WO2012175292A1 - Dishwashing detergents with improved protection of decoration - Google Patents

Abstract

Machine dishwashing detergents which contain a combination of a zinc salt and a polymer comprising N-containing heterocycles reduce glass and porcelain corrosion and especially result in an improvement in protection of decoration.

Description

 "Dishwashing detergent with improved decor protection"

The present application describes automatic dishwashing detergents as well as automatic dishwashing processes using these dishwashing detergents as well as the use of these dishwashing detergents for reducing glass and porcelain corrosion and / or for improving decor protection.

Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, in particular the automatic dishwashing detergents have gained great importance with the spread of household dishwashers. These automatic dishwashing detergents are the consumer

typically offered in solid form, for example as a powder or as tablets, but increasingly also in liquid form.

One of the major objectives of the machine cleaners manufacturers is to improve the cleaning and rinse performance of these compositions, with more emphasis being placed recently on the cleaning and rinse performance in low temperature or reduced water consumption cleaning cycles. However, in addition to the cleaning and rinsing performance of these agents, it is also desirable that the means advantageously fulfill additional functions.

Problems with dishwashing can occur, for example, with glasses and porcelain. Over time, the glasses and porcelain corrode after frequent dishwashing and, in particular, the decoration on the glasses and porcelain is eroded over time. By adding special corrosion inhibitors, such as zinc salts, the glass and porcelain corrosion as well as the removal of the decoration can be reduced. However, there is still a need to further improve glass, porcelain and decor protection.

This application was therefore based on the object to provide a machine dishwashing detergent with improved glass, porcelain and / or decor protection properties. The improved glass, porcelain and / or Dekorschutzeigenschaften should preferably also in low-temperature cleaning operations, ie in cleaning processes with Spülflottentemperaturen of 50 ° C or below and / or in short-term cleaning process, especially in cleaning process with a duration of less than 60 minutes achieved can be. The improved glass, porcelain and / or decor protection properties should furthermore preferably be given even with high alkalinity and / or in the presence of strong complexing agents. The object according to the invention was achieved by a dishwashing agent which, in addition to a zinc salt, additionally contains a polymer comprising N-containing heterocycles. The polymer is preferably a polyvinylpyrrolidone.

A first subject of the present invention are therefore automatic dishwashing detergents, characterized in that they comprise at least one zinc salt and at least one polymer comprising N-containing heterocycles, wherein the polymer containing N-containing heterocycles is preferably a polyvinylpyrrolidone. The polymer, in particular the

Polyvinylpyrrolidone, may be branched or linear. In a preferred

Embodiment, the polymer, in particular the polyvinylpyrrolidone, in branched and crosslinked form, in particular in the form of particles before. The polymer particles, in particular 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 detergent according to the invention, in particular for the protection of the treated glass and porcelain ware, especially for the reduction of glass and

Porcelain corrosion and / or to improve 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, more preferably a maximum of 60 minutes. In particular embodiments, the dishwashing process lasts for a maximum of 50, 40, or 30 minutes.

Another object of the present invention is the use of a combination of a zinc salt and a polymer containing N-containing heterocycles, to effect improved glass, porcelain and / or decor protection or to reduce glass and porcelain corrosion and / or to reduce the decor removal or to reduce the fading of the decoration, wherein the polymer is preferably a polyvinylpyrrolidone. A combination of zinc salt and N-containing heterocycle-containing polymer in this case preferably a dishwashing agent according to the invention is used.

The decor, whose removal or its fading is reduced, is preferably located on a glass or porcelain surface.

The present application relates to automatic dishwashing detergents. Automatic dishwashing detergents, according to this application, are compositions which are used to clean soiled dishes in a dishwashing process can be. Thus, the automatic dishwasher detergents according to the invention differ, for example, from the machine rinse aid agents, which are always used in combination with automatic dishwashing detergents and do not develop their own cleaning action.

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

The automatic dishwashing compositions according to the invention are present in a particularly preferred embodiment as a shaped body, preferably as a compact, in particular as a tablet. However, they may also be present in combination with other forms of supply, in particular in combination with solid forms such as powders, granules or extrudates or in combination with liquid formulations based on water and / or organic solvents.

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 prefabricated dosing unit with two or more phases, are particularly preferred. Particularly preferred are in particular two- 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 dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering 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 metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units on the

Dosing of a dishwasher is guaranteed. 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% strength solution of a dishwasher 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 dishwasher detergents according to the invention, in particular the prefabricated ones

Dosing units, most preferably have a water-soluble coating.

Dishwashing agents according to the invention comprise at least one polymer containing N-containing

Includes heterocycles. Preferably, at least 20%, in particular at least 50%, particularly preferably at least 80%, very particularly preferably all of the monomer units present in the polymer have an N-containing heterocycle. In the N-containing

Heterocycle is preferably a 5- or 6-membered ring which may be unsaturated, partially saturated or fully saturated, with fully saturated heterocycles being particularly preferred. It is further preferred that the heterocycle comprises an N atom and at least one carbonyl group, wherein the carbonyl group is preferably arranged in the alpha position to the N atom. In a particularly preferred embodiment, the heterocycle is a pyrrolidone which is preferably bonded to the backbone of the polymer via the N atom. In a preferred embodiment according to the invention, the polymer is accordingly a polymer in which at least 20%, preferably at least 50%, in particular at least 80% of the monomer units of the polymer

Pyrrolidone units have. In a very particularly preferred embodiment, the polymer is a polyvinylpyrrolidone.

Dishwashing agents preferred according to the invention, in particular shaped bodies according to the invention, comprise polyvinylpyrrolidone in the form of polyvinylpyrrolidone particles. Polyvinylpyrrolidone particles have the additional advantage that they facilitate the disintegration of the moldings and thus additionally serve as disintegration aids or tablet disintegrating agents. The function of the PVP particles is therefore not limited solely to improved glass, porcelain and decor protection.

It has been found to be particularly advantageous according to the invention, Polyvinylpyrrolidon particles having an average particle diameter of 100 to 150 μιη, in particular with an average particle diameter of 1 10 to 130 μιη, use.

The term "average particle diameter" or "average diameter" is meant ₅₀ particle diameter in the present invention, the volume mean D, which can be determined by conventional methods. The volume average D ₅₀ particle diameter is that point in the particle size at which 50 % By volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter

Particle diameters can be determined in particular by means of dynamic light scattering, which are usually carried out on dilute suspensions containing, for example, from 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 μιη, in particular from 1 10 to 130 μιη, but moreover, the particle size of the particles used is preferably completely within the specified intervals. This is ensured by using grain size fractions with the indicated particle sizes obtained by a sieving process.

According to the invention, it has also surprisingly been found that granules which contain PVP particles and are used according to the invention for producing the shaped bodies can be pressed particularly well. Thus, compacts having a hardness in the range from 150 to 250 N, in particular in the range from 200 to 230 N, which in addition is a particularly good one, can preferably be obtained by using a pressing force of 40 to 65 kN, more preferably 48 to 60 kN Have trickle behavior. The granules can thus preferably be pressed with relatively low pressing force into compact materials having a relatively high hardness, which moreover preferably have a very good trickling behavior. Accordingly, it is conversely advantageous for the production of compact materials of lower hardness preferably a lower pressing force must be used, as for the production of conventional compactates.

A further particularly preferred subject according to the invention therefore also exists

Shaped body, especially a Kompaktat, especially a cleaning tablet, which contains a mixture of polyvinylpyrrolidone particles having a mean particle diameter of 100 to 150 μιη, in particular from 1 10 to 130 μιη, and at least one zinc salt and preferably a particularly good trickling having.

The polymer comprising N-containing heterocycles, in particular the polyvinylpyrrolidone, is preferably present in compositions according to the invention in an amount of 0.1 to 5% by weight, more preferably in an amount of 0.2 to 3% by weight all in an amount of 0.3 to 1, 8 wt .-%, wherein the polymer, in particular the polyvinylpyrrolidone, in a preferred embodiment as described above in particulate form.

The effect of disintegrants is usually that they increase their volume upon ingress of water, whereby on the one hand increases the intrinsic volume (swelling), but on the other hand by the release of gases, a pressure can be generated, which can disintegrate the tablet into smaller particles , In addition or instead of PVP particles, further or alternative disintegrants may be present in dishwashing compositions 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 theirs Derivatives and alginates or casein derivatives. Furthermore, as further or alternative disintegrants also gas-developing effervescent systems are used. Preferred effervescent systems consist of at least two constituents which react with one another to form gas, for example alkali metal carbonate and / or bicarbonate and an acidifier which is suitable for liberating 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.

The further disintegration aids are, if used, preferably in amounts of 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-% and in particular 0.5 to 2 wt .-%, each based on the total weight of Dishwashing agent, used.

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

Dishwashing compositions according to the invention contain as further constituent at least one zinc salt. The zinc salt may 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, more preferably above 1 g / l and especially 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 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 is preferably present in dishwashing detergents according to the invention in an amount of from 0.01 to 3% by weight, more preferably in an amount of from 0.05 to 2% by weight, in particular in an amount of from 0.1 to 1% by weight. %, contain.

Preferred automatic dishwashing agents according to the invention contain as further constituent at least one bleaching agent, oxygen bleaching agents being preferred. Among the compounds which serve as bleaches and deliver in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaches which can be used are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates,

Diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, more preferably a coated sodium percarbonate. The weight fraction of the bleaching agent, based on the total weight of the washing or cleaning agent, is in preferred

Embodiments between 2 and 30 wt .-%, preferably between 4 and 20 wt .-% and in particular between 6 and 15 wt .-%.

Machine dishwashing detergents according to the invention may further contain bleach activators. These compounds give under perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are the O- and / or N-acyl groups of the mentioned carbon atom number and / or optionally substituted

Wear benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

Automatic dishwashing detergents, characterized in that they contain as bleach activator a bleach activator from the group of the acetylated amines, preferably tetraacetylenediamine (TAED), 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, especially 0.5 to 8% by weight and more preferably 1, 0 to 6 Wt .-%, used.

In addition or as an alternative to the conventional bleach activators, the

Machine dishwashing detergents according to the invention preferably at least one

Bleach catalyst. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

With particular preference complexes of manganese in the oxidation state II, III, IV or V are used, which preferably one or more macrocyclic (s) ligand (s) with the

Donor functions N, NR, PR, O and / or S included. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (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

[Μη^ι"₂(μ-0)₁(μ-ΟΑο)2(Μ^β-ΤΑΟΝ)2](ΟΙθ4)2, [Μη^ι"Μη^ιν(μ-0)₁(μ-ΟΑο)2(Μ^β-ΤΑΟΝ)2](ΟΙ0₄)3,

und [Μη'^ν ₂(μ- 0)₃(Me/Me-TACN)₂](PF₆)₂ (OAc = OC(0)CH₃). Manganese complexes are, for example, [ ^{Μη ΙΜ} 2 (μ-0) ₁ (μ-ΟΑο) 2 (ΤΑΟΝ) 2] (ΟΙ0 ₄ ) 2, [Μη "'Μη' ^ν (μ-0) ₂ (μ-OAc) ₁ ( TACN) ₂ ] (BPh ₄ ) ₂ ,

^[Μη ι _"2 (μ-0) ₁ (μ-ΟΑο) 2 ^(Μ β -ΤΑΟΝ) 2] (ΟΙθ4) 2, ^[Μη ι" ^Μη ιν (μ-0) ₁ (μ-ΟΑο) 2 (Μ ^β -ΤΑΟΝ) 2] (ΟΙ0 ₄ ) 3,

and [Μη ^'ν ₂ (μ- 0) ₃ (Me / Me-TACN) _2] (PF _{6) 2} (OAc = OC (0) _CH3).

Automatic dishwashing detergent, characterized in that it further comprises a

Bleach 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 by the aforementioned

Bleaching catalysts, in particular the cleaning result can be significantly improved.

The aforementioned bleach-enhancing transition metal complexes, in particular with the

Central atoms Mn and Co are in conventional amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and particularly preferably from

0.01 wt .-% to 0.30 wt .-%, each based on the total weight of

bleach catalyst-containing agent used. In special cases, however, more can be done

Bleaching catalyst can be used.

Preferred machine dishwasher detergents according to the invention contain as further constituent at least one anionic polymer. Preferred anionic polymers here are the copolymeric polycarboxylates and the copolymeric polysulfonates.

The proportion by weight of the anionic polymer in the total weight of the inventive automatic dishwashing agent in a preferred embodiment 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 wt .-%.

Machine dishwashing detergents according to the invention, characterized in that the copolymeric anionic polymer is selected from the group of hydrophobically modified polycarboxylates and polysulfonates is a particularly preferred object, as represented by the hydrophobic

Modification of the anionic copolymers an improvement of the rinse aid and

Drying properties of these agents can be achieved with low deposit formation.

The copolymers may have two, three, four or more different monomer units. Preferred copolymeric polysulfonates contain sulfonic acid group-containing (s)

Monomer (s) at least one monomer from the group of unsaturated carboxylic acids.

Unsaturated carboxylic acid (s) used are / are unsaturated carboxylic acids of the formula R (R ² ) C =C (R ³ ) COOH, 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, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein 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, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

Copolymers of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid are particularly preferably used according to the invention 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 from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

In the sulfonic acid-containing monomers are those of the formula

R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ^7, independently of one another, is -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 alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH, or by -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, is straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional 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

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , - CH ₂ CH ₂ Cl-I ₃ and -CH (CH ₃ ) ₂ and X is an optionally present spacer group which is selected from - (CH ₂ ) _n - where 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-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

 In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized

Sulfonsäuregruppenhaltigen copolymers is inventively preferred.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the share of

Carboxylic acid-containing monomers 10 to 50 wt .-%, the monomers are hereby 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 end use. Preferred automatic dishwasher detergents are characterized in that the copolymers have molar masses of 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 another preferred embodiment, the copolymers include besides

Carboxyl-containing monomer and sulfonic acid-containing monomer further at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.

Automatic dishwashing detergent, characterized in that the automatic dishwashing detergent comprises as anionic copolymer a copolymer comprising

 i) carboxylic acid group-containing monomer (s)

 ii) sulfonic acid group-containing monomer (s)

 iii) nonionic monomer (s)

contains are preferred according to the invention.

As nonionic monomers are preferably monomers of the general formula

R (R ² ) C = C (R ³ ) -XR ⁴ used, in which R to R ^{3 are} independently -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group selected is from -CH ₂ -, -C (0) 0- and -C (0) -NH-, and R ^{4 is} a straight or branched chain saturated alkyl radical having 2 to 22 carbon atoms or 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-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, a Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid pentyl ester,

Hexyl acrylate, methyl methacrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, A / - (2-ethylhexyl) acrylamide, octyl acrylate, octyl methacrylate, A / - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, acrylic acid stearyl ester, methacrylic acid stearyl ester, A / - (stearyl) acrylamide, acrylic acid behenyl ester, methacrylic acid behenyl ester and A / - (behenyl) acrylamide or mixtures thereof. In a preferred embodiment dishwashing agents according to the invention further comprise at least one nonionic surfactant of the general formula R 0 (AlkO) _x M (OAlk) _y OR ² , where R and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical with 4 to 22 carbon atoms;

Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms;

x and y independently represent values between 1 and 70; and

M is 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 are a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.

In a first preferred embodiment machine according to the invention contain

Dishwashing agent here as a nonionic surfactant, a surfactant of the general formula

R is -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 and R ² independently represent an alkyl or alkenyl radical having 6 to 22 carbon atoms;

 - x and y independently represent values between 1 and 40.

Particular preference is given here to compounds of the general formula R -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 which 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 of 20 to 30. Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH ₂ -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close the free OH functions to form a dihydroxy ether.

In a further preferred embodiment machine according to the invention contain

Dishwashing detergent as nonionic surfactant, a surfactant of the general formula

R-O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ^{2 is} used in the

R and R ² independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms;

R ³ and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and

 - x and y independently represent values between 1 and 40.

Preference is given here in particular to compounds of the general formula R - 0 (CH ₂ CH ₂ 0) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which R ³ and R ⁴ are H, and the subscripts x and y are independently from each other assume values from 1 to 40, preferably from 1 to 15. Especially preferred particular compounds of the general formula R - 0 (CH ₂ CH ₂ 0) _x CR ³ R ⁴ (OCH ₂ CI l _{2) y} OR ^2, in which the radicals R and R ² are independently saturated alkyl radicals having from 4 to Represent 14 carbon atoms and the indices x and y independently of one another assume values of 1 to 15 and in particular of 1 to 12.

Preference is furthermore given to those compounds of the general formula R - O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which one of the radicals R and R ^{2 is} branched.

Very particular preference is given to compounds of the general formula R - O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the indices x and y independently of one another assume values of 8 to 12.

The weight fraction of the nonionic surfactant of the general formula R 0 (AlkO) _x M (OAlk) _y OR ^{2 in} the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.05 and 10% by weight, preferably between 0, 1 and 8 Wt .-%, preferably between 0.5 and 5 wt .-% and in particular between 1 and 3 wt .-%.

Dishwashing agents according to the invention furthermore preferably contain builder (s) and / or enzyme (s) to ensure their cleaning action.

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

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of from 2 to 30 wt .-%, preferably from 4 to 28 wt .-% and in particular from 8 to 24 wt .-%, each based on the weight of the automatic dishwashing detergent.

 Preference is also the use of phosphate. Among the large number of commercially available phosphates, the alkali metal phosphates have, with particular preference of pentasodium or. Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) in the washing and

Detergent industry the biggest importance.

Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which one

Metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 _{4 in} addition to high molecular weight representatives can differentiate. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Particularly preferred phosphates according to the invention are the pentasodium triphosphate, Na ₅ P ₃ Oi ₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ Oi ₀ (potassium tripolyphosphate). In accordance with the invention, the

Sodium potassium tripolyphosphates.

If phosphates are used as washing or cleaning substances in automatic dishwasher detergents in the context of the present application, these contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or

Pentakaliumtriphosphat (sodium or potassium tripolyphosphate), in amounts of 5 to 60 wt .-%, preferably from 15 to 45 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the automatic dishwashing detergent.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.

Useful 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 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), if such use is not objectionable for ecological reasons, and mixtures thereof. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred machine dishwasher detergents according to the invention contain citrate as one of their essential builders. Machine 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 citrate, are preferred according to the invention. The citrates, like the phosphates, are preferably used in combination with carbonates and / or bicarbonate. Preferred automatic dishwasher detergents are therefore characterized by a builder combination of phosphate and carbonate / bicarbonate or of citrate and carbonate / bicarbonate (see Tables 1a and 1b below). Of course, however, builder combinations of phosphate, citrate and carbonate / bicarbonate can be realized.

Particularly preferred automatic dishwashing detergents are characterized in that the dishwashing detergent 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 from 5 to 80% by weight, preferably 15 to 75 wt .-% and in particular 30 to 70 wt .-% is. The combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass 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 of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

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

Inventive automatic dishwashing agents as a builder crystalline schichtformige silicates of general formula NaMSi _x 0 _2x + i ^■ y H ₂ 0 wherein M is 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.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.

In preferred machine dishwashing detergents according to the invention, the content of silicates, based on the total weight of the automatic dishwashing detergent, is less than 10 Wt .-%, preferably below 5 wt .-% and in particular below 2 wt .-% limited.

Particularly preferred automatic dishwasher detergents according to the invention are silicate-free.

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

In addition to the abovementioned builders, the agents according to the invention may contain alkali metal hydroxides. These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of

Detergent used. Alternative automatic dishwashing detergents are free from

Alkali metal hydroxides.

Inventive agents also preferably contain phosphonates. Preference is given to using hydroxyalkane and / or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are present in agents according to the invention preferably in amounts of from 0.1 to 10% by weight, in particular in amounts of from 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 comprise enzyme (s) as a further constituent. These include in particular proteases, amylases, lipases, hemicellulases, cellulases,

Perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples include the subtilisins BPN 'and Carlsberg and their advanced 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 are attributed to the subtilases, but not 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 β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae, as well as those improved for use in detergents and cleaners

Further developments of the aforementioned amylases. Furthermore, the a-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, those originally from Humicola lanuginosa

(Thermomyces lanuginosus) available, or further developed lipases, especially those with the amino acid exchange D96L.

Furthermore, enzymes can be used which are termed hemicellulases

be summarized. These include, for example, mannanases, xanthanlyases,

Pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases.

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 to increase the bleaching effect. Advantageously, it is additionally preferable to add organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the

Stains to ensure the flow of electrons (mediators).

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention. Washing or cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or

Chemical-impermeable protective layer is coated. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Preferably used according to the invention

Protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and

in particular between 0.8 and 10% by weight of the enzyme protein.

Particular preference is given to those automatic dishwashing detergents which, based in each case 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 ,

The automatic dishwashing compositions according to the invention may additionally comprise, in addition to the abovementioned nonionic surfactants to be used according to the invention, other nonionic surfactants. The proportion by weight of the further nonionic surfactant in the total weight of the

Machine dishwashing agent of the invention is in a preferred

Embodiment between 0, 1 and 30 wt .-%, preferably between 0.5 and 20 wt .-%, preferably between 1 and 10 wt .-% and in particular between 2 and 6 wt .-%.

Preferred further nonionic surfactants in a preferred embodiment have the general formula R 0 [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 the R for a linear or branched aliphatic 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 and z represents values between 0 and 40 and y is a value of at least 15.

The addition of these nonionic surfactants has proved to be advantageous, in particular with regard to the rinse power and the drying. In a preferred embodiment, the automatic dishwashing detergent contains, based on its total weight, nonionic surfactant of the general formula R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _{z is} CH ₂ CH (OH) R ² in amounts of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.5 to 8% by weight and in particular from 1.0 to 6% by weight.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R 0 [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in the R is a linear or branched aliphatic 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 y is a value between 15 and 120, preferably 20 to 100, in particular 20 to 80. The group of these non-ionic surfactants include, for example, hydroxy mixed ethers of the general formula C ₆ -22-CH (OH) CH ₂ 0- (EO) 2o-i2o- 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 -8o-2-hydroxyalkyl ethers.

Machine dishwashing detergent according to the invention, characterized in that as further nonionic surfactant a surfactant of the general formula

R is CH (OH) CH ₂ O- (CH ₂ CH ₂ O) 2o-i2o-R ² , where R and R ² independently of one another are a linear or branched aliphatic hydrocarbon radical having 2 to 20

Carbon atoms are particularly preferred.

Also preferred are surfactants of the formula R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ Cl-1 (OI-l) R ² , in which R is a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched one Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 4, preferably 0.5 to 1, 5, and y is a value of at least 15.

Also according to the invention are surfactants of the general formula

R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² in which R is a linear or branched aliphatic 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, wherein the alkylene units [CH ₂ CH (CH ₃ ) 0] and [CH ₂ CH ₂ 0] randomized, ie in Form a random statistical distribution.

The group of preferred end-capped poly (oxyalkylated) nonionic surfactants also includes nonionic surfactants of the formula R 0 [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² in which R and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 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 , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are most preferred.

By using the above-described nonionic surfactants with a free

Hydroxyl group on one of the two terminal alkyl radicals, the clear rinse and drying can be significantly improved compared to conventional polyalkoxylated fatty alcohols without free hydroxyl group.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the methods II trade products of the formulas mentioned are usually not from an individual representative, but from mixtures, which may result in both the C chain lengths and for the degrees of ethoxylation and degrees of alkoxylation averages and resulting broken numbers.

Of course, the aforementioned nonionic surfactants can not only be used as

Single substances, but also as surfactant mixtures of two, three, four or more surfactants are used. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which may be described by any of the foregoing or other general formulas.

Particular preference is given to those nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred ,

Particularly preferred automatic dishwasher detergents according to the invention contain

a) 0.1 to 1 wt .-% zinc salt, in particular water-soluble zinc salt, especially zinc acetate; b) 0.1 to 5 wt .-% polyvinylpyrrolidone, preferably polyvinylpyrrolidone particles having an average particle diameter of 100 to 150 μιη, in particular from 1 10 to 130 μιη; c) 2 to 30% by weight of bleaching agent, in particular sodium percarbonate;

d) bleach catalyst and / or bleach activator;

e) optionally 0.5 to 5 wt .-% of a nonionic surfactant of the general formula R -0 (CH ₂ CH ₂ 0) _x CH ₂ (OCH ₂ CH ₂ ) _y OR ² , in the

R and R ² independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms; and

 - x and y independently represent values between 1 and 40.

Further particularly preferred automatic dishwashing agents according to the invention comprise a) from 0.1 to 5% by weight of polyvinylpyrrolidone particles, preferably those having an average particle diameter of from 100 to 150 μm, in particular from 10 to 130 μm;

b) 0.1 to 1 wt .-% zinc salt, in particular water-soluble zinc salt, especially zinc acetate; c) 2 to 30% by weight of bleaching agent, in particular sodium percarbonate;

d) bleach catalyst and / or bleach activator;

e) optionally 1 to 15 wt .-% of a copolymeric anionic polymer comprising carboxylic acid group-containing monomers, sulfonic acid-containing monomers and optionally nonionic monomers.

In addition to the ingredients described above, the agents according to the invention may contain further washing or cleaning-active substances, preferably from the group of

Corrosion inhibitors, fragrances and perfume carriers included.

The active substance combinations described above are particularly suitable for cleaning dishes in automatic dishwashing processes. Another object of the present application is a method for cleaning dishes in a dishwasher, using a machine dishwashing detergent according to the invention, wherein the machine Dishwashing agent are preferably metered during the passage of a dishwashing program, before the start of the main wash cycle or in the course of the main wash cycle in the interior of a dishwasher. The dosing or the entry of

 agent according to the invention in the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber of the dishwasher in the interior of the dishwasher.

The automatic dishwasher detergents according to the invention show their advantageous cleaning and decor protection properties, in particular also in low-temperature cleaning processes.

 Preferred dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C.

Some exemplary formulations for preferred machine according to the invention

 Dishwashing detergent tablets can be taken from the following tables:

Ingredient Recipe 5 Recipe 6 Recipe 7 Recipe 8

 [Wt%] [wt%] [wt%] [wt%]

Tripolyphosphate 5 to 50 15 to 40 -

Citrate _* 5 to 40 15 to 30

Carbonate 2 to 45 2 to 35 2 to 45 2 to 35

Enzyme ^** 0.2 to 10 0.2 to 10 0.5 to 8 0.5 to 8

Anionic copolymer C ¹ 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18

Polyvinylpyrrolidone particles; 0.1 to 5 0, 1 to 5 0, 1 to 5 0, 1 to 5 diameter: 100-150 μιη

 Zinc salt 0.01 to 10, 1 to 0.5 0.01 to 1 0.1 to 0.5

Mise Add 100 Add 100 Add 100 Add 100 Ingredient Recipe 9 Recipe 10 Recipe 1 1 Recipe 12

 [Wt%] [wt%] [wt%] [wt%]

Tripolyphosphate 5 to 50 15 to 40 -

Citrate _* 5 to 40 15 to 30

Carbonate 2 to 45 2 to 35 2 to 45 2 to 35

Enzyme ^** 0.2 to 10 0.2 to 10 0.5 to 8 0.5 to 8

Nonionic surfactant A ¹ 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10

Zinc salt 0.01 to 10, 1 to 0.5 0.01 to 1 0.1 to 0.5

Polyvinylpyrrolidone particles 0.1 to 5 0, 1 to 5 0, 1 to 5 0, 1 to 5

Mise Add 100 Add 100 Add 100 Add 100

Ingredient Recipe 17 Recipe 18 Recipe 19 Recipe 20

 [Wt%] [wt%] [wt%] [wt%]

Tripolyphosphate 5 to 50 15 to 40 -

Citrate _* 5 to 40 15 to 30

Carbonate 2 to 45 2 to 35 2 to 45 2 to 35

Nonionic surfactant A '0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10

Anionic copolymer C 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18

Polyvinylpyrrolidone particles 0.1 to 5 0, 1 to 5 0, 1 to 5 0, 1 to 5

Zinc salt 0.01 to 10, 1 to 0.5 0.01 to 1 0.1 to 0.5

Sodium percarbonate 2 to 30 2 to 30 4 to 20 4 to 20

Bleaching catalyst 0 to 2 0.0025 to 1 0 to 2 0.0025 to 1

Mise Add 100 Add 100 Add 100 Add 100 Ingredient Recipe 21 Recipe 22 Recipe 23 Recipe 24

 [Wt%] [wt%] [wt%] [wt%]

Tripolyphosphate 5 to 50 15 to 40 -

Citrate _* 5 to 40 15 to 30

Carbonate 2 to 45 2 to 35 2 to 45 2 to 35

Nonionic surfactant A ¹ 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10

Anionic copolymer C 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18

Polyvinylpyrrolidone particles; 0.1 to 5 0, 1 to 5 0, 1 to 5 0, 1 to 5 diameter: 100-150 μιη

 Zinc salt 0.01 to 10, 1 to 0.5 0.01 to 1 0.1 to 0.5

Sodium percarbonate 2 to 30 2 to 30 4 to 20 4 to 20

Bleaching catalyst 0 to 2 0.0025 to 1 0 to 2 0.0025 to 1

Mise Add 100 Add 100 Add 100 Add 100

Ingredient Recipe 29 Recipe 30 Recipe 31 Recipe 32

 [Wt%] [wt%] [wt%] [wt%]

Tripolyphosphate 5 to 50 15 to 40 -

Citrate _* 5 to 40 15 to 30

Carbonate 2 to 45 2 to 35 2 to 45 2 to 35

Nonionic surfactant A ^{1 b} 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10

Anionic copolymer C ¹ 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18

Polyvinylpyrrolidone particles; 0.1 to 5 0, 1 to 5 0, 1 to 5 0, 1 to 5 diameter: 100-150 μιη Zinc salt 0.01 to 10, 1 to 0.5 0.01 to 1 0.1 to 0.5

Sodium percarbonate 2 to 30 2 to 30 4 to 20 4 to 20

Bleaching catalyst 0 to 2 0.0025 to 1 0 to 2 0.0025 to 1

Mise Add 100 Add 100 Add 100 Add 100

a nonionic surfactant A of the general formula R 0 (AlkO) _x M (OAlk) _y OR ² in which

R and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;

 Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms;

- x and y independently for values between 1 and 70; and

M is 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 having 1 to 18 carbon atoms

a nonionic surfactant A of the general formula R -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 is} used, in of the

R, R and R ² independently represent an alkyl or alkenyl radical having 6 to 22 carbon atoms;

 - x and y independently represent values between 1 and 40

a nonionic surfactant A of the general formula R-O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y O-R ^{2 is} used in the

R and R ² independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms; R ³ and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and

 - x and y independently represent values between 1 and 40;

 an anionic polymer C from the group of copolymeric polycarboxylates and copolymeric polysulfonates

 an anionic polymer C comprising

 i) carboxylic acid group-containing monomer (s)

 ii) sulfonic acid group-containing monomer (s)

 iii) optionally nonionic monomer (s).

 "-" means: the recipe is free of this ingredient

embodiments

 In a commercial dishwashing tablet containing zinc acetate, PVP particles having a particle diameter of 100-150 μιη were incorporated. 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 passing through 50 and 100 cycles. Both the glass corrosion and the decorative removal of the treated glassware were assessed visually on a scale of 0 to 5, with 5 being the best grade. The results are shown in the following table:

 The results show that the addition of the PVP particles reduced both the corrosion of the glass and the removal of the decoration, the improvement of the decoration protection being even more pronounced than the reduction of the glass corrosion.

Claims

claims Machine dishwashing detergent containing at least one zinc salt and at least one polymer containing N-containing heterocycles. A machine dishwashing detergent according to claim 1, characterized in that the polymer containing N-containing heterocycles is a polyvinylpyrrolidone. Machine dishwashing detergent according to claim 2, characterized in that the polyvinylpyrrolidone is in particulate form, wherein the polyvinylpyrrolidone particles preferably have an average particle diameter of 100 to 150 μιη and preferably in an amount of 0, 1 to 5 wt .-%, in particular an amount of 0.2 to 3 wt .-%, especially in an amount of 0.3 to 1, 8 wt .-% in the dishwashing detergent are included. Machine dishwashing detergent according to one of claims 1 to 3, 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 that the zinc salt is preferably in an amount of 0.01 to 3 wt .-%, preferably in an amount of 0.05 to 2 wt .-%, in particular in an amount of 0.1 to 1 wt. %, which contains dishwashing detergent. Machine 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. Machine 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) monomer (s) containing carboxylic acid groups, ii) sulfonic acid group-containing monomer (s) and iii) optionally nonionic monomer (s), wherein the anionic polymer is preferably in an amount of 0, 1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably from 1, 0 to 15 wt .-% and especially from 4 to 14 Wt .-% is included. 7. Machine dishwashing detergent according to one of the preceding claims, characterized in that a 10% solution of the composition in distilled water (20 ° C) has a pH of 7 to 13, in particular 8 to 12, particularly preferably 9 to 1 1, having. 8. Machine dishwashing detergent according to one of the preceding claims, characterized in that it is present as a pressed molded body, in particular as Kompaktat, especially as a tablet. 9. A machine dishwashing process, characterized in that a machine dishwashing detergent according to one of the preceding claims is used, in particular for effecting improved glass, porcelain and / or decorative protection or for reducing glass and porcelain corrosion and / or  Reduction of decor removal. 10. Use of a combination of a zinc salt and a polymer containing N-containing heterocycles, wherein the polymer is preferably a  Polyvinylpyrrolidone acts to effect improved glass, porcelain and / or decorative protection or to reduce glass and porcelain corrosion and / or to reduce the decorative ablation.