CLEANING PRODUCTS

Description

[0001] This patent application describes cleaning agents, in particular cleaning agents for the machine cleaning of dishes. The subject matter of this application is specifically phosphate-free machine dishwashing detergents.

[0002] Today, higher standards are often placed on machine-washed dishes than on hand-washed dishes. For example, after machine washing, dishes should not only be completely free of food residue, but also free of whitish spots caused by water hardness or other mineral salts, which result from dried water droplets due to a lack of wetting agents.

[0003] Modern dishwasher detergents meet these requirements by integrating cleaning, conditioning, water-softening, and rinsing agents, and are known to consumers as "2-in-1" or "3-in-1" detergents, for example. As an essential component for both cleaning and rinsing success, dishwasher detergents intended for private consumers contain builders. These builders increase the alkalinity of the cleaning solution, thereby emulsifying and saponifying fats and oils. They also reduce the water hardness by complexing the calcium ions present in the aqueous solution. Alkali metal phosphates have proven to be particularly effective builders and therefore constitute the main component of the vast majority of commercially available dishwasher detergents.

[0004] While phosphates are highly valued for their beneficial effects as a component of machine dishwashing detergents, their use is problematic from an environmental perspective. A significant portion of phosphate enters waterways via household wastewater and plays a particularly concerning role in the eutrophication of stagnant waters (lakes, reservoirs). As a consequence of this phenomenon, also known as eutrophication, the use of pentasodium triphosphate in textile detergents has been considerably reduced by legal regulations in several countries, such as the USA, Canada, Italy, Sweden, and Norway, and completely prohibited in Switzerland. In Germany, detergents have been limited to a maximum of 20% of this building block since 1984.

[0005] In textile detergents, sodium aluminum silicates (zeolites) are primarily used as phosphate substitutes or replacements, alongside nitrilotriacetic acid. However, these substances are unsuitable for use in machine dishwashing detergents for various reasons. Therefore, a number of alternatives to alkali metal phosphates in machine dishwashing detergents are discussed in the literature, with citrates being particularly noteworthy.

[0006] Phosphate-free machine dishwashing detergents, which contain carbonates, bleach and enzymes in addition to a citrate, are described, for example, in European patents EP 662 117 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).

[0007] Another alternative to alkali metal phosphates, which is used as a sole building block, but preferably in combination with citrates, is methylglycine diacetic acid (MGDA). MGDA-containing machine dishwashing detergents are described, for example, in European patent EP 906 407 B1 (Reckitt Benckiser) and European patent application EP 1 113 070 A2 (Reckitt Benckiser). They are also used in European patent application EP 1 721 962 A1.

[0008] Despite previous efforts, manufacturers of machine dishwashing detergents have not yet succeeded in providing phosphate-free detergents that are comparable to or even surpass phosphate-containing detergents in terms of cleaning and rinsing performance, and especially in their limescale-inhibiting properties. Such performance parity is, however, a prerequisite for the successful market launch of phosphate-free detergents, since, despite widespread public discussion of environmental issues, the vast majority of consumers will always choose against an ecologically advantageous product if it does not meet market standards in terms of price and / or performance.

[0009] In view of this initial situation, the objective of the present application was therefore to provide a phosphate-free machine dishwashing detergent which is comparable to or even surpasses conventional phosphate-containing detergents in terms of its cleaning performance, rinsing results and deposit inhibition performance.

[0010] It has been found that machine dishwashing detergents containing phosphonate in addition to sulfonic acid group-containing copolymers exhibit excellent cleaning and rinsing performance even without the addition of alkali metal phosphates.

[0011] A first subject matter of the present application is therefore a phosphate-free machine dishwashing detergent containing a builder, bleaching agent, non-ionic surfactant, and furthermore a) Copolymer comprising i) sulfonic acid group-containing monomers ii) other nonionic monomers b) phosphonate, containing polycarboxylic acids as a structural material.

[0012] A first characteristic component of the compositions according to the invention are the sulfonic acid group-containing copolymers a), which, in addition to a sulfonic acid group-containing monomer, comprise at least one further ionic or non-ionic monomer. The copolymers a) can have two, three, four or more different monomer units.

[0013] For sulfonic acid group-containing monomers, those of the formula R 5< (R 6< )C=C(R 7< )-X-SO 3 H are preferred, in which R 5< to R 7< independently represent -H, -CH 3 , a straight-chain or branched saturated alkyl group with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl group with 2 to 12 carbon atoms, alkyl or alkenyl groups substituted with -NH 2 , -OH or -COOH, or -COOH or -COOR 4<, where R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon group with 1 to 12 carbon atoms, and X represents an optional spacer group selected from -(CH 2 ) n - with n = 0 to 4. -COO-(CH 2 ) k - with k = 1 to 6, -C(O)-NH-C(CH 3 ) 2 - and -C(O)-NH-CH(CH 2 CH 3 )-.

[0014] Among these monomers, those of the formulas H₂C=CH-X-SO₃H, H₂C=C(CH₃)-X-SO₃H, and HO₃SX-(R₆<)C=C(R₇<)-X-SO₃H are preferred.

[0015] in which R 6< and R 7< are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 and X represents an optionally existing spacer group selected from -(CH 2 ) n - with n = 0 to 4, -COO-(CH 2 ) k - with k = 1 to 6, -C(O)-NH-C(CH 3 ) 2 - and -C(O)-NH-CH(CH 2 CH 3 )-.

[0016] Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, metallylsulfonic acid, allyloxybenzenesulfonic acid, metallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and mixtures of the aforementioned acids or their water-soluble salts. In the polymers, the sulfonic acid groups can be present wholly or partially in neutralized form, i.e., the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and especially for sodium ions.The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

[0017] The monomer distribution of the copolymers preferably used according to the invention is, in the case of copolymers containing only monomers from groups i) and ii), preferably 5 to 95 wt.% i) and ii), respectively, and particularly preferably 50 to 90 wt.% monomer from group i) and 10 to 50 wt.% monomer from group ii), each based on the polymer.

[0018] The molar mass of the sulfo copolymers preferably used according to the invention can be varied to adapt the properties of the polymers to the desired application. Preferred machine dishwashing detergents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol⁻¹, preferably of 4000 to 25,000 gmol⁻¹, and particularly of 5000 to 15,000 gmol⁻¹.

[0019] The copolymers comprise, in addition to at least one sulfonic acid group-containing monomer, at least one non-ionic, preferably hydrophobic monomer.

[0020] Preferably, nonionic monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< are used, in which R 1< to R 3< independently represent -H, -CH 3 or -C 2 H 5, X represents an optional spacer group selected from -CH 2 -, -C(O)O- and -C(O)-NH-, and R 4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms.

[0021] A preferred subject matter of this application is therefore phosphate-free machine dishwashing detergents containing a builder, bleach, non-ionic surfactant, and furthermore a) Copolymer comprising i) sulfonic acid group-containing monomers ii) monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< , in which R 1< to R 3< independently represent -H, -CH 3 or -C 2 H 5, X represents an optional spacer group selected from -CH 2-, -C(O)O- and -C(O)-NH-, and R 4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms b) Phosphonate, containing polycarboxylic acids as a structural material.

[0022] Particularly favored nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-diemethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, and □-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, and 1-hexadecene. 1-Octadecene and C22-α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2,vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N-(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, N-(2-ethylhexyl)acrylamide, octyl acrylateMethacrylic acid octyl ester, N-(octyl)acrylamide, acrylic acid lauryl ester, methacrylic acid lauryl ester, N-(lauryl)acrylamide, acrylic acid stearyl ester, methacrylic acid stearyl ester, N-(stearyl)acrylamide, acrylic acid behenyl ester, methacrylic acid behenyl ester and N-(behenyl)acrylamide or mixtures thereof.

[0023] The second essential component of the machine dishwashing detergents according to the invention contains phosphonate. The complexing phosphonates comprise a number of different compounds, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP). In this application, hydroxyalkane and aminoalkane phosphonates are particularly preferred. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is of particular importance as a cobuilder. It is preferably used as a sodium salt, with the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and their higher homologs are preferably suitable as aminoalkane phosphonates. They are preferably used in the form of the neutral sodium salts, e.g., as the hexasodium salt of EDTMP or DTPMP.The hepta- and octa-sodium salts of DTPMP are used. HEDP, from the phosphonate class, is preferred as a builder. Aminoalkanephosphonates also possess a pronounced heavy metal binding capacity. Accordingly, especially when the products also contain bleach, it may be preferable to use aminoalkanephosphonates, particularly DTPMP, or mixtures of the aforementioned phosphonates.

[0024] A preferred machine dishwashing detergent under this application contains one or more phosphonates from the group a) Aminotrimethylenephosphonic acid (ATMP) and / or its salts; b) Ethylenediaminetetra(methylenephosphonic acid) (EDTMP) and / or its salts; c) Diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and / or its salts; d) 1-Hydroxyethane-1,1-diphosphonic acid (HEDP) and / or its salts; e) 2-Phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or its salts; f) Hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP) and / or its salts; g) Nitrilotri(methylenephosphonic acid) (NTMP) and / or its salts.

[0025] Machine dishwashing detergents containing 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred.

[0026] According to the invention, machine dishwashing detergents containing 1-hydroxyethane-1,1-diphosphonic acid (HEDP) as a phosphonate are particularly preferred.

[0027] Naturally, the machine dishwashing detergents according to the invention can contain two or more different phosphonates. Machine dishwashing detergents containing both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred, wherein the weight ratio of HEDP to DTPMP is between 20:1 and 1:20, preferably between 15:1 and 1:15, and especially between 10:1 and 1:10.

[0028] In a preferred embodiment of the present invention, the weight fraction of the phosphonate(s) b) in the total weight of the machine dishwashing detergent is less than the weight fraction of the polymer(s) a). In other words, such agents are particularly preferred in which the ratio of the weight fraction of polymer a) to the weight fraction of phosphonate b) is 200:1 to 2:1, preferably 150:1 to 2:1, particularly preferably 100:1 to 2:1, most preferably 80:1 to 3:1 and particularly preferably 50:1 to 5:1.

[0029] According to the invention, machine dishwashing detergents preferably contain one or more builders as a further essential component. These builders include, in particular, silicates, carbonates, and organic cobuilders.

[0030] Examples of organic cobuilders include polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins, and other organic cobuilders. These classes of substances are described below.

[0031] Useful organic building blocks include polycarboxylic acids, which can be used in the form of the free acid and / or its sodium salts. Polycarboxylic acids are defined as carboxylic acids that possess more than one acidic function. Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, amino acids, and nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, as well as mixtures thereof. In addition to their building block effect, free acids typically also possess the property of an acidifying component and thus serve to adjust the pH of detergents or cleaning agents to a lower and milder value. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof are particularly noteworthy in this regard.

[0032] Particularly preferred machine dishwashing detergents according to the invention contain citrate as one of their essential building blocks. Machine dishwashing detergents characterized in that they contain 5 to 60 wt.%, preferably 10 to 50 wt.%, and particularly 15 to 40 wt.% citrate are preferred according to the invention. Citrate or citric acid has proven to be the most effective building blocks, in combination with phosphonate, in particular 1-hydroxyethane-1,1-diphosphonic acid, and copolymers containing sulfonic acid groups, with regard to cleaning performance, rinsing performance, and especially deposit inhibition.

[0033] Phosphate-free machine dishwashing detergents containing 5 to 60 wt.%, preferably 10 to 50 wt.% and particularly 15 to 40 wt.% citrate, bleach, non-ionic surfactant, and furthermore a) Copolymer comprising i) sulfonic acid group-containing monomers ii) other non-ionic monomers b) phosphonate are preferred according to the invention.

[0034] Another preferred embodiment is: Phosphate-free machine dishwashing detergents containing 10 to 50 wt% citrate, bleach, non-ionic surfactant, and furthermore a) Copolymer comprising i) sulfonic acid group-containing monomers ii) monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< , in which R 1< to R 3< independently represent -H, -CH 3 or -C 2 H 5, X represents an optionally present spacer group selected from -CH 2 -, -C(O)O- and -C(O)-NH-, and R 4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms b) Phosphonate.

[0035] Preferably, machine dishwashing detergents according to the invention contain as a framework material crystalline layered silicates of the general formula NaMSi x O 2x+1 · y H 2 O, wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, wherein particularly preferred values ​​for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.

[0036] Amorphous sodium silicates with a Na2O :SiO2 modulus of 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and especially from 1:2 to 1:2.6, which are preferably dissolution-retardant and have secondary washing properties, can also be used.

[0037] Within the scope of the present invention, preferred machine dishwashing detergents contain 2 to 15 wt.%, preferably 3 to 12 wt.% and in particular 4 to 8 wt.% silicate(s).

[0038] Particularly preferred is the use of carbonate(s) and / or hydrogen carbonate(s), preferably alkali carbonate(s), particularly preferably sodium carbonate, in amounts of 5 to 50 wt.%, preferably 10 to 40 wt.% and particularly 15 to 30 wt.%, in each case based on the weight of the machine dishwashing detergent.

[0039] Polymeric polycarboxylates are also suitable as framework materials; these include, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, such as those with a relative molecular mass of 500 to 70000 g / mol.

[0040] Suitable polymers are, in particular, polyacrylates, preferably having a molecular mass of 2000 to 20000 g / mol. Due to their superior solubility, short-chain polyacrylates from this group, having molecular masses of 2000 to 10000 g / mol, and particularly preferably 3000 to 5000 g / mol, are also preferred.

[0041] Copolymer polycarboxylates are also suitable, 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 containing 50 to 90 wt% acrylic acid and 50 to 10 wt% maleic acid have proven particularly suitable. Their relative molecular mass, based on free acids, is generally 2000 to 70000 g / mol, preferably 20000 to 50000 g / mol, and particularly 30000 to 40000 g / mol.

[0042] The (co-)polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co-)polymeric polycarboxylates in machine dishwashing detergents is preferably 0.5 to 20 wt.% and particularly 3 to 10 wt.%.

[0043] Preferred machine dishwashing detergents according to the invention further contain one or more bleaching agents. Among the compounds that act as bleaching agents and release water (H₂O₂), sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate are of particular importance. Other suitable bleaching agents include, for example, peroxypyrophosphates, citrate perhydrates, and H₂O₂-releasing pericytal salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid, or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxy acids, with alkyl peroxy acids and aryl peroxy acids being particularly noteworthy examples.

[0044] Machine dishwashing detergents, characterized in that they contain 1 to 20 wt.%, preferably 2 to 15 wt.% and particularly 4 to 12 wt.% sodium percarbonate, are preferred according to the invention.

[0045] Phosphate-free machine dishwashing detergents containing builder, 1 to 20 wt.%, preferably 2 to 15 wt.% and particularly 4 to 12 wt.% sodium percarbonate, non-ionic surfactant, and furthermore a) Copolymer comprising i) sulfonic acid group-containing monomers ii) other non-ionic monomers b) phosphonate. are preferred according to the invention.

[0046] Another preferred embodiment is: Phosphate-free machine dishwashing detergents containing builder, 2 to 15 wt% sodium percarbonate, non-ionic surfactant, and furthermore a) Copolymer comprising i) sulfonic acid group-containing monomers ii) monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< , in which R 1< to R 3< independently represent -H, -CH 3 or -C 2 H 5, X represents an optional spacer group selected from -CH 2-, -C(O)O- and -C(O)-NH-, and R 4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms b) Phosphonate, containing polycarboxylic acids as a structural material.

[0047] Chlorine- or bromine-releasing substances can also be used as bleaching agents. Suitable chlorine- or bromine-releasing materials include, for example, heterocyclic N-bromoamides and N-chloroamides, such as trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid, and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin, are also suitable.

[0048] To achieve improved bleaching efficacy when cleaning at temperatures of 60 °C and below, the machine dishwashing detergents according to the invention can additionally contain bleach activators. Suitable bleach activators include compounds that, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, particularly 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances bearing O- and / or N-acyl groups of the aforementioned number of carbon atoms and / or optionally substituted benzoyl groups are suitable. Multiply acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) proving particularly suitable.

[0049] These bleach activators, in particular TAED, are preferably used in amounts up to 10 wt.%, in particular 0.1 wt.% to 8 wt.%, particularly 2 to 8 wt.% and particularly preferably 2 to 6 wt.%, in each case based on the total weight of the bleach activator-containing agents.

[0050] In addition to or instead of conventional bleaching activators, so-called bleaching catalysts can also be used. These substances are bleaching-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru, or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V, and Cu complexes with nitrogen-containing tripod ligands, as well as Co, Fe, Cu, and Ru ammine complexes, can also be used as bleaching catalysts.

[0051] Manganese complexes in oxidation states II, III, IV, or IV are particularly preferred, preferably containing one or more macrocyclic ligands with the donor functions N, NR, PR, O, and / or S. Ligands with nitrogen donor functions are especially preferred. It is particularly preferred to use bleaching catalyst(s) in the compositions according to the invention, 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).Suitable manganese complexes are, for example, [Mn III< 2 (µ-O) 1 (µ-OAc) 2 (TACN) 2 ](ClO 4 ) 2 , [Mn III< Mn IV< (µ-O) 2 (µ-OAc) 1 (TACN) 2 ](BPh 4 ) 2 , [Mn IV< 4 (µ-O) 6 (TACN) 4 ](ClO 4 ) 4 , [Mn III< 2 (µ-O) 1 (µ-OAc) 2 (Me-TACN) 2 ](ClO 4 ) 2 , [Mn III< Mn IV< (µ-O) 1 (µ-OAc) 2 (Me-TACN) 2 ](ClO 4 ) 3 , [Mn IV< 2 (µ-O) 3 (Me-TACN) 2 ](PF 6 ) 2 and [Mn IV< 2 (µ-O) 3 (Me / Me-TACN) 2 ](PF 6 ) 2 (OAc = OC(O)CH 3 ).

[0052] Machine dishwashing detergents, characterized in that they further contain a bleaching catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of manganese complexes with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since the cleaning result can be significantly improved by the aforementioned bleaching catalysts.

[0053] The aforementioned bleach-enhancing transition metal complexes, particularly those with the central atoms Mn and Co, are used in customary amounts, preferably up to 5 wt.%, particularly from 0.0025 wt.% to 1 wt.%, and most preferably from 0.01 wt.% to 0.30 wt.%, in each case based on the total weight of the bleach activator-containing agents. In special cases, however, even higher amounts of bleach activator may be used.

[0054] Surprisingly, it was found that the bleaching effect of lead catalysts from the group of bleaching-enhancing transition metal salts and transition metal complexes can be increased by the addition of hydrophobically modified acid-containing copolymers.

[0055] A preferred subject matter of this application is therefore a phosphate-free machine dishwashing detergent containing a builder, bleach, non-ionic surfactant, and furthermore a) Copolymer comprising i) sulfonic acid group-containing monomers ii) other nonionic monomers b) phosphonate c) citrate d) bleaching catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes

[0056] Some exemplary recipes for such preferred phosphate-free machine dishwashing detergents can be found in the table below: ingredient Recipe 1 [wt%] Formula 2 [wt%] Formula 3 [wt%] Recipe 4 [wt%] Citrate 5 to 60 10 to 55 15 to 50 15 to 50 Sodium percarbonate 1 to 20 2 to 15 4 to 10 4 to 10 Bleach catalyst 0.01 to 3 0.02 to 2 0.02 to 2 0.02 to 1 Copolymer 1< 0.1 to 30 0.5 to 25 1.0 to 20 1.0 to 20 Phosphonate 0.5 to 10 0.5 to 10 0.5 to 5 0.5 to 2 Non-ionic surfactant 1 to 10 2 to 8 2 to 8 3 to 6 Misc Add 100 Add 100 Add 100 Add 100 1< Copolymer comprising i) sulfonic acid group-containing monomers ii) other nonionic monomers

[0057] The compositions according to the invention further contain surfactants. The group of surfactants includes nonionic, anionic, cationic, and amphoteric surfactants.

[0058] Machine dishwashing detergents, characterized in that they contain non-ionic surfactant(s) in amounts of 1 to 10 wt.%, preferably 2 to 8 wt.% and particularly 3 to 6 wt.%, are preferred according to the invention.

[0059] All nonionic surfactants known to those skilled in the art can be used. Suitable nonionic surfactants include, for example, alkyl glycosides of the general formula RO(G) x, where R corresponds to a primary straight-chain or methyl-branched, particularly 2-position methyl-branched, aliphatic residue with 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol representing a glucose unit with 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.

[0060] Non-ionic surfactants of the amine oxide type, for example N-cocosalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides, may also be suitable. The amount of these non-ionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, and in particular not more than half of it.

[0061] Another class of preferably used non-ionic surfactants, which are used either as the sole non-ionic surfactant or in combination with other non-ionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

[0062] Weakly foaming nonionic surfactants are preferred. Washing and cleaning agents, especially those for machine dishwashing, preferably contain nonionic surfactants from the group of alkoxylated alcohols. These nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, and in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol. The alcohol residue may be linear or, preferably, methyl-branched at the 2-position, or the mixture may contain both linear and methyl-branched residues, as is commonly found in oxo alcohol residues. However, alcohol ethoxylates with linear residues derived from native alcohols with 12 to 18 carbon atoms, e.g., from coconut, palm, tallow, or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol, are particularly preferred.Preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 or 4 EO, C9-11 alcohols with 7 EO, C13-15 alcohols with 3, 5, 7, or 8 EO, C12-18 alcohols with 3, 5, 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 may correspond to a whole number or a fraction for a specific product. Preferred alcohol ethoxylates exhibit a narrow range of homologs (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

[0063] Ethoxylated niotenes obtained from C6-20 monohydroxyalkanols, C6-20 alkylphenols, or C16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles, and particularly more than 20 moles of ethylene oxide per mole of alcohol, are therefore particularly preferred. A particularly preferred niotene is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C16-20 alcohol), preferably a C18 alcohol, and at least 12 moles, preferably at least 15 moles, and particularly at least 20 moles of ethylene oxide. Among these, the so-called "narrow-range ethoxylates" are particularly preferred.

[0064] Combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are still particularly preferred.

[0065] Nonionic surfactants with a melting point above room temperature are particularly preferred. Nonionic surfactant(s) with a melting point above 20°C, preferably above 25°C, particularly preferably between 25 and 60°C, and especially between 26.6 and 43.3°C, is / are particularly preferred.

[0066] Suitable nonionic surfactants with melting or softening points within the specified temperature range include, for example, low-foaming nonionic surfactants that can be solid or highly viscous at room temperature. If nonionic surfactants that 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 particularly above 40 Pa·s. Nonionic surfactants that have a waxy consistency at room temperature are also preferred, depending on their intended use.

[0067] Niotonic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and especially from the group of EO-AO-EO niotonic surfactants, are also used with particular preference.

[0068] The niotenoid, which is solid at room temperature, preferably contains propylene oxide units in the molecule. Preferably, such PO units constitute up to 25 wt.%, particularly preferably up to 20 wt.%, and especially up to 15 wt.% of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols that additionally contain polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol content of such niotenoid molecules preferably constitutes more than 30 wt.%, particularly preferably more than 50 wt.%, and especially more than 70 wt.% of the total molar mass of such niotenoids. Preferred compositions are characterized in that they contain ethoxylated and propoxylated niotenoids in which the propylene oxide units in the molecule constitute up to 25 wt.%, preferably up to 20 wt.%, and especially up to 15 wt.% of the total molar mass of the nonionic surfactant.

[0069] Preferred surfactants come from the groups of alkoxylated niotonic 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) niotonic surfactants are also characterized by good foam control.

[0070] Other particularly preferred niotenes with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend comprising 75 wt% of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol ethylene oxide and 44 mol propylene oxide, and 25 wt% of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 mol ethylene oxide and 99 mol propylene oxide per mol trimethylolpropane.

[0071] Particularly preferred niotenes within the scope of the present invention are low-foaming niotenes having alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are preferred, wherein one to ten EO or AO groups are bonded together before a block of the other groups follows. Here, nonionic surfactants of the general formula are used.

[0072] preferably, in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 -alkyl or -alkenyl group; each group R 2< or R 3< is 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 independently represent integers from 1 to 6.

[0073] The preferred niotenes of the above formula can be prepared from the corresponding alcohols R1-OH and ethylene or alkylene oxide by known methods. The R1 group in the above formula can vary depending on the origin of the alcohol. If native sources are used, the R1 group has an even number of carbon atoms and is generally unbranched, with linear groups from native alcohols with 12 to 18 carbon atoms, e.g., from coconut, palm, tallow, or oleyl alcohol, being preferred. Alcohols accessible from synthetic sources include, for example, the Guerbet alcohols or methyl-branched groups at the 2-position, or linear and methyl-branched groups in the mixture, as are commonly found in oxo alcohol groups.Regardless of the type of alcohol used to produce the niotenes contained in the agents, niotenes are preferred in which R 1< in the above formula represents an alkyl group with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and particularly 9 to 11 carbon atoms.

[0074] In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit, which alternates with the ethylene oxide unit in the preferred niotenes. However, other alkylene oxides are also suitable, where R2 and R3 are independently selected from -CH2CH2-CH3 or -CH(CH3)2, respectively. Niotenes of the above formula are preferably used, where R2 and R3 represent a residue of -CH3, w and x independently represent values ​​of 3 or 4, and y and z independently represent values ​​of 1 or 2.

[0075] In summary, nonionic surfactants are particularly preferred which have a C9-15 alkyl group 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. These surfactants exhibit the required low viscosity in aqueous solution and are particularly advantageous for use according to the invention.

[0076] 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 represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 alkyl or -alkenyl group; A, A', A" and A‴ independently represent a group from the set -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH(CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH(CH 3 )-CH 2 -, -CH 2 -CH(CH 2 -CH 3 ); 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.

[0077] Particularly preferred are end-group-capped poly(oxyalkylated) niotenes which, according to the formula R 1< O[CH 2 CH 2 O] x CH 2 CH(OH)R 2< , in addition to a residue R 1< , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, further comprise a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue R 2< with 1 to 30 carbon atoms, where x represents values ​​between 1 and 90, preferably values ​​between 30 and 80 and particularly values ​​between 30 and 60.

[0078] Particularly preferred are surfactants of the formula R 1< O[CH 2 CH(CH 3 )O] x [CH 2 CH 2 O] y CH 2 CH(OH)R 2< , in which R 1< represents a linear or branched aliphatic hydrocarbon residue with 4 to 18 carbon atoms or mixtures thereof, R 2< represents a linear or branched hydrocarbon residue with 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.

[0079] By using the previously described non-ionic surfactants with a free hydroxyl group on one of the two terminal alkyl groups, the formation of deposits during machine dishwashing can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

[0080] Particularly preferred are end-group-capped poly(oxyalkylated) niotenes 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 R 2< independently represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon residue with 2 to 26 carbon atoms, R 3< is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH(CH 3 ) 2 , preferably, however, represents -CH 3, and x and y independently represent values ​​between 1 and 32, wherein niotenes with R 3< = -CH 3 and values ​​for x from 15 to 32 and y from 0.5 and 1.5 are particularly preferred.

[0081] Other preferably usable niotenes are the end-capped poly(oxyalkylated) niotenes of the formula R 1< O[CH 2 CH(R 3< )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2< , in which R 1< and R 2< represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 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 residue, 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[CH 2 CH(R 3< )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2< can be different. R 1< and R 2< are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 6 to 22 carbon atoms, with residues having 8 to 18 carbon atoms being particularly preferred.For the remainder R 3<, H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values ​​for x are in the range of 1 to 20, especially from 6 to 15.

[0082] As described above, each R3< in the formula above can be different if x ≥ 2. This allows the alkylene oxide unit within the square brackets to be varied. For example, if x represents 3, the R3< group can be chosen to form ethylene oxide (R3<= H) or propylene oxide (R3<= CH3) units, which can be joined together in any order, such as (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO), and (PO)(PO)(PO). The value 3 for x is chosen here as an example and can certainly be larger, with the range of variation increasing with increasing x values ​​and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.

[0083] Particularly preferred end-capped poly(oxyalkylated) alcohols of the formula above have values ​​of k = 1 and j = 1, so that the above formula simplifies to R1< O[CH2CH(R3< )O] x CH2CH(OH)CH2OR2<. In the latter formula, R1<, R2<, and R3< are defined as above, and x represents numbers from 1 to 30, preferably from 1 to 20, and particularly from 6 to 18. Surfactants in which the R1< and R2< groups have 9 to 14 carbon atoms, R3< represents hydrogen, and x takes on values ​​from 6 to 15 are particularly preferred.

[0084] The stated carbon chain lengths and degrees of ethoxylation or alkoxylation of the aforementioned niotenes represent statistical averages, which may be whole numbers or fractions for a specific product. Due to the manufacturing processes, commercial products of the given formulas usually do not consist of a single individual compound, but rather of mixtures, which can result in average values ​​and consequently fractions for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.

[0085] Naturally, the aforementioned non-ionic surfactants can be used not only as single substances but also as surfactant mixtures of two, three, four, or more surfactants. Surfactant mixtures, in this context, do not refer to mixtures of non-ionic surfactants that, as a whole, fall under one of the general formulas mentioned above, but rather to mixtures containing two, three, four, or more non-ionic surfactants that can be described by different general formulas mentioned above.

[0086] Phosphate-free machine dishwashing detergent containing builder, bleach, non-ionic surfactant in amounts of 1 to 10 wt.%, preferably 2 to 8 wt.% and particularly 3 to 6 wt.%, and furthermore a) Copolymer comprising i) sulfonic acid group-containing monomers ii) other non-ionic monomers b) phosphonate, wherein it contains polycarboxylic acids as a framework material, are preferred according to the invention.

[0087] Another preferred embodiment is: Phosphate-free machine dishwashing detergents, containing a builder, bleach, 2 to 8 wt% non-ionic surfactant, and furthermore a) copolymer, comprising i) sulfonic acid group-containing monomers ii) monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< , in which R 1< to R 3< independently represent -H, -CH 3 or -C 2 H 5, X represents an optional spacer group selected from -CH 2-, -C(O)O- and -C(O)-NH-, and R 4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms b) phosphonate, wherein they contain polycarboxylic acids as a builder.

[0088] When anionic surfactants are used as a component of machine dishwashing detergents, their content, based on the total weight of the detergent, is preferably less than 4% by weight, more preferably less than 2% by weight, and most preferably less than 1% by weight. Machine dishwashing detergents that do not contain anionic surfactants are particularly preferred.

[0089] Cationic and / or amphoteric surfactants can also be used instead of or in combination with the surfactants mentioned above.

[0090] In summary, the following base formulations are particularly preferred due to their outstanding cleaning and rinsing results: Phosphate-free machine dishwashing detergents, containing a builder, 2 to 15 wt% sodium percarbonate, 2 to 8 wt% non-ionic surfactant, and further comprising: a) copolymer, comprising: i) sulfonic acid group-containing monomers; ii) monomers of the general formula R1< (R2< )C=C(R3< )-XR4< , in which R1< to R3< independently represent -H, -CH3 or -C2H5, X represents an optional spacer group selected from -CH2-, -C(O)O- and -C(O)-NH-, and R4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms; b) phosphonate, wherein they contain polycarboxylic acids as a builder. as well as phosphate-free machine dishwashing detergents containing 10 to 50 wt% citrate, 2 to 15 wt% sodium percarbonate, 2 to 8 wt.-% non-ionic surfactant, and furthermore a) copolymer, comprising i) sulfonic acid group-containing monomers ii) monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< , in which R 1< to R 3< independently represent -H, -CH 3 or -C 2 H 5, X represents an optionally present spacer group selected from -CH 2-, -C(O)O- and -C(O)-NH-, and R 4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms b) phosphonate. .

[0091] Preferred machine dishwashing detergents according to the invention have proven to be particularly effective with regard to optimal cleaning and rinsing results as well as optimal deposit inhibition, in which the weight fraction of the copolymer a) is 4 to 18 wt.%, preferably 6 to 15 and in particular 6 to 12 wt.%.

[0092] Machine dishwashing detergents in which the weight fraction of phosphonate b) is 0.5 to 10 wt.%, preferably 0.5 to 5 wt.% and particularly 0.5 to 2 wt.%, also exhibit particularly good cleaning and rinsing results and are therefore preferred according to the invention.

[0093] Phosphate-free dishwasher detergents containing phosphate are therefore particularly preferred. a) 6 to 15 wt% copolymer comprising i) sulfonic acid group-containing monomers ii) monomers of the general formula R1< (R2< )C=C(R3< )-XR4< , in which R1< to R3< independently represent -H, -CH3 or -C2H5, X represents an optional spacer group selected from -CH2-, -C(O)O- and -C(O)-NH-, and R4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms b) 0.5 to 5 wt% 1-hydroxyethane-1,1-diphosphonic acid c) 10 to 50 wt% citrate d) 2 to 15 wt% sodium percarbonate e) 2 to 8 wt% non-ionic surfactant

[0094] In a further preferred embodiment, the copolymers a) comprise, in addition to the sulfonic acid group-containing monomers, ionic and non-ionic monomers.

[0095] Phosphate-free machine dishwashing detergent containing builder, bleach, non-ionic surfactant, and further ingredients. a) Copolymer comprising i) sulfonic acid group-containing monomers ii) other ionic monomers iii) non-ionic monomers b) phosphonate, wherein they contain polycarboxylic acids as a structural material, are preferred according to the invention.

[0096] These terpolymers are particularly advantageous as carboxyl group-containing monomers.

[0097] A particularly preferred subject matter of the present application is therefore a phosphate-free machine dishwashing detergent containing a builder, bleaching agent, non-ionic surfactant, and furthermore a) Copolymer comprising i) sulfonic acid group-containing monomers ii) carboxyl group-containing monomers iii) non-ionic monomers b) phosphonate, containing polycarboxylic acids as a structural material.

[0098] In a final preferred embodiment, the copolymers contain, in addition to at least one sulfonic acid group-containing monomer, a carboxyl group-containing monomer and, as nonionic monomers, corresponding monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< , in which R 1< to R 3< independently represent -H, -CH 3 or -C 2 H 5, X represents an optionally present spacer group selected from -CH 2 -, -C(O)O- and -C(O)-NH-, and R 4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic, group with 6 to 22 carbon atoms.

[0099] In summary, phosphate-free machine dishwashing detergents are preferred, which, in addition to builder, bleach and non-ionic surfactant, also contain a) Copolymer comprising i) sulfonic acid group-containing monomers ii) carboxyl group-containing monomers iii) monomers of the general formula R1< (R2< )C=C(R3< )-XR4< , in which R1< to R3< independently represent -H, -CH3 or -C2H5, X represents an optional spacer group selected from -CH2-, -C(O)O- and -C(O)-NH-, and R4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms b) Phosphonate They contain polycarboxylic acids as a structural component.

[0100] Preferred machine dishwashing detergents containing terpolymers include, in particular: Phosphate-free machine dishwashing detergents containing a) 6 to 15 wt% copolymer comprising i) sulfonic acid group-containing monomers ii) carboxyl group-containing monomers ii) non-ionic monomers b) 0.5 to 5 wt% phosphonate c) 10 to 50 wt% citrate d) 2 to 15 wt% sodium percarbonate e) 2 to 8 wt% non-ionic surfactant

[0101] In addition to the ingredients described above, such as the builder, the bleaching agent, the non-ionic surfactant, the copolymer a) and the phosphonate, preferred machine dishwashing detergents contain further ingredients, preferably active ingredients from the group of polymers, enzymes, corrosion inhibitors, fragrances or dyes.

[0102] Examples of washing- or cleaning-active polymers include rinse aid polymers and / or polymers that act as water softeners. Generally, in addition to nonionic polymers, cationic, anionic, and amphoteric polymers can also be used in washing or cleaning agents.

[0103] "Cationic polymers" within the meaning of the present invention are polymers that carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl)ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers are those from the groups of quaternary cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, copolymers of vinylpyrrolidone with quaternary derivatives of dialkylaminoacrylate and methacrylate, vinylpyrrolidone-methoimidazolinium chloride copolymers, quaternary polyvinyl alcohols, or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18, and Polyquaternium 27.

[0104] "Amphoteric polymers" as defined in the present invention, in addition to a positively charged group in the polymer chain, also have negatively charged groups or monomer units. These groups can be, for example, carboxylic acids, sulfonic acids, or phosphonic acids.

[0105] Preferred washing or cleaning agents, in particular preferred machine dishwashing detergents, are characterized in that they contain a polymer a) which has monomer units of the formula R 1< R 2< C=CR 3< R 4<, in which each residue R 1< , R 2< , R 3< , R 4< is independently selected from hydrogen, derivatized hydroxyl group, C 1-30 linear or branched alkyl groups, aryl, aryl-substituted C 1-30 linear or branched alkyl groups, polyalcoxylated alkyl groups, heteroatomic organic groups with at least one positive charge without charged nitrogen, at least one quaternary N atom or at least one amino group with a positive charge in the subrange of the pH range from 2 to 11, or salts thereof, with the proviso that at least one residue R 1< , R 2< , R 3< , R 4< is a heteroatomic organic group with at least one positive charge without charged nitrogen,at least one quaternary nitrogen atom or at least one amino group with a positive charge.

[0106] Within the scope of the present application, particularly preferred cationic or amphoteric polymers contain as a monomer unit a compound of the general formula where R1< and R4< independently represent H or a linear or branched hydrocarbon residue with 1 to 6 carbon atoms; R2< and R3< independently represent an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl residue is linear or branched and has between 1 and 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X□< represents a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate, xylenesulfonate, phosphate, citrate, formate, acetate, or mixtures thereof.

[0107] Preferred residues R1< and R4< in the above formula are selected from -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, and -(CH2CH2-O)nH.

[0108] Polymers with a cationic monomer unit of the above general formula, where R<1 and R<4 represent H, R<2 and R<3 represent methyl, and x and y are each 1, are particularly preferred. The corresponding monomer unit of the formula H2C=CH-(CH2)-N+(CH3)2-(CH2)-CH=CH2X- is also referred to as DADMAC (diallyldimethylammonium chloride) in the case of X-.

[0109] Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula R 1< HC=CR 2< -C(O)-NH-(CH 2 ) x -N +< R 3< R 4< R 5< X -< ,

[0110] in which R 1< , R 2< , R 3< , R 4< and R 5< independently of each other represents a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl group with 1 to 6 carbon atoms, preferably a linear or branched alkyl group selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH(CH 3 )-CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH(OH)-CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH(OH)-CH 3 , -CH(OH)-CH 2 -CH 3 , and -(CH 2 CH 2 -O) n H and x represents an integer between 1 and 6.

[0111] Particularly preferred within the scope of the present application are polymers comprising a cationic monomer unit of the above general formula, where R<1< represents H and R<2<, R<3<, R<4< and R<5< represent methyl, and x represents 3. The corresponding monomer units of the formula H2C=C(CH3)-C(O)-NH-(CH2)x-N<+<(CH3)3X- are also referred to as MAPTAC (methylacrylamidopropyltrimethylammonium chloride) in the case of X-<<>-= chloride.

[0112] According to the invention, polymers are preferably used which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

[0113] The aforementioned amphoteric polymers possess not only cationic groups but also anionic groups or monomer units. Such anionic monomer units originate, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates, or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units include acrylic acid, (meth)acrylic acid, (dimethyl)acrylic acid, (ethyl)acrylic acid, cyanoacrylic acid, vinylacetic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and their derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid, or allylphosphonic acids.

[0114] Preferred amphoteric polymers for use are from the group of alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methyl methacrylic acid copolymers, alkylacrylamide / acrylic acid / alkyl aminoalkyl(meth)acrylic acid copolymers, alkylacrylamide / methacrylic acid / alkyl aminoalkyl(meth)acrylic acid copolymers, alkylacrylamide / methyl methacrylic acid / alkyl aminoalkyl(meth)acrylic acid copolymers, alkyl acrylamide / alkyl methacrylate / alkyl aminoethyl methacrylate / alkyl methacrylate copolymers, and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids, and optionally further ionic or nonionic monomers.

[0115] Preferred zwitterionic polymers are derived from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts, and methacroylethyl betaine / methacrylate copolymers.

[0116] Amphoteric polymers are still preferred, which, in addition to one or more anionic monomers, comprise methacrylamidoalkyl-trialkylammonium chloride and dimethyl(diallyl)ammonium chloride as cationic monomers.

[0117] Particularly preferred amphoteric polymers come from the group of methacrylamidoalkyl-trialkylammonium chloride / dimethyl(diallyl)ammonium chloride / acrylic acid copolymers, methacrylamidoalkyltrialkylammonium chloride / dimethyl(diallyl)ammonium chloride / methacrylic acid copolymers and methacrylamidoalkyltrialkylammonium chloride / dimethyl(diallyl)ammonium chloride / alkyl-(meth)acrylic acid copolymers as well as their alkali and ammonium salts.

[0118] Particularly preferred are amphoteric polymers from the group consisting of methacrylamidopropyltrimethylammonium chloride / dimethyl(diallyl)ammonium chloride / acrylic acid copolymers, methacrylamidopropyltrimethylammonium chloride / dimethyl(diallyl)ammonium chloride / acrylic acid copolymers and methacrylamidopropyltrimethylammonium chloride / dimethyl(diallyl)ammonium chloride / alkyl-(meth)acrylic acid copolymers, as well as their alkali and ammonium salts.

[0119] In a particularly preferred embodiment of the present invention, the polymers are in pre-assembled form. Among other things, the following are suitable for assembling the polymers: the encapsulation of the polymers by means of water-soluble or water-dispersible coating agents, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30°C; the cogranulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing or cleaning active substances, particularly preferably from the group of builders or cobuilders.

[0120] Washing or cleaning agents preferably contain the aforementioned cationic and / or amphoteric polymers in amounts between 0.01 and 10 wt.%, based on the total weight of the washing or cleaning agent. However, within the scope of this application, washing or cleaning agents are preferred 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.%, more preferably between 0.01 and 4 wt.%, particularly preferably between 0.01 and 2 wt.%, and especially between 0.01 and 1 wt.%, based on the total weight of the machine dishwashing detergent.

[0121] Enzymes can be used to increase the washing or cleaning performance of detergents or cleaning agents. These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are essentially of natural origin; however, improved versions based on the natural molecules are available for use in detergents or cleaning agents and are therefore preferred. 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 using known methods, for example, the BCA method or the biuret method.

[0122] Among the proteases, those of the subtilisin type are favored. Examples include the subtilisins BPN' and Carlsberg, as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, and the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are to be classified as subtilases but no longer as subtilisins in the narrower sense.

[0123] Examples of amylases that can be used according to the invention are the α-amylases from Bacillus licheniformis, out of B. amyloliquefaciens, out of B. stearothermophilus, out of Aspergillus niger and A. oryzae as well as the improved developments of the aforementioned amylases for use in detergents and cleaning agents. Furthermore, the α-amylase from [missing information] is suitable for this purpose. Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) to be highlighted.

[0124] Lipases or cutinases can also be used according to the invention, particularly because of their triglyceride-cleaving activities, but also to produce suitable precursors. in situ to produce peracids. These include, for example, those originally from Humicola lanuginosa ( Thermomyces lanuginosus ) available or further developed lipases, especially those with the amino acid substitution D96L. Furthermore, cutinases, for example, which originally came from Fusarium solani pisi and Humicola insolens have been isolated. Lipases or cutinases, whose starting enzymes originally came from, can also be used. Pseudomonas mendocina and Fusarium solanii have been isolated.

[0125] Furthermore, enzymes collectively known as hemicellulases can be used. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases, and β-glucanases.

[0126] To enhance the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases), can be used according to the invention. Advantageously, preferably organic, and especially aromatic, compounds that interact with the enzymes are added to enhance the activity of the respective oxidoreductases (enhancers) or to ensure electron flow in cases of significantly different redox potentials between the oxidizing enzymes and the contaminants (mediators).

[0127] The enzymes can be used in any form established according to the state of the art. This includes, for example, solid preparations obtained by granulation, extrusion or lyophilization, or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with low water content and / or containing stabilizers.

[0128] 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, such as those in which the enzymes are enclosed as if in a solidified gel, or in core-shell type capsules in which an enzyme-containing core is coated with a protective layer impermeable to water, air, and / or chemicals. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are produced using methods known per se, for example, by shake or roll granulation or in fluid-bed processes. Advantageously, such granules are low-dust, for example, due to the application of polymeric film formers, and have a long shelf life due to the coating.

[0129] Furthermore, it is possible to combine two or more enzymes so that a single granule has multiple enzyme activities.

[0130] A protein and / or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation, or degradation caused by physical influences, oxidation, or proteolytic cleavage. When proteins and / or enzymes are produced microbially, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Washing or cleaning agents can contain stabilizers for this purpose; the provision of such agents represents a preferred embodiment of the present invention.

[0131] 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.

[0132] Phosphate-free dishwasher detergents containing phosphate are therefore particularly preferred. a) 6 to 15 wt% copolymer comprising i) sulfonic acid group-containing monomers ii) monomers of the general formula R1< (R2< )C=C(R3< )-XR4< , in which R1< to R3< independently represent -H, -CH3 or -C2H5, X represents an optional spacer group selected from -CH2-, -C(O)O- and -C(O)-NH-, and R4< represents a straight-chain or branched saturated alkyl group having 2 to 22 carbon atoms or an unsaturated, preferably aromatic group having 6 to 22 carbon atoms b) 0.5 to 5 wt% 1-hydroxyethane-1,1-diphosphonic acid c) 10 to 50 wt% citrate d) 2 to 15 wt% sodium percarbonate e) 2 to 8 wt% non-ionic surfactant f) 1.0 to 6 wt% enzyme. or

[0133] Phosphate-free machine dishwashing detergents containing a) 6 to 15 wt% copolymer comprising i) sulfonic acid group-containing monomers ii) carboxyl group-containing monomers of the formula R1< (R2< )C=C(R3< )COOH, in which R1< to R3< independently represent -H, -CH3, a straight-chain or branched saturated alkyl group with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl group with 2 to 12 carbon atoms, alkyl or alkenyl groups substituted with -NH2, -OH or -COOH as defined above, or -COOH or -COOR4<, wherein R4< is a saturated or unsaturated, straight-chain or branched hydrocarbon group with 1 to 12 carbon atoms iii) monomers of the general formula R1< (R2< )C=C(R 3< )-XR 4< , in which R 1< to R 3< independently represent -H, -CH 3 or -C 2 H 5, X represents an optional spacer group selected from -CH 2 -, -C(O)O- and -C(O)-NH-,and R 4< for a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or for an unsaturated, preferably aromatic group with 6 to 22 carbon atoms stands b) 0.5 to 5 wt.% 1-hydroxyethane-1,1-diphosphonic acid c) 10 to 50 wt.% citrate d) 2 to 15 wt.% sodium percarbonate e) 2 to 8 wt.% nonionic surfactant f) 1.0 to 6 wt.% enzyme. ,

[0134] Some exemplary recipes for such preferred phosphate-free machine dishwashing detergents can be found in the following tables: ingredient Formula 5 [wt%] Formula 6 [wt%] Recipe 7 [wt%] Formula 8 [wt%] Citrate 5 to 60 10 to 55 15 to 50 15 to 50 Sodium percarbonate 1 to 20 2 to 15 4 to 10 4 to 10 enzyme 0.1 to 6 0.2 to 5 0.4 to 5 0.4 to 5 Copolymer 1< 0.1 to 30 0.5 to 25 1.0 to 20 1.0 to 20 Phosphonate 0.5 to 10 0.5 to 10 0.5 to 5 0.5 to 2 Non-ionic surfactant 1 to 10 2 to 8 2 to 8 3 to 6 Misc Add 100 Add 100 Add 100 Add 100 ingredient Formula 9 [wt%] Formula 10 [wt%] Formula 11 [wt%] Formula 12 [wt%] Citrate 5 to 60 10 to 55 15 to 50 15 to 50 Carbonate / Bicarbonate 2 to 40 2 to 40 2 to 40 2 to 40 silicate 0 to 15 0 to 15 0 to 15 0.1 to 10 Phosphonate 0 to 14 0 to 14 0 to 14 2 to 8 Sodium percarbonate 1 to 20 2 to 15 4 to 10 4 to 10 Bleach catalyst 0.01 to 3 0.02 to 2 0.02 to 2 0.02 to 1 Copolymer 1< 0.1 to 30 0.5 to 25 1.0 to 20 1.0 to 20 Phosphonate 0.5 to 10 0.5 to 10 0.5 to 5 0.5 to 2 Non-ionic surfactant 1 to 10 2 to 8 2 to 8 3 to 6 enzyme 0.1 to 6 0.2 to 5 0.4 to 5 0.4 to 5 Misc Add 100 Add 100 Add 100 Add 100 1< Copolymer comprising i) sulfonic acid group-containing monomers ii) nonionic monomers

[0135] Glass corrosion inhibitors prevent the formation of cloudiness, streaks, and scratches, as well as iridescence, on the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors belong to the group of magnesium and zinc salts and magnesium and zinc complexes.

[0136] The spectrum of zinc salts preferred according to the invention, preferably of organic acids, particularly preferably of organic carboxylic acids, ranges from salts that are sparingly or insoluble in water, i.e., exhibiting a solubility below 100 mg / l, preferably below 10 mg / l, and particularly below 0.01 mg / l, to those salts that exhibit a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l, and particularly above 5 g / l (all solubilities at a water temperature of 20°C). Examples of zinc salts belonging to the first group include zinc citrate, zinc oleate, and zinc stearate; examples of zinc formate, zinc acetate, zinc lactate, and zinc gluconate belong to the group of soluble zinc salts.

[0137] A zinc salt of an organic carboxylic acid is particularly preferred as a glass corrosion inhibitor, especially a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate, and zinc citrate. Zinc ricinoleate, zinc abitate, and zinc oxalate are also preferred.

[0138] Within the scope of the present invention, the zinc salt content in washing or cleaning agents is preferably between 0.1 and 5 wt.%, preferably between 0.2 and 4 wt.% and in particular between 0.4 and 3 wt.%, or the zinc content in oxidized form (calculated as Zn 2+< ) is between 0.01 and 1 wt.%, preferably between 0.02 and 0.5 wt.% and in particular between 0.04 and 0.5 wt.%, in each case based on the total weight of the glass corrosion inhibitor-containing agent.

[0139] Corrosion inhibitors serve to protect the items being washed or the machine, with silver preservatives being of particular importance in the field of machine dishwashing. Known substances from the prior art can be used. In general, silver preservatives selected from the group consisting of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and transition metal salts or complexes can be used. Benzotriazole and / or alkylaminotriazole are particularly preferred. According to the invention, 3-amino-5-alkyl-1,2,4-triazoles or their physiologically compatible salts are preferably used, with these substances being particularly preferred in a concentration of 0.001 to 10 wt.%, preferably 0.0025 to 2 wt.%, and most preferably 0.01 to 0.04 wt.%.

[0140] To facilitate the disintegration of pre-molded components, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these components to shorten the disintegration times.

[0141] These substances, also known as "explosive" agents due to their effect, increase in volume upon contact with water. This occurs both through swelling and the release of gases, which can generate pressure that causes the tablet to break down into smaller particles. Well-known disintegration agents include carbonate / citric acid systems, although other organic acids can also be used. Examples of swelling disintegration agents include synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates, or casein derivatives.

[0142] Disintegration aids are preferably used in amounts of 0.5 to 10 wt.%, preferably 3 to 7 wt.% and in particular 4 to 6 wt.%, in each case based on the total weight of the agent containing the disintegration aid.

[0143] Preferred disintegration agents are cellulose-based, such that preferred washing or cleaning agents contain such a cellulose-based disintegration agent in amounts of 0.5 to 10 wt.%, preferably 3 to 7 wt.%, and particularly 4 to 6 wt.%. The cellulose used as a disintegration aid is preferably not used in finely particled form, but rather converted into a coarser form before being added to the premixes to be pressed, for example, by granulation or compaction. The particle sizes of such disintegration agents are mostly above 200 µm, preferably at least 90 wt.% between 300 and 1600 µm, and particularly at least 90 wt.% between 400 and 1200 µm.

[0144] Preferred disintegration aids, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, are contained in the disintegration agent-containing agents in amounts of 0.5 to 10 wt.%, preferably 3 to 7 wt.% and particularly 4 to 6 wt.%, in each case based on the total weight of the disintegration agent-containing agent.

[0145] Furthermore, according to the invention, gas-generating effervescent systems can preferably be used as tablet disintegration aids. The gas-generating effervescent system can consist of a single substance that releases a gas upon contact with water. Among these compounds, magnesium peroxide, which releases oxygen upon contact with water, is particularly noteworthy. However, preferred effervescent systems consist of at least two components that react with each other to form gas, for example, alkali metal carbonate and / or bicarbonate, and an acidifying agent suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution. Examples of suitable acidifying agents that release carbon dioxide from the alkali salts in aqueous solution include boric acid, alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates, and other inorganic salts.Organic acidifying agents are preferred, with citric acid being a particularly preferred acidifying agent. Acidifying agents in effervescent systems from the group of organic di-, tri-, and oligocarboxylic acids or mixtures thereof are preferred.

[0146] Within the scope of the present invention, individual odorant compounds, such as synthetic products of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type, can be used as perfume oils or fragrances. However, mixtures of different odorants that together produce an appealing fragrance are preferred. Such perfume oils can also contain natural odorant mixtures, such as those available from plant sources, for example, pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil.

[0147] The fragrances can be processed directly, but it can also be advantageous to apply them to carriers that ensure a longer-lasting fragrance through slower release. Cyclodextrins, for example, have proven effective as such carrier materials, and the cyclodextrin-perfume complexes can also be coated with other additives.

[0148] Preferred dyes, the selection of which presents no difficulty to the expert, possess high storage stability and insensitivity to the other ingredients of the products and to light, as well as no pronounced substantivity towards the substrates to be treated with the dye-containing products, such as textiles, glass, ceramics or plastic tableware, in order not to stain them.

[0149] The machine dishwashing detergents according to the invention can be packaged in solid or liquid form, but can also be offered, for example, as a combination of solid and liquid forms.

[0150] Suitable solid dosage forms include powders, granules, extrudates, or compacts, especially tablets. Liquid dosage forms based on water and / or organic solvents can be thickened or presented as gels.

[0151] The inventive agents can be formulated as single-phase or multi-phase products. Machine dishwashing detergents with one, two, three, or four phases are particularly preferred. Machine dishwashing detergents characterized in that they are in the form of a pre-assembled dosing unit with two or more phases are especially preferred.

[0152] The individual phases of multiphase agents can have the same or different states of matter. Machine dishwashing detergents are particularly preferred if they have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase.

[0153] According to the invention, machine dishwashing detergents are preferably pre-packaged into dosing units. These dosing units preferably comprise the amount of washing or cleaning active substances necessary for one cleaning cycle. Preferred dosing units have a weight between 12 and 30 g, preferably between 14 and 26 g, and particularly between 15 and 22 g.

[0154] The volume and shape of the aforementioned dosing units are preferably selected to ensure that the pre-assembled units can be dispensed via the dosing chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, more preferably between 12 and 30 ml, and particularly between 15 and 25 ml.

[0155] The machine dishwashing detergents according to the invention, in particular the pre-made dosing units, preferably have a water-soluble coating.

[0156] The present application further relates to a method for cleaning dishes in a dishwasher using machine-based dishwashing agents according to the invention, wherein the machine-based dishwashing agents are preferably dosed into the interior of a dishwasher during the execution of a dishwashing program, before the start of the main wash cycle, or during the main wash cycle. The dosing or introduction of the agent according to the invention into the interior of the dishwasher can be carried out manually; however, preferably the agent is dosed into the interior of the dishwasher by means of the dosing chamber of the dishwasher. Preferably, no additional water softener or rinse aid is dosed into the interior of the dishwasher during the cleaning process.

[0157] As described at the outset, the compositions according to the invention are distinguished from conventional machine dishwashing detergents by an improved rinsing effect. The use of a machine dishwashing detergent according to the invention as a rinse aid in machine dishwashing is therefore a further subject matter of the present application. Examples

[0158] In a first cleaning test, soiled dishes were washed in a dishwasher with 21 g of a commercially available phosphate-containing machine dishwashing detergent V1 or 21 g of the three phosphate-free machine dishwashing detergents V2, V3 and E1 at a water hardness of 21°dH.

[0159] The composition of the dishwashing detergents used can be found in the following table: raw material V1 V2 V3 E1 phosphate 33 -- -- -- Citrate -- 23 23 23 MGDA -- 8,0 8,0 8,0 Copolymer 1< 12,0 12,0 -- 12,0 HEDP 2,0 -- 2,0 2,0 soda 28,0 28,0 28,0 28,0 Sodium percarbonate 10,0 10,0 10,0 10,0 TAED 2,4 2,4 2,4 2,4 Protease / Amylase 4,0 4,0 4,0 4,0 Non-ionic surfactant 5,0 5,0 5,0 5,0 Misc Add 100 Add 100 Add 100 Add 100 1< Sulfonic acid group-containing copolymer

[0160] The overall appearance of the washed items was assessed using the rating scale listed below. The results are given in the table below (the values ​​shown are averages of 3 trials): V1 V2 V3 E1 Cleaning result 8,1 6,9 7,5 8,2

[0161] Cleaning rating scale: 10 = no contamination to 0 = heavy contamination (average of seven specific types of soiling)

[0162] In a second experiment to determine the formation of deposits, unsoiled dishes were washed in a continuously operated dishwasher with 21 g of a commercially available phosphate-containing machine dishwashing detergent V1 or 21 g of the three phosphate-free machine dishwashing detergents V2, V3 and E1 at a water hardness of 21°dH.

[0163] The overall appearance of the washed items was assessed using the rating scale listed below. The results are given in the table below (the values ​​shown are averages of 3 trials): V1 V2 V3 E1 Deposit formation Porcelain 3.5 Porcelain 1.0 Porcelain 2.5 Porcelain 3.0 Plastic 4.2 Plastic 1.0 Plastic 3.0 Plastic 4.5 Rating scale for deposit formation: 10 = no deposit formation to 0 = heavy deposit formation;

Claims

1. Phosphate-free automatic dishwashing detergent containing builder, bleaching agent, non-ionic surfactant, and furthermore a) copolymer including i) Monomers containing sulfonic acid groups ii) further non-ionic monomers b) phosphonate, characterized in that it contains polycarboxylic acids as a builder.

2. Automatic dishwashing detergent according to claim 1, characterized in that the proportion by weight of copolymer a) is from 4 to 18% by weight, preferably from 6 to 15% by weight and in particular from 6 to 12% by weight.

3. Automatic dishwashing detergent according to one of the preceding claims, characterized in that the copolymer a) contains i) Monomers containing sulfonic acid groups ii) Monomers of the general formula R1(R2)C=C(R3)-X-R4, in which R1 to R3 independently of one another represent -H, -CH3 or -C2H5, X represents an optionally present spacer group which is selected from -CH2-, -C(O)O- and -C(O)-NH-, and R4 represents a linear or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

4. Automatic dishwashing detergent according to one of the preceding claims, characterized in that the proportion by weight of the phosphonate b) is 0.5 to 10% by weight, preferably 0.5 to 5% by weight and in particular 0.5 to 2% by weight.

5. The automatic dishwashing detergent according to any one of the preceding claims, characterized in that the phosphonate is 1-hydroxyethane-1,1-diphosphonic acid (HEDP).

6. Automatic dishwashing detergent according to one of the preceding claims, characterized in that it contains 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight of citrate7. Automatic dishwashing detergent according to one of the preceding claims, characterized in that it contains 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 12% by weight of sodium percarbonate.

8. Automatic dishwashing detergent according to one of the preceding claims, characterized in that it contains the nonionic surfactant in amounts of 1 to 10% by weight, preferably 2 to 8% by weight and in particular 3 to 6% by weight.

9. The automatic dishwashing detergent according to any one of the preceding claims, comprising a) 6 to 15 % by weight of copolymer comprising i) Monomers containing sulfonic acid groups ii) Monomers of the general formula R1(R2)C=C(R3)-X-R4, in which R1 to R3 independently of one another represent -H, -CH3 or -C2H5, X represents an optionally present spacer group which is selected from -CH2-, -C(O)O- and -C(O)-NH-, and R4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms b) 0.5 to 5 % by weight of 1-hydroxyethane-1,1-diphosphonic acid c) 10 to 50 % by weight citrate d) 2 to 15 % by weight sodium percarbonate e) 2 to 8 % by weight non-ionic surfactant10. A machine dishwashing detergent according to any one of the preceding claims, comprising a) 6 to 15 % by weight of copolymer comprising i) Monomers containing sulfonic acid groups ii) Monomers of the general formula R1(R2)C=C(R3)-X-R4, in which R1 to R3 independently of one another represent -H, -CH3 or -C2H5, X represents an optionally present spacer group which is selected from -CH2-, -C(O)O- and -C(O)-NH-, and R4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms b) 0.5 to 5 % by weight of 1-hydroxyethane-1,1-diphosphonic acid c) 10 to 50 % by weight citrate d) 2 to 15 % by weight sodium percarbonate e) 2 to 8 % by weight non-ionic surfactant f) 1.0 to 6 % by weight of enzyme.

11. A method for cleaning dishes in a dishwasher, using automatic dishwashing detergents according to any one of claims 1 to 10.

12. Method according to claim 11, characterized in that no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher during the cleaning process.