EP2187796A1

EP2187796A1 - Cleaning process

Info

Publication number: EP2187796A1
Application number: EP08759944A
Authority: EP
Inventors: Johannes Zipfel; Nadine Warkotsch; Arnd Kessler; Christian Nitsch
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2007-09-10
Filing date: 2008-05-23
Publication date: 2010-05-26
Anticipated expiration: 2028-05-23
Also published as: EP2187796B1; PL2187796T5; EP2187796B2; DE102007042859A1; ES2383245T3; US20100154832A1; ATE554694T1; ES2383245T5; WO2009033830A1; PL2187796T3

Abstract

The invention relates to a process for cleaning dishes in a dishwasher, in the course of 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, characterized in that a dishwasher detergent A, containing a) surfactant(s), b) anionic polymer(s) is metered 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 the formation of deposits is reduced and the drying efficiency improved.

Description

cleaning process

The present application relates to a method for cleaning dishes. In particular, this application relates to a method for cleaning crockery, wherein detergent is dosed with a time delay in the interior of a dishwasher.

Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, machine dishwashing detergents are particularly important with the spread of household dishwashers. These automatic dishwashing agents are typically offered to the consumer in solid form, for example as powders or as tablets, but increasingly also in liquid form.

One of the major goals of the machine cleanser manufacturers is to improve the cleaning performance of these agents, with a recent focus on cleaning performance in low temperature or reduced water consumption cleaning cycles. For this purpose, the cleaning agents were preferably added to new ingredients, for example, more effective surfactants, polymers or bleach. However, since new ingredients are available only to a limited extent and the amount of ingredients used for each cleaning cycle can not be increased to any extent for ecological and economic reasons, this approach has natural limits.

Another approach to improving the performance profile of existing detergents or cleaners is to develop new ready-made forms, for example, in the combination of solid and liquid detergents or cleanser ingredients. Corresponding detergents are combined, for example, in novel water-soluble packaging.

This application was based on the object to improve the known methods for machine dishwashing to the effect that these methods without the use of additional ingredients or an increase in the dosage even at low temperature cleaning cycles or cleaning cycles with low water consumption improved cleaning performance and improved drying of the cleaned dishes.

This object has been achieved by a special dishwashing method in which a surfactant- and polymer-containing detergent is metered in a time-displaced manner into the interior of a dishwasher. A first subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous rinse liquor 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 a ) Surfactant (e) b) anionic polymer (s) is metered into the interior of the dishwasher at a time t1 <t in an amount m1 and at a time t2> t in an amount m2.

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

The machine cleaning program is usually determined in a dishwasher before the dishwashing process by the consumer by selecting from a list of programs, which in particular the temperature of the wash liquor during the cleaning process, the duration of the process or the cleaning agents and - tools used are defined (" 2in1 "and" 3in1 "programs).

Regardless of the temperature and time, the automatic dishwashing process or the consumer-selected dishwashing detergent program comprises at least two rinses selected from a pre-rinse cycle, a cleaning cycle, and a rinse cycle. These rinses are characterized, for example, by different durations, water consumption and temperature profiles, wherein the aqueous rinse liquor located in the interior of the dishwasher is at least partially removed from the interior of the dishwasher between the rinses and optionally supplemented by the inflow of fresh water. As a rule, this replacement of the rinsing liquor takes place by means of a pump system integrated in the dishwasher.

The proportionate pumping out of the wash liquor from the interior of the dishwasher is preferably carried out such that at least 5 vol .-%, preferably 10 vol .-%, more preferably at least 20 vol .-%, most preferably at least 40 vol .-% and in particular at least 60 Vol .-% of the rinsing liquor are pumped out of the interior of the dishwasher. In particularly preferred processes, between 5 and 99% by volume of the rinsing liquor, preferably between 10 and 90% by volume of the rinsing liquor, more preferably between 20 and 80% by volume and in particular between 40 and 70% by volume of the rinsing liquor pumped out.

A preferred subject matter of the present application is therefore a process for cleaning dishes in a dishwasher, in the course of which the aqueous rinse liquor in the interior of the dishwasher is at a time t of between 5 and 99% by volume, preferably between 10 and 90% by volume, more preferably between 20 and 80% by volume and in particular between 40 and 70% by volume of the rinsing liquor is removed from the interior of the dishwasher, characterized in that a machine dishwashing detergent A containing a) nonionic surfactant (s) b) anionic polymer (s) is metered into the interior of the dishwasher at a time t1 <t in an amount m1 and at a time t2> t in an amount m2.

Of course, a complete pumping out of the wash liquor is possible, however, the complete removal of the wash liquor from the interior of the dishwasher is associated with comparatively great expenditure of time and energy and, for this reason, less preferred.

The inventive method is characterized in that both before and after the proportionate pumping out of the wash liquor from the interior of the dishwasher, a machine dishwashing detergent containing nonionic surfactants and anionic polymers in the interior of the dishwasher and thus in the interior of the wash liquor is metered. The time interval between the times t1 and t2 may vary, wherein method according to the invention, characterized in that the time difference between the times t1 and t2 is 5 to 50 minutes, preferably 10 to 40 minutes and especially 15 to 30 minutes, are preferred.

The temperature of the wash liquor is at time t1, preferably 12-45 ⁰ C, preferably between 15 and 4O ⁰ C and in particular between 20 and 35 ⁰ C and at the time t2 is preferably between 30 and 65 ⁰ C, preferably between 35 and 6O ⁰ C and in particular between 40 and 55 ⁰ C. In a particularly preferred embodiment of the inventive method, the temperature of the wash liquor is at time t2 above the temperature of the wash liquor at the time t1. A corresponding temperature profile, at which the temperature of the rinsing liquor at time t2 is above the temperature of the rinsing liquor 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 wash liquor at time t2 is below the temperature of the wash liquor at time t1 or identical thereto.

The weight ratio of the metered quantities m1 and m2 in preferred process variants is between 20: 1 and 2: 1, preferably between 15: 1 and 3: 1 and in particular between 12: 1 and 4: 1. Characteristic of the automatic dishwashing agents used in the process according to the invention is their content of surfactants and anionic polymers.

The nonionic surfactants, the anionic surfactants and the amphoteric surfactants have proven to be particularly effective in terms of cleaning performance and drying, with the nonionics in this group again giving the best results, nionic and amphoteric surfactants preferably being used in combination with defoaming agents or drying agents Foam inhibitors used.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.

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

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

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C _t2 - _U - alcohols with 3 EO or 4 EO, C ₉ .n alcohol containing 7 EO, C-ms alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci ₂ - ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -i ₄ -alcohol with 3 EO and C ₁₂ -i ₈ -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

With particular preference, therefore, ethoxylated nonionic surfactant selected from C ₆ - alkanols ₂ o-monohydroxy or C ₆ - ₂ o-alkyl phenols or C ₆ - ₂ o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol were used. A particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C-ι ₆ - ₂ o alcohol), preferably obtained a d ₈ alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide. Of these, particularly preferred are the so-called "narrow-range ethoxylates." With particular preference, furthermore, combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are used.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) (e) with a melting point above 2O ⁰ C, preferably above 25 ⁰ C, more preferably between 25 and 6O ⁰ C and in particular from 26.6 to 43.3 ⁰ C, is / are particularly preferred ,

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.

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

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols additionally having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

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

Further particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25 Wt .-% 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 contains.

In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

Ri-O- (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) - (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) -H

R2 R3

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

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

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

Nonionic surfactants are summary particularly preferred which have a C. _9-i ₅ alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants of the general formula R ¹ -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; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ - CH ₂ , -CH ₂ -CH (CHs) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60. Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ OI _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 to R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1, 5 and y is at least 15.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nitinol surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² in which R ¹ and R ^{2 is} independently a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ - CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are most preferred.

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

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

As described above, each R ³ in the above formula may be different if x> 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x-values and thus increasing For example, a large number (EO) groups, combined with a small number (PO) groups includes, 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 is R ¹ O [CH ₂ CH (R ³ ) O] _X CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

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

In preferred process variants, the automatic dishwashing agent A contains, in each case based on the total weight of the automatic dishwashing agent A, nonionic surfactant in amounts of from 0.1 to 30% by weight, preferably from 0.2 to 20% by weight, particularly preferably 0.5 to 10 wt .-% and in particular from 1, 0 to 8 wt .-%. Process variants in which the nonionic surfactant is contained in the automatic dishwashing detergent A, based on its total weight, in amounts of from 0.5 to 5.0% by weight, are particularly preferred.

A preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous rinse liquor in the interior of the dishwasher is removed at least partially from the interior of the dishwasher at a time t, characterized in that a machine Dishwashing detergent A, containing, based on the total weight of the automatic dishwashing detergent A a) 0.5 to 5% by weight of nonionic surfactant (s) b) anionic polymer (s) at a time t1 <t in an amount m1 and at a time t2> t in an amount m2 is metered into the interior of the dishwasher.

A further preferred subject matter of the present application is therefore a process for cleaning dishes in a dishwasher, in the course of which the aqueous rinsing liquor in the interior of the dishwasher is at a time t between 5 and 99% by volume, preferably between 10 and 90% by volume .-%, more preferably between 20 and 80 vol .-% and in particular between 40 to 70 Vol .-% of the washing liquor is removed from the interior of the dishwasher, characterized in that a machine dishwashing detergent A, containing, based on the total weight of Machine dishwashing agent A a) 0.5 to 10% by weight of nonionic surfactant (s) b) anionic polymer (s) at a time t1 <t in an amount m1 and at a time t2> t in a quantity m2 is metered into the interior of the dishwasher.

Alternatively or 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.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Suitable surfactants of the sulfonate type are preferably C _{_9-13} alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates of the gaseous they example, from C _12-i ₈ monoolefins with terminal or internal double bond by sulfonation with Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates, from C ₁₂ - alkanes are obtained for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization - _18th Likewise suitable are the esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

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 in the preparation 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 Glycerol can be obtained. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. Suitable alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid semiesters of the C ₁₂ -C ₁₈ FeKaIkOhoIs, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂ o- Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and 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.

Also, the sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 moles of ethylene oxide. ₂₁ -alcohols, such as 2-methyl-branched C ^ -π-alcohols having 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 only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

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

Suitable amphoteric surfactants are, for example, betaines or alkylamidoalkylamines.

Suitable betaines are the alkylbetaines, 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 ^C 00 ^- , in which R ^{A is} a optionally interrupted by hetero atoms or heteroatom groups alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and R ^B and R ^{c are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C-io-C-alkyl-alkylcarboxymethylbetaine and C -ι-ι-C- _17- Alkylamidopropyl-dimethyl- carboxymethylbetaine, or formula R ^l - [CO-X- (CH ₂ ) _n ] _x -N ⁺ (R ^M ) (R ^m ) - (CH ₂ ) _m - [CH (OH) -CH ₂ ] _y -Y ^" , in the R ¹ is a saturated or unsaturated C _{_6-22} -alkyl radical, preferably C ₈ -i ₈ -alkyl radical, preferably a saturated C ₁₀ -i ₆ alkyl radical, for example a saturated C ₁₂ -i ₄ alkyl radical,

X NH, NR ^IV with the d. _4- alkyl radical R ¹ , O or S, n is a number from 1 to 10, preferably 2 to 5, in particular 3, x 0 or 1, preferably 1,

R ^M , R ^MI independently of one another C- |. _4- alkyl radical, optionally hydroxy-substituted such. As a hydroxy ethyl radical, but especially a methyl radical, m is a number from 1 to 4, in particular 1, 2 or 3, y 0 or 1 and

Y is COO, SO ₃ , OPO (OR ^V ) O or P (O) (OR ^V ) O, where R ^{v is} a hydrogen atom H or a d. ₄ alkyl.

The alkyl and alkylamidobetaines, betaines of the abovementioned formula having 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, RN ⁺ (CHs) ₂ -CH ₂ COO ^" (A1)

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

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

R'-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 carbo-betaines, in particular the carbo-betaines of the formula A1 and A2, most preferably the alkylamido-betaines of the formula A2. Examples of suitable betaines and sulfobetaines are the following compounds designated as INCI: almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, caprylic / capramidopropyl betaines, carnitines, cetyl betaines, cocamidoethyl betaines , Cocamidopropyl Betaine, 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, Dimethicone Propyl PG Betaine, Erucamidopropyl Hydroxysultaines, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydroxys ultaine, oleyl betaine, olivamidopropyl betaine, palmamidopropyl betaine, palmitamido propyl betaine, palmitoyl carnitine, palm kernelamidopropyl betaine, polytetrafluoroethylene acetoxypropyl betaine, ricinoleamidopropyl betaine, sesamidopropyl betaine, soyamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallowamidopropyl propoxysultaine, Tallow Betaine, Tallow Dihydroxyethyl Betaine, undecylenamidopropyl Betaine and Wheat Germamidopropyl Betaine. A preferred amphoteric surfactant is cocamidopropyl betaine (cocoamidopropyl betaine). A particularly preferred amphoteric surfactant is caprylic / Capramido- propyl betaine (CAB), which is available for example under the trade name Tegotens ^® B 810 from Th. Goldschmidt AG.

The alkylamidoalkylamines (INCI alkylamido alkylamine) are amphoteric surfactants having the formula R -CO-NR ^vl ^v "- (CH ₂₎ _l -N (R ^vl") - (CH ₂ CH ₂ O) - (CH ₂₎ _k - ([CH OH)] _l -CH ₂ -Z-OM in which R ^VI is a saturated or unsaturated C _{_6-22} -alkyl radical, preferably C ₈ -i ₈ -alkyl radical, preferably a saturated C-ι -i _O ₆ alkyl, for example a saturated C ₂ _i ₄ alkyl radical, R ^v "is a hydrogen atom H or a CI_ ₄ alkyl radical, preferably H, i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,

R ^vι "is a hydrogen atom H or CH ₂ COOM (to M su), j is a number from 1 to 4, preferably 1 or 2, in particular 1, k is a number from 0 to 4, preferably 0 or 1,

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

Z is CO, SO ₂ , OPO (OR ¹² ) or P (O) (OR ¹² ), where R ^{12 is} a d_ ₄ -alkyl radical or M (su), and

M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, eg.

B. protonated mono-, di- or triethanolamine, is. Preferred representatives satisfy the formulas B1 to B4,

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

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

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

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VI ") -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -OPO ₃ HM (B4) where R ^vι , R ^vι " and M have the same meaning as in formula B.

Exemplary alkylamidoalkylamines are the following named compounds according to INCI: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodi- acetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropyl- sulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium amphodiacetates Isostearo-, Disodium isostearoamphodipropionate, disodium laureth-5 carboxyamphodi-acetate, disodium lauroamphodiacetate, disodium lauroamphodipropionate, disodium oleo-amphodipropionate, disodium PPG-2-lsodeceth-7 carboxyamphodiacetate, disodium stearo-amphodiacetate, disodium tallowamphodiacetate, disodium wheatgermamphodiacetate, lauro-amphodipropionic acid, quaternium 85, sodium caproamphoacetate, sodium caproampho-hydroxypropylsulfonate, sodium caproamphopropionate, sodium capryloamphoacetate, sodium capryloamphohydroxypropylsulfonate e, Sodium Capryloamphopropionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoampho- Propionate, Sodium Lauroamphoacetate, Sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium acetate Myristoampho-, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium amphopropionates oleo, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, amphohydroxypropylsulfonate Stearo- Sodium, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopro - Pionate, Sodium Wheat Germamphoacetate and Trisodium Lauroampho PG-Acetate Chloride Phosphate.

Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials. In the context of the present application preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R ₂ SiO) X and are also referred to as silicone oils.

As a second essential ingredient, the cleaning agents used in the process according to the invention contain anionic polymers. 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, in each case based on the total weight of the automatic dishwashing agent A, contains the anionic polymer in amounts of from 0.1 to 40% by weight, preferably from 0.2 to 20% by weight, preferably 0.5 to 15 wt .-% and in particular from 1, 0 to 10 wt .-%. Corresponding agents have proved to be advantageous in the process according to the invention, in particular with regard to optimum cleaning and rinse-aid results.

A particularly preferred subject matter of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous rinsing liquor 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 detergent A containing, based on the total weight of the automatic dishwashing detergent A a) 0.5 to 10% by weight of nonionic surfactant (s) b) 0.2 to 20% by weight of anionic polymer (s) ( e) is metered into the interior of the dishwasher at a time t1 <t in an amount m1 and at a time t2> t in an amount m2. A further preferred subject matter of the present application is therefore a process for cleaning dishes in a dishwasher, in the course of which the aqueous rinsing liquor in the interior of the dishwasher is at a time t between 5 and 99% by volume, preferably between 10 and 90% by volume .-%, more preferably between 20 and 80 vol .-% and in particular between 40 to 70 Vol .-% of the washing liquor is removed from the interior of the dishwasher, characterized in that a machine dishwashing detergent A, containing, based on the total weight of Machine dishwashing detergent A a) 0.5 to 10% by weight of nonionic surfactant (s) b) 0.2 to 20% by weight of anionic polymer (s) at a time t 1 <t in an amount m1 and at a time t2> t in an amount m2 is metered into the interior of the dishwasher.

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

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

Inventive methods, characterized in that it is the anionic polymer is a homo- and / or copolymer of acrylic acid or methacrylic acid, are preferred.

Alternatively or in addition to the aforementioned polycarboxylates, the anionic polymers used in the process according to the invention may also contain sulfonic acid groups.

Process according to the invention, characterized in that the anionic polymer is a copolymer of i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionic monomers are preferred.

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

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CHz) _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 (CHs) 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 is an optional spacer group which is selected from - (CHz) _n - with n = O to 4, -C00- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₂ ) 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-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against Sodium ions, can be replaced. The use of partially or fully neutralized sulfonic acid-containing copolymers 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 end use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1, and in particular from 5000 to 15,000 gmol ^-1 .

Further suitable anionic polymers are the hydrophobically modified anionic polymers, for example anionic polymers, comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids 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 are -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} 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 iii) optionally other monomers

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

A particularly preferred subject matter of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous rinsing liquor 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 detergent A, containing, based on the total weight of the automatic dishwashing detergent A a) 0.5 to 10 wt .-% nonionic (s) surfactant (s) b) anionic polymer, comprising i) monomers from the group of one or more times unsaturated carboxylic acids 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 are -H, -CH ₃ or -C ₂ H ₅ , X. for an optional one A spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated iii) optionally further monomers are metered into the interior of the dishwasher at a time t1 <t in an amount m1 and at a time t2> t in an amount m2.

A further preferred subject matter of the present application is therefore a process for cleaning dishes in a dishwasher, in the course of which the aqueous rinsing liquor in the interior of the dishwasher is at a time t between 5 and 99% by volume, preferably between 10 and 90% by volume .-%, more preferably between 20 and 80 vol .-% and in particular between 40 to 70 Vol .-% of the washing liquor is removed from the interior of the dishwasher, characterized in that a machine dishwashing detergent A, containing, based on the total weight of automatic dishwashing detergent A a) 0.5 to 10% by weight of nonionic surfactant (s) b) anionic polymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of general formula R ¹ ( R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ^3, independently of one another, is -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group, which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical If there are 6 to 22 carbon atoms, iii) optionally further monomers are metered into the interior of the dishwasher at a time t1 <t in an amount m1 and at a time t2> t in a quantity m2.

Particularly preferred carboxyl-containing monomers i) of the abovementioned 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.

The nonionic monomers ii) used are monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ . 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-2,3,3-dimethylhexene-1,2,4-dimethylhexene-1,2,5-dimethlyhexene-1,3,5 dimethyl hexene-1, 4,4-dimethylhexane-1, ethylcyclohexene, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid pentyl ester, Acrylic acid hexyl ester, methyl methacrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Λ / - (2-ethylhexyl) acrylamide, octyl acrylate, octyl methacrylate, / V- (octyl) -acrylamide, Lauryl acrylate, lauryl methacrylate, Λ / (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, Λ / (stearyl) acrylamide, behenyl acrylate, methacrylic acid behenyl ester and Λ / (behenyl) acrylamide or mixtures thereof.

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

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

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CHz) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H,

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CHz) _n - with n = 0 to 4, -C00- (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, S-methacrylamido-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylannid and mixtures of said acids or their water-soluble salts.

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

A further particularly preferred subject matter of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous rinse 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 detergent A containing, based on the total weight of the automatic dishwashing detergent A a) 0.5 to 10% by weight of nonionic surfactant (s) b) anionic polymer comprising i) monomers from the group of the on or polyunsaturated carboxylic acids 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 are -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical with 2 iii) up to 22 carbon atoms or for an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms, iii) sulfonic acid group-containing monomers are metered into the interior of the dishwasher at a time t1 <t in an amount m1 and at a time t2> t becomes. A further preferred subject matter of the present application is therefore a process for cleaning dishes in a dishwasher, in the course of which the aqueous rinsing liquor in the interior of the dishwasher is at a time t between 5 and 99% by volume, preferably between 10 and 90% by volume .-%, more preferably between 20 and 80 vol .-% and in particular between 40 to 70 Vol .-% of the washing liquor is removed from the interior of the dishwasher, characterized in that a machine dishwashing detergent A, containing, based on the total weight of automatic dishwashing detergent A a) 0.5 to 10% by weight of nonionic surfactant (s) b) anionic polymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of general formula R ¹ ( R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ^3, independently of one another, is -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group, which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical If there are 6 to 22 carbon atoms, iii) sulfonic acid group-containing monomers are metered into the interior of the dishwasher at a time t1 <t in an amount m1 and at a time t2> t in a quantity m2.

As a further component, the automatic dishwashing agent A used in the process according to the invention may contain one or more builders. The builders include in particular silicates, carbonates and organic cobuilders as well as the phosphates.

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

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. Particularly preferred machine dishwasher detergents according to the invention contain citrate as one of their essential builders. Processes preferred according to the invention are characterized in that the dishwashing agent A, based in each case on the total weight of the automatic dishwashing agent A, contains 5 to 60 wt.%, Preferably 10 to 50 wt.% And in particular 15 to 40 wt.% Citrate.

A preferred subject of the present application is therefore a method for cleaning dishes in a dishwasher, in the course of which the aqueous rinse liquor in the interior of the dishwasher is removed at least partially from the interior of the dishwasher at a time t, characterized in that a machine Dishwashing detergent A containing, based on the total weight of the automatic dishwashing detergent A a) 0.5 to 10% by weight of nonionic surfactant (s) b) 0.2 to 20% by weight of anionic polymer (s) ) c) 10 to 50 wt .-% citrate at a time t1 <t in an amount m1 and at a time t2> t in an amount m2 is metered into the interior of the dishwasher.

Preference is furthermore given to a process for cleaning dishes in a dishwasher, in the course of which the aqueous dishwashing liquor in the interior of the dishwasher is at a time t 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 and 70% by volume of the rinsing liquor is removed from the interior of the dishwasher, characterized in that a machine dishwashing detergent A containing, based on the total weight of the automatic dishwashing detergent A a) 0 , 5 to 10% by weight of nonionic surfactant (s) b) 0.2 to 20% by weight of anionic polymer (s) c) 10 to 50% by weight of citrate at a time t1 < t in an amount m1 and at a time t2> t in an amount m2 is metered into the interior of the dishwasher.

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 greatest importance in the washing and cleaning agent industry.

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

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

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

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

In addition to 1-hydroxyethane-1, 1-diphosphonic acid, the complex-forming phosphonates comprise a number of different compounds, such as, for example, diethylene triamine penta (methylene phosphonic 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 neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

An automatic dishwashing agent A preferred in the context of this application contains one or more phosphonate (s) from the group a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof; b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof; c) diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and / or salts thereof; d) 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) and / or salts thereof; e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof; f) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or salts thereof; g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.

Particular preference is given to automatic dishwashing detergents which contain, as phosphonates, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).

Of course, the automatic dishwashing compositions of the invention may contain two or more different phosphonates. Particular preference is given to those automatic dishwashing agents A which contain as phosphonates both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylene triamine penta (methylenephosphonic acid) (DTPMP), the weight ratio of HEDP to DTPMP being 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 weight fraction of the phosphonate (s) in the total weight of the automatic dishwashing agent is less than the weight proportion 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 to 2: 1, most 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 weight proportions of 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) and methylglycinediacetic acid (MGDA) is preferably 0.5 to 14 wt .-%, preferably 1 to 12 wt .-% and in particular 2 to 8 wt .-%.

A further preferred subject matter of the present application is a method for cleaning dishes in a dishwasher, in the course of which the aqueous rinse 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 detergent A containing, based on the total weight of the automatic dishwashing detergent A a) 0.5 to 10% by weight of nonionic surfactant (s) b) 0.2 to 20% by weight of anionic polymer (s) c) 15 to 40% by weight of phosphate or 15 to 40% by weight of citrate d) 0.5 to 8 wt .-% phosphonate (e) at a time t1 <t in an amount m1 and at a time t2> t in an amount m2 is metered into the interior of the dishwasher.

Preference is furthermore given to a process for cleaning dishes in a dishwasher, in the course of which the aqueous dishwashing liquor in the interior of the dishwasher is at a time t 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 and 70% by volume of the rinsing liquor is removed from the interior of the dishwasher, characterized in that a machine dishwashing detergent A containing, based on the total weight of the automatic dishwashing detergent A a) 0 , 5 to 10% by weight of nonionic surfactant (s) b) 0.2 to 20% by weight of anionic polymer (s) c) 15 to 40% by weight of phosphate or 15 to 40% by weight % Citrate d) 0.5 to 8% by weight phosphonate (e) is metered into the interior of the dishwasher at a time t1 <t in an amount m1 and at a time t2> t in an amount m2.

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

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

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae, as well as improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, the α-amylase are off for this purpose Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

The enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are prepared by methods known per se, for example by Shaking or rolling granulation or applied in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

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

A further preferred subject matter of the present application is a method for cleaning dishes in a dishwasher, in the course of which the aqueous rinse 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 detergent A containing, based on the total weight of the automatic dishwashing detergent A a) 0.5 to 10% by weight of nonionic surfactant (s) b) 0.2 to 20% by weight of anionic polymer (s) c) 15 to 40% by weight of phosphate or 15 to 40% by weight of citrate d) 0.5 to 5% by weight of enzyme (s) at a time t1 <t in an amount m1 and at a time t2> t in an amount m2 is metered into the interior of the dishwasher.

Preference is furthermore given to a process for cleaning dishes in a dishwasher, in the course of which the aqueous dishwashing liquor in the interior of the dishwasher is at a time t between 5 and 99% by volume, preferably between 10 and 90% by volume, particularly preferred between 20 and 80 vol .-% and in particular between 40 to 70 vol .-% of the rinsing liquor is removed from the interior of the dishwasher, characterized in that a Machine dishwashing detergent A containing, based on the total weight of the automatic dishwashing detergent A a) 0.5 to 10% by weight of nonionic surfactant (s) b) 0.2 to 20% by weight of anionic polymer (s) ( e), preferably sulfonic acid group-containing polymer (s) c) 15 to 40 wt .-% phosphate or 15 to 40 wt .-% citrate d) 0.5 to 5 wt .-% enzyme (s) to a Time t1 <t in an amount m1 and at a time t2> t in an amount m2 is metered into the interior of the dishwasher.

Preferably used machine dishwashing agents A further contain one or more bleaching agents. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaches that can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which yield H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

A process, characterized in that the dishwashing agent A, in each case based on the total weight of the automatic dishwashing agent A, 1 to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 4 to 12 wt .-% sodium percarbonate, are according to the invention prefers.

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

In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ^° C. and below, the automatic dishwashing agents used according to the invention may additionally contain bleach activators. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given several times acylated alkylenediamines, with tetraacetylethylenediamine (TAED) has been found to be 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, especially 2 to 8% by weight and more preferably 2 to 6% by weight. , in each case based on the total weight of the bleach activator-containing agents used.

In addition to, or in place of, the conventional bleach activators, so-called bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

With particular preference complexes of manganese in the oxidation state II, III, IV or IV are used, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (MeMe-TACN) and / or 2-methyl-1, 4,7-triazacyclononane (Me / TACN). Examples of suitable manganese complexes are [Mn ^m ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) 2, [Mn "'Mn' ^v (μ-O) ₂ (μ-OAc) ₁ (TACN) ₂ ] (BPh ₄ ) Z, [Mn ^IV 4 (μ-O) ₆ (TACN) 4] (CIO ₄ ) 4, [Mn "' ₂ (μ-O) ₁ (μ-OAc) ₂ ( Me-TACN) ₂ ] (CIO ₄ ) ₂ , [Mn " ¹ Mn ^lv (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (CIO ₄ ) 3, [Mn ' ^v ₂ (μ -O) ₃ (Me-TACN) _2] (PF ₆₎ ₂ and [Mn ^'v ₂ (μ- O) ₃ (Me / Me-TACN) _2] (PF ₆₎ ₂ (OAc = OC (O) CH ₃ ).

Machine dishwashing detergent, characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me ₃ -TACN) or 1, 2, 4,7-tetramethyl-1, 4,7-triazacyclononane (Me ₄ - TACN) are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.

The above-mentioned bleach-enhancing transition metal complexes, in particular with the central atoms Mn and Co, in each case based on the total weight of the automatic dishwashing agent A, in conventional amounts, preferably in an amount up to 5 wt .-%, in particular Quantities of 0.01 to 2 wt .-%, preferably 0.02 to 1 wt .-% and in particular 0.05 to 0.8 wt .-% used.

In addition to the active substances contained in the automatic dishwashing detergent, in particular the pH of the automatic dishwashing detergent used has proven to be relevant for the cleaning, rinsing and drying results of the process according to the invention. Particularly good results are thus obtained with machine dishwashing detergents, whose 1% aqueous solution (2O ⁰ C) has a pH above 7, preferably particularly preferably between 7 and 12 has 9-1. 1 Corresponding methods, characterized in that the automatic dishwashing agent A has a pH (2O ⁰ 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. The rinse water used for carrying 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 agents A used in accordance with the invention can be formulated in solid or liquid form but can also be present, for example, as a combination of solid and liquid forms.

Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms, preferably based on water and / or organic solvents, may be thickened, in the form of gels.

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

The individual phases of multiphase agents may have the same or different states of matter. Machine dishwashing detergents 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 preferred. According to the invention driving, characterized in that the dishwashing agent A is in liquid form, but are preferred due to improved cleaning, rinsing and drying results.

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

The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

The automatic dishwasher detergents according to the invention, in particular the prefabricated metering units, have a water-soluble coating, with particular preference.

In an alternative form of supply, the automatic dishwashing agent A used in the method according to the invention can be metered 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 agent A is present, for example, in the form of separate partial formulations. The water-insoluble storage container can be integrated in the dishwasher, but can also have the shape of a conventional two- or multi-chamber bottle.

As described above, cleaning methods according to the invention are distinguished from conventional methods by improved cleaning and rinsing action, as well as improved drying of the cleaned dishes. The use of a machine dishwashing process according to the invention for reducing the deposit formation in automatic dishwashing or for improving the drying in automatic dishwashing are further objects of this application. Examples

The drying, coating and cleaning performance of a machine dishwashing process were determined as a function of the type of metering of the automatic dishwashing detergent used.

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

The composition of the dishwasher detergents F1 and F2 used can be found in the following table:

Hydroxymix ethers of the general formula C6-24-CH (OH) CH2O- (EO) 2o - i2o-C2-26

The following three experiments were performed:

Experiment V1: In each case 16.5 ml of the composition F1 and F2 were metered into the machine interior at the same time in the main rinse cycle of the dishwashing process;

Experiment V2: 12.5 ml of the composition F1 and 16.5 ml of the composition F2 were metered into the machine interior in the main wash cycle of the dishwashing process; In addition, 4 ml of the composition F1 were metered into the interior of the machine in the subsequent rinse cycle (after partial replacement of the wash liquor);

Experiment E1: In each case 14.5 ml of the compositions F1 and F2 were metered into the machine interior at the same time as the main dishwashing cycle of the dishwashing process; to- In addition, 2 ml of the compositions F1 and F2 were metered into the machine interior in the subsequent rinse cycle (after partial replacement of the rinsing 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 according to EN standard. The results are given in the table below (The values given are average values from 3 experiments):

Based on the results in experiment V1, the drying index could therefore be improved in experiment V2 by the subsequent metering of a surfactant-containing cleaning agent, but at the same time the formation of deposits on the dish surface was observed. Only by the subsequent dosage of surfactant and anionic polymer in experiment E1 both good drying and coating results were achieved.

Claims

claims

1. A method for cleaning dishes in a dishwasher, in the course of which is located in the interior of the dishwasher aqueous rinsing liquor at a time t at least partially removed from the interior of the dishwasher, characterized in that a machine dishwashing detergent A containing a) surfactant (e) b) anionic polymer (s) is metered into the interior of the dishwasher at a time t1 <t in an amount m1 and at a time t2> t in an amount m2.

2. The method according to claim 1, characterized in that the automatic dishwashing agent A, in each case based on the total weight of the automatic dishwashing agent A, nonionic surfactant in amounts of 0.1 to 30 wt .-%, preferably 0.2 to 20 wt. %, particularly preferably 0.5 to 10 wt .-% and in particular from 1, 0 to 8 wt .-%.

3. The method according to any one of the preceding claims, characterized in that the automatic dishwashing agent A, in each case based on the total weight of the automatic dishwashing agent A, the anionic polymer in amounts of 0.1 to 40 wt .-%, preferably 0.2 to 20 Wt .-%, preferably 0.5 to 15 wt .-% and in particular from 1, 0 to 10 wt .-%.

4. The method according to any one of the preceding claims, characterized in that it is the anionic polymer is a homo- and / or copolymer of acrylic acid or methacrylic acid.

5. The method according to any one of the preceding claims, characterized in that it is the anionic polymer is a copolymer of i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iv) optionally further ionic or nonionic monomers.

6. The method according to any one of the preceding claims, characterized in that the dishwashing agent A, in each case based on the total weight of the automatic dishwashing agent A, 5 to 60 wt .-%, preferably 10 to 50 wt .-% and in particular 15 to 40 wt. - contains% phosphate.

7. The method according to any one of the preceding claims, characterized in that the dishwashing detergent A, in each case based on the total weight of the automatic dishwashing agent A, 5 to 60 wt .-%, preferably 10 to 50 wt .-% and in particular 15 to 40 Wt .-% citrate.

8. The method according to any one of the preceding claims, characterized in that the dishwashing A contains a complexing agent, preferably 1-hydroxyethane-1, 1-diphosphonic acid and / or methylglycinediacetic.

9. The method according to any one of the preceding claims, characterized in that the dishwashing agent A, in each case based on the total weight of the automatic dishwashing agent A, 0.2 to 5 wt .-%, preferably 0.5 to 5 wt .-% and in particular 1 to 4 wt .-% enzyme (s).

10. The method according to any one of the preceding claims, characterized in that the automatic dishwashing agent A a) 0.5 to 10 wt .-% nonionic (s) surfactant (s) b) 0.2 to 20 wt .-% sulfonic acid groups (s) polymer (e) c) 10 to 40% by weight of phosphate or 10 to 40% by weight of citrate d) 0.5 to 5% by weight of enzyme (s).

11. The method according to any one of the preceding claims, characterized in that the dishwashing agent A, in each case based on the total weight of the automatic dishwashing agent A, 1 to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 4 to 12 wt. - contains% sodium percarbonate.

12. The method according to any one of the preceding claims, characterized in that the dishwashing agent A, in each case based on the total weight of the automatic dishwashing agent A, 0.01 to 2 wt .-%, preferably 0.02 to 1 wt .-% and in particular 0 , 05 to 0.8 wt .-% bleach catalyst.

13. The method according to any one of the preceding claims, characterized in that the automatic dishwashing agent A has a pH (2O ⁰ C, 1% aqueous solution) above 7, preferably between 7 and 12, more preferably between 9 and 11.

14. The method according to any one of the preceding claims, characterized in that the dishwashing agent A is in liquid form.

15. The method according to any one of the preceding claims, characterized in that the dishwashing agent A is metered from a water-insoluble reservoir into the interior of the dishwasher.

16. The method according to any one of the preceding claims, characterized in that the dishwashing detergent A is metered from a water-insoluble two- or multi-chamber reservoir into the interior of the dishwasher.

17. The method according to any one of the preceding claims, characterized in that the weight ratio of metered 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 ,

18. The method according to any one of the preceding claims, characterized in that the time difference between the times t1 and t2 is 5 to 50 minutes, preferably 10 to 40 minutes and in particular 15 to 30 minutes.

19. The method according to any one of the preceding claims, characterized in that the temperature of the rinsing liquor at time t1 between 12 and 45 ⁰ C, preferably between 15 and 40 ⁰ C and in particular between 20 and 35 ⁰ C.

20. The method according to any one of the preceding claims, characterized in that the temperature of the wash liquor at time t2 is between 30 and 65 ⁰ C, preferably between 35 and 60 ⁰ C and in particular between 40 and 55 ⁰ C.

21. Use of a method according to one of the preceding claims for improving the drying in automatic dishwashing.

22. Use of a method according to any one of claims 1 to 20 for reducing the formation of deposits in automatic dishwashing.