WO2013010701A1

WO2013010701A1 - Rinsing and cleaning agent

Info

Publication number: WO2013010701A1
Application number: PCT/EP2012/060079
Authority: WO
Inventors: Paula Barreleiro; Stefanie Juntermanns; Dorota SENDOR-MÜLLER; Thomas Eiting
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2011-07-15
Filing date: 2012-05-30
Publication date: 2013-01-24
Also published as: DE102011079260A1; EP2732017A1

Abstract

The invention relates to polymers comprising a) at least one monomer according to formula (I), where R₁ and R₄ stand for hydrogen or C_1-6-alkyl, independently of each other; R₂ and R₃ stand for C_1-6-alkyl, hydroxy-C_1-6-alkyl or amino-C_1-6-alkyl, independently of each other; x and y stand for a value from 1 to 3, independently of each other; and X^- stands for a counterion; b) at least one hydrophilic monomer which carries at least one acid group; and c) at least one hydrophilic, non-ionic monomer; wherein, according to the invention, said polymers have proven to be suitable rinsing agents, in particular for reducing spot build-up on dishes.

Description

Rinse aid and cleaning agent

The present application relates to agents for rinsing and for cleaning dishes. In particular, this application relates to liquid means for machine dishwashing and their use for rinsing and for cleaning dishes.

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

In addition to improving the cleaning performance of these compositions, one of the main objectives of the machine-washing machine manufacturers is also to improve the rinse-through performance of these products, with a recent focus on cleaning performance and rinsing performance in low-temperature cleaning cycles or in reduced-water cleaning cycles becomes.

In order to increase the rinsing performance, new ingredients, for example more active surfactants or polymers, have preferably been added to the cleaning agents. 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.

This application was therefore based on the object to provide a detergent for dishwashing, which is characterized compared to conventional Geschirreinigungsmitteln, preferably in low-temperature cleaning operations and / or cleaning operations with low water consumption, by improved rinse performance, in particular by effectively preventing staining ,

Surprisingly, it has been found according to the invention that polymers containing

a) at least one monomer according to formula (I)

H ₂ C = X ^"

R-ι and R ₄ is hydrogen or CI_ ₆ alkyl, independently from each other;

R ₂ and R ₃ are each independently CI_ ₆ alkyl, hydroxy-alkyl or amino CI_ ₆

Ci.6 alkyl;

x and y independently represent a value of 1 to 3; X ^"stands for a counterion;

b) at least one hydrophilic monomer bearing at least one acid group; c) at least one hydrophilic nonionic monomer;

provide very good rinse results and in particular reduce the formation of stains.

The use of such polymers in detergents and cleaners is already described in the published patent applications WO 2010/107554 and WO 2010/000629. However, only the suitability of these polymers as soil release agents and to accelerate the drying of the washed dishes is disclosed here.

A first object of the present invention is therefore the use of polymers containing

a) at least one monomer according to formula (I)

(I)

in which

Ri and R _{4 are} independently hydrogen or C- |. ₆ alkyl;

Ci- ₆ alkyl;

x and y independently represent a value of 1 to 3; X ^"stands for a counterion;

as a rinse aid, especially in a machine dishwashing, especially to reduce the formation of deposits and / or stains on dishes. A further subject of the present invention is therefore also a preferably automatic dishwashing process, characterized in that in at least one process step such a polymer is used as a rinse aid, in particular to avoid the formation of deposits and / or stains.

According to the invention, it has surprisingly been found that the effect observed according to the invention can be achieved particularly well by a combination product which contains a packaging agent and at least two separate liquid washing or cleaning agents present in this packaging means.

Another object of the present invention is therefore also a combination product comprising a packaging means and at least two, preferably exactly two, located in this packaging means, separate liquid detergent or cleaning agent A and B of the composition:

A: - 10 to 75% by weight of builder (s);

- 0, 1 to 10 wt .-% enzyme (s);

24.9 to 89.9% by weight of water; and

B: - 10 to 75% by weight of builder (s);

- 25 to 90 wt .-% water;

wherein the liquid detergent A has a pH (20 ° C) between 6 and 9 and the liquid detergent B has a pH (20 ° C) between 9 and 14, characterized in that at least one of the washing or cleaning agents A and B contains a polymer comprising the following monomers:

a) at least one monomer according to formula (I)

(I)

in which

Ri and _R4 independently of one another are hydrogen or C _-6 alkyl;

R ₂ and R ₃ are each independently C _-6 alkyl, hydroxy-C |. ₆ -alkyl or amino-C- |. ₆ -alkyl;

x and y independently represent a value of 1 to 3;

X ^"stands for a counterion;

b) at least one hydrophilic monomer bearing at least one acid group;

c) at least one hydrophilic nonionic monomer.

The subject matter of the present invention is therefore likewise a preferably automatic dishwashing process in which a combination product according to the invention is used comes, in particular to reduce the formation of deposits and / or stains on the dishes.

The present application further relates to the use of a combination product according to the invention as a cleaning and rinse aid for hard surfaces, especially for reducing the formation of deposits and / or stains on dishes, in particular in automatic dishwashing.

The proportion of monomer (a) in the polymer is preferably 10-30%, more preferably 15-25%, based on the total number of monomers.

The hydrophilic monomer (b) according to the invention is preferably acrylic acid or methacrylic acid. The proportion of monomer (b) in the polymer is preferably less than 15%, particularly preferably less than 10%, in particular 3-6%, based on the total number of monomers.

The hydrophilic non-ionic monomer (c) is according to the invention preferably is optionally monosubstituted on the nitrogen atom or disubstituted by CI_ ₆ alkyl substituted acrylamide, being employed in a preferred embodiment of unsubstituted acrylamide. The proportion of the monomer (c) on the polymer is preferably at least 50%, particularly preferably at least 65%, in particular 75-85%, based on the total number of monomers.

The liquid cleaning agents A and B present separately from one another in the combination products according to the invention contain builders in addition to other ingredients which are active in washing or cleaning. The builders include, in particular, the zeolites, amorphous silicates, crystalline phyllosilicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

Among the large number of commercially available phosphates, technically particularly important phosphates in the detergents and cleaners industry are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P 3 O-10 (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used according to the invention.

If phosphates are used as washing or cleaning substances in the liquid detergents A and / or B in the context of the present application, preferred combination products contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate), in amounts of 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 respective cleaning agent A or B, are included.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances 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. A combination product containing citric acid or a salt of citric acid, wherein the weight fraction of citric acid or the salt of citric acid, based on the total weight of the combination product, between 0.2 and 12 wt .-%, preferably between 0.2 and 8 wt. % and in particular between 0.2 and 6 wt .-%, is preferred according to the invention.

Another important class of phosphate-free builders are aminocarboxylic acids and / or their salts. Combination products containing methylglycinediacetic acid or its salts and / or glutamic diacetic acid or its salts, wherein the weight fraction of MGDA or GLDA, based on the total weight of the combination product, is between 0, 2 and 12 wt .-%, preferably between 0.2 and 8 wt .-% and in particular between 0.2 and 6 wt .-%, are inventively preferred.

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

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

As a further component, the combination products according to the invention contain to increase the washing or cleaning performance enzymes. These include in particular proteases, amylases, lipases, cutinases, hemicellulases, which include in particular mannanases, xanthan lyases, pectin lyases, pectin esterases, pectate lyases, xyloglucanases, pullulanases and β-glucanases, cellulases 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 and cleaners, 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 usable amylases 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, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948).

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.

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

The proportion by weight of the enzymes in the total weight of the liquid cleaning agent A can be 0, 1 to 10 wt .-%. In particularly preferred combination products, the proportion by weight of the enzyme in the total weight of the cleaning agent A is from 0.2 to 9% by weight and in particular from 0.5 to 8% by weight.

Although the liquid detergent B may of course also contain enzymes, it is preferred that the enzyme content of the detergent B be less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight. and in particular less than 0.1 wt .-% is. Particularly preferred combination products are characterized in that the liquid cleaning agent B contains no enzymes. Preferably, one or more enzymes and / or enzyme preparations, preferably solid or liquid protease preparations and / or amylase preparations are used. In a particularly preferred embodiment, the liquid cleaning agent A comprises a combination of protease and amylase preparations.

The combination products according to the invention preferably contain less than 2% by weight of bleaching agent and may also be free from bleach.

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

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

To adjust the pH values and to improve the cleaning performance, in a further preferred embodiment, the liquid cleaning agents B additionally contain alkali carriers. A further subject of the present application is therefore a combination product comprising a packaging means with two separate receiving chambers, as well as two separate liquid cleaning agents A and B of the composition located in these receiving chambers:

A: - 10 to 75% by weight of builder (s);

- 0, 1 to 10 wt .-% enzyme (s);

24.9 to 89.9% by weight of water; and

B: - 10 to 74.9% by weight of builder (s);

- 0, 1 to 10 wt .-% alkali carrier;

25 to 89.9% by weight of water;

characterized in that the liquid detergent A has a pH (20 ° C) between 6 and 9, while the liquid detergent B has a pH (20 ° C) between 9 and 14, characterized in that at least one of Washing or cleaning agent A and B comprises a polymer comprising the following monomers:

a) at least one monomer according to formula (I)

Ri and _R4 independently represent hydrogen or CI_ ₆ alkyl;

x and y independently represent a value of 1 to 3;

X ^"stands for a counterion;

b) at least one hydrophilic monomer bearing at least one acid group;

c) at least one hydrophilic nonionic monomer.

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

The combination products according to the invention are distinguished not only by a very good rinse aid performance but also by improved cleaning performance on dried-on and / or burnt-on soils on hard surfaces, especially in automatic dishwashing.

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

It has surprisingly been found that the cleaning performance of combination products according to the invention can be improved by the addition of organic solvents. The preferred subject of the present application are therefore furthermore combination products according to the invention in which at least one of the cleaning agents A or B also contains an organic solvent.

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

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

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

Particularly preferred combination products contain, based on the total weight of the combination product, between 0.1 and 10 wt .-%, preferably between 0.5 and 8 wt .-% and in particular between 1, 5 and 6 wt.% Of an organic solvent from the Group of organic amines and alkanolamines. Particularly preferred are combination products whose liquid detergent B, based on the total weight of the detergent B, a weight fraction of an organic solvent from the group of organic amines and alkanolamines between 0, 1 and 10 wt .-%, preferably between 0.5 and 8 wt .-% and in particular between 1, 5 and 6 wt.%, While the weight fraction of organic solvent from the group of organic amines and alkanolamines in the liquid detergent A, based on the total weight of the cleaning agent A, preferably less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt.% And most preferably less than 0.1 wt .-%, and in particular no organic solvent from the group of organic amines and alkanolamines in the cleaning agent A is included.

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

The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art.

These include, for example, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated alcohols or fatty alcohols as well as nonionic surfactants of the amine oxide and fatty acid alkanolamide type.

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 having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene Block polymer blends comprising 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 Mole 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 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 nichionic surfactants of the general formula

R -0- (CH ₂ -CH ₂ -0) - (CH ₂ -C H-0) - (CH ₂ -CH ₂ -0) _r (C H2-C H-0) -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.

In summary, nonionic surfactants are 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 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 preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which are of the formula

R 0 [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ^{2 in} addition to a radical R, which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms , furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where x stands for values between 1 and 90, preferably for values between 40 and 80 and in particular for values between 40 and 60.

Particularly preferred are surfactants of the 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 18 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) 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 are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ - CH ₃ , CH (CH ₃ ) ₂ , but preferably represents -CH ₃ , and x and y independently of one another are 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 may be} selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO ) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO ) (PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

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

R 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.

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 methods II trade products of the formulas mentioned are usually not from an individual representative, but from mixtures, which may result in both the C chain lengths and for the degrees of ethoxylation and degrees of alkoxylation averages and resulting 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 ,

Combination products, characterized in that the washing or cleaning agent A further contains 0.2 to 10 wt .-%, preferably 0.4 to 7 wt .-% and in particular 0.6 to 4 wt .-% nonionic surfactants, according to the invention prefers.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

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

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

Preferred washing or cleaning agents, in particular preferred automatic dishwasher detergents, are characterized in that they contain a polymer a), which monomer units of the formula RR ² C = CR ³ R ⁴ , in which each R, R ² , R ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, Ci. ₃₀ linear or branched alkyl, aryl, aryl substituted Ci. ₃₀ linear or branched alkyl groups, polyalkoyxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 1 1, or salts thereof with the proviso that at least one radical R, R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group having a positive charge.

In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

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

Preferred radicals R and R ⁴ in the above formula are selected from -CH _3, -CH ₂ -CH _3, - CH ₂ -CH ₂ -CH _3, -CH (CH ₃₎ -CH _3, -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

CH - (CH 2) -N ⁺ (CH ₃ ) 2 - (CH ₂ ) -CH = CH

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

Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

R1 HC = CR2-C (0) -NH- _(CH2) -N ⁺ R3R4R5

X ^"

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

For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R is H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

H ₂ C = C (CH ₃ ) -C (O) -NH- (CH ₂ ) _X -N ⁺ (CH ₃ ) 3

X ^" in the case of X = chloride also referred to as MAPTAC (Methyacrylamidopropyl trimethylammonium chloride).

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

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

Preferred usable amphoteric polymers are from the group of alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacryla mid / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and also the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferred zwitterionic polymers originate from the group of acrylamidoalkyltri alkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Particularly preferred amphoteric polymers are selected from the group of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl ( meth) acrylic acid copolymers and their alkali metal and ammonium salts.

Particular preference is given to amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / Alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;

the encapsulation of the polymers by means of water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;

the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.

Preferred combination products contain the abovementioned cationic and / or amphoteric polymers, preferably in amounts of from 0.01 to 8% by weight, based in each case on the total weight of the combination product. Within the scope of the present application, however, preference is given to those combination products in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, more preferably between 0 and 01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the combination product is.

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

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

In the case of the monomers containing sulfonic acid groups, preference is given to 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 one or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH or -COOH or -COOR ⁴ wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO - (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -. Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

H0 ₃ SX- (R ⁶ ) C =C (R ⁷ ) -X-S0 ₃ H in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -

CH ₂ CH ₃ , -CH ₂ CH ₂ Cl-I ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - where n = 0 to 4, - COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -

C (O) -NH-CH (CH ₂ CH ₃ ) -.

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

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R (R ² ) C =C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-S0 ₃ H.

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 sulfonic acid group-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 washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ¹ , preferably from 4000 to 25,000 gmol ¹ and in particular from 5000 to 15,000 gmol ^"1 . Combination products, characterized in that the cleaning agent A and / or the cleaning agent B further based on the total weight of the cleaning agent A or B 0.01 to 15 wt .-%, preferably 0.02 to 12 wt .-% and in particular 0, 1 to 8 wt .-% of one or more washing or cleaning active polymers, are preferred according to the invention.

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

In terms of their performance and storage stability, a number of combination products have proven to be particularly advantageous:

A combination product comprising a packaging means and two separate liquid washing or cleaning agents A and B of the composition in said packaging means:

A: according to the following table

B: according to the following table

characterized in that the liquid cleaning agent A has a pH (20 ° C) between 6 and 9, while the liquid cleaning agent B has a pH (20 ° C) between 9 and 14 and wherein at least one of the cleaning agent A or B, preferably the cleaning agent B, contains a polymer as described above.

Ser. Cleaning Agent A, containing cleaning agent B, containing mer

1 10 to 75% by weight builder (s); 10 to 74.9% by weight builder (s);

0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 10% by weight of alkanolamine

2 10 to 75% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water;

24.9 to 89.9% by weight of water; 0.01 to 15 wt.% Sulfonsäuregruppen- containing polymer

10 to 74.9% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water;

24.9 to 89.8% by weight of water; 0.01 to 15% by weight of sulfonic acid groups 0.01 to 15% by weight of sulfonic acid-containing polymer

Group-containing polymer

From 10% to 75% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water;

24.9 to 89.9% by weight of water; 0.1 to 10% by weight of alkanolamine;

0.01 to 15 wt.% Sulfonsäuregruppen- containing polymer

10 to 74.9% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water;

24.9 to 89.8% by weight of water; 0.1 to 10% by weight of alkanolamine;

0.01 to 15 wt.% Sulfonsäuregrup- 0.01 to 15 wt.% Sulfonsäuregruppen- pen-containing polymer polymer

From 10 to 74.8% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water;

24.9 to 89.7% by weight of water; 0, 1 to 10 wt .-% alkanolamine 0.2 to 10.0 nonionic surfactant

24.9 to 89, 7 wt .-% water; 0.01 to 15% by weight of sulfonic acid group 0.2 to 10.0 nonionic surfactant-containing polymer

10 to 74.7% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water;

24.9 to 89, 6 wt .-% water; 0.01 to 15% by weight sulfonic acid group 0.2 to 10.0 nonionic surfactant; containing polymer

0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer

From 10 to 74.8% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water;

24.9 to 89, 7 wt .-% water; 0.1 to 10% by weight of alkanolamine;

0.2 to 10.0 nonionic surfactant 0.01 to 15 wt.% Sulfonsäuregruppen- containing polymer

10 to 74.7% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water;

24.9 to 89.6% by weight of water; 0.1 to 10% by weight of alkanolamine;

0.2 to 10.0 nonionic surfactant; 0.01 to 15 wt.% Sulfonic acid groups 0.01 to 15 wt.% Sulfonsäuregrup- containing polymer

pen-containing polymer

From 10% to 75% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water;

24.9 to 89.9% by weight of water; 0.1 to 10% by weight of alkali metal hydroxide

24.9 to 89.9% by weight of water; 0.1 to 10% by weight of alkali hydroxide;

0.01 to 15 wt.% Sulfonsäuregruppen- containing polymer

24.9 to 89.8% by weight of water; 0.1 to 10% by weight of alkali hydroxide;

24.9 to 89.7% by weight of water; 0, 1 to 10 wt .-% alkali hydroxide 0.2 to 10.0 nonionic surfactant

24.9 to 89, 7 wt .-% water; 0.1 to 10% by weight of alkali hydroxide;

24.9 to 89.6% by weight of water; 0.1 to 10% by weight of alkali hydroxide;

pen-containing polymer

24.9 to 89.9% by weight of water; 0.1 to 10% by weight of alkanolamine

0.01 to 8 wt .-% cationic and / or amphoteric polymers From 10% to 75% by weight of builder (s); 10 to 74.9% by weight builder (s);

0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water;

0.01 to 8 wt .-% cationic and / or amphoteric polymers

10 to 74.9% by weight of builder (s); 10 to 74.9% by weight builder (s);

0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water;

24.9 to 89.8% by weight of water; 0.01 to 15 wt.% Sulfonic acid groups 0.01 to 15 wt.% Sulfonsäuregrup- containing polymer

pen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers

From 10% to 75% by weight of builder (s); 10 to 74.8% by weight builder (s);

0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water;

24.9 to 89.9% by weight of water; 0.1 to 10% by weight of alkanolamine;

0.01 to 15 wt.% Sulfonsäuregruppen- containing polymer

24.9 to 89.8% by weight of water; 0.1 to 10% by weight of alkanolamine;

0.01 to 8 wt .-% cationic and / or amphoteric polymers

24.9 to 89.7% by weight of water; 0.1 to 10% by weight of alkanolamine

0.2 to 10.0 nonionic surfactant 0.01 to 8 wt .-% cationic and / or amphoteric polymers

0.01 to 8 wt .-% cationic and / or amphoteric polymers

24.9 to 89, 6 wt .-% water; 0.01 to 15% by weight of sulfonic acid group 0.2 to 10.0 nonionic surfactant; containing polymer

0.01 to 15 wt.% Of sulfonic acid group 0.01 to 8 wt.% Of cationic and / or pen-containing polymer amphoteric polymers

24.9 to 89, 7 wt .-% water; 0.1 to 10% by weight of alkanolamine;

0.01 to 8 wt .-% cationic and / or amphoteric polymers

24.9 to 89.6% by weight of water; 0.1 to 10% by weight of alkanolamine;

pen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers

24.9 to 89.9% by weight of water; 0.1 to 10% by weight of alkali hydroxide;

0.01 to 15 wt.% Sulfonsäuregruppen- containing polymer

0.01 to 8 wt .-% cationic and / or amphoteric polymers

24.9 to 89.8% by weight of water; 0.1 to 10% by weight of alkali hydroxide;

0.01 to 8 wt .-% cationic and / or amphoteric polymers

24.9 to 89.7% by weight of water; 0, 1 to 10 wt .-% alkali hydroxide 0.2 to 10.0 nonionic surfactant 0.01 to 8 wt .-% cationic and / or amphoteric polymers

31 10 to 74.8% by weight builder (s); 10 to 74.8% by weight builder (s);

0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89, 7 wt .-% water; 0.1 to 10% by weight of alkali hydroxide;

0.01 to 8 wt .-% cationic and / or amphoteric polymers

32 10 to 74.7% by weight builder (s); 10 to 74.8% by weight builder (s);

0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.6% by weight of water; 0.1 to 10% by weight of alkali hydroxide;

pen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers

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

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

In order to achieve the desired viscosity of the washing and cleaning agent form according to the invention (solubility, washing and cleaning performance, stability of the gel), thickening agents of known type can be added to the compositions.

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

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

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

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

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

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

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

In a preferred embodiment, the inventive method for machine cleaning dishes in a dishwasher is characterized in that in the course of a cleaning program, which includes a prewash and a cleaning cycle, in this cleaning cycle on two consecutive times t1 and t2 two liquid cleaning agents A and B of the composition:

A: - 10 to 75% by weight of builder (s);

- 0, 1 to 10 wt .-% enzyme (s);

24.9 to 89.9% by weight of solvent; and

B: - 10 to 74.9% by weight of builder (s);

25 to 89.9% by weight of solvent;

are metered into the interior of the dishwasher, wherein the liquid detergent A has a pH (20 ° C) between 6 and 9 and is metered at time t1, while the liquid detergent B a pH (20 ° C) between 9 and 14 and is metered in at time t2 and wherein at least one of the cleaning agents A or B contains a polymer comprising the following monomers:

a) at least one monomer according to formula (I)

in which

Ri and _R4 independently represent hydrogen or CI_ ₆ alkyl;

C 1-6 alkyl;

x and y independently represent a value of 1 to 3; X ^"stands for a counterion;

b) at least one hydrophilic monomer bearing at least one acid group; c) at least one hydrophilic nonionic monomer.

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

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

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

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

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

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

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

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

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

Examples

Terpolymer A: terpolymer of acrylamide, DADMAC and acrylic acid in the mixing ratio 75.6: 20: 4.4

Terpolymer B: terpolymer of Ν, Ν-dimethylacrylamide, DADMAC and acrylic acid in a mixing ratio of 75.6: 20: 4.4

To the alkaline phase of a commercial two-phase liquid dishwashing detergent comprising an alkaline and an enzyme-containing phase, in each case 0.19% by weight (based on the total formulation) of the terpolymer A (formulation II) or of the terpolymer B (formulation III) added and then examined the rinse performance. Comparative experiments were carried out with the formulation without terpolymer (formulation I). The experiments were carried out in a Miele 698 SC dishwasher at 50 ° C. with water having a hardness of 21 ° dH. Before starting the dishwashing program, 19.3 grams of each of the two phases were metered into the dosing chamber of the dishwasher.

The rinse performance was tested on glass (Willybecher, Whiskeybecher); Porcelain (dessert dish, black, Friesland plate); Plastic (melamine plate, blue plastic plates) and stainless steel (knife, butter dish, serving tray). A total of 3 determinations were carried out and then the mean value was formed. The worst grade is 0, the best grade is 10. On the one hand the formation of fouling was determined, on the other hand staining.

Table 1: staining

Recipe I Recipe II Recipe III

Glass 5.1 10.0 9.0

Porcelain 8.0 10.0 7.8

Plastic 3.3 3.0 3, 1

Steel 9.7 10.0 10.0 It can be seen that both terpolymers reduce the formation of stains on glass, with the terpolymer A exhibiting higher activity than the terpolymer B. Furthermore, when the terpolymer A is used, significantly less staining of porcelain is also discernible.

Table 2: deposit formation

With regard to the formation of deposits, it can be seen that in the presence of the terpolymer A slight deterioration of the deposit formation on glass occurs, while the terpolymer B on the contrary causes an improvement of the deposit inhibition on glass. The terpolymer B also causes an improvement in the deposit inhibition on porcelain.

Claims

claims

1. Use of a polymer comprising

a) at least one monomer according to formula (I)

in which

Ri and _R4 independently represent hydrogen or CI_ ₆ alkyl;

Ci_ ₆ alkyl;

x and y independently represent a value of 1 to 3; X ^"stands for a counterion;

as a rinse aid, in particular to reduce the formation of deposits and / or stains on the dishes.

2. Embodiment according to claim 1, characterized in that it is in the

hydrophilic monomer (b) is acrylic acid or methacrylic acid.

3. The embodiment of claim 1 or 2, characterized in that it is the hydrophilic nonionic monomer (c) to the nitrogen atom optionally mono- or disubstituted by Ci_ ₆ alkyl acrylamide, wherein used in a preferred embodiment unsubstituted acrylamide becomes.

4. The embodiment according to any one of the preceding claims, characterized in that the proportion of the monomer (a) on the polymer is 10-30%, preferably 15-25%, based on the total number of monomers.

5. The embodiment according to any one of the preceding claims, characterized in that the proportion of the monomer (b) on the polymer is less than 15%, preferably less than 10%, in particular 3-6%, based on the total number of monomers.

6. The embodiment according to any one of the preceding claims, characterized in that the proportion of the monomer (c) on the polymer is at least 50%, preferably at least 65%, in particular 75-85%, based on the total number of monomers.

7. Machine dishwashing process, characterized in that comprising at least one process step, a polymer

a) at least one monomer according to formula (I)

in which

Ri and _R4 independently represent hydrogen or CI_ ₆ alkyl;

Ci_ ₆ alkyl;

x and y independently represent a value of 1 to 3; X ^"stands for a counterion;

as a rinse aid, in particular for reducing the formation of patches and / or stains, is used.

8. A machine dishwashing process according to claim 7, characterized in that the polymer is used in at least one cleaning agent of a combination product, wherein the combination product comprises a packaging means and two cleaning agents A and B in this packaging means of the following composition:

A: - 10 to 75% by weight of builder (s);

- 0, 1 to 10 wt .-% enzyme (s);

24.9 to 89.9% by weight of water; and

B: - 10 to 75% by weight of builder (s);

- 25 to 90 wt .-% water;

and wherein the liquid detergent A has a pH (20 ° C) between 6 and 9 and the liquid detergent B has a pH (20 ° C) between 9 and 14.

A combination product comprising a packaging means and two separate liquid detergents A and B of the composition contained in said packaging means

A: - 10 to 75% by weight of builder (s);

- 0, 1 to 10 wt .-% enzyme (s);

24.9 to 89.9% by weight of water; and

B: - 10 to 75% by weight of builder (s);

- 25 to 90 wt .-% water; wherein the liquid cleaning agent A has a pH (20 ° C) between 6 and 9 and the liquid cleaning agent B has a pH (20 ° C) between 9 and 14, characterized in that at least one of the cleaning agents A and / or B contains a polymer comprising the following monomers:

a) at least one monomer according to formula (I)

Ri and _R4 independently represent hydrogen or CI_ ₆ alkyl;

C 1-6 alkyl;

x and y independently represent a value of 1 to 3; X ^"stands for a counterion;

10. Use of a combination product according to claim 9 as cleaning and rinsing agent for hard surfaces, preferably for reducing the formation of deposits and / or stains on dishes, in particular in automatic dishwashing.