EP2118255B1 - DETERGENTt COMPOSITION - Google Patents

Description

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

Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So the dishes after machine cleaning should not only be completely free of food particles free but also, for example, no whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water drops.

Modern automatic dishwashing detergents meet these requirements by integrating cleansing, caring, water-softening and clear-rinsing active ingredients and are known to the consumer, for example, as "2in1" or "3in1" dishwashing detergents. As essential for the cleaning as for the rinse aid success constituent intended for the private consumer dishwasher automatic dishwashing contain builders. On the one hand, these builders increase the alkalinity of the cleaning liquor, whereby fats and oils are emulsified and saponified with increasing alkalinity, and on the other hand reduce the water hardness of the cleaning liquor by complexing the calcium ions contained in the aqueous liquor. Particularly effective builders have proved to be the alkali metal phosphates which, for this reason, form the main constituent of the vast majority of commercially available automatic dishwashing detergents.

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

In addition to nitrilotriacetic acid, especially sodium aluminosilicates (zeolites) are used as phosphate substitutes or substitutes in textile detergents. However, these substances are not suitable for use in automatic dishwashing detergents for various reasons. As an alternative to the alkali metal phosphates in automatic dishwashing detergents are therefore in the Literature discussed a number of substitutes, of which the citrates are particularly noteworthy.

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

Another alternative to the alkali metal phosphates used as the sole builder but preferably in combination with citrates is methylglycine diacetic acid (MGDA). Machine 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).

EP-A-1721962 describes phosphate-free, automatic dishwashing agents containing nonionic surfactants, MGDA, percarbonate and citrate, but no sulfonic acid-containing copolymers. WO 2006/106332 describes non-phosphate machine dishwashing detergents which contain nonionic surfactants, MGDA, citrate and sulfonic acid group-containing copolymers, but no bleaches.

Potthoff-Karl et al. (SOFW Journal Soaps, Oils, Fats, Waxes, Verlag für Chemische Industrie, Augsburg, DE, Vol. 122, No. 6, May 1, 1996, pages 392-394 and 396 describe phosphate-free, automatic dishwashing detergents containing nonionic surfactants, MGDA, percarbonate and citrate, but no sulfonic acid-containing copolymers.

WO 2005/090541 discloses, inter alia, a phosphate-free, automatic dishwashing detergent containing surfactants, citrate, bleach and sulfonic acid-containing copolymers, but no MGDA.

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

The post-published international Pafentveröffentlichung WO 2007/052064 describes phosphate-free, automatic dishwashing detergents containing surfactants, citrate, bleach and sulfonic acid-containing copolymers, and MGDA.

Despite previous efforts, the manufacturers of automatic dishwashing detergents have so far failed to provide phosphate-free automatic dishwashing detergents which are comparable with cleaning detergents or rinsing agents with phosphate-containing detergents or even exceed them. However, such an equality of performance is a precondition for the successful market introduction of phosphene-free cleaning agents, since the vast majority of end consumers will always decide against an ecologically advantageous product despite broad public discussion of environmental issues, if this does not meet the market standard in terms of its Prelses and / or its performance.

In view of this initial situation, therefore, the object of the present application to provide a phosphate-free automatic dishwashing detergent, which is comparable in terms of its cleaning performance and in terms of its rinse results and its performance in terms of scale inhibition with conventional phosphorous cleaning agents or even better.

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

1. i) Sulfonsäuregruppen-haltige Monomere
2. ii) weitere ionische und/oder nichtionische Monomere

b) Methylglydndiessigsäure, mit Ausnahme folgender pulverförmiger Formulierung mit einem pH-Wert von 7,5: Komponente Gew.-% MGDA 5,0 Natriumcitrat 69,8 Citronensäure ca. 2,0 PAP-Bleiche 7,0 Amylase (Duramyl™) 0,4 Protease (Properase™) 1,1 Sulfoniertes Polyacrylsäure Copolymer (Acusol 687™, Acusol 588™ oder Alcoguard 4080™) 5,0 PEG 6000 2,0 PEG 1500 7,0 Tensid (C16-18 Fettalkohol 3EO-3PO) 0,5 BTA 0,1 Parfüm 0,1 A first subject of the present application is therefore a non-phosphate machine dishwashing detergent containing builder, bleach, nonionic surfactant and further
a) copolymer comprising

1. i) sulfonic acid group-containing monomers
2. ii) further ionic and / or nonionic monomers

b) methylglydndiacetic acid, with the exception of the following powdered formulation with a pH of 7.5: component Wt .-% MGDA 5.0 sodium citrate 69.8 citric acid about 2.0 PAP bleaching 7.0 Amylase (Duramyl ™) 0.4 Protease (Properase ™) 1.1 Sulfonated polyacrylic acid copolymer (Acusol 687 ™, Acusol 588 ™ or Alcoguard 4080 ™) 5.0 PEG 6000 2.0 PEG 1500 7.0 Surfactant (C16-18 fatty alcohol 3EO-3PO) 0.5 BTA 0.1 Perfume 0.1

A first characteristic constituent of agents according to the invention are the sulfonic acid-containing copolymers a) which, in addition to a monomer containing sulfonic acid groups, comprise at least one further ionic or nonionic monomer. The copolymers a) may have two, three, four or more different monomer units.

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

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

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

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃

H ₂ C = C (CH ₃ ) -X-SO ₃ H

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

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

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

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metallians, preferably for alkali metal ions and especially for sodium ions. The use of partially or vollrieutralisierten sulfonsäuregruppenhaltigen copolymers is inventively preferred.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which are only monomers from the groups. i) and ii), preferably in each case 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 molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In a first preferred embodiment, the copolymers further comprise at least one ionic monomer in addition to at least one sulfonic acid group-containing monomer.

1. i) Sulfonsauregruppen-haltige Monomere
2. ii) weitere ionische Monomere

b) Methylglycindiessigsäure, mit Ausnahme folgender pulverförmiger Formulierung mit einem pH-Wert von 7,5: Komponente Gew.-% MGDA 5,0 Natriumcitrat 69,8 Citronensäure ca. 2,0 PAP-Bleiche 7,0 Amylase (Duramyl™) 0,4 Protease (Properase™) 1,1 Sulfoniertes Polyacrylsäure Copolymer (Acusol 687™, Acusol 588™ oder Alcoguard 4080™) 5,0 PEG 6000 2,0 PEG 1500 7,0 Tensid (C16-18 Fettalkohol 3EO-3PO) 0,5 BTA 0,1 Parfüm 0,1 werden erfindungsgemäß bevorzugt.A phosphate-free automatic dishwashing detergent containing builder, bleach, nonionic surfactant, and further
a) copolymer comprising

1. i) sulfonic acid group-containing monomers
2. ii) other ionic monomers

b) methylglycine diacetic acid, except for the following powdered formulation having a pH of 7.5: component Wt .-% MGDA 5.0 sodium citrate 69.8 citric acid about 2.0 PAP bleaching 7.0 Amylase (Duramyl ™) 0.4 Protease (Properase ™) 1.1 Sulfonated polyacrylic acid copolymer (Acusol 687 ™, Acusol 588 ™ or Alcoguard 4080 ™) 5.0 PEG 6000 2.0 PEG 1500 7.0 Surfactant (C16-18 fatty alcohol 3EO-3PO) 0.5 BTA 0.1 Perfume 0.1 are preferred according to the invention.

As ionic monomers unsaturated carboxylic acids are used with particular preference. Particular preference is given to 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 are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, substituted with -NH ₂ , -OH or -COOH alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

1. i) Sulfonsauregruppen-haltlge Monomere
2. ii) Carboxylgruppen-haltige Monomere der Formel R¹(R²)C=C(R¹COOH, 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 ungesättigte, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist

b) Methylglycindiessigsäure, mit Ausnahme folgender pulverförmiger Formulierung mit einem pH-Wert von 7,5: Komponente Gew.-% MGDA 5,0 Natriumcitrat 69,8 Citronensäure ca. 2,0 PAP-Bleiche 7,0 Amylase (Duramyl™) 0,4 Protease (Properase™) 1,1 Sulfoniertes Polyacrylsäure Copolymer (Acusol 687™, Acusol 588™ oder Alcoguard 4080™) 5,0 PEG 6000 2,0 PEG 1500 7,0 Tensid (C16-18 Fettalkohol 3EO-3PO) 0,5 BTA 0,1 Parfüm 0,1 .Accordingly, phosphate-free automatic dishwashing detergents containing gum, bleaching agent, nonionic surfactant, and furthermore are particularly preferred
a) copolymer comprising

1. i) sulfonic acid group-containing monomers
2. ii) carboxyl-containing monomers of the formula R ¹ (R ² ) C = C (R ¹ COOH, in which R ¹ to R ^{3 are} independently -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms , a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms

b) methylglycine diacetic acid, except for the following powdered formulation having a pH of 7.5: component Wt .-% MGDA 5.0 sodium citrate 69.8 citric acid about 2.0 PAP bleaching 7.0 Amylase (Duramyl ™) 0.4 Protease (Properase ™) 1.1 Sulfonated polyacrylic acid copolymer (Acusol 687 ™, Acusol 588 ™ or Alcoguard 4080 ™) 5.0 PEG 6000 2.0 PEG 1500 7.0 Surfactant (C16-18 fatty alcohol 3EO-3PO) 0.5 BTA 0.1 Perfume 0.1 ,

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

In a second preferred embodiment, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer in addition to at least one sulfonic acid-containing monomer.

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

werden erfindungsgemäß bevorzugt,Phosphate-free automatic dishwashing detergents containing builder, bleach, nonionic surfactant and further

1. a) copolymer comprising
   1. i) sulfonic acid group-containing monomers
   2. ii) other nonionic monomers
2. b) methylglycinediacetic acid

are preferred according to the invention,

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X represents an optionally present spacer group selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

1. a) 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) Methylglycindiessigsäure

A further preferred subject matter of this application is therefore phosphate-free automatic dishwashing compositions containing builder, bleaching agent, nonionic surfactant and furthermore

1. a) copolymer comprising
   1. i) sulfonic acid group-containing monomers
   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 are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms
2. b) methylglycinediacetic acid

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-Trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1,2,4-dimethylhexene-1,2,5-dimethylhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octacenecene and C22-olefin, 2-styrene, - methylstyrene, 3-methylstyrene, 4-propylslyrole, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methacrylic acid methyl ester, N- (methyl) acrylamide, acrylic acid 2-ethylhexyl ester, methacrylic acid 2-ethylhexyl ester, N - (2-ethylhexyl) acrylamide, Acrylsäureoctyle ster, Methacrylsäureoctylester, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, Acrylsaurestearylester, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, Methacrylsaurebehenylester and N - (behenyl) acrylamide or mixtures thereof.

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

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

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

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

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

werden erfindungsgemäß bevorzugt.Phosphate-free automatic dishwashing compositions containing 5 to 60 wt .-%, preferably 10 to 50 wt .-% and in particular 15 to 40 wt .-% citrate, bleaching agent, nonionic surfactant, and further

1. a) copolymer comprising
   1. i) sulfonic acid group-containing monomers
   2. ii) further ionic and / or nonionic monomers
2. b) methylglycinediacetic acid

are preferred according to the invention.

• Phosphatfreie maschinelle Geschirrspülmittel, enthaltend 10 bis 50 Gew.-% Citrat, Bleichmittel, nichtionisches Tensid, sowie weiterhin
  1. a) 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
  2. b) Methylglycindiessigsäure.
  sowie
• Phosphatfreie maschinelle Geschirrspülmittel, enthaltend 10 bis 50 Gew.-% Citrat, Bleichmittel, nichtionisches Tensid, sowie weiterhin
  1. a) 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) Methylglycindiessigsäure.

Further preferred embodiments are:

• A phosphate-free automatic dishwashing detergent containing 10 to 50% by weight citrate, bleaching agent, nonionic surfactant, and further
  1. a) copolymer comprising
     1. i) sulfonic acid group-containing monomers
     2. ii) carboxyl-containing monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
  2. b) methylglycinediacetic acid.
  such as
• A phosphate-free automatic dishwashing detergent containing 10 to 50% by weight citrate, bleaching agent, nonionic surfactant, and further
  1. a) copolymer comprising
     1. i) sulfonic acid group-containing monomers
     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 are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms
  2. b) methylglycinediacetic acid.

With preference, automatic dishwashing agents according to the invention contain as builder crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4 where particularly preferred values for x are 2, 3 or 4 and y is a number from 0 to 33, preferably from 0 to 20.

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

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

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

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

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

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

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

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

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

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

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

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

Of course, the automatic dishwashing compositions of the invention may contain two or more different phosphonates. Particular preference is given to those automatic dishwashing compositions which contain as phosphonates both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), 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 fraction of the phosphonate (s) in the total weight of the automatic dishwashing agent is less than the weight proportion of the polymer (s) a). In other words, those agents are particularly preferred in which the ratio of the weight fraction of polymer a) to the weight fraction of the phosphonate is 200: 1 to 2: 1, preferably 150: 1 to 2: 1, particularly preferably 100: 1 to 2: 1, most preferably 80: 1 to 3: 1 and in particular 50: 1 to 5: 1.

Preferred automatic dishwashing agents according to the invention also contain one or more bleaching agents. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

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

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

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

1. a) copolymer comprising
   1. i) sulfonic acid group-containing monomers
   2. ii) further ionic and / or nonionic monomers
2. b) methylglycinediacetic acid.

are preferred according to the invention.

• Phosphatfreie maschinelle Geschirrspülmittel, enthaltend Gerüststoff, 2 bis 15 Gew.-% Natriumpercarbonat, nichtionisches Tensid, sowie weiterhin
  1. a) 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
  2. b) Methylglycindiessigsäure.
  sowie
• Phosphatfreie maschinelle Geschirrspülmittel, enthaltend Gerüststoff, 2 bis 15 Gew.-% Natriumpercarbonat, nichtionisches Tensid, sowie weiterhin
  1. a) 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) Methylglycindiessigsäure.

Further preferred embodiments are:

• Phosphate-free automatic dishwashing detergent containing builder, 2 to 15 wt .-% sodium percarbonate, nonionic surfactant, and further
  1. a) copolymer comprising
     1. i) sulfonic acid group-containing monomers
     2. ii) carboxyl-containing monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ one saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
  2. b) methylglycinediacetic acid.
  such as
• Phosphate-free automatic dishwashing detergent containing builder, 2 to 15 wt .-% sodium percarbonate, nonionic surfactant, and further
  1. a) copolymer comprising
     1. i) sulfonic acid group-containing monomers
     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 are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms
  2. b) methylglycinediacetic acid.

As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine releasing materials are, for example, 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-dimethylhydantoin are also suitable.

In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below, the automatic dishwasher detergents according to the invention may additionally contain bleach activators. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

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

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

It is particularly preferred to use 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 compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) 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 ).

Machine dishwashing detergent, characterized in that it further comprises 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 in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.

The abovementioned bleach-enhancing transition metal complexes, in particular with the central atoms Mn and Co, are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0, 01 wt .-% to 0.30 wt .-%, each based on the total weight of the bleach activator-containing agents used. 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 nonionic, anionic, cationic and amphoteric surfactants.

Surprisingly, it has been found that the bleaching action 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, umfassend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) weitere ionische und/oder nichtionische Monomere
2. b) Methylglycindiessigsäure.
3. c) Citrat
4. d) Bleichkatalysator ausgewählt aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe

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

1. a) copolymer comprising
   1. i) sulfonic acid group-containing monomers
   2. ii) further ionic and / or nonionic monomers
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 exemplary formulations for such preferred phosphate-free automatic dishwashing detergents can be found in the following table: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 5 to 60 10 to 55 15 to 50 15 to 50 sodium 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 comprising
i) sulfonic acid group-containing monomers
ii) other nonionic monomers

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

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

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

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

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

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

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

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

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

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

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

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

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

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

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

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

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

In summary, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in which R ¹ and R ² independently of one another represents a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or -alkenyl radical; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

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

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH _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 is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

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

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

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

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

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

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

werden erfindungsgemäß bevorzugt.A phosphate-free machine dishwashing detergent containing builder, bleaching agent, nonionic surfactant in amounts of from 1 to 10% by weight, preferably from 2 to 8% by weight and in particular from 3 to 6% by weight, and also

1. a) copolymer comprising
   1. i) sulfonic acid group-containing monomers
   2. ii) further ionic and / or nonionic monomers
2. b) methylglycinediacetic acid.

are preferred according to the invention.

Some exemplary formulations for such preferred phosphate-free automatic dishwashing detergents can be found in the following table: ingredient Recipe 5 [% by weight] Recipe 6 [% by weight] Recipe 7 [% by weight] Recipe 8 [% by weight] citrate 5 to 60 10 to 55 15 to 50 15 to 50 sodium 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 Nonionic surfactant 1 to 10 1 to 10 2 to 8 3 to 6 Copoylmer 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 comprising
i) sulfonic acid group-containing monomers
ii) further ionic and / or nonionic monomers

• Phosphatfreie maschinelle Geschirrspülmittel, enthaltend Gerüststoff, Bleichmittel, 2 bis 8 Gew.-% nichtionisches Tensid, sowie weiterhin
  1. a) 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
  2. b) Methylglycindiessigsäure.
  sowie
• Phosphatfreie maschinelle Geschirrspülmittel, enthaltend Gerüststoff, Bleichmittel, 2 bis 8 Gew.-% nichtionisches Tensid, sowie weiterhin
  1. a) 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) Methylglycindiessigsäure.

Further preferred embodiments are:

• Phosphate-free automatic dishwashing detergent containing builder, bleach, 2 to 8 wt .-% nonionic surfactant, and further
  1. a) copolymer comprising
     1. i) sulfonic acid group-containing monomers
     2. ii) carboxyl-containing monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
  2. b) methylglycinediacetic acid.
  such as
• Phosphate-free automatic dishwashing detergent containing builder, bleach, 2 to 8 wt .-% nonionic surfactant, and further
  1. a) copolymer comprising
     1. i) sulfonic acid group-containing monomers
     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 are -H, -CH ₃ or -C ₂ H ₅ , X is a optional is present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
  2. b) methylglycinediacetic acid.

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

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

• Phosphatfreie maschinelle Geschirrspülmittel, enthaltend Gerüststoff, 2 bis 15 Gew.-% Natriumpercarbonat, 2 bis 8 Gew.-% nichtionisches Tensid, sowie weiterhin
  1. a) 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
  2. b) Methylglycindiessigsäure.
  sowie
• Phosphatfreie maschinelle Geschirrspülmittel, enthaltend Gerüststoff, 2 bis 15 Gew.-% Natriumpercarbonat, 2 bis 8 Gew.-% nichtionisches Tensid, sowie weiterhin
  1. a) 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) Methylglycindiessigsäure.
  sowie
• Phosphatfreie maschinelle Geschirrspülmittel, enthaltend 10 bis 50 Gew.-% Citrat, 2 bis 15 Gew.-% Natriumpercarbonat, 2 bis 8 Gew.-% nichtionisches Tensid, sowie weiterhin
  1. a) 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
  2. b) Methylglycindiessigsäure.
  sowie
• Phosphatfreie maschinelle Geschirrspülmittel, enthaltend 10 bis 50 Gew.-% Citrat, 2 bis 15 Gew.-% Natriumpercarbonat, 2 bis 8 Gew.-% nichtionisches Tensid, sowie weiterhin
  1. a) 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) Methylglycindiessigsäure.

In summary, the following framework formulations are particularly preferred because of their outstanding cleaning and rinse-aid results:

• Phosphate-free automatic dishwashing compositions containing builder, 2 to 15 wt .-% sodium percarbonate, 2 to 8 wt .-% nonionic surfactant, and further
  1. a) copolymer comprising
     1. i) sulfonic acid group-containing monomers
     2. ii) carboxyl-containing monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
  2. b) methylglycinediacetic acid.
  such as
• Phosphate-free automatic dishwashing compositions containing builder, 2 to 15 wt .-% sodium percarbonate, 2 to 8 wt .-% nonionic surfactant, and further
  1. a) copolymer comprising
     1. i) sulfonic acid group-containing monomers
     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 are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms
  2. b) methylglycinediacetic acid.
  such as
• A phosphate-free automatic dishwashing detergent containing 10 to 50% by weight of citrate, 2 to 15% by weight of sodium percarbonate, 2 to 8% by weight of nonionic surfactant, and furthermore
  1. a) copolymer comprising
     1. i) sulfonic acid group-containing monomers
     2. ii) carboxyl-containing monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
  2. b) methylglycinediacetic acid.
  such as
• A phosphate-free automatic dishwashing detergent containing 10 to 50% by weight of citrate, 2 to 15% by weight of sodium percarbonate, 2 to 8% by weight of nonionic surfactant, and furthermore
  1. a) copolymer comprising
     1. i) sulfonic acid group-containing monomers
     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 are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms
  2. b) methylglycinediacetic acid.

Dishwasher detergents according to the invention have proved to be particularly effective with regard to optimum cleaning and rinse-aid results, in which the weight fraction of the copolymer a) is 4 to 18% by weight, preferably 6 to 15 and in particular 6 to 12% by weight.

Machine dishwashing detergents in which the weight fraction of 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, likewise have particularly good cleaning properties. , Rinse and pad results and are therefore 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

bzw.Very particular preference is therefore given to phosphate-free automatic dishwashing compositions containing

1. a) 6 to 15 wt .-% copolymer comprising
   1. i) sulfonic acid group-containing monomers
   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 are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms
2. b) 0.5 to 10% by weight of methylglycinediacetic acid
3. c) 10 to 50 wt .-% citrate
4. d) 2 to 15 wt .-% sodium percarbonate
5. e) 2 to 8% by weight of nonionic surfactant

respectively.

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
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

Phosphate-free automatic dishwashing detergents containing

1. a) 6 to 15 wt .-% copolymer comprising
   1. i) sulfonic acid group-containing monomers
   2. ii) carboxyl-containing monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
2. b) 0.5 to 10% by weight of methylglycinediacetic acid
3. c) 10 to 50 wt .-% citrate
4. d) 2 to 15 wt .-% sodium percarbonate
5. e) 2 to 8% by weight of nonionic surfactant

In a further preferred embodiment, the copolymers comprise a) in addition to the sulfonic acid-containing monomers further ionic and nonionic monomers.

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

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

1. a) copolymer comprising
   1. i) sulfonic acid group-containing monomers
   2. ii) other ionic monomers
   3. iii) other nonionic monomers
2. b) methylglycinediacetic acid.

are preferred according to the invention.

Most preferably, these include terpolymers as carboxyl group-containing monomers.

1. a) Copolymer, umfassend
   1. i) Sulfonsäuregruppen-haltige Monomere
   2. ii) Carboxylgruppen-haltige Monomere
   3. iii) weitere nichtionische Monomere
2. b) Methylglycindiessigsäure.

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

1. a) copolymer comprising
   1. i) sulfonic acid group-containing monomers
   2. ii) carboxyl group-containing monomers
   3. iii) other nonionic monomers
2. b) methylglycinediacetic acid.

In a last preferred embodiment, the copolymers additionally contain, in addition to at least one sulfonic acid group-containing monomer, a carboxyl-containing monomer and 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 are} independently -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O ) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

1. a) Copolymer, umfassend
   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, preference is given to phosphate-free automatic dishwashing detergents which, in addition to builder, bleaching agent and nonionic surfactant, continue to be used

1. a) copolymer comprising
   1. i) sulfonic acid group-containing monomers
   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 are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms
2. b) methylglycinediacetic acid

contain.

• Phosphatfreie maschinelle Geschirrspülmittel, enthaltend
  1. a) 6 bis 15 Gew.-% Copolymer, umfassend
     • i) Sulfonsäuregruppen-haltige Monomere
     • ii) Carboxylgruppen-haltige Monomere
     • ii) weitere nichtionische Monomere
  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 comprising
     • i) sulfonic acid group-containing monomers
     • ii) carboxyl group-containing monomers
     • ii) other nonionic monomers
  2. b) 0.5 to 10% by weight of methylglycinediacetic acid
  3. c) 10 to 50 wt .-% citrate
  4. d) 2 to 15 wt .-% sodium percarbonate
  5. e) 2 to 8% by weight of nonionic surfactant

In addition to the ingredients described above, such as builder, the bleach, the nonionic surfactant, the copolymer a) and methylglycinediacetic preferred automatic dishwashing 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, the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

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

For the purposes of the present invention, "amphoteric polymers" further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may 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 R ¹ , R ² , R ⁴ radical ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, 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 having at least one positive charge without charged nitrogen , at least one quaternized nitrogen atom or at least one amino group having a positive charge in the partial range of the pH range of 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 having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one Aminogr uppe with a positive charge is.

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

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ³ independently 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 being a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, 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.

werden im Falle von X^-= Chlorid auch als DADMAC (Diallyldimethylammonium-Chlorid) bezeichnet.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

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

in der R¹, R², R³, R⁴ und R⁵ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ungesättigen Alkyl-, oder Hydroxyalkylrest mit 1 bis 6 Kohlenstoffatomen, vorzugsweise für einen linearen oder verzweigten Alkylrest ausgewählt aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, und -(CH₂CH₂-O)_nH steht und x für eine ganze Zahl zwischen 1 und 6 steht.Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are 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 is an integer between 1 and 6.

werden im Falle von X^-= Chlorid auch als MAPTAC (Methyacrylamidopropyl-trimethylammonium-Chlorid) bezeichnet.For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{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

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

Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

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

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

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

• 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 present in prefabricated form. For the preparation of the polymers is suitable inter alia

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

Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent. In the context of the present application, however, preference is given to those detergents or cleaners in which the weight fraction 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 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing agent is.

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

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

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis , from B. amyloliquefaciens , from B. stearothermophilus , from Aspergillus niger and A. oryzae as well as the further developments of the abovementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens . It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .

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

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

The enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

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

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

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.Very particular preference is therefore given to phosphate-free automatic dishwashing compositions containing

1. a) 6 to 15 wt .-% copolymer comprising
   1. i) sulfonic acid group-containing monomers
   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 are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms
2. b) 0.5 to 10% by weight of methylglycinediacetic acid
3. c) 10 to 50 wt .-% citrate
4. d) 2 to 15 wt .-% sodium percarbonate
5. e) 2 to 8% by weight of nonionic surfactant
6. f) 1.0 to 6 wt .-% enzyme.

respectively.

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
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.

sowie
Phosphatfreie maschinelle Geschirrspülmittel, enthaltend

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) sulfonic acid group-containing monomers
   2. ii) carboxyl-containing monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
2. b) 0.5 to 10% by weight of methylglycinediacetic acid
3. c) 10 to 50 wt .-% citrate
4. d) 2 to 15 wt .-% sodium percarbonate
5. e) 2 to 8% by weight of nonionic surfactant
6. f) 1.0 to 6 wt .-% enzyme.

such as
Phosphate-free automatic dishwashing detergents containing

1. a) 6 to 15 wt .-% copolymer comprising
   1. i) sulfonic acid group-containing monomers
   2. ii) carboxyl-containing monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 Carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
   3. iii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms
2. b) 0.5 to 10% by weight of methylglycinediacetic acid
3. c) 10 to 50 wt .-% citrate
4. d) 2 to 15 wt .-% sodium percarbonate
5. e) 2 to 8% by weight of nonionic surfactant
6. f) 1.0 to 6 wt .-% enzyme.

Some exemplary formulations for such preferred phosphate-free automatic dishwashing detergents can be found in the following tables:

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

The spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

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

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

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

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times.

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

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

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

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

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water. However, preferred effervescent systems consist of at least two components which react with one another to form gas, for example from alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution. As Acidifizierungsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.

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

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers, by a slower release of fragrance for long-lasting fragrance to care. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

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

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

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

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

The individual phases of multiphase agents may have the same or different states of matter. Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred.

Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.

The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

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

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 metered into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle. The metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher.

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

Examples

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

The composition of the dishwashing agents used can be found in the following table: 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 10.0 10.0 10.0 10.0 TAED 2.4 2.4 2.4 2.4 Protease / Amylase 4.0 4.0 4.0 4.0 Nonionic surfactant 5.0 5.0 5.0 5.0 Misc Add 100 Add 100 Add 100 Add 100 ¹ sulfonic acid group-containing copolymer

The overall appearance of the items to be washed was assessed on the basis of the rating scale listed below. The results are given in the table below (The values given are average values from 3 experiments): V1 V2 V3 E1 cleaning result 8.1 7.1 7.5 8.2

Rating Scale Cleaning: 10 = no contamination to 0 = heavy contamination (mean over seven specific soils)

In a second experiment to determine the formation of deposits was not soiled dishes in a continuously operated dishwasher with 21 g of a commercial Washing machine dishwasher detergent containing 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 items to be washed was assessed on the basis of the rating scale listed below. The results are given in the table below (The values given are average values from 3 experiments): V1 V2 V3 E1 fouling Porcelain 3,5 Porcelain 1.5 Porcelain 2,5 Porcelain 3.0 Plastic 4.2 Plastic 1.0 Plastic 3.0 Plastic 4.5

Evaluation scale formation of deposits: 10 = no deposit formation to 0 = heavy deposit formation

Claims (11)

1. A phosphate-free automatic dishwashing agent which contains builder, bleaching agent, nonionic surfactant, and furthermore

   a) copolymer comprising

   i) monomers containing sulfonic acid groups

   ii) further ionic and/or nonionic monomers

   b) methylglycinediacetic acid,

   with the exception of the following pulverulent formulation with a pH of 7.5: Component wt.% MGDA 5.0 Sodium citrate 69.8 Citric acid approx. 2.0 PAP bleach 7.0 Amylase (Duramyl™) 0.4 Protease (Properase™) 1.1 Sulfonated polyacrylic acid copolymer (Acusol 587™, Acusol 588™ or Alcoguard 4080™) 5.0 PEG 6000 2.0 PEG 1500 7.0 Surfactant (C16-18 fatty alcohol 3EO-3PO) 0.5 BTA 0.1 Perfume 0.1
2. An automatic dishwashing agent according to claim 1, characterised in that the proportion by weight of copolymer a) amounts to 4 to 18 wt.%, preferably 6 to 15 and in particular 6 to 12 wt.%.
3. An automatic dishwashing agent according to either of the preceding claims, characterised in that the copolymer a) contains

   i) monomers containing sulfonic acid groups

   ii) monomers of the general formula R¹(R²)C=C(R³)-X-R⁴, in which R¹ to R³ mutually independently denote -H, -CH₃ or -C₂H₅, X denotes an optionally present spacer group which is selected from -CH₂-, -C(O)O- and -C(O)-NH-, and R⁴ denotes a straight-chain or branched saturated alkyl residue with 2 to 22 carbon atoms or denotes an unsaturated, preferably aromatic residue with 6 to 22 carbon atoms.
4. An automatic dishwashing agent according to any one of the preceding claims, characterised in that the proportion by weight of methylglycinediacetic acid b) amounts to 0.5 to 20 wt.%, preferably 0.5 to 10 wt.% and in particular 0.5 to 8 wt.%.
5. An automatic dishwashing agent according to any one of the preceding claims, characterised in that it contains 5 to 60 wt.%, preferably 10 to 50 wt.% and in particular 15 to 40 wt.% of citrate.
6. An automatic dishwashing agent according to any one of the preceding claims, characterised in that it contains 1 to 20 wt.%, preferably 2 to 15 wt.% and in particular 4 to 12 wt.% of sodium percarbonate.
7. An automatic dishwashing agent according to any one of the preceding claims, characterised in that it contains the nonionic surfactant in quantities of 1 to 10 wt.%, preferably of 2 to 8 wt.% and in particular of 3 to 6 wt.%.
8. An automatic dishwashing agent according to any one of the preceding claims which contains

   a) 6 to 15 wt.% of 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 mutually independently denote -H, -CH₃ or -C₂H₅, X denotes an optionally present spacer group which is selected from -CH₂-, -C(O)O- and -C(O)-NH-, and R⁴ denotes a straight-chain or branched saturated alkyl residue with 2 to 22 carbon atoms or denotes an unsaturated, preferably aromatic residue with 6 to 22 carbon atoms

   b) 0.5 to 10 wt.% of methylglycinediacetic acid

   c) 10 to 50 wt. % of citrate

   d) 2 to 15 wt.% of sodium percarbonate

   e) 2 to 8 wt.% of nonionic surfactant.
9. An automatic dishwashing agent according to any one of the preceding claims which contains

   a) 6 to 15 wt.% of 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, mutually independently, denote -H, -CH₃ or -C₂H₅, X denotes an optionally present spacer group which is selected from -CH₂-, -C(O)O- and -C(O)-NH-, and R⁴ denotes a straight-chain or branched saturated alkyl residue with 2 to 22 carbon atoms or denotes an unsaturated, preferably aromatic residue with 6 to 22 carbon atoms

   b) 0.5 to 10 wt.% of methylglycinediacetic acid

   c) 10 to 50 wt. % of citrate

   d) 2 to 15 wt.% of sodium percarbonate

   e) 2 to 8 wt.% of nonionic surfactant

   f) 1.0 to 6 wt.% of enzyme.
10. A method for washing dishes in an automatic dishwasher, utilizing an automatic dishwashing agent according to any one of claims 1 to 9.
11. A method according to claim 10, characterised in that no additional water softener and no additional rinse agent is dispensed into the interior of the automatic dishwasher in the course of the washing process.