DE102011005695A1 - Dishwashing liquid - Google Patents

Abstract

Liquid dishwashing detergents which contain at least one anionic surfactant with at least one sulfate or sulfonate group and at least one nonionic surfactant are characterized by very good cleaning performance, in particular in automatic dishwashing processes.

Description

The present application relates to liquid dishwashing compositions, in particular to liquid dishwashing detergents and automatic dishwashing processes using these agents.

Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, in particular the automatic dishwashing detergents have gained great importance with the spread of household dishwashers. These automatic dishwashing agents are typically offered to the consumer in solid form, for example as a powder or as tablets.

One of the major goals of the machine cleanser manufacturers is to improve the cleaning performance of these agents, with a recent focus on cleaning performance in low temperature or reduced water consumption cleaning cycles.

This application was based on the object to provide a machine dishwashing detergent with improved cleaning properties, in particular against greasy stains, these improved cleaning properties especially in low-temperature cleaning cycles, ie in cleaning processes with Spülflottentemperaturen of 50 ° C or below, and / or in short-term cleaning process, especially in cleaning processes lasting less than 60 minutes.

This object has been achieved by a liquid dishwashing detergent which contains at least one anionic surfactant having at least one sulfate or sulfonate group and at least one nonionic surfactant.

The prior art generally describes that anionic surfactants can be used for dishwashing. However, a well-known problem with anionic surfactants is their foaming behavior. Foaming on use results in a pressure drop in the dishwasher, which is generally associated with inadequate cleaning performance. For this reason, it is customary to dispense with the use of anionic surfactants in automatic dishwashing. According to the invention, however, it has now surprisingly been found that the cleaning performance of dishwashing detergents containing nonionic surfactants can be increased by the addition of surfactants with sulfate and / or sulfonate groups.

A first subject of the present invention are therefore liquid dishwashing detergents, in particular liquid automatic dishwashing detergents containing at least one anionic surfactant having at least one sulfate or sulfonate group and at least one nonionic surfactant.

A "liquid dishwashing detergent" is to be understood here as meaning a dishwashing detergent which is in the liquid state at 25 ° C. under a pressure of 1 bar.

The anionic surfactant is preferably selected from fatty alcohol sulfates, alkanesulfonates and alkylbenzenesulfonates. Preference is given here C ₁₂ -C ₁₈ fatty alcohol sulfates (FAS), z. Sulfopone K 35 (Cognis, Germany), secondary C ₁₃ -C ₁₇ alkanesulfonates (SAS), e.g. B. Hostapur SAS 93 (Clariant, Germany), and linear C ₈ -C ₁₈ alkylbenzenesulfonates, in particular dodecylbenzenesulfonate (LAS).

According to the invention, the terms "sulfate" and "sulfonate" in addition to the relevant anionic compounds which are present in the form of salts, also include the free acids, ie the corresponding alkyl sulfuric acids or alkylsulfonic acids.

The anionic surfactant is preferably present in dishwashing agents according to the invention in an amount of 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, in particular 1.5 to 7% by weight.

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.

in der R für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.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 can usually be 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.

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, detergents, 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 native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 moles of EO per mole of alcohol. 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. When 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 native origin having 12 to 18 C atoms, eg. B. 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 which R ¹ and R ^2, independently of one another, represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or alkenyl radical A, A ', A''andA''' independently of one another 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 ); 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 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 .

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.

Inventive automatic dishwashing agent, characterized in that as low-foaming nonionic surfactant is a surfactant of the general formula R ¹ CH (OH) CH ₂ O- (CH ₂ CH ₂ O) _{20 120} -R ² is used, wherein R ¹ and R ^{2 are} independently 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.

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 R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² , where

• R, R ¹ and R ² independently 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 -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which

• - 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 automatic dishwashing agent according to the invention is preferably from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, in particular from 1.5 to 7% by weight, In In a preferred embodiment, the weight% ratio of anionic surfactant having at least one sulphate or sulphonate group to nonionic surfactant is from 3: 1 to 1: 3, in particular from 2: 1 to 1: 2, more preferably from 1, 5: 1 to 1: 1.5.

In a preferred embodiment, the liquid dishwashing detergent contains at least one builder. The builders include in particular the zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.

Particular preference is given to using crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which 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 are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are for example sold by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ .yH ₂ O and furthermore especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t- Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

The dishwashing detergent preferably contains a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} · yH ₂ O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0.4 to 10% by weight.

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. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle ,

Alternatively or in combination with the abovementioned amorphous sodium silicates, it is also possible to use X-ray-amorphous silicates whose silicate particles produce blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

In the context of the present invention, it is preferred that these (s) silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in the dishwashing detergent in amounts of 2 to 40 wt .-%, preferably from 3 to 30 wt. % and in particular from 5 to 25 wt .-%, based on the weight of the dishwashing detergent are included.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

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

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

If phosphates are used as washing or cleaning substances in the context of the present application, preferred dishwashing agents contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) Amounts of 5 to 60 wt .-%, preferably from 15 to 45 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the dishwashing detergent.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. 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 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.

The citric acid or salts of citric acid are used with particular preference as builder substance. Dishwashing detergent, characterized in that the dishwashing detergent contains citric acid or a salt of citric acid and that the weight proportion of citric acid or the salt of citric acid, based on the total weight of the dishwashing detergent, between 0.2 and 12 wt .-%, preferably between 0.2 and 8% by weight and in particular between 0.2 and 6% by weight, are preferred according to the invention.

Another particularly preferred builder substance is methylglycine diacid (MGDA). Dishwashing detergent, characterized in that the dishwashing detergent contains methylglycinediacetic acid or a salt of methylglycinediacetic acid and the weight fraction of methylglycinediacetic acid or the salt of methylglycinediacetic acid, based on the total weight of the combination product, between 0.2 and 12 wt .-%, preferably between 0.2 and 8% by weight and in particular between 0.2 and 6% by weight, are preferred according to the invention.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

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.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid 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.

The content of dishwashing agents in (co) polymeric polycarboxylates is preferably 0.1 to 10% by weight, preferably 0.2 to 8% by weight, particularly preferably 0.4 to 6% by weight and in particular between 0, 4 and 4 wt .-%.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as builders.

As a further constituent, the dishwasher detergents according to the invention preferably contain enzymes for increasing the washing or cleaning performance. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; starting from the natural molecules For use in detergents and cleaners improved variants are available, which are preferably used accordingly. Dishwashing agents according to the invention preferably contain enzymes in total amounts of from 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.

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 P692, 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, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned 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).

• (1) M9L/M202I,
• (2) M9L/M202I/M323T,
• (3) M9L/M202I/M323T/M382Y,
• (4) M9L/M202I/Y295F/A339S,
• (5) M9L/M202I/Y295F,
• (6) M9L/M202I/A339S,
• (7) M9L/M202I/Y295F/A339S,
• (8) M9L/M202I/Y295F/A339S/E345R,
• (9) M9L/G149A/M202I/Y295F/A339S/E345R,
• (10) M9L/M202L,
• (11) M9L/M202L/M323T,
• (12) M9L/M202L/M323T/M382Y,
• (13) M9L/M202L/Y295F/A339S,
• (14) M9L/M202L/Y295F,
• (15) M9L/M202L/A339S,
• (16) M9L/M202L/Y295F/A339S,
• (17) M9L/M202L/Y295F/A339S, E345R,
• (18) M9L/G149A/M202L/Y295F/A339S/E345R,
• (19) M9L/M202T,
• (20) M9L/M202T/M323T,
• (21) M9L/M202T/M323T/M382Y,
• (22) M9L/M202T/Y295F/A339S,
• (23) M9L/M202T/Y295F,
• (24) M9L/M202T/A339S,
• (25) M9L/M202T/Y295F/A339S,
• (26) M9L/M202T/Y295F/A339S/E345R,
• (27) M9L/G149A/M202T/Y295F/A339S/E345R,
• (28) M9L/G149A/M202I/V214T/Y295F/N299Y/M323T/A339S/E345R,
• (29) M9L/G149A/M202L/V214I/Y295F/M323T/A339S/E345R/M382Y,
• (30) M9L/G149A/G182T/G186A/M202I/V214I/Y295F/N299Y/M323T/A339S,
• (31) M9L/G149A/G182T/G186A/M202L/T257I/Y295F/N299Y/M323T/A339S/E345R,
• (32) M9L/G149A/M202L/V214T/Y295F/N299Y/M323T/A339S/E345R,
• (33) M9L/G149A/M202I/V214I/Y295F/M323T/A339S/E345R/M382Y,
• (34) M9L/G149A/G182T/G186A/M202L/V214I/Y295F/N299Y/M323T/A339S,
• (35) M9L/G149A/G182T/G186A/M202I/T257I/Y295F/N299Y/M323T/A339S/E345R,
• (36) M9L/G149A/M202I/V214T/Y295F/N299Y/M323T/A339S/E345R/N471E,
• (37) M9L/G149A/M202L/V214I/Y295F/M323T/A339S/E345R/M382Y/N471E,
• (38) M9L/G149A/G182T/G186A/M202I/V214I/Y295F/N299Y/M323T/A339S/N471E,
• (39) M9L/G149A/G182T/G186A/M202L/1257I/Y295F/N299Y/M323T/A339S/E345R/N471E,
• (40) M202L/M105F/M208F,
• (41) G133E/M202L/Q361E,
• (42) G133E/M202L/R444E,
• (43) M202L/Y295F,
• (44) M202L/A339S,
• (45) M202L/M323T,
• (46) M202L/M323T/M309L,
• (47) M202L/M323T/M430I,
• (48) M202L/V214T/R444Y,
• (49) M202L/N283D/Q361E,
• (50) M202L/M382Y/K383R,
• (51) M202L/K446R/N484Q,
• (52) M202I/Y295F,
• (53) M202I/A339S,
• (54) M202I/M105F/M208F,
• (55) G133E/M202I/Q361E,
• (56) G133E/M202I/R444E,
• (57) M202I/M323T,
• (58) M202I/M323T/M309L,
• (59) M202I/M323T/M430I,
• (60) M202I/V214T/R444Y,
• (61) M202I/N283D/0361E.
• (62) M202I/M382Y/K383R,
• (63) M202I/K446R/N484Q,
• (64) M202V/M105F/M208F,
• (65) G133E/M202V/Q361E,
• (66) G133E/M202V/R444E,
• (67) M202V/M323T,
• (68) M202V/M323T/M309L,
• (69) M202V/M323T/M430I,
• (70) M202V/M323T/M9L,
• (71) M202V/V214T/R444Y,
• (72) M202V/N283D/Q361E,
• (73) M202V/M382Y/K383R,
• (74) M202V/K446R/N484Q,
• (75) M202T/M105F/M208F,
• (76) G133E/M202T/Q361E,
• (77) G133E/M202T/R444E,
• (78) M202T/Y295F,
• (79) M202T/A339S,
• (80) M202T/M323T,
• (81) M202T/M323T/M309L,
• (82) M202T/M323T/M430I,
• (83) M202T/M323T/M9L,
• (84) M202T/V214T/R444Y,
• (85) M202T/N283D/Q361E,
• (86) M202T/A339S,
• (87) M202T/Y295F
• (88) M202T/N299F, Y,
• (89) M202T/M382Y/K383R oder
• (90) M202T/K446R/N484Q

An α-amylase variant has proven to be particularly suitable for use in compositions according to the invention which can be obtained either from a starting α-amylase which can be homologated with the α-amylase AA560 via amino acid changes in the following positions: 9, 149, 182, 186, 202, 257, 295, 299, 323, 339, 345 and optionally further (in the count according to the α-amylase AA560) or which can be obtained from the α-amylase AA560 via the following amino acid changes:

• (1) M9L / M202I,
• (2) M9L / M202I / M323T,
• (3) M9L / M202I / M323T / M382Y,
• (4) M9L / M202I / Y295F / A339S,
• (5) M9L / M202I / Y295F,
• (6) M9L / M202I / A339S,
• (7) M9L / M202I / Y295F / A339S,
• (8) M9L / M202I / Y295F / A339S / E345R,
• (9) M9L / G149A / M202I / Y295F / A339S / E345R,
• (10) M9L / M202L,
• (11) M9L / M202L / M323T,
• (12) M9L / M202L / M323T / M382Y,
• (13) M9L / M202L / Y295F / A339S,
• (14) M9L / M202L / Y295F,
• (15) M9L / M202L / A339S,
• (16) M9L / M202L / Y295F / A339S,
• (17) M9L / M202L / Y295F / A339S, E345R,
• (18) M9L / G149A / M202L / Y295F / A339S / E345R,
• (19) M9L / M202T,
• (20) M9L / M202T / M323T,
• (21) M9L / M202T / M323T / M382Y,
• (22) M9L / M202T / Y295F / A339S,
• (23) M9L / M202T / Y295F,
• (24) M9L / M202T / A339S,
• (25) M9L / M202T / Y295F / A339S,
• (26) M9L / M202T / Y295F / A339S / E345R,
• (27) M9L / G149A / M202T / Y295F / A339S / E345R,
• (28) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R,
• (29) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y,
• (30) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S,
• (31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R,
• (32) M9L / G149A / M202L / V214T / Y295F / N299Y / M323T / A339S / E345R,
• (33) M9L / G149A / M202I / V214I / Y295F / M323T / A339S / E345R / M382Y,
• (34) M9L / G149A / G182T / G186A / M202L / V214I / Y295F / N299Y / M323T / A339S,
• (35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / A339S / E345R,
• (36) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R / N471E,
• (37) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y / N471E,
• (38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S / N471E,
• (39) M9L / G149A / G182T / G186A / M202L / 1257I / Y295F / N299Y / M323T / A339S / E345R / N471E,
• (40) M202L / M105F / M208F,
• (41) G133E / M202L / Q361E,
• (42) G133E / M202L / R444E,
• (43) M202L / Y295F,
• (44) M202L / A339S,
• (45) M202L / M323T,
• (46) M202L / M323T / M309L,
• (47) M202L / M323T / M430I,
• (48) M202L / V214T / R444Y,
• (49) M202L / N283D / Q361E,
• (50) M202L / M382Y / K383R,
• (51) M202L / K446R / N484Q,
• (52) M202I / Y295F,
• (53) M202I / A339S,
• (54) M202I / M105F / M208F,
• (55) G133E / M202I / Q361E,
• (56) G133E / M202I / R444E,
• (57) M202I / M323T,
• (58) M202I / M323T / M309L,
• (59) M202I / M323T / M430I,
• (60) M202I / V214T / R444Y,
• (61) M202I / N283D / 0361E.
• (62) M202I / M382Y / K383R,
• (63) M202I / K446R / N484Q,
• (64) M202V / M105F / M208F,
• (65) G133E / M202V / Q361E,
• (66) G133E / M202V / R444E,
• (67) M202V / M323T,
• (68) M202V / M323T / M309L,
• (69) M202V / M323T / M430I,
• (70) M202V / M323T / M9L,
• (71) M202V / V214T / R444Y,
• (72) M202V / N283D / Q361E,
• (73) M202V / M382Y / K383R,
• (74) M202V / K446R / N484Q,
• (75) M202T / M105F / M208F,
• (76) G133E / M202T / Q361E,
• (77) G133E / M202T / R444E,
• (78) M202T / Y295F,
• (79) M202T / A339S,
• (80) M202T / M323T,
• (81) M202T / M323T / M309L,
• (82) M202T / M323T / M430I,
• (83) M202T / M323T / M9L,
• (84) M202T / V214T / R444Y,
• (85) M202T / N283D / Q361E,
• (86) M202T / A339S,
• (87) M202T / Y295F
• (88) M202T / N299F, Y,
• (89) M202T / M382Y / K383R or
• (90) M202T / K446R / N484Q

With particular preference, the α-amylase variant is characterized by additionally one or more amino acid changes in the following positions relative to a α-amylase AA560 homologizable starting α-amylase 118, 183, 184, 195, 320 and 458 (in the count according to the α-amylase AA560), wherein the α-amylase variant preferably has in particular the following amino acid position assignments 118K, 183- (deletion), 184- (deletion), 195F, 320K and / or 458K (in the count according to the α-amylase AA560 ),

An α-amylase variant which can be derived from the α-amylase AA560 or a derivative thereof and is preferably derived therefrom itself is particularly preferred. Particular preference is given in particular to detergents according to the invention which comprise an α-amylase variant, which has one of the following amino acid changes to α-amylase AA560
(10) M9L / M202L,
(28) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R,
(31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R,
(35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / A339S / E345R,
(38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S / N471E,
(39) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R / N471E,
(45) M202L / M323T,
(46) M202L / M323T / M309L,
(62) M202I / M382Y / K383R,
(68) M202V / M323T / M309L,
(73) M202V / M382Y / K383R
(82) M202T / M323T / M430I
(84) M202T / V214T / R444Y.

• – In Ergänzung der beschriebenen α-Amylase Variante enthalten erfindungsgemäß bevorzugte Geschirrspülmittel mindestens eine Protease, vorzugsweise eine Subtilisin-Protease, wobei es sich bei der Subtilisin-Protease um eine Wildtyp-Protease oder um eine Protease-Variante handelt und es sich bei der Protease-Variante vorzugsweise um eine mit einer Aminosäureänderung gegenüber einer mit der Alkalischen Protease aus Bacillus lentus homologisierbaren Ausgangs-Protease in einer oder mehreren der folgenden Positionen handelt: 3, 4, 36, 42, 43, 47, 56, 61, 69, 87, 96, 99, 101, 102, 104, 114, 118, 120, 130, 139, 141, 142, 154, 157, 188, 193, 199, 205, 211, 224, 229, 236, 237, 242, 243, 250, 253, 255 und 268, in der Zählung der Alkalischen Protease aus Bacillus lentus.

The above-mentioned preferred α-amylase variants have been distinguished by an above-average storage stability and cleaning performance, in particular during storage and metering by means of automatic metering systems which contain sufficient dishwashing detergent for a plurality of cleaning cycles, which is why these cleaning agents are stored in these metering systems for a relatively long time.

• In addition to the described α-amylase variant, dishwashing agents preferred according to the invention comprise at least one protease, preferably a subtilisin protease, the subtilisin protease being a wild-type protease or a protease variant and the protease Variant is preferably an amino acid change relative to a starting protease homologizable with the Bacillus lentus alkaline protease in one or more of the following positions: 3, 4, 36, 42, 43, 47, 56, 61, 69, 87, 96 , 99, 101, 102, 104, 114, 118, 120, 130, 139, 141, 142, 154, 157, 188, 193, 199, 205, 211, 224, 229, 236, 237, 242, 243, 250 , 253, 255 and 268, in the count of the alkaline protease from Bacillus lentus.

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, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

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.

The enzymes can be used in any form known in the art. These 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, sparing in water and / or added with stabilizers.

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.

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.

A protein and / or enzyme contained in an agent according to the invention can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Preferred agents according to the invention contain stabilizers for this purpose.

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. Certain organic acids used as builders are capable of, as in WO 97/18287 discloses additionally stabilizing a contained enzyme.

Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation due to physical influences. Likewise, calcium and / or magnesium salts are used, such as calcium acetate or calcium formate.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors. Other polymeric stabilizers are linear C ₈ -C ₁₈ polyoxyalkylenes. Also, alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and, preferably, are capable of additionally increasing their performance. Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase.

Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation; For example, sulfur-containing reducing agents are familiar. Other examples are sodium sulfite and reducing sugars.

Particularly preferred combinations of stabilizers are used, for example, polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and Succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is favorably enhanced by the combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions.

Another agent used with particular preference for stabilizing the enzymatic preparations is potassium sulfate (K ₂ SO ₄ ).

The proportion by weight of the enzymes in the total weight of the dishwashing agent according to the invention is preferably between 0.1 and 10% by weight. In particularly preferred dishwashing detergents, the weight fraction of the enzyme in the total weight of the dishwashing detergent is between 0.2 and 9% by weight and in particular between 0.5 and 8% by weight.

Preferably, one or more enzymes and / or enzyme preparations, preferably solid or liquid protease preparations and / or amylase preparations are used. In a particularly preferred embodiment, a combination of protease and amylase preparations is used.

A further subject of the present invention is also a combination product comprising a packaging means and two separate liquid cleaning agents A and B of the composition located in this packaging means: A: - 10 to 75 wt .-% builder (s); 0.1 to 10% by weight of enzyme (s); 24.9 to 89.9% by weight of water; and B: - 10 to 75 wt .-% builder (s); From 25 to 90% by weight of water, characterized in that the liquid detergent A has a pH (20 ° C) between 6 and 9, while the liquid detergent B has a pH (20 ° C) between 9 and 14, wherein at least one of the cleaning agents A and B, preferably the cleaning agent A, 0.1 to 10 wt .-% of nonionic (s) surfactant (s) and at least one of the cleaning agents A and B, preferably the cleaning agent A, 0.1 to 10 wt .-% of anionic (s ) Containing surfactant (s) with at least one sulfate or sulfonate group.

The present application further relates to the use of a liquid dishwashing detergent according to the invention or the use of a combination product according to the invention, for cleaning or removal of stains, preferably for cleaning or removal of stains by egg yolk or tea, on hard surfaces, especially in dishwashing, in particular in automatic dishwashing.

The anionic surfactants, nonionic surfactants, builders and enzymes of the cleaning agents A and B and their preferred amounts used are preferably selected as described above for the dishwashing detergent according to the invention.

The liquid cleaning agent B may of course also contain enzymes, but in a preferred embodiment, the enzyme content of the cleaning agent B is less than 2 wt .-%, preferably less than 1 wt .-%, more preferably less than 0.5 wt .-% and in particular less than 0.1% by weight. In a particularly preferred embodiment, the liquid detergent B contains no enzymes.

In a further preferred embodiment, none of the cleaning agents A or B contains more than 2% by weight of a bleaching agent. Preferred combination products here are characterized in that the bleach content of the cleaning agents A and / or B is in each case less than 1% by weight, more preferably less than 0.5% by weight and in particular less than 0.1% by weight. Combination products, characterized in that the bleach content of the cleaning agent A and / or B is in each case less than 1 wt .-%, preferably less than 0.5 wt .-% and in particular less than 0.1 wt .-%, according to the invention still more preferred. Particularly preferred combination products are characterized in that the washing or cleaning agents A and / or B contain no bleaching agents.

In addition to H ₂ O ₂ , the group of bleaches includes, for example, the compounds H ₂ O _{2 which} supply water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate. Further bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Typical organic bleaching agents are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)] , o-Carboxybenzamidoperoxycaproic acid, N-Nonenylamidoperadipic Acid and N-Nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-Diperoxycarboxylic acid, 1,9-Diperoxyazelaic acid, Diperocysebacic acid, Diperoxybrassic acid, the Diperoxyphthalic acids, 2-Decyldiperoxybutan-1,4- diacid, N, N-terephthaloyl-di (6-aminopercapronate).

The group of bleaches further includes the chlorine or bromine releasing substances such as 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 also belong to the group of these bleaching agents.

The adjustment of the pH values of the liquid detergents A and B is important for the cleaning performance of the resulting combination product. Combination products in which the pH (20 ° C.) of the liquid cleaning agent A is between 6.5 and 8.5 and in particular between 7 and 8 are particularly preferred. By contrast, the pH (20 ° C.) of the liquid cleaning agent B is preferably between 9.5 and 13 and in particular between 10 and 12.

Particular preference is given to combination products, characterized in that the pH (20 ° C.) of the liquid cleaning agent A differs from the pH (20 ° C.) of the liquid cleaning agent B by at least two units.

To adjust the pH values and to improve the cleaning performance, in a further preferred embodiment, the liquid cleaning agents B additionally contain alkali carriers. A further subject of the present application is therefore a combination product comprising a packaging means with two separate receiving chambers, as well as two separate liquid cleaning agents A and B of the composition located in these receiving chambers: A: - 10 to 75 wt .-% builder (s); 0.1 to 10% by weight of enzyme (s); 24.9 to 89.9% by weight of water; and B: - 10 to 74.9 wt .-% builder (s); 0.1 to 10% by weight of alkali carrier, From 25 to 89.9% by weight of water, characterized in that the liquid detergent A has a pH (20 ° C) between 6 and 9, while the liquid detergent B has a pH (20 ° C) between 9 and 14, wherein at least one of the cleaning agents A and B, preferably the cleaning agent A, 0.1 to 10 wt .-% of nonionic (s) surfactant (s) and at least one of the cleaning agents A and B, preferably also the cleaning agent A, 0.1 to 10 wt .-% of anionic ( s) containing surfactant (s) with at least one sulfate or sulfonate group.

Very particular preference is given to a preferably bleach-free combination product comprising a packaging means with two separate receiving chambers, and two separate liquid cleaning agents A and B of the composition located in these receiving chambers: A: - 15 to 75 wt .-% builder (s); 0.1 to 10% by weight of enzyme (s); - 24.9 to 84.9 wt .-% water, and B: - 15 to 75 wt .-% builder (s); - 0.1 to 10 wt .-% alkali carrier; 25 to 85% by weight of water; characterized in that the liquid detergent A has a pH (20 ° C) between 6 and 9, preferably between 6.5 and 8.5 and in particular between 7 and 8, while the liquid detergent B has a pH (20 ° C) between 9 and 14, preferably between 9.5 and 13 and in particular between 10 and 12, and the pH (20 ° C) of the liquid cleaning agent A of the pH (20 ° C) of the liquid cleaning agent B differs by at least two units, wherein at least one of the cleaning agents A and B, preferably the cleaning agent A, 0.1 to 10 wt .-% of nonionic (s) surfactant (s) and at least one of the cleaning agents A and B, preferably also the Detergent A, 0.1 to 10 wt .-% anionic (s) surfactant (s) having at least one sulfate or sulfonate group, as well as the use of such a combination products for cleaning stains, in particular for cleaning stains when (machine Gesc hirrspülen.

Examples of alkali carriers are the hydroxides, preferably alkali metal hydroxides, the carbonates, bicarbonates or sesquicarbonates, preferably alkali metal carbonates or alkali metal bicarbonates or alkali metal sesquicarbonates, preference being given to using the alkali metal hydroxides and alkali metal carbonates, in particular sodium hydroxide, potassium hydroxides, sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.

The alkali metal hydroxides are preferred in the cleaning agents A and / or B 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 B used. Particular preference is given to combination products in which the cleaning agent A, based on its total weight, contains less than 0.5% by weight and in particular no hydroxides, in particular alkali metal hydroxides.

Particularly preferred is the use of alkali carriers from the group of carbonates and / or bicarbonates, preferably alkali metal carbonates, more preferably sodium carbonate, in amounts of 0.1 to 15 wt .-%, preferably from 0.2 to 10 wt .-% and in particular from 0.5 to 8 wt .-%, each based on the weight of the detergent B. Particularly preferred are combination products in which the detergent A, based on its total weight, less than 0.5 wt .-% and in particular no carbonate (e ) and bicarbonate (s) and sesquicarbonates.

The products described above are distinguished from conventional compositions of the same composition, in particular by an improved cleaning performance of dried-on and / or baked stains on hard surfaces.

A further subject of this application is the use of detergents according to the invention and combination products for the purification of dried-on and / or burnt-on soils, preferably on hard surfaces. The subject matter of this application is, in particular, the use of combination products according to the invention for the purification of dried-on and / or burnt-on soils, in particular for the cleaning of dried-on and / or burnt-on soils during automatic dishwashing.

The group of dried-on or burnt-on soils includes, for example, dried starch soils, for example oatmeal, or burnt-on residues from casseroles which, in addition to starch components such as noodles or potatoes, continue to include meat residues.

Surprisingly, it has been found that the cleaning performance of dishwashing detergents and combination products according to the invention can be improved by the addition of organic solvents. The preferred subject of the present application are therefore furthermore inventive Dishwashing detergent and combination products, characterized in that the dishwashing detergent or at least one of the detergent A or B further contains an organic solvent.

These organic solvents are derived, for example, from the groups of the monoalcohols, diols, triols or polyols, the ethers, esters and / or amides. Particular preference is given to organic solvents which are water-soluble, "water-soluble" solvents for the purposes of the present application are solvents which at room temperature with water completely, d. H. without miscibility, are miscible.

Organic solvents which can be used in the compositions according to the invention preferably originate from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the given concentration range. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, di- ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether as well as mixtures of these solvents.

The organic solvents from the group of the organic amines and / or the alkanolamines have proven to be particularly effective with regard to the cleaning performance and again with regard to the cleaning performance of bleachable soilings, in particular of tea stains.

Particularly preferred organic amines are the primary and secondary alkylamines, the alkyleneamines and mixtures of these organic amines. The group of preferred primary alkylamines include monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine and cyclohexylamine. The group of preferred secondary alkylamines includes in particular dimethylamine.

Preferred alkanolamines are in particular the primary, secondary and tertiary alkanolamines and mixtures thereof. Particularly preferred primary alkanolamines are monoethanolamine (2-aminoethanol, MEA), monoisopropanolamine, diethylethanolamine (2- (diethylamino) ethanol). Particularly preferred secondary alkanolamines are diethanolamine (2,2'-iminodiethanol, DEA, bis (2-hydroxyethyl) amine), N-methyl-diethanolamine, N-ethyl-diethanolamine. Diisopropanolamine and morpholine. Particularly preferred tertiary alkanolamines are triethanolamine and triisopropanolamine.

Dishwashing detergent and combination products, characterized in that they contain an organic solvent, wherein the organic solvent is an organic amine and / or an alkanolamine, preferably monoethanolamine, wherein the weight ratio of water to organic amine and / or alkanolamine in the Dishwashing or cleaning agent A or B is more than 1: 1, preferably more than 2: 1 and in particular more than 5: 1, are preferred according to the invention.

Particularly preferred dishwashing detergent and combination products contain, based on the total weight of the combination product, between 0.1 and 10 wt .-%, preferably between 0.5 and 8 wt .-% and in particular between 1.5 and 6 wt .-% of an organic Solvent from the group of organic amines and alkanolamines. Particularly preferred are combination products whose liquid detergent B, based on the total weight of the detergent B, a weight fraction of an organic solvent from the group of organic amines and alkanolamines between 0.1 and 10 wt .-%, preferably between 0.5 and 8 wt. % and in particular between 1.5 and 6 wt .-%, while the weight fraction of organic solvent from the group of organic amines and alkanolamines in the liquid detergent A, based on the total weight of the cleaning agent A, preferably less than 5 wt %, preferably less than 3 wt .-%, more preferably less than 1 wt .-% and most preferably less than 0.1 wt .-%, and in particular no organic solvent from the group of organic amines and alkanolamines contained in the cleaning agent A.

The compositions according to the invention described above may contain, in addition to the ingredients described above, other washing and cleaning substances, preferably washing and cleaning substances from the group of polymers, bleach activators, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, fragrances and perfume carriers, dyes and preservatives. In particular, other surfactants can also be used. These preferred ingredients will be described in more detail below.

The group of other surfactants which can be used according to the invention include in particular the cationic and the amphoteric surfactants.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, for example, cationic compounds of the following formulas can be used:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

"Cationic polymers" in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, dimethyldiallylammonium polymeric salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrolidone 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.

For the purposes of the present invention, "amphoteric polymers" further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphoric acids.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X^– repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ⁴ radical ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen , at least one quaternized nitrogen atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one Aminogr uppe with a positive charge is. In the context of the present Application particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X ^- represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, - CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

werden im Falle von X^– = Chlorid auch als DADMAC (Diallyldimethylammonium-Chlorid) bezeichnet.Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

in the case of X ^- = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

in der R¹, R², R³, R⁴ und R⁵ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ungesättigen Alkyl-, oder Hydroxyalkylrest mit 1 bis 6 Kohlenstoffatomen, vorzugsweise für einen linearen oder verzweigten Alkylrest ausgewählt aus -CH₃, -CH₂-CH₃, -CH₂-CH₂CH₃, -CH(CH₃)-CH₃, -CH₂OH, -CH₂CH₂OH, -CH(OH)-CH₃, -CH₂CH₂CH₂OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, und -(CH₂CH₂-O)_nH steht und x für eine ganze Zahl zwischen 1 und 6 steht.Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ OH, -CH ₂ CH ₂ OH, -CH (OH) -CH ₃ , -CH ₂ CH ₂ CH ₂ OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H and x is an integer between 1 and 6 stands.

werden im Falle von X^– = Chlorid auch als MAPTAC (Methyacrylamidopropyl-trimethylammonium-Chlorid) bezeichnet.For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

in the case of X ^- = chloride, also referred to as MAPTAC (methylacrylamidopropyltrimethylammonium chloride).

According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

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

Preferred employable amphoteric polymers are from the group of the alkylacylamide / 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.

Preferably usable zwitterionic polymers are selected 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.

Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride. Particularly preferred amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts. Particular preference is given to amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

• – 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 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.

Preferred dishwashing detergents and combination products preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of between 0.01 and 8% by weight, based in each case on the total weight of the particular cleaning agent. In the context of the present application, however, preference is given to dishwashing detergents and combination products in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, more preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the cleaning agent is.

Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.

Particularly preferred as sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.

In the context of the present invention are as unsaturated monomer 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, 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.

Among the unsaturated carboxylic acids which can be described by the above formula are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is 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 , 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 - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

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 , -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 - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

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-methacylamido-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 water-soluble salts of said acids.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H.

• i) ungesättigten Carbonsäuren der Formel R¹(R²)C=C(R³)COOH in der R¹ bis R³ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel R⁵(R⁶)C=C(R⁷)-X-SO₃H in der R⁵ bis R⁷ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren besonders bevorzugt.

In summary, copolymers are made of

• i) unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH in the 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 , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• ii) sulfonic acid group-containing monomers of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H in the R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals 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, 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 and -C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers are particularly preferred.

• i) einer oder mehreren ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln: H₂C=CH-X-SO₃H H₂C=C(CH₃)-X-SO₃H HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H, in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren.

Further particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more sulfonic acid group-containing monomers 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 , -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 - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionogenic or nonionic monomers.

The copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

For example, copolymers which are structural units of the formula are preferred - [CH ₂ CHCOOH] _m - [CH ₂ CHC (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula - [CH ₂ C (CH ₃ ) COOH] _m - (CH ₂ CHC (O) -Y-SO ₃ H] _p -, in which m and p are each an integer between 1 and 2, and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y is -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C ( CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula - [CH ₂ CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, as preferred as copolymers, the structural units of the formula - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred. Also preferred according to the invention are copolymers which contain structural units of the formula - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ )- stands.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas - [CH ₂ CHCOOH] _m [CH ₂ CHC (O) -Y-SO ₃ H] _p - - [CH ₂ C (CH ₃ ) COOH] _m - (CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -CHCOOH] _m [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [CH ₂ C (CH ₃ ) COOH] _m [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ CHC (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, d. H. in that 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 is in the case of copolymers which contain only monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), more preferably from 50 to 90% by weight of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

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 washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

Dishwashing detergent and combination products, characterized in that the dishwashing detergent or the cleaning agent A and / or the cleaning agent B further based on the total weight of the respective cleaning agent 0.01 to 15 wt .-%, preferably 0.02 to 12 wt .-% and In particular, 0.1 to 8 wt .-% of one or more washing or cleaning active polymers containing, are inventively preferred.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.If the dishwashing or combination products contain bleaches, bleach activators are preferably used in the detergents in order to achieve an improved bleaching action when cleaning at temperatures of 60 ° C. and below. 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. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), 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), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran. Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ OH , -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^– besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂CN X^–, in welcher X^– für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt ist.Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ CN X ^- , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, wherein in turn from the group of these substances, the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ CN X ^- in which X ^{- represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate , is particularly preferred.

As bleach activators it is also 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. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), 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), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and also acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl-fructose, tetraacetyl-xylose and octaacetyl lactose as well as acetylated, optionally N- alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

If, in addition to the nitrile quats, further bleach activators are to be used, preference is given to bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (US Pat. n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA).

In addition to, or in place of, the conventional bleach activators, so-called bleach catalysts can also be used. 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.

Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complex, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate used.

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 / or zinc salts and / or magnesium and / or zinc complexes.

The spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference, the glass corrosion inhibitor used is at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

Also suitable for glass corrosion protection are the soluble inorganic zinc salts, in particular the zinc sulfate, zinc nitrate and zinc chloride.

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to 3-amino-5-alkyl 1,2,4-triazoles or their physiologically acceptable salts used, these substances with particular preference in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1,2,4-triazoles and mixtures of these substances.

In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds used. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

Instead of or in addition to the silver protectants described above, for example the benzotriazoles, redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III, IV, V or VI are present.

The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation include all conventional mono-, di-, or tri-negatively charged inorganic anions, e.g. As oxide, sulfate, nitrate, fluoride, but also organic anions such. Stearate.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ , and mixtures thereof, such that the metal salts and / or metal complexes selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - (1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) _{3 are used} with particular preference ,

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, d. H. completely coated with a waterproof, but easily soluble in the cleaning temperatures material to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.

As perfume oils or fragrances can in the present invention, individual fragrance compounds, eg. As the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons 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 as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note" or "body note" ) and "base note" (end note or dry out). Since odor perception is also largely based on the odor intensity, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, ie adherent fragrances. In the composition of perfumes can more easily volatile fragrances for example, be bound to certain fixatives, thereby preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.

When choosing the colorant, it must be remembered that the colorants have a high storage stability and insensitivity to light as well as not too strong affinity to glass, ceramic or plastic dishes. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ^-3 % by weight are typically selected. By contrast, in the case of the particularly preferred, but less readily water-soluble, pigment dyes due to their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 ^-3 to 10 ^-4 % by weight.

Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for. B. anionic nitrosofarbstoffe.

The detergents or cleaners according to the invention may also contain preservatives. Preservatives from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable according to the invention 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 terms of their performance and storage stability, a number of combination products have proven to be particularly advantageous:
A combination product comprising a packaging means and two separate liquid detergents A and B of the composition contained in said packaging means: A: according to the following table B: according to the following table characterized in that the liquid detergent A has a pH (20 ° C) between 6 and 9, while the liquid detergent B has a pH (20 ° C) between 9 and 14 and it is in the nonionic surfactant to a surfactant 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 ,
wherein R ¹ and R ² independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 alkyl or alkenyl radical; 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 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0. Ser. number Cleaning agent A containing (in% by weight) Cleaning agent B containing (in% by weight) 1 10 to 74.8 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89.7 of water; 0.2 to 10.0 nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group 10 to 74.9 builder (s); From 25 to 89.9% of water; 0.1 to 10 alkanolamine 2 10 to 74.8 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89, 7 water; 0.2 to 10.0 nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group 10 to 74.9 builder (s); 25 to 89.9% water, 0.01 to 15 sulfonic acid group-containing polymer 3 10 to 74.7 builder (s); 0.1 to 10 enzyme (s); 24.9-89.6% water, 0.2-10.0% nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group; 0.01 to 15 sulfonic acid group-containing polymer 10 to 74.9 builder (s); 25 to 89.9% water, 0.01 to 15 sulfonic acid group-containing polymer 4 10 to 74.8 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89, 7 water; 0.2 to 10.0 nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group 10 to 74.8 builder (s); 25 to 89.8% water, 0.1 to 10% alkanolamine; 0.01 to 15 sulfonic acid group-containing polymer 5 10 to 74.7 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89.6% water; 0.2 to 10.0 nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group; 0.01 to 15 sulfonic acid group-containing polymer 10 to 74.8 builder (s); 25 to 89.9% water, 0.1 to 10% alkanolamine; 0.01 to 15 sulfonic acid group-containing polymer 6 10 to 74.8 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89.7 of water; 0.2 to 10.0 nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group 10 to 74.9 builder (s); From 25 to 89.9% of water; 0.1 to 10 alkali hydroxide 7 10 to 74.8 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89, 7 water; 0.2 to 10.0 nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group 10 to 74.8 builder (s); 25 to 89.8% water, 0.1 to 10% alkali hydroxide; 0.01 to 15 sulfonic acid group-containing polymer 8th 10 to 74.7 builder (s); 0.1 to 10 enzyme (s); 24.9-89.6% water, 0.2-10.0% nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group; 0.01 to 15 sulfonic acid group-containing polymer 10 to 74.8 builder (s); 25 to 89.9% water, 0.1 to 10% alkali hydroxide; 0.01 to 15 sulfonic acid group-containing polymer 9 10 to 74.8 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89.7% water, 0.2 to 10.0% nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group 10 to 74.9 builder (s); From 25 to 89.9% of water; 0.1 to 10 alkanolamine 0.01 to 8 cationic and / or amphoteric polymers 10 10 to 74.8 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89, 7 water, 0.2 to 10.0 nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group 10 to 74.9 builder (s); From 25 to 89.9% of water; 0.01 to 15 sulfonic acid-containing polymer 0.01 to 8 cationic and / or amphoteric polymers 11 10 to 74.7 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89, 6 water, 0.2 to 10.0 nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group; 0.01 to 15 wt .-% sulfonic acid-containing polymer 10 to 74.9 builder (s); 25 to 89.9 water 0.01 to 15 polymer containing sulfonic acid 0.01 to 8 cationic and / or amphoteric polymers 12 10 to 74.8 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89.7 of water; 0.2 to 10.0 nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group 10 to 74.8 builder (s); 25 to 89.8% water, 0.1 to 10% alkanolamine; 0.01 to 15 sulfonic acid-containing polymer 0.01 to 8 cationic and / or amphoteric polymers 13 10 to 74.7 builder (s); 0.1 to 10 enzyme (s); 24.9-89.6% water, 0.2-10.0% nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group; 0.01 to 15 sulfonic acid group-containing polymer 10 to 74.8 builder (s); From 25 to 89.9% of water; 0.1 to 10 alkanolamine; 0.01 to 15 sulfonic acid-containing polymer 0.01 to 8 cationic and / or amphoteric polymers 14 10 to 74.8 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89.7% water, 0.2 to 10.0% nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group 10 to 74.9 builder (s); 25 to 89.9% water, 0.1 to 10% alkali hydroxide 0.01 to 8 cationic and / or amphoteric polymers 15 10 to 74.8 builder (s); 0.1 to 10 enzyme (s); 24.9 to 89, 7 water; 0.2 to 10.0 nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group 10 to 74.8 builder (s); 25 to 89.8% water, 0.1 to 10% alkali hydroxide; 0.01 to 15 sulfonic acid-containing polymer 0.01 to 8 cationic and / or amphoteric polymers 16 10 to 74.7 builder (s); 0.1 to 10 enzyme (s); 24.9-89.6% water, 0.2-10.0% nonionic surfactant; 0.2 to 10.0 anionic surfactant with sulfate and / or sulfonate group; 0.01 to 15 sulfonic acid group-containing polymer 10 to 74.8 builder (s); From 25 to 89.9% of water; 0.1 to 10 alkali hydroxide; 0.01 to 15 sulfonic acid-containing polymer 0.01 to 8 cationic and / or amphoteric polymers

With regard to their fillability and meterability, such combination products have proven advantageous in which at least one of the cleaning agents A or B has a viscosity of more than 10,000 mPas, preferably more than 50,000 mPas and in particular more than 100,000 mPas. Combination products, characterized in that the viscosity (Brookfield viscometer LVT-II at 20 U / min and 20 ° C, spindle 3) of at least one of the cleaning agent A or B between 200 and 10,000 mPas, preferably between 500 and 7000 mPas and in particular between 1000 and 4000 mPas, are preferred according to the invention.

The viscosity (Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) of particularly preferred cleaning agents is above 500 mPas, preferably above 1000 mPas and in particular above 2000 mPas.

In order to achieve the desired viscosity of the washing and cleaning agent form according to the invention (solubility, washing and cleaning performance, stability of the gel), these agents are preferably thickening agents, in particular thickeners from the group agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins , Polyols, guar gum, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose, staple ethers, polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicic acids it has proved to be particularly advantageous if the washing or cleaning agent, the thickener in amounts between 0.1 and 8 wt .-%, preferably between 0.2 and 6 wt .-% and particularly preferably between 0.4 and 4 wt .-% based on the total weight of the washing or cleaning agent, included.

Natural-derived polymers used as thickening agents in the present invention are, as described above, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein. Modified natural products come mainly from the group of modified starches and celluloses, examples which may be mentioned here carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers.

A large group of thickeners, which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Thickening agents from these classes of compounds are widely available commercially and are sold for example under the trade name Acusol ^® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^® GT-282- S (alkyl polyglycol ethers, Akzo), DEUTEROL ^® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ^® -xg (anionic heteropolysaccharide based on β-D-glucose, D-mannose, D-glucuronic acid, Schoner GmbH) deuteron ^® -XN (nonionic polysaccharide Schoner GmbH), DICRYLAN ^® -Verdicker-O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene-maleic anhydride copolymer, Monsanto), thickener QR-1001 (polyurethane emulsion, 19-21% in water / diglyme, Rohm & Haas), Mirox ^® AM (anionic acrylic acid-acrylate copolymer dispersion, 25% in water, Stockhausen), SER -AD-FX-1100 (hydrophobic urethane polymer, servo Delden), Shellflo ^® -S (high molecular weight P olysaccharid stabilized with formaldehyde, Shell), and Shellflo XA ^® (xanthan biopolymer, stabilized with formaldehyde, Shell) is.

The combination products according to the invention further comprise, in addition to the two liquid detergents A and B, a packaging means. In this packaging means, the two cleaning agents A and B are separated from each other, that is, they do not form a common phase boundary, but are rather in separate areas of the packaging means.

As such a packaging means, for example, water-insoluble a two- or multi-chamber container is suitable. Such a two- or multi-chamber container typically has a total volume between 100 and 5000 ml, preferably between 200 and 2000 ml. The volume of the individual chambers is preferably between 50 and 2000 ml, preferably between 100 and 1000 ml. Preferred two- or multi-chamber containers have a bottle shape.

For metering the liquid detergent, the two- or multi-chamber container preferably has at least one spout, which may be configured, for example, in the form of a common spout for all means contained in the bottle. However, preferred are those two- or multi-chamber container, in which each of the receiving chambers of the container has its own spout. By such a configuration, for example, a contamination of individual chambers by ingredients from another chamber is avoided.

Combination products according to the invention, characterized in that the packaging means is a two- or multi-chamber container, wherein preferably each of the receiving chambers of the packaging means is provided with a spout, are preferred.

In an alternative embodiment, the packaging means is a water-soluble two- or multi-chamber container, for example a water-soluble bag with two or more separate receiving chambers.

The thermoforming bodies can have two, three or more receiving chambers. These receiving chambers can be arranged in the deep-drawn part next to each other and / or one above the other and / or one inside the other.

Water-soluble polymers such as, for example, cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch are particularly suitable as packaging materials for the water-soluble containers.

The water-soluble bags are preferably thermoformed or injection-molded bodies.

In the context of the present application, the term "thermoforming body" refers to such containers which are obtained by deep drawing of a first film-like wrapping material. The deep drawing is preferably carried out by bringing the wrapping material over a receiving trough located in a die forming the deep-drawing tray and shaping the wrapping material into this receiving trough by the action of pressure and / or vacuum. The shell material may be pre-treated before or during the molding by the action of heat and / or solvent and / or conditioning by relative to ambient conditions changed relative humidity and / or temperatures. The pressure action can be carried out by two parts of a tool, which behave as positive and negative to each other and deform a spent between these tools film when squeezed. However, the action of compressed air and / or the weight of the film and / or the weight of an active substance applied to the upper side of the film is also suitable as pressure forces.

The deep-drawn shell materials are preferably fixed after deep drawing by use of a vacuum within the receiving troughs and in their achieved by the deep-drawing process spatial form. The vacuum is preferably applied continuously from deep drawing to filling until sealing and in particular until the separation of the receiving chambers. With comparable results, however, the use of a discontinuous vacuum, for example, for deep drawing of the receiving chambers and (after an interruption) before and during the filling of the receiving chambers, possible. Also, the continuous or discontinuous vacuum can vary in its thickness and, for example, take higher values at the beginning of the process (during deep drawing of the film) than at its end (during filling or sealing or singulation).

As already mentioned, the shell material can be pre-treated by the action of heat before or during the molding into the receiving troughs of the matrices. The shell material, preferably a water-soluble or water-dispersible polymer film, is heated to temperatures above 60 ° C. for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds. preferably above 80 ° C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C. To dissipate this heat, but in particular for the discharge of the filled through the deep-drawn receiving chambers means introduced heat (for example, melting), it is preferable to cool the matrices used and the receiving troughs located in these matrices. The cooling is preferably carried out at temperatures below 20 ° C, preferably below 15 ° C, more preferably at temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ° C. Preferably, the cooling takes place continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers. Cooling fluids, preferably water, which are circulated in special cooling lines within the matrix, are particularly suitable for cooling.

This cooling, as well as the previously described continuous or discontinuous application of a vacuum has the advantage of preventing shrinkage of the deep-drawn containers after deep drawing, whereby not only the appearance of the process product is improved, but also at the same time the discharge of the filled into the receiving chambers means the edge of the receiving chamber, for example in the sealing areas of the chamber, is avoided. Problems with the sealing of the filled chambers are thus avoided.

In the deep-drawing process can be between methods in which the shell material is guided horizontally in a forming station and from there in a horizontal manner for filling and / or sealing and / or separating and methods in which the shell material via a continuously rotating Matrizenformwalze (optionally with optional a counter-guided Patrizenformwalze, which lead the forming upper punch to the cavities of Matrizenformwalze) is different. The first-mentioned process variant of the flat bed process is to operate both continuously and discontinuously, the process variant using a molding roll is usually continuous. All of the mentioned deep drawing methods are suitable for the production of the inventively preferred means. The receiving troughs located in the matrices can be arranged "in series" or staggered.

The water-soluble containers can also be produced by injection molding. Injection molding refers to the forming of a molding material such that the mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool. The method is mainly applied to non-hardenable molding compounds which solidify in the tool by cooling. Injection molding is a very economical modern process for producing non-cutting shaped objects and is particularly suitable for automated mass production. In practical operation, the thermoplastic molding compounds (powders, granules, cubes, pastes, etc.) are heated to liquefaction (up to 180 ° C) and injected under high pressure (up to 140 MPa) in closed, two-piece, that is from Gesenk (earlier Die) and core (formerly male) existing, preferably water-cooled molds, where they cool and solidify. Piston and screw injection molding machines can be used.

Combination products according to the invention, characterized in that the packaging means are a water-soluble container with two separate receiving chambers, are preferred.

As stated so far, the combination product according to the invention is particularly suitable as a machine dishwashing detergent. A further subject of the present application is therefore a machine dishwashing process, in which two liquid cleaning agents A and B are metered into the interior of a dishwasher, wherein the cleaning agents A and B have the following composition: A: - 10 to 75 wt .-% builder (s); 0.1 to 10% by weight of enzyme (s); 24.9 to 89.9% by weight of water, and B: - 10 to 75 wt .-% builder (s); - 25 to 90 wt .-% water and the liquid detergent A has a pH (20 ° C) between 6 and 9, while the liquid detergent B has a pH (20 ° C) between 9 and 14, wherein at least one of the cleaning agents A and B, preferably the cleaning agent A, 0.1 to 20% by weight of nonionic surfactant (s) and at least one of the cleaning agents A and B, preferably the cleaning agent A, 0.1 to 20% by weight of anionic surfactant ( e) containing at least one sulfate or sulfonate group.

If the cleaning agents A or B are formulated in water-soluble containers, they have a viscosity of more than 10,000 mPas, preferably more than 50,000 mPas and in particular more than 100,000 mPas, notwithstanding the details given above. Combination products, characterized in that they are present in a packaging with two separate receiving chambers, wherein the viscosity (Brookfield LVT-II at 20 rev / min and 20 ° C, spindle 3) at least one of the cleaning agent A or B between 5000 and 200,000 mPas, preferably between 10,000 and 150,000 mPas and in particular between 20,000 and 100,000 mPas, are preferred according to the invention.

The metering of the two liquid detergents A and B can take place, for example, in the metering chamber in the door or an additional metering container in the interior of the dishwasher or directly on the soiled dishes. Alternatively, the two cleaning agents can also be metered onto one of the inner walls of the dishwasher, for example the inside of the door.

Preferred embodiments of the automatic dishwashing process according to the invention result mutatis mutandis from the previous description of preferred embodiments of the combination product according to the invention, to which reference is made to avoid repetition at this point.

In a preferred embodiment, the inventive method for machine cleaning dishes in a dishwasher is characterized in that in the course of a cleaning program, which includes a prewash and a cleaning cycle, in this cleaning cycle on two consecutive times t1 and t2 two liquid detergents A and B. the composition: A: - 10 to 75 wt .-% builder (s); 0.1 to 10% by weight of enzyme (s); 24.9 to 89.9% by weight of solvent; and B: - 10 to 74.9 wt .-% builder (s); 25 to 89.9% by weight of solvent; are metered into the interior of the dishwasher, wherein the liquid detergent A has a pH (20 ° C) between 6 and 9 and is metered at time t1, while the liquid detergent B a pH (20 ° C) between 9 and 14 and is metered in at time t2 and at least one of the cleaning agents A and B, preferably the cleaning agent A, 0.1 to 20 wt .-% of nonionic (s) surfactant (s) and at least one of the cleaning agents A and B, preferably the cleaning agent A, 0.1 to 20 wt .-% anionic (s) surfactant (s) having at least one sulfate or sulfonate group.

In the processes according to the invention, the nonionic and anionic surfactants which have previously been found to be preferred are used with particular preference in the amounts given above as being preferred.

Particular preference is given according to an anionic surfactant selected from fatty alcohol sulfates, alkanesulfonates and alkylbenzenesulfonates, in particular selected from C ₁₂ -C ₁₈ fatty alcohol sulfates, secondary C ₁₃ -C ₁₇ -alkanesulfonates and linear C ₈ -C ₁₈ -alkylbenzenesulfonates in inventive processes in amounts from particularly preferably 0.5 to 15 wt .-%, in particular 1.5 to 7 wt .-%, used.

Furthermore, it is correspondingly particularly preferable to use a nonionic surfactant selected from 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 15 to 120, especially 20 to 80;
and from 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 for a branched or unbranched alkyl radical having 2 to 4, preferably 2, carbon atoms; x and y independently represent values between 1 and 70; and
M is an alkyl radical selected from the group consisting of 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;
in the method according to the invention particularly preferably in an amount of 0.5 to 15 wt .-%, in particular 1.5 to 7 wt .-%, used.

The implementation of this preferred method according to the invention takes place in the interior of a commercial dishwasher. The cleaning program can be selected and determined in a dishwasher usually before the dishwashing process by the consumer. The dishwashing machine cleaning program used in this method according to the invention preferably comprises at least one prewash cycle and one cleaning cycle. Cleaning programs which include further cleaning or rinsing cycles, for example a rinse cycle, are preferred according to the invention. The inventive method is therefore not limited to such cleaning programs that consist exclusively of a pre-rinse and a cleaning cycle.

The process according to the invention is particularly preferably part of a cleaning program, comprising a prewash cycle, a cleaning cycle and a rinse cycle. The automatic dishwashing detergent programs may differ in terms of their duration, their water consumption and the temperature of the cleaning liquor. The inventive method is preferably used in conjunction with such cleaning programs in which the wash liquor is heated in the course of the cleaning cycle.

In a preferred embodiment of the method according to the invention the cleaning cycle, in the course of which the cleaning agents A and B are metered into the interior of the dishwasher, characterized in that in its course, the temperature of the cleaning liquor to values above 30 ° C, preferably above 40 ° C and especially above 50 ° C increases.

The temperature of the wash liquor at time t1 is in a preferred embodiment between 12 and 45 ° C, preferably between 15 and 40 ° C and in particular between 20 and 35 ° C, while the temperature of the wash liquor at time t2 preferably between 30 and 65 ° C. , preferably between 35 and 60 ° C and in particular between 40 and 55 ° C.

At the time of dosing the detergent A and B, the wash liquor may have the same or different temperatures. Preferably, the temperature of the wash liquor at time t1 is different from the temperature of the wash liquor at time t2, wherein the temperature at time t1 may be above or below the temperature at time t2. Particularly advantageous cleaning results could be achieved in methods according to the invention in which the temperature of the wash liquor was below the temperature of the wash liquor at time t 2 at time t 1. Corresponding methods are therefore preferred.

To optimize the cleaning performance in the process according to the invention, the temperature of the wash liquor at time t2 is preferably at least 5 ° C, preferably at least 10 ° C and especially between 10 and 40 ° C, but especially between 10 and 20 ° C above the temperature of the wash liquor at time t1.

The metering of the two liquid cleaning agents A and B takes place in the course of the cleaning cycle at two successive times t1 and t2, the cleaning agent A being metered in at time t1 and the cleaning agent B at time t2 and the time t1 being earlier than time t2.

The time t1 is preferably within the first ten minutes after the beginning of the cleaning cycle, preferably within the first eight minutes after the beginning of the cleaning cycle and in particular within the first five minutes after the beginning of the cleaning cycle.

The time difference between the times t1 and t2 is preferably between 2 and 30 minutes, preferably between 4 and 25 minutes and in particular between 6 and 20 minutes.

To optimize the cleaning performance in the method according to the invention, it is further provided to keep the pH values of the cleaning agents A and B within narrow limits. Preferred methods are characterized in that the cleaning agent A has a pH (20 ° C) between 6.5 and 8.5, preferably between 7 and 8, while the pH (20 ° C) of the cleaning agent B between 9.5 and 13, preferably between 10 and 12 lies.

Particular preference is given to processes in which the pH (20 ° C.) of the liquid cleaning agent A differs from the pH (20 ° C.) of the liquid cleaning agent B by at least two units, since particularly good cleaning results can be achieved in these processes ,

The cleaning agents A and B are preferably conveyed from a self-sufficient dosing device into the interior of the dishwasher. As "self-sufficient" while a dosing device is called, which is not an integral part of the dishwasher used. Such a metering device preferably has its own storage container for the cleaning agents A and B and its own metering device for conveying and metering the cleaning agents A and B into the interior of the dishwasher. In a particularly preferred embodiment, the dosing device is further provided with a stand-alone power supply.

The cleaning agents A and B can each be conveyed via an independent dosing device into the interior of the dishwasher. However, it is preferable to combine the cleaning agents A and B in a common metering device with each other. The liquid detergents A and B are in a preferred embodiment in a water-insoluble two- or multi-chamber reservoir ago. The cleaning agents A and B are preferably spatially separated from each other in this container and are metered from this container into the interior of the dishwasher. By separating the detergents from each other, physical and chemical interactions of the detergents are prevented.

The volume of the respective chambers of the reservoir is preferably sufficient for receiving at least five, preferably at least ten and more preferably at least 20 dosing units of a cleaning agent A or B. Since the dosage amount of the cleaning agent A and B in the course of a cleaning process preferably between 5 and 50 ml, preferably between 10 and 40 ml and in particular between 10 and 30 ml, the preferred volume of the storage chamber for the cleaning agent A and for the cleaning agent B is at least 25 ml, preferably at least 50 and in particular at least 100 ml. Preference is given metering devices, each having a chamber for the cleaning agents A and B, wherein the volume of each of these chambers is between 50 and 1000 ml, preferably between 100 and 800 ml and in particular between 200 and 600 ml.

Surprisingly, it was found that the cleaning performance in the method according to the invention in addition to the aforementioned parameters can continue to be influenced by the metering rate of the metering device. The metering rate of the metering device is preferably between 1 and 40 ml per minute, preferably between 2 and 30 ml per minute and in particular between 4 and 20 ml per minute.

The cleaning agents A and B used in the process according to the invention contain builders in addition to other ingredients which are active in washing or cleaning. The builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates. A detailed description of these builders can be found earlier in the text.

The liquid detergents A and / or B preferably contain a proportion _by weight of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} · yH ₂ O of 0.1 to 20 wt .-% of 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the weight of the respective cleaning agent A or B, are included.

In the context of the present invention, it is preferred that these silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in the liquid detergent A and / or B in amounts of 2 to 40 wt .-%, preferably from 3 to 30 wt .-% and in particular from 5 to 25 wt .-%, each based on the weight of the respective cleaning agent A or B, are included.

If phosphates are used as washing or cleaning substances in the liquid detergents A and / or B in the context of the present application, preferred combination products contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate), in amounts of from 5 to 60% by weight, preferably from 15 to 45 wt .-%, in particular from 20 to 40 wt .-%, each based on the weight of the respective cleaning agent A or B, are included.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances have already been described in previous sections of the description.

The citric acid or salts of citric acid are used with particular preference as builder substance. Combination products, characterized in that the at least one of the cleaning agent A or B contains citric acid or a salt of citric acid and the weight fraction of citric acid or the salt of citric acid, based on the total weight of the cleaning agent, between 0.2 and 12 wt .-% , preferably between 0.2 and 8 wt .-% and in particular between 0.2 and 6 wt .-%, are inventively preferred.

Another particularly preferred builder substance is methylglycine diacid (MGDA). Process according to the invention, characterized in that the cleaning agent contains methylglycinediacetic acid or a salt of methylglycinediacetic acid and that the weight fraction of methylglycinediacetic acid or the salt of methylglycinediacetic acid is preferably between 0.2 and 12% by weight, preferably between 0.2 and 8% by weight and in particular between 0.2 and 6 wt .-%, are preferred according to the invention.

The content of cleaning agents in (co) polymeric polycarboxylates is preferably 0.1 to 10% by weight, preferably 0.2 to 8% by weight, more preferably 0.4 to 6% by weight and in particular between 0, 4 and 4 wt .-%.

As a further constituent, the composition used as cleaning agent A in the process according to the invention contains enzymes. To avoid repetition, reference is made here to the detailed description above in the text.

As stated at the outset, the proportion by weight of the enzymes in the total weight of the liquid cleaning agent A is between 0.1 and 10% by weight. In particularly preferred combination products, the proportion by weight of the enzyme in the total weight of the cleaning agent A is between 0.2 and 9% by weight and in particular between 0.5 and 8% by weight.

Although the liquid detergent B may of course also contain enzymes, it is preferred that the enzyme content of the detergent B be less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight. and in particular less than 0.1 wt .-% is. Particularly preferred methods according to the invention are characterized in that the liquid cleaning agent B contains no enzymes.

Preferably, one or more enzymes and / or enzyme preparations, preferably solid or liquid protease preparations and / or amylase preparations are used. In a particularly preferred embodiment, the liquid cleaning agent A comprises a combination of protease and amylase preparations.

In addition to water, the organic solvents already described above are also suitable as solvents in the cleaning agents A and B used in the process according to the invention, the organic amines and / or alkanolamines also described being of particular importance organic amines, in particular the aforementioned organic amines and / or alkanolamines in the process according to the invention, for the purification of bleachable stains, preferably for cleaning Teeanschmutzungen on hard surfaces.

Particularly preferred cleaning agents A and / or B contain, based on the total weight of the respective cleaning agent, between 0.1 and 10 wt .-%, preferably between 0.5 and 8 wt .-% and in particular between 1.5 and 6 wt. % of an organic solvent from the group of organic amines and alkanolamines. Particular preference is given to processes according to the invention in which the liquid cleaning agent B, based on the total weight of the cleaning agent B, has a weight fraction of an organic solvent from the group of the organic amine and the alkanolamines between 0.1 and 10% by weight, preferably between 0, 5 and 8 wt .-% and in particular between 1.5 and 6 wt .-%, while the weight fraction of organic solvent from the group of organic amines and the Alkanolamines in the liquid cleaning agent A, based on the total weight of the cleaning agent A, preferably less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt .-% and most preferably less than 0, 1 wt .-%, and in particular no organic solvent from the group of organic amines and alkanolamines in the cleaning agent A is included.

With regard to their meterability in the course of the cleaning method according to the invention with time-delayed metering, cleaning agents which have a viscosity of more than 10,000 mPas, preferably more than 50,000 mPas and in particular more than 100,000 mPas have proven advantageous.

In a preferred embodiment, the bleach content of the liquid detergents A and B is chosen to be low and is preferably less than 2% by weight. Surprisingly, a cleaning performance could be achieved by the process control according to the invention with time-staggered metering and by the use of bleach-poor cleaning agent, which is comparable to the cleaning performance bleach-containing cleaner. By dispensing with bleaching agents, however, it was possible at the same time to increase the reciprocal freedom with decreasing production costs.

embodiments

Example 1: Cleaning performance in automatic dishwashing

The cleaning performance of a commercial liquid automatic dishwashing detergent to which various anionic surfactants have been added was tested. For comparison, the cleaning performance of the same dishwashing detergent without anionic surfactant was checked. The liquid automatic dishwashing detergent is a combination product of two detergents A and B, wherein the cleaning agent A contains, in addition to a end-capped nonionic surfactant in particular builder and enzyme and has a pH of 7.5 and the detergent B, which also builder contains, has a pH of 11.2. The anionic surfactant was added to the cleaning agent A. Before starting the cleaning process, the cleaning agents A and B were applied to the dosing device of the dishwasher.

The dishwashing process was carried out in the dishwasher Bosch SMS86M12 DE / 01 (program: 40 ° C, water hardness 21 ° dH). There were 3 determinations each. Each trial was counted and at the end the average was formed. The worst grade is 0, the best grade is 10.

The cleaning results are shown in the following table: egg yolk Dishwashing liquid 3.1 +2 g Sulfopone K 35 4.3 +1 g Hostapur SAS 60 3.8 +2 g Hostapur SAS 60 4.2

Sulfopon K35 is a C12-C18 fatty alcohol sulfate (FAS), while Hostapur SAS 60 is a C13-C17 secondary alkanesulfonate (SAS).

The addition of anionic surfactants of sulfate and sulfonate type leads to an improvement in the cleaning performance of egg yolk (32% fat). The foaming of the anionic surfactant in the dishwasher is obviously so low that the cleaning performance is not adversely affected.

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 97/18287 [0100]

Claims (10)

Liquid dishwashing detergent, characterized in that it contains at least one anionic surfactant having at least one sulfate or sulfonate group and at least one nonionic surfactant. Dishwashing detergent according to claim 1, characterized in that the anionic surfactant is selected from alkyl sulfates, alkyl sulfonates and alkylbenzenesulfonates and preferably in an amount of 0.1 to 20 wt .-%, particularly preferably 0.5 to 15 wt .-%, in particular 1 , 5 to 7 wt .-%, is included. Dishwashing detergent according to claim 1 or 2, characterized in that the nonionic surfactant is selected from 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 15 to 120, in particular from 20 to 80; and from 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 are 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, preferably 2, carbon atoms; x and y independently represent values between 1 and 70; and M is an alkyl radical selected 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; and the nonionic surfactant is preferably contained in an amount of 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, especially 1.5 to 7% by weight. A combination product comprising a packaging means and two separate liquid detergents A and B of the composition contained in said packaging means A: - 10 to 75 wt .-% builder (s); 0.1 to 10% by weight of enzyme (s); 24.9 to 89.9% by weight of water, and B: - 10 to 75 wt .-% builder (s); - 25 to 90 wt .-% water; wherein the liquid detergent A has a pH (20 ° C) between 6 and 9 and the liquid detergent B has a pH (20 ° C) between 9 and 14, characterized in that at least one of the cleaning agents A and B anionic surfactant (s) having at least one sulfate or sulfonate group and at least one of the cleaning agents A and B contains nonionic surfactant (s). Combination product according to claim 4, characterized in that the anionic surfactant is selected from alkyl sulfates, alkyl sulfonates and alkylbenzenesulfonates, in particular from C ₁₂ -C ₁₈ fatty alcohol sulfates, secondary C ₁₃ -C ₁₇ alkanesulfonates and linear C ₈ -C ₁₈ -alkylbenzenesulfates , And preferably in an amount of 0.1 to 20 wt .-%, particularly preferably 0.5 to 15 wt .-%, in particular 1.5 to 7 wt .-%, is contained in the detergent in question. Combination product according to claim 4 or 5, characterized in that the nonionic surfactant is selected from nonionic 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 , wherein R ¹ and R ² independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 alkyl or alkenyl radical; 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 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0; and from nonionic surfactants of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , wherein R ¹ and R ² independently 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 selected 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; and the nonionic surfactant is preferably contained in an amount of from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, more preferably from 1.5 to 7% by weight, in the respective detergent. Combination product according to one of claims 4 to 6, characterized in that at least one of the cleaning agent A or B further contains an organic solvent, wherein the organic solvent is an organic amine and / or an alkanolamine, preferably ethanolamine, wherein the weight ratio of water to organic amine in the cleaning agent A or B is more than 1: 1, preferably more than 2: 1 and in particular more than 5: 1, and / or that at least one of the cleaning agents A or B is 0.01 to 15 Wt .-%, preferably 0.02 to 12 wt .-% and in particular 0.1 to 8 wt .-% of one or more washing or cleaning active polymers. Combination product according to one of the preceding claims, characterized in that it is the packaging means is a water-insoluble two- or multi-chamber container, wherein preferably each of the receiving chambers of the packaging means is provided with a spout. Process for the automatic cleaning of dishes in a dishwasher, characterized in that two liquid detergents A and B are metered into the interior of a dishwasher, wherein the cleaning agents A and B have the following composition: A: - 10 to 75 wt .-% builder (s); 0.1 to 10% by weight of enzyme (s); 24.9 to 89.9% by weight of water, and B: - 10 to 75 wt .-% builder (s); - 25 to 90 wt .-% water; wherein the liquid detergent A has a pH (20 ° C) between 6 and 9 and the liquid detergent B has a pH (20 ° C) between 9 and 14 and at least one of the cleaning agent A or B anionic (s) surfactant (s) having at least one sulfate or sulfonate group and at least one of the cleaning agent A or B nonionic (s) surfactant (s). Method for machine cleaning of dishes in a dishwasher, characterized in that in the course of a cleaning program comprising a prewash cycle and a cleaning cycle, two liquid detergents A and B of the composition in this cleaning cycle on two consecutive times t1 and t2: A: - 10 to 75 wt .-% builder (s); 0.1 to 10% by weight of enzyme (s); 24.9 to 89.9% by weight of water; and B: - 10 to 75 wt .-% builder (s); - 25 to 90 wt .-% water; are metered into the interior of the dishwasher, wherein the liquid detergent A has a pH (20 ° C) between 6 and 9 and is metered at time t1, while the liquid detergent B a pH (20 ° C) between 9 and 14 and is metered in at time t2 and at least one of the cleaning agents A or B anionic surfactant (s) having at least one sulfate or sulfonate group and at least one of the cleaning agent A or B nonionic (s) surfactant (s) contains.