the invention is preferably free of further compounds that produce peroxycarboxylic acid under perhydrolysis conditions.

[0035] Both for agents which exclusively comprise one or more bleach activators according to formula (I) and for agents which, in addition to the bleach activators according to formula (I), comprise further bleach activators as described above, it is preferred that the agent according to the invention 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.

[0036] It is also preferred according to the invention that the bleach activator according to formula (I) is present in the composition in a total amount of 0.4 to 1.0 g / job, preferably 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 according to 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.

[0037] In known citrate-based automatic dishwashing detergents, a transition metal-containing or transition metal-based bleach catalyst is typically used in addition to sodium percarbonate as a bleaching agent and TAED as a bleach activator to achieve the desired bleaching performance. The agents claimed here and according to the invention do not contain a transition metal-based bleach catalyst. This means, in particular, that none of the usual bleach-enhancing transition metal salts or transition metal complexes, such as Mn, Fe, Co, Ru, or Mo salen complexes or carbonyl complexes, are used. Mn, Fe, Co, Ru, Mo, Ti, V, and Cu complexes with N-containing tripod ligands, as well as Co, Fe, Cu, and Ru ammine complexes, are also used. This applies accordingly 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, e.g.these, known as macromolecular ligands 1 ,4,7-Trimethyl- 1 ,4,7-triazacyclones (Me-TACN), 1 ,4,7-Triazacyclones (TACN), 1 ,5,9-Trimethyl- 1 ,5,9- triazacyclododecane (Me-Methyl-TACD), contain 7-trimethyl-1 ,4,7-triazacyclones (Me / Me-TACN) and / or 2-Methyl-1 ,4,7-triazacyclones (Me / TACN). Corresponding Manganese complexes are exemplary [Mn. IH 2(pO)i(p-OAc)2(TACN)2](CIO4)2, [Mn IH Mn lv (pO)2(p- OAc)i(TACN)2](BPh4)2, [Mn lv 4(pO)6(TACN)4](CIO4)4, [Mn lll 2(pO)i(p-OAc)2(Me-TACN)2](CIO4)2, [Mn lll Mn lv (pO)i(p-OAc)2(Me-TACN)2](CIO4)3, [Mn lv 2(pO)3(Me-TACN)2](PF6)2 and [Mn lv 2(p- O)3(Me / Me-TACN)2](PF6)2 (OAc = OC(O)CH3).

[0038] In addition to the active ingredients already described in more detail, the agent according to the invention may contain one or more further ingredients from the group of builders, surfactants, polymers, enzymes, glass corrosion inhibitors, corrosion inhibitors, fragrances, dyes.

[0039] The group of surfactants includes nonionic, anionic, cationic, and amphoteric surfactants. It is preferred that the agent according to the invention contain at least one nonionic surfactant. Dishwashing detergents containing nonionic surfactant(s) in amounts of 1 to 10 wt.%, preferably 2 to 8 wt.%, and especially 3 to 6 wt.%, are preferred according to the invention.

[0040] All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Suitable nonionic surfactants include, 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, carbon atoms, and G is the symbol representing a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably, x is between 1.2 and 1.4.

[0041] Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, in particular no more than half that amount.

[0042] Another class of preferably used nonionic surfactants, 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 with 1 to 4 carbon atoms in the alkyl chain.

[0043] Low-foaming non-ionic surfactants are preferred. Washing or cleaning agents, in particular detergents for automatic dishwashing, particularly preferably contain non-ionic surfactants from the group of alkoxylated alcohols. The non-ionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and an average of 1 to 12 mol of ethylene oxide (EO) per mole 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 found in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 C atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 mol of EO per mole of alcohol are preferred.Preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C8-n-alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO, or 8 EO, C12-18 alcohols with 3 EO, 5 EO, or 7 EO, and mixtures thereof, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which for a specific product can correspond to a whole or fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

[0044] Therefore, ethoxylated nonionic surfactants obtained from C6-20 monohydroxyalkanols or C6-20 alkylphenols or C6-20 fatty alcohols and more than 12 mol, preferably more than 15 mol, and in particular more than 20 mol of ethylene oxide per mol of alcohol are particularly preferred. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C16-20 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. Among these, the so-called "narrow-range ethoxylates" are particularly preferred.

[0045] Combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are also particularly preferred.

[0046] Nonionic surfactants which have a melting point above room temperature are particularly preferred. Nonionic surfactant(s) with a melting point above 20°C, preferably above 25°C, more preferably between 25 and 60°C and in particular between 26.6 and 43.3°C are particularly preferred. Suitable nonionic surfactants which have melting or softening points in the stated temperature range 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. Nonionic surfactants which have a wax-like consistency at room temperature are also preferred, depending on their intended use.

[0047] Nonionic 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 nonionic surfactants, are also used with particular preference.

[0048] The nonionic surfactant, which is solid at room temperature, preferably contains propylene oxide units in its molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to 20% by weight, and especially up to 15% by weight of the total molecular weight of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally contain polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight, and especially more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred agents are characterized by containing ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule make up to 25% by weight, preferably up to 20% by weight, and especially up to 15% by weight of the total molecular weight of the nonionic surfactant.

[0049] Preferred surfactants come from the group of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control. Other particularly preferred nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 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.

[0050] Particularly preferred nonionic surfactants in the context of the present invention are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups bonded to one another before a block of the respective other groups follows. These are nonionic surfactants of the general formula

[0051] R 1 -O-(CH2-CH2-O)w-(CH2-CHR 2 -O)x-(CH2-CH2-O)y-(CH2-CHR 3 -O)zH is preferred, in which R1 represents a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24 alkyl or alkenyl radical; each group R2 or R3 is independently selected from -CH3, -CH2CH3, -CH2CH2CH3, CH(CH3)2 and the indices w, x, y, z independently represent integers from 1 to 6.

[0052] The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide. The residue R 1 in the above formula can vary depending on the origin of the alcohol. If native sources are used, the residue R 1 has an even number of carbon atoms and is generally unbranched, with linear residues from alcohols of native origin with 12 to 18 C atoms, e.g. from coconut, palm, tallow or oleyl alcohol, being preferred. Alcohols accessible from synthetic sources include, for example, Guerbet alcohols or residues methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually found in oxo alcohol residues. Regardless of the type of alcohol used to produce the nonionic surfactants contained in the products, nonionic surfactants are preferred in which R 1in 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.

[0053] In addition to propylene oxide, butylene oxide is particularly suitable as an alkylene oxide unit that is present alternately with the ethylene oxide unit in the preferred nonionic surfactants. However, other alkylene oxides in which R 2 or R 3 are independently selected from -CH2CH2CH3 or -CH(CH3)2 are suitable. Nonionic surfactants of the above formula are preferably used, in which R 2 or R 3represents a -CH3 radical, w and x independently of one another represent values ​​of 3 or 4, and y and z independently of one another represent values ​​of 1 or 2. In summary, nonionic surfactants which have a Cg-15 alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, are particularly preferred. These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.

[0054] Surfactants of the general formula R 1 -CH(OH)CH2O-(AO)w-(A'O)x-(A"O) y -(A"'O)zR 2 , in the R 1 and R 2independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C2-4o-alkyl or alkenyl radical; A, A', A" and A'" independently of one another represent a radical from the group -CH2CH2, -CH2CH2CH2, -CH2CH(CH3), - CH2CH2CH2CH2, -CH2CH(CH3)-CH2, -CH2CH(CH2CH3); and w, x, y and z represent values ​​between 0.5 and 90, where x, y and / or z can also be 0, are preferred according to the invention.

[0055] Particularly preferred are those end-capped poly(oxyalkylated) nonionic surfactants which, according to the formula R 1 O[CH2CH2O]xCH2CH(OH)R 2 , besides a remainder R 1 , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R2 having 1 to 30 carbon atoms, where x stands for values ​​between 1 and 90, preferably for values ​​between 30 and 80 and in particular for values ​​between 30 and 60.

[0056] Particularly preferred surfactants are those of the formula R 1 O[CH2CH(CH3)O]x[CH2CH2O] y CH2CH(OH)R 2 , in the R 1 represents a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x stands for values ​​between 0.5 and 1.5 and y for a value of at least 15.

[0057] By using the previously described non-ionic surfactants with a free hydroxyl group on one of the two terminal alkyl residues, the formation of deposits during machine dishwashing can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

[0058] Particularly preferred are also those end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 O[CH2CH2O]x[CH2CH(R 3 )O] y CH2CH(OH)R 2 , in the R 1 and R 2 independently of one another represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH3 , -CH2CH3 , -CH2CH r CH3 , -CH(CH3)2, but preferably -CH3, and x and y independently represent values ​​between 1 and 32, where nonionic surfactants with R3 = -CH3 and values ​​for x from 15 to 32 and y from 0.5 to 1.5 are particularly preferred.

[0059] Other preferred nonionic surfactants are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 O[CH2CH(R 3 )O]x[CH2]kCH(OH)[CH2]jOR 2 , in the R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x represents values ​​between 1 and 30, k and j represent values ​​between 1 and 12, preferably between 1 and 5. If the value x > 2, each R 3 in the above formula R 1 O[CH2CH(R 3 )O]x[CH2]kCH(OH)[CH2]jOR 2 be different. R 1 and R 2are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R 3 H, -CH3, or -CH2CH3 are particularly preferred. Particularly preferred values ​​for x are in the range from 1 to 20, in particular from 6 to 15.

[0060] As described above, each R3 in the above formula can be different if x > 2. This allows the alkylene oxide moiety in the square brackets to be varied. For example, if x is 3, the R3 residue can be selected to form ethylene oxide (R 3 = H) or propylene oxide (R 3= CH3 ) units which can be joined together in any order, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x has been chosen as an example and can certainly be larger, whereby the range of variation increases with increasing x values ​​and includes, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa. Particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values ​​of k = 1 and j = 1, so that the above formula is R 1 O[CH2CH(R 3 )O]xCH2CH(OH)CH2OR 2 simplified. In the latter formula, R 1 , R 2 and R 3 as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred surfactants are those in which the radicals R 1 and R2 have 9 to 14 C atoms, R 3 stands for H and x takes values ​​from 6 to 15.

[0061] The stated carbon chain lengths and degrees of ethoxylation or alkoxylation of the aforementioned nonionic surfactants represent statistical averages, which can be a whole or fractional number for a specific product. Due to the manufacturing processes, commercial products of the above-mentioned formulas usually consist of mixtures rather than individual components, which can result in averages and, consequently, fractional numbers for both the carbon chain lengths and 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 consisting of two, three, four, or more surfactants.Surfactant mixtures do not refer to mixtures of non-ionic surfactants which as a whole fall under one of the general formulas mentioned above, but rather to mixtures which contain two, three, four or more non-ionic surfactants which can be described by different ones of the general formulas mentioned above.

[0062] In addition to citrate, agents according to the invention can of course also contain other builders. These builders include, in particular, silicates, carbonates, and organic cobuilders. Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, polyaspartic acid, polyacetals, dextrins, other organic cobuilders, and phosphonates. These substance classes are described below.

[0063] Useful organic builders include, for example, polycarboxylic acids, which can be used in the form of the free acid and / or their sodium salts. Polycarboxylic acids are understood to be carboxylic acids that have more than one acid function. Examples include adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is acceptable on ecological grounds, and mixtures thereof. In addition to their builder effect, the free acids typically also possess the property of an acidifying component and thus also serve to adjust a lower and milder pH value of detergents or cleaning agents. Particularly suitable are succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof.

[0064] Preferably, automatic dishwashing detergents according to the invention contain crystalline layered silicates of the general formula NaMSi as builder x O2x+i • y H2O, wherein M is 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.

[0065] Amorphous sodium silicates with a modulus of Na2 can also be used. <D : SiÜ2 von 1 :2 bis 1 :3,3, vorzugsweise von 1 :2 bis 1 :2,8 und insbesondere von 1 :2 bis 1 :2,6, welche vorzugsweise löseverzögert sind und Sekundärwascheigenschaften aufweisen.

[0066] In the context of the present invention, preferred automatic dishwashing detergents contain 1 to 10 wt.%, preferably 2 to 8 wt.% and in particular 2 to 6 wt.% silicate(s).

[0067] Particularly preferred is the use of carbonate(s) and / or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably 10 to 40% by weight and in particular 15 to 30% by weight, in each case based on the weight of the automatic dishwashing detergent.

[0068] Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g / mol.

[0069] Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g / mol. Due to their superior solubility, short-chain polyacrylates, which have molecular weights of 2000 to 10,000 g / mol, and particularly preferably of 3000 to 5000 g / mol, may be preferred from this group.

[0070] Also suitable are polycarboxylate copolymers, particularly 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 wt.% acrylic acid and 50 to 10 wt.% maleic acid, have proven particularly suitable. Their relative molecular weight, based on the free acids, is generally 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol, and especially 30,000 to 40,000 g / mol.

[0071] The (co)polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The (co)polymeric polycarboxylate content of the automatic dishwashing detergents is preferably 0.5 to 20 wt.% and in particular 3 to 10 wt.%.

[0072] Other suitable builders are phosphonates. The complex-forming phosphonates include a series of different compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP). In this application, hydroxyalkane or aminoalkanephosphonates are particularly preferred. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, with the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably used in the form of the neutrally reacting sodium salts, e.g. B. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP.HEDP, a phosphonate class of phosphonates, is the preferred builder. Aminoalkanephosphonates also possess a pronounced heavy metal binding capacity.

[0073] Accordingly, it may be preferable to use aminoalkanephosphonates, especially DTPMP, or mixtures of the aforementioned phosphonates, especially if the detergents also contain bleach. Particular preference is given to automatic dishwashing detergents containing 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates.

[0074] Preferred detergents according to the invention contain phosphonate, particularly preferably HEDP. Preferred detergents 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 detergent. Preferred detergents according to the invention contain phosphonate, preferably HEDP, in an amount of 0.5 to 2.5 g / job, preferably 1.0 to 1.7 g / job.

[0075] The group of washing or cleaning-active polymers includes, for example, rinse aid polymers and / or polymers that act as water softeners. In general, in addition to non-ionic polymers, cationic, anionic, and amphoteric polymers can also be used in washing or cleaning agents.

[0076] The agents according to the invention can preferably contain the aforementioned cationic and / or amphoteric polymers in amounts between 0.01 and 10 wt. %, based in each case on the total weight of the washing or cleaning agent. However, within the scope of the present application, preference is given to agents in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 8 wt. %, preferably between 0.01 and 6 wt. %, preferably between 0.01 and 4 wt. %, particularly preferably between 0.01 and 2 wt. %, and in particular between 0.01 and 1 wt. %, based in each case on the total weight of the automatic dishwashing agent.

[0077] 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 essentially of natural origin; based on the natural molecules, improved versions are available for use in detergents and cleaning agents, which are therefore preferred. Detergents and cleaning agents preferably contain enzymes in total amounts of 1 x 10-6 to 5 wt.% based on active protein.

[0078] The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

[0079] The enzymes can be used in any form established according to the state of the art. These include, for example, solid preparations obtained by granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, with little water content, and / or containing stabilizers. Alternatively, the enzymes can be encapsulated for both solid and liquid dosage forms, for example by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as if in a solidified gel, or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air, and / or chemicals.

[0080] Furthermore, it is possible to package two or more enzymes together so that a single granulate exhibits multiple enzyme activities. A protein and / or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation, or degradation, for example, due to physical influences, oxidation, or proteolytic cleavage. In the case of microbial extraction of the proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents or cleaning agents can contain stabilizers for this purpose; the provision of such agents represents a preferred embodiment of the present invention.

[0081] Preferably, one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, are used in amounts of 0.1 to 5 wt.%, preferably 0.2 to 5 wt.% and in particular 0.4 to 5 wt.%, in each case based on the total enzyme-containing agent.

[0082] The agent according to the invention can be in the form of a pre-packaged single dose or portion unit. According to the invention, it is preferred that the agent be present in a water-soluble coating as a pre-packaged single dose. Furthermore, agents in a water-soluble coating as a pre-packaged 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.

[0083] The water-soluble coating can be formed by one or more water-soluble films. The water-soluble film can comprise one or more structurally different water-soluble polymer(s). Particularly suitable water-soluble polymer(s) are polymers from the group of (optionally acetalized) polyvinyl alcohols (PVAL) and their copolymers. Water-soluble films for producing the portion unit are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight 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 especially at least 70 wt.% polyvinyl alcohol or polyvinyl alcohol copolymers.The production of polyvinyl alcohol and polyvinyl alcohol copolymers generally 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 especially 82 to 88 mol%. Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester. 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 monomers that can be considered are ethylenically unsaturated dicarboxylic acids, for example itaconic acid, maleic acid, fumaric acid and mixtures thereof.

[0084] Suitable water-soluble films for use in the portion units according to the invention are films sold by MonoSol LLC, for example, under the designation M8630, M8720, M8310, C8400, or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL from Aicello Chemical Europe GmbH, or the VF-HP films from Kuraray and the Hi-Selon series from Mitsubishi Chemical Corporation.

[0085] A further subject matter of the present application is also a method for cleaning dishes in a dishwasher, comprising the steps of: a) providing a washing or rinsing liquor comprising an agent according to the invention, b) bringing the washing or rinsing liquor according to a) into contact with the dishes to be cleaned.

[0086] It is preferred according to the invention that in the process the washing or rinsing liquor according to a) has a temperature of 15 to 75 °C, preferably of 30 to 60 °C, particularly preferably of 35 to 50 °C.

[0087] According to the invention, processes are preferred in which individual ingredients or combinations of ingredients are present in specific concentration ranges. In the case of cleaning performance as considered here, this particularly relates to the concentration of builder and bleach activator. Therefore, processes are preferred in which the wash or rinse liquor contains the bleach activator according to formula (I) in concentrations of 80 to 500 ppm, preferably 120 to 400 ppm, particularly preferably 140 to 300 ppm, in particular 180 to 250 ppm. Furthermore, processes are preferred in which the wash or rinse liquor contains citrate in a concentration of 500 to 2000 ppm, preferably 700 to 1700 ppm, particularly preferably 900 to 1500 ppm. This information also refers to citrate anhydrate, e.g.

[0088] Sodium citrate anhydrate. Furthermore, processes are preferred in which the wash or rinse liquor contains phosphonate, preferably HEDP, in a concentration of 100 to 800 ppm, preferably 200 to 600 ppm, particularly preferably 250 to 500 ppm, and especially preferably 300 to 450 ppm. In preferred processes, the concentration of the bleach activator according to 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, especially preferably from 300 to 450 ppm, in the washing or rinsing liquor.

[0089] Examples of implementation:

[0090] Example 1 :

[0091] The preparation processes of the bleach-activating compounds according to formula (I) are known from WO2021 / 099244A1.

[0092] According to the procedure, 4-methyl-4-(4-((2-oxoazepan-1-yl)carbonyl)benzyl)morpholin-4-ium chloride was prepared, which is referred to as Akt1 in the following.

[0093] Table 1 :

[0094] The cleaning performance of the compositions was tested according to the IKW method (Miele GSL, program 45 8 55 at 21 °dH; IKW 2015, sofwjournal, 142, 06 / 16), using two types of tea to intensively test their performance. According to the IKW method, a comparison can only be made within one experiment, as, among other things, the soils are subject to batch variations, which can change the absolute values ​​from experiment to experiment. Table 2: avg. (tea averaged): Average of the stains, with the average of the two tea types being used in the calculation instead of both tea types. tea only: Average of the two tea results.

[0095] The cleaning performance of the inventive composition E1 on tea soils is comparable to that of the bleach catalyst-containing formula V1, or even exceeds it in the case of tea (BOP). A comparison of the inventive formulations from E4 to E1 shows that the cleaning performance on tea is improved with an increase in the proportion of the bleach activator according to formula (I) in the total amount of bleach activator.

[0096] The cleaning performance of the compositions according to the invention does not differ significantly from the cleaning performance of the comparative composition V1 with regard to other soilings.

[0097] Example 2:

[0098] Table 3:

[0099]

[0100] The cleaning performance of compositions V2, V3, and E5 was tested according to the IKW method (Miele GSL, program 45 8 55 at 21 °dH; IKW 2015, sofwjournal, 142, 06 / 16), using two types of tea to intensively test their cleaning performance. According to the IKW method, a comparison can only be made within one experiment, as, among other things, the soiling is subject to batch variations, which can change the absolute values ​​from experiment to experiment.

[0101] Table 4: avg. (tea averaged): Average of the soiling, whereby the average of the two tea types is used in the calculation instead of both tea types.

[0102] It was found that the composition according to the invention provided improved cleaning performance on both tea types compared to both composition V3 and composition V2. Furthermore, the cleaning performance on spaghetti was also superior to both V3 and V2.

[0103] Example 3:

[0104] The concentration-dependence of bleaching performance was also tested. The test was conducted according to the IKW method (Miele GSL, program 45 8 55 at 21 °dH; IKW 2015, sofwjournal, 142, 06 / 16), using two types of tea to intensively test their performance in this regard. Only the tea soils were sampled. According to the IKW method, a comparison can only be made within a single experiment because, among other things, the soils are subject to batch variations, which can alter the absolute values ​​from experiment to experiment. For this purpose, citrate-based automatic dishwashing detergents without bleach activator / bleach catalyst were used, to which TAED or Akt1 was added in the specified amounts.

[0105] Table 5:

[0106] It was shown that the cleaning performance on tea was already significantly higher at an amount of Akt1 of 1.1 mmol / job than at an amount of 3.5 mmol / job TAED.

Claims

Patent claims:

1. An automatic dishwashing detergent comprising a) citrate, b) bleaching agent, c) at least one bleach activator, wherein the detergent does not contain 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 the A for O, S, Se; Z represents an optionally substituted C1-30 alkylene, C3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene radical; X- represents 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 6independently of one another represent H, a C1-30 alkyl, C3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical; and n represents a number in the range from 1 to 2, where in the hydrocarbon radicals 1 or more non-adjacent carbon atoms not bonded to a heteroatom may be replaced by a heteroatom, in particular N, O, S and / or Se.

2. Agent according to claim 1, wherein tetraacetylethylenediamine (TAED) is used as a further bleach activator.

3. A composition according to claim 1, wherein the composition does not contain tetraacetylethylenediamine (TAED) as a further bleach activator.

4. Agent according to one of the preceding claims, wherein the agent contains 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.

5. Agent according to one of the preceding claims, wherein the bleaching agent is sodium percarbonate and the agent preferably contains sodium percarbonate in an amount of 5 to 25% by weight, particularly preferably in an amount of 10 to 20% by weight, based on the total amount of the agent.

6. Agent according to 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 represent H or a C1-alkyl radical.

7. 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.

8. A composition 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.

9. A method for cleaning dishes in a dishwasher comprising the steps of: a) providing a washing or rinsing liquor comprising an agent according to one of claims 1 to 8, b) bringing the washing or rinsing liquor according to a) into contact with the dishes to be cleaned.

10. The process according to claim 9, wherein in the process the washing or rinsing liquor according to a) has a temperature of 15 to 75 °C, preferably of 30 to 60 °C, particularly preferably of 35 to 50 °C.

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