DE102012209506A1 - Dishwashing liquid - Google Patents

Abstract

Dishwashing compositions which comprise at least one cyclic compound having at least two carboxylate groups and at least one phosphorus-free builder are characterized by very good inhibition of coating in automatic dishwashing.

Description

The present application describes dishwashing detergents, which are preferably in the form of tablets, as well as automatic dishwashing processes using these dishwashing detergents, and the use of these dishwashing detergents for removing soiling and for inhibiting coating in automatic dishwashing.

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. Machine dishwashing detergents commonly used today generally contain phosphorus-containing ingredients, in particular phosphates and / or phosphonates, which are used as builders in the compositions.

Since phosphorus-containing ingredients are considered harmful to the environment and according to statutory regulations, a limitation of the use of phosphorus-containing ingredients is expected, there is a need to provide dishwashing detergents, which even without phosphorus-containing ingredients an equivalent replacement for today's common phosphorus -containing, in particular phosphonate and / or phosphate-containing means. One object was to provide phosphate- and / or phosphonate-free compositions which have an equivalent cleaning performance to corresponding phosphate and / or phosphonate-containing agents. A further object was to provide agents with an equivalent secondary performance, in particular with an equivalent deposit inhibition. In this case, these improved properties 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, can be achieved.

This object has been achieved by dishwashing agents which comprise at least one cyclic compound having at least two carboxylate groups and at least one phosphorus-free builder.

Because according to the invention it has surprisingly been found that the cleaning performance of dishwashing detergents containing a phosphorus-free builder can be increased by the addition of cyclic compounds containing at least two carboxylate groups.

A first subject of the present invention are therefore dishwashing detergents containing at least one cyclic compound having at least two carboxylate groups and at least one phosphorus-free builder.

The dishwashing agent is preferably a solid dishwashing detergent. A "solid dishwashing detergent" is to be understood as meaning a dishwashing detergent which is in a solid state of aggregation at 25 ° C. and a pressure of 1 bar.

In a preferred embodiment, the solid dishwashing detergent is in the form of a shaped body, in particular a compactate, above all a tablet.

The cyclic compound comprising at least two carboxylate groups may in particular be an alicyclic, a bicyclic or a saturated heterocyclic compound.

The alicyclic compound is preferably cyclopropane, cyclobutane, cyclopentane, cyclohexane or cycloheptane, more preferably cyclopropane, cyclobutane or cyclopentane, most preferably cyclopentane.

The saturated heterocyclic compound is preferably tetrahydrofuran.

The bicyclic compound is preferably bicyclo [2.2.1] heptane or bicyclo [2.2.2] octane.

The cyclic compound comprises at least two carboxylate groups, preferably at least three carboxylate groups, in particular at least four carboxylate groups.

In a particularly preferred embodiment of the invention, the cyclic compound comprises four carboxylate groups.

A compound which is very particularly preferred according to the invention is the cyclopentane tetracarboxylate.

According to the invention, the term "carboxylate" in addition to the anionic form also includes the hydrogenated form of the carboxylate, ie the carboxylic acid group. Furthermore, the term "carboxylate" according to the invention is also understood as meaning carboxylic anhydride groups. The formation of anhydride groups can be effected in this case in particular by adjacent carboxylate groups in the molecule.

According to the invention, it is preferred that at least two, preferably at least three, more preferably at least four carboxylate groups are located on the same side of the cyclic compound, that is, they are arranged in the cis configuration. In a particularly preferred embodiment, at least 75%, preferably all, carboxylate groups are on the same side of the cyclic compound.

In this sense, cyclic compounds in which two out of a total of two carboxylate groups are arranged in a cis configuration, three out of a total of three carboxylate groups in a cis configuration are preferred, are three or four of a total of four carboxylate groups in cis Configuration, four or five of a total of five carboxylate groups are arranged in cis configuration.

It is likewise preferred that at least two of the carboxylate groups which are located on the same side of the cyclic compound are immediately adjacent, that is to say they are arranged in the ortho position.

For the purposes of the present invention, the following cyclic compounds are particularly preferably used molecules: 1c, 2c, 3c, 4c-cyclopentanetetracarboxylate, 1c, 2c, 3c, 4t-cyclopentanetetracarboxylate, 1c, 2c, 3t, 4t-cyclopentanetetracarboxylate, 1c , 2t, 3t, 4c-cyclopentanetetracarboxylate, tetrahydrofuran-2c, 3c, 4c, 5c-tetracarboxylate, tetrahydrofuran-2c, 3c, 4c, 5t-tetracarboxylate, tetrahydrofuran-2c, 3c, 4t, 5t-tetracarboxylate, tetrahydrofuran-2c, 3t , 4t, 5c-tetracarboxylate.

Very particularly preferred according to the invention is 1c, 2c, 3c, 4c-cyclopentanetetracarboxylate. The cyclic compound which comprises at least two carboxylate groups is preferably present in agents according to the invention in an amount of from 0.01 to 10% by weight, more preferably in an amount of from 0.02 to 5% by weight, in particular in one Amount of 0.05 to 2 wt .-%, contained.

As a further constituent, automatic dishwasher detergents according to the invention comprise one or more phosphorus-free builders. The proportion by weight of the phosphorus-free builders in the total weight of automatic dishwashing detergents according to the invention is preferably from 5 to 80% by weight, more preferably from 15 to 75% by weight and in particular from 30 to 70% by weight.

The preferred phosphorus-free builders include, in particular, carbonates, citrates, organic cobuilders, silicates, methylglycine diacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS).

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.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins. 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. These are, for example, 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 of these. 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 one 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 are preferably used in combination with carbonates and / or bicarbonates. Preferred automatic dishwashing detergents are therefore characterized by a builder combination of citrate and carbonate / bicarbonate.

Particularly preferred automatic dishwashing detergents are characterized in that the dishwashing detergent contains, in addition to citrate and (hydrogen) carbonate, at least one further phosphorus-free builder, the further phosphorus-free builder preferably being selected from MGDA, GLDA, ASDA, HEIDA, IDS and EDDS, particularly preferably from MGDA and GLDA, wherein the weight fraction of the builders, based on the total weight of the automatic dishwashing agent, is preferably 5 to 80 wt .-%, preferably 15 to 75 wt .-% and in particular 30 to 70 wt .-%. The wt .-% - proportion of (hydrogen) carbonate and citrate is preferably as stated above. The percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably from 2 to 40% by weight, in particular from 5 to 30% by weight, especially from 7 to 20% by weight. The combination of at least three 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 is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.

Machine dishwashing detergents according to the invention can furthermore comprise, as builder, crystalline stratiform silicates of the general formula NaMSi _x O _{2x + 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, where 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 limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight. Particularly preferred automatic dishwasher detergents according to the invention are silicate-free.

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 the cleaning agent used. Alternative automatic dishwashing detergents are free of alkali metal hydroxides.

Compositions according to the invention can furthermore contain phosphonate (e) as builder. Phosphonates which can be used according to the invention are preferably selected from aminotrimethylenephosphonic acid (ATMP); Ethylenediaminetetra (methylenephosphonic acid) (EDTMP); Diethylene triamine penta (methylenephosphonic acid) (DTPMP); 1-hydroxyethane-1,1-diphosphonic acid (HEDP); 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC); Hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and nitrilotri (methylenephosphonic acid) (NTMP), with particular preference 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriamine penta (methylenephosphonic acid) (DTPMP) are used. Phosphonate (s) are preferably used in inventive compositions in amounts of 0.5 to 20 wt .-%, in particular from 0.5 to 10 wt .-% and especially from 0.5 to 8 wt .-%.

Inventive agents are preferably largely phosphate-free. In preferred automatic dishwasher detergents according to the invention, the content of phosphates, based on the total weight of the automatic dishwashing agent, is below 10% by weight, preferably below 5% by weight, in particular below 2% by weight, above all below 0.5 % By weight limited. Particularly preferred automatic dishwasher detergents according to the invention are completely phosphate-free.

In addition, in a preferred embodiment, in general, the content of phosphorus-containing builders, based on the total weight of the automatic dishwashing agent, to amounts below 10 wt .-%, preferably below 5 wt .-%, especially below 2 wt .-%, especially below 0.5 wt .-% limited. Particularly preferred machine dishwasher detergents according to the invention are generally free of phosphorus-containing builders.

Dishwashing agents according to the invention contain in a preferred embodiment 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.

In a preferred embodiment, the dishwashing agent according to the invention contains at least one nonionic surfactant. 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 is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol 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.

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

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 polyhydroxy fatty acid amides of the formula

wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes. The group of polyhydroxy fatty acid amides also includes compounds of the formula

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is therefore given to ethoxylated nonionic surfactants consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

With particular preference surfactants are further used which contain one or more tallow fatty alcohols with 20 to 30 EO in combination with a silicone defoamer.

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 nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa · s, preferably above 35 Pa · s and in particular above 40 Pa · s. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

Nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also used with particular preference.

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.

The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the 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 also characterized by good foam control.

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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. In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants 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.

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.

In summary, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants 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 and R ² independently represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 alkyl or alkenyl radical; A, A ', A''andA''' are independently of one another a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ - CH _{2 is} -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0, are particularly preferred according to the invention.

Very particular preference is given here to nonionic surfactants of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and x and z are values between 0 and 40 and y is a value of at least 15, preferably from 15 to 120, particularly preferably from 20 to 80.

In a preferred embodiment, the automatic dishwashing detergent contains, based on its total weight, nonionic surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O ] _z CH ₂ CH (OH) R ² in amounts of 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 wt .-%.

Particularly preferred are end-capped poly (oxyalkylated) nonionic surfactants according to the formula R ¹ O [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 16, carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and y for a value between 15 and 120, preferably 20 to 100, in particular 20 to 80 stands. The group of these nonionic surfactants includes, for example, hydroxy _mixed ethers of the general formula C _6-22 -CH (OH) CH ₂ O- (EO) _20-120 -C _{2 -26} , for example the C _8-12 fatty alcohol (EO) ₂₂ - 2-hydroxydecyl ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ethers.

Automatic dishwashing detergent according to the invention, characterized in that the weakly foaming nonionic surfactant used is a surfactant of the general formula R ¹ CH (OH) CH ₂ O- (CH ₂ CH ₂ O) _20-120 -R ² , where R ¹ and R ^{2 are} independently are each a linear or branched aliphatic hydrocarbon radical having 2 to 20, in particular 4 to 16, carbon atoms, are particularly preferred.

Also preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 4, preferably 0.5 to 1.5, and y for a value of at least 15 stands.

Also preferred according to the invention are also surfactants of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² in which R ^{1 is} a linear or branched aliphatic radical Hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x 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 ) O] and [CH ₂ CH ₂ O] randomized, ie in the form of a random random distribution available.

The group of preferred end-capped poly (oxyalkylated) nonionic surfactants also includes nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ^{2 is} independently 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.

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, so that the above formula zu 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.

Further preferably used nonionic surfactants are nonionic surfactants of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , where
R ¹ 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 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 represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.

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

Nonionic surfactants of the general formula are preferred here R ^{1 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 , in which

• R, R ¹ and R ² independently represent an alkyl radical 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 ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² , in where R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values 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.

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

In a further preferred embodiment, the nonionic surfactant is selected from nonionic surfactants of the general formula R ^{1 is} -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in the

• - R ¹ and R ² independently represent an alkyl radical 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 ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, are in which R ³ and R ⁴ is H, and the subscripts x and y are independently of one another assume values from 1 to 40, preferably from 1 to 15.

Especially preferred particular compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which the radicals R ¹ and R ² 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.

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

Very particularly preferred compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which the indices x and y are independently values 8-12 accept.

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 manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. 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 can be described by different 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 ,

The proportion by weight of the nonionic surfactant in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight. %.

In a preferred embodiment, the weight% ratio of anionic surfactant having at least one sulfate or sulfonate group to nonionic surfactant is from 3: 1 to 1: 3, especially from 2: 1 to 1: 2, more preferably from 1 , 5: 1 to 1: 1.5.

Another object of the present invention is also a machine dishwashing process using the aforementioned solid dishwashing detergent, in particular in the form of a previously mentioned shaped body, in particular for the removal, especially improved removal, of greasy soilings, especially for the removal of stains by egg yolk.

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.

The present application relates to automatic dishwashing detergents. Automatic dishwashing detergents, according to this application, are compositions which can be used to clean soiled dishes in a dishwasher automatic dishwashing process. 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 compositions according to the invention are preferably in the form of a shaped body, in particular a compactate, in particular 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. The shaped body may, for example, also be a granulate which is contained in a bag or a casting mold.

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. Two-phase or multi-phase tablets, for example two-layer tablets, in particular two-layer tablets with a trough and a shaped body located in the trough, are particularly preferred.

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 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 and in particular between 15 and 25 ml.

The automatic dishwashing compositions according to the invention, in particular the prefabricated dosage units, in a preferred embodiment have a water-soluble coating.

Inventive moldings contain in a preferred embodiment polyvinylpyrrolidone particles. These particles facilitate, inter alia, the disintegration of the moldings and serve insofar as disintegration aids or tablet disintegrating agents. It has been found according to the invention to be particularly advantageous to use polyvinylpyrrolidone particles having an average particle diameter of 100 to 150 .mu.m, in particular having an average particle diameter of 110 to 130 .mu.m.

For the purposes of the present invention, the term "average particle diameter" or "average diameter" is to be understood as meaning the volume-average D ₅₀ particle diameter which can be determined by customary methods. The volume average D ₅₀ particle diameter is that point in the particle size distribution in which 50% by volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter. The average particle diameter can be determined in particular by means of dynamic Light scattering can be determined, which are usually carried out on dilute suspensions containing, for example 0.01 to 1 wt .-% of particles.

Particularly preferably, the PVP particles not only have an average particle diameter of 100 to 150 .mu.m, in particular from 110 to 130 .mu.m, but moreover, the particle size of the particles used is preferably completely in the specified intervals. This is ensured by using grain size fractions with the indicated particle sizes obtained by a sieving process.

The PVP particles are preferably present in compositions according to the invention in an amount of from 0.1 to 5% by weight, in particular in an amount of from 0.2 to 3% by weight, in particular in an amount of from 0.3 to 1, 8 wt .-%, contained.

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 also on the release of gases, a pressure can be generated, which can disintegrate the tablet into smaller particles , In addition or as an alternative to the PVP particles, other disintegrants may also be present in moldings according to the invention, for example carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their derivatives and Alginates or casein derivatives. Furthermore, gas-evolving effervescent systems can also be used as further disintegrants. 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 desintegrationshilfsmittelhaltigen agent used.

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

The production of the shaped bodies according to the invention, in particular of the detergent tablets, preferably takes place in a manner known to the person skilled in the art by compression of particulate starting substances. To prepare the tablets, the premix is compressed in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tableting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection. The tabletting is preferably carried out on so-called rotary presses.

• – Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• – Geringe Umdrehungszahl des Rotors
• – Große Füllschuhe
• – Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• – Füllschuh mit konstanter Pulverhöhe
• – Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. The minimization of weight variations can be achieved in the following ways:

• - Use of plastic inserts with small thickness tolerances
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Matching of the Füllschuhflügeldrehzahl on the speed of the rotor
• - filling shoe with constant powder height
• - Decoupling of filling shoe and powder template

The ingredients provided for tabletting can be added in the form of a common particulate premix at the same time or in the form of individual, separate powders or granules offset in time or at the same time in the mold, the dosage of a prefabricated particulate premix is preferred.

According to the invention, it has surprisingly been found that granules used according to the invention for producing the shaped bodies can be pressed particularly well. Thus, preferably using a pressing force of 40 to 65 kN, more preferably 48 to 60 kN, compactates having a hardness in the range of 150 to 250 N, in particular in the range of 200 to 230 N are obtained, the above In addition, have a particularly good 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.

Automatic dishwashing detergents according to the invention contain as further constituent in a preferred embodiment 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 .-%.

Automatic 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, since the hydrophobic modification of the anionic copolymers improves the rinsing and drying properties of these agents with simultaneously low deposit formation can be achieved.

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

Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of 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, 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 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 , 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 -.

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. 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 sulfonic acid-containing copolymers is preferred according to the invention.

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 proportion of the carboxylic acid group-containing monomer 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 dishwashing agents 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 a further preferred embodiment, in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise 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.

• i) Carbonsäuregruppen-haltige Monomer(e)
• ii) Sulfonsäuregruppen-haltige Monomer(e)
• iii) nichtionische Monomer(e)

enthält, werden erfindungsgemäß bevorzugt. 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.

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

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-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, α 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, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate ter, octyl methacrylate, N- (octyl) acrylamide, Acryloyl acrylate, methacrylic acid lauryl ester, N- (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) acrylamide, or mixtures thereof.

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

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

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 abovementioned amylases which are improved for use in detergents and cleaners. 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.

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 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 by extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are 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 covered. 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.

Preference is given in particular to those automatic dishwashing detergents which contain, based in each case on their total weight, from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight, of enzyme preparations ,

• a) 0,5 bis 15 Gew.-%, insbesondere 1,5 bis 7 Gew.-%, CP-TCA;
• b) 2 bis 30 Gew.-%, vorzugsweise 4 bis 28 Gew.-%, insbesondere von 8 bis 24 Gew.-%, (Hydrogen-)Carbonat;
• c) 2 bis 40 Gew.-%, insbesondere 7 bis 20 Gew.-%, Citrat;
• d) 2 bis 40 Gew.-%, insbesondere 7 bis 20 Gew.-%, MGDA und/oder GLDA, vorzugsweise MGDA.

Particularly preferred machine dishwasher detergents according to the invention contain

• a) 0.5 to 15 wt .-%, in particular 1.5 to 7 wt .-%, CP-TCA;
• b) 2 to 30 wt .-%, preferably 4 to 28 wt .-%, in particular from 8 to 24 wt .-%, (hydrogen) carbonate;
• c) 2 to 40 wt .-%, in particular 7 to 20 wt .-%, citrate;
• d) 2 to 40 wt .-%, in particular 7 to 20 wt .-%, MGDA and / or GLDA, preferably MGDA.

• a) 0,5 bis 15 Gew.-%, insbesondere 1,5 bis 7 Gew.-%, CP-TCA;
• b) 2 bis 30 Gew.-%, vorzugsweise 4 bis 28 Gew.-%, insbesondere von 8 bis 24 Gew.-%, (Hydrogen-)Carbonat;
• c) 2 bis 40 Gew.-%, insbesondere 7 bis 20 Gew.-%, Citrat;
• d) 2 bis 40 Gew.-%, insbesondere 7 bis 20 Gew.-%, MGDA und/oder GLDA, vorzugsweise MGDA;
• e) 0,01 bis 3 Gew.-% Zinksalz, vorzugsweise wasserlösliches Zinksalz.

Further particularly preferred machine dishwasher detergents according to the invention contain

• a) 0.5 to 15 wt .-%, in particular 1.5 to 7 wt .-%, CP-TCA;
• b) 2 to 30 wt .-%, preferably 4 to 28 wt .-%, in particular from 8 to 24 wt .-%, (hydrogen) carbonate;
• c) 2 to 40 wt .-%, in particular 7 to 20 wt .-%, citrate;
• d) 2 to 40 wt .-%, in particular 7 to 20 wt .-%, MGDA and / or GLDA, preferably MGDA;
• e) 0.01 to 3 wt .-% zinc salt, preferably water-soluble zinc salt.

• a) 0,5 bis 15 Gew.-%, insbesondere 1,5 bis 7 Gew.-%, CP-TCA;
• b) 4 bis 28 Gew.-% und insbesondere von 8 bis 24 Gew.-% (Hydrogen-)Carbonat;
• c) 5 bis 30 Gew.-% und insbesondere 7 bis 20 Gew.-% Citrat;
• d) 5 bis 30 Gew.-%, insbesondere 7 bis 20 Gew.-%, MGDA und/oder GLDA, vorzugsweise MGDA;
• e) 0,1 bis 20 Gew.-%, vorzugsweise 0,5 bis 15 Gew.-%, insbesondere 2,5 bis 10 Gew.-% nichtionische(s) Tensid(e) der allgemeinen Formel R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_y[CH₂CH(CH₃)O]_zCH₂CH(OH)R², in der R¹ für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22, insbesondere 6 bis 18, Kohlenstoffatomen oder Mischungen hieraus steht, R² einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26, insbesondere 4 bis 20, Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x und z für Werte zwischen 0 und 40 und y für einen Wert von 15 bis 120, insbesondere von 20 bis 80, steht;
• f) gegebenenfalls 1 bis 15 Gew.-% eines copolymeren anionischen Polymers umfassend Carbonsäuregruppen-haltige Monomer(e) und Sulfonsäuregruppen-haltige Monomer(e).

Further particularly preferred machine dishwasher detergents according to the invention contain

• a) 0.5 to 15 wt .-%, in particular 1.5 to 7 wt .-%, CP-TCA;
• b) 4 to 28 wt .-% and in particular from 8 to 24 wt .-% (hydrogen) carbonate;
• c) 5 to 30 wt .-% and in particular 7 to 20 wt .-% citrate;
• d) 5 to 30 wt .-%, in particular 7 to 20 wt .-%, MGDA and / or GLDA, preferably MGDA;
• e) 0.1 to 20 wt .-%, preferably 0.5 to 15 wt .-%, in particular 2.5 to 10 wt .-% of nonionic (s) surfactant (s) of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and x and z are values between 0 and 40 and y is a value of 15 to 120, in particular from 20 to 80;
• f) optionally 1 to 15 wt .-% of a copolymeric anionic polymer comprising carboxylic acid group-containing monomer (s) and sulfonic acid group-containing monomer (s).

In addition to the ingredients described above, the compositions according to the invention may contain further washing or cleaning-active substances, preferably from the group of bleaches, bleach activators and bleach catalysts, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.

Machine dishwashing detergents according to the invention may contain a bleaching agent as further constituent, with oxygen bleaches being preferred. 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 -forming 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 proportion by weight of the bleaching agent, based on the total weight of the washing or cleaning agent, in preferred embodiments is between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.

As bleach activators, the automatic dishwasher detergents according to the invention may 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 those which carry O- and / or N-acyl groups of the stated carbon atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

Automatic dishwashing detergent, characterized in that it is a bleach activator bleach activator from the group of 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 automatic dishwasher detergents according to the invention preferably contain at least one bleach catalyst. These substances are bleach-enhancing transition metal salts or transition metal complexes such as 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.

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 ).

Machine 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 in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.

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

The active substance combinations described above are particularly suitable for cleaning dishes in automatic dishwashing processes. Another object of the present application is therefore a method for cleaning dishes in a dishwasher using a dishwashing detergent according to the invention, wherein the dishwashing detergent is preferably 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 into the interior of the dishwasher by means of the metering chamber of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher.

• a) ein erfindungsgemäßes maschinelles Geschirrspülmittel;
• b) eine Anleitung, die den Verbraucher darauf hinweist, das maschinelle Geschirrspülmittel ohne Zusatz eines Klarspülers und/oder eines Enthärtersalzes zu verwenden ist, ist ein weiterer Gegenstand dieser Anmeldung.

A kit for a dishwasher, comprising

• a) a machine dishwashing detergent according to the invention;
• (b) instructions instructing the consumer to use the automatic dishwashing detergent without the addition of a rinse aid and / or a softening salt are another subject of this application.

The dishwasher detergents according to the invention exhibit their advantageous cleaning properties, in particular also in low-temperature cleaning processes and in short-lasting purification 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., and / or a time of less than 90 minutes, preferably less than 60 minutes, in particular less than 45 Minutes.

embodiments

Example 1: Pad inhibition of a phosphate-free agent

It was the pad inhibition of a phosphate-free dishwashing detergent containing in addition to conventional ingredients soda, citrate, phosphonate and MGDA and the different cyclic compounds with carboxy groups (cyclopentane tetracarboxylate and tetrahydrofuran tetracarboxylate) were added tested. For comparison, the scale inhibition of the same dishwashing detergent was checked without adding the cyclic compound. The dishwashing detergent was used in the form of a tablet. The cyclic compound was added in powder form (0.5 grams per rinse cycle). The dosage of the dishwashing agent took place via the metering device of the dishwasher. The dishwashing process was carried out in a dishwasher Miele G1355 SC (program: 50 ° C light turbo, water hardness 21 ° dH).

A total of 30 rinsing cycles were carried out in succession and the deposit inhibition was determined after the end of the last rinsing cycle. The dishwasher contained the following load:
3 Willybecher 0,2l, 3 whiskey cups, 3 black breakfast plates, 3 glass plates black, 3 blue Mepal melamine plates, 3 blue PP plates, 3 blue SAN dessert plates, 3 stainless steel knives from WMF, 3 stainless steel knives from BSF, 2 shiny ones Coffee trays, 2 stainless steel butter dishes.

Before the start of the rinse cycle, 50 grams of standard soil were added. The evaluation was done visually in a black box on a scale of 1 to 10 (the higher the value, the better the coating inhibition).

The scale inhibition results are shown in the following table: product Glass Glass plate black Plastic (melamine) Steel (tray) phosphate-free agent 3.7 3.7 5 4 Phosphate-free agent + THF-TCA 4.3 4.3 4.7 5.5 phosphate-free agent + CP-TCA 4.7 5.3 6.3 5.5

It can be seen a significant effect of cyclopentane tetracarboxylate (CP-TCA) on the tableware shown in the table. On the remaining dishes, the performance is comparable to the phosphate-free agent alone. The tetrahydrofuran tetracarboxylate (THF-TCA) shows a lower deposit inhibition on glass, but as significant a deposit inhibition as the CP-TCA on stainless steel (tray). The results for the CP-TCA were also confirmed with an increased concentration of 1 g / job.

Example 2: Pad inhibition of a phosphate- and phosphonate-free agent The pad inhibition of a phosphate- and phosphonate-free dishwashing detergent containing, in addition to conventional constituents, soda, citrate and MGDA and added to the cyclopentane tetracarboxylate was tested. For comparison, the scale inhibition of the same dishwashing detergent was checked without adding the cyclic compound. Further, for comparison, the scale inhibition of the same dishwashing detergent to which phosphonate was added in place of the cyclopentane tetracarboxylate was checked. The dishwashing detergent was used in the form of a tablet. The cyclic compound or phosphonate was added in powder form (0.5 grams per rinse cycle). The dosage of the dishwashing agent took place via the metering device of the dishwasher. The dishwashing process was carried out in a dishwasher Miele G1355 SC (program: 50 ° C light turbo, water hardness 21 ° dH).

A total of 30 rinsing cycles were carried out in succession and the deposit inhibition was determined after the end of the last rinsing cycle. The dishwasher contained the following load:
3 Willybecher 0,2l, 3 whiskey cups, 3 black breakfast plates, 3 glass plates black, 3 blue Mepal melamine plates, 3 blue PP plates, 3 blue SAN dessert plates, 3 stainless steel knives from WMF, 3 stainless steel knives from BSF, 2 shiny ones Coffee trays, 2 stainless steel butter dishes.

Before the start of the rinse cycle, 50 grams of standard soil were added. The evaluation was done visually in a black box on a scale of 1 to 10 (the higher the value, the better the coating inhibition).

The scale inhibition results on stainless steel are shown in the following table: product knife butter dish Serving Tray Phosphate and phosphonate-free agent 3.0 3.6 4.5 Phosphate- and phosphonate-free agent + CP-TCA 7.3 10.0 7.0 Phosphate-free agent + phosphonate 7.0 10.0 6.5

The plaque inhibition results on plastic are shown in the following table: product Friesland plate Plastic SAN Phosphate and phosphonate-free agent 4.0 2.7 Phosphate- and phosphonate-free agent + CP-TCA 5.0 4.3 Phosphate-free agent + phosphonate 4.7 6.0

It can be seen a significant effect of cyclopentane tetracarboxylate (CP-TCA) on the dishes shown in the tables. The comparison with the phosphonate-containing formulations shows that the CP-TCA represents an equivalent replacement for the phosphonate.

Claims (10)

Dishwashing detergent, characterized in that it contains at least one cyclic compound having at least two carboxylate groups and at least one phosphorus-free builder.  Dishwashing detergent according to claim 1, characterized in that the cyclic compound having at least two carboxylate groups is selected from the group consisting of cyclopropane, cyclobutane, cyclopentane and cyclohexane, more preferably cyclopentane, comprising at least three, preferably four or five, carboxylate groups, and preferably in an amount of 0.01 to 10 wt .-%, particularly preferably 0.02 to 5 wt .-%, in particular 0.05 to 2 wt .-%, is included.  Dishwashing detergent according to claim 1 or 2, characterized in that the phosphorus-free builder is selected from the group consisting of citrate, (hydrogen) carbonate, MGDA, GLDA, ASDA, HEIDA, IDS and EDDS and mixtures thereof, and preferably in an amount from 5 to 80 wt .-%, particularly preferably 15 to 75 wt .-% and in particular 30 to 70 wt .-%, is contained.  Dishwashing detergent according to one of claims 1 to 3, characterized in that it contains 2 to 30 wt .-%, preferably from 4 to 28 wt .-% and in particular from 8 to 24 wt .-% (hydrogen) carbonate, 2 to 40 Wt .-%, preferably 5 to 30 wt .-% and in particular 7 to 20 wt .-% citrate and 2 to 40 wt .-%, in particular 5 to 30 wt .-%, especially 7 to 20 wt .-% a further phosphorus-free builder selected from MGDA, GLDA, ASDA, HEIDA, IDS and EDDS, in particular selected from MGDA and GLDA contains.  Dishwashing detergent according to one of the preceding claims, characterized in that it contains cyclopentanetetracarboxylate in an amount of 0.5 to 15 wt .-%, in particular 1.5 to 7 wt .-%, (hydrogen) carbonate in an amount of 2 to 30 % By weight, in particular 8 to 24% by weight, citrate in an amount of 2 to 40% by weight, in particular 7 to 20% by weight, and MGDA in an amount of 2 to 40% by weight, especially 7 to 20 wt .-%, contains.  Dishwashing detergent according to one of the preceding claims, characterized in that it contains less than 10% by weight, preferably less than 5% by weight, in particular less than 2% by weight, especially less than 0.5% by weight, most preferably contains no phosphate.  Dishwashing detergent according to one of the preceding claims, characterized in that it contains from 0.5 to 20 wt .-%, in particular from 0.5 to 10 wt .-% and especially from 0.5 to 8 wt .-% phosphonate (e ) contains.  Dishwashing detergent according to one of claims 1 to 6, characterized in that it contains less than 10 wt .-%, preferably less than 5 wt .-%, in particular less than 2 wt .-%, especially less than 0.5 wt. %, particularly preferably contains no phosphorus-containing builders.  Dishwashing composition according to one of claims 1 to 8, characterized in that it is a solid dishwashing agent and preferably in the form of a shaped body, in particular a Kompaktats, especially a tablet, is present.  A machine dishwashing process, characterized in that a machine dishwashing detergent according to one of the preceding claims is used.