EP2723844B1 - Dishwashing detergents with improved protection of decoration - Google Patents

Description

The present application describes machine dishwashing detergents and machine dishwashing methods using these dishwashing agents and the use of these dishwashing agents to reduce glass and porcelain corrosion and / or to improve the decor protection.

Dishwashing detergents are available to consumers in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, machine dishwashing detergents in particular have become very important with the spread of household dishwashing machines. These machine dishwashing agents are typically offered to the consumer in solid form, for example as powder or as tablets, but increasingly also in liquid form.

One of the main goals of the manufacturers of machine cleaning agents is to improve the cleaning and rinsing performance of these agents, with a recent focus on cleaning and rinsing performance in low-temperature cleaning cycles or in cleaning cycles with reduced water consumption. In addition to the cleaning and rinsing performance of these agents, however, it is also desirable that the agents advantageously perform other functions.

Dishwashing problems can occur with glasses and porcelain, for example. The glasses and the porcelain corrode over time after frequent dishwashing and in particular the decor on the glasses and the porcelain is worn away over time. The addition of special corrosion inhibitors, such as zinc salts, can reduce glass and porcelain corrosion and remove the decor. The international patent application WO 07/049250 A1 is concerned with improved dirt removal using automatic dishwashing detergents. The international patent application WO 03/104370 A1 deals with glass corrosion protection through zinc salts and crystalline layered silicates. The German patent application DE 10153555 A1 deals with dishwasher detergents that contain magnesium and / or zinc salts of at least one organic acid to protect against glass corrosion. The German patent application DE 102008020275 A1 deals with zinc-containing cogranulate in automatic dishwashing detergents. However, there is still a need to further improve glass, porcelain and decor protection.

This application was therefore based on the object of providing a machine dishwashing detergent with improved glass, porcelain and / or decorative protection properties. The Improved glass, porcelain and / or decorative protective properties should preferably also be achieved with low-temperature cleaning cycles, i.e. in cleaning processes with rinsing liquor temperatures of 50 ° C. or below and / or in short-lasting cleaning processes, in particular in cleaning processes with a duration of less than 60 minutes can. The improved glass, porcelain and / or decorative protective properties should also preferably be present even with high alkalinity and / or in the presence of strong complexing agents.
The object of the invention was achieved by a dishwashing detergent which, in addition to a zinc salt, additionally contains a polymer which comprises N-containing heterocycles. The polymer is a polyvinylpyrrolidone, which is in particulate form.
A first subject of the present invention are therefore dishwasher detergents, characterized in that they contain at least one zinc salt and at least one polymer which comprises N-containing heterocycles, the polymer with N-containing heterocycles being a polyvinylpyrrolidone, the polyvinylpyrrolidone is in particulate form, the polyvinylpyrrolidone particles preferably having an average particle diameter of 100 to 150 μm. The polyvinyl pyrrolidone can be branched or linear. In a preferred embodiment, the polyvinylpyrrolidone is in a branched and crosslinked form. The polyvinylpyrrolidone particles (PVP particles) preferably have an average particle diameter of 100 to 150 μm.
Another object of the present invention is also a machine dishwashing process using the dishwashing agents according to the invention, in particular for protecting the treated glass and porcelain goods, especially for reducing glass and porcelain corrosion and / or for improving the decor protection. The dishwashing process is preferably carried out at a liquor temperature below 60 ° C., preferably below 50 ° C. In a preferred embodiment, the dishwashing process takes a maximum of 90 minutes, in particular a maximum of 75 minutes, particularly preferably a maximum of 60 minutes. In particular embodiments, the dishwashing process takes a maximum of 50, 40 or 30 minutes.
Another object of the present invention is also the use of a combination of a zinc salt and a polymer which contains N-containing heterocycles to effect improved glass, porcelain and / or decor protection or to reduce glass and porcelain corrosion and / or to reduce the removal of decor or to reduce the fading of the decor, the polymer being a polyvinylpyrrolidone. A dishwashing agent according to the invention is preferably used as a combination of zinc salt and polymer containing N-containing heterocycles, the polymer being a polyvinylpyrrolidone.

The decor, the removal or fading of which is reduced, is preferably on a glass or porcelain surface.

The present application relates to automatic dishwashing detergents. According to this application, machine dishwashing detergents are compositions which can be used for cleaning soiled dishes in an automatic dishwashing process. The machine dishwashing detergents according to the invention thus differ, for example, from the machine rinse aids which are always used in combination with machine dishwashing agents and do not have their own cleaning action.

The automatic dishwashing detergents according to the invention can be in solid or liquid form. In a preferred embodiment, they are in powder, granulated or compressed form.

In a particularly preferred embodiment, the automatic dishwashing detergents according to the invention are in the form of moldings, preferably as compact, in particular as tablets. However, they can also be in combination with other offer forms, in particular in combination with solid offer forms such as powders, granules or extrudates or in combination with liquid offer forms based on water and / or organic solvents.

Agents according to the invention can be packaged 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 prefabricated metering unit with two or more phases, are particularly preferred. Particularly preferred are two-phase or multi-phase tablets, for example two-layer tablets, in particular two-layer tablets with a trough and a molded body located in the trough.

Automatic dishwashing agents according to the invention are preferably prefabricated into dosing units. These metering units preferably comprise the amount of washing or cleaning-active substances necessary for a cleaning cycle. Preferred dosing units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.

The volume of the aforementioned dosing units and their spatial shape are selected with particular preference such that the pre-assembled units can be dosed via the dosing chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

The pH of a 10% solution of an automatic dishwashing agent according to the invention in distilled water (stated in% by weight, measurement at 20 ° C.) is preferably between 7 and 13, particularly preferably between 8 and 12, in particular between 9 and 11.

The automatic dishwashing agents according to the invention, in particular the prefabricated metering units, particularly preferably have a water-soluble coating.

Dishwashing detergents according to the invention contain at least one polymer which comprises N-containing heterocycles, the polymer being a polyvinylpyrrolidone.

Dishwashing agents according to the invention, in particular moldings according to the invention, contain polyvinylpyrrolidone in the form of polyvinylpyrrolidone particles. Polyvinylpyrrolidone particles have the additional advantage that they facilitate the disintegration of the shaped bodies and, in this respect, also serve as disintegration aids or tablet disintegrants. The function of the PVP particles is therefore not limited to improved glass, porcelain and decor protection.

It has proven to be particularly advantageous according to the invention to use polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 μm, in particular with an average particle diameter of 110 to 130 μm.

In the context of the present invention, the term “average particle diameter” or “average diameter” is understood to mean the volume-average D ₅₀ particle diameter, which can be determined by customary methods. The volume-average D ₅₀ particle diameter is the point in the particle size distribution at which 50% by volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter. The average particle diameters can be determined in particular with the aid of dynamic light scattering, which are usually carried out on dilute suspensions which contain, for example, 0.01 to 1% by weight of particles.

Particularly preferably, the PVP particles used not only have an average particle diameter of 100 to 150 μm, in particular 110 to 130 μm, but moreover the particle size of the particles used is preferably completely within the stated intervals. This is ensured by using grain size fractions with the specified particle sizes, which were obtained by a sieving process. According to the invention, it was also surprisingly found that granules which are used according to the invention for the production of the moldings and contain PVP particles can be pressed particularly well. Thus, preferably using a pressing force of 40 to 65 kN, particularly preferably from 48 to 60 kN, compactates with a hardness in the range from 150 to 250 N, in particular in the range from 200 to 230 N, can be obtained, which are also particularly good Show trickle behavior. The granules can thus preferably be pressed with a relatively low pressing force to give compacts with a relatively high hardness, which moreover preferably have very good flow behavior. Conversely, it is accordingly advantageous that a lower pressing force must preferably be used to produce compacts of lower hardness than for the production of conventional compacts.

Another object which is particularly preferred according to the invention is therefore also a shaped body, in particular a compact, in particular a cleaning tablet, which comprises a mixture of polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 μm, in particular 110 to 130 μm, and at least one Contains zinc salt and which preferably has a particularly good flow behavior.

The polyvinylpyrrolidone in compositions according to the invention is preferably in an amount of 0.1 to 5% by weight, particularly preferably in an amount of 0.2 to 3% by weight, especially in an amount of 0.3 to 1.8 % By weight.

The effect of disintegrants is usually that they increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling), but on the other hand a pressure can be generated by the release of gases, which disintegrates the tablet into smaller particles , In addition to or instead of PVP particles, further or alternative disintegrants can also be present in dishwashing detergents according to the invention, for example carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their Derivatives and alginates or casein derivatives. Furthermore, gas-developing shower systems can also be used as further or alternative disintegrants. Preferred effervescent systems consist of at least two constituents which react with one another to form a gas, for example alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution. An acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.

If used, the further disintegration aids are preferably used in amounts of 0.1 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 2% by weight, in each case based on the total weight of the Dishwashing detergent used.

In a preferred embodiment, the shaped body according to the invention contains no further disintegration aids apart from the PVP particles.

Dishwashing detergents according to the invention contain at least one zinc salt as a further constituent. The zinc salt can be an inorganic or organic zinc salt. The zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature). The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate. In a particularly preferred embodiment according to the invention, zinc acetate is used as the zinc salt.
The zinc salt in dishwashing detergents according to the invention is preferably in an amount of 0.01 to 3% by weight, particularly preferably in an amount of 0.05 to 2% by weight, in particular in an amount of 0.1 to 1% by weight. %, contain.

Preferred automatic dishwashing agents according to the invention contain at least one bleaching agent as a further constituent, oxygen bleaching agents being preferred. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic 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 peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.

Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleach, preferably sodium percarbonate, particularly preferably a coated sodium percarbonate. The proportion by weight of the bleaching agent, based on the total weight of the washing or cleaning agent, is in preferred embodiments between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.

Automatic dishwashing detergents according to the invention can furthermore contain bleach activators. Under perhydrolysis conditions, these compounds give aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven to be particularly suitable.

Automatic dishwashing agents, characterized in that they contain a bleach activator from the group of acetylated amines, preferably tetraacetylenediamine (TAED), as the bleach activator, are preferred according to the invention. These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 10% by weight, particularly 0.5 to 8% by weight and particularly preferably 1.0 to 6 % By weight.

In addition or as an alternative to the conventional bleach activators, the automatic dishwashing agents according to the invention preferably contain at least one bleaching catalyst. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Complexes of manganese in oxidation state II, III, IV or V are used with particular preference, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S. Ligands which have nitrogen donor functions are preferably used. It is particularly preferred to use bleaching catalyst (s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) as macromolecular ligands ), 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 ) contain. 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 ).

Automatic dishwashing detergents, characterized in that they also contain a bleaching catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese 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 in particular the cleaning result can be significantly improved by the aforementioned bleaching catalysts.

The aforementioned bleach-enhancing transition metal complexes, in particular with the central atoms Mn and Co, are used in customary amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0, 01% by weight to 0.30% by weight, in each case based on the total weight of the bleach catalyst-containing agents. In special cases, however, more bleaching catalyst can also be used.

Preferred automatic dishwashing agents according to the invention contain at least one anionic polymer as a further constituent. Preferred anionic polymers are the copolymeric polycarboxylates and the copolymeric polysulfonates.

In a preferred embodiment, the weight fraction of the anionic polymer in the total weight of the automatic dishwashing detergent according to the invention is from 0.1 to 20% by weight, preferably from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight. % and in particular from 4 to 14% by weight.

Automatic dishwashing detergents according to the invention, characterized in that the copolymeric anionic polymer is selected from the group of the hydrophobically modified polycarboxylates and polysulfonates is a particularly preferred object, since the hydrophobic modification of the anionic copolymers improves the rinse aid and drying properties of these agents while at the same time reducing the formation of deposits can be achieved.

The copolymers can have two, three, four or more different monomer units.

In addition to monomer (s) containing sulfonic acid groups, preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.

Unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH are used as unsaturated carboxylic acid (s), in which R ¹ to R ³ independently of one another are —H, —CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or for -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylene malonic acid, sorbic acid, cinnamic acid or mixtures thereof. Of course, the unsaturated dicarboxylic acids can also be used.

According to the invention, copolymers of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid are particularly preferably used as copolymeric polycarboxylates. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The monomers containing sulfonic acid groups are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

preferably in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is 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 - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H,

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is 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 -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Particularly preferred monomers containing sulfonic acid groups 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, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
The sulfonic acid groups in the polymers can be wholly or partly in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight in each case in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are preferably selected from the aforementioned.

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In a further preferred embodiment, in addition to the monomer containing carboxyl groups and monomer containing sulfonic acid groups, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer. By using these hydrophobically modified polymers, in particular the rinse aid performance of automatic dishwashing detergents according to the invention could be improved.

1. i) Carbonsäuregruppen-haltige Monomer(e)
2. ii) Sulfonsäuregruppen-haltige Monomer(e)
3. iii) nichtionische Monomer(e)

enthält, werden erfindungsgemäß bevorzugt.Machine dishwashing detergent, characterized in that the machine dishwashing detergent comprises a copolymer as an anionic copolymer

1. i) monomer (s) containing carboxylic acid groups
2. ii) Monomer (s) Containing Sulfonic Acid Groups
3. iii) nonionic monomer (s)

contains are preferred according to the invention.

Monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , are preferably used as nonionic monomers , X stands for an optionally available spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ⁴ for a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred 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-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α -Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid butyl ester, acrylate, methacrylate, acrylate - (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, octyl acrylate ster, methacrylic 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 - or behenyl mixtures.

In a preferred embodiment, dishwashing detergents according to the invention further comprise at least one nonionic surfactant of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , where R ¹ and R ² independently of one another are a branched or unbranched, saturated or unsaturated, optionally hydroxylated Alkyl radical having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M represents an alkyl radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical with 1 are up to 18 carbon atoms.

• R, R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen;
• x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen.

In a first preferred embodiment, dishwasher detergents according to the invention contain a nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² , where

• R, R ¹ and R ² independently of one another are an alkyl radical or alkenyl radical having 6 to 22 carbon atoms;
• x and y independently represent values between 1 and 40.

Compounds of the general formula R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² , in are particularly preferred where R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms and n and m independently of one another have values from 20 to 30. Corresponding compounds can be obtained, for example, by reacting HO-CHR-CH ₂ -OH alkyldiols with ethylene oxide, followed by a reaction with an alkyl epoxide to block the free OH functions to form a dihydroxy ether.

• R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen;
• R³ und R4 unabhängig voneinander für H oder für einen Alkylrest oder Alkenylrest mit 1 bis 18 Kohlenstoffatomen und
• x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen.

In a further preferred embodiment, machine dishwashing detergents according to the invention contain as a nonionic surfactant a surfactant of the general formula R ¹ -O (CH ₂ CH ₂ O) _× CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which

• R ¹ and R ² independently of one another are an alkyl radical or alkenyl radical having 4 to 22 carbon atoms;
• R ³ and R4 independently of one another for H or for an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and
• x and y independently represent values between 1 and 40.

Compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which R ³ and R ^{4 are} H and the indices x and y are preferred independently of one another assume values from 1 to 40, preferably from 1 to 15.

Particularly preferred are particularly compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the radicals R ¹ and R ² independently of one another are saturated alkyl radicals with 4 to Represent 14 carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.

Also preferred are those compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _× CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which one of the radicals R ¹ and R ^{2 is} branched.

Compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _× CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² are very particularly preferred, in which the indices x and y independently assume values from 8 to 12.

The weight fraction of the nonionic surfactant of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ^{2 in} the total weight of the automatic dishwashing detergent according to the invention is in a preferred embodiment between 0.05 and 10% by weight, preferably between 0.1 and 8% by weight, preferably between 0.5 and 5% by weight and in particular between 1 and 3% by weight.

Dishwashing agents according to the invention preferably further contain builders (e) and / or enzymes (e) to ensure their cleaning action.

As a further component, automatic dishwashing agents according to the invention preferably contain one or more builders. The weight fraction of the builders in the total weight of automatic dishwashing agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight. The builders in particular include carbonates, phosphates, citrates, organic cobuilders and silicates.

It is particularly preferred to use carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonate (s), particularly preferably sodium carbonate, in amounts of 2 to 30% by weight, preferably 4 to 28% by weight and in particular from 8 to 24% by weight, based in each case on the weight of the dishwasher detergent.
The use of phosphate is also preferred. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one uses metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives can distinguish. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.

Phosphates which are particularly preferred according to the invention are pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used according to the invention.

If phosphates are used as washing or cleaning-active substances in automatic dishwashing detergents in the context of the present application, they contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in quantities from 5 to 60% by weight, preferably from 15 to 45% by weight and in particular from 20 to 40% by weight, in each case based on the weight of the dishwasher detergent.

Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder action, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Particularly preferred automatic dishwashing agents according to the invention contain citrate as one of their essential builders. Automatic dishwashing detergents, characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight, of citrate are preferred according to the invention.

Like the phosphates, the citrates are preferably used in combination with carbonates and / or hydrogen carbonate. Preferred machine dishwashing detergents are therefore characterized by a combination of builders consisting of phosphate and carbonate / hydrogen carbonate or of citrate and carbonate / hydrogen carbonate (cf. Tables 1a and 1b below). However, it is of course also possible to implement combinations of phosphate, citrate and carbonate / hydrogen carbonate.

Particularly preferred automatic dishwashing agents are characterized in that the dishwashing agent contains at least two builders from the group of the phosphates, carbonates and citrates, the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably 5 to 80% by weight, preferably 15 is up to 75 wt .-% and in particular 30 to 70 wt .-%. The combination of two or more builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of automatic dishwashing detergents according to the invention.

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 weight of 500 to 70,000 g / mol.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

The amount of (homo) polymeric polycarboxylates in the automatic dishwashing detergent is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.

Automatic dishwashing agents according to the invention can contain crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .y H ₂ O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where are particularly preferred values for x 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties.

In preferred automatic dishwashing agents according to the invention, the silicate content, based on the total weight of the automatic dishwashing agent, is below 10 Limited by weight, preferably below 5% by weight and in particular below 2% by weight. Particularly preferred automatic dishwashing agents according to the invention are silicate-free.

Other suitable builders, which can be used as sole builders, but in particular in combination with citrate, are methylglycinediacetic acid (MGDA) and glutamic acid-N, N-diacetic acid (GLDA). These builders are preferably used in amounts of 5 to 60 % By weight, in particular 10 to 40% by weight, are used in automatic dishwashing agents according to the invention.

In addition to the builders mentioned above, the agents according to the invention can contain alkali metal hydroxides. These alkali carriers are preferably used in the cleaning agents only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight. and in particular between 0.5 and 5% by weight, in each case based on the total weight of the cleaning agent. Alternative automatic dishwashing detergents are free from alkali metal hydroxides.

Agents according to the invention preferably also contain phosphonates. Hydroxyalkane and / or aminoalkane phosphonates are preferably used. Of the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are present in the agents according to the invention preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, in each case based on the total weight of the cleaning agent.

Dishwashing agents according to the invention preferably contain enzyme (s) as a further constituent. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, which are accordingly preferred. Detergents or cleaning agents preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, Subtilisin DY and the enzymes Thermitase, Proteinase K and the proteases TW3 and TW7, which can no longer be assigned to the subtilisins in the narrower sense.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the further developments of the aforementioned amylases, which have been improved for use in detergents and cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. to highlight agaradherens (DSM 9948).

Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or developed further, in particular those with the amino acid exchange D96L.

Furthermore, enzymes can be used, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

To increase 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, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling.

A protein and / or enzyme can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Detergents or cleaning agents can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

Proteases and amylases that are active in washing or cleaning are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or 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. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

As can be seen from the previous explanations, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein.

Particularly preferred are automatic dishwashing agents which, based on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations ,

In addition to the aforementioned nonionic surfactants to be used according to the invention, the automatic dishwashing detergents according to the invention can also contain further nonionic surfactants.

In a preferred embodiment, the weight fraction of the further nonionic surfactant in the total weight of the automatic dishwashing detergent according to the invention is between 0.1 and 30% by weight, preferably between 0.5 and 20% by weight, preferably between 1 and 10% by weight in particular between 2 and 6% by weight.

In a preferred embodiment, preferred further nonionic surfactants have the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH ) R ² , in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y is at least 15.

The addition of these nonionic surfactants has proven to be particularly advantageous in terms of rinse aid and drying. In a preferred embodiment, the dishwasher detergent, based on its total weight, contains nonionic surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O ] _z CH ₂ CH (OH) R ² in amounts of 0.1 to 15% by weight, preferably 0.2 to 10% by weight, particularly preferably 0.5 to 8% by weight and in particular 1, 0 to 6% by weight.

Those end group-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R ¹ O [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 up to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and y stands for a value between 15 and 120, preferably 20 to 100, in particular 20 to 80. The group of these nonionic surfactants includes, for example, hydroxy _mixed ethers of the general formula C _6-22 -CH (OH) CH ₂ O- (EO) _20-120 -C _2-26 , for example the C _8-12 fatty alcohol (EO) ₂₂ - 2-hydroxydecyl ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

Automatic dishwashing detergent according to the invention, characterized in that a surfactant of the general formula R ¹ CH (OH) CH ₂ O- (CH ₂ CH ₂ O) _20-120 -R ^{2 is} used as a further nonionic surfactant, R ¹ and R ^{2 being} independent from each other represent a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms are particularly preferred.

Also 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 is} a linear or branched aliphatic hydrocarbon radical with 4 up to 22 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched Designated hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 4, preferably 0.5 to 1.5, and y stands for a value of at least 15.

According to the invention, surfactants of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ^{2 are also} preferred, in which R ^{1 is} a linear or branched aliphatic Is a hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is a value between 1 and 40 and y is a value between 15 and 40, the alkylene units [CH ₂ CH (CH ₃ ) O] and [CH ₂ CH ₂ O] randomized, ie in the form of a statistical, random distribution.

The group of preferred end-capped poly (oxyalkylated) nonionic surfactants also includes nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and 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} selected independently of one another from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ - CH ₃ , -CH (CH ₃ ) ₂ , but preferably stands for -CH ₃ , and x and y independently of one another have values between 1 and 32, nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are particularly preferred.

By using the above-described nonionic surfactants with a free hydroxyl group on one of the two terminal alkyl residues, the rinse aid and drying can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the above-mentioned nonionic surfactants represent statistical mean values, which can be an integer or a fraction for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but rather of mixtures, which can result in mean values and broken numbers both for the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Surfactant mixtures are not mixtures of nonionic surfactants which, in their entirety, fall under one of the general formulas mentioned above, but rather mixtures which contain two, three, four or more nonionic surfactants included, which can be described by different of the aforementioned or other general formulas.

Those 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., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C. is / are particularly preferred ,

1. a) 0,1 bis 1 Gew.-% Zinksalz, insbesondere wasserlösliches Zinksalz, vor allem Zinkacetat;
2. b) 0,1 bis 5 Gew.-% Polyvinylpyrrolidon-Partikel mit einem mittleren Teilchendurchmesser von 100 bis 150 µm, insbesondere von 110 bis 130 µm;
3. c) 2 bis 30 Gew.-% Bleichmittel, insbesondere Natriumpercarbonat;
4. d) Bleichkatalysator und/oder Bleichaktivator;
5. e) gegebenenfalls 0,5 bis 5 Gew.-% eines nichtionischen Tensids der allgemeinen Formel R¹-O(CH₂CH₂O)_xCH₂(OCH₂CH₂)_yO-R², in der
   • R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen; und
   • x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen.

Particularly preferred automatic dishwashing detergents according to the invention

1. a) 0.1 to 1 wt .-% zinc salt, in particular water-soluble zinc salt, especially zinc acetate;
2. b) 0.1 to 5 wt .-% polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 microns, in particular from 110 to 130 microns;
3. c) 2 to 30% by weight of bleach, in particular sodium percarbonate;
4. d) bleach catalyst and / or bleach activator;
5. e) optionally 0.5 to 5 wt .-% of a nonionic surfactant of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CH ₂ (OCH ₂ CH ₂ ) _y OR ² , in which
   • R ¹ and R ² independently of one another are an alkyl radical or alkenyl radical having 4 to 22 carbon atoms; and
   • x and y independently represent values between 1 and 40.

1. a) 0,1 bis 5 Gew.-% Polyvinylpyrrolidon-Partikel, vorzugsweise solche mit einem mittleren Teilchendurchmesser von 100 bis 150 µm, insbesondere von 110 bis 130 µm;
2. b) 0,1 bis 1 Gew.-% Zinksalz, insbesondere wasserlösliches Zinksalz, vor allem Zinkacetat;
3. c) 2 bis 30 Gew.-% Bleichmittel, insbesondere Natriumpercarbonat;
4. d) Bleichkatalysator und/oder Bleichaktivator;
5. e) gegebenenfalls 1 bis 15 Gew.-% eines copolymeren anionischen Polymers umfassend Carbonsäuregruppen-haltige Monomere, Sulfonsäuregruppen-haltige Monomere und gegebenenfalls nichtionische Monomere.

Contain further particularly preferred automatic dishwashing agents according to the invention

1. a) 0.1 to 5 wt .-% polyvinylpyrrolidone particles, preferably those with an average particle diameter of 100 to 150 microns, in particular from 110 to 130 microns;
2. b) 0.1 to 1% by weight of zinc salt, in particular water-soluble zinc salt, especially zinc acetate;
3. c) 2 to 30% by weight of bleach, in particular sodium percarbonate;
4. d) bleach catalyst and / or bleach activator;
5. e) optionally 1 to 15% by weight of a copolymeric anionic polymer comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and optionally nonionic monomers.

In addition to the ingredients described above, the agents according to the invention can contain further washing or cleaning substances, preferably from the group of corrosion inhibitors, fragrances and perfume carriers.

The combinations of active ingredients described above are particularly suitable for cleaning dishes in automatic dishwashing processes. Another subject of the present application is a method for cleaning dishes in a dishwasher, using an automatic dishwashing agent according to the invention, the automatic Dishwashing agents are preferably metered into the interior of a dishwasher during the course of a dishwashing program, before the start of the main wash cycle or in the course of the main wash cycle. The agent according to the invention can be metered into the interior of the dishwasher manually, but the agent is preferably metered into the interior of the dishwasher by means of the dosing chamber of the dishwasher.

The automatic dishwashing detergents according to the invention show their advantageous cleaning and decorative protective properties, in particular also in low-temperature cleaning processes. Preferred dishwashing methods using agents according to the invention are therefore characterized in that the dishwashing methods are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C.

Some exemplary recipes for preferred automatic dishwasher tablets according to the invention can be found in the tables below:

embodiments

PVP particles with a particle diameter of 100-150 μm were incorporated into a commercially available dishwasher detergent tablet which contains zinc acetate. Comparative tests were now carried out in a dishwasher (Miele G 1355 SC, light 50 ° C turbo, 21 ° dH) with the tablet containing PVP particles on the one hand and the tablet without PVP particles on the other hand. An evaluation was made after going through 50 and 100 cycles. Both the glass corrosion and the decor removal of the treated glassware were assessed visually on a scale from 0 to 5, 5 being the best grade. The results are shown in the following table: Dishwashing liquid with PVP Dishwashing liquid without PVP Number of cycles glass corrosion decor glass corrosion decor 50 4.14 4.2 3.96 3.8 100 3.13 3.3 3.08 2.8

The results show that by adding the PVP particles, both glass corrosion and decor removal could be reduced, with the improvement in decor protection being even more pronounced than the reduction in glass corrosion.

Claims (9)

1. An automatic dishwashing detergent, containing at least one zinc salt and at least one polymer which contains N-containing heterocycles, characterized in that the polymer which contains N-containing heterocycles is a polyvinylpyrrolidone, the polyvinylpyrrolidone being in particulate form, the polyvinylpyrrolidone particles preferably having an average particle diameter of from 100 to 150 µm.
2. The automatic dishwashing detergent according to claim 1, characterized in that the polyvinylpyrrolidone particles are contained in the dishwashing detergent in an amount of from 0.1 to 5 wt.%, in particular in an amount of from 0.2 to 3 wt.%, especially in an amount of from 0.3 to 1.8 wt.%.
3. The automatic dishwashing detergent according to one of claims 1 to 2, characterized in that the zinc salt is selected from the group consisting of inorganic and organic zinc salts, in particular zinc bromide, zinc chloride, zinc iodide, zinc nitrate, zinc sulfate, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate, and in that the zinc salt is preferably contained in the dishwashing detergent in an amount of from 0.01 to 3 wt.%, more preferably in an amount of from 0.05 to 2 wt.%, in particular in an amount of from 0.1 to 1 wt.%.
4. The automatic dishwashing detergent according to one of the preceding claims, characterized in that it contains at least one builder, in particular selected from salts of tripolyphosphate, carbonic acid and citric acid.
5. The automatic dishwashing detergent according to one of the preceding claims, characterized in that it contains at least one anionic polymer which is selected from the group of copolymers, comprising

   i) carboxylic acid group-containing monomer(s),

   ii) sulfonic acid group-containing monomer(s) and

   iii) optionally non-ionic monomer(s),

   the anionic polymer preferably being contained in an amount of from 0.1 to 20 wt.%, in particular of from 0.5 to 18 wt.%, particularly preferably of from 1.0 to 15 wt.% and especially of from 4 to 14 wt.%.
6. The automatic dishwashing detergent according to one of the preceding claims, characterized in that a 10% solution of the agent in distilled water (20 °C) has a pH value of from 7 to 13, in particular from 8 to 12, particularly preferably from 9 to 11.
7. The automatic dishwashing detergent according to one of the preceding claims, characterized in that it is present as a pressed shaped body, in particular as a compacted body, especially as a tablet.
8. An automatic dishwashing method, characterized in that an automatic dishwashing detergent according to one of the preceding claims is used, in particular for effecting improved glass, porcelain and/or decorative design protection or for reducing glass and porcelain corrosion and/or for reducing removal of the decorative design.
9. The use of a combination of a zinc salt and a polymer which contains N-containing heterocycles, wherein the polymer is a polyvinylpyrrolidone, for effecting improved glass, porcelain and/or decorative design protection or for reducing glass and porcelain corrosion and/or for reducing removal of the decorative design.