DE102015213942A1 - Machine dishwashing detergent containing bleaching agents and polymers - Google Patents

Abstract

The present invention relates to automatic dishwashing compositions which contain at least one bleach, at least one bleach catalyst, at least one homopolymer of α, β-ethylenically unsaturated carboxylic acids and at least one copolymer containing at least one sulfonic acid group-containing monomer and at least one monomer from the group of α, β ethylenic unsaturated carboxylic acids and their use in a dishwasher automatic machine and corresponding methods for automatic dishwashing.

Description

The present invention relates to a machine dishwashing detergent which exhibits improved cleaning performance, especially on bleach-sensitive soiling, the use of this dishwashing detergent and a machine dishwashing method using this dishwashing detergent.

The most important criterion in automatic dishwashing is the cleaning performance on a wide variety of soiling, which are introduced into the dishwasher in the form of food residues. In this respect, there is generally a need for dishwashing detergents with increased cleaning performance. In addition, a general trend for reasons of environmental protection in machine dishwashing to dispense with phosphates is observed. The problem thus arises of providing phosphate-free automatic dishwashing detergents without impairing the cleaning performance.

The object of the present invention was therefore to provide a, preferably phosphate-free, machine dishwashing agent which has an increased cleaning performance.

It has now been found that the use of certain polymers in automatic dishwashing detergents containing a bleaching agent and a bleach catalyst surprisingly results in increased bleaching performance and thus improved cleaning performance on bleach-sensitive stains without changing the bleach catalyst amount.

A first object of the present invention is therefore a machine dishwashing detergent containing at least one bleach, at least one bleach catalyst, at least one homopolymer of an α, β-ethylenically unsaturated carboxylic acid and at least one copolymer containing at least one sulfonic acid-containing monomer and at least one monomer from the group α, β ethylenically unsaturated carboxylic acids.

Likewise provided by the present invention is the use of a machine dishwashing detergent according to the invention in a machine dishwashing process, in particular the use for improving the cleaning performance on bleach-sensitive soiling on dishes during its cleaning in an automatic dishwashing machine.

Finally, the present invention is also directed to a machine dishwashing process in which a machine dishwashing agent according to the invention is used, in particular for the purpose of improving the cleaning performance of bleach-sensitive soiling.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples. All percentages are by weight unless otherwise specified. Numeric ranges indicated in the format "from x to y" include the above values. If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints are also captured.

"At least one" as used herein means 1 or more, i. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the type of ingredient, not the absolute number of molecules. Thus, "at least one bleach catalyst" means, for example, at least one type of bleach catalyst, i. that is, one type of bleach catalyst or a mixture of several different bleach catalysts may be meant. The term, together with weights, refers to all compounds of the type indicated which are included in the composition / mixture, i. that the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.

When referring to molecular weights herein, these references always refer to the number average molecular weight Mn, unless otherwise stated. The number average molecular weight can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1: 2007-08 be determined with THF as the eluent. The weight average molecular weight Mw can also be determined by GPC as described for Mn.

All percentages given in connection with the compositions described herein, unless explicitly stated otherwise, relate to% by weight, in each case based on the mixture in question.

A phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by various features, such as ingredients, physical properties, appearance, etc. Preferably, different phases can be visually distinguished. Thus, for the consumer, the at least one first phase is clearly distinguishable from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, then these can likewise be differentiated from one another by the naked eye, because they differ, for example, from one another in color. The same applies if two or more second phases are present. Also in this case, a visual differentiation of the phases, for example due to a color or transparency difference is possible. Phases in the sense of the present invention are thus self-contained areas that can be optically distinguished from the consumer by the naked eye. The individual phases may have different properties in use, such as the rate at which the phase dissolves in water and thus the rate and order of release of the ingredients contained in the respective phase.

The phases are typically spatially separated. This can be done in various embodiments such that when one or both of the phases are liquid phases, the liquid phase is separate from the other phase in a separate, sealed area, for example the chamber of a pouch. Such Konfektionsformen are known in the art. For solid agents, i. Means in which both phases are solids, the two phases are also made up spatially separated from each other, for example in the form of a multi-chamber pouches, each of the phases is present in a separate chamber. Alternatively, in the case of compacted agents, such as tabs or tablets, in particular multi-phase tabs as known in the art, the two phases may be arranged directly adjacent to each other spatially in such a way that the phases are formulated separately and contact each other, but can not mix.

In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms. In particular, the oxo alcohols or their derivatives which are obtainable, for example, by the ROELEN's oxo synthesis can also be used correspondingly.

Whenever alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.

The homopolymers used according to the invention are homopolymers of α, β-ethylenically unsaturated carboxylic acids. Unsaturated carboxylic acid (s) used are, with particular preference, unsaturated carboxylic acids of the formula R ¹ (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, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -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 (methylmaleic acid), methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Very particular preference is given to acrylic acid. In various embodiments of the invention, the homopolymer is therefore a polyacrylic acid.

In the polymers, the carboxylic acid groups may be wholly or partially in neutralized form, i. in that the acidic carbon atom of the carboxylic acid group in some or all of the carboxylic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or completely neutralized polymers is preferred according to the invention.

The molecular weight of the homopolymers used can be varied in order to adapt the properties of the polymers to the desired end use. Preferred dishwashing detergents are characterized in that the homopolymers, in particular the polyacrylic acids, have molar masses M _{n of} from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1100 to 10 000 g / mol, and more preferably from 1200 to 5000 g / mol, may again be preferred from this group.

The copolymers of the invention may have two, three, four or more different monomer units. Preferred copolymers contain, in addition to sulfonic acid-containing monomer (s), at least one monomer from the group of unsaturated carboxylic acids.

As the unsaturated carboxylic acid (s), the above-described unsaturated carboxylic acids are / are used with particular preference. Acrylic acid is very particularly preferred.

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 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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -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 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 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 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 -.

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-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

Also in the copolymers, the acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic and / or carboxylic acid group in some or all 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 copolymers is preferred according to the invention.

The monomer distribution of the copolymers preferably used 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 the proportion of the sulfonic acid group-containing monomer is from 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

In various embodiments, in addition to the above-described carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, the copolymers may contain other monomers, particularly unsaturated carboxylic acid ester group-containing monomers. In such terpolymers are the carboxylic acid ester group-containing monomers, for example those of the formula R ¹ (R ² ) C =C (R ³ ) COOR ⁴ , in which R ¹ to R ^{3 are} as defined above and R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acid esters are alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, sorbic acid, cinnamic acid or mixtures thereof. Very particular preference is given to C _1-8 -alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate. Very particular preference is given to ethyl acrylate.

The molecular weight of the copolymers used can also be varied in order to adapt the properties of the polymers to the desired end use. Preferred dishwashing detergents are characterized in that the copolymers have molar masses Mn of 2,000 to 200,000 g / mol, preferably of 4,000 to 25,000 g / mol and in particular of 5,000 to 15,000 g / mol.

The homopolymers and copolymers can each be used in amounts of 0.5 to 10 wt .-%, preferably 1 to 5 wt .-%, based on the total weight of the composition. Absolute amounts are typically in the range of 0.1 to 2 g / job, preferably in the range of 0.2 to 1.0 g / job. The mass ratio of the polymers to each other, i. Homopolymer to copolymer, is in various embodiments, 5: 1 to 1: 5, preferably 2: 1 to 1: 2.

Surprisingly, the polymer combinations used according to the invention, which are as defined above, have the property of improving the performance of bleach catalysts contained in the dishwashing detergent and therefore lead to an improved cleaning performance on bleach-sensitive soiling.

In this case, the improvement in bleach catalyst performance or improvement in the cleaning or bleaching performance is generally to be understood as meaning that when using the dishwashing detergent according to the invention, the removal of stains, in particular bleach-sensitive stains, on dishes during its cleaning in an automatic dishwashing machine in comparison with the use of Dishwashing agents that do not contain the complexing agents according to the invention, is significantly improved.

The dishwashing agents may further contain other polymers. Suitable polymers include, in particular, the cleaning-active amphoteric, zwitterionic or cationic polymers, for example the rinse aid polymers and / or polymers which act as softeners.

Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Further usable zwitterionic polymers are from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

Useful cationic polymers come from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

• – die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• – die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• – die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the abovementioned amphoteric, zwitterionic or cationic polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• The encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• - The encapsulation of the polymers by means of water-insoluble, fusible coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
• - The cogranulation of the polymers with inert support materials, preferably with support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

Machine dishwashing detergents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of from 0.01 to 10% by weight, based in each case on the total weight of the automatic dishwashing detergent. In the context of the present application, however, preference is given to those automatic dishwasher detergents in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0, 01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing detergent is.

The bleach catalysts useful in this invention include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru or Mo salicene 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.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. 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 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 detergent, characterized in that it 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-TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN) are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.

The abovementioned bleach-enhancing transition metal complexes, in particular having the central atoms Mn and Co, are preferably used in an amount of up to 1% by weight, in particular from 0.001% by weight to 0.1% by weight and more preferably of 0.01% by weight. % to 0.05 wt .-%, each based on the total weight of the bleach catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.

The bleaching agents which can be used according to the invention are washing or cleaning-active substances. Among the compounds serving as bleaches in water H ₂ O ₂ , 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, phthaloimino peracid 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. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.

As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine releasing materials are, for example heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Preferably, the bleaching agent is in an amount of 1-35 wt%, and more preferably 2-30 wt%, 3.5-25 wt%, 4-20 wt%, and most preferably 5 -15 wt .-% in the dishwashing detergent according to the invention, each based on the total weight of the dishwashing detergent. Preferred dishwashing detergents are further characterized in that the dishwashing detergent, based in each case on the total weight of the dishwashing detergent, contains from 2 to 20% by weight, preferably from 3 to 18% by weight and in particular from 4 to 15% by weight of sodium percarbonate.

Particularly preferred embodiments of dishwasher detergents according to the invention are characterized in that the bleach catalyst is selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of the complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me). TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or the source of hydrogen peroxide is sodium percarbonate, sodium perborate tetrahydrate or sodium perborate monohydrate, or a combination thereof. Most preferably, the bleach catalyst is a complex of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), in particular [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ , or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN) or a mixture thereof, and the hydrogen peroxide source sodium percarbonate. In the said combinations, the bleach catalyst and the hydrogen peroxide source are preferably present in the amounts stated above.

In various embodiments of the invention, the automatic dishwashing agents additionally contain at least one bleach activator. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Of all the bleach activators known to the person skilled in the art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Very particular preference is TAED. Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.

The agents according to the invention preferably comprise at least one further constituent, in particular at least two further constituents selected from the group consisting of builders, surfactants, enzymes, corrosion inhibitors and glass corrosion inhibitors, disintegration auxiliaries, fragrances and perfume carriers.

The following describes possible ingredients which can be advantageously used in the machine dishwashing detergents according to the invention.

The use of builders (builders) such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, may be advantageous.

In a preferred embodiment according to the invention, the use of phosphates (including polyphosphates) is largely or completely omitted. The agent in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s). Most preferably, in this embodiment, the agent is completely phosphate-free, i. the agents contain less than 0.1% by weight of phosphate (s).

The builders include in particular carbonates, citrates, phosphonates, organic builders and silicates. The proportion by weight of the total builders in the total weight of compositions according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.

Suitable organic builders according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, such polycarboxylic acids being carboxylic acids of this type be understood that carry more than one, in particular two to eight acid functions, preferably two to six, in particular two, three, four or five acid functions in the entire molecule. Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, for example nitrilotriacetic acid (NTA), glutamine-N, N -diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA)) and their derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures thereof.

Also suitable as organic builders are polymeric polycarboxylates (organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

In addition to their builder effect, the free acids also typically have the property of an acidifying component and can thus, if desired, also serve to set a lower pH. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwasher detergents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 28 wt .-%, particularly preferably 10 to 25 wt .-%, most preferably 15 to Contain 20 wt .-%, each based on the total weight of the composition.

Also particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate (soda), in amounts of 2 to 50 wt .-%, preferably from 4 to 40 wt. -% and in particular from 10 to 30 wt .-%, most preferably 10 to 24 wt .-%, each based on the weight of the composition.

Particularly preferred cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, are characterized in that they comprise at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the weight fraction of these builders, based on the total weight of the inventive detergent, preferably 5 to 70 wt .-%, preferably 15 to 60 wt .-% and in particular 20 to 50 wt .-% is. The combination of two or more builders from the above-mentioned group has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents. In addition to the builders mentioned here, one or more other builders may additionally be present.

Preferred cleaning agents, in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate.

In a very particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight. and the amount of citrate is preferably from 5 to 35 wt .-%, in particular 10 to 25 wt .-%, most preferably 15 to 20 wt .-%, each based on the total amount of the cleaning agent, wherein the total amount of these two Builders preferably 20 to 65 wt .-%, in particular 25 to 60 wt .-%, preferably 30 to 50 wt .-%, is. In addition, one or more further builders may additionally be included.

The detergents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, may in particular contain phosphonates as further builder. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Ethylenediamine tetramethylene phosphonate (EDTMP) preferably comes as Aminoalkanphosphonate, Diethylenetriamine pentamethylenephosphonate (DTPMP) and their higher homologues in question. Phosphonates are preferably present in compositions according to the invention in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5% by weight, in each case based on the total weight of the agent.

Particularly preferred is the combined use of citrate, (hydrogen) carbonate and phosphonate. These can be used in the above quantities. In particular, in this combination amounts of, in each case based on the total weight of the composition, 10 to 25 wt .-% citrate, 10 to 30 wt .-% carbonate (or bicarbonate), and 2.5 to 7.5 wt .-% Phosphonate used.

Further particularly preferred cleaning agents, in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized in that in addition to citrate and (hydrogen) carbonate and optionally phosphonate they contain at least one further phosphorus-free builder. In particular, it is selected from among the aminocarboxylic acids, wherein the further phosphorus-free builder is preferably selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), more preferably MGDA or GLDA. A particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.

The percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight. Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules. Advantageous in this case are those MGDA granules which contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25 ° C., normal pressure) compared to the non-granulated powder. The combination of at least three, in particular at least four, builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwasher detergents. In addition, other builders may be included.

As organic builders, polymeric polycarboxylates are furthermore suitable; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 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 cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, of (homo) polymeric polycarboxylates is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight.

Detergents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, can furthermore comprise, as builder, crystalline stratiform silicates of the general formula NaMSi _x O _{2 x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being 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 certain detergents according to the invention, in particular dishwashing detergents, preferably dishwasher detergents, the content of silicates, based on the total weight of the detergent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight ,

In addition to the abovementioned builders, the washing or cleaning agents according to the invention may furthermore comprise alkali metal hydroxides. These alkali carriers are preferred in the washing or 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 the detergent or cleaning agent used. Alternative cleaning agents according to the invention are free of alkali metal hydroxides.

The compositions of the invention may contain surfactants, wherein the nonionic, the anionic, the cationic and the amphoteric surfactants are counted among the group of surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R corresponds to a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

However, low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. With particular preference, the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.

A class of useful nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Preferably used surfactants come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are characterized by good foam control.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen. Suitable nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

Of these, particular preference is given to nonionic surfactants which have a C _9-15 -alkyl radical containing 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.

• – R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• – R² für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• – A, A’, A’’ und A’’’ unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃) stehen,
• – w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Preferred nonionic surfactants here are those of the general formula R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A''O) _y - (A '''O) _z -R ² , in the

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• - A, A ', A''andA''' are independently a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),
• - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.

Preference is given in particular to those end-capped, poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60. Especially preferred are surfactants of the above formula in which R ^{1 is} C ₇ to C ₁₃ , x is an integer from 16 to 28 and R ^{2 is} C ₈ to C ₁₂ .

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 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.

The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether. Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and 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 very particularly preferred.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

• – R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• – R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• – A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• – w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht

Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proven to be particularly effective, in which

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ), preferably CH ₂ CH ₂ , and
• W stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40

The group of these nonionic surfactants include, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

In various embodiments of the invention, instead of the above-defined end-capped hydroxy mixed ethers, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These may satisfy the above formulas, but R ² is hydrogen and R ¹ , R ³ , A, A ', A'',A''', w, x, y and z are as defined above.

The compositions described herein, which comprise at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the surfactant in various embodiments in an amount based on the total weight of the composition of at least 2 wt.%, Preferably at least 5 wt. %. For example, the amounts used per application may be in the range of 0.5-10 g / job, preferably in the range of 0.5-5 g / job.

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

Suitable anionic surfactants in dishwashing detergents are all anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Instead of or in combination with the surfactants mentioned, it is also possible to use cationic and / or amphoteric surfactants, such as betaines or quaternary ammonium compounds. However, it is preferred that no cationic and / or amphoteric surfactants are used.

The amounts given above for the described surfactants and builders usually refer to the amounts that are used when the particular surfactant or the respective builders used alone, unless explicitly stated otherwise. It is therefore natural that when using multiple surfactants or builders, the quantities are adjusted accordingly.

Preferably, the agents of the present invention contain at least one enzyme preparation or enzyme composition containing one or more enzymes. Suitable enzymes include, but are not limited to, 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, which are preferably used accordingly. Detergents ^according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Proteases are among the most technically important enzymes of all. For detergents and cleaners, they are the longest established and contained in virtually all modern, powerful detergents and cleaners enzymes. They cause the degradation of protein-containing stains on the items to be cleaned. Of these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are due to the catalytically active amino acids serine proteases. They act as nonspecific endopeptidases and hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range. For an overview of this family, for example, the article "Subtilases: Subtilisin-like Proteases" by R. Siezen, pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996 , Subtilases are naturally produced by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.

Examples of the subtilisin-type proteases preferably used in detergents and cleaners are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the the subtilases, but not the subtilisins in the narrower sense attributable enzyme thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of said proteases, which have a relation to the parent protease modified amino acid sequence. Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and cleaners. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, correspondingly optimized variants are known for most proteases known from the prior art.

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 as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. 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, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L, T213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-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 preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

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 the case of microbial recovery of the 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.

Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage 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 is coated with a water, air and / or chemical impermeable protective layer. 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. 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 wt .-% of the enzyme protein.

Particular preference is given to 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 compositions described herein may also include enzyme stabilizers. One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Also, peptide aldehydes, that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose. Among the peptidic reversible protease inhibitors include ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art.

In general, the pH of the dishwashing detergent can be adjusted by means of customary pH regulators, the pH value being chosen as a function of the desired intended use. In various embodiments, the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, more preferably 7 to 9, especially greater than 7, especially in the range 7.5 to 8.5 , The pH adjusting agents are acids and / or alkalis, preferably alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. However, particularly preferred is volatile alkali, for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule. The alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.

To adjust and / or stabilize the pH, the composition according to the invention may also contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents). Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate.2H ₂ O and tripotassium citrate H ₂ O.

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes. In the context of the present invention, the content of zinc salt in dishwasher detergents is preferably between 0.1 and 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight .-%, each based on the total weight of the glass corrosion inhibitor-containing agent. Additionally or alternatively to the above-mentioned salts (especially zinc salts) may polyethyleneimines described, for example, under the name Lupasol ^® (BASF) can be obtained, preferably in an amount of 0 to 5 wt .-%, particularly 0.01 to second %, are used as glass corrosion inhibitors.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

Furthermore, preservatives may be included in the compositions. Suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2 Benzyl 4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4- Chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.

In general, the formulation of automatic dishwashing agents described herein can be carried out in different ways. The agents may be in solid or liquid form as well as in a combination of solid and liquid forms. Powder, granules, extrudates, compacts, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels. The agents can be formulated in the form of single-phase or multi-phase products. The individual phases of multiphase agents may have the same or different states of matter.

A phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by various features, such as ingredients, physical properties, appearance, etc. Preferably, different phases can be visually distinguished. Thus, for the consumer, the at least one first phase is clearly distinguishable from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, then these can likewise be differentiated from one another by the naked eye, because they differ, for example, from one another in color. The same applies if two or more second phases are present. Also in this case, a visual differentiation of the phases, for example due to a color or transparency difference is possible. Phases in the sense of the present invention are thus self-contained areas that can be optically distinguished from the consumer by the naked eye. The individual phases may have different properties in use, such as the rate at which the phase dissolves in water and thus the rate and order of release of the ingredients contained in the respective phase.

The dishwashing detergents can be present as shaped bodies. In order to facilitate the disintegration of such prefabricated moldings, it is possible Disintegrationshilfsmittel, so-called tablet disintegrants in this To incorporate means to reduce the disintegration times. By tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients. Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

The automatic dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the amount of cleaning-active substances necessary for a cleaning cycle. 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 is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

The automatic dishwashing agents, in particular the prefabricated metering units, have a water-soluble coating, with particular preference.

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.

The water soluble package may have one or more chambers. The agent may be contained in one or more chambers, if any, of the water soluble envelope. The amount of agent preferably corresponds to the full or half dose needed for a rinse.

It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 5,000 to 1,000,000 gmol ^-1 , preferably 20,000 to 500,000 gmol ^-1 , more preferably 30,000 to 100,000 gmol ^-1 and especially from 40,000 to 80,000 gmol ^-1 .

The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

In addition, a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above can be additionally used as a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers. A preferred additional polymer is polylactic acids.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.

It may be preferred that the film material contains further additives. The film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films with the label Solublon ^® PT, Solublon ^® GA, Solublon KC ^® or Solublon ^® KL by Aicello Chemical Europe GmbH, or VF-HP film available from Kuraray.

According to a preferred embodiment, the multi-phase dishwashing detergent is closely enveloped by a water-soluble film

The water-soluble film, which is preferably used in the narrow envelope, particularly preferably comprises polyvinyl alcohol, as described above, wherein as starting thickness preferably a thickness of 10 .mu.m to 100 .mu.m, in particular from 12 .mu.m to 60 .mu.m, particularly preferably from 15 .mu.m to 50 μm, especially from 20 microns to 40 microns, in particular from 22 microns to 35 microns is used.

In the case of a tight envelope, a disposable portion of the washing or cleaning agent is wrapped in each case. For the coated detergent or cleaning agent portion according to the invention, it is important that the coating rests close to its surface at any point of the tablets. Ideally, the envelope is even under tension, which is not absolutely necessary. This dense covering of the envelope is conducive to disintegration: upon first contact with water, the envelope will pass a small amount of water at some point, and at first it does not need to dissolve at all. At this point, the disintegrant contained in the tablet begins to swell. As a result, the wrapper suddenly ruptures as a result of the volume increase of the tablet and releases the tablet. If the wrapper is not tight, the mechanism described here will not work as the tablet can swell without bursting the wrapper. In this case, the use of a swellable disintegrating agent is superior to a gas-developing system, since its explosive effect in each case leads to a rupture of the casing. In a gas-evolving system, the explosive effect may "fizzle out" of the enclosure by leakage of the gas from a leak.

Preferred detergent or cleaning agent portions according to the invention are characterized in that the distance between the disposable portion and water-soluble coating over the entire surface is 0.1 to 1000 μm, preferably 0.5 to 500 μm, particularly preferably 1 to 250 μm and in particular 2.5 to 100 microns, is.

In a preferred embodiment, the film wrapping is first loosely wrapped around a detergent or cleaning agent portion and sealed and then shrunk onto it so that there is close contact between the film package and the detergent concentrate. Accordingly, washing or cleaning agent disposable portions according to the invention are characterized in that the wrapping is a film packaging shrunk onto the latter.

For example, this wrapping can be done by placing a water-soluble lower film on a conveyor chain or a mold (s) tool, then one or more detergent or cleaning agent portion (s) are placed on the lower film; then a water-soluble upper film is placed on the washing or cleaning agent portion (s) on the lower film and this is then fixed on the lower film, including the washing or cleaning agent portion (s),

Alternatively, this step can also be done by a single-stranded film, which is then placed around the disposable portions as a tube. This is followed by sealing and optional cutting of the films. Subsequently, then the shrinking of the film by the use of hot air or infrared radiation, optionally with pressing done.

Such water-soluble coatings are also in the patent applications WO 2004/031338 A such as WO 2003/099985 A , the disclosure of which is hereby incorporated by reference, already described.

Exemplary formulations of the agents according to the invention also include, in particular, phosphate-free dishwashing detergents. An exemplary formulation in which the polymers described herein can be used in the stated amounts as an additional ingredient is the following: Table 1: Phosphate-free, solid dishwashing detergent formulation (tab), Active In% by weight based on the total weight of the formulation: raw material Amount (wt%) Na citrate 15.00 to 20.00 Phosphonate (eg HEDP) 2.50 to 7.50 MGDA 0.00 to 25.00 Silicate (Na disilicate) 5.00 to 35.00 soda 12.50 to 25.00 Na Percarbonate 10.00 to 15.00 bleach catalyst 0.02-0.50 TAED 2.00-3.00 nonionic surfactant 2.50 to 10.00 Cationic copolymer 0.25-0.75 PVP (cross-linked) 0.00 to 1.50 Sulfonic acid containing polymer 0.5 to 10.00 Polyacrylathomopolymer 0.5 to 10.00 protease 1.50 to 5.00 amylase 0.50 to 3.00 Benzotriazole (silver protection) 0.00 to 0.50 Perfume 0.05-0.15 dye solution 0.00-1.00 Zn acetate anhydrous 0.10-0.30 Na sulfate 0.00 to 25.00 water 0.00 to 1.50 pH adjusting agent (citric acid) 1.00-1.50 processing aids 0.00 to 5.00

The corresponding use of the automatic dishwasher detergents according to the invention is likewise an object of the invention. The invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a dishwashing detergent according to the invention is used. The subject matter of the present application is therefore furthermore a process for the cleaning of dishes in a dishwashing machine, in which the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the main wash cycle or during the main wash cycle. The metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.

The embodiments described in context with the agents according to the invention are readily transferable to the methods and uses of the invention and vice versa.

Examples

Example 1: Cleaning performance

Table 2: Comparative Experiments Data Active In% by Weight Based on the Total Weight of the Formulation: raw materials standard formula Standard formula + combination sulfopolymer + polyacrylate (E1) Standard formula + sulfopolymer (V1) Standard formula + polyacrylate (V2) % * g / job addition addition addition from to from to g / job g / job g / job Sodium citrate / citric acid 15 20 2 4 Citric acid (pH adjuster) 1 1.5 0.2 0.3 phosphonate 2.5 7.5 0.5 1.50 silicate 5 35 1 7 soda 12.5 25 2.5 5.00 Na Percarbonate 10 15 2.00 3.00 bleach catalyst 0.02 0.5 0,00 3 0.1 TAED 2.0 3.0 0.40 0.60 Nonionic surfactants 2.5 10.0 0.50 2.0 benzotriazole 0.0 0.5 0.0 0.1 sulfopolymer * 0.6 1.2 0 Polyacrylate (homopolymer) 0.6 0 1.2 cationic co-polymer 0.25 0.75 0.05 0.15 Crosslinked PVP 0.00 1.5 0.0 0.30 Protease (s) (tq) 1.5 5.00 0.30 1.00 Amylase (s) (tq) 0.5 3.0 0.1 0.60 Perfume 0.05 0.15 0.01 0.03 dyes 0 1.0 0.00 0.2 Zn acetate 0.1 0.3 0.02 0.06 0 Na sulfate 0 25 0.1 5.0 water 0.0 1.5 0.0 0.30 * based on 20 g tablet weight * Copolymer (AMPS and acrylic acid containing)

The cleaning performance was determined in Bosch dishwashers in the 40 ° C program. Water hardness 21 ° dH. For this purpose, 20 g of the above formulations (tab) were used. After completion of the rinse cycle, the dishes were visually peeled off on a scale of 1-10. The higher the value, the better the Cleaning performance. It can be seen that the formulation according to the invention, which contains both polymers, shows a better cleaning performance on various soils, especially on tea, compared to the comparative formulations, which contain only one of the polymers in each case (Table 3). Table 3: Cleaning performance ADW product Tea (Assam) Creme brulee minced meat V1 4.9 7.1 4.2 V2 5.7 6.2 4.8 E1 6.7 7.3 5.4

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2004/031338 A [0137]
• WO 2003/099985 A [0137]

Cited non-patent literature

• DIN 55672-1: 2007-08 [0010]
• "Subtilases: Subtilisin-like Proteases" by R. Siezen, pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996. [0096]

Claims (10)

A machine dishwashing detergent, characterized in that the automatic dishwashing detergent contains: (i) at least one bleaching agent; (ii) at least one bleach catalyst; (iii) at least one homopolymer of α, β ethylenically unsaturated carboxylic acids; and (iv) at least one copolymer containing at least one sulfonic acid group-containing monomer and at least one monomer selected from the group of α, β-ethylenically unsaturated carboxylic acids. Machine dishwashing detergent according to claim 1, characterized in that the at least one homopolymer is a polymer of an α, β-ethylenically unsaturated carboxylic acid of the formula R ¹ (R ² ) C = C (R ³ ) COOH, where R ¹ to R ^{3 are} independently 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, alkyl radical substituted by -NH ₂ , -OH or -COOH or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, in particular of acrylic acid. Machine dishwashing detergent according to claim 1 or 2, characterized in that the at least one copolymer is a copolymer of (i) at least one monomer from the group of α, β ethylenically unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH, where 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, 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, in particular acrylic acid; and (ii) at least one sulfonic acid group-containing monomer of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, where 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, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH or -COOH or -COOR ⁴ wherein R ^{4 is} a saturated or unsaturated, 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 -, preferably at least one monomer of the formula H ₂ C =CH-X-SO ₃ H, H ₂ C =C (CH ₃ ) -X-SO ₃ H or HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, where R ⁶ and R ^{7 are} independently v are selected from among -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ 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 -, more preferably a monomer selected from the group consisting of 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-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, and sulfomethylmethacrylamide, most preferably 2-acrylamido-2-methyl-1-propanesulfonic acid; and (iii) optionally at least one α, β-ethylenically unsaturated carboxylic acid ester group-containing monomer of the formula R ¹ (R ² ) C =C (R ³ ) COOR ⁴ , wherein R ¹ to R ^{3 are} as defined above and R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, in particular an alkyl acrylate, particularly preferably ethyl acrylate. Machine dishwashing detergent according to one of claims 1 to 3, characterized in that (i) the at least one homopolymer has a molecular weight Mn in the range from 1000 to 20,000 g / mol, more preferably 1100 to 10,000 g / mol and particularly preferably from 1200 to 5000 g / has mol; and / or (ii) the at least one copolymer has a molecular weight Mn of from 2000 to 200,000 g / mol, preferably from 4000 to 25,000 g / mol and in particular from 5000 to 15,000 g / mol. Machine dishwashing detergent according to one of claims 1 to 4, characterized in that (I) the at least one homopolymer and / or the at least one copolymer is in each case in an amount of 0.5 to 10 wt .-%, preferably 1 to 5 wt .-%, based on the total weight of the automatic dishwashing agent is included; and / or (ii) the mass ratio of the at least one homopolymer and the at least one copolymer is 5: 1 to 1: 5, preferably 2: 1 to 1: 2. A machine dishwashing detergent according to any one of claims 1 to 5, characterized in that the bleach catalyst is selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably the complexes of manganese in the oxidation state II, III, IV or IV, one or more macrocyclic (n ) Ligand (s) with the donor functions N, NR, PR, O and / or S, more preferably the macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1.4 , 7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN), most preferably the ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN). or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN). A machine dishwashing detergent according to any one of claims 1 to 6, characterized in that the bleach catalyst in an amount of 0.001 to 0.1 wt .-%, preferably 0.01 to 0.05 wt .-% based on the total weight of the automatic dishwashing agent is. A machine dishwashing detergent according to any one of claims 1 to 7, characterized in that (1) the at least one bleaching agent is selected from the group consisting of sodium percarbonate, sodium perborate tetrahydrate, sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates, perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid, diperdodecanedioic acid, diacyl peroxides, Alkyl peroxyacids and aryl peroxyacids, preferably sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate, more preferably sodium percarbonate; and / or (2) the at least one bleaching agent in an amount of 1-35 wt.%, and more preferably 2-30 wt.%, 3.5-25 wt.%, of 4-20 wt. % and more preferably from 5-15% by weight in the dishwashing detergent, in each case based on the total weight of the dishwashing detergent; and / or (3) the machine dishwashing detergent is in solid form; and / or (4) the automatic dishwashing detergent is in preportioned form; and / or (5) the automatic dishwashing detergent has a plurality of spatially separate compositions of which at least one composition is solid and / or a composition is liquid; and / or (6) the automatic dishwashing agent contains at least one bleach activator; and / or (7) the automatic dishwashing agent contains at least one further constituent, preferably at least two further constituents selected from the group consisting of builders, surfactants, enzymes, corrosion inhibitors, glass corrosion inhibitors, disintegration aids, fragrances and perfume carriers.  Use of a machine dishwashing detergent according to any one of claims 1-8 in a machine dishwashing process. Machine dishwashing process, characterized in that a machine dishwashing detergent according to any one of claims 1-8 is used.