EP2366010B1 - Machine dishwashing detergent - Google Patents

Description

The present application describes automatic dishwashing detergents, automatic dishwashing processes using these dishwashing detergents, and the use of these dishwashing detergents for improving the dishwashing of machine dishwashing.

On machine-washed dishes are often made higher demands than manually rinsed dishes. Thus, a tableware that has been completely cleaned at first sight by food waste is then rated as not having any flaw if, after machine dishwashing, it still has discolorations which are due, for example, to the attachment of vegetable dyes to the dish surface.

In order to obtain spotless dishes, bleaching agents are used in automatic dishwashing detergents. In order to activate these bleaching agents and to achieve an improved bleaching effect during cleaning at temperatures of 60 ° C. and below, automatic dishwashing detergents generally also contain bleach activators or bleach catalysts, with the bleach catalysts in particular having proven to be particularly effective.

The use of these bleaches is limited due to incompatibilities with other detergent or cleaning active ingredients, such as enzymes, or because of stability issues in the storage of bleach-containing detergents and cleaners. This is especially true for liquid detergents or cleaning agents.

One technical option for improving the cleaning performance of automatic dishwashing detergents, in particular bleach-free automatic dishwasher detergents, is to increase the alkalinity of these detergents. While, on the one hand, with increasing alkalinity, the cleaning performance of automatic dishwashing detergents increases, on the other hand strongly alkaline cleaners also cause damage in the silicate structure of glasses and can cause strong irritation on contact with the skin.

Particularly effective builders for increasing the alkalinity have proved to be the alkali metal phosphates, which for this reason form the main constituent of the vast majority of commercially available automatic dishwashing detergents.

While the phosphates are highly valued for their beneficial effect as a component of automatic dishwashing detergents, their use is not unproblematic from an environmental point of view, since a substantial portion of the phosphate enters the water via domestic effluent and especially in stagnant water (lakes, barrages ) a questionable Role in their over-fertilization plays. As a result of this phenomenon, also referred to as eutrophication, the use of pentasodium triphosphate in laundry detergents in a number of countries, eg USA, Canada, Italy, Sweden, Norway, has been considerably reduced by law and regulations. completely prohibited in Switzerland. In Germany, detergents since 1984 may contain no more than 20% of this builder.

Limiting the alkalinity as well as the phosphate content of automatic dishwashing detergents is therefore desirable from the point of view of the user and with a view to sustainable product development.

The DE102007006630 A1 describes phosphate-free automatic dishwashing detergents containing builder, bleach copolymers comprising, inter alia, monomers containing sulfonic acid groups, nonionic surfactant and salts of mono- or di-phosphonic acids.

This application was therefore based on the object to provide a detergent for dishwashing, which is distinguished from conventional dishwashing detergents even with low-temperature cleaning cycles or cleaning cycles with low water consumption by improved cleaning performance. In particular, the dishwashing detergent should be characterized by a good cleaning performance despite freedom from phosphates and bleach, with an improved cleaning performance, for example against bleachable stains, being preferred without at the same time causing increased damage to glass or ceramic surfaces. The bleachable stains include, for example, stains caused by tea or vegetable dyes, for example from vegetables or fruits.

Surprisingly, it has been found that the above object can be achieved in a citrate-based, phosphate and bleach-free base formulation by the use of polyphosphonic acid.

1. a) 10 bis 40 Gew.-% Citrat
2. b) 4 bis 26 Gew.-% Polyphosphonsäure,
3. c) 0,1 bis 8 Gew.-% Amylase- und/oder Protease Enzymzubereitung, enthaltend 0,1 bis 40 Gew.-% Enzymprotein, bezogen auf das Gesamtgewicht der Enzymzubereitung,
4. d) 2,0 bis 20 Gew.-% anionisches Copolymer, umfassend
   1. i) ein- oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren
   2. ii) ein- oder mehrfach ungesättigte Monomere aus der Gruppe der Sulfonsäuren
   3. iii) optional weitere ionische oder nichtionische Monomere
5. e) 0,2 bis 10 Gew.-% nichtionisches Tensid,

wobei das maschinelle Geschirrspülmittel eine Polyphosphonsäure, umfassend

1. i) ein- oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren
2. ii) ein- oder mehrfach ungesättigte Monomere aus der Gruppe der Phosphonsäuren
3. iii) optional weitere ionische oder nichtionische Monomere

enthält.A first subject of this application is a phosphate and bleach-free machine dishwashing detergent containing:

1. a) 10 to 40 wt .-% citrate
2. b) 4 to 26% by weight of polyphosphonic acid,
3. c) 0.1 to 8% by weight of amylase and / or protease enzyme preparation containing 0.1 to 40% by weight of enzyme protein, based on the total weight of the enzyme preparation,
4. d) 2.0 to 20% by weight of anionic copolymer comprising
   1. i) mono- or polyunsaturated monomers from the group of carboxylic acids
   2. ii) mono- or polyunsaturated monomers from the group of sulfonic acids
   3. iii) optionally further ionic or nonionic monomers
5. e) 0.2 to 10% by weight of nonionic surfactant,

wherein the automatic dishwashing agent comprises a polyphosphonic acid

1. i) mono- or polyunsaturated monomers from the group of carboxylic acids
2. ii) mono- or polyunsaturated monomers from the group of phosphonic acids
3. iii) optionally further ionic or nonionic monomers

contains.

The automatic dishwashing compositions according to the invention are preferably low-alkaline. Preferred automatic dishwasher detergents according to the invention are characterized in that the automatic dishwasher detergent has a pH (10% solution, 20 ° C.) between 9 and 11.5, preferably between 9.5 and 11.5, in particular between 10.0 and 11.0.

A first essential ingredient of the composition of the invention is the citrate. The term "citrate" also includes citric acid as well as its salts, in particular their alkali metal salts. Machine dishwashing detergents according to the invention contain citrate, preferably sodium citrate, in amounts of 12 to 40% by weight, preferably 15 to 40% by weight. and in particular 15 to 30 wt .-%, each based on the total weight of the automatic dishwashing detergent. Citrate or citric acid has proven to be particularly effective over other builders in combination with the anionic copolymer in terms of tea cleaning.

Some exemplary automatic dishwashing formulations can be found in Table 1 below: ingredient Formulation 1 [% by weight] (not according to the invention) Formulation 2 [% by weight] (not according to the invention) Formulation 3 [% by weight] (not according to the invention) Formulation 4 [% by weight] (not according to the invention) citrate 12 to 50 15 to 40 15 to 30 15 to 30 polyphosphonic 1.0 to 30 1.0 to 30 1.0 to 30 1.0 to 30 phosphate - * - - - bleach - - - - PH value kA kA kA 9 to 11.5 Misc Add 100 Add 100 Add 100 Add 100 * "-" interpreted in this as in all the following tables: the recipe is free of this ingredient

The automatic dishwashing compositions according to the invention may contain, in addition to the citrates, additional builders, in particular carbonates or organic cobuilders.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 5 to 50 wt .-%, preferably from 10 to 40 wt .-% and in particular from 15 to 30 wt .-%, each based on the weight of the automatic dishwashing detergent.

Some exemplary automatic dishwashing formulations can be found in Table 2 below: ingredient Formulation 1 [% by weight] (not according to the invention) Formulation 2 [% by weight] (not according to the invention) Formulation 3 [% by weight] (not according to the invention) Formulation 4 [% by weight] (not according to the invention) citrate 12 to 50 15 to 40 15 to 40 15 to 30 polyphosphonic 1.0 to 30 1.0 to 30 1.0 to 30 1.0 to 30 carbonate 5 to 50 10 to 40 5 to 50 10 to 40 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, dextrins 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. For example, these are 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, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these may be mentioned here.

In addition to 1-hydroxyethane-1,1-diphosphonic acid, the complex-forming phosphonates comprise a number of different compounds such as, for example, diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

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

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

1. a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof;
2. b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof;
3. c) diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and / or salts thereof;
4. d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or salts thereof;
5. e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof;
6. f) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or salts thereof;
7. g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.

Particularly preferred are automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).

Of course, the automatic dishwashing compositions of the invention may contain two or more different phosphonates.

The proportion by weight of the phosphonates in the total weight of automatic dishwashing detergents according to the invention is preferably from 1 to 8% by weight, preferably from 1.2 to 6% by weight and in particular from 1.5 to 4% by weight.

Some exemplary automatic dishwashing formulations can be found in Table 3 below: ingredient Formulation 1 [% by weight] (not according to the invention) Formulation 2 [% by weight] (not according to the invention) Formulation 3 [% by weight] (not according to the invention) Formulation 4 [% by weight] (not according to the invention) citrate 12 to 50 15 to 40 12 to 50 15 to 40 Polyphosphonic acid 1.0 to 30 1.0 to 30 1.0 to 30 1.0 to 30 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100

Another group of organic builders are the polymeric sulfonates. Preferred polysulfonates contain, in addition to sulfonic acid-containing (s) monomer (s) at least one monomer from the group of unsaturated carboxylic acids.

As unsaturated carboxylic acid (s) is / are used with particular preference unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH, in which R ¹ to R ³ independently of each other is -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or -COOR ⁴ , 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.

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

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

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

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

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

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

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts. In the polymers, the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
The monomer distribution of the polymeric sulfonates preferably used according to the invention in copolymers containing only monomers from the groups of the unsaturated carboxylic acids i) and the unsaturated sulfonic acids ii), preferably in each case 5 to 95 wt .-% i) or ii), particularly preferably 50 to 90% by weight of monomer from group ii) and from 10 to 50% by weight of monomer from group i), in each case based on the polymer.

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred automatic dishwashing agents 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 a further preferred embodiment, the polymeric sulfonates in addition to carboxyl-containing monomer and sulfonic acid-containing monomer further comprise 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.

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X represents an optionally present spacer group selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents 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, ethylcyclohexyne, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Acrylsäurepentylester, Acrylsäurehexylester, methyl methacrylate, N- (methyl) acrylamide, acrylic acid 2-ethylhexyl ester, methacrylic acid 2-ethylhexyl ester, N - (2-ethylhexyl) acrylamide, octyl acrylate, Methacrylsäureoctylester, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, Methacrylsäurebehenylester and N - (behenyl) acrylamide or mixtures thereof.

1. i) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren
2. ii) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Sulfonsäuren
3. iii) optional weitere ionische oder nichtionische Monomere enthält, sind erfindungsgemäß.

Machine dishwashing detergent, characterized in that the automatic dishwashing agent, based on its total weight, contains 2.0 to 20% by weight, preferably 2.5 to 15% by weight and in particular 2.5 to 10% by weight of anionic copolymer, full

1. i) one or more polyunsaturated monomers from the group of carboxylic acids
2. ii) one or more polyunsaturated monomers from the group of sulfonic acids
3. iii) optionally containing further ionic or nonionic monomers are in accordance with the invention.

A second essential ingredient of the invention is the polyphosphonic acid b). The proportion by weight of the polyphosphonate b) in the total weight of automatic dishwashing agents according to the invention is 4 to 26% by weight and in particular 8 to 24% by weight.

The homopolymeric polyphosphonic acids have been found to be superior in terms of the scavenging achieved with the compositions as simple homopolymers of unsaturated monocarboxylic acids or copolymers of unsaturated monocarboxylic acids. In turn, the dough cleaning of homopolymeric phosphonic acids is surpassed by the dough cleaning performance of copolymeric polyphosphonic acids. Polyphosphonic acids comprising unsaturated monocarboxylic acid (s) A and unsaturated phosphonic acid (s) B are therefore according to the invention.

1. i) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren
2. ii) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Phosphonsäuren
3. iii) optional weitere ionische oder nichtionische Monomere
   enthält.

Automatic dishwasher detergents according to the invention are characterized in that the automatic dishwashing agent comprises a polyphosphonic acid

1. i) one or more polyunsaturated monomers from the group of carboxylic acids
2. ii) one or more polyunsaturated monomers from the group of phosphonic acids
3. iii) optionally further ionic or nonionic monomers
   contains.

Particularly suitable are copolymers of acrylic acid or methacrylic acid with a phosphonic acid. Copolymers of acrylic acid with a phosphonic acid have proven to be particularly suitable, preferred copolymers containing from 50 to 90% by weight of acrylic acid and from 50 to 10 Wt .-% phosphonic acid. The 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.

1. i) 50 bis 90 Gew.-% ungesättigte Monocarbonsäure(n) A
2. ii) 10 bis 50 Gew.-% ungesättigte Phosphonsäure(n) B enthält.

Preferred automatic dishwasher detergents according to the invention are characterized in that the automatic dishwashing agent comprises as polyphosphonic acid b) a copolymer comprising

1. i) 50 to 90% by weight of unsaturated monocarboxylic acid (s) A
2. ii) contains 10 to 50 wt .-% of unsaturated phosphonic acid (s) B.

1. i) 50 bis 90 Gew.-% Acrylsäure
2. ii) 10 bis 50 Gew.-% Phosphonsäure.

Preferred machine dishwasher detergents according to the invention comprise as polyphosphonic acid b) a copolymer comprising

1. i) 50 to 90 wt .-% acrylic acid
2. ii) 10 to 50% by weight of phosphonic acid.

The polyphosphonic acid b) can be used in the machine dishwasher according to the invention, for example as a powder or as an aqueous solution.

Some exemplary automatic dishwashing formulations can be found in the following Tables 3a and 3b: ingredient Formulation 1 [% by weight] (not according to the invention) Formulation 2 [% by weight] (not according to the invention) Formulation 3 [% by weight] (not according to the invention) Formulation 4 [% by weight] (not according to the invention) citrate 12 to 50 15 to 40 12 to 50 15 to 40 Polyphosphonic acid ¹ 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 ingredient Formulation 1 [% by weight] (not according to the invention) Formulation 2 [% by weight] (not according to the invention) Formulation 3 [% by weight] (not according to the invention) Formulation 4 [% by weight] (not according to the invention) citrate 12 to 50 15 to 40 12 to 50 15 to 40 Polyphosphonic acid ¹ 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 ¹ polyphosphonic acid b) a copolymer comprising 50 to 90 wt .-% monocarboxylic acid and 10 to 50 wt .-% phosphonic acid

In addition to the ingredients described above, the compositions according to the invention may contain further washing or cleaning-active substances, preferably from the group of surfactants, enzymes, organic solvents, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.

In principle, all nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

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

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture may contain, as they 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. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is therefore given to ethoxylated nonionic surfactants consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

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

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 content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50%
Wt .-% and in particular more than 70 wt .-% of the total molecular weight of such nonionic surfactants. Preferred agents are characterized by being ethoxylated and propoxylated nonionic surfactants contain in which the propylene oxide 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 surfactant make up.

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

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

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

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

In summary, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -R ² , in which R ¹ and R ² independently of one another represents a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 alkyl or alkenyl radical; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (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, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

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

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _{x [} CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² 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 very particularly preferred.

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

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

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. Is for example, x 3, the radical R may be selected ³ to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃₎ units which can be joined together 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 is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

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

• R¹ und R² unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen;
• Alk für eine verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen;
• x und y unabhängig voneinander für Werte zwischen 1 und 70; und
• M für einen Alkylrest aus der Gruppe CH₂, CHR³, CR³R⁴, CH₂CHR³ und CHR³CHR⁴, wobei R³ und R⁴ unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen;

Another group of preferred nonionic surfactants are surfactants of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , in which

• R ¹ and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
• Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms;
• x and y independently represent values between 1 and 70; and
• M is an alkyl radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently of one another are a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms;

The proportion by weight of this nonionic surfactant in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.05 and 10% by weight, preferably between 0.1 and 8% by weight, preferably between 0.5 and 5% by weight. and in particular between 1 and 3 wt .-%.

The group of nonionic surfactants of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² comprises a number of particularly preferred compounds.

• R, R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen;
• x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen

In a first preferred embodiment, automatic dishwashing agents according to the invention contain as nonionic surfactant A a surfactant of the general formula R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ^{2 is} used in the

• R, R ¹ and R ² independently represent an alkyl group or alkenyl group having 6 to 22 carbon atoms;
• x and y independently represent values between 1 and 40

Particular preference is given to compounds of the general formula R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² , in 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.

• R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen;
• R³ und R4 unabhängig voneinander für H oder für einen Alkylrest oder Alkenylrest mit 1 bis 18 Kohlenstoffatomen und
• x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen;

In a further preferred embodiment, automatic dishwasher detergents according to the invention contain nonionic surfactant of the general formula
R ^{1 is} -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y O- in which

• R ¹ 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;

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

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

Also preferred are those compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which one of the radicals R ¹ and R ^{2 is} branched.

Very particularly preferred compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which the indices x and y are independently values 8-12 accept.

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

The proportion by weight of the nonionic surfactant in the total weight of the automatic dishwashing agent according to the invention is between 0.2 and 10% by weight, preferably between 0.5 and 8% by weight and in particular between 1.0 and 6% by weight.

Some exemplary automatic dishwashing formulations can be found in Tables 4a and 4b below: ingredient Formulation 1 [% by weight] (not according to the invention) Formulation 2 [% by weight] (not according to the invention) Formulation 3 [% by weight] (not according to the invention) Formulation 4 [% by weight] (not according to the invention) citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 ingredient Formulation 1 [% by weight] (not according to the invention) Formulation 2 [% by weight] (not according to the invention) Formulation 3 [% by weight] (not according to the invention) Formulation 4 [% by weight] (not according to the invention) citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100

As a further constituent dishwashing agents according to the invention may contain enzyme (s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; starting from the natural molecules are available for use in washing or cleaning agents improved variants available, which are used according to preferred. 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, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L.

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

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

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

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

A preferred machine dishwashing detergent according to the invention is characterized in that the dishwashing agent, based on its total weight, enzyme preparation (s) in amounts of 0.1 to 12 wt .-%, preferably from 0.2 to 10 wt .-% and in particular from 0.5 to 8 wt .-% contains.

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used according to the invention comprise between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight of the enzyme protein.

1. a) 10 bis 40 Gew.-% Citrat
2. b) 4 bis 26 Gew.-% Polyphosphonsäure
3. c) 0,1 bis 8 Gew.-% Amylase- und/oder Protease Enzymzubereitung, enthaltend zwischen 0,1 und 40 Gew.-% des Enzymproteins, bezogen auf das Gewicht der Enzymzubereitung,
4. d) 2,0 bis 20 Gew.-% anionischen Copolymers, umfassend
   1. i) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren
   2. ii) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Sulfonsäuren
   3. iii) optional weitere ionische oder nichtionische Monomere
5. e) 0,2 bis 10 Gew.-% nichtionisches Tensid,

wobei das maschinelle Geschirrspülmittel eine Polyphosphonsäure, umfassend

1. i) ein- oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren
2. ii) ein- oder mehrfach ungesättigte Monomere aus der Gruppe der Phosphonsäuren
3. iii) optional weitere ionische oder nichtionische Monomere
   enthält.

A particularly preferred automatic dishwashing detergent according to the invention comprises

1. a) 10 to 40 wt .-% citrate
2. b) 4 to 26% by weight of polyphosphonic acid
3. c) 0.1 to 8% by weight of amylase and / or protease enzyme preparation containing between 0.1 and 40% by weight of the enzyme protein, based on the weight of the enzyme preparation,
4. d) 2.0 to 20% by weight of anionic copolymer comprising
   1. i) one or more polyunsaturated monomers from the group of carboxylic acids
   2. ii) one or more polyunsaturated monomers from the group of sulfonic acids
   3. iii) optionally further ionic or nonionic monomers
5. e) 0.2 to 10% by weight of nonionic surfactant,

wherein the automatic dishwashing agent comprises a polyphosphonic acid

1. i) mono- or polyunsaturated monomers from the group of carboxylic acids
2. ii) mono- or polyunsaturated monomers from the group of phosphonic acids
3. iii) optionally further ionic or nonionic monomers
   contains.

Some other exemplary automatic dishwashing formulations can be found in Tables 5a and 5b below: ingredient Formulation 1 [% by weight] (not according to the invention) Formulation 2 [% by weight] (not according to the invention) Formulation 3 [% by weight] (not according to the invention) Formulation 4 [% by weight] (not according to the invention) citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 Sulfocopolymer 0 to 20 0 to 20 0 to 20 0 to 20 Nonionic surfactant 0 to 15 0 to 15 0 to 8 0 to 8 Enzyme preparation (s) 0.1 to 12 0.1 to 12 0.5 to 8 0.5 to 8 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 ingredient Formulation 1 [% by weight] (not according to the invention) Formulation 2 [% by weight] (not according to the invention) Formulation 3 [% by weight] (not according to the invention) Formulation 4 [% by weight] (not according to the invention) citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Sulfocopolymer 0 to 20 2.0 to 20 2.0 to 20 2.5 to 15 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 Enzyme preparation (s) 0.1 to 12 0.1 to 12 0.5 to 8 0.5 to 8 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100

The automatic dishwasher detergents according to the invention can be present in the ready-to-use form known to the person skilled in the art, that is to say, for example, in solid or liquid form but also as a combination of solid and liquid supply forms.

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

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

The individual phases of multiphase agents may have the same or different states of matter. Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred. 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 mold 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 is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

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

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain. The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.

Preferred disintegration aids, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries. However, preferred effervescent systems consist of at least two components which react with one another to form gas, for example 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.

It was found that the cleaning performance according to the invention by machine Dishwashing detergent can be improved by the addition of organic solvents.

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

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

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

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

Combination products, characterized in that they contain an organic solvent, wherein the organic solvent is an organic amine and / or an alkanolamine, preferably monoethanolamine, are particularly preferred according to the invention.

A further subject of this application is a machine dishwashing detergent according to the invention, characterized in that the automatic dishwashing agent, based on its total weight, organic amine and / or an alkanolamine, preferably ethanolamine, 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 .-%.

1. a) 10 bis 40 Gew.-% Citrat
2. b) 4 bis 26 Gew.-% Polyphosphonsäure
3. c) 0,1 bis 8 Gew.-% Amylase- und/oder Protease Enzymzubereitung, enthaltend 0,1 bis 40 Gew.-% Enzymprotein, bezogen auf das Gesamtgewicht der Enzymzubereitung,
4. d) 2,0 bis 20 Gew.-% anionischen Copolymers, umfassend
   1. i) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren
   2. ii) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Sulfonsäuren
   3. iii) optional weitere ionische oder nichtionische Monomere
5. e) 0,2 bis 10 Gew.-% nichtionisches Tensid
6. f) 20 bis 70 Gew.-% Wasser,

wobei das maschinelle Geschirrspülmittel eine Polyphosphonsäure, umfassend

1. i) ein- oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren
2. ii) ein- oder mehrfach ungesättigte Monomere aus der Gruppe der Phosphonsäuren
3. iii) optional weitere ionische oder nichtionische Monomere
   enthält.

These solvent-containing automatic dishwashing agents are preferably in liquid form. A particularly preferred liquid automatic dishwashing detergent according to the invention comprises

1. a) 10 to 40 wt .-% citrate
2. b) 4 to 26% by weight of polyphosphonic acid
3. c) 0.1 to 8% by weight of amylase and / or protease enzyme preparation containing 0.1 to 40% by weight of enzyme protein, based on the total weight of the enzyme preparation,
4. d) 2.0 to 20% by weight of anionic copolymer comprising
   1. i) one or more polyunsaturated monomers from the group of carboxylic acids
   2. ii) one or more polyunsaturated monomers from the group of sulfonic acids
   3. iii) optionally further ionic or nonionic monomers
5. e) 0.2 to 10% by weight of nonionic surfactant
6. f) from 20 to 70% by weight of water,

wherein the automatic dishwashing agent comprises a polyphosphonic acid

1. i) mono- or polyunsaturated monomers from the group of carboxylic acids
2. ii) mono- or polyunsaturated monomers from the group of phosphonic acids
3. iii) optionally further ionic or nonionic monomers
   contains.

Some example formulations for liquid automatic dishwashing detergents can be found in the following Tables 5a and 5b: ingredient Formulation 1 [% by weight] (not according to the invention) Formulation 2 [% by weight] (not according to the invention) Formulation 3 [% by weight] (not according to the invention) Formulation 4 [% by weight] (not according to the invention) citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 Sulfocopolymer 0 to 20 0 to 20 0 to 20 0 to 20 Nonionic surfactant 0 to 15 0 to 15 0 to 8 0 to 8 Enzyme preparation (s) 0 to 12 0 to 12 0 to 8 0 to 8 Org. Solvent 0.1 to 15 0.5 to 8 0.1 to 15 0.5 to 8 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 ingredient Formulation 1 [% by weight] (not according to the invention) Formulation 2 [% by weight] (not according to the invention) Formulation 3 [% by weight] (not according to the invention) Formulation 4 [% by weight] (according to the invention) citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Sulfocopolymer 0 to 20 2.0 to 20 2.0 to 20 2.5 to 15 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 Enzyme preparation (s) 0.1 to 12 0.1 to 12 0.5 to 8 0.5 to 8 Org. Solvent 0.1 to 15 0.5 to 8 0.1 to 15 0.5 to 8 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100

If the agents according to the invention are in liquid form, these agents preferably contain from 20 to 80% by weight, preferably from 30 to 70% by weight and in particular from 40 to 60% by weight, of water. The metering units of these liquid supply forms preferably comprise the amount of washing or cleaning-active substances necessary for a cleaning cycle. Preferred liquid metering units have a weight between 25 and 60 g, preferably between 30 and 55 g and in particular between 55 and 50 g.

1. a) ein erfindungsgemäßes maschinelles Geschirrspülmittel;
2. b) eine Anleitung, die den Verbraucher darauf hinweist, das maschinelle Geschirrspülmittel ohne Zusatz eines Klarspülers und/oder eines Enthärtersalzes zu verwenden ist, ist ein weiterer Gegenstand dieser Anmeldung.

The active substance combinations described above are particularly suitable for cleaning dishes in automatic dishwashing processes. Another object of the present application is a method for cleaning dishes in a dishwasher, using a machine dishwashing detergent according to the invention, wherein the automatic dishwashing detergents are preferably metered into the interior of a dishwasher during the passage of a dishwashing program, before the start of the main wash cycle or during the course of the main wash cycle. The metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher. A kit for a dishwasher, comprising

1. a) a machine dishwashing detergent according to the invention;
2. (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 exhibit their advantageous cleaning and drying properties, in particular also in low-temperature cleaning processes. 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.

As described at the beginning, agents according to the invention are distinguished from conventional automatic dishwasher detergents by improved tea cleaning. Another object of the present application is therefore the use of a machine dishwashing detergent according to the invention for improving the dough cleaning in automatic dishwashing.

Examples

In a dishwasher dishwashing process, soiled dishes were rinsed in a dishwashing machine (Miele G 698) at a water hardness of 21 ° dH and a temperature of 50 ° C. with 42.5 g ml of the automatic dishwashing detergent listed in the table below. ingredient V1 E1 Data in% by weight sodium citrate 9.0 9.0 potassium hydroxide 7.0 7.0 sodium 14 14 polyphosphonic - ¹⁾ sulfopolymer 4.2 4.2 HEDP 1.5 1.5 Nonionic surfactant 2.0 2.0 Protease preparation 2.0 2.0 Amylase preparation 0.8 0.8 alkanolamine 1.5 1.5 thickener 2.0 2.0 Water, Misc Add 100 Add 100 ¹⁾ 11.7 g polyphosphonic acid "on top"

The tea cleaning performance of the automatic dishwashing detergents was evaluated by the IKW method. The results are given in the table below (The values given are average values from 3 experiments) cleaning performance V1 E1 tea 1 3 (Evaluation scale cleaning performance: 10 = no contamination to 0 = heavy contamination)

Claims (13)

1. A phosphate-free and bleaching agent-free automatic dishwasher detergent, containing:

   a) 10 to 40 wt.% citrate

   b) 4 to 26 wt.% polyphosphonic acid,

   c) 0.1 to 8 wt.% amylase and/or protease enzyme preparation, containing 0.1 to 40 wt.% enzyme protein, based on the total weight of the enzyme preparation,

   d) 2.0 to 20 wt.% anionic copolymer, comprising

   i) mono- or polyunsaturated monomers from the group of the carboxylic acids

   ii) mono- or polyunsaturated monomers from the group of the sulfonic acids

   iii) optional additional ionic or non-ionic monomers

   e) 0.2 to 10 wt.% non-ionic surfactant,
   wherein the automatic dishwasher detergent contains a polyphosphonic acid, comprising

   i) mono- or polyunsaturated monomers from the group of the carboxylic acids

   ii) mono- or polyunsaturated monomers from the group of the phosphonic acids

   iii) optional additional ionic or non-ionic monomers.
2. The automatic dishwasher detergent according to claim 1, characterized in that the automatic dishwasher detergent contains, based on its total weight, 15 to 40 wt.% and in particular 15 to 30 wt.% citrate.
3. The automatic dishwasher detergent according to one of the preceding claims, characterized in that the automatic dishwasher detergent contains, based on its total weight, 8 to 24 wt.% polyphosphonic acid.
4. The automatic dishwasher detergent according to one of the preceding claims, characterized in that the automatic dishwasher detergent contains, based on its total weight, 2.5 to 15 wt.% and in particular 2.5 to 10 wt.% anionic copolymer, comprising

   i) mono- or polyunsaturated monomers from the group of the carboxylic acids

   ii) mono- or polyunsaturated monomers from the group of the sulfonic acids

   iii) optional additional ionic or non-Ionic monomers.
5. The automatic dishwasher detergent according to one of the preceding claims, characterized in that the automatic dishwasher detergent contains, based on its total weight, 1 to 8 wt.%, preferably 1.2 to 6 wt.% and in particular 1.5 to 4 wt.% phosphonate.
6. The automatic dishwasher detergent according to one of the preceding claims, characterized in that the dishwasher detergent contains, based on its total weight, non-ionic surfactant in amounts of 0 5 to 8 wt.% and in particular from 1.0 to 6 wt.%.
7. The automatic dishwasher detergent according to one of the preceding claims, charactarized in that the dishwasher detergent contains a non-ionic surfactant A of the general formula R¹O(AlkO)_xM(OAlk)_yOR², in which

   - R¹ and R² represent, independently of one another, a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl functional group having 4 to 22 carbon atoms;

   - Alk represents a branched or unbranched alkyl functional group having 2 to 4 carbon atoms;

   - x and y represent, independently of one another, values between 1 and 70;
   and

   - M represents an alkyl functional group from the group CH₂, CHR³, CR³R⁴, CH₂CHR³ and CHR³CHR⁴, R³ and R⁴ representing, independently of one another, a branched or unbranched, saturated or unsaturated alkyl functional group having 1 to 18 carbon atoms.
8. The automatic dishwasher detergent according to one of the preceding claims, characterized in that the automatic dishwasher detergent contains, based on its total weight, organic amine and/or an alkanolamine, preferably an ethanolamine, in amounts of 0.1 to 15 wt.%, preferably 0.2 to 10 wt.%, particularly preferably 0.5 to 8 wt.% and in particular of 1.0 to 6 wt.%.
9. The automatic dishwasher detergent according to one of the preceding claims, characterized in that the dishwasher detergent contains, based on its total weight, enzyme preparations in amounts of 0.1 to 12 wt.%, preferably 0.2 to 10 wt.% and in particular 0.5 to 8 wt.%.
10. A liquid automatic dishwasher detergent according to one of the preceding claims, containing

    a) 10 to 40 wt.% citrate

    b) 4 to 26 wt.% polyphosphonic acid

    c) 0.1 to 8 wt.% amylase and/or protease enzyme preparation, containing 0.1 to 40 wt.% enzyme protein, based on the total weight of the enzyme preparation,

    d) 2.0 to 20 wt.% anionic copolymers, comprising

    i) mono- or polyunsaturated monomers from the group of the carboxylic acids

    ii) mono- or polyunsaturated monomers from the group of the sulfonic acids

    iii) optional additional ionic or non-ionic monomers

    e) 0.2 to 10 wt.% non-ionic surfactant

    f) 20 to 70 wt.% water,
    wherein the automatic dishwasher detergent contains a polyphosphonic acid, comprising

    i) mono- or polyunsaturated monomers from the group of the carboxylic acids

    ii) mono- or polyunsaturated monomers from the group of the phosphonic acids

    iii) optional additional ionic or non-ionic monomers.
11. A method for cleaning dishes in a dishwasher using an automatic dishwasher detergent according to one of the preceding claims.
12. The method according to claim 11, characterized in that the dishwashing process is carried out at a bath temperature of less than 60°C.
13. The use of an automatic dishwasher detergent according to one of the preceding claims for improving the cleaning of tea stains during automatic dishwashing.