EP2185677B1 - Detergents - Google Patents

Abstract

Liquid, low-alkaline and bleach-free dishwasher detergent having a pH value (20° C.) of 8 to 12 and containing: a) 10 to 60 percent by weight of a builder; b) more than 1.5 percent by weight of a phosphonate; c) 0.1 to 20 percent by weight of an anionic copolymer comprising: i) unsaturated carboxylic acid(s) and ii) sulfonic acid group-containing monomer(s). Detergents according to the invention exhibit a good cleaning power on bleachable dirt, particularly tea stains.

Description

The present patent application describes detergents, in particular detergents for the machine cleaning of dishes. This application relates in particular to liquid, low-alkaline and bleach-free automatic dishwashing detergents.

Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. Thus, a tableware that has been completely cleaned at first glance of food waste is then rated as not having any flaw if, after machine dishwashing, it still has discolorations which are based, for example, on 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. A limitation of the alkalinity of the automatic dishwashing detergent is therefore desirable from the user's point of view.

DE 10133137 discloses liquid aqueous machine dishwashing detergents which may contain copolymer and phosphorate.

This application was therefore based on the object to provide a liquid detergent for dishwashing, which is distinguished from conventional dishwashing detergents even at low temperature cleaning cycles or cleaning cycles with low water consumption by improved cleaning performance. In particular, the dishwashing detergent should, despite its bleach-free properties, have an improved cleaning performance compared with bleachable soiling without, at the same time, increasing damage to glassware. 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 aforementioned object can be achieved by a combination of builders, phosphonates and polymers containing sulfonic acid groups.

1. a) 10 bis 60 Gew.-% Gerüststoff
2. b) > 1,5 Gew.-% Phosphonat
3. c) 0,1 bis 20 Gew.-% anionisches Copolymer, umfassend
   1. i) ungesättigte Carbonsäure(n)
   2. ii) Sulfonsäuregruppen-haltige(s) Monomer(e).

A first subject of this application is therefore a liquid, low alkaline and bleach-free machine dishwashing detergent having a pH (20 ° C) between 8 and 12, comprising:

1. a) 10 to 60 wt .-% builder
2. b)> 1.5% by weight of phosphonate
3. c) 0.1 to 20 wt .-% anionic copolymer comprising
   1. i) unsaturated carboxylic acid (s)
   2. ii) sulfonic acid group-containing monomer (s).

As described above, increased alkalinity of the automatic dishwashing detergent on the one hand, although beneficial to the cleaning performance of this agent, on the other hand increases the corrosive and irritating effect of this agent. Preferred automatic dishwasher detergents according to the invention are therefore characterized in that the automatic dishwasher detergent has a pH (20 ° C.) between 9 and 11.5, preferably between 9.5 and 11.5.

Aqueous automatic dishwasher detergents are preferred according to the invention. The water content of these aqueous automatic dishwashing agents, based on the total weight of the automatic dishwashing agent, is preferably between 10 and 80% by weight, preferably between 20 and 70% by weight and in particular between 30 and 60% by weight.

As a first essential ingredient machine dishwashing detergents according to the invention contain one or more builders. The builders include in particular carbonates, phosphates, organic cobuilders and silicates.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 30 wt .-%, preferably from 3 to 20 wt .-% and in particular from 4 to 15 wt .-%, each based on the weight of the automatic dishwashing detergent.

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

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred machine dishwasher detergents according to the invention contain citrate as one of their essential builders. Machine dishwashing detergents, characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight citrate, are preferred according to the invention. Citrate or citric acid have proved to be the most effective builders in addition to the phosphates, in combination with phosphonate, in particular 1-hydroxyethane-1,1-diphosphonic acid, and the sulfonic acid-containing copolymers with respect to the cleaning performance, such as the final rinse performance and, in particular, the scale inhibition.

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

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

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

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

Automatic dishwashing detergents according to the invention can be prepared as builder crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, Particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.

In addition to citrates, phosphates have proven to be the most effective builders in terms of cleaning performance. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

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

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

If phosphates are used as detergents or cleaning agents in the context of the present application, preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate), in amounts of 2 to 40 wt .-%, preferably from 2 to 30 wt .-% and in particular from 3 to 25 wt .-%, particularly preferably from 3 to 15 wt .-%, each based on the Weight of washing or cleaning agent.

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

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

Of course, the automatic dishwashing compositions according to the invention may contain the aforementioned builders both in the form of individual substances and in the form of substance mixtures of two, three, four or more builders.

Particularly preferred liquid automatic dishwashing detergents are characterized in that the dishwashing detergent contains at least two builders from the group of the phosphates, carbonates and citrates, wherein the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably 2 to 50 wt .-%, preferably 5 to 40 wt .-% and in particular 10 to 30 wt .-% is. The combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.

Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in the following tables: ingredient Recipe 1 Recipe 2 Recipe 3 Recipe 4 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 2 to 40 3 to 15 - - citrate - ** - 5 to 30 7 to 20 carbonate 3 to 20 4 to 15 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5 Anionic copolymer * 0.1 to 20 0.1 to 20 0.1 to 20 0.1 to 20 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 ingredient Recipe 5 Recipe 6 Recipe 7 Recipe 8 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] potassium 2 to 40 3 to 15 - - sodium citrate - - 5 to 30 7 to 20 sodium 3 to 20 4 to 15 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5 Anionic copolymer * 0.1 to 20 0.1 to 20 0.1 to 20 0.1 to 20 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 Anionic copolymer comprising
i) unsaturated carboxylic acid (s)
ii) sulfonic acid group-containing monomer (s)
** "-" means in this, as in all the following tables: the recipe is free from this ingredient

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

Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in the following table: ingredient Recipe 9 Recipe 10 Recipe 11 Recipe 12 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 2 to 40 3 to 15 - - citrate - - 5 to 30 7 to 20 carbonate 3 to 20 4 to 15 3 to 20 4 to 15 alkali hydroxide 0.1 to 10 0.1 to 6 0.1 to 5 0.1 to 5 phosphonate > 1.5 > 1.5 > 1.5 > 1, 5 Anionic copolymer * 0.1 to 20 0.1 to 20 0.1 to 20 0.1 to 20 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 Anionic copolymer comprising
i) unsaturated carboxylic acid (s)
ii) sulfonic acid group-containing monomer (s)

As a second essential ingredient, the automatic dishwashing compositions of the invention contain phosphonate (s). The proportion by weight of the phosphonate, based on the total weight of the automatic dishwashing agent, is preferably more than 1.8% by weight, preferably more than 2.2% by weight and in particular more than 2.4% by weight of phosphonate. The phosphonate content is preferably between 2 and 30 wt .-%, preferably between 2 and 20 wt .-%, particularly preferably between 2 and 15 wt .-% and in particular between 2 and 15 wt .-%. The complexing phosphonates include a number of different compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriamine penta (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. Preference is given to using HEDP from the group of phosphonates.

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).

Liquid automatic dishwashing compositions which contain as phosphonate 1-hydroxyethane-1,1-diphosphonic acid (HEDP) are particularly preferred according to the invention.

Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in the following tables: ingredient Recipe 13 Recipe 14 Recipe 15 Recipe 16 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 2 to 40 2 to 30 3 to 15 3 to 15 carbonate 3 to 20 3 to 20 4 to 15 4 to 15 phosphonate > 1.5 > 2 > 1.5 > 2 Anionic copolymer * 0.1 to 20 0.1 to 20 0.1 to 20 0.1 to 20 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 ingredient Recipe 17 Recipe 18 Recipe 19 Recipe 20 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] potassium 2 to 40 2 to 30 3 to 15 3 to 15 sodium 3 to 20 3 to 20 4 to 15 4 to 15 phosphonate > 1.5 > 2 > 1.5 > 2 Anionic copolymer * 0.1 to 20 0.1 to 20 0.1 to 20 0.1 to 20 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 * comprising anionic copolymer
i) unsaturated carboxylic acid (s)
ii) sulfonic acid group-containing monomer (s)

As an alternative to the phosphonates used according to the invention, it is also possible to use methylglycinediacetic acid (MGDA) as a complexing agent in the automatic dishwashing detergent. However, with phosphonates, significantly better cleaning results on bleachable stains and improved rinse results are achieved, which is why the phosphonate is preferred to the MGDA.

1. a) 10 bis 60 Gew.-% Gerüststoff
2. b) > 8 Gew.-% MGDA
3. c) 0,1 bis 20 Gew.-% anionisches Copolymer, umfassend
   1. i) ungesättigte Carbonsäure(n)
   2. ii) Sulfonsäuregruppen-haltige(s) Monomer(e).

An alternative, independent subject matter of the present application is therefore a liquid, low alkaline and bleach-free machine dishwashing detergent having a pH (20 ° C) between 8 and 12, comprising:

1. a) 10 to 60 wt .-% builder
2. b)> 8% by weight of MGDA
3. c) 0.1 to 20 wt .-% anionic copolymer comprising
   1. i) unsaturated carboxylic acid (s)
   2. ii) sulfonic acid group-containing monomer (s).

Preferred alternative cleaning agents contain MGDA in amounts above 10 wt .-%, preferably above 15 wt .-%, each based on the total weight of the automatic dishwashing detergent.

With regard to the other essential and preferred features of these alternative MGDA-containing automatic dishwashing detergents, the statements made above and below for the inventive phosphonate-containing automatic dishwashing detergents apply correspondingly.

A third characteristic constituent of inventive dishwasher detergents containing phosphonate are the sulfonic acid-containing copolymers c), which in addition to sulfonic acid-containing monomer (s) comprise at least one unsaturated carboxylic acid. The copolymers c) may have two, three, four or more different monomer units. Preferred liquid automatic dishwasher detergents contain the polymer c) in amounts of 0.2 to 18 wt .-%, preferably 0.5 to 15 wt .-% and in particular 1.0 to 12 wt .-%, each based on the total weight of automatic dishwashing detergent.

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

1. a) 10 bis 60 Gew.-% Gerüststoff
2. b) > 1,5 Gew.-% Phosphonat
3. c) 0,1 bis 20 Gew.-% anionisches Copolymer, umfassend
   1. i) Carboxylgruppen-haltige Monomere der Formel R¹(R²)C=C(R³)COOH, in der R¹ bis R³ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist
   2. ii) Sulfonsäuregruppen-haltige(s) Monomer(e).

Accordingly, a liquid, low-alkaline and bleach-free machine dishwashing detergent with a pH (20 ° C.) between 8 and 12, comprising:

1. a) 10 to 60 wt .-% builder
2. b)> 1.5% by weight of phosphonate
3. c) 0.1 to 20 wt .-% anionic copolymer comprising
   1. i) carboxyl-containing monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
   2. ii) sulfonic acid group-containing monomer (s).

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-propenylsulfonic 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 copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight 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 .

1. a) 10 bis 60 Gew.-% Gerüststoff
2. b) > 1,5 Gew.-% Phosphonat
3. c) 0,1 bis 20 Gew.-% anionisches Copolymer, umfassend
   1. i) Carboxylgruppen-haltige Monomere der Formel R¹(R²)C=C(R³)COOH, in der R¹ bis R³ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist;
   2. ii) Sulfonsäuregruppen-haltige(s) Monomer(e) der Formel R⁵(R⁶)C=C(R⁷)-X-SO₃H, in der R⁵ bis R⁷ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-.

According to the invention, a liquid, low alkaline and bleach-free machine dishwashing detergent with a pH (20 ° C.) between 8 and 12, comprising

1. a) 10 to 60 wt .-% builder
2. b)> 1.5% by weight of phosphonate
3. c) 0.1 to 20 wt .-% anionic copolymer comprising
   1. i) carboxyl-containing monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms;
   2. ii) sulfonic acid group-containing monomer (s) 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, 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 ) -.

Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in the following tables: ingredient Recipe 21 Recipe 22 Recipe 23 Recipe 24 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 2 to 40 2 to 30 2 to 30 3 to 15 carbonate 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5 Anionic copolymer * 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 ingredient Recipe 25 Recipe 26 Recipe 27 Recipe 28 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] potassium 2 to 40 2 to 30 2 to 30 3 to 15 sodium 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5 Anionic copolymer * 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 Anionic copolymer comprising
i) carboxyl-containing monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms;
ii) sulfonic acid group-containing monomer (s) 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, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH or -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an 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 ) -.

In a further preferred embodiment, the copolymers c) comprise, besides carboxyl-containing monomer and monomer containing sulfonic acid groups, 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.

1. i) ungesättigte Carbonsäure(n)
2. ii) Sulfonsäuregruppen-haltige(s) Monomer(e)
3. iii) weitere(s) nichtionogene(s) Monome(e)
   enthält, werden erfindungsgemäß bevorzugt.

Liquid automatic dishwashing detergent, characterized in that the automatic dishwashing agent as anionic polymer c) comprises a copolymer comprising

1. i) unsaturated carboxylic acid (s)
2. ii) sulfonic acid group-containing monomer (s)
3. iii) other nonionic monomers (s)
   contains are preferred 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.

1. a) 10 bis 60 Gew.-% Gerüststoff
2. b) > 1,5 Gew.-% Phosphonat
3. c) 0,1 bis 20 Gew.-% anionisches Copolymer, umfassend
   1. i) ungesättigte Carbonsäure(n)
   2. ii) Sulfonsäuregruppen-haltige(s) Monomer(e).
   3. iii) Monomere der allgemeinen Formel R¹(R²)C=C(R³)-X-R⁴, in der R¹ bis R³ unabhängig voneinander für -H, -CH₃ oder -C₂H₅ steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH₂-, -C(O)O- und -C(O)-NH-, und R⁴ für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht

A further preferred subject of this application is therefore a liquid, low alkaline and bleach-free machine dishwashing detergent having a pH (20 ° C) between 8 and 12, comprising:

1. a) 10 to 60 wt .-% builder
2. b)> 1.5% by weight of phosphonate
3. c) 0.1 to 20 wt .-% anionic copolymer comprising
   1. i) unsaturated carboxylic acid (s)
   2. ii) sulfonic acid group-containing monomer (s).
   3. iii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, 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, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate ter, octyl methacrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, methacrylic acid stearyl ester, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) acrylamide or mixtures thereof.

With respect to the rinsing performance as well as with respect to the cleaning performance of bleachable stains, a weight ratio of the components c) and b) of less than 3: 1 has proven to be advantageous. The weight ratio of components c) and b) denotes the ratio of the weight proportions c) and b) of the total weight of the automatic dishwashing agent to one another. With a weight ratio of the constituents c) to b) of less than 3: 1, the weight fraction of the phosphonate b) should therefore amount to at least one third of the weight fraction of the anionic polymer c). At a weight proportion of the anionic polymer of 9 wt .-% of the total weight of the automatic dishwashing agent, the weight proportion of the phosphonate is thus at least 3 wt .-% of the total weight of the automatic dishwashing detergent.

Liquid automatic dishwashing detergent according to one of the preceding claims, characterized in that the weight ratio of the components c) and b) less than 3: 1, preferably less than 2.5: 1, more preferably less than 2: 1 and in particular between 2: 1 and 1: 5, are preferred according to the invention.

As an additional ingredient, preferred dishwashing detergents according to the invention may contain surfactants. The addition of surfactants has been found to be particularly advantageous in terms of cleaning performance and drying, the nonionic gave the best results from the group of non-ionic surfactants used with particular preference, anionic surfactants and amphoteric surfactants. Anionic and amphoteric surfactants are preferably used in combination with defoamers or foam inhibitors.

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

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides 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 can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, _C9-11 alcohol containing 7 EO, C _13-15 alcohols containing 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 Gained alcohol were 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.

With particular preference further combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are used.

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

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

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

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols 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% 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 more 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.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.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 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 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 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values 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 represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ³ independently of one another is selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably is -CH ₃ , and x and y independently represent values between 1 and 32 where nonionic surfactants with R ³ = -CH ₃ and values for x of 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 is a} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical 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. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, 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.

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

In a preferred embodiment, the automatic dishwashing detergent contains, based on its total weight, nonionic surfactant in amounts of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.5 to 8% by weight. % and in particular from 1.0 to 6 wt .-%.

Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in the following table: ingredient Recipe 29 Recipe 30 Recipe 31 Recipe 32 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 3 to 40 3 to 30 3 to 30 2 to 15 carbonate 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5 Anionic copolymer * 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 Nonionic surfactant 01, to 15 0.2 to 10 0.5 to 8 1 to 6 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 ingredient Recipe 33 Recipe 34 Recipe 35 Recipe 36 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] potassium 3 to 40 3 to 30 3 to 30 2 to 15 sodium 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5 Anionic copolymer * 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 Nonionic surfactant 01, to 15 0.2 to 10 0.5 to 8 1 to 6 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 Anionic copolymer comprising
i) unsaturated carboxylic acid (s)
ii) sulfonic acid group-containing monomer (s)

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

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-16 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

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

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of Shell Oil Company under the name DAN ^® , are suitable anionic surfactants.

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

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

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

R¹

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

X

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

n

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

x

0 oder 1, vorzugsweise 1,

R^II, R^III

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

m

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

y

0 oder 1 und

Y

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

Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy the formula (R ^A ) (R ^B ) (R ^C ) N ⁺ CH ₂ COO ^- , in which R ^{A is} a optionally interrupted by hetero atoms or heteroatom groups alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and R ^B and R ^{C are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ alkyl dimethylcarboxymethylbetaine and C ₁₁ -C ₁₇ -Alkylamidopropyl-dimethylcarboxymethylbetaine, or formula R ¹ - [CO-X- (CH ₂ ) _n ] _x -N + (R ^II ) (R ^III ) - (CH ₂ ) _m - [CH (OH) -CH ₂ ] _y -Y ^- , in the

R ¹

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

X

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

n

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

x

0 or 1, preferably 1,

R ^II , R ^III

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

m

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

y

0 or 1 and

Y

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

The alkyl and alkylamido betaines, betaines of the abovementioned formula having a carboxylate group (Y ^- = COO ^- ) are also called carbobetaines.

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

R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (A1)

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

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

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

in which R ^{1 has} the same meaning as in formula A.

Particularly preferred amphoteric surfactants are the carbo-betaines, in particular the carbo-betaines of the formula A1 and A2, most preferably the alkylamido-betaines of the formula A2.

Examples of suitable betaines and sulfobetaines are the following compounds designated as INCI: almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, caprylic / capramidopropyl betaines, carnitines, cetyl betaines, cocamidoethyl betaines, cocamidopropyl Betaines, cocamidopropyl hydroxysultaines, coco-betaines, coco-hydroxysultaines, coco / oleamidopropyl betaines, coco-sultaines, decyl betaines, dihydroxyethyl oleyl glycinates, dihydroxyethyl soy glycinates, dihydroxyethyl stearyl glycinates, dihydroxyethyl tallow glycinates, dimethicones, propyl PG-betaines, erucamidopropyl hydroxysultaines, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysult aine, oleyl betaine, olivamidopropyl betaine, palmamidopropyl betaine, palmitamidopropyl betaine, palmitoyl carnitine, palm kernel amidopropyl betaine, polytetrafluoroethylene acetoxypropyl betaine, ricinoleamidopropyl betaine, sesamidopropyl betaine, soyamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallowamidopropyl hydroxysultaine, tallow betaine, tallow Dihydroxyethyl betaines, undecylenamidopropyl Betaine and Wheat Germamidopropyl Betaine. A preferred amphoteric surfactant is cocamidopropyl betaine (cocoamidopropyl betaine). A particularly preferred amphoteric surfactant is caprylic / Capramidopropyl Betaine (CAB), which is available for example under the trade name Tegotens ^® B 810 from Th. Goldschmidt AG.

R^VI

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

R^VII

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

i

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

R^VIII

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

j

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

k

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

I

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

Z

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

M

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

The alkylamidoalkylamines ( INCI alkylamido alkylamines) are amphoteric surfactants of the formula
R ^VI -CO-NR ^VII - (CH ₂ ) _i -N (R ^VIII ) - (CH ₂ CH ₂ O) _j - (CH ₂ ) _k - [CH (OH)] ₁ -CH ₂ -Z-OM, in the

R ^VI

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

R ^VII

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

i

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

R ^VIII

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

j

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

k

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

I

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

Z

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

M

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

Preferred representatives satisfy the formulas B1 to B4,

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

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

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

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

in which R ^VI , R ^VIII and M have the same meaning as in formula B.

Exemplary alkylamidoalkylamines are the following named according to INCI compounds: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium laureth 5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate, Sodium Capryl oamphopropionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoamphopropionate, Sodium Lauroamphoacetate, Sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetate and Trisodium Lauroampho PG-Acetate Chloride Phosphate.

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

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

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

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the abovementioned 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, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens . It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .

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

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

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

Particular preference is given to those automatic dishwashing processes in which the automatic dishwashing detergent, based in each case on its total weight, contains from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight. Contains enzyme preparations.

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. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-form detergents, solutions of the enzymes, preferably as concentrated as possible, sparingly mixed with water and / or with stabilizers or other 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.

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 preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.

Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in the following tables: ingredient Recipe 37 Recipe 38 Recipe 39 Recipe 40 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 3 to 40 3 to 30 3 to 30 2 to 15 carbonate 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5 Anionic copolymer * 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 Nonionic surfactant 01, to 15 0.2 to 10 0.5 to 8 1 to 6 Protease preparation 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 Amylase preparation 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 ingredient Recipe 41 Recipe 42 Recipe 43 Recipe 44 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] potassium 3 to 40 3 to 30 3 to 30 2 to 15 sodium 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 of> 1.5 > 1.5 > 1.5 Anionic copolymer * 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 Nonionic surfactant 01, to 15 0.2 to 10 0.5 to 8 1 to 6 Protease preparation 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 Amylase preparation 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 Anionic copolymer comprising
i) unsaturated carboxylic acid (s)
ii) sulfonic acid group-containing monomer (s)

The cleaning performance of automatic dishwashing detergents according to the invention can be improved by the addition of organic solvents. The preferred subject of the present application are therefore automatic dishwashing detergents which, in addition to the other ingredients listed, furthermore contain at least one organic solvent. Preferred liquid automatic dishwashing detergents are characterized in that the dishwashing agent, based on its total weight, organic solvent in amounts of 0.2 to 15 wt .-%, preferably 0.5 to 12 wt .-%, particularly preferably 1.0 to 10 Wt .-% contains.

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, in particular 1,2-propanediol, 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, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, Methoxy, ethoxy or Butoxytriglykol, 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 proven 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 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.

The proportion by weight of alkanolamine in the total weight of preferred automatic dishwashing agent according to the invention is from 0.1 to 10% by weight, preferably from 0.2 to 8% by weight, preferably from 0.4 to 6% by weight and in particular from 1 to 5% by weight. %

Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in the following table: ingredient Recipe 45 Recipe 46 Recipe 47 Recipe 48 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 3 to 40 3 to 30 3 to 30 2 to 15 carbonate 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5 Anionic copolymer * 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 Nonionic surfactant 01, to 15 0.2 to 10 0.5 to 8 1 to 6 Protease preparation 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 Amylase preparation 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 alkanolamine 0.1 to 10 0.2 to 8 0.4 to 6 1 to 5 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 ingredient Recipe 49 Recipe 50 Recipe 51 Recipe 52 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] potassium 3 to 40 3 to 30 3 to 30 2 to 15 sodium 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5 Anionic copolymer * 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 Nonionic surfactant 01, to 15 0.2 to 10 0.5 to 8 1 to 6 Protease preparation 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 Amylase preparation 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 alkanolamine 0.1 to 10 0.2 to 8 0.4 to 6 1 to 5 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 Anionic copolymer comprising
i) unsaturated carboxylic acid (s)
ii) sulfonic acid group-containing monomer (s)

Glass corrosion inhibitors are further preferred ingredients of automatic dishwashing detergents 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 zinc salts and magnesium and zinc complexes.

The spectrum of the inventively preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or are not soluble, ie have a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference is used as the glass corrosion inhibitor at least one zinc salt of an inorganic or organic carboxylic acid, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

In the context of the present invention, the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight. , or the content of zinc in oxidized form (calculated as Zn ²⁺ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 5 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.

In order to achieve the desired viscosity of the automatic dishwashing detergent according to the invention, thickening agents are preferably added to these agents.

A large group of particularly preferred thickeners are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Thickening agents from these classes of compounds are widely available commercially and are sold for example under the trade name Acusol ^® -810, Acusol ^® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^®-GT-282-S (alkyl polyglycol ethers, Akzo), DEUTEROL ^® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ^® -xg (anionic heteropolysaccharide based on β-D-glucose, D-mannose, D- glucuronic acid, Schoner GmbH), -XN deuteron ^® (non-ionic polysaccharide, Schoner GmbH), DICRYLAN ^® -Verdicker-O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ^® -81 and -91 EMA ^® (ethylene-maleic anhydride copolymer, Monsanto), thickener QR-1001 (polyurethane emulsion, 19-21% in water / diglyme, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylate copolymer dispersion, 25% ig (in water, Stockhausen), SER-AD FX 1100 (hydrophobic urethane polymer, servo Delden), Shellflo ^® -S stabilized high molecular polysaccharide, stabilized with formaldehyde, Shell), and Shellflo XA ^® (xanthan biopolymer with formaldehyde, Shell) is.

Examples of other thickening agents are agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose, gum ethers, polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids , Polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas.

It has proved to be particularly advantageous if the machine dishwashing detergents according to the invention contain the thickener in amounts of between 0.1 and 8% by weight, preferably between 0.2 and 6% by weight and more preferably between 0.4 and 4% by weight. % based on the total weight of the automatic dishwashing detergent

The pourability and settling stability of the liquid automatic dishwasher detergents according to the invention can, in addition to the thickeners, also be influenced by the ratio of the potassium and sodium ions in this agent. Machine dishwashing agents according to the invention which have a ratio of potassium to sodium ions above 1: 1, preferably above 2: 1, more preferably above 4: 1 and in particular above 8.1, have proved to be advantageous.

The packaging and packaging of agents according to the invention is carried out using the water-soluble or water-insoluble packaging materials known to the person skilled in the art. The packaging means may be one, two or more chamber container.

Particularly preferred are water-insoluble two- or multi-chamber container. Such two- or multi-chamber containers typically have a total volume of 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. The automatic dishwashing compositions according to the invention are present in these packaging materials, preferably in the form of separate partial formulations. These sub-formulations do not form a common phase boundary, but rather are located in separate regions of the packaging means and have different compositions from each other.

For metering the liquid automatic dishwashing detergent, the two-chamber or multi-chamber container preferably has at least one spout, which can be configured, for example, in the form of a common spout for all the 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.

1. a) 10 bis 60 Gew.-% Gerüststoff
2. b) > 1,5 Gew.-% Phosphonat
3. c) 0,1 bis 20 Gew.-% anionisches Copolymer, umfassend
   1. i) ungesättigte Carbonsäure(n)
   2. ii) Sulfonsäuregruppen-haltige(s) Monomer(e).
   dadurch gekennzeichnet, dass das maschinelle Geschirrspülmittel in einem Zwei- oder Mehrkammerbehälter vorliegt, dessen einzelne Kammern mit Teilrezepturen des maschinellen Geschirrspülmittels befüllt sind.

Another preferred subject matter of the present application is therefore a liquid, low alkaline and bleach-free machine dishwashing detergent having a pH (20 ° C) between 8 and 12, comprising:

1. a) 10 to 60 wt .-% builder
2. b)> 1.5% by weight of phosphonate
3. c) 0.1 to 20 wt .-% anionic copolymer comprising
   1. i) unsaturated carboxylic acid (s)
   2. ii) sulfonic acid group-containing monomer (s).
   characterized in that the automatic dishwashing detergent is present in a two- or multi-chamber container whose individual chambers are filled with partial formulations of the automatic dishwashing detergent.

Of course, the weights given above for the washing and cleaning ingredients and the pH values refer to the automatic dishwashing detergent obtained by combining all the partial formulations. In the above-described packaging by means of a two-chamber or multi-chamber container, individual sub-formulations contained in the chambers may deviate from the characteristics characterizing the machine dishwashing detergent according to the invention, provided that only the combination of all sub-formulations comprises a machine dishwashing detergent according to the invention having the above-mentioned characterizing and optionally preferred Features.

For example, individual sub-formulations may be free of phosphonate or anionic copolymer, provided that the combination of all sub-formulations results in a machine dishwashing detergent which comprises> 1.5% by weight of phosphonate and 0.1 to 20% by weight of anionic copolymer comprising i) unsaturated carboxylic acid (n) and ii) contains sulfonic acid group-containing (s) monomer (s).

The details of the pH value of the low-alkaline dishwashing detergents according to the invention mentioned above also relate to the pH of the overall composition and not to the pH of any partial formulations. Thus, individual partial formulations may have pH values (20 ° C.) below 8 or above 12, provided that the combination of the partial formulations results in a machine dishwashing detergent which has a pH (20 ° C.) between 8 and 12.

When preparing automatic dishwashing agents according to the invention in two-chamber or multi-compartment containers, it has proven advantageous for the stability of any enzymes contained in these agents to assemble these enzymes together with a nonionic surfactant in one of the chambers of the container. The combined preparation of enzyme and surfactant, the cleaning performance of these agents could be improved.

Some exemplary formulations for such preferred automatic dishwashing detergents according to the invention can be found in the following tables: Machine dishwashing detergent 1 Machine dishwashing detergent 2 ingredient Partial formulation 1 [% by weight] Partial formulation 2 [% by weight] Partial formulation 1 [% by weight] Partial formulation 2 [% by weight] tripolyphosphate 3 to 40 3 to 30 3 to 30 2 to 15 carbonate 0 to 10 3 to 20 - 4 to 15 phosphonate 0 to 4 2 to 6 0 to 4 2 to 6 Anionic copolymer * 0 to 10 0.2 to 18 - 1 to 12 Nonionic surfactant 0.1 to 15 0 to 4 0.5 to 8 - Enzyme preparation 0.1 to 12 - 0.5 to 8 - water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 Machine dishwashing detergent 3 Machine dishwashing detergent 4 ingredient Partial formulation 1 Partial recipe 2 Partial formulation 1 Partial recipe 2 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] potassium 3 to 40 3 to 30 3 to 30 2 to 15 sodium 0 to 10 3 to 20 - 4 to 15 phosphonate 0 to 4 2 to 6 0 to 4 2 to 6 Anionic copolymer * 0 to 10 0.2 to 18 - 1 to 12 Nonionic surfactant 0.1 to 15 0 to 4 0.5 to 8 - Enzyme preparation 0.1 to 12 - 0.5 to 8 - water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 Machine dishwashing detergent 5 Machine dishwasher 6 ingredient Partial formulation 1 Partial recipe 2 Partial formulation 1 Partial recipe 2 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 3 to 40 3 to 30 3 to 30 2 to 15 carbonate 0 to 10 3 to 20 - 4 to 15 HEDP 0 to 4 2 to 6 0 to 4 2 to 6 Anionic copolymer * 0 to 10 0.2 to 18 - 1 to 12 Nonionic surfactant 0.1 to 15 0 to 4 0.5 to 8 - Protease preparation 0.1 to 12 - 0.5 to 8 - Amylase preparation 0.1 to 12 - 0.5 to 8 - alkanolamine - 0.2 to 8 - 1 to 5 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 Machine dishwashing detergent 7 Machine dishwasher 8 ingredient Partial formulation 1 Partial recipe 2 Partial formulation 1 Partial recipe 2 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] potassium 3 to 40 3 to 30 3 to 30 2 to 15 sodium 0 to 10 3 to 20 - 4 to 15 HEDP 0 to 4 2 to 6 0 to 4 2 to 6 Anionic copolymer * 0 to 10 0.2 to 18 - 1 to 12 Nonionic surfactant 0.1 to 15 0 to 4 0.5 to 8 - Protease preparation 0.1 to 12 - 0.5 to 8 - Amylase preparation 0.1 to 12 - 0.5 to 8 - alkanolamine - 0.2 to 8 - 1 to 5 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 Anionic copolymer comprising
i) unsaturated carboxylic acid (s)
ii) sulfonic acid group-containing monomer (s)

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 present application further relates to a method for cleaning dishes in a dishwasher, using liquid, low-alkaline and bleach-free automatic dishwashing detergent according to the invention, wherein the automatic dishwashing detergents preferably be 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 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 automatic dishwasher detergents according to the invention show their advantageous cleaning properties, in particular also low-temperature cleaning processes. Preferred dishwashing processes using agents according to the invention are therefore characterized in that these processes are carried out at temperatures up to a maximum of 55 ° C., preferably up to a maximum of 50 ° C.

As described above, compositions according to the invention are distinguished from conventional automatic dishwashing agents by an improved cleaning performance on bleachable soiling. An object of the present application is therefore also the use of a machine dishwashing detergent according to the invention for cleaning bleachable stains in automatic dishwashing.

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 33 ml of the automatic dishwashing detergent listed in the table below. ingredient V1 V2 E1 E2 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] potassium 14 14 14 14 sodium 4.0 4.0 4.0 4.0 HEDP 1.0 1.5 1.8 3.0 Anionic copolymer * 4.0 4.0 4.0 4.0 Nonionic surfactant 2.0 2.0 2.0 2.0 Protease preparation 2.0 2.0 2.0 2.0 Amylase preparation 0.8 0.8 0.8 0.8 alkanolamine 1.5 1.5 1.5 1.5 water 55 55 55 55 Misc Add 100 Add 100 Add 100 Add 100 Anionic copolymer comprising
i) unsaturated carboxylic acid (s)
ii) sulfonic acid group-containing monomer (s)

The dough cleaning 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): V1 V2 E1 E2 Teereinigung 1.0 1.5 2.5 3.0

Claims (14)

1. A liquid, low-alkaline and bleach-free automatic dishwashing agent having a pH value (20°C) between 8 and 12, comprising:

   a) 10 to 60 wt.% builder

   b) > 1.5 wt.% phosphonate

   c) 0.1 to 20 wt.% anionic copolymer, containing

   i) unsaturated carboxylic acid(s)

   ii) sulfonic acid group-containing monomer(s).
2. The liquid automatic dishwashing agent according to claim 1, characterised in that the automatic dishwashing agent has a pH value (20 °C) between 9 and 11.5, preferably between 9.5 and 11.5.
3. The liquid automatic dishwashing agent according to one of the previous claims, characterised in that the dishwashing agent comprises at least two builders from the group of the phosphates, carbonates and citrates, wherein the weight fraction of these builders, based on the total weight of the automatic dishwashing agent, is preferably 2 to 50 wt.%, preferably 5 to 40 wt.% and especially 10 to 30 wt.%.
4. The liquid automatic dishwashing agent according to one of the previous claims, characterised in that the automatic dishwashing agent, based on its total weight, comprises more than 1.8 wt.%, preferably more than 2.2 wt.% and in particular more than 2.4 wt.% phosphonate.
5. The liquid automatic dishwashing agent according to one of the previous claims, characterised in that it comprises 1-hydroxyethane-1,1-diphosphonic acid (HEDP) as the phosphonate b).
6. The liquid automatic dishwashing agent according to one of the previous claims, characterised in that the automatic dishwashing agent, based on its total weight, comprises 0.2 to 18 wt.%, preferably 0.5 to 15 wt.% and especially 1.0 to 12 wt.% of the anionic polymer c).
7. The liquid automatic dishwashing agent according to one of the previous claims, characterised in that the automatic dishwashing agent comprises a copolymer, containing

   iii) unsaturated carboxylic acid(s)

   iv) sulfonic acid group-containing monomer(s)

   v) additional non-ionic monomer(s).

   as the anionic polymer c).
8. The liquid automatic dishwashing agent according to one of the previous claims, characterised in that the weight ratio of the ingredients c) and b) is less than 2: 1, preferably less than 1.8:1, particularly preferably less than 1.5:1 and especially between 1.5:1 and 1:5.
9. The liquid automatic dishwashing agent according to one of the previous claims, characterised in that the automatic dishwashing agent, based on its total weight, comprises non-ionic surfactant in quantities of 0.1 to 15 wt.%, preferably 0.2 to 10 wt.%, particularly preferably 0.5 to 8 wt.% and especially from 1.0 to 6 wt.%.
10. The liquid automatic dishwashing agent according to one of the previous claims, characterised in that the automatic dishwashing agent, based on its total weight, comprises enzyme in quantities of 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and particularly 0.5 to 8 wt.%.
11. A process for washing table ware in a dishwasher by using an automatic dishwashing agent according to one of claims 1 to 10.
12. The process according to claim 11, characterised in that no additional water softener and no additional rinse aid is metered into the interior of the dishwasher in the course of the cleaning process.
13. The process according to one of the previous claims, characterised in that said process is carried out at temperatures up to a maximum of 55 °C, preferably up to a maximum of 50 °C.
14. Use of an automatic dishwashing agent according to one of claims 1 to 10 for cleaning bleachable stains during automatic dishwashing.