EP2187796B2 - Cleaning process - Google Patents

Abstract

Process for cleaning dishes in a dishwasher during which the aqueous washing liquor contained in the interior of the dishwasher is at least partly removed from the interior of the dishwasher at a point in time t. The process involves metering a dishwasher detergent A containing one or more surfactants and one or more anionic polymers at a time t1<t in an amount m1 and at a time t2>t in an amount m2 into the interior of the dishwasher. The process according to the invention differs from conventional cleaning processes in that formation of deposits is reduced and drying efficiency improved.

Description

The present application relates to a method for cleaning dishes. In particular, this application relates to a method for cleaning dishes, in which cleaning agents are dosed into the interior of a dishwasher with a time delay.

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

One of the main goals of the manufacturers of machine cleaning agents is to improve the cleaning performance of these agents, with more recent attention being paid to the cleaning performance in low-temperature cleaning processes or in cleaning processes with reduced water consumption. For this purpose, new ingredients, for example more effective surfactants, polymers or bleaching agents, were preferably added to the cleaning agents. However, since new ingredients are only available to a limited extent and the amount of ingredients used per cleaning cycle cannot be increased to any desired extent for ecological and economic reasons, there are natural limits to this approach.

Another approach to improving the performance profile of existing detergents or cleaning agents consists in the development of new forms of packaging, for example in the combination of solid and liquid detergent or cleaning agent ingredients. Corresponding cleaning agents are combined with one another, for example, in new types of water-soluble packaging.

This application was based on the object of improving the known methods for machine dishwashing in such a way that these methods provide improved cleaning performance and improved drying without the use of additional ingredients or an increase in the dosage even for low-temperature cleaning cycles or for cleaning cycles with low water consumption of the cleaned dishes.

This object was achieved by a special dishwashing process in which a detergent containing surfactants and polymers is dosed into the interior of a dishwasher with a time delay.

1. a) nichtionische(s) Tensid(e)
2. b) anionische(s) Polymer(e)

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird; wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.A first subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is at least partially removed from the interior of the dishwasher at a time t, characterized in that a

1. a) non-ionic surfactant (s)
2. b) anionic polymer (s)

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher; the weight ratio of the metered amounts m1 and m2 being between 20: 1 and 2: 1, preferably between 15: 1 and 3: 1 and in particular between 12: 1 and 4: 1.

The method according to the invention is carried out in the interior of a commercially available dishwasher, in particular a commercially available household dishwasher.

In the case of a dishwasher, the automatic cleaning program is usually specified by the consumer before the dishwashing process is carried out by selecting from a program list, whereby in particular the temperature of the washing solution during the cleaning process, the duration of the process or the cleaning agents and aids used are defined (" 2in1 "and" 3in1 "programs).

Regardless of the temperature and the duration, the automatic dishwashing process or the cleaning program of the dishwasher selected by the consumer comprises at least two wash cycles selected from a pre-wash cycle, a cleaning cycle and a final rinse cycle. These wash cycles are characterized, for example, by different duration, water consumption and temperature profiles, with the aqueous wash liquor located in the interior of the dishwasher being at least partially removed from the interior of the dishwasher between the wash cycles and, if necessary, supplemented by an inflow of fresh water. As a rule, this replacement of the washing liquor takes place by means of a pump system integrated in the dishwasher.

The partial pumping of the washing liquor from the interior of the dishwasher is preferably carried out in such a way that at least 5% by volume, preferably 10% by volume, particularly preferably at least 20% by volume, very particularly preferably at least 40% by volume and in particular at least 60% by volume of the washing liquor are pumped out of the interior of the dishwasher. In particularly preferred processes, between 5 and 99% by volume of the washing liquor, preferably between 10 and 90% by volume of the washing liquor, particularly preferably between 20 and 80% by volume and in particular between 40 to 70% by volume of the washing liquor pumped out.

1. a) nichtionische(s) Tensid(e)
2. b) anionische(s) Polymer(e)

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.A preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is between 5 and 99% by volume, preferably between 10 and 90% by volume, at a point in time t. -%, particularly preferably between 20 and 80% by volume and in particular between 40 to 70% by volume of the washing liquor is removed from the interior of the dishwasher, characterized in that an automatic dishwashing detergent A containing

1. a) non-ionic surfactant (s)
2. b) anionic polymer (s)

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

Of course, the washing liquor can also be pumped out completely, but the complete removal of the washing liquor from the interior of the dishwasher requires a comparatively large amount of time and energy and is therefore less preferred.

The method according to the invention is characterized in that both before and after the washing liquor has been partially pumped out of the interior of the dishwasher, an automatic dishwashing detergent containing nonionic surfactants and anionic polymers is metered into the interior of the dishwasher and thus into the washing liquor located in the interior. The period of time between times t1 and t2 can vary, the method according to the invention, characterized in that the time difference between times t1 and t2 being 5 to 50 minutes, preferably 10 to 40 minutes and in particular 15 to 30 minutes, being preferred.

The temperature of the washing solution at time t1 is preferably between 12 and 45 ° C, preferably between 15 and 40 ° C and in particular between 20 and 35 ° C and at time t2 preferably between 30 and 65 ° C, preferably between 35 and 60 ° C and especially between 40 and 55 ° C. In a particularly preferred embodiment of the method according to the invention, the temperature of the washing solution at time t2 is above the temperature of the washing solution at time t1. A corresponding temperature profile at which the temperature of the washing solution at time t2 is above the temperature of the washing solution at time t1 has proven to be superior in terms of cleaning and rinsing performance.
Alternatively, the dishwashing method according to the invention can of course also be carried out in such a way that the temperature of the washing solution at time t2 is below the temperature of the washing solution at time t1 or is identical to this.

The weight ratio of the metered amounts m1 and m2 is between 20: 1 and 2: 1, preferably between 15: 1 and 3: 1 and in particular between 12: 1 and 4: 1.

The automatic dishwashing detergents used in the process according to the invention are characterized by their content of nonionic surfactants and anionic polymers.

The nonionic surfactants have proven to be particularly effective in terms of cleaning performance and drying.

All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x , in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms, and G the symbol is, which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

Another class of preferably used nonionic surfactants, which are 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 with 1 to 4 carbon atoms in the alkyl chain.

Low-foaming nonionic surfactants are used as preferred surfactants. Washing or cleaning agents, in particular cleaning agents for automatic dishwashing, particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 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 may contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _{12-14 alcohols} 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohol with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohol 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 mean values which, for a specific product, can correspond to a whole number 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 are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is therefore given to ethoxylated nonionic surfactants made from C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide were obtained per mole of alcohol, used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide. Among these, the so-called “narrow range ethoxylates” are particularly preferred. Combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are also used with particular preference.

Nonionic surfactants which have a melting point above room temperature are particularly preferred. Nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C., is / are particularly preferred .

Suitable nonionic surfactants which have melting points or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can 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 a waxy consistency at room temperature, are also preferred depending on their intended use.

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

The nonionic surfactant which is solid at room temperature preferably has propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol content of such nonionic surfactant molecules makes up preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass 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 are up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic Make up surfactants.

Surfactants to be used with preference come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) non-ionic surfactants are also characterized by good foam control.

Other particularly preferred nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted 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.Low-foaming non-ionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants in the context of the present invention. Among these, surfactants with EO-AO-EO-AO blocks are again preferred, one to ten EO or AO groups being bonded to one another before a block from the other groups follows. Here are nonionic surfactants of the general formula

preferably, in which R ^{1 stands} for 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 of one another stand for whole numbers from 1 to 6.

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

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

In summary, preference is given in particular to nonionic surfactants which have a C _9-15 -alkyl radical with 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 with particular advantage according to the invention.
Surfactants of the general formula R ¹ -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 "and A'" independently of one another for a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -H 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 stand for values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Particularly preferred are those end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² with 1 to 30 carbon atoms, where x for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH _y O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4, are particularly preferred up to 18 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 stands for values between 0.5 and 1.5 and y stands for a value of at least 15.

Also particularly preferred are those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R 2 ² independently of one another represent 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 represents —CH ₃ , and x and y independently of one another represent values between 1 and 32, nonionic surfactants with R ³ = —CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are particularly preferred.

By using the nonionic surfactants described above with a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits during machine dishwashing can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

Further nonionic surfactants which can be used with preference are the end group-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 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j for 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 OCH (OH) [CH ₂ ] _j OR ² can 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, 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 can be different if x 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if 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 are present in either Sequence can be joined together, 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 chosen as an example and can be larger, the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (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 becomes R ¹ O [CH ₂ CH (R ³ ) O] xCH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers 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 have} 9 to 14 carbon atoms, R ³ stands for H and x assumes values of 6 to 15.

The specified carbon chain lengths and degrees of ethoxylation or degrees of alkoxylation of the aforementioned nonionic surfactants represent statistical mean values which, for a specific product, can be a whole number or a fractional number. Because of the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative, but rather of mixtures, which can result in mean values and fractional numbers for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.

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

In preferred process variants, the automatic dishwashing agent A, based in each case on the total weight of the automatic dishwashing agent A, contains nonionic surfactant in amounts of 0.1 to 30% by weight, preferably 0.2 to 20% by weight, particularly preferably 0.5 to 10% by weight and in particular from 1.0 to 8% by weight. Process variants in which the nonionic surfactant is contained in the automatic dishwashing detergent A in amounts of 0.5 to 5.0% by weight, based on its total weight, are particularly preferred.

1. a) 0,5 bis 5 Gew.-% nichtionische(s) Tensid(e)
2. b) anionische(s) Polymer(e)

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.A preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is at least partially removed from the interior of the dishwasher at a time t, characterized in that a machine Dishwashing agent A containing, based on the total weight of the automatic dishwashing agent A.

1. a) 0.5 to 5% by weight of nonionic surfactant (s)
2. b) anionic polymer (s)

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) anionische(s) Polymer(e)

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.Another preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is between 5 and 99% by volume, preferably between 10 and 90% by volume, at a time t .-%, particularly preferably between 20 and 80% by volume and in particular between 40 to 70% by volume of the washing liquor is removed from the interior of the dishwasher, characterized in that an automatic dishwashing detergent A containing, based on the total weight of the automatic dishwashing detergent A

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) anionic polymer (s)

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

In addition to the nonionic surfactants, anionic or amphoteric surfactants, preferably in combination with defoamers or foam inhibitors, can also be used in the machine dishwashing process according to the invention.

The anionic surfactants used are, for example, those of the sulfonate and sulfate type. Surfactants of the sulfonate type are preferably C _9-13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C _12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is possible. _{Alkane sulfonates obtained from C 12-18} alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable. The esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the production by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid _{half esters of the C 12} -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior similar to that of the appropriate compounds based on oleochemical raw materials. From the point of view of washing technology, the C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and also C ₁₄ -C ₁₅ -alkyl sulfates are preferred. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and represent the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants. Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Betaines or alkylamidoalkylamines, for example, are suitable as amphoteric surfactants.

R^I

ein gesättigter oder ungesättigter C_6-22-Alkylrest, vorzugsweise C_8-18-Alkylrest, insbesondere ein gesättigter C_10-16-Alkylrest, beispielsweise ein gesättigter C_12-14-Alkylrest,

X

NH, NR^IV mit dem C_1-4-Alkylrest R^IV, O oder S,

n

eine Zahl von 1 bis 10, vorzugsweise 2 bis 5, insbesondere 3,

x

0 oder 1, vorzugsweise 1,

R^II, R^III

unabhängig voneinander ein C_1-4-Alkylrest, ggf. hydroxysubstituiert wie z. B. ein Hydroxyethylrest, insbesondere aber ein Methylrest,

m

eine Zahl von 1 bis 4, insbesondere 1, 2 oder 3,

y

0 oder 1 und

Y

COO, SO₃, OPO(OR^v)O oder P(O)(OR^v)O, wobei R^v ein Wasserstoffatom H oder ein C_1-4-Alkylrest ist.

Die Alkyl- und Alkylamidobetaine, Betaine der vorgenannten Formel mit einer Carboxylatgruppe (Y = COO^-), heißen auch Carbobetaine.Suitable betaines are the alkyl betaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy the formula (R ^A ) (R ^B ) (R ^C ) N ⁺ CH ₂ COO, in which R ^A optionally contains one alkyl radicals interrupted by heteroatoms or heteroatom groups and having 8 to 25, preferably 10 to 21 carbon atoms and R ^B and R ^C denote identical or different alkyl radicals with 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyl-dimethylcarboxymethylbetaines and C ₁₁ -C ₁₇ - Alkylamidopropyl-dimethyl-carboxymethylbetaine, or formula R ¹ - [CO-X- (CH ₂ ) _n ] _x- N ⁺ (R ^II ) (R ^III ) -CH ₂ ) _m - [CH (OH) -CH ₂ ] _y -Y ^- , in the

R ^I

a saturated or unsaturated C _6-22 -alkyl radical, preferably a C _8-18 -alkyl radical, in particular a saturated C _10-16 -alkyl radical, for example a saturated C _12-14 -alkyl radical,

X

NH, NR ^IV with the C _1-4 -alkyl radical R ^IV , O or S,

n

a number from 1 to 10, preferably 2 to 5, especially 3,

x

0 or 1, preferably 1,

R ^II , R ^III

independently of one another a C _1-4 -alkyl radical, optionally hydroxy-substituted such as, for. B. a hydroxyethyl radical, but especially a methyl radical,

m

a number from 1 to 4, in particular 1, 2 or 3,

y

0 or 1 and

Y

COO, SO ₃ , OPO (OR ^v ) O or P (O) (OR ^v ) O, where R ^{v is} a hydrogen atom H or a C _1-4 -alkyl radical.

The alkyl and alkyl amido betaines, betaines of the above formula with a carboxylate group (Y = COO ^- ), are also called carbobetaines.

Preferred amphoteric surfactants are the alkylbetaines of the formula A1, the alkylamidobetaines of the formula A2, the sulfobetaines of the formula A3 and the amidosulfobetaines of the formula A4,

R'-N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (A1)

R ¹ -CO-NH-CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (A2)

R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ ^- (A3)

R ¹ -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ - (A4)

in which R ^{1 has} the same meaning as in formula A.
Particularly preferred amphoteric surfactants are the carbobetaines, in particular the carbobetaines of the formulas A1 and A2, extremely preferably the alkylamido betaines of the formula A2.
Examples of suitable betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl Betaine, Apricotamidopropyl Betaine, Avocadamidopropyl Betaine, Babassuamidopropyl Betaine, Behenamidopropyl Betaine, Behenyl Betaine, Betaine, Canolamidopropyl Betaine, Capryl / Capramidopropyl Betaine, Carnitine, Cocamamidopropyl Betaine, Carnitine, Cetamido-propyl Betaine Betaines, Cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco / Oleamidopropyl Betaine, Coco-Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl, Tallow Glycinate-Betaine, Hydroxopropaine, Dimethicone PG Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysultai ne, oleyl betaine, olivamidopropyl betaine, palmamidopropyl betaine, palmitamidopropyl betaine, palmitoyl carnitine, palm kernelamidopropyl betaine, polytetrafluoroethylene acetoxypropyl betaine, ricinoteamidopropyl betaine, sesamidopropyl betaine, soyamidopropyl betaine, stearamidopropyl betaine, tallowamidopropyl betaine, tallowamidopropyl betaine, tallowamidopropyl betaine, tallowamidopropyl betaine, tallowo propaine, tallowamidopropyl betaine, tallowo propyl Dihydroxyethyl Betaine, Undecylenamidopropyl Betaine, and Wheat Germamidopropyl Betaine. A preferred amphoteric surfactant is cocamidopropyl betaine (cocoamidopropyl betaine). A particularly preferred amphoteric surfactant is caprylic / Capramidopropyl Betaine (CAB), for example, under the trade name Tegofens ^® B 810th from Th Goldschmidt AG is available.

R^VI

ein gesättigter oder ungesättigter C_6-22-Alkylrest, vorzugsweise C_8-18-Alkylrest, insbesondere ein gesättigter C_10-16-Alkylrest, beispielsweise ein gesättigter C_12-14-Alkylrest,

R^VII

ein Wasserstoffatom H oder ein C_1-4-Alkylrest, vorzugsweise H,

i

eine Zahl von 1 bis 10, vorzugsweise 2 bis 5, insbesondere 2 oder 3,

R^VIII

ein Wasserstoffatom H oder CH₂COOM (zu M s.u.),

j

eine Zahl von 1 bis 4, vorzugsweise 1 oder 2, insbesondere 1,

k

eine Zahl von 0 bis 4, vorzugsweise 0 oder 1,

I

0 oder 1, wobei k = 1 ist, wenn I = 1 ist,

Z

CO, SO₂, OPO(OR¹²) oder P(O)(OR¹²), wobei R¹² ein C_1-4-Alkylrest oder M (s.u.) ist, und

M

ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alkanolamin, z. B. protoniertes Mono-, Di- oder Triethanolamin, ist.

Bevorzugte Vertreter genügen den Formeln B1 bis B4,

        R^VI-CO-NH-(CH₂)₂-N(RV^IIICH₂CH₂O-CH₂-COOM     (B1)

        R^VI-CO-NH-(CH₂)₂-N(R^VIII)-CH₂CH₂O-CH₂CH₂-COOM     (B2)

        R^VI-CO-NH-(CH₂)₂-N(R^VIII)-CH₂CH₂-CH₂CH(OH)CH₂-SO₃M     (B3)

        R^VI-CO-NH-(CH₂)₂-N(R^VIII)CH₂CH₂O-CH₂CH(OH)CH₂-OPO₃HM     (B4)

in denen R^VI, R^VIII und M die gleiche Bedeutung wie in Formel B haben.
Beispielhafte Alkylamidoalkylamine sind die folgenden gemäß INCI benannten Verbindungen: Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate, Sodium Capryloamphopropionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoamphopropionate, Sodium Lauroamphoacetate, Sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetate und Trisodium Lauroampho PG-Acetate Chloride Phosphate.The alkylamidoalkylamines (INCI alkylamido alkylamines) are amphoteric surfactants of the formula R ^VI -CO-NR ^VII - (CH ₂ ) _i -N (R ^VIII ) - (CH ₂ CH ₂ O) _j - (CH ₂ ) _k - [CH (OH )] _l -CH ₂ -Z-OM, in the

R ^VI

a saturated or unsaturated C _6-22 -alkyl radical, preferably a C _8-18 -alkyl radical, in particular a saturated C _10-16 -alkyl radical, for example a saturated C _12-14 -alkyl radical,

R ^VII

a hydrogen atom H or a C _1-4 alkyl radical, preferably H,

i

a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,

R ^VIII

a hydrogen atom H or CH ₂ COOM (to M su),

j

a number from 1 to 4, preferably 1 or 2, in particular 1,

k

a number from 0 to 4, preferably 0 or 1,

I.

0 or 1, where k = 1 when I = 1,

Z

CO, SO ₂ , OPO (OR ¹² ) or P (O) (OR ¹² ), where R ^{12 is} a C _1-4 alkyl radical or M (see below), and

M.

a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. B. protonated mono-, di- or triethanolamine.

Preferred representatives satisfy the formulas B1 to B4,

R ^VI -CO-NH- (CH ₂ ) ₂ -N (RV ^III CH ₂ CH ₂ O-CH ₂ -COOM (B1)

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VIII ) -CH ₂ CH ₂ O-CH ₂ CH ₂ -COOM (B2)

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VIII ) -CH ₂ CH ₂ -CH ₂ CH (OH) CH ₂ -SO ₃ M (B3)

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VIII ) CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -OPO ₃ HM (B4)

in which R ^VI , R ^VIII and M have the same meaning as in formula B.
Exemplary alkylamidoalkylamines are the following named according to INCI compounds: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium laureth 5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate, Sodium Capryloa mphopropionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoamphopropionate, Sodium Lauroamphoacetate, Sodium Lauroamphoacetate, Sodium-Sodium-Lauro-amphetropate, Sodium-Sodium-lauro-amphetropate, Sodium-Sodium-Lauroamphoacetate, Sodium lauroamphohydroxypropate, Sodium-Sodium-Lauroamphoacetate, Sodium-Sodium-Sodium-Lauro-amphetropate, Sodium-Sodium-Lauro-amphetropate, Sodium-Sodium-lauro-amphetropate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetate and Trisodium Lauroampho PG-Acetate Chloride Phosphate.

Foam inhibitors that can be used include soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials. Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear polymeric silicones, which are built up according to the scheme (R ₂ SiO) x and are also referred to as silicone oils.

The cleaning agents used in the process according to the invention contain anionic polymers as a second essential component. As anionic polymers it is possible to use all washing- or cleaning-active anionic polymers known to the person skilled in the art.

Preferred processes according to the invention are characterized in that the automatic dishwashing agent A, based in each case on the total weight of the automatic dishwashing agent A, contains the anionic polymer in amounts of 0.1 to 40% by weight, preferably 0.2 to 20% by weight, preferably 0.5 to 15% by weight and in particular from 1.0 to 10% by weight. Corresponding agents have proven to be advantageous in the method according to the invention, particularly with regard to optimal cleaning and rinsing results.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) 0,2 bis 20 Gew.-% anionische(s) Polymer(e)

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.A particularly preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is at least partially removed from the interior of the dishwasher at a time t, characterized in that a Automatic dishwashing agent A, based on the total weight of the automatic dishwashing agent A

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) 0.2 to 20% by weight of anionic polymer (s)

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) 0,2 bis 20 Gew.-% anionische(s) Polymer(e)

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.Another preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is between 5 and 99% by volume, preferably between 10 and 90% by volume, at a time t .-%, particularly preferably between 20 and 80% by volume and in particular between 40 to 70% by volume of the washing liquor is removed from the interior of the dishwasher, characterized in that an automatic dishwashing detergent A containing, based on the total weight of the automatic dishwashing detergent A

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) 0.2 to 20% by weight of anionic polymer (s)

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

Suitable anionic polymers are, for example, the polymeric polycarboxylates, in particular the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

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

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and 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 particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

Processes according to the invention, characterized in that the anionic polymer is a homo- and / or copolymer of acrylic acid or methacrylic acid, are preferred.

As an alternative or in addition to the aforementioned polycarboxylates, the anionic polymers used in the process according to the invention can also contain sulfonic acid groups.

1. i) ungesättigten Carbonsäuren
2. ii) Sulfonsäuregruppen-haltigen Monomeren
3. iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren handelt werden bevorzugt.

Process according to the invention, characterized in that the anionic polymer is a copolymer

1. i) unsaturated carboxylic acids
2. ii) Monomers containing sulfonic acid groups
3. iii) where appropriate, further ionic or nonionic monomers are preferred.

The monomers ii) containing sulfonic acid groups are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

preferred, in which R ⁵ to R ⁷ independently represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH-substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ CH ₂ - and -C (O) -NH-CH (CH 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 represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ CH ₂ - and -C (O) -NH-CH (CH 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-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3-styrenesulphonic acid, vinylsulphonic acid, vinylsulphonic acid, 3-sulfylacrylate, 3-sulfonyl-sulfonic acid -Sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In the polymers, the sulfonic acid groups can be wholly or partly in neutralized form, i.e. the acidic hydrogen atom 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 copolymers containing sulfonic acid groups is preferred according to the invention.

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

1. i) Monomeren aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren
2. ii) Monomere der allgemeinen Formel R¹(R²)C=C(R³)X-R⁴, in der R¹ bis R³ unabhängig voneinander für -H, -CH₃ oder -C₂H₅ steht, × für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH₂-, -C(O)O- und -C(O)-NH-, und R⁴ für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht
3. iii) gegebenenfalls weitere Monomere

Further suitable anionic polymers are the hydrophobically modified anionic polymers, for example anionic polymers

1. i) Monomers from the group of mono- or polyunsaturated carboxylic acids
2. ii) Monomers of the general formula R ¹ (R ² ) C =C (R ³ ) XR ⁴ , in which R ¹ to R ³ independently of one another represent -H, -CH ₃ or -C ₂ H ₅ , × is an optional one existing spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably an aromatic radical having 6 to 22 carbon atoms
3. iii) optionally further monomers

As monomers i) from the group of the monounsaturated or polyunsaturated carboxylic acids, unsaturated carboxylic acids of the general formula R ¹ (R ² ) C RC (R ³ ) COOH are used ^{with particular preference, in which R 1} to R ³ independently of one another are - H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted _{with -NH 2, -OH or -COOH} as defined above or for -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) anionisches Polymer, umfassend
   1. i) Monomeren aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren
   2. ii) Monomere der allgemeinen Formel R1(R2)C=C(R3)-X-R4, in der R1 bis R3 unabhängig voneinander für -H, -CH3 oder -C2H5 steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH2-, -C(O)O- und -C(O)-NH-, und R4 für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomenoder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht
   3. iii) gegebenenfalls weitere Monomere

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.A particularly preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is at least partially removed from the interior of the dishwasher at a time t, characterized in that a Automatic dishwashing agent A, based on the total weight of the automatic dishwashing agent A

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) anionic polymer comprising
   1. i) Monomers from the group of mono- or polyunsaturated carboxylic acids
   2. ii) Monomers of the general formula R1 (R2) C =C (R3) -X-R4, in which R1 to R3 independently of one another stand for -H, -CH3 or -C2H5, X stands for an optionally present spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
   3. iii) optionally further monomers

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) anionisches Polymer, umfassend
   1. i) Monomeren aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren
   2. ii) Monomere der allgemeinen Formel R1(R2)C=C(R3)-X-R4, in der R1 bis R3 unabhängig voneinander für -H, -CH3 oder -C2H5 steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH2-, -C(O)O- und -C(O)-NH-, und R4 für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomenoder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht
   3. iii) gegebenenfalls weitere Monomere

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.Another preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is between 5 and 99% by volume, preferably between 10 and 90% by volume, at a time t .-%, particularly preferably between 20 and 80% by volume and in particular between 40 to 70% by volume of the washing liquor is removed from the interior of the dishwasher, characterized in that an automatic dishwashing detergent A containing, based on the total weight of the automatic dishwashing detergent A

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) anionic polymer comprising
   1. i) Monomers from the group of mono- or polyunsaturated carboxylic acids
   2. ii) Monomers of the general formula R1 (R2) C =C (R3) -X-R4, in which R1 to R3 independently of one another stand for -H, -CH3 or -C2H5, X stands for an optionally present spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
   3. iii) optionally further monomers

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

Particularly preferred carboxyl group-containing monomers i) of the aforementioned hydrophobically modified anionic polymers are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid , Cinnamic acid or mixtures thereof.

Monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ are used as nonionic monomers ii). Particularly preferred such monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefones with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α -Methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, methyl acrylate, methyl acrylate, butyl acrylate, acrylate - (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate, methacrylate ureoctyl ester, N- (octyl) acrylamide, acrylic acid lauryl ester, methacrylic acid lauryl ester, N- (lauryl) acrylamide, acrylic acid stearyl ester, methacrylic acid stearyl ester, N- (stearyl) acrylamide, acrylic acid behenyl ester, methacrylic acid behenyl ester and N- (behenyl) acrylamide or mixtures thereof.

In a particularly preferred embodiment, the copolymer d) furthermore comprises, in addition to the monomers i) and ii), a third monomer iii) from the group of monomers containing sulfonic acid groups.

The monomers containing sulfonic acid groups are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

preferred, in which R ⁵ to R ⁷ independently represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH-substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - 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 , -H ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - 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-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3-styrenesulphonic acid, vinylsulphonic acid, vinylsulphonic acid, 3-sulfylacrylate, 3-sulfonyl-sulfonic acid -Sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In the polymers, the sulfonic acid groups can be wholly or partly in neutralized form, i.e. the acidic hydrogen atom 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 copolymers containing sulfonic acid groups is preferred according to the invention.

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

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) anionisches Polymer, umfassend
   1. i) Monomeren aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren
   2. ii) Monomere der allgemeinen Formel R1(R2)C=C(R3)-X-R4, in der R1 bis R3 unabhängig voneinander für -H, -CH3 oder -C2H5 steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH2-, -C(O)O- und -C(O)-NH-, und R4 für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht
   3. iii) Sulfonsäuregruppen-haltige Monomere

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.Another particularly preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is at least partially removed from the interior of the dishwasher at a time t, characterized in that an automatic dishwashing agent A containing, based on the total weight of the automatic dishwashing agent A.

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) anionic polymer comprising
   1. i) Monomers from the group of mono- or polyunsaturated carboxylic acids
   2. ii) Monomers of the general formula R1 (R2) C =C (R3) -X-R4, in which R1 to R3 independently of one another stand for -H, -CH3 or -C2H5, X stands for an optionally present spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
   3. iii) Monomers containing sulfonic acid groups

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) anionisches Polymer, umfassend
   1. i) Monomeren aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren
   2. ii) Monomere der allgemeinen Formel R1(R2)C=C(R3)-X-R4, in der R1 bis R3 unabhängig voneinander für -H, -CH3 oder -C2H5 steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH2-, -C(O)O- und -C(O)-NH-, und R4 für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht
   3. iii) Sulfonsäuregruppen-haltige Monomere

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.Another preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is between 5 and 99% by volume, preferably between 10 and 90% by volume, at a time t .-%, particularly preferably between 20 and 80% by volume and in particular between 40 to 70% by volume of the washing liquor is removed from the interior of the dishwasher, characterized in that an automatic dishwashing detergent A containing, based on the total weight of the automatic dishwashing detergent A

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) anionic polymer comprising
   1. i) Monomers from the group of mono- or polyunsaturated carboxylic acids
   2. ii) Monomers of the general formula R1 (R2) C =C (R3) -X-R4, in which R1 to R3 independently of one another stand for -H, -CH3 or -C2H5, X stands for an optionally present spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
   3. iii) Monomers containing sulfonic acid groups

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

The automatic dishwashing agent A used in the process according to the invention can contain one or more builders as a further constituent. The builders include, in particular, silicates, carbonates and organic cobuilders, but also the phosphates.

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

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

Particularly preferred automatic dishwashing agents according to the invention contain citrate as one of their essential builders. Processes preferred according to the invention are characterized in that the dishwashing detergent A, based in each case on the total weight of the automatic dishwashing detergent A, contains 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight citrate.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) 0,2 bis 20 Gew.-% anionische(s) Polymer(e)
3. c) 10 bis 50 Gew.-% Zitrat

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.A preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is at least partially removed from the interior of the dishwasher at a time t, characterized in that a machine Dishwashing agent A containing, based on the total weight of the automatic dishwashing agent A.

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) 0.2 to 20% by weight of anionic polymer (s)
3. c) 10 to 50% by weight citrate

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) 0,2 bis 20 Gew.-% anionische(s) Polymer(e)
3. c) 10 bis 50 Gew.-% Zitrat

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.Also preferred is a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is between 5 and 99% by volume, preferably between 10 and 90% by volume, particularly preferred between 20 and 80% by volume and in particular between 40 to 70% by volume of the washing liquor is removed from the interior of the dishwasher, characterized in that an automatic dishwasher detergent A containing, based on the total weight of the automatic dishwasher detergent A

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) 0.2 to 20% by weight of anionic polymer (s)
3. c) 10 to 50% by weight citrate

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.

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

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

If, in the context of the present application, phosphates are used as washing or cleaning-active substances in the automatic dishwashing detergent, preferred detergents contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or pentapotassium triphosphate). Potassium tripolyphosphate), in amounts of 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight, each based on the weight of the automatic dishwashing detergent A.

In a preferred variant of the method, complexing agents, preferably phosphonates, are used to supplement the active ingredient combination of nonionic surfactant and anionic polymer. Particularly preferred automatic dishwashing processes are characterized in that dishwashing agent A contains a complexing agent, preferably 1-hydroxyethane-1,1-diphosphonic acid and / or methylglycine diacetic acid.

In addition to 1-hydroxyethane-1,1-diphosphonic acid, the complex-forming phosphonates include a number of different compounds such as, for example, diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9). Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates. They are preferably in the form of the neutrally reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. From the class of phosphonates, HEDP is preferably used as the builder. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, it can be preferred to use aminoalkanephosphonates, in particular DTPMP, or mixtures of the phosphonates mentioned.

1. a) Aminotrimethylenphosphonsäure (ATMP) und/oder deren Salze;
2. b) Ethylendiamintetra(methylenphosphonsäure) (EDTMP) und/oder deren Salze;
3. c) Diethylentriaminpenta(methylenphosphonsäure) (DTPMP) und/oder deren Salze;
4. d) 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und/oder deren Salze;
5. e) 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC) und/oder deren Salze;
6. f) Hexamethylendiamintetra(methylenphosphonsäure) (HDTMP) und/oder deren Salze;
7. g) Nitrilotri(methylenphosphonsäure) (NTMP) und/oder deren Salze.

An automatic dishwashing agent A preferred in the context of this application contains one or more phosphonate (s) from the group

1. a) aminotrimethylene phosphonic acid (ATMP) and / or its salts;
2. b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof;
3. c) Diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) and / or salts thereof;
4. d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or its salts;
5. e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof;
6. f) hexamethylene diamine tetra (methylene phosphonic acid) (HDTMP) and / or salts thereof;
7. g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.

Automatic dishwashing agents which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred.

The automatic dishwashing agents according to the invention can of course contain two or more different phosphonates. Machine dishwashing detergents A are particularly preferred which contain both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) as phosphonates, the weight ratio of HEDP to DTPMP between 20: 1 and 1:20 , preferably between 15: 1 and 1:15 and in particular between 10: 1 and 1:10.

In a preferred embodiment of the present invention, the proportion by weight of the phosphonate (s) in the total weight of the automatic dishwasher detergent is less than the proportion by weight of the polymer (s) b). In other words, those agents are particularly preferred in which the ratio of the weight fraction of polymer b) to the weight fraction of the phosphonate is 200: 1 to 2: 1, preferably 150: 1 to 2: 1, particularly preferably 100: 1 up to 2: 1, very particularly preferably 80: 1 to 3: 1 and in particular 50: 1 to 5: 1.

The proportion by weight of these complexing agents, in particular the sum of the proportions by weight of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and methylglycine diacetic acid (MGDA), is preferably 0.5 to 14% by weight, preferably 1 to 12% by weight and in particular 2 to 8% by weight.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) 0,2 bis 20 Gew.-% anionische(s) Polymer(e)
3. c) 15 bis 40 Gew.-% Phosphat oder 15 bis 40 Gew.-% Zitrat
4. d) 0,5 bis 8 Gew.-% Phosphonat(e)

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.Another preferred subject of the present application is a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing solution located in the interior of the dishwasher is at least partially removed from the interior of the dishwasher at a time t, characterized in that a machine Dishwashing agent A containing, based on the total weight of the automatic dishwashing agent A.

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) 0.2 to 20% by weight of anionic polymer (s)
3. c) 15 to 40% by weight of phosphate or 15 to 40% by weight of citrate
4. d) 0.5 to 8% by weight of phosphonate (s)

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) 0,2 bis 20 Gew.-% anionische(s) Polymer(e)
3. c) 15 bis 40 Gew.-% Phosphat oder 15 bis 40 Gew.-% Zitrat
4. d) 0,5 bis 8 Gew.-% Phosphonat(e)

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.Also preferred is a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is between 5 and 99% by volume, preferably between 10 and 90% by volume, particularly preferably between 20 and 80% by volume and in particular
between 40 to 70% by volume of the washing liquor is removed from the interior of the dishwasher, characterized in that an automatic dishwashing agent A containing, based on the total weight of the automatic dishwashing agent A

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) 0.2 to 20% by weight of anionic polymer (s)
3. c) 15 to 40% by weight of phosphate or 15 to 40% by weight of citrate
4. d) 0.5 to 8% by weight of phosphonate (s)

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

To increase the cleaning performance, enzymes can also be used in the method according to the invention. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, and these are accordingly preferred. Washing or cleaning agents preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined with the aid of known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples are the subtilisins BPN 'and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus , subtilisin DY and the subtilase enzymes, but no longer the subtilisins in the narrower sense of the term, thermitase, Proteinase K and the proteases TW3 and TW7.

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

According to the invention, lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid substitution D96L. Furthermore, for example, the cutinases can be used which were originally isolated from Fusarium solani pisi and Humicola insolens. Lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.

It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

To increase the bleaching effect, according to the invention, 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. Advantageously, preferably organic, particularly preferably aromatic, compounds interacting with the enzymes are added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.

The enzymes can be used in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or mixed with stabilizers.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer which is impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granulates are advantageously low in dust, for example through the application of polymeric film-forming agents, and, owing to the coating, are stable in storage.

It is also possible to pack two or more enzymes together so that a single granulate has several enzyme activities.

A protein and / or enzyme can be protected against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage. In the case of microbial production of the proteins and / or enzymes, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Washing or cleaning agents can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.

In particular, those automatic dishwashing processes are preferred in which the dishwashing agent A, based in each case on the total weight of the automatic dishwashing agent A, is 0.2 to 5% by weight, preferably 0.5 to 5% by weight and in particular 1 to 4% by weight. -% enzyme (s) contains.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) 0,2 bis 20 Gew.-% anionische(s) Polymer(e), vorzugsweise Sulfonsäure Gruppen haltige(s) Polymer(e)
3. c) 15 bis 40 Gew.-% Phosphat oder 15 bis 40 Gew.-% Zitrat
4. d) 0,5 bis 5 Gew.-% Enzym(e)

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.Another preferred subject of the present application is a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing solution located in the interior of the dishwasher is at least partially removed from the interior of the dishwasher at a time t, characterized in that a machine Dishwashing agent A containing, based on the total weight of the automatic dishwashing agent A.

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) 0.2 to 20% by weight of anionic polymer (s), preferably polymer (s) containing sulfonic acid groups
3. c) 15 to 40% by weight of phosphate or 15 to 40% by weight of citrate
4. d) 0.5 to 5% by weight of enzyme (s)

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

1. a) 0,5 bis 10 Gew.-% nichtionische(s) Tensid(e)
2. b) 0,2 bis 20 Gew.-% anionische(s) Polymer(e), vorzugsweise Sulfonsäure Gruppen haltige(s) Polymer(e)
3. c) 15 bis 40 Gew.-% Phosphat oder 15 bis 40 Gew.-% Zitrat
4. d) 0,5 bis 5 Gew.-% Enzym(e)

zu einem Zeitpunkt t1 < t in einer Menge m1 und zu einem Zeitpunkt t2 > t in einer Menge m2 in den Innenraum der Geschirrspülmaschine eindosiert wird, wobei das Gewichtsverhältnis der eindosierten Mengen m1 und m2 zwischen 20:1 und 2:1, vorzugsweise zwischen 15:1 und 3:1 und insbesondere zwischen 12:1 und 4:1 beträgt.Also preferred is a method for cleaning dishes in a dishwasher, in the course of which the aqueous washing liquor located in the interior of the dishwasher is between 5 and 99% by volume, preferably between 10 and 90% by volume, particularly preferred between 20 and 80% by volume and in particular between 40 to 70% by volume of the washing liquor is removed from the interior of the dishwasher, characterized in that an automatic dishwasher detergent A containing, based on the total weight of the automatic dishwasher detergent A

1. a) 0.5 to 10% by weight non-ionic surfactant (s)
2. b) 0.2 to 20% by weight of anionic polymer (s), preferably polymer (s) containing sulfonic acid groups
3. c) 15 to 40% by weight of phosphate or 15 to 40% by weight of citrate
4. d) 0.5 to 5% by weight of enzyme (s)

at a point in time t1 <t in an amount m1 and at a point in time t2> t in an amount m2 into the interior of the dishwasher, the weight ratio of the dispensed amounts m1 and m2 between 20: 1 and 2: 1, preferably between 15 : 1 and 3: 1 and in particular between 12: 1 and 4: 1.

Machine dishwashing detergents A which are preferably used also contain one or more bleaches. Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H ₂ O _{2 in water.} Further bleaching agents that can be used are, for example, peroxypyrophosphates, citrate perhydrates and _{peracid salts or peracids which provide H 2} O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
Furthermore, bleaches from the group of organic bleaches can also be used. Typical organic bleaching agents are the diacyl peroxides, such as, for example, dibenzoyl peroxide. Further typical organic bleaching agents are the peroxy acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned as examples.
Process, characterized in that the dishwashing detergent A, based in each case on the total weight of the automatic dishwashing detergent A, contains 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 12% by weight of sodium percarbonate are according to the invention prefers.

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

In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below, the automatic dishwashing detergents used according to the invention can additionally contain bleach activators. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry O and / or N-acyl groups with the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Polyacylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) having proven particularly suitable.

These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight , each based on the total weight of the bleach activator-containing agents.

In addition to the conventional bleach activators or instead of them, so-called bleach catalysts can also be used. These substances are bleach-intensifying transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen 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-amine complexes can also be used as bleach catalysts.

Manganese complexes in the II, III, IV or IV oxidation state, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, are used with particular preference. Ligands are preferably used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV 4 (µ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (Me-TACN ) ₂ (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (µ-O) ₁ (µ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (µ-O) ₃ (Me -TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (µ-O) ₃ (Me / Me-TACN ₆ ) ₂ (PF ₆ ) 2 (OAC = OC (O) CH ₃ ).

Automatic dishwashing detergents, characterized in that they also contain a bleach catalyst selected from the group of the bleach-intensifying transition metal salts and transition metal complexes, preferably from the group of the complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me ₄ -TACN) are preferred according to the invention, since the aforementioned bleach catalysts in particular can significantly improve the cleaning result.

The aforementioned bleach-intensifying transition metal complexes, in particular with the central atoms Mn and Co, are each based on the total weight of the automatic dishwashing detergent A, in the usual amounts, preferably in an amount of up to 5% by weight, in particular in amounts of 0.01 to 2% by weight %, preferably 0.02 to 1% by weight and in particular 0.05 to 0.8% by weight are used.

In addition to the active substances contained in the automatic dishwashing agent, in particular the pH value of the automatic dishwashing agent used has proven to be relevant for the cleaning, rinsing and drying results of the method according to the invention. Accordingly, particularly good results are achieved with automatic dishwashing detergents whose 1% aqueous solution (20 ° C.) has a pH value above 7, preferably between 7 and 12, particularly preferably between 9 and 11. Corresponding methods, characterized in that the automatic dishwashing detergent A has a pH (20 ° C., 1% aqueous solution) above 7, preferably between 7 and 12, particularly preferably between 9 and 11, are therefore also preferred according to the invention.

The surprising advantages of the process according to the invention are particularly evident in those automatic dishwashing processes in which no softened rinse water is used. (As "rinsing water" this is the Rinsing liquor called water). The rinsing water used to carry out the method according to the invention therefore preferably has a hardness above 5 ° dH, preferably above 10 ° dH, particularly preferably above 15 ° dH and in particular above 20 ° dH.

The automatic dishwashing detergents A used according to the invention can be packaged in solid or liquid form, but also, for example, as a combination of solid and liquid supply forms.

Powders, granules, extrudates or compacts, in particular tablets, are particularly suitable as solid supply forms. The liquid supply forms, preferably based on water and / or organic solvents, can be thickened, in the form of gels.

The automatic dishwashing detergents A used according to the invention can be packaged as single-phase or multiphase products. Automatic dishwashing detergents with one, two, three or four phases are particularly preferred. Machine dishwashing detergents, characterized in that they are in the form of a prefabricated dosage unit with two or more phases, are particularly preferred.

The individual phases of multiphase agents can have the same or different states of aggregation. Automatic dishwashing agents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are particularly preferred. Processes according to the invention, characterized in that the dishwashing detergent A is in liquid form, are preferred because of improved cleaning, rinsing and drying results.

The automatic dishwashing detergents A are preferably pre-packaged into metering units. These metering units preferably comprise the amount of washing or cleaning-active substances necessary for a cleaning cycle. Preferred dosing units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.

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

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

In an alternative supply form, the automatic dishwashing detergents A used in the method according to the invention can be dosed into the interior of the dishwasher by means of a water-insoluble storage container. This storage container preferably has two or more chambers in which the automatic dishwashing detergent A is present, for example, in the form of separate partial recipes. The water-insoluble storage container can be integrated into the dishwasher, but can also have the shape of a conventional two- or multi-chamber bottle.

As described at the outset, cleaning methods according to the invention are distinguished from conventional methods by an improved cleaning and rinsing effect, as well as an improved drying of the cleaned dishes. The use of an automatic dishwashing process according to the invention to reduce the formation of deposits in automatic dishwashing or to improve drying in automatic dishwashing are further subjects of this application.

Examples

The drying, coating and cleaning performance of an automatic dishwashing process were determined as a function of the type of dosage of the automatic dishwashing agent used.

For this purpose, dishes were washed in a dishwasher (Miele 1730; 55 ° normal 3in1 extra drying program) with 33 ml (16.5 ml F1 and 16.5 ml F2) of an automatic dishwashing detergent with a water hardness of 21 ° dH.

The composition of the dishwashing detergents F1 and F2 used can be found in the table below: raw material F1 [% by weight] F2 [% by weight] KTTP 17.5 10.0 Nonionic surfactant 4.0 - Protease 2.0 - Amylase 1.0 - Phosphonate 3.0 5.0 Thickener 4.0 - Org. Solvent 3.0 3.0 Anionic polymer - 8.6 soda - 7.0 Water, misc Add 100 Add 100 _{Hydroxy mixed} ethers of the general formula C 6-24 -CH (OH) CH ₂ O- (EO) _20-120 -C _2-26

Versuch V1:

Jeweils 16,5 ml der Zusammensetzung F1 und F2 wurden zeitgleich im Hauptspülgang des Geschirrspülverfahrens in den Maschineninnenraum eindosiert;

Versuch V2:

Es wurden 12,5 ml der Zusammensetzung F1 und 16,5 ml der Zusammensetzung F2 im Hauptspülgang des Geschirrspülverfahrens in den Maschineninnenraum eindosiert; zusätzlich wurden im nachfolgenden Klarspülgang (nach anteilsweisem Austausch der Spülflotte) 4 ml der Zusammensetzung F1 in den Maschineninnenraum eindosiert;

Versuch E1:

Jeweils 14,5 ml der Zusammensetzungen F1 und F2 wurden zeitgleich im Hauptspülgang des Geschirrspülverfahrens in den Maschineninnenraum eindosiert; zu- sätzlich wurden im nachfolgenden Klarspülgang (nach anteilsweisem Austausch der Spülflotte) jeweils 2 ml der Zusammensetzungen F1 und F2 in den Maschineninnenraum eindosiert

The following three experiments were carried out:

Experiment V1:

16.5 ml each of the composition F1 and F2 were dosed into the interior of the machine at the same time in the main wash cycle of the dishwashing process;

Experiment V2:

12.5 ml of the composition F1 and 16.5 ml of the composition F2 were dosed into the interior of the machine in the main wash cycle of the dishwashing process; In addition, 4 ml of the composition F1 were dosed into the interior of the machine in the subsequent rinse cycle (after partial replacement of the washing liquor);

Experiment E1:

14.5 ml each of the compositions F1 and F2 were dosed into the interior of the machine at the same time in the main wash cycle of the dishwashing process; In addition, 2 ml of the compositions F1 and F2 were metered into the interior of the machine in the subsequent rinse cycle (after partial replacement of the washing liquor)

With regard to the cleaning performance (determined according to IKW), no significant differences were found between the two process variants.
The drying index was determined in accordance with the EN standard. The results are given in the table below (the values given are the mean values from 3 experiments): V1 V2 E1 Drying index 0.60 0.85 0.80 Deposit formation No toppings Deposit formation No toppings

On the basis of the results in experiment V1, the drying index could therefore be improved in experiment V2 by the subsequent addition of a surfactant-containing cleaning agent, but at the same time the formation of deposits on the surface of the dishes could be observed. It was only through the subsequent metering of surfactant and anionic polymer in experiment E1 that both good drying and coating results could be achieved.

Claims (14)

1. A method for cleaning dishes in a dishwasher, in the course of which the aqueous rinsing liquor located in the interior of the dishwasher is at least partially removed from the interior of the dishwasher at a point in time t, characterized in that an automatic dishwashing detergent A containing

   a) non-ionic surfactant(s)

   b) anionic polymer(s)

   is dispensed into the interior of the dishwasher in an amount m1 at a point in time t1 < t and in an amount m2 at a point in time t2 > t, the weight ratio of the dispensed amounts m1 and m2 being between 20:1 and 2:1, preferably between 15:1 and 3:1 and in particular between 12:1 and 4:1.
2. The method according to claim 1, characterized in that the automatic dishwashing detergent A contains, in each case based on the total weight of the automatic dishwashing detergent A, non-ionic surfactant in amounts of from 0.1 to 30 wt.%, preferably 0.2 to 20 wt.%, particularly preferably 0.5 to 10 wt.% and in particular 1.0 to 8 wt.%.
3. The method according to one of the preceding claims, characterized in that the automatic dishwashing detergent A contains, in each case based on the total weight of the automatic dishwashing detergent A, the anionic polymer in amounts of from 0.1 to 40 wt.%, preferably 0.2 to 20 wt.%, particularly preferably 0.5 to 15 wt.% and in particular 1.0 to 10 wt.%.
4. The method according to one of the preceding claims, characterized in that the anionic polymer is a homo- and/or copolymer of acrylic acid or methacrylic acid.
5. The method according to one of the preceding claims, characterized in that the anionic polymer is a copolymer of

   i) unsaturated carboxylic acids

   ii) sulfonic acid group-containing monomers

   iii) optionally other ionic or non-ionic monomers.
6. The method according to one of the preceding claims, characterized in that the automatic dishwashing detergent A contains

   a) 0.5 to 10% wt.% non-ionic surfactant(s)

   b) 0.2 to 20 wt.% sulfonic acid group-containing polymer(s)

   c) 10 to 40 wt.% phosphate or 10 to 40 wt.% citrate

   d) 0.5 to 5 wt.% enzyme(s).
7. The method according to one of the preceding claims, characterized in that the dishwashing detergent A contains, in each case based on the total weight of the automatic dishwashing detergent A, 1 to 20 wt.%, preferably 2 to 15 wt.% and in particular 4 to 12 wt.% sodium percarbonate.
8. The method according to one of the preceding claims, characterized in that the dishwashing detergent A contains, in each case based on the total weight of the automatic dishwashing detergent A, 0.01 to 2 wt.%, preferably 0.02 to 1 wt.% and in particular 0.05 to 0.8 wt.% bleach catalyst.
9. The method according to one of the preceding claims, characterized in that the dishwashing detergent A is in liquid form.
10. The method according to one of the preceding claims, characterized in that the time difference between the points in time t1 and t2 is 5 to 50 minutes, preferably 10 to 40 minutes and in particular 15 to 30 minutes.
11. The method according to one of the preceding claims, characterized in that the temperature of the rinsing liquor at the point in time t1 is between 12 and 45 °C, preferably between 15 and 40 °C and in particular between 20 and 35 °C.
12. The method according to one of the preceding claims, characterized in that the temperature of the washing liquor at the point in time t2 is between 30 and 65 °C, preferably between 35 and 60 °C and in particular between 40 and 55 °C.
13. The use of a method according to one of the preceding claims for improving drying in automatic dishwashing.
14. The use of a method according to one of claims 1 to 12 for reducing the formation of deposits during automatic dishwashing.