WO2013007410A1

WO2013007410A1 - Rinse and dishwasher agents

Info

Publication number: WO2013007410A1
Application number: PCT/EP2012/057877
Authority: WO
Inventors: Thomas Eiting; Nina Mussmann; Thorsten Bastigkeit; Konstantin Benda; Arnd Kessler; Inga Kerstin Vockenroth; Melanie SZEMAIT
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2011-07-14
Filing date: 2012-04-30
Publication date: 2013-01-17
Also published as: DE102011079146A1

Abstract

The invention relates to rinse and dishwasher agents which contain anionic surfactant(s) comprising at least one sulphate- or sulphonate group as well as low-foaming non-ionic surfactants(s), and which display very good rinsing properties during machine dishwashing.

Description

"Rinse aid and dishwashing detergent"

The present application describes rinsing and dishwashing detergents as well as automatic dishwashing processes using these agents and the use of these detergents in automatic dishwashing.

Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, in particular the automatic dishwashing detergents have gained great importance with the spread of household dishwashers. These automatic dishwashing detergents are the consumer

typically offered in solid form, for example as a powder or as tablets, but increasingly also in liquid form.

One of the major objectives of the machine cleaners manufacturers is to improve the cleaning and rinse performance of these compositions, with more emphasis being placed recently on the cleaning and rinse performance in low temperature or reduced water consumption cleaning cycles.

It was an object of this application to provide machine rinse aids and dishwashing detergents having improved rinsing properties, which improved

Klarspüleigenschaften especially in low-temperature cleaning operations, ie in cleaning processes with Spülflottentemperaturen of 50 ° C or below, and / or in short-term cleaning process, especially in cleaning process with a duration of less than 60 minutes, should be achieved. In particular, the formation of drops on the treated dishes should be reduced.

This object has been achieved by rinse aid compositions containing at least one anionic surfactant having at least one sulfate or sulfonate group and at least one nonionic surfactant. The object was further achieved by dishwashing agents which contain at least one anionic surfactant having at least one sulfate or sulfonate group, at least one nonionic surfactant and at least one compound selected from phosphonates, MGDA and GLDA.

It has generally already been described in the prior art that anionic surfactants can be used in automatic dishwashing processes (for dishwashing). However, a well-known problem with anionic surfactants is their foaming behavior.

Due to the foaming in their use, there is a pressure drop in the

Dishwasher, which generally with insufficient cleaning performance connected is. For this reason, the use of anionic surfactants in automatic dishwashing is usually dispensed with.

According to the invention, however, it has now surprisingly been found that the rinsing performance of dishwashing detergents containing nonionic surfactants can be increased by the addition of surfactants with sulfate and / or sulfonate groups.

A first subject of the present invention are therefore automatic rinse aids which contain at least one anionic surfactant having at least one sulfate or sulfonate group and at least one nonionic surfactant.

Another object of the present invention are machine dishwashing detergents containing at least one anionic surfactant having at least one sulfate or sulfonate group, at least one nonionic surfactant and at least one compound selected from phosphonates, MG DA and GLDA.

Another object of the present invention are dishwashing processes using inventive machine rinse aid or dishwashing detergent.

Another object of the present invention is also the use of a

Combination of at least one anionic surfactant with at least one sulfate or sulfonate group and at least one nonionic surfactant for rinsing dishes in a machine cleaning process, in particular for reducing the formation of drops on the dishes, wherein the surfactants in the form of a machine rinse aid or in the form of a machine dishwashing detergent can be used.

As automatic dishwashing detergents are in accordance with this application

Refers to compositions that can be used to clean soiled dishes in a machine dishwashing process. Thus, the automatic dishwashing detergents differ, for example, from the automatic rinse aids which are always used in combination with automatic dishwashing detergents and do not have their own

Unfold cleaning effect.

Under a machine rinse aid are according to the invention accordingly

To understand compositions which contain no further potentially active cleaning substances except the said surfactants and optionally Acidifizierungsmitteln.

While machine rinse aids according to the invention are preferably in liquid form, machine dishwashing detergents in which the combination of anionic surfactants are present at least one sulfate or sulfonate group is used, in a preferred embodiment in solid form.

A "liquid dishwashing detergent or rinse aid" is to be understood here as meaning an agent which is in the liquid state at 25 ° C. and a pressure of 1 bar. "A" solid dishwashing or rinse aid "is to be understood as meaning an agent which at 25 ° C and a pressure of 1 bar in solid state.

The solid dishwashing detergent is in the form of a preferred embodiment

Shaped body, in particular a Kompaktats, especially a tablet ago.

The anionic surfactant having at least one sulfate or sulfonate group is preferably selected from fatty alcohol sulfates, alkanesulfonates and alkylbenzenesulfonates. Preference is given here Ci ₂ -Ci ₈ fatty alcohol sulfates (FAS), eg Sulfopon K 35 (Cognis, Germany), secondary Ci ₃ -Ci7 alkanesulfonates (SAS), eg Hostapur SAS 93 (Clariant, Germany), and linear C8 C18-alkylbenzenesulfonates, in particular dodecylbenzenesulfonate (LAS).

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

Preferably, the anionic surfactant having at least one sulfate or sulfonate group in dishwashing compositions according to the invention in an amount of 0, 1 to 20 wt .-%, more preferably, 0.5 to 15 wt .-%, in particular 2.5 to 10 Wt .-%, contained.

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.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula

R ⁱ

I

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

The group of polyhydroxy fatty acid amides also includes compounds of the formula

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8

Carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein Ci_ ₄ alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain with substituted at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[Z] is preferably obtained by reductive amination of a reduced sugar,

For example, glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be prepared by reaction with

Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired

Polyhydroxyfatty acid amides are transferred. 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 12-14 alcohols containing 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, C ₃ .i ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci2 -i8-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-i4-alcohol with 3 EO and Ci ₂ -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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

With particular Ethoxylated nonionic surfactants which -2o- from C ₆ monohydroxy alkanols or C ₆ -2O alkylphenols or C ₆ -2O fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole Alcohol was used. A particularly preferred nonionic surfactant is derived from a straight chain fatty alcohol having 16 to 20 carbon atoms _(C16. ₂ o alcohol), preferably a C ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide. Of these, the so-called "narrow ranks ethoxylates" are particularly preferred.

With particular preference surfactants are further used, which one or more

Tallow fat alcohols containing 20 to 30 EO in combination with a silicone defoamer.

Particular preference is given to nonionic surfactants which have a melting point above

Have room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred , Suitable nonionic surfactants, the melting or softening points in said

Temperature range, 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. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

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

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

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

Further particularly preferred nonionic surfactants with melting points above

Room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

In the context of the present invention, particularly preferred nonionic surfactants have been low-foaming nonionic surfactants which contain alternating ethylene oxide and ethylene oxide Have 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 -CH-O) - (CH ₂ -CH ₂ -O) _r (CH ₂ -CH-O) -H

R2 R3 preferred, in which R stands for a straight-chain or branched, saturated or mono- or polyunsaturated _C6 -24 alkyl or alkenyl group; 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 -OH and ethylene or alkylene oxide. The radical R in the above formula may vary depending on the origin of the alcohol. When native sources are used, the group R has an even number of carbon atoms and is usually unbranched, the linear groups being selected from alcohols of native origin having 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

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

Nonionic surfactants are particularly preferred In summary, the ₉ have a C .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 exhibit in aqueous solution to the required low viscosity and are inventively used with particular preference.

In rinse aids according to the invention, those low-foaming nonionic surfactants are preferably used which have a linear or branched alkyl radical having 10 to 20, preferably 12 to 18 carbon atoms and 2 to 30, preferably 4 to 15 ethylene oxide units and optionally up to 5 propylene oxide units and up to 5 butylene oxide units.

Surfactants of the general formula

R is -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A" O) _z -R ² in which

R and R ² independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C ₂ -4-alkyl or alkenyl radical; A, A, A "and A '" independently of one another are radicals from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ - CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0, are particularly preferably used according to the invention, in particular in automatic dishwasher detergents.

Very particular preference is given here to nonionic surfactants of the general formula

R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² , in which R is a linear or branched aliphatic Hydrocarbon radical with 4 to 22, in particular 6 to 18,

Carbon atoms or mixtures thereof, R ^{2 is} a linear or branched

Hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and x and z are values between 0 and 40 and y is a value of at least 15, preferably from 15 to 120, particularly preferably from 20 to 80, stands.

In a preferred embodiment, the automatic dishwashing detergent contains, based on its total weight, nonionic surfactant of the general formula

R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² in amounts of 0.1 to 15 wt. -%, preferably 0.2 to 10 wt .-%, particularly preferably 0.5 to 8 wt .-% and in particular from 1, 0 to 6 wt .-%.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants according to the formula R 0 [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 16, carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and y for a Value between 15 and 120, preferably 20 to 100, in particular 20 to 80 stands. The group of these nonionic surfactants include, for example, hydroxy mixed ethers of the general formula C ₆ -22-CH (OH) CH ₂ O- (EO) 2o-i 2o-C2-OZ, for example the C _8- i ₂ fatty alcohol (EO) ₂₂ -2 hydroxydecyl ether and the C ₄ . ₂₂ fatty alcohol (EO) ₄₀ -8o-2-hydroxyalkyl ethers.

Automatic dishwashing detergent according to the invention, characterized in that the low-foaming nonionic surfactant is a surfactant of the general formula

R CH (OH) CH ₂ O- (CH ₂ CH ₂ O) 2o-i2o-R ^{2 is} used, wherein R and R ² independently of one another are a linear or branched aliphatic hydrocarbon radical having 2 to 20, in particular 4 to 16, carbon atoms prefers.

Also preferred are surfactants of the formula R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ Cl-1 (OI-l) R ² , in which R is a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched one

Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 4, preferably 0.5 to 1, 5, and y is a value of at least 15.

Also according to the invention are surfactants of the general formula

R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof , R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26

Carbon atoms or mixtures thereof and x is a value between 1 and 40 and y is a value between 15 and 40, wherein the alkylene units [CH ₂ CH (CH ₃ ) 0] and [CH ₂ CH ₂ 0] randomized, ie in Form a random statistical distribution.

The group of preferred end-capped poly (oxyalkylated) nonionic surfactants also includes nonionic surfactants of the formula R 0 [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² in which R and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are most preferred.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² , in which R and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals 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 is in 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 above formula

R 0 [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 be} different. R and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic

Hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x> 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO),

(PO) (PO) (EO) and (PO) (PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula zu

R 0 [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R, 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 and R ² Have 9 to 14 carbon atoms, R ^{3 is} H and x assumes values of 6 to 15.

Further preferred nonionic surfactants used are nonionic surfactants of the general formula R 0 (AlkO) _x M (OAlk) _y OR ² , where

R and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;

Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms;

x and y independently represent values between 1 and 70; and M is an alkyl radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently of one another are a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.

Nonionic surfactants of the general formula are preferred here

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

R, R and R ² independently represent an alkyl or alkenyl radical having 6 to 22 carbon atoms;

- x and y independently represent values between 1 and 40

Particular preference is given here to compounds of the general formula R -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² , in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30. Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH ₂ -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close the free OH functions to form a dihydroxy ether.

In a further preferred embodiment, the nonionic surfactant is selected from nonionic surfactants of the general formula

R -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which

R and R ² independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms;

R ³ and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and

- x and y independently represent values between 1 and 40.

Preference is given here in particular to compounds of the general formula R - 0 (CH ₂ CH ₂ 0) _x CR ³ R ⁴ (OCH ₂ CH ₂₎ _y OR ^2, in which R ³ and R ⁴ are H, and the subscripts x and y are independently from each other assume values from 1 to 40, preferably from 1 to 15.

Especially preferred particular compounds of the general formula R - 0 (CH ₂ CH ₂ 0) _x CR ³ R ⁴ (OCH ₂ CH ₂₎ _y OR ^2, in which the radicals R and R ² are independently saturated alkyl groups having 4 to 14 carbon atoms and the indices x and y independently of one another assume values of 1 to 15 and in particular of 1 to 12.

Preference is furthermore given to those compounds of the general formula R - O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which one of the radicals R and R ^{2 is} branched. Very particularly preferred compounds of the general formula R - 0 (CH ₂ CH ₂ 0) _x CR ³ R ⁴ (OCH ₂ CI l ₂₎ _y OR ^2, in the accept the indices x and y are independently values 8-12 ,

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 Heresten II procedure exist

Commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which may result in both the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation averages and resulting broken numbers.

Of course, the aforementioned nonionic surfactants can not only be used as

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

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

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

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

Rinse aids according to the invention are preferably liquid and have an acidic pH, preferably a pH of from 3 to 6. Rinse aids according to the invention comprise, in addition to the at least one nonionic surfactant and in addition to the at least one anionic surfactant having at least one sulfate or sulfonate group preferably at least one acidifying agent. As Acidifizierungsmittel both inorganic acids and organic acids can be used. Preferred organic acids are the solid mono-, oligo- and polycarboxylic acids. Particularly preferred organic acids to be used are acetic acid, Citric, tartaric, succinic, malonic, adipic, maleic, fumaric, glutaric, oxalic, polyacrylic and mixtures thereof. Organic sulfonic acids such as sulfamic acid are also usable. The acidifying agent is preferably used in amounts of from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.4 to 8.0% by weight, in rinse aids according to the invention.

Dishwashing agents according to the invention comprise, in addition to the at least one nonionic surfactant and in addition to the at least one anionic surfactant having at least one sulfate or sulfonate group, at least one further compound selected from phosphonates, MGDA and GLDA.

As the phosphonate compound is preferably a hydroxyalkane and / or

Aminoalkanephosphonat used. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. Phosphonates are in

agents according to the invention preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the dishwashing detergent.

MGDA (methylglycinediacetic acid) and GLDA (glutamic acid-N, N-diacetic acid) are used in automatic dishwasher detergents according to the invention preferably in amounts of from 5 to 60% by weight, in particular in amounts of from 10 to 40% by weight.

Dishwashing processes according to the invention are preferably carried out at a liquor temperature below 60 ° C., preferably below 50 ° C. In a preferred embodiment, the dishwashing process takes a maximum of 90 minutes, in particular a maximum of 75 minutes, more preferably a maximum of 60 minutes. In particular embodiments this takes

Dishwashing process maximum 50, 40 or 30 minutes.

The automatic dishwashing compositions according to the invention are preferably in the form of a shaped body, in particular a compactate, in particular a tablet. However, they may also be present in combination with other forms of supply, in particular in combination with solid forms such as powders, granules or extrudates or in combination with liquid formulations based on water and / or organic solvents.

The shaped body may, for example, also be a granulate which is contained in a bag or a casting mold. Inventive agents can be formulated as single-phase or multi-phase products. Machine dishwashing detergents with one, two, three or four phases are particularly preferred. Machine dishwashing detergents, characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred. Particularly preferred are in particular two- or multi-phase tablets, for example

Two-layer tablets, in particular two-layer tablets with a trough and a molded body located in the trough.

Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.

The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units on the

Dosing of a dishwasher is guaranteed. 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 ones

In a preferred embodiment, metering units have a water-soluble coating.

Inventive moldings contain in a preferred embodiment

Polyvinylpyrrolidone particles. These particles facilitate, inter alia, the disintegration of the moldings and serve insofar as disintegration aids or tablet disintegrating agents. It has been found to be particularly advantageous according to the invention, polyvinylpyrrolidone particles having an average particle diameter of 100 to 150 μιη, in particular with a middle

Particle diameter of 1 10 to 130 μιη, use.

The term "average particle diameter" or "average diameter" is meant ₅₀ particle diameter in the present invention, the volume mean D, which can be determined by conventional methods. The volume average D ₅₀ particle diameter is that point in the particle size at which 50 % By volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter

Particle diameters can be determined in particular by means of dynamic light scattering, which are usually carried out on dilute suspensions containing, for example, from 0.01 to 1% by weight of particles. Particularly preferably, the PVP particles not only have an average particle diameter of 100 to 150 μιη, in particular from 1 10 to 130 μιη, but beyond that lies

Particle size of the particles used preferably completely in the specified intervals. This is ensured by using grain size fractions with the indicated particle sizes obtained by a sieving process.

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

The effect of disintegrants is usually that they increase their volume upon ingress of water, whereby on the one hand increases the intrinsic volume (swelling), but on the other hand by the release of gases, a pressure can be generated, which can disintegrate the tablet into smaller particles , In addition or as an alternative to the PVP particles, further disintegrants may also be contained in moldings according to the invention, for example

Carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their derivatives as well as alginates or casein derivatives. Furthermore, gas-evolving effervescent systems can also be used as further disintegrants. preferred

Effervescent systems consist of at least two components which react with one another to form gas, for example from alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution. An acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.

The further disintegration aids are, if used, preferably in amounts of 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-% and in particular 0.5 to 2 wt .-%, each based on the total weight of desintegrationshilfsmittelhaltigen agent used.

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

The production of the shaped bodies according to the invention, in particular of the detergent tablets, preferably takes place in a manner known to the person skilled in the art by pressing more particulately

Starting materials. To prepare the tablets, the premix is compressed in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tableting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection. The tabletting is preferably carried out on so-called rotary presses. When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. The minimization of

Weight variations can be achieved in the following ways:

Use of plastic inserts with small thickness tolerances

Low number of revolutions of the rotor

Big filling shoes

Tuning of the filling paddle speed to the speed of the rotor

Filling shoe with constant powder height

Decoupling of filling shoe and powder template

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

According to the invention, it has surprisingly been found that granules used according to the invention for producing the shaped bodies can be pressed particularly well. Thus, compacts having a hardness in the range from 150 to 250 N, in particular in the range from 200 to 230 N, which in addition is a particularly good one, can preferably be obtained by using a pressing force of 40 to 65 kN, more preferably 48 to 60 kN Have trickle behavior. The granules can thus preferably be pressed with relatively low pressing force into compact materials having a relatively high hardness, which moreover preferably have a very good trickling behavior. Accordingly, it is conversely advantageous for the production of compact materials of lower hardness preferably a lower pressing force must be used, as for the production of conventional compactates.

Automatic dishwashing detergents according to the invention contain as further constituent in a preferred embodiment at least one anionic polymer. Preferred anionic polymers here are the copolymeric polycarboxylates and the copolymeric polysulfonates.

The proportion by weight of the anionic polymer in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is from 0.1 to 20% by weight, preferably from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight. % and in particular from 4 to 14 wt .-%. Machine dishwashing detergents according to the invention, characterized in that the copolymeric anionic polymer is selected from the group of hydrophobically modified polycarboxylates and polysulfonates is a particularly preferred object, as represented by the hydrophobic

Modification of the anionic copolymers an improvement of the rinse aid and

Drying properties of these agents can be achieved with low deposit formation.

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

Preferred copolymeric polysulfonates contain sulfonic acid group-containing (s)

Monomer (s) at least one monomer from the group of unsaturated carboxylic acids.

Unsaturated carboxylic acid (s) used are / are unsaturated carboxylic acids of the formula R (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12

Carbon atoms, 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.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid,

Maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

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

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

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , - CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH ( CH ₃ ) -CH ₂ -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized

Sulfonsäuregruppenhaltigen copolymers is inventively preferred.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the share of Carboxylic acid-containing monomers 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred automatic dishwasher 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 .

In another preferred embodiment, the copolymers include besides

Carboxyl-containing monomer and sulfonic acid-containing monomer further at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.

Automatic dishwashing detergent, characterized in that the automatic dishwashing detergent comprises as anionic copolymer a copolymer comprising

i) carboxylic acid group-containing monomer (s)

ii) sulfonic acid group-containing monomer (s)

iii) nonionic monomer (s)

contains are preferred according to the invention.

As nonionic monomers are preferably monomers of the general formula

R (R ² ) C = C (R ³ ) -XR ⁴ used, in which R to R ^{3 are} independently -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group selected is from -CH ₂ -, -C (0) 0- and -C (0) -NH-, and R ^{4 is} a straight or branched chain saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, a Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (methyl) acrylamide, acrylic acid-2 Ethylhexyl ester, 2-ethylhexyl methacrylate, A / - (2-ethylhexyl) acrylamide, octyl acrylate, octyl methacrylate, A / - (octyl) acrylamide, acryloyl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, A / - (stearyl ) acrylamide, behenyl acrylate, methacrylic acid behenyl ester and A / - (behenyl) acrylamide or mixtures thereof.

Dishwashing agents according to the invention furthermore preferably contain further builder (s) and / or enzyme (s) to ensure their cleaning action.

As a further constituent, machine dishwashing detergents according to the invention preferably comprise one or more further builders besides MGDA, GLDA and / or the phosphonates. The proportion by weight of these further builders in the total weight of automatic dishwashing detergents according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight. These builders include in particular carbonates, phosphates, citrates, organic cobuilders and silicates.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of from 2 to 30 wt .-%, preferably from 4 to 28 wt .-% and in particular from 8 to 24 wt .-%, each based on the weight of the automatic dishwashing detergent.

Preference is also the use of phosphate. Among the large number of commercially available phosphates, the alkali metal phosphates have, with particular preference of pentasodium or. Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) in the washing and

Detergent industry the biggest importance.

Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which one

Metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 ₄ can distinguish in addition to higher molecular weight representatives. The phosphates combine several advantages: they act as

Alkaline carriers, prevent limescale deposits on machine parts or Kalkinkrustationen in tissues and also contribute to the cleaning performance.

According to the invention particularly preferred phosphates are pentasodium triphosphate, Na ₅ P3O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₀ (potassium tripolyphosphate). In accordance with the invention, the

Sodium potassium tripolyphosphates.

If phosphates are used as washing or cleaning substances in automatic dishwasher detergents in the context of the present application, these contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or

Pentakaliumtriphosphat (sodium or potassium tripolyphosphate), in amounts of 5 to 60 wt .-%, preferably from 15 to 45 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the automatic dishwashing detergent.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and 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. 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), if such use is not objectionable for ecological reasons, and mixtures thereof. 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. Machine dishwashing detergents, characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight citrate, are preferred according to the invention.

The citrates, like the phosphates, are preferably used in combination with carbonates and / or bicarbonate. Preferred automatic dishwasher detergents are therefore characterized by a builder combination of phosphate and carbonate / bicarbonate or of citrate and carbonate / bicarbonate (see Tables 1a and 1b below). Of course, however, builder combinations of phosphate, citrate and carbonate / bicarbonate can be realized.

Particularly preferred automatic dishwashing detergents are characterized in that the dishwashing detergent contains at least two builders from the group of the phosphates, carbonates and citrates, the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably from 5 to 80% by weight, preferably 15 to 75 wt .-% and in particular 30 to 70 wt .-% is. The combination of two or more builders The above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwasher detergents according to the invention.

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

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

The content of the automatic dishwashing agents on (homo) polymeric polycarboxylates n is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.

Inventive automatic dishwashing agents as a builder crystalline schichtformige silicates of general formula NaMSi _x 0 _{2x +} i ^■ y H ₂ 0 wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.

In preferred machine dishwashing detergents according to the invention, the content of silicates, based on the total weight of the automatic dishwashing detergent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight. Particularly preferred automatic dishwasher detergents according to the invention are silicate-free.

In addition to the abovementioned builders, the agents according to the invention may contain alkali metal hydroxides. These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of

Detergent used. Alternative automatic dishwashing detergents are free from

Alkali metal hydroxides.

Dishwashing agents according to the invention preferably comprise enzyme (s) as a further constituent. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle 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 those improved for use in detergents and cleaners

Further developments of the aforementioned amylases. Furthermore, the a-amylase from 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, those originally from Humicola lanuginosa

(Thermomyces lanuginosus) available, or further developed lipases, especially those with the amino acid exchange D96L.

Furthermore, enzymes can be used which are termed hemicellulases

be summarized. These include, for example, mannanases, xanthanlyases,

Pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-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 preferable to add organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the

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

Washing or cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or 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 with a water, air and / or

Chemical-impermeable protective layer is coated. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Preferably used according to the invention

Protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and

in particular between 0.8 and 10% by weight of the enzyme protein. Particular preference is given to those automatic dishwashing detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations ,

Particularly preferred machine rinse aid according to the invention have a pH of 3 to 6 and contain

a) from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight, of anionic surfactant (s) having at least one sulfate or sulfonate Group, preferably selected from alkyl sulfates, alkyl sulfonates and alkylbenzenesulfonates;

b) 0.1 to 20 wt .-%, preferably 0.5 to 15 wt .-%, in particular 2.5 to 10 wt .-% of nonionic (s) surfactant (s) comprising a linear or branched alkyl radical having 10 to 20, preferably 12 to 18, carbon atoms and 2 to 30, preferably 4 to 15, ethylene oxide units and optionally up to 5, in particular up to 2, propylene oxide units and up to 5, in particular up to 2, butylene oxide units;

c) optionally 0.1 to 12 wt .-%, preferably 0.2 to 10 wt .-%, Acidifizierungsmittel, in particular selected from organic acids.

Particularly preferred machine dishwasher detergents according to the invention contain

a) 0.1 to 20 wt .-%, preferably 0.5 to 15 wt .-%, in particular 2.5 to 10 wt .-%, anionic (s) surfactant (s) selected from alkyl sulfates, alkyl sulfonates and

Alkylbenzenesulfonates, in particular from Ci ₂ -Ci ₈ fatty alcohol sulfates, secondary d ₃ - Ci ₇ -Alkansulfonaten and linear C ₈ -C ₈ alkylbenzenesulfonic acids;

b) 0.1 to 20 wt .-%, preferably 0.5 to 15 wt .-%, in particular 2.5 to 10 wt .-% of nonionic (s) surfactant (s) of the general formula

R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ²

in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20,

Carbon atoms or mixtures thereof, and x and z are values between 0 and 40 and y is a value of 15 to 120, especially 20 to 80;

c) at least one compound selected from MGDA, GLDA and phosphonate compounds in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, wherein the phosphonate compound is in particular selected from

Hydroxyalkane and / or Aminoalkanphosphonaten, particularly preferably from HEDP, EDTMP and DTPMP.

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

Machine dishwashing detergents according to the invention may contain a bleaching agent as further constituent, with oxygen bleaches being preferred. Among the compounds which serve as bleaches and deliver in water H ₂ O ₂ , the sodium percarbonate, the

Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents 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 bleaching agents are the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, more preferably a coated sodium percarbonate. The weight fraction of the bleaching agent, based on the total weight of the washing or cleaning agent, is in preferred

Embodiments between 2 and 30 wt .-%, preferably between 4 and 20 wt .-% and in particular between 6 and 15 wt .-%.

As bleach activators, the dishwasher detergents according to the invention can be used

Bleach activators included. These compounds give under perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated carbon atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylene-diamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

Automatic dishwashing detergent, characterized in that it is a bleach activator bleach activator from the group of acetylated amines, preferably tetraacetylenediamine (TAED), are preferred according to the invention. These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 10% by weight, especially 0.5 to 8% by weight and more preferably 1, 0 to 6 Wt .-%, used.

In addition or as an alternative to the conventional bleach activators, the

Machine dishwashing detergents according to the invention preferably at least one Bleach catalyst. 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 included. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). suitable

Manganese complexes are, for example, [Mn ^m ₂ (-O) i (-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) ₂ , [ηη "'ηη' ^v (μ-O) ₂ (μ-OAc) ₁ (TACN) ₂ ] (BPh ₄ ) ₂ , [Mn ^ -O) ₆ (TACN) ₄ ] (CI0 ₄ ) ₄ , [Mn ^I " ₂ (-0) ₁ (-OAc) ₂ (Me-TACN) ₂ ] (CI0 ₄ ) 2, [Mn " ¹ Mn ^lv (-O) ₁ (-OAc) ₂ (Me-TACN) ₂ ] (CI0 ₄ ) 3, [Mn ' ^v ₂ (-0) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ and [Μη ' ^ν ₂ (μ-0) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (0) CH ₃ ).

Automatic dishwashing detergent, characterized in that it further comprises a

Bleaching catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1, 4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN) or 1, 2, 4, 7 tetramethyl-1, 4, 7-triazacyclononane (Me ₄ -TACN) are preferred according to the invention, since by the aforementioned

Bleaching catalysts, in particular the cleaning result can be significantly improved.

The aforementioned bleach-enhancing transition metal complexes, in particular with the

Central atoms Mn and Co are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0.01% by weight to 0, 30 wt .-%, each based on the total weight of

bleach catalyst-containing agent used. In special cases, however, more can be done

Bleaching catalyst can be used.

The active substance combinations described above are particularly suitable for cleaning dishes in automatic dishwashing processes. A further subject of the present application is therefore a method for cleaning dishes in a dishwasher using a dishwasher detergent according to the invention, wherein the dishwasher detergent preferably during the passage of a dishwashing program, before the beginning of Main wash or in the course of the main wash cycle in the interior of a

Dishwasher is metered. The metering or the entry of the agent according to the invention in the interior of the dishwasher can be done manually, but preferably the means by means of the metering chamber of the dishwasher in the interior of the

Dishwasher dosed. In the course of the cleaning process preferably no additional water softener and no additional rinse aid in the interior of the

Dishwasher dosed.

A kit for a dishwasher, comprising

a) a machine dishwashing detergent according to the invention;

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

The dishwasher detergents according to the invention show their advantageous

Cleaning properties, especially in low-temperature cleaning and short-term cleaning procedures. Preferred dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C., and / or a time of less than 90 minutes, preferably less than 60 minutes, in particular less than 45 Minutes.

Some exemplary formulations for preferred machine according to the invention

Dishwashing detergent tablets can be taken from the following tables:

Ingredient Recipe 1 Recipe 2 Recipe 3 Recipe 4

[Wt%] [wt%] [wt%] [wt%]

Tripolyphosphate 5 to 50 15 to 40 -

Citrate _* 5 to 40 15 to 30

Carbonate 2 to 45 2 to 35 2 to 45 2 to 35

Phosphonate 0.1 to 10 0.5 to 8 0, 1 to 10 0.5 to 8

Enzyme ^** 0.2 to 10 0.2 to 10 0.5 to 8 0.5 to 8

Nonionic surfactant A ¹ 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10

LAS, SAS or FAS 0.5 to 20 2.5 to 10 0.5 to 20 2.5 to 10

Mise Add 100 Add 100 Add 100 Add 100 Ingredient Recipe 5 Recipe 6 Recipe 7 Recipe 8

[Wt%] [wt%] [wt%] [wt%]

Tripolyphosphate 5 to 50 15 to 40 -

Citrate _* 5 to 40 15 to 30

Carbonate 2 to 45 2 to 35 2 to 45 2 to 35

Phosphonate 0.1 to 10 0.5 to 8 0, 1 to 10 0.5 to 8

Enzyme ^** 0.2 to 10 0.2 to 10 0.5 to 8 0.5 to 8

Nonionic surfactant A ^la 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10

LAS, SAS or FAS 0.5 to 20 2.5 to 10 0.5 to 20 2.5 to 10

Mise Add 100 Add 100 Add 100 Add 100

Ingredient Recipe 13 Recipe 14 Recipe 15 Recipe 16

[Wt%] [wt%] [wt%] [wt%]

Tripolyphosphate 5 to 50 15 to 40 -

Citrate _* 5 to 40 15 to 30

Carbonate 2 to 45 2 to 35 2 to 45 2 to 35

Phosphonate 0.1 to 10 0.5 to 8 0, 1 to 10 0.5 to 8

Enzyme ^** 0.2 to 10 0.2 to 10 0.5 to 8 0.5 to 8

Nonionic surfactant A '0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10

Anionic copolymer C ^J 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18

LAS, SAS or FAS 0.5 to 20 2.5 to 10 0.5 to 20 2.5 to 10

Mise Add 100 Add 100 Add 100 Add 100 Ingredient Recipe 17 Recipe 18 Recipe 19 Recipe 20

[Wt%] [wt%] [wt%] [wt%]

Tripolyphosphate 5 to 50 15 to 40 -

Citrate _* 5 to 40 15 to 30

Carbonate 2 to 45 2 to 35 2 to 45 2 to 35

Phosphonate 0.1 to 10 0.5 to 8 0, 1 to 10 0.5 to 8

Enzyme ^** 0.2 to 10 0.2 to 10 0.5 to 8 0.5 to 8

Nonionic surfactant A ¹ 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10

Nonionic surfactant B 1 to 10 1 to 10 1 to 10 1 to 10

Anionic copolymer C ^J 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18

LAS, SAS or FAS 0.5 to 20 2.5 to 10 0.5 to 20 2.5 to 10

Mise Add 100 Add 100 Add 100 Add 100

Ingredient Recipe 25 Recipe 26 Recipe 27 Recipe 28

[Wt%] [wt%] [wt%] [wt%]

Tripolyphosphate 5 to 50 15 to 40 -

Citrate _* 5 to 40 15 to 30

Carbonate 2 to 45 2 to 35 2 to 45 2 to 35

Phosphonate 0.1 to 10 0.5 to 8 0, 1 to 10 0.5 to 8

Nonionic surfactant A ^la 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10

Nonionic surfactant B ^a 1 to 10 1 to 10 1 to 10 1 to 10

Anionic copolymer C ^Yes 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 LAS, SAS or FAS 0.5 to 20 2.5 to 10 0.5 to 20 2.5 to 10

Mise Add 100 Add 100 Add 100 Add 100

Ingredient Recipe 29 Recipe 30 Recipe 31 Recipe 32

[Wt%] [wt%] [wt%] [wt%]

Tripolyphosphate 5 to 50 15 to 40 -

Citrate _* 5 to 40 15 to 30

Carbonate 2 to 45 2 to 35 2 to 45 2 to 35

Phosphonate 0.1 to 10 0.5 to 8 0, 1 to 10 0.5 to 8

Nonionic surfactant A ^la 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10

Nonionic surfactant B ¹⁰ 1 to 10 1 to 10 1 to 10 1 to 10

Anionic copolymer C ⁰³ 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18

LAS, SAS or FAS 0.5 to 20 2.5 to 10 0.5 to 20 2.5 to 10

Mise Add 100 Add 100 Add 100 Add 100 a nonionic surfactant A of the general formula

R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² in which

R is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x and z represent values between 0 and 40 and y represents a value of at least 15 stands;

a nonionic surfactant A of the general formula R 0 [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R ^{2 is} a linear one or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and y is a value between 15 and 80;

a nonionic surfactant B of the general formula R 0 (AlkO) _x M (OAlk) _y OR ² in which

Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms;

- x and y independently for values between 1 and 70; and

M is an alkyl radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms

a nonionic surfactant B of the general formula R -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ^{2 is} used, in of the R, R and R ² independently represent an alkyl or alkenyl radical having 6 to 22 carbon atoms;

- x and y independently represent values between 1 and 40

^{2b is} a nonionic surfactant B of the general formula R -0 (CH ₂ CH ₂ 0) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y O-R ^{2 is} used in the

- x and y independently represent values between 1 and 40

^{3 is} an anionic polymer C from the group of copolymeric polycarboxylates and

copolymeric polysulfonates

3 ^{a is} an anionic polymer C comprising

i) carboxylic acid group-containing monomer (s)

ii) sulfonic acid group-containing monomer (s)

iii) optionally nonionic monomer (s).

^* "-" means: the recipe is free of this ingredient

LAS is a linear C8-C18 alkyl benzene sulfonic acid, SAS is a secondary C13-C17 alkane sulfonate and FAS for a C ₂ -C ₈ fatty alcohol sulfate.

embodiment

Example 1: Rinse performance

The rinse performance of a commercial automatic dishwashing detergent tablet containing a terminal-capped nonionic surfactant to which different anionic surfactants had been added was tested. For comparison, the rinse performance of the same dishwashing detergent without anionic surfactant was checked.

The dishwashing process was carried out in the dishwasher Miele G698SC Plus 3 (program: normal, 50 ° C, water hardness 21 ° dH). The dishwasher tablet was added to the dosing device before the start of the cleaning program. The second to fourth rinse cycles were each scored on a scale of 1 to 10, where "10" means "no drops" and "1" means "many large drops". The rinse results are shown in the following table:

Sulfopon 1214G is a C12-C18 fatty alcohol sulfate (FAS), while Marlon ARL is a Ci2-Ci8 fatty alcohol sulfate (FAS).

The addition of anionic surfactants of the sulfate and sulfonate type leads to a significant improvement in the rinse performance. Foaming of the anionic surfactant in the

Dishwasher is obviously so small that the cleaning performance is not adversely affected.

Claims

claims

1. Machine rinse aid, characterized in that it contains at least one anionic surfactant having at least one sulfate or sulfonate group and at least one nonionic surfactant.

2. Machine dishwashing detergent, characterized in that there is at least one

anionic surfactant having at least one sulfate or sulfonate group, at least one nonionic surfactant and at least one compound selected from phosphonates, MG DA and GLDA.

3. Composition according to claim 1 or 2, characterized in that the anionic surfactant is selected from alkyl sulfates, alkyl sulfonates and alkylbenzenesulfonates and preferably in an amount of 0, 1 to 20 wt .-%, particularly preferably 0.5 to 15 wt. %, in particular 2.5 to 10 wt .-%, is included.

4. Composition according to one of the preceding claims, characterized in that the nonionic surfactant is selected from nonionic surfactants of the general formula R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH ( CH ₃ ) 0] _z CH ₂ CH (OH) R ² , in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof, and x and z are values between 0 and 40 and y is a value of 15 to 120, in particular from 20 to 80;

and from nonionic surfactants of the general formula R 0 (AlkO) _x M (OAlk) _y OR ² , where R and R ² independently of one another are a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk is a branched or unbranched alkyl radical having 2 to 4, preferably 2, carbon atoms; x and y independently represent values between 1 and 70; and

M is an alkyl radical selected from the group consisting of CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms;

and the nonionic surfactant is preferably contained in an amount of 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, especially 2.5 to 10% by weight.

5. Machine dishwashing detergent according to one of claims 2 to 4, characterized

characterized in that the phosphonate compound is selected from hydroxyalkane and / or aminoalkane phosphonates, particularly preferably from HEDP, EDTMP and DTPMP, and preferably in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight.

6. Machine dishwashing process, characterized in that a machine rinse aid or machine dishwashing detergent according to one of the preceding claims is used.

7. Use of a combination of at least one anionic surfactant with at least one sulfate or sulfonate group and at least one nonionic surfactant for rinsing dishes in a machine cleaning process, in particular for reducing the formation of drops (spotting).

8. Embodiment according to claim 7, characterized in that the surfactants are used in the form of a rinse aid or dishwashing detergent.

9. The embodiment according to claim 8, characterized in that the dishwashing detergent contains at least one detergent-active ingredient selected from phosphonates, other builders, in particular from salts of tripolyphosphate, carbonic acid and / or citric acid, bleaches, bleach activators, bleach catalysts, polymers and enzymes.

10. Embodiment according to claim 9, characterized in that it is anionic

Polymer in an amount of 0, 1 to 20 wt .-%, preferably from 0.5 to 18 wt .-%, wherein the anionic polymer is preferably selected from the group of copolymers, comprising

i) monomer (s) containing carboxylic acid groups,

ii) sulfonic acid group-containing monomer (s) and

iii) optionally nonionic monomer (s).