EP2185674B2 - Detergents - Google Patents

Description

The present patent application describes cleaning agents, in particular cleaning agents for machine cleaning of dishes. This application relates in particular to automatic dishwashing agents which contain a combination of specific nonionic surfactants and anionic polymers.

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

One of the main goals of the manufacturers of machine cleaning agents is to improve the cleaning performance of these agents, and recently more attention has been paid to the cleaning performance in low-temperature cleaning processes or in cleaning processes with reduced water consumption. For this purpose, new ingredients, for example more effective surfactants, polymers or bleaching agents, were preferably added to the cleaning agents. However, since new ingredients are only available to a limited extent and the amount of ingredients used per cleaning cycle cannot be increased to any desired extent for ecological and economic reasons, there are natural limits to this approach.

In addition to the cleaning and rinsing capacity, the drying performance is another essential characteristic of automatic dishwashing detergents. Since the drying of the dishes is essentially brought about by the own heat of the dishes after the machine cleaning process has ended, high-temperature cleaning processes are generally distinguished by improved drying compared to low-temperature cleaning processes. However, high-temperature cleaning processes are necessarily characterized by increased energy consumption and consequently increased costs for people and the environment.

So while low-temperature cleaning processes are increasingly becoming the focus of consumer interest due to their economic and ecological advantages and the manufacturers of dishwashers are increasingly taking this customer request into account with appropriate cleaning programs, there is a need for manufacturers of automatic dishwashing detergents to provide detergents that also work under these changed framework conditions , preferably in the entire area of the framework conditions represented in the market (ie cleaning programs) have a proven, if possible improved, performance profile.

DE 101 331 37 discloses liquid, aqueous machine dishwashing detergents which may contain end-capped poly (oxyalkylated) note lines.

Against this technical background, the object of this application was to provide an automatic dishwashing agent which has good cleaning and rinsing performance and improved drying of the cleaned dishes even in low-temperature cleaning cycles or in cleaning cycles with low water consumption.

This object was achieved by means of an automatic dishwashing agent with a specific combination of nonionic surfactants and anionic polymers.

1. a) 10 bis 60 Gew.-% Gerüststoff
2. b) nichtionisches Tensid der allgemeinen Formel
   R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_y[CH₂CH(CH₃)O]_zCH₂CH(OH)R², in der R¹ für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht, R² einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x und z für Werte zwischen 0 und 40 und y für einen Wert von mindestens 15 steht.
3. c) anionisches Copolymer, umfassend
   1. i) ungesättigten Carbonsäuren
   2. ii) Sulfonsäuregruppen-haltigen Monomeren,
   dadurch gekennzeichnet, dass das Gewichtsverhältnis der Bestandteile c) und b) weniger als 3:1 beträgt, wobei das Geschirrspülmittel, bezogen auf das Gesamtgewicht des maschinellen Geschirrspülmittels, Phosphonat in Mengen von 2,0 bis 5 Gew.-% enthält.

A first subject matter of the present application is therefore an automatic dishwashing agent containing

1. a) 10 to 60% by weight of builder
2. b) nonionic surfactant of the general formula
   R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² , where R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z represent values between 0 and 40 and y represents a value of at least 15.
3. c) anionic copolymer comprising
   1. i) unsaturated carboxylic acids
   2. ii) monomers containing sulfonic acid groups,
   characterized in that the weight ratio of components c) and b) is less than 3: 1, the dishwashing agent containing phosphonate in amounts of 2.0 to 5% by weight, based on the total weight of the automatic dishwashing agent.

Automatic dishwashing agents according to the invention contain one or more builders as the first essential component. The weight proportion of the builders in the total weight of automatic dishwashing agents according to the invention is preferably 15 to 50% by weight and in particular 20 to 40% by weight. The builders include, in particular, carbonates, phosphates, organic cobuilders and silicates.

The use of carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate, in amounts of from 2 to 30% by weight, preferably from 3 to 20% by weight and in particular, is particularly preferred from 4 to 15% by weight, based in each case on the weight of the automatic dishwasher detergent.

Organic cobuilders that may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These substance classes are described below.

Organic builder substances which can be used are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or its sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, as well as mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value in detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.

Particularly preferred automatic dishwashing agents according to the invention contain citrate as one of their essential builders. Automatic 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. In addition to phosphates, citrate and citric acid have proven to be the most effective builders in combination with phosphonate, in particular 1-hydroxyethane-1,1-diphosphonic acid, and the copolymers containing sulfonic acid groups in terms of cleaning performance, such as rinsing performance and, in particular, deposit inhibition.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

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

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and 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 particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70,000 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 (co) polymeric polycarboxylates in the automatic dishwashing detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.

Automatic dishwashing agents according to the invention can use crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} · y H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, as a builder 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 the citrates, the phosphates have proven to be the most effective builders in terms of cleaning performance. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference being given to pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphate is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO ₄ can be distinguished in addition to higher molecular representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in fabrics and also contribute to cleaning performance.

Technically important phosphates are 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). Sodium potassium tripolyphosphates are also preferably used according to the invention.

If, in the context of the present application, phosphates are used as washing or cleaning-active substances in detergents or cleaning agents, then preferred agents contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or Potassium tripolyphosphate), in amounts from 2 to 50% by weight, preferably from 2 to 30% by weight and in particular from 3 to 25% by weight, particularly preferably from 3 to 15% by weight, in each case based on the Weight of the detergent or cleaning agent.

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

In preferred automatic dishwashing agents according to the invention, the content of silicates, based on the total weight of the automatic dishwashing agent, is below 10% by weight, preferably below 5% by weight and in particular below 2% by weight. Automatic dishwashing agents according to the invention which are particularly preferred are silicate-free. The automatic dishwashing agents according to the invention can of course contain the aforementioned builders both in the form of individual substances and in the form of substance mixtures composed of two, three, four or more builders.

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

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

Some exemplary formulations for preferred automatic dishwashing agents according to the invention can be found in the following tables: (not according to the invention): ingredient Formula 1 [% by weight] Formulation 2 [% by weight] Formulation 3 [% by weight] Formulation 4 [% by weight] Tripolyphosphate 5 to 50 5 to 35 - - Citrate - *** - 5 to 30 5 to 20 Carbonate 2 to 45 2 to 35 2 to 45 2 to 35 Nonionic surfactant * 0.1 to 15 0.2 to 10 0.5 to 8 1 to 6 Anionic copolymer ** 0.1 to 20 0.1 to 20 0.1 to 20 0.1 to 20 Misc Add 100 Add 100 Add 100 Add 100 ingredient Formulation 5 [% by weight] Recipe 6 [% by weight] Formula 7 [% by weight] Formulation 8 [% by weight] Potassium tripolyphosphate 5 to 50 5 to 35 - - Citrate - *** - 5 to 30 5 to 20 sodium 2 to 45 2 to 35 2 to 45 2 to 35 Nonionic surfactant * 0.1 to 15 0.2 to 10 0.5 to 8 1 to 6 Anionic copolymer ** 0.1 to 20 0.1 to 20 0.1 to 20 0.1 to 20 Misc Add 100 Add 100 Add 100 Add 100 * nonionic surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² contains, in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y stands for a value of at least 15. ** anionic copolymer comprising i) unsaturated carboxylic acid (s) ii) Monomer (s) containing sulfonic acid groups *** "-" means in this, as in all of the following tables: the formulation is free from this component

Dishwashing detergents according to the invention contain nonionic surfactants of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) as a second essential component ) R ² . The addition of surfactants has proven to be particularly advantageous with regard to the rinsing performance and drying. In a preferred embodiment, the automatic dishwashing agent contains, based on its total weight, nonionic surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O ] _z CH ₂ CH (OH) R ² in amounts from 0.1 to 15 % By weight, preferably 0.2 to 10% by weight, particularly preferably 0.5 to 8% by weight and in particular from 1.0 to 6% by weight.

Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x (A "O) _y - (A"'O) _z -R ² , in which R ¹ and R. ² independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or -alkenyl radical; A, A ', A "and A"' independently of one another for 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 stand for values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Particularly preferred are those end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R ¹ O [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ¹ denotes a linear or branched aliphatic hydrocarbon radical with 4 up to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and y stands for a value between 15 and 120, preferably 20 to 100, in particular 20 to 80. The group of these nonionic surfactants includes, for example, hydroxy _mixed ethers of the general formula C 6-22 -CH (OH) CH ₂ O- (EO) _20-120 -C _2-26 , for example the C _8-12 fatty alcohol (EO) ₂₂ - 2-hydroxyecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ethers.

Also preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x represents values between 0.5 and 4, preferably 0.5 to 1.5, and y represents a value of at least 15 stands.

According to the invention, surfactants of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ^{2 are also} preferred, in which R ^{1 is} a linear or branched aliphatic Hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for a value between 1 and 40 and y stands for a value between 15 and 40, the alkylene units [CH ₂ CH (CH ₃ ) O] and [CH ₂ CH ₂ O] are randomized, ie in the form of a statistical, random distribution.

The group of preferred end-capped poly (oxyalkylated) nonionic surfactants b) also includes 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 represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH _{2 - CH 3} , --CH (CH ₃ ) ₂ , but preferably - CH ₃ , and x and y independently of one another stand for values between 1 and 32, 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 nonionic surfactants described above with a free hydroxyl group on one of the two terminal alkyl radicals, the rinsing performance and drying can be significantly improved compared to conventional polalkoxylated fatty alcohols without a free hydroxyl group.

The specified carbon chain lengths and degrees of ethoxylation or degrees of alkoxylation of the aforementioned nonionic surfactants represent statistical mean values which, for a specific product, can be an integer or a fraction. Due to the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative, but rather of mixtures, which can result in mean values and fractional numbers for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.

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

Nonionic surfactants b) which have a melting point above room temperature are particularly preferred. Nonionic surfactant (s) b) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C., is / are particularly preferred.

A third characteristic component of automatic dishwashing detergents according to the invention are the copolymers c) containing sulfonic acid groups, which, in addition to monomer (s) containing sulfonic acid groups, comprise at least one unsaturated carboxylic acid. The copolymers c) can have two, three, four or more different monomer units. Preferred automatic dishwashing detergents contain the polymer c) in amounts of 0.2 to 18% by weight, preferably 0.5 to 15% by weight and in particular 1.0 to 12% by weight, based in each case on the total weight of the machine Dishwashing detergent.

The unsaturated carboxylic acid (s) used is / are particularly preferably unsaturated carboxylic acids. Particularly preferred are 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, represent -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 with - NH 2} , --OH or --COOH as defined above or for - COOH or --COOR ⁴ stands, where 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) nichtionisches Tensid der allgemeinen Formel
   
           R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_y[CH₂CH(CH₃)O]_zCH₂CH(OH)R²
   
   enthält, in der R¹ für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht, R² einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x und z für Werte zwischen 0 und 40 und y für einen Wert von mindestens 15 steht.
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, an automatic dishwashing detergent containing:

1. a) 10 to 60% by weight of builder
2. b) nonionic surfactant of the general formula
   
   R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ²
   
   contains, in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y stands for a value of at least 15.
3. c) 0.1 to 20 weight percent anionic copolymer comprising
   1. i) Carboxyl group-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 represent -H, -CH ₃ , a straight-chain or branched, saturated alkyl radical with 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 with -NH 2} , -OH or -COOH as defined above or -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms
   2. ii) Monomer (s) containing sulfonic acid groups.

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. The unsaturated dicarboxylic acids can of course also be used.

The monomers containing sulfonic acid groups are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

preferred, in which R ⁵ to R ⁷ independently of one another represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH-substituted alkyl or alkenyl radicals 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 optionally present 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 represents an optionally present 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-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3-sulphate, 3-sulphonyl methacrylate, vinylsulpho-propyl, 3-sulphate, sulfo methacrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.

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

The monomer distribution of the copolymers preferably used according to the invention is, in the case of copolymers which contain only monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably from 50 to 90% by weight of monomer from group ii) and 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 application. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses 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) nichtionisches Tensid der allgemeinen Formel
   
           R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_y[CH₂CH(CH₃)O]_zCH₂CH(OH)R²
   
   enthält, in der R¹ für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht, R² einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x und z für Werte zwischen 0 und 40 und y für einen Wert von mindestens 15 steht.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, an automatic dishwashing detergent containing:

1. a) 10 to 60% by weight of builder
2. b) nonionic surfactant of the general formula
   
   R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ²
   
   contains, in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y is a value of at least 15. c) 0.1 to 20% by weight of anionic copolymer comprising
   1. i) Carboxyl group-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 represent -H, -CH ₃ , a straight-chain or branched, saturated alkyl radical with 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 with -NH 2} , -OH or -COOH as defined above 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;
   2. ii) Monomer (s) containing sulfonic acid groups 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 represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, _{alkyl or alkenyl radicals substituted with -NH 2} , -OH or -COOH or for -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 optionally present 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 ) -.

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 sustituierte 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)-.

Some exemplary formulations for preferred automatic dishwashing agents according to the invention can be found in the following tables (not according to the invention): ingredient Formulation 9 [% by weight] Formulation 10 [% by weight] Formulation 11 [% by weight] Recipe 12 [% by weight] Tripolyphosphate 5 to 50 5 to 35 5 to 55 5 to 35 Carbonate 2 to 45 2 to 35 2 to 35 2 to 35 Nonionic surfactant 0.1 to 15 0.2 to 10 0.5 to 8 1 to 6 Anionic copolymer * 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 Misc Add 100 Add 100 Add 100 Add 100 ingredient Formulation 13 [% by weight] Formulation 14 [% by weight] Formulation 15 [% by weight] Formulation 16 [% by weight] Potassium tripolyphosphate 5 to 50 5 to 35 5 to 55 5 to 35 sodium 2 to 45 2 to 35 2 to 35 2 to 35 Nonionic surfactant 0.1 to 15 0.2 to 10 0.5 to 8 1 to 6 Anionic copolymer * 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 Misc Add 100 Add 100 Add 100 Add 100 * nonionic surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² contains, in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y stands for a value of at least 15. ** anionic copolymer comprising

1. i) Carboxyl group-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 represent -H, -CH ₃ , a straight-chain or branched, saturated alkyl radical with 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 with -NH 2} , -OH or -COOH as defined above 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;
2. ii) Monomer (s) containing sulfonic acid groups 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 represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, _{alkyl or alkenyl radicals substituted with -NH 2} , -OH or -COOH or for -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 optionally present 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 ) -.

In a further preferred embodiment, the copolymers c) furthermore comprise at least one nonionic, preferably hydrophobic, monomer in addition to carboxyl group-containing monomer and sulfonic acid group-containing monomer. The use of these hydrophobically modified polymers made it possible in particular to improve the rinsing performance of automatic dishwashing agents according to the invention.

1. i) ungesättigte Carbonsäure(n)
2. ii) Sulfonsäuregruppen-haltige(s) Monomer(e)
3. iii) weitere(s) nichtionogene(s) Monomer(e)

enthält, werden erfindungsgemäß bevorzugt.Automatic dishwashing detergents, characterized in that the automatic dishwashing detergent comprises as anionic polymer c) a copolymer

1. i) unsaturated carboxylic acid (s)
2. ii) Monomer (s) containing sulfonic acid groups
3. iii) other non-ionic monomer (s)

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 represent -H, -CH ₃ or -C ₂ H ₅ , X stands for an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 stands} for 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) nichtionisches Tensid der allgemeinen Formel
   
           R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_y[CH₂CH(CH₃)O]_zCH₂CH(OH)R²
   
   enthält, in der R¹ für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht, R² einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x und z für Werte zwischen 0 und 40 und y für einen Wert von mindestens 15 steht.
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

Another preferred subject of this application is therefore an automatic dishwashing detergent containing:

1. a) 10 to 60% by weight of builder
2. b) nonionic surfactant of the general formula
   
   R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ²
   
   contains, in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y stands for a value of at least 15.
3. c) 0.1 to 20 weight percent anionic copolymer comprising
   1. i) unsaturated carboxylic acid (s)
   2. ii) Monomer (s) containing sulfonic acid groups.
   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 stands} for a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or for an unsaturated one , preferably an 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, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefones with 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-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, methyl acrylate, methyl acrylate, butyl acrylate, acrylate - (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate, methacr yl acid octyl ester, N- (octyl) acrylamide, acrylic acid lauryl ester, methacrylic acid lauryl ester, N- (lauryl) acrylamide, acrylic acid stearyl ester, methacrylic acid stearyl ester, N- (stearyl) acrylamide, acrylic acid behenyl ester, methacrylic acid behenyl ester and N- (behenyl) acrylate or mixtures thereof.

With regard to the rinsing performance and the drying of the dishes, a weight ratio of components c) and b) of less than 2.8: 1 has proven to be advantageous, particularly in the case of low-temperature cleaning processes. The weight ratio of components c) and b) denotes the ratio of the weight fractions c) and b) to one another in relation to the total weight of the automatic dishwasher detergent. With a weight ratio of the constituents c) to b) of less than 3: 1, the proportion by weight of the surfactant b) should accordingly be at least one third of the proportion by weight of the anionic polymer c). With a weight proportion of the anionic polymer of 9% by weight of the total weight of the automatic dishwashing agent, the weight proportion of the surfactant is therefore at least 3% by weight of the total weight of the automatic dishwashing agent.

Automatic dishwashing detergent according to one of the preceding claims, characterized in that the weight ratio of components c) and b) is less than 2.8: 1, preferably less than 2.5: 1, particularly preferably less than 2.2: 1 and in particular between 2.2: 1 and 1:10 are preferred according to the invention.

The automatic dishwashing agents according to the invention can contain phosphonate (s) as a further constituent. The weight fraction of the phosphonate, based on the total weight of the automatic dishwasher detergent, is preferably 0.5 to 10% by weight, more preferably 1.0 to 9% by weight and in particular 1.5 to 7% by weight, particularly preferably 2 , 0 to 5% by weight.

The complex-forming phosphonates include a number of different compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9). Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates. They are preferably in the form of the neutrally reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. From the group of phosphonates, HEDP is preferably used.

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) aminotrimethylene phosphonic acid (ATMP) and / or its salts;
2. b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof;
3. c) Diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) and / or salts thereof;
4. d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or its salts;
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.

Automatic dishwashing agents which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred.

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

1. i) ungesättigte Carbonsäure(n)
2. ii) Sulfonsäuregruppen-haltige(s) Monomer(e)

Some exemplary formulations for preferred automatic dishwashing agents according to the invention can be found in the following tables: ingredient Formulation 17 [% by weight] Formulation 18 [% by weight] Formulation 19 [% by weight] Formulation 20 [wt .-%] Tripolyphosphate 5 to 50 5 to 35 5 to 55 5 to 35 Carbonate 2 to 45 2 to 35 2 to 35 2 to 35 Nonionic surfactant * 0.1 to 15 0.2 to 10 0.5 to 8 1 to 6 Anionic copolymer ** 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 Phosphonate 0.5 to 10 1 to 9 1.5 to 7 2.0 to 5 Misc Add 100 Add 100 Add 100 Add 100 ingredient Formula 21 [% by weight] Formula 22 [% by weight] Formulation 23 [wt .-%] Formulation 24 [% by weight] Potassium tripolyphosphate 5 to 50 5 to 35 5 to 55 5 to 35 sodium 2 to 45 2 to 35 2 to 35 2 to 35 Nonionic surfactant * 0.1 to 15 0.2 to 10 0.5 to 8 1 to 6 Anionic copolymer ** 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 Phosphonate 0.5 to 10 1 to 9 1.5 to 7 2.0 to 5 Misc Add 100 Add 100 Add 100 Add 100 * nonionic surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² contains, in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y stands for a value of at least 15. ** anionic copolymer comprising

1. i) unsaturated carboxylic acid (s)
2. ii) Monomer (s) containing sulfonic acid groups

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

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilases, but no longer the subtilisins in the narrower sense of the term, thermitase, Proteinase K and the proteases TW3 and TW7.

Examples of amylases that can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaclens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the improved developments of the aforementioned amylases for use in detergents and cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be emphasized.

According to the invention, lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, especially those with the amino acid exchange D96L. Furthermore, for example, the cutinases which were originally isolated from Fusarium solani pisi and Humicola insolens can be used. Lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.

It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

According to the invention, 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 to increase the bleaching effect. Advantageously, preferably organic, particularly preferably aromatic, compounds that interact with the enzymes are added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.

A protein and / or enzyme can be protected against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage. In the case of microbial production of the proteins and / or enzymes, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Washing or cleaning agents can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.

In particular, those automatic dishwashing processes are preferred in which the automatic dishwashing agent, based in each case on its total weight, is 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight Contains enzyme preparations.

Proteases and amylases which are active in washing or cleaning are generally not provided in the form of the pure protein, but rather in the form of stabilized preparations that can be stored and transported. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously As concentrated as possible, low in water and / or mixed with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or roller granulation or in fluid bed processes. Such granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.

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

As can be seen from the previous statements, 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% by weight of the enzyme protein.

1. i) ungesättigte Carbonsäure(n)
2. ii) Sulfonsäuregruppen-haltige(s) Monomer(e)

Some exemplary recipes for preferred automatic dishwashing agents according to the invention can be found in the following tables (not according to the invention): ingredient Formulation 25 [% by weight] Formulation 26 [% by weight] Formulation 27 [% by weight] Formulation 28 [% by weight] Tripolyphosphate 5 to 50 5 to 35 5 to 55 5 to 35 Carbonate 2 to 45 2 to 35 2 to 35 2 to 35 Nonionic surfactant * 0.1 to 15 0.2 to 10 0.5 to 8 1 to 6 Anionic copolymer ** 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 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 Misc Add 100 Add 100 Add 100 Add 100 ingredient Formulation 29 [wt .-%] Formulation 30 [wt .-%] Formulation 31 [% by weight] Formula 32 [% by weight] Potassium tripolyphosphate 5 to 50 5 to 35 5 to 55 5 to 35 sodium 2 to 45 2 to 35 2 to 35 2 to 35 Nonionic surfactant * 0.1 to 15 0.2 to 10 0.5 to 8 1 to 6 Anionic copolymer ** 0.1 to 20 0.2 to 18 0.5 to 15 1 to 12 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 Misc Add 100 Add 100 Add 100 Add 100 * nonionic surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² contains, in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y stands for a value of at least 15. ** Anionic copolymer comprising

1. i) unsaturated carboxylic acid (s)
2. ii) Monomer (s) containing sulfonic acid groups

Glass corrosion inhibitors are further preferred ingredients of dishwasher detergents according to the invention. Glass corrosion inhibitors prevent the appearance of cloudiness, streaks and scratches, but also the iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of the magnesium and zinc salts and the magnesium and zinc complexes.

The spectrum of zinc salts preferred according to the invention, preferably organic acids, particularly preferably organic carboxylic acids, ranges from salts that are sparingly or insoluble in water, i.e. a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / l, up to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly 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.

At least one zinc salt of an inorganic or organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate, is used with particular preference as the glass corrosion inhibitor. 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 cleaning agents is preferably between 0.1 to 5% by weight, more preferably between 0.2 to 4% by weight and in particular between 0.4 to 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% by weight, based in each case on the total weight of the agent containing the glass corrosion inhibitor.

Automatic dishwashing agents according to the invention can contain an oxygen bleaching agent as a further essential component. Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H ₂ O _{2 in water.} Further bleaching agents which can be used are, for example, peroxypyrophosphates, citrate perhydrates and _{peracid salts or peracids which provide H 2} O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. Furthermore, bleaches from the group of organic bleaches can also be used. Typical organic bleaching agents are the diacyl peroxides such as dibenzoyl peroxide. Further typical organic bleaching agents are the peroxy acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned as examples.

Preferred automatic dishwashing agents are characterized in that the dishwashing agent, based in each case on the total weight of the dishwashing agent, contains 1.0 to 20% by weight, preferably 4.0 to 18% by weight and in particular 8 to 15% by weight of an oxygen bleaching agent , preferably 1.0 to 20% by weight, preferably 4.0 to 18% by weight and in particular 8 to 15% by weight sodium percarbonate.

In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below, the automatic dishwashing agents according to the invention can additionally contain bleach activators. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups with the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multiple acylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) having proven particularly suitable.

These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight , each based on the total weight of the bleach activator-containing agents.

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

Manganese complexes in the II, III, IV or IV oxidation state, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, are used with particular preference. Ligands are preferably used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are for example [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (µ-O) (µ-OAc) ₁ (TACN) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (µ-O) ₆ (TACN) ₄ ] (ClO ₄ ) _4, [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (µ-O) ₁ (µ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (µ-O) ₃ (Me -TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (µ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

Automatic dishwashing detergents, characterized in that they also selected a bleach catalyst from the group of the bleach-intensifying transition metal salts and transition metal complexes, preferably from the group of the complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN) or 1,2,4,7-tetramethyl- 1,4,7-triazacyclononane (Me ₄ -TACN) are preferred according to the invention, since the abovementioned bleach catalysts in particular can significantly improve the cleaning result.

The automatic dishwashing detergents used according to the invention can be packaged in solid or liquid form, but also, for example, as a combination of solid and liquid supply forms.

Powders, granules, extrudates or compacts, in particular tablets, are particularly suitable as solid supply forms. The liquid supply forms, preferably based on water and / or organic solvents, can be thickened, in the form of gels.

Aqueous automatic dishwashing agents 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.

Since an increased alkalinity of the automatic dishwashing agent is on the one hand beneficial to the cleaning performance of this agent, but on the other hand increases the corrosive and irritating effect of this agent, preferred automatic dishwashing agents according to the invention are characterized in that the automatic dishwashing agent has a pH value (20 ° C) between 8 and 12, preferably between 9 and 11.5, preferably between 9.5 and 11.5. Machine dishwashing detergents which are in the form of a liquid, aqueous, low-alkaline preparation with a pH (20 ° C.) between 8 and 12, preferably between 9 and 11.5, preferably between 9.5 and 11.5, are particularly preferred.

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

These organic solvents originate, for example, from the groups of monoalcohols, diols, triols or polyols, ethers, esters and / or amides. Organic solvents which are water-soluble are particularly preferred, "water-soluble" solvents in the context of the present application being solvents which are completely miscible with water at room temperature, i.e. without a miscibility gap.

Organic solvents which can be used in the agents according to the invention preferably come from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, especially 1,2 propanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono 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 butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, Propylene glycol t-butyl ether and mixtures of these solvents.

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

The primary and secondary alkylamines, the alkyleneamines and mixtures of these organic amines are particularly preferred as organic amines. The group of preferred primary alkylamines includes 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 the alkanolamine in the total weight of machine dishwashing agents preferred according to the invention is 0.1 to 10% by weight, preferably 0.2 to 8% by weight, preferably 0.4 to 6% by weight and in particular 1 to 5% by weight. %

In order to achieve the desired viscosity of the automatic dishwashing agent according to the invention, thickeners 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 ether, Akzo), Deuterol ^® -Polymer-11 (dicarboxylic acid copolymer, Schöner GmbH), Deuteron ^® -XG (anionic heteropolysaccharide based on β-D-glucose, D-manose, D- Glucuronic acid, Schöner GmbH), Deuteron ^® -XN (non-ionic polysaccharide, Schöner GmbH), Dicrylan ^® -Verdicker-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (Ethylene-maleic anhydride copolymer, Monsanto), thickener-QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylic ester copolymer dispersion, 25% ig in Wasser, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^® -S (high molecular weight Polysac charid, stabilized with formaldehyde, Shell) and Shellflo ^® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell).

Examples of further thickeners are agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, carob 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 proven particularly advantageous if the automatic dishwashing agents according to the invention contain the thickener in amounts between 0.1 and 8% by weight, preferably between 0.2 and 6% by weight and particularly preferably between 0.4 and 4% by weight. -% based on the total weight of the automatic dishwasher detergent.

The pourability and settling stability of the liquid automatic dishwashing agents preferred according to the invention can, in addition to the thickeners, also be influenced by the ratio of the potassium and sodium ions in these agents. Liquid automatic dishwashing agents which are preferred according to the invention and have a ratio of potassium to sodium ions above 1: 1, preferably above 2: 1, particularly preferably above 4: 1 and in particular above 8.1, have proven advantageous.

Liquid agents preferred according to the invention are made up and packaged using the water-soluble or water-insoluble packaging agents known to those skilled in the art. The packaging means can be single, double or multi-chamber containers.

Water-insoluble two- or multi-chamber containers are particularly preferred. Such two- or multi-chamber containers typically have a total volume between 100 and 5000 ml, preferably between 200 and 2000 ml. The volume of the individual chambers is preferably between 50 and 2000 ml, preferably between 100 and 1000 ml. Preferred two- or multi-chamber containers have the shape of a bottle. The automatic dishwashing agents according to the invention are preferably present in these packaging agents in the form of separate partial recipes. These sub-formulations do not form a common phase boundary, but rather are located in separate areas of the packaging means and have compositions that differ from one another.

For dosing the preferred liquid automatic dishwashing detergents, the two- or multi-chamber container preferably has at least one spout, which can be designed, for example, in the form of a common spout for all the agents 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. Such a configuration avoids, for example, contamination of individual chambers by ingredients from another chamber.

1. a) 10 bis 60 Gew.-% Gerüststoff
2. b) nichtionisches Tensid der allgemeinen Formel
   
           R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_y[CH₂CH(CH₃)O]_zCH₂CH(OH)R²
   
   enthält, in der R¹ für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht, R² einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x und z für Werte zwischen 0 und 40 und y für einen Wert von mindestens 15 steht.
3. c) 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 of the present application is therefore a liquid, low-alkaline automatic dishwasher detergent with a pH value (20 ° C.) between 8 and 12, containing:

1. a) 10 to 60% by weight of builder
2. b) nonionic surfactant of the general formula
   
   R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ²
   
   contains, in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y stands for a value of at least 15.
3. c) anionic copolymer comprising
   1. i) unsaturated carboxylic acid (s)
   2. ii) Monomer (s) containing sulfonic acid groups.

characterized in that the automatic dishwashing detergent is in a two- or multi-chamber container, the individual chambers of which are filled with partial recipes of the automatic dishwashing detergent.

The weight information given above for the active washing and cleaning ingredients and the information on the pH value naturally relate to the automatic dishwashing detergent obtained by combining all sub-formulations. In the packaging described above by means of a two- or multi-chamber container, individual partial recipes contained in the chambers can therefore differ from the features characterizing the inventive automatic dishwasher detergent, provided that only the combination of all partial recipes of an inventive automatic dishwasher detergent with the above-mentioned characteristic and possibly preferred Has features.

For example, individual sub-recipes can be free of phosphonate or anionic copolymers, provided that the combination of all sub-recipes results in an automatic dishwashing agent which contains nonionic surfactant b) and anionic copolymer, comprising i) unsaturated carboxylic acid (s) and ii) sulfonic acid group-containing monomer (s) ( e) contains.

The information given above on the pH of the lower alkaline dishwashing detergents preferred according to the invention also relate to the pH of the overall composition and not to the pH of any partial recipes. Individual sub-recipes can therefore have pH values (20 ° C) below 8 or above 12, provided that the combination of the sub-recipes results in an automatic dishwashing agent with a pH (20 ° C) between 8 and 12.

When packaging machine dishwashing detergents according to the invention in two- or multi-chamber containers, it has proven advantageous for the stability of any enzymes contained in these agents to pack these enzymes together with a nonionic surfactant in one of the chambers of the container. By combining enzyme and surfactant, the cleaning performance of these agents could be improved.

1. i) ungesättigte Carbonsäure(n)
2. ii) Sulfonsäuregruppen-haltige(s) Monomer(e)

Some exemplary formulations for such preferred liquid automatic dishwashing agents can be found in the following tables (not according to the invention): Automatic 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 Nonionic surfactant * 0.1 to 15 0 to 4 0.5 to 8 - Anionic copolymer ** 0 to 10 0.2 to 18 - 1 to 12 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 [% by weight] Partial formulation 2 [% by weight] Partial formulation 1 [% by weight] Partial formulation 2 [% by weight] Potassium tripolyphosphate 3 to 40 3 to 30 3 to 30 2 to 15 sodium 0 to 10 3 to 20 - 4 to 15 Nonionic surfactant * 0.1 to 15 0 to 4 0.5 to 8 - Anionic copolymer ** 0 to 10 0.2 to 18 - 1 to 12 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 dishwashing detergent 6 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 HEDP 0 to 4 2 to 6 0 to 4 2 to 6 Nonionic surfactant 0.1 to 15 0 to 4 0.5 to 8 - Anionic copolymer * 0 to 10 0.2 to 18 - 1 to 12 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 dishwashing detergent 8 ingredient Partial formulation 1 [% by weight] Partial formulation 2 [% by weight] Partial formulation 1 Partial formulation 2 [% by weight] Potassium tripolyphosphate 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 Nonionic surfactant 0.1 to 15 0 to 4 0.5 to 8 - Anionic copolymer * 0 to 10 0.2 to 18 - 1 to 12 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 * nonionic surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² contains, in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y stands for a value of at least 15. ** Anionic copolymer comprising

1. i) unsaturated carboxylic acid (s)
2. ii) Monomer (s) containing sulfonic acid groups

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 also relates to a method for cleaning dishes in a dishwasher, using automatic dishwashing agents according to the invention, the automatic dishwashing agents preferably being metered into the interior of a dishwasher while a dishwasher program is running, before the start of the main wash cycle or during the main wash cycle. The dosing or introduction of the agent according to the invention into the interior of the dishwasher can take place manually, but the agent is preferably introduced into the interior by means of the dosing chamber of the dishwasher dosed in the dishwasher. In the course of the cleaning process, no additional water softener and no additional rinse aid are preferably dosed into the interior of the dishwasher. A kit for a dishwasher, comprising

1. a) an inventive automatic dishwashing agent;
2. b) Instructions that advise the consumer to use the automatic dishwashing detergent without the addition of a rinse aid and / or a softening salt are another subject matter of this application.

The automatic dishwashing 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 at the outset, agents according to the invention are distinguished from conventional automatic dishwashing agents by an improved cleaning performance on bleachable soiling. The present application therefore also relates to the use of an inventive automatic dishwashing agent to improve drying in automatic dishwashing.

Examples

The drying, coating and cleaning performance of an automatic dishwashing process were determined as a function of the type of dosage of the automatic dishwashing agent used.

For this purpose, dishes were placed in a dishwasher (Miele 1730; 55 ° Normal 3in1 Extra Drying program) with 33 ml (16.5 ml V1 / V2 or 16.5 ml E1 / E2 each) of an automatic dishwasher detergent with a water hardness of 21 ° dH flushed. The detergents were dispensed in the main wash cycle of the dishwashing process.

The composition of the dishwashing detergents V and E used can be found in the table below: Cleaning agent V (mixture of 50% by weight V1 and 50% by weight V2) Cleaning agent E (mixture of 50% by weight E1 and 50% by weight E2) raw material V1 [% by weight] V2 [% by weight] E1 [% by weight] E2 [wt .-%] KTTP 17.5 10.0 17.5 10.0 Nonionic surfactant ¹ - - 4.0 - Nonionic surfactant ² 4.0 - - - Protease 2.0 - 2.0 - Amylase 1.0 - 1.0 - Phosphonate 3.0 5.0 3.0 5.0 Thickener 4.0 - 4.0 - Org. Solvent 3.0 3.0 3.0 3.0 Anionic polymer - 8.6 - 8.6 soda - 7.0 - 7.0 Water, misc Add 100 Add 100 Add 100 Add 100 ¹ _{hydroxy mixed} ether of the general formula C 6-22 -CH (OH) CH ₂ O- (EO) _20-120 -C _2-26 ² polyalkoxylated fatty alcohol

With regard to the cleaning performance (determined according to IKW), no significant differences were found between the two process variants. The drying index was determined in accordance with the EN standard (maximum value for best drying 1.0). The results are given in the table below (the values given are the mean values from 3 experiments): V1 E1 Drying index 0.40 0.60 Deposit formation Toppings No toppings

Claims (14)

1. An automatic dishwashing detergent containing:

   a) 10 to 60 wt.% builder,

   b) nonionic surfactant of the general formula
   R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_y[CH₂CH(CH₃)O]_zCH₂CH(OH)R², in which R¹ represents a linear or branched aliphatic hydrocarbon functional group having 4 to 22 carbon atoms or mixtures thereof, R² represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms or mixtures thereof, x and z represent values between 0 and 40, and y represents a value of at least 15,

   c) anionic copolymer comprising

   i) unsaturated carboxylic acids

   ii) sulfonic acid group-containing monomers,

   characterized in that the weight ratio of components c) and b) is less than 3:1, the dishwashing detergent containing, based on the total weight of the automatic dishwashing detergent, phosphonate in amounts of 2.0 to 5 wt.%.
2. The automatic dishwashing detergent according to claim 1, characterized in that the weight ratio of components c) and b) is less than 2.8:1, preferably less than 2.5:1, particularly preferably less than 2.2:1, in particular between 2.2:1 and 1:10 and very particularly preferably between 2.2:1 and 1:5.
3. The automatic dishwashing detergent according to one of the preceding claims,
   characterized in that the automatic dishwashing detergent contains, as nonionic surfactant b), a surfactant of the general formula R¹O[CH₂CH₂O]_yCH₂CH(OH)R², in which R¹ represents a linear or branched aliphatic hydrocarbon functional group having 4 to 22 carbon atoms or mixtures thereof, R² represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms or mixtures thereof, and y represents a value between 15 and 120.
4. The automatic dishwashing detergent according to one of the preceding claims,
   characterized in that the automatic dishwashing detergent contains, as nonionic surfactant b), a surfactant of the general formula
   R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_yCH₂CH(OH)R², in which R¹ represents a linear or branched aliphatic hydrocarbon functional group having 4 to 22 carbon atoms or mixtures thereof, R² represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms or mixtures thereof, x represents values between 0.5 and 4, and y represents a value of at least 15.
5. The automatic dishwashing detergent according to one of the preceding claims, characterized in that the automatic dishwashing detergent contains, as nonionic surfactant b), a surfactant of the general formula
   R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_yCH₂CH(OH)R², in which R¹ represents a linear or branched aliphatic hydrocarbon functional group having 4 to 22 carbon atoms or mixtures thereof, R² represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms or mixtures thereof, x represents a value between 1 and 40, and y represents a value between 15 and 40, the alkylene units [CH₂CH(CH₃)O] and [CH₂CH₂O] being randomized, i.e. in the form of a statistical random distribution.
6. The automatic dishwashing detergent according to one of the preceding claims,
   characterized in that the dishwashing detergent contains, based on its total weight, nonionic surfactant in amounts of 0.1 to 15 wt.%, preferably 0.2 to 10 wt.%, particularly preferably 0.5 to 8 wt.% and in particular 1.0 to 6 wt.%.
7. The automatic dishwashing detergent according to one of the preceding claims,
   characterized in that the automatic dishwashing detergent contains, as anionic polymer c), a copolymer comprising

   i) unsaturated carboxylic acids,

   ii) sulfonic acid group-containing monomers,

   iii) other non-ionogenic monomers.
8. The automatic dishwashing detergent according to one of the preceding claims,
   characterized in that the automatic dishwashing detergent contains, based on its total weight, 0.2 to 18 wt.%, preferably 0.5 to 15 wt.% and in particular 1.0 to 12 wt.%, of anionic polymer c).
9. The automatic dishwashing detergent according to one of the preceding claims,
   characterized in that it contains, based on its total weight, enzyme in amounts of 0.1 to 12 wt.%, preferably 0.2 to 10 wt.% and in particular 0.5 to 8 wt.%.
10. The automatic dishwashing detergent according to one of the preceding claims,
    characterized in that it is in the form of a liquid, aqueous, low-alkaline preparation having a pH (20 °C) between 8 and 12.
11. A method for cleaning dishes in a dishwasher using an automatic dishwashing detergent according to one of claims 1 to 10.
12. The method according to claim 11, characterized in that, in the course of the cleaning process, no additional water softener and no additional rinse aid is dispensed into the interior of the dishwasher.
13. The method according to one of the preceding claims, characterized in that this method is carried out at temperatures up to a maximum of 55 °C, preferably up to a maximum of 50 °C.
14. The use of an automatic dishwashing detergent according to one of claims 1 to 10 for improving drying in automatic dishwashing.