EP2118255B2 - DETERGENTt COMPOSITION - Google Patents

Description

The present patent application describes cleaning agents, in particular cleaning agents for the machine cleaning of dishes. The subject matter of this application is in particular phosphate-free machine dishwashing detergents.

Today, machine-washed dishes are often subject to higher requirements than those washed by hand. After machine cleaning, the dishes should not only be completely free of food residues, but also not have any whitish stains caused by water hardness or other mineral salts, which come from dried water drops due to the lack of wetting agents.

Modern dishwasher detergents meet these requirements by integrating cleaning, care, water softening and rinse-active ingredients and are known to consumers as "2in1" or "3in1" dishwasher detergents, for example. Dishwasher detergents intended for private end users contain builders as an essential component for cleaning and rinse success. These builders increase the alkalinity of the cleaning solution, whereby fats and oils are emulsified and saponified as alkalinity increases, and they also reduce the water hardness of the cleaning solution by complexing the calcium ions contained in the aqueous solution. Alkali metal phosphates have proven to be particularly effective builders, which is why they are the main component of the majority of commercially available dishwasher detergents.

While phosphates are highly valued for their beneficial effect as a component of automatic dishwashing detergents, their use is not without problems from an environmental protection perspective, as a significant proportion of the phosphate enters the waterways via household wastewater and plays a worrying role in over-fertilizing standing waters (lakes, dams), in particular. As a result of this phenomenon, also known as eutrophication, the use of pentasodium triphosphate in textile detergents has been considerably reduced by law in a number of countries, e.g. the USA, Canada, Italy, Sweden and Norway, and is completely prohibited in Switzerland. In Germany, detergents may contain a maximum of 20% of this builder since 1984.

In addition to nitrilotriacetic acid, sodium aluminum silicates (zeolites) are mainly used as phosphate substitutes or replacements in textile detergents. However, these substances are not suitable for use in automatic dishwashing detergents for various reasons. A number of substitutes are therefore discussed in the literature as alternatives to the alkali metal phosphates in automatic dishwashing detergents, of which citrates are particularly noteworthy.

Phosphate-free dishwasher detergents, which contain carbonates, bleaches and enzymes in addition to citrate, are, for example, covered by the European patents EP 662 117 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).

Another alternative to alkali metal phosphates, which is used as the sole builder but preferably in combination with citrates, is methylglycinediacetic acid (MGDA). Dishwashing detergents containing MGDA are described, for example, in the European patent EP 906 407 B1 (Reckitt Benckiser ) or in the European patent application EP 1 113 070 A2 (Reckitt Benckiser ) described.

EP-A-1721962 describes phosphate-free, automatic dishwashing detergents that contain non-ionic surfactants, MGDA, percarbonate and citrate, but no copolymers containing sulfonic acid groups. WO 2006/106332 describes phosphate-free, automatic dishwashing detergents that contain non-ionic surfactants, MGDA, citrate and sulfonic acid group-containing copolymers, but no bleach.

Potthoff-Karl et al. (SOFW Journal Soaps, Oils, Fats, Waxes, Publisher for Chemical Industry, Augsburg, DE, Vol. 122, No.6, 1 May 1996, pages 392-394 and 396 ) describe phosphate-free automatic dishwashing detergents that contain non-ionic surfactants, MGDA, percarbonate and citrate, but no copolymers containing sulfonic acid groups.

WO 2005/090541 discloses, among other things, a phosphate-free automatic dishwashing detergent which contains surfactants, citrate, bleach and sulfonic acid group-containing copolymers, but no MGDA.

US$5,308,532 describes aminoacryloyl-containing terpolymers and automatic dishwashing detergents containing them, although the disclosed dishwashing detergents do not contain MGDA.

The republished international patent publication WO 2007/052064 describes phosphate-free, automatic dishwashing detergents that contain surfactants, citrate, bleach and sulfonic acid group-containing copolymers, as well as MGDA.

Despite previous efforts, the manufacturers of automatic dishwashing detergents have not yet succeeded in providing phosphate-free automatic dishwashing detergents that are comparable to or even better than phosphate-containing detergents in terms of their cleaning and rinsing performance. However, such equal performance is a prerequisite for the successful market launch of phosphate-free detergents, since the majority of end users are still against ecologically sound products despite broad public discussion of environmental issues. advantageous product if it does not correspond to the market standard in terms of price and/or performance.

In view of this initial situation, the object of the present application was therefore to provide a phosphate-free automatic dishwashing detergent which is comparable to or even surpasses conventional phosphate-containing detergents in terms of its cleaning performance as well as its rinsing results and its performance with regard to deposit inhibition.

It has been found that automatic dishwashing detergents containing methylglycinediacetic acid in addition to copolymers containing sulfonic acid groups have excellent cleaning and rinsing performance even without the addition of alkali metal phosphates.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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, b) Methylglycindiessigsäure.

A first subject of the present invention is therefore a phosphate-free automatic dishwashing detergent containing builder, bleach, non-ionic surfactant, and furthermore

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms, b) Methylglycinediacetic acid.

A first characteristic component of agents according to the invention are the sulfonic acid group-containing copolymers a), which, in addition to a sulfonic acid group-containing monomer, contain at least one further monomer 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms. The copolymers a) can have two, three, four or more different monomer units.

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 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 or represent -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 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 CH3} )-.

Preferred among these monomers are those of the formulas

H ₂ C=CH-X-SO ₃

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 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-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In the polymers, the sulfonic acid groups can be present in completely or partially neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the 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, for copolymers which contain only monomers from groups i) and ii), preferably 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

The molecular weight 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 intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molecular weights of 2000 to 200,000 gmol ^-1 , preferably of 4000 to 25,000 gmol ^-1 and in particular of 5000 to 15,000 gmol ^-1 .

Unsaturated carboxylic acids are particularly preferably used as ionic monomers. Particularly preferred are unsaturated carboxylic acids of the general 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 represent -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred carboxyl group-containing monomers are acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, cyanoacrylic acid, crotonic acid, phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.

Copolymers according to the invention contain, in addition to at least one monomer containing sulfonic acid groups, at least one monomer 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 represents an optionally present spacer group which is 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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,
2. b) Methylglycindiessigsäure.

According to the invention, phosphate-free automatic dishwashing detergents containing builder, bleach, non-ionic surfactant, and furthermore

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,
2. b) Methylglycinediacetic acid.

According to the invention, monomers of the general formula R ¹ (R ² )C=C(R ³ )-XR ⁴ are used, in which R ¹ to R ³ independently of one another represent -H, -CH ₃ or -C ₂ H ₅ , X represents an optionally present spacer group which is 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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
2. b) Methylglycindiessigsäure

The subject of this application is therefore phosphate-free automatic dishwashing detergents containing builder, bleach, non-ionic surfactant, and furthermore

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
2. b) Methylglycinediacetic acid

Particularly preferred monomers of the general formula R ¹ (R ² )C=C(R ³ )-XR ⁴ 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, ethylcyclohexyne, 1-octene, olefins having 10 or more carbon atoms such as, for example, 1-decene, 1-dodecene, 1-Hexadecene, 1-Octaclecene and C22-Olefin, 2-Styrene, - Methylstyrene, 3-Methylstyrene, 4-Propylslyrene, 4-Cyclohexylstyrene, 4-Dodecylstyrene, 2-Ethyl-4-Benzylstyrene, 1-Vinylnaphthalene, 2-Vinylnaphthalene, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-Ethylhexyl acrylate, 2-Ethylhexyl methacrylate, N -(2-Ethylhexyl)acrylamide, octyl acrylate, octyl methacrylate, N -(Octyl)acrylamide, lauryl acrylate, lauryl methacrylate, N -(Lauryl)acrylamide, stearyl acrylate, stearyl methacrylate, N -(Stearyl)acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl)acrylamide or mixtures thereof.

The machine dishwashing detergents according to the invention contain methylglycinediacetic acid (MGDA) as a second essential component. The methylglycinediacetic acid can be present in the detergents according to the invention in the form of the free acid, as a partial neutralizer or completely neutralized. In a particularly preferred embodiment, the methylglycinediacetic acid is present in the form of an alkali metal salt.

According to the invention, automatic dishwashing detergents preferably contain one or more builders as a further essential component. The builders include in particular silicates, carbonates and organic cobuilders.

Organic cobuilders include, in particular, polycarboxylates/polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These classes of substances are described below.

Useful organic builders are, for example, polycarboxylic acids that can be used in the form of the free acid and/or their sodium salts, whereby polycarboxylic acids are understood to be carboxylic acids that have more than one acid function. Examples of 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, and 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 of washing or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are particularly worth mentioning here.

Particularly preferred automatic dishwashing detergents according to the invention contain citrate as one of their essential builders. Automatic dishwashing detergents characterized in that they contain 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight of citrate are preferred according to the invention. Citrate or citric acid have proven to be the most effective builders in combination with MGDA and the copolymers containing sulfonic acid groups in terms of cleaning performance and rinsing performance.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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 KohIenstoffatomen steht,
2. b) Methylglycindiessigsäure werden erfindungsgemäß bevorzugt.

Phosphate-free automatic dishwashing detergents containing 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight of citrate, bleach, nonionic surfactant, and furthermore

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,
2. b) Methylglycinediacetic acid are preferred according to the invention.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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
2. b) Methylglycindiessigsäure.

Further preferred embodiments are:
Phosphate-free automatic dishwashing detergents containing 10 to 50% by weight of citrate, bleach, non-ionic surfactant, and furthermore

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
2. b) Methylglycinediacetic acid.

Machine dishwashing detergents according to the invention preferably contain, as a builder, crystalline layered silicates of the general formula NaMSi _x O _2x+1 · y H ₂ O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.

Also usable are amorphous sodium silicates with a Na ₂ O : SiO ₂ modulus of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and in particular 1:2 to 1:2.6, which preferably have delayed dissolution and secondary washing properties.

In the context of the present invention, preferred automatic dishwashing detergents contain 2 to 15% by weight, preferably 3 to 12% by weight and in particular 4 to 8% by weight of silicate(s).

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

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 mass of 500 up to 70000 g/mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular mass of 2000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates from this group, which have molecular masses of 2000 to 10,000 g/mol, and particularly preferably of 3000 to 5000 g/mol, may be preferred.

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 particularly suitable. Their relative molecular mass, based on free acids, is generally 2000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol and in particular 30,000 to 40,000 g/mol.

The (co)polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The (co)polymeric polycarboxylates content of the automatic dishwashing detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.

Other suitable builders are phosphonates. The complex-forming phosphonates include a number of different compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP). In this application, hydroxyalkane or aminoalkanephosphonates are particularly preferred. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, with the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably used in the form of the neutrally reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. HEDP is the preferred builder from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned, especially if the agents also contain bleach.

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.

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

1. a) Aminotrimethylenephosphonic acid (ATMP) and/or its salts;
2. b) ethylenediaminetetra(methylenephosphonic acid) (EDTMP) and/or its salts;
3. c) diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and/or its salts;
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 its salts;
6. f) hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP) and/or its salts;
7. g) Nitrilotri(methylenephosphonic acid) (NTMP) and/or its salts.

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

Of course, the automatic dishwashing detergents according to the invention can contain two or more different phosphonates. Particularly preferred are those automatic dishwashing detergents which contain both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates, the weight ratio of HEDP to DTPMP being between 20:1 and 1:20, preferably between 15:1 and 1:15 and in particular between 10:1 and 1:10.

In a preferred embodiment of the present invention, the weight proportion of the phosphonate(s) in the total weight of the automatic dishwashing detergent is less than the weight proportion of the polymer(s) a). In other words, particularly preferred detergents are those in which the ratio of the weight proportion of polymer a) to the weight proportion of the phosphonate is 200:1 to 2:1, preferably 150:1 to 2:1, particularly preferably 100:1 to 2:1, very particularly preferably 80:1 to 3:1 and in particular 50:1 to 5:1.

Preferred machine dishwashing detergents according to the invention also contain one or more bleaching agents. Among the compounds used as bleaching agents and which provide H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peracidic salts or peracids which provide H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, with alkyl peroxyacids and aryl peroxyacids being particularly examples.

Automatic dishwashing detergents, characterized in that they contain 1 to 20 wt.%, preferably 2 to 15 % by weight and in particular 4 to 12 % by weight of sodium percarbonate are preferred according to the invention.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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,
2. b) Methylglycindiessigsäure.

werden erfindungsgemäß bevorzugt.Phosphate-free automatic dishwashing detergents containing builder, 1 to 20 wt.%, preferably 2 to 15 wt.% and in particular 4 to 12 wt.% sodium percarbonate, nonionic surfactant, and furthermore

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,
2. b) Methylglycinediacetic acid.

are preferred according to the invention.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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
2. b) Methylglycindiessigsäure.

Further preferred embodiments are:
Phosphate-free automatic dishwashing detergents containing builder, 2 to 15 wt.% sodium percarbonate, non-ionic surfactant, and further

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
2. b) Methylglycinediacetic acid.

Substances that release chlorine or bromine can also be used as bleaching agents. Suitable chlorine or bromine-releasing materials include heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

In order to achieve an improved bleaching effect when cleaning at temperatures of 60°C and below, the machine dishwashing detergents according to the invention can additionally contain bleach activators. Compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and/or optionally substituted perbenzoic acid, can be used as bleach activators. Substances which carry O- and/or N-acyl groups of the stated number of C atoms and/or optionally substituted benzoyl groups are suitable. Multiply acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) proving to be 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-enhancing transition metal salts or transition metal complexes such as 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 as well as Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Particular preference is given to using complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and/or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst(s) in the agents according to the invention which contain 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) as macromolecular ligands. 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) ₂ (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 further contain a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN) or 1,2, 4,7-tetramethyl-1,4,7-triazacyclononane (Me ₄ -TACN), are preferred according to the invention, since the aforementioned bleach catalysts in particular can significantly improve the cleaning result.

The aforementioned bleach-enhancing transition metal complexes, in particular with the central atoms Mn and Co, are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.30% by weight, in each case based on the total weight of the bleach activator-containing agents. In special cases, however, more bleach activator can also be used.

The agents according to the invention also contain surfactants. The group of surfactants includes non-ionic, anionic, cationic and amphoteric surfactants.

Surprisingly, it was found that the bleaching effect of lead catalysts from the group of bleach-enhancing transition metal salts and transition metal complexes can be increased by the addition of hydrophobically modified acid-containing copolymers.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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,
2. b) Methylglycindiessigsäure.
3. c) Citrat
4. d) Bleichkatalysator ausgewählt aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe

A preferred subject matter of this application is therefore a phosphate-free, bleach-containing automatic dishwashing detergent containing

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,
2. b) Methylglycinediacetic acid.
3. c) Citrate
4. d) Bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes

Some example recipes for such preferred phosphate-free automatic dishwashing detergents can be found in the table below: ingredient Formulation 1 [wt.%] Formulation 2 [wt.%] Formulation 3 [wt.%] Formulation 4 [wt.%] Citrate 5 to 60 10 to 55 15 to 50 15 to 50 Sodium percarbonate 1 to 20 2 to 15 4 to 10 4 to 10 Bleach catalyst 0.01 to 3 0.02 to 2 0.02 to 2 0.02 to 1 Copolymer ¹ 0.1 to 30 0.5 to 25 1.0 to 20 1.0 to 20 MGDA 0.5 to 20 0.5 to 20 0.5 to 10 0.5 to 8 Misc Add 100 Add 100 Add 100 Add 100 ¹ copolymer containing i) Monomers containing sulfonic acid groups ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,

Automatic dishwashing detergents, characterized in that they contain nonionic surfactant(s) in amounts of 1 to 10 wt.%, preferably 2 to 8 wt.% and in particular 3 to 6 wt.%, are preferred according to the invention.

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

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

Another class of preferably used nonionic surfactants, which are 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 with 1 to 4 carbon atoms in the alkyl chain.

Low-foaming nonionic surfactants are used as preferred surfactants. Washing or cleaning agents, in particular cleaning agents for machine dishwashing, particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages which can correspond to a whole or fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

It is therefore particularly preferred to use ethoxylated nonionic surfactants obtained from C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

Combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are also particularly preferred.

Particularly preferred are nonionic surfactants which have a melting point above room temperature. Nonionic surfactant(s) 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.

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

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

The nonionic surfactant, which is solid at room temperature, preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass 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 make up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.

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

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

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

preferred 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 represent 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 can 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 generally unbranched, with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol, being preferred. Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or radicals methyl-branched in the 2-position or linear and methyl-branched radicals in a mixture, as are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to produce the nonionic surfactants contained in the agents, nonionic surfactants are preferred in which R ¹ in the above formula represents an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as an alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² and R ³ are independently selected from -CH ₂ CH ₂ -CH ₃ and -CH(CH ₃ ) ₂ are also suitable. Preference is given to using nonionic surfactants of the above formula in which R ² and R ³ are a radical -CH ₃ , w and x are independently of one another values of 3 or 4 and y and z are independently of one another values of 1 or 2.

In summary, nonionic surfactants which have a C _9-15 alkyl radical with 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 are particularly preferred. These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.

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

Particularly preferred surfactants are those 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 having 4 to 18 carbon atoms or mixtures thereof, R ² is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15.

Particularly preferred are also those end-capped poly(oxyalkylated) nonionic surfactants of the formula R ¹ O[CH ₂ CH _z 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 represents -CH ₃ , and x and y independently of one another represent values between 1 and 32, with nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y from 0.5 to 1.5 being very particularly preferred.

By using the previously described non-ionic surfactants with a free hydroxyl group on one of the two terminal alkyl residues, the formation of deposits during machine dishwashing can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

Other nonionic surfactants which can preferably be used are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R ¹ O[CH ₂ CH(R ³ )O] _x [CH ₂ ] _k CH(OH)[CH ₂ ] _j OR ² , in which R ¹ and R ² are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ³ is H or a methyl, ethyl, n-propyl, isopropyl, 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. If 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 can 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 C 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 can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if 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 can be joined together in any order, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x has been chosen here as an example and can certainly be larger, whereby the range of variation increases with increasing x values and includes, for example, a large number of (EO) groups combined with a small number of (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 simplified to R ¹ O[CH ₂ CH(R ³ )O] _x CH ₂ CH(OH)CH ₂ OR ² . In the latter formula, R ¹ , R ² and R ³ are as defined above and x stands for numbers 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 have 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15.

The stated C-chain lengths and degrees of ethoxylation or alkoxylation of the aforementioned nonionic surfactants represent statistical averages, which can be a whole or a fractional number for a specific product. Due to the manufacturing processes, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in averages and, consequently, fractional numbers for both the C-chain lengths and the degrees of ethoxylation or alkoxylation.

Of course, the aforementioned non-ionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Surfactant mixtures do not refer to mixtures of non-ionic surfactants that as a whole fall under one of the general formulas mentioned above, but rather to mixtures that contain two, three, four or more non-ionic surfactants that can be described by different ones of the general formulas mentioned above.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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 Kohlenstoffatornen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen,
2. b) Methylglycindiessigsäure. werden erfindungsgemäß bevorzugt.

Phosphate-free automatic dishwashing detergent containing builder, bleach, nonionic surfactant in amounts of 1 to 10 wt.%, preferably 2 to 8 wt.% and in particular 3 to 6 wt.%, and furthermore

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,
2. b) Methylglycinediacetic acid are preferred according to the invention.

Some example recipes for such preferred phosphate-free automatic dishwashing detergents can be found in the table below: ingredient Formulation 5 [wt.%] Formulation 6 [wt.%] Formulation7 [wt.%] Formulation 8 [wt.%] Citrate 5 to 60 10 to 55 15 to 50 15 to 50 Sodium percarbonate 1 to 20 2 to 15 4 to 10 4 to 10 Bleach catalyst 0.01 to 3 0.02 to 2 0.02 to 2 . 0.02 to 1 Non-ionic surfactant 1 to 10 1 to 10 2 to 8 3 to 6 Copolymer ¹ 0.1 to 30 0.5 to 25 1.0 to 20 1.0 to 20 MGDA 0.5 to 20 0.5 to 20 0.5 to 10 0.5 to 8 Misc Add 100 Add 100 Add 100 Add 100 ¹ copolymer containing i) Monomers containing sulfonic acid groups ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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
2. b) Methylglycindiessigsäure.

Further preferred embodiments are:
Phosphate-free automatic dishwashing detergents containing builder, bleach, 2 to 8 wt.% non-ionic surfactant, and further

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
2. b) Methylglycinediacetic acid.

If anionic surfactants are used as a component of automatic dishwashing detergents, their content, based on the total weight of the detergent, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Automatic dishwashing detergents which do not contain anionic surfactants are particularly preferred.

Cationic and/or amphoteric surfactants can also be used instead of the surfactants mentioned or in combination with them.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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
2. b) Methylglycindiessigsäure.

sowieIn summary, the following framework formulations are particularly preferred due to their outstanding cleaning and rinsing results:
Phosphate-free automatic dishwashing detergents containing builder, 2 to 15% by weight sodium percarbonate, 2 to 8% by weight non-ionic surfactant, and furthermore

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
2. b) Methylglycinediacetic acid.

as well as

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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
2. b) Methylglycindiessigsäure.

Phosphate-free automatic dishwashing detergents containing 10 to 50% by weight citrate, 2 to 15% by weight sodium percarbonate, 2 to 8% by weight non-ionic surfactant, and furthermore

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
2. b) Methylglycinediacetic acid.

Preferred automatic dishwashing detergents according to the invention in which the weight proportion of the copolymer a) is 4 to 18 wt. %, preferably 6 to 15 and in particular 6 to 12 wt. % have proven to be particularly effective in terms of optimum cleaning and rinsing results.

Automatic dishwashing detergents in which the weight proportion of methylglycinediacetic acid b) is 0.5 to 20 wt.%, preferably 0.5 to 10 wt.% and in particular 0.5 to 8 wt.%, also have particularly good cleaning, rinsing and deposit removal results and are preferred according to the invention for this reason.

1. a) 6 bis 15 Gew.-% Copolymer, umfassend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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
2. b) 0,5 bis 10 Gew.-% Methylglycindiessigsäure
3. c) 10 bis 50 Gew.-% Citrat
4. d) 2 bis 15 Gew.-% Natriumpercarbonat
5. e) 2 bis 8 Gew.-% nichtionisches Tensid

Particularly preferred are therefore phosphate-free automatic dishwashing detergents containing

1. a) 6 to 15 wt.% copolymer comprising
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
2. b) 0.5 to 10 wt.% methylglycinediacetic acid
3. c) 10 to 50 wt.% citrate
4. d) 2 to 15 wt.% sodium percarbonate
5. e) 2 to 8 wt.% non-ionic surfactant

In a further preferred embodiment, the copolymers a) contain, in addition to the sulfonic acid group-containing monomers, ionic monomers
and 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

1. a) Copolymer, umfassend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) weitere ionische Monomere
   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,
2. b) Methylglycindiessigsäure.

werden erfindungsgemäß bevorzugt.Phosphate-free automatic dishwashing detergent, containing builder, bleach, non-ionic surfactant, and further

1. a) Copolymer comprising
   1. i) Monomers containing sulfonic acid groups
   2. ii) other ionic monomers
   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 represent -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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,
2. b) Methylglycinediacetic acid.

are preferred according to the invention.

These terpolymers particularly preferably contain carboxyl group-containing monomers.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) Carboxylgruppen-haltige Monomere
   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,
2. b) Methylglycindiessigsäure.

A particularly preferred subject matter of the present application is therefore a phosphate-free automatic dishwashing detergent containing builder, bleach, non-ionic surfactant, and furthermore

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) Carboxyl group-containing monomers
   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 represent -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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,
2. b) Methylglycinediacetic acid.

In a last preferred embodiment, the copolymers contain, in addition to at least one monomer containing sulfonic acid groups, a monomer containing carboxyl groups and, as nonionic monomers, corresponding 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 represents an optionally present spacer group which is 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

1. a) Copolymer, enthaltend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) Carboxylgruppen-haltige Monomere
   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
2. b) Methylglycindiessigsäure

enthalten.In summary, phosphate-free automatic dishwashing detergents are preferred, which, in addition to builder, bleach and non-ionic surfactant, also contain

1. a) Copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) Carboxyl group-containing monomers
   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 represent -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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
2. b) Methylglycinediacetic acid

contain.

1. a) 6 bis 15 Gew.-% Copolymer, enthalrend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) Carboxylgruppen-haltige Monomere
   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 Kohlenstolffatornen steht,
2. b) 0,5 bis 10 Gew.-% Methylglycindiessigsäure
3. c) 10 bis 50 Gew.-% Citrat
4. d) 2 bis 15 Gew.-% Natriumpercarbonat
5. e) 2 bis 8 Gew.-% nichtionisches Tensid

Preferred automatic dishwashing detergents containing terpolymers are in particular:
Phosphate-free automatic dishwashing detergents containing

1. a) 6 to 15 wt.% copolymer containing
   1. i) Monomers containing sulfonic acid groups
   2. ii) Carboxyl group-containing monomers
   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 represent -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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,
2. b) 0.5 to 10 wt.% methylglycinediacetic acid
3. c) 10 to 50 wt.% citrate
4. d) 2 to 15 wt.% sodium percarbonate
5. e) 2 to 8 wt.% non-ionic surfactant

In addition to the ingredients described above, such as builder, bleach, non-ionic surfactant, copolymer a) and methylglycinediacetic acid, preferred automatic dishwashing detergents contain other ingredients, preferably active ingredients from the group of polymers, enzymes, corrosion inhibitors, fragrances or dyes.

The group of washing or cleaning-active polymers includes, for example, rinse aid polymers and/or polymers that act as softeners. In general, cationic, anionic and amphoteric polymers can be used in washing or cleaning agents in addition to non-ionic polymers.

"Cationic polymers" in the sense of the present invention are polymers which carry a positive charge in the polymer molecule. This can be achieved, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, vinylpyrrolidone-methoimidazolinium chloride copolymers, quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

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

Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C=CR ³ R ⁴ , in which each radical R ¹ , R ² , R ³ , R ⁴ is independently selected from hydrogen, derivatized hydroxy group, C _1-30 linear or branched alkyl groups, aryl, aryl-substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups with at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group with a positive charge in the partial range of the pH range from 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ⁴ is a heteroatomic organic group with at least one positive charge without charged nitrogen, at least one quaternized N-atom or at least one amino group with a positive charge.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, lodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.Particularly preferred cationic or amphoteric polymers in the context of the present application contain as monomer unit a compound of the general formula

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

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -CH ₃ , -CH ₂ -CH ₃ , - CH ₂ -CH ₂ -CH ₃ , -CH(CH ₃ )-CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH(OH)-CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH(OH)-Ch ₃ , -CH(OH)-CH ₂ -CH ₃ , and -(CH ₂ CH ₂ -O) _n H.

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

H ₂ C=CH-(CH ₂ )-N ⁺ (CH ₃ ) ₂ -(CH ₂ )-CH=CH ₂ X ^-

In case of X ^- = chloride they are also called DADMAC (diallyldimethylammonium chloride).

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

R ¹ HC=CR ² -C(O)-NH-(CH ₂ )-N ⁺ R ³ R ⁴ R ⁵ X ^-

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

Very particular preference is given in the context of the present application to polymers which have a cationic monomer unit of the above general formula, in which R ¹ is H and R ² , R ³ , R ⁴ and R ⁵ are methyl and x is 3. The corresponding monomer units of the formula

H ₂ C=C(CH ₃ )-C(O)-NH-(CH ₂ ) _x -N ⁺ (CH ₃ ) ₃ X ^-

In case of X ^- = chloride they are also called MAPTAC (methylacrylamidopropyltrimethylammonium chloride).

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

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

Preferred amphoteric polymers that can be used come from the group of alkylacrylamide/acrylic acid copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/alkylmethacrylate/alkylaminoethylmethacrylate/alkylmethacrylate copolymers and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.

Preferred zwitterionic polymers come from the group of acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and their alkali and ammonium salts and methacroylethylbetaine/methacrylate copolymers. Also preferred are amphoteric polymers which, in addition to one or more anionic monomers, comprise methacrylamidoalkyltrialkylammonium chloride and dimethyl(diallyl)ammonium chloride as cationic monomers.

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

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

• die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the polymers are in prefabricated form. The following are suitable for preparing the polymers:

• encapsulation of the polymers by means of water-soluble or water-dispersible coating agents, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• the encapsulation of the polymers by means of water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30°C;
• the cogranulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders or cobuilders.

Detergents or cleaning agents preferably contain the aforementioned cationic and/or amphoteric polymers in amounts of between 0.01 and 10% by weight, based in each case on the total weight of the detergent or cleaning agent. However, in the context of the present application, preference is given to detergents or cleaning agents in which the weight proportion of the cationic and/or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, particularly preferably between 0.01 and 2% by weight and in particular between 0.01 and 1% by weight, based in each case on the total weight of the automatic dishwashing detergent.

Enzymes can be used to increase the washing or cleaning performance of washing or cleaning agents. 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 washing or cleaning agents, which are therefore preferred. Washing or cleaning agents preferably contain enzymes in total quantities of 1 x 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 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, proteinase K and the proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense.

Examples of amylases that 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 aforementioned amylases that have been improved for use in washing 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) are particularly suitable for this purpose.

Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to produce peracids from suitable precursors in situ . These include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed lipases, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases that 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.

Enzymes that are grouped under the term hemicellulases can also be used. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases and β-glucanases.

To increase the bleaching effect, 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. Advantageously, organic compounds, particularly aromatic ones, which interact with the enzymes are also added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons in the event of very different redox potentials between the oxidizing enzymes and the soiling (mediators).

The enzymes can be used in any form established according to the state of the art. These include, for example, 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, with little water and/or mixed with stabilizers.

Alternatively, the enzymes can be encapsulated for both the solid and liquid dosage forms, 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 if in a solidified gel or in those of the core-shell type in which an enzyme-containing core is covered with a water, air and/or chemical-impermeable protective layer. In superimposed layers, additional Active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents or dyes, are applied. Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules, for example by applying polymeric film formers, are advantageously low in dust and are stable in storage due to the coating.

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

A protein and/or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage. When the proteins and/or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Washing or cleaning agents can contain stabilizers for this purpose; the provision of such agents represents a preferred embodiment of the present invention.

Preferably, one or more enzymes and/or enzyme preparations, preferably solid protease preparations and/or amylase preparations, are used in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 5% by weight and in particular from 0.4 to 5% by weight, in each case based on the total enzyme-containing agent.

1. a) 6 bis 15 Gew.-% Copolymer, umfassend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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
2. b) 0,5 bis 10 Gew.-% Methylglycindiessigsäure
3. c) 10 bis 50 Gew.-% Citrat
4. d) 2 bis 15 Gew.-% Natriumpercarbonat
5. e) 2 bis 8 Gew.-% nichtionisches Tensid
6. f) 1,0 bis 6 Gew.-% Enzym.

bzw.Particularly preferred are therefore phosphate-free automatic dishwashing detergents containing

1. a) 6 to 15 wt.% copolymer comprising
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
2. b) 0.5 to 10 wt.% methylglycinediacetic acid
3. c) 10 to 50 wt.% citrate
4. d) 2 to 15 wt.% sodium percarbonate
5. e) 2 to 8 wt.% non-ionic surfactant
6. f) 1.0 to 6 wt.% enzyme.

or.

1. a) 6 bis 15 Gew.-% Copolymer, umfassend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) 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
   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
2. b) 0,5 bis 10 Gew.-% Methylglycindiessigsäure
3. c) 10 bis 50 Gew.-% Citrat
4. d) 2 bis 15 Gew.-% Natriumpercarbonat
5. e) 2 bis 8 Gew.-% nichtionisches Tensid
6. f) 1,0 bis 6 Gew.-% Enzym.

Phosphate-free automatic dishwashing detergents containing

1. a) 6 to 15 wt.% copolymer comprising
   1. i) Monomers containing sulfonic acid groups
   2. ii) 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 represents -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 represents -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
   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 represent -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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
2. b) 0.5 to 10 wt.% methylglycinediacetic acid
3. c) 10 to 50 wt.% citrate
4. d) 2 to 15 wt.% sodium percarbonate
5. e) 2 to 8 wt.% non-ionic surfactant
6. f) 1.0 to 6 wt.% enzyme.

• ¹a) Copolymer, enthaltend
  1. i) Sulfonsäuregruppen-haltige Monomere
  2. ii) 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,
• b) Methylglycindiessigsäure.

Some example recipes for such preferred phosphate-free automatic dishwashing detergents can be found in the following tables: ingredient Formulation 9 [wt.%] Formulation 10 [wt.%] Formulation 11 [wt.%] Formulation 12 [wt.%] Citrate 5 to 60 10 to 55 15 to 50 15 to 50 Sodium percarbonate 1 to 20 2 to 15 4 to 10 4 to 10 Non-ionic surfactant 1 to 10 2 to 8 2 to 8 3 to 6 enzyme 0.1 to 6 0.2 to 5 0.4 to 5 0.4 to 5 Copolymer ¹ 0.1 to 30 0.5 to 25 1.0 to 20 1.0 to 20 MGDA 0.5 to 20 0.5 to 20 0.5 to 10 0.5 to 8 Misc Add 100 Add 100 Add 100 Add 100 ingredient Formulation 13 [wt.%] Formulation 14 [wt.%] Formulation 15 [wt.%] Formulation 16 [wt.%] Citrate 5 to 60 10 to 55 15 to 50 15 to 50 Carbonate/Hydrogen carbonate 2 to 40 2 to 40 2 to 40 2 to 40 silicate 0 to 15 0 to 15 0 to 15 0.1 to 10 Sodium percarbonate 1 to 20 2 to 15 4 to 10 4 to 10 Bleach catalyst 0.01 to 3 0.02 to 2 0.02 to 2 0.02 to 1 Non-ionic surfactant 1 to 10 2 to 8 2 to 8 3 to 6 enzyme 0.1 to 6 0.2 to 5 0.4 to 5 0.4 to 5 Copolymer ¹ 0.1 to 30 0.5 to 25 1.0 to 20 1.0 to 20 MGDA 0.5 to 20 0.5 to 20 0.5 to 10 0.5 to 8 Misc Add 100 Add 100 Add 100 Add 100

• ¹ a) Copolymer containing
  1. i) Monomers containing sulfonic acid groups
  2. ii) 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 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 an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,
• b) Methylglycinediacetic acid.

Glass corrosion inhibitors prevent the appearance of clouding, streaks and scratches, as well as the 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 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. have a solubility below 100 mg/l, preferably below 10 mg/l, in particular below 0.01 mg/l, to those salts that 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, while the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

It is particularly preferred to use at least one zinc salt of an organic carboxylic acid as a glass corrosion inhibitor, 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 washing or cleaning agents 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⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.5% by weight, in each case based on the total weight of the glass corrosion inhibitor-containing agent.

Corrosion inhibitors serve to protect the items being washed or the machine, with silver protection agents being particularly important in the field of machine dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used. Benzotriazole and/or alkylaminotriazole are particularly preferred. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically acceptable salts, with these substances being used with particular preference in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight.

In order to facilitate the disintegration of prefabricated molded articles, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these agents in order to shorten the disintegration times.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when exposed to water, whereby on the one hand the volume itself increases (swelling), and on the other hand pressure can be generated through the release of gases, which causes the tablet to break down into smaller particles. Well-known disintegration aids are, for example, carbonate/citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

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

Cellulose-based disintegrants are used as preferred disintegrants, so that preferred washing or cleaning agents contain such a cellulose-based disintegrant in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight. The cellulose used as a disintegrant is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being mixed into the premixes to be pressed. The particle sizes of such disintegrants are usually above 200 µm, preferably at least 90% by weight between 300 and 1600 µm and in particular at least 90% by weight between 400 and 1200 µm.

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

According to the invention, gas-generating effervescent systems can also preferably be used as tablet disintegration aids. The gas-generating effervescent system can consist of a single substance that releases a gas when it comes into contact with water. Among these compounds, magnesium peroxide is particularly worth mentioning, which releases oxygen when it comes into contact with water. However, preferred effervescent systems consist of at least two components that react with one another to form gas, for example alkali metal carbonate and/or hydrogen carbonate and an acidifying agent that is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution. Acidifying agents that release carbon dioxide from the alkali metal salts in aqueous solution can be, for example, boric acid, alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, with citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system are preferably from the group of organic di-, tri- and oligocarboxylic acids or mixtures.

Within the scope of the present invention, individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. However, mixtures of different fragrances are preferably used which together produce an appealing scent. Such perfume oils can also contain natural fragrance mixtures, such as those available from plant sources, e.g. pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers that ensure a long-lasting fragrance through a slower release of the fragrance. Cyclodextrins, for example, have proven to be suitable carrier materials, although the cyclodextrin perfume complexes can also be coated with other auxiliary substances.

Preferred dyes, the selection of which presents no difficulty to the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, as well as no pronounced substantivity towards the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic tableware, in order not to stain them.

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

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

Agents according to the invention can be packaged as single-phase or multi-phase products. In particular, automatic dishwashing agents with one, two, three or four phases are preferred. Automatic dishwashing agents characterized by being in the form of a prefabricated dosing unit with two or more phases are particularly preferred.

The individual phases of multiphase agents can have the same or different states of aggregation. Particularly preferred are automatic dishwashing agents which have at least two different solid phases and/or at least two liquid phases and/or at least one solid and at least one liquid phase.

Machine dishwashing detergents according to the invention are preferably pre-packaged into dosing units. These dosing units preferably contain the amount of washing or cleaning active substances required for one cleaning cycle. Preferred dosing units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.

The volume of the aforementioned dosing units and their spatial shape are particularly preferably selected so that the pre-assembled units can be dosed via the dosing chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

The automatic dishwashing detergents according to the invention, in particular the prefabricated dosing units, particularly preferably have a water-soluble coating.

The present application further relates to a method for cleaning dishes in a dishwasher using automatic dishwashing agents according to the invention, wherein the automatic dishwashing agents are preferably dosed into the interior of a dishwasher while a dishwashing program is running, before the start of the main wash cycle or during the main wash cycle. The agent according to the invention can be dosed or introduced into the interior of the dishwasher manually, but the agent is preferably dosed into the interior of the dishwasher using the dosing chamber of the dishwasher. During the cleaning process, preferably no additional water softener or rinse aid is dosed into the interior of the dishwasher.

As described at the outset, agents according to the invention are distinguished from conventional automatic dishwashing agents by an improved rinse effect. The use of an automatic dishwashing agent according to the invention as a rinse agent in automatic dishwashing is therefore a further subject matter of the present application.

Examples

In a first cleaning test, soiled dishes were washed in a dishwasher with 21 g of a commercially available phosphate-containing machine dishwashing detergent V1 or 21 g of the three phosphate-free machine dishwashing detergents V2, V3 and E1 at a water hardness of 21 °dH.

The composition of the dishwashing detergents used can be found in the table below: raw material V1 V2 V3 E1 phosphate 33 -- -- -- Citrate -- 23 23 23 MGDA -- -- 8.0 8.0 Copolymer ¹ 12.0 12.0 -- 12.0 HEDP 2.0 2.0 2.0 2.0 soda 28.0 28.0 28.0 28.0 Sodium percarbonate 10.0 10.0 10.0 10.0 TAE 2.4 2.4 2.4 2.4 Protease/Amylase 4.0 4.0 4.0 4.0 Non-ionic surfactant 5.0 5.0 5.0 5.0 Misc Add 100 Add 100 Add 100 Add 100 ¹ Copolymer containing sulfonic acid groups

The overall appearance of the dishes was assessed using the rating scale below. The results are shown in the table below (the values given are the averages of 3 tests): V1 V2 V3 E1 Cleaning result 8.1 7.1 7.5 8.2

Cleaning rating scale: 10 = no contamination to 0 = severe contamination (average of seven specific soilings)

In a second experiment to determine the formation of deposits, unsoiled dishes were washed in a continuously operated dishwasher with 21 g of a commercially available phosphate-containing machine dishwashing detergent V1 or 21 g of the three phosphate-free machine dishwashing detergents V2, V3 and E1 at a water hardness of 21°dH.

The overall appearance of the dishes was assessed using the rating scale below. The results are shown in the table below (the values given are the averages of 3 tests): V1 V2 V3 E1 Deposit formation Porcelain 3.5 Porcelain 1.5 Porcelain 2.5 Porcelain 3.0 Plastic 4.2 Plastic 1.0 Plastic 3.0 Plastic 4.5

Rating scale for deposit formation: 10 = no deposit formation to 0 = heavy deposit formation

Claims (10)

1. Phosphate-free automatic dishwashing detergent containing builder, bleaching agent, nonionic surfactant, and furthermore

   a) copolymer containing

   i) monomers containing sulfonic acid groups

   ii) monomers of the general formula R¹(R²)C=C(R³)-X-R⁴, in which R¹ to R³ independently of one another represent -H, -CH₃ or -C₂H₅, X represents an optionally present spacer group which is selected from -CH₂-, C(O)O- and C(O)-NH-, and R⁴ represents 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,

   b) methylglycinediacetic acid.
2. Automatic dishwashing detergent according to claim 1, characterized in that the proportion by weight of the copolymer a) is from 4 to 18% by weight, preferably from 6 to 15% by weight and in particular from 6 to 12% by weight.
3. Automatic dishwashing detergent according to one of the preceding claims, characterized in that the proportion by weight of the methylglycinediacetic acid b) is 0.5 to 20% by weight, preferably 0.5 to 10% by weight and in particular 0.5 to 8% by weight.
4. Automatic dishwashing detergent according to one of the preceding claims, characterized in that it contains 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight of citrate.
5. Automatic dishwashing detergent according to one of the preceding claims, characterized in that it contains 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 12% by weight of sodium percarbonate.
6. Automatic dishwashing detergent according to one of the preceding claims, characterized in that it contains the non-ionic surfactant in quantities of 1 to 10% by weight, preferably 2 to 8% by weight and in particular 3 to 6% by weight.
7. Automatic dishwashing detergent according to one of the preceding claims, containing

   a) 6 to 15% by weight of a copolymer comprising

   i) monomers containing sulphonic acid groups

   ii) monomers of the general formula R¹(R²)C=C(R³)-X-R⁴, in which R¹ to R³ independently of one another represent -H, -CH₃ or -C₂H₅, X represents an optionally present spacer group which is selected from -CH₂-, C(O)O- and C(O)-NH-, and R⁴ represents 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

   b) 0.5 to 10% by weight of methylglycinediacetic acid

   c) 10 to 50 wt.% citrate

   d) 2 to 15 wt.% sodium percarbonate

   e) 2 to 8 % by weight of non-ionic surfactant
8. Automatic dishwashing detergent according to one of the preceding claims, containing

   a) 6 to 15% by weight of a copolymer comprising

   i) monomers containing sulfonic acid groups

   ii) monomers of the general formula R¹(R²)C=C(R³)-X-R⁴, in which R¹ to R³ independently of one another represent -H, -CH₃ or -C₂H₅, X represents an optionally present spacer group which is selected from -CH₂-, C(O)O- and C(O)-NH-, and R⁴ represents 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

   b) 0.5 to 10% by weight of methylglycinediacetic acid

   c) 10 to 50 wt.% citrate

   d) 2 to 15 wt.% sodium percarbonate

   e) 2 to 8% by weight of non-ionic surfactant

   f) 1.0 to 6% by weight of enzyme.
9. Process for cleaning dishes in a dishwashing machine, using automatic dishwashing detergents according to one of claims 1 to 8.
10. Process according to claim 9, characterized in that no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher during the cleaning process.