EP2364351B1 - Cleaning composition - Google Patents

Description

The present patent application describes detergents, in particular detergents for the machine cleaning of dishes. This application relates to phosphate-free automatic dishwashing detergents which contain a combination of cleaning-active polymers and nonionic surfactant and citrate / citric acid.

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

Modern automatic dishwashing detergents meet these requirements by integrating cleansing, caring, water-softening and clear-rinse 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 have been allowed to contain no more than 20% of this builder since 1984.

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 alternatives to the Alkali metal phosphates in automatic dishwashing detergents are therefore discussed in the literature as a number of substitutes, of which the citrates are particularly noteworthy.

Phosphate-free automatic 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). MGDA-containing automatic dishwashing detergents 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).

As coating-inhibiting ingredients of automatic dishwasher detergents are also sulfonsäuregruppenhaltige polymers, so-called sulfopolymers, in the German patent application DE 102007006630 A1 , the international patent applications WO 2005/090540 A1 . WO 2006/018107 A1 and WO 2008/017620 , the German utility model DE20019913 U1 and the US patent US Pat. No. 6,207,780 B1 beschirieben.

Despite the efforts so far, the manufacturers of automatic dishwashing detergents have hitherto not been able to provide phosphate-free automatic dishwashing detergents which are comparable or even exceed phosphate-containing cleaners in terms of their cleaning and rinsing performance and, in particular, their coating-inhibiting performance. However, such an equality of performance is a prerequisite for the successful market introduction of phosphate-free detergents, since the vast majority of end consumers will always decide against an ecologically beneficial product despite wide public discussion of environmental issues, if this does not meet the market standard in terms of its price and / or performance.

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

It has been found that automatic dishwashing detergents which, in addition to builder and bleach, furthermore comprise a mixture of specific sulfonic acid group-containing polymers and nonionic Surfactant and 5 to 60 wt .-% citrate and citric acid, even without the addition of alkali metal phosphates have excellent pad inhibition and cleaning and rinsing performance.

1. a) hydrophob modifiziertes Copolymer A, umfassend Monomere ai) aus der Gruppe der ein- oder mehrfach ungesättigten Sulfonsäuren, Monomere aii) aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren und Monomere aiii) 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) nicht hydrophob modifiziertes Copolymer B, umfassend Monomere bi) aus der Gruppe der ein- oder mehrfach ungesättigten Sulfonsäuren und Monomere bii) aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren,
3. c) nichtionisches Tensid C
4. d) 5 bis 60 Gew.-% Citrat und Citronensäure.

A first subject of the present application is therefore a non-phosphate machine dishwashing detergent containing builder, bleach, and further

1. a) hydrophobically modified copolymer A, comprising monomers ai) from the group of mono- or polyunsaturated sulfonic acids, monomers aii) from the group of mono- or polyunsaturated carboxylic acids and monomers aiii) of general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ^3, independently of one another, is -H, -CH ₃ or -C ₂ H ₅ , X is an 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) non-hydrophobically modified copolymer B comprising monomers bi) from the group of mono- or polyunsaturated sulfonic acids and monomers bii) from the group of mono- or polyunsaturated carboxylic acids,
3. c) nonionic surfactant C
4. d) 5 to 60 wt .-% citrate and citric acid.

The dishwasher detergents according to the invention contain builders, bleaches and the copolymers A and B, the nonionic surfactant C and 5 to 60 wt .-% citrate and citric acid. By using a mixture of copolymers A and B, it is surprisingly possible to obtain better rinse-aid results than by adding the same amount of copolymer A or B.

A first essential component of agents according to the invention are the builders. The group of these builders includes, in particular, the citrates and also the carbonates and the organic cobuilders.

The term "citrate" also includes citric acid as well as its salts, in particular their alkali metal salts. Machine dishwashing detergents according to the invention contain citric acid and citrate, preferably sodium citrate, in amounts of from 5 to 60% by weight, preferably from 10 to 50% by weight and in particular from 15 to 40% by weight.

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% by weight and in particular from 15 to 30% by weight, in each case based on the weight of the automatic dishwashing detergent.

Some further exemplary formulations for preferred automatic dishwasher detergents according to the invention can be found in the following Table 1: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 5.0 to 60 10 to 50 10 to 50 15 to 40 carbonate 5.0 to 50 5.0 to 50 10 to 40 15 to 30 bleach 1.0 to 20 2.0 to 15 2.0 to 15 4.0 to 12 Copolymer A 1.0 to 12 2.0 to 10 2.0 to 10 3.0 to 8.0 Copolymer B 2.0 to 16 4.0 to 14 4.0 to 14 6.0 to 12 Nonionic surfactant C 0.5 to 8 1.0 to 7.0 1.0 to 7.0 2.0 to 6.0 Misc Add 100 Add 100 Add 100 Add 100

Particular examples of organic cobuilders include polycarboxylates / polycarboxylic acids, dextrins and phosphonates. These classes of substances are described below.

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

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

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

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

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

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

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

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

A second essential constituent of automatic dishwashing agents according to the invention are the bleaching agents, oxygen bleaching agents being preferred according to the invention.

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. Further useful bleaching agents are, for example, peroxypyrophosphates, Citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaches can furthermore be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

Preferred phosphate-free automatic dishwashing detergents are characterized in that the dishwashing detergent, based in each case on the total weight of the dishwashing detergent, contains 1.0 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 12% by weight sodium percarbonate.

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 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 [I, III, IV or [V, 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, bleach catalyst (s) in the agents which are used as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7- triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) 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 catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.

Some further exemplary formulations for preferred automatic dishwasher detergents according to the invention can be found in the following Table 2: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 5.0 to 60 10 to 50 10 to 50 15 to 40 carbonate 5.0 to 50 5.0 to 50 10 to 40 15 to 30 sodium 1.0 to 20 2.0 to 15 2.0 to 15 4.0 to 12 Copolymer A 1.0 to 12 2.0 to 10 2.0 to 10 3.0 to 8.0 Copolymer B 2.0 to 16 4.0 to 14 4.0 to 14 6.0 to 12 Nonionic surfactant C 0.5 to 8 1.0 to 7.0 1.0 to 7.0 2.0 to 6.0 bleach 0 to 8 0 to 8 0 to 8 2.0 to 6.0 bleach catalyst 0 to 5.0 0 to 1.0 0 to 1.0 0.0025 to 1.0 phosphonate 0 to 8.0 1 to 8.0 0 to 8.0 0 to 8.0 Misc Add 100 Add 100 Add 100 Add 100

The hydrophobically modified copolymers A are a third essential constituent of automatic dishwashing agents according to the invention. These copolymers comprise in addition to a monomer ai) from the group of mono- or polyunsaturated sulfonic acids furthermore at least one monomer aii) from the group of mono- or polyunsaturated carboxylic acids and at least one hydrophobic monomer aiii) of 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 an 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 ..

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 - , -C (O) -NH-C (CH ₃ ) ₂ CH ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

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

wherein 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 selected 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 -, -C (O) -NH-C (CH ₃ ) ₂ CH ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

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

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

The hydrophobic monomers used are 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 an 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 is an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred hydrophobic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1,2,4,4-trimethylpentene-2,3,3-dimethylhexene-1,2,4-dimethylhexene-1,2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, octyl acrylate, M ethacrylsäureoctylester, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, Methacrylsäurebehenylester and N - (behenyl) acrylamide or mixtures thereof.

Furthermore, machine dishwashing agents according to the invention contain, as constituent of the hydrophobically modified copolymers A, monomers aii) from the group of mono- or polyunsaturated carboxylic acids.

As monomers aii) it is preferred to use monomers from the group of the carboxylic acids having the general formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred carboxyl-containing monomers i) are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Particularly preferred are acrylic acid and methacrylic acid.

The proportion by weight of the copolymer A in the total weight of phosphate-free automatic dishwashing agents according to the invention is preferably from 1 to 12% by weight, preferably from 2 to 10% by weight and in particular from 3 to 8% by weight.

The copolymer B contains at least one monomer bi) from the group of mono- or polyunsaturated sulfonic acids and at least one monomer bii) from the group of mono- or polyunsaturated carboxylic acids. The preferred monomers for use in the copolymer B from the group of sulfonic acids are identical to those provided above for use in the copolymers A preferred compounds, which is why at this point to. Avoiding repetition of the statements there is referenced.

The proportion by weight of the copolymer B in the total weight of phosphate-free automatic dishwasher detergents according to the invention is preferably from 2 to 16% by weight, preferably from 4 to 14% by weight and in particular from 6 to 12% by weight.

The molar mass of the sulfo copolymers A and B 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 A and B have molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

Some further exemplary formulations for preferred automatic dishwasher detergents according to the invention can be found in the following Table 3: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 5.0 to 60 10 to 50 10 to 50 15 to 40 carbonate 5.0 to 50 5.0 to 50 10 to 40 15 to 30 sodium 1.0 to 20 2.0 to 15 2.0 to 15 4.0 to 12 Copolymers A ¹⁾ 1.0 to 12 2.0 to 10 2.0 to 10 3.0 to 8.0 Copolymer B ²⁾ 2.0 to 16 4.0 to 14 4.0 to 14 6.0 to 12 Nonionic surfactant C 0.5 to 8 1.0 to 7.0 1.0 to 7.0 2.0 to 6.0 bleach 0 to 8 0 to 8 0 to 8 2.0 to 6.0 bleach catalyst 0 to 5.0 0 to 1.0 0 bits 1.0 0.0025 to 1.0 phosphonate 0 to 8.0 1 to 8.0 0 to 8.0 0 to 8.0 Misc Add 100 Add 100 Add 100 Add 100 ¹⁾ Copolymer A, comprising - monomers ai) from the group of mono- or polyunsaturated sulfonic acids - monomers aii) from the group of mono- or polyunsaturated carboxylic acids - monomers aiii) 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, is -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group which is selected from -CH ₂ -, - C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
²⁾ Copolymer B, comprising - monomers bi) from the group of mono- or polyunsaturated sulfonic acids - monomers bii) from the group of mono- or polyunsaturated carboxylic acids

The agents according to the invention also contain surfactants. The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants. Preferably The automatic dishwashing detergents contain nonionic surfactants in amounts of between 0.5 and 8% by weight.

Phosphate-free automatic dishwashing detergent, characterized in that the weight fraction of the nonionic surfactant C in the total weight of the automatic dishwashing agent is 0.5 to 8 wt .-%, preferably 1 to 7 wt .-% and in particular 2 to 6 wt .-%, according to the invention prefers.

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

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

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

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture 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 which consist of C _8-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

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 fuming 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 AOA groups are bonded to each other before a block of the other groups follows. Here are nichionic surfactants of the general formula

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

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

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

In summary, 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.

Particular preference is given to using nonionic surfactants from the group of hydroxy mixed ethers, since these nonionic surfactants, compared to nonionic surfactants from other classes of surfactants, produce significantly better rinsing properties of the automatic dishwashing detergents.

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 is} independently a straight-chain or branched, saturated or on or polyunsaturated C _2-40 alkyl or alkenyl, A, A ', A "and A"' is independently 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.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw, mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe
• CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃) stehen,
• w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Particularly preferred phosphate-free automatic dishwashing agents are therefore characterized in that they contain a nonionic surfactant C of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - ( A '"O) _z -R ² contained in the

• R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A, A ', A "and A'" independently represent a group 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 ),
• w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.

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 4 to 22 carbon atoms, further having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon group R ² having 1 to 30 carbon atoms, wherein x is a value between 1 and 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.

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.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ However, -CH (CH _{3) 2,} preferably is -CH _3, and x and y are independently values between 1 and 32, wherein nonionic surfactants with R ³ = -CH _3, and values for x and y from 15 to 32 of 0.5 and 1.5 are very particularly preferred

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 ] ₁ 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 becomes R ¹ O (CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ^2. In the latter formula, R ^1, R ² and R ^{3 are} as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. particularly preferred are surfactants wherein where the radicals R ¹ and R ^{2 have} g 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) 2 bis 10 Gew.-% hydrophob modifiziertes Copolymer A, umfassend
   • Monomere ai) aus der Gruppe der ein- oder mehrfach ungesättigten Sulfonsäuren
   • Monomere aii) aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren
   • Monomere wiii) 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) 4 bis 14 Gew.-% nicht hydrophob modifiziertes Copolymer B, umfassend
   • Monomere bi) aus der Gruppe der ein- oder mehrfach ungesättigten Sulfonsäuren
   • Monomere bii) aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren
3. c) 1 bis 7 Gew.-% nichtionisches Tensid der allgemeinen Formel
   
           R¹-CH(OH)CH₂O-(AO)_w-(A'O)_x(A"O)_y-(A"'O)_z-R²,
   
   in der
   • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw mehrfach ungesättigten C_6-21-Alkyl- oder -Alkenylrest steht;
   • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
   • A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe
   • CH₂CH₂, -CH₂CH₂-CH₂, "CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃) stehen,
   • w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.
4. d) 10 bis 50 Gew.-% Citrat und Citronensäure
5. e) 2 bis 15 Gew.-% Natriumpercarbonat

In a particularly preferred embodiment, the phosphate-free automatic dishwasher detergents according to the invention comprise

1. a) 2 to 10 wt .-% hydrophobically modified copolymer A, comprising
   • Monomers ai) from the group of mono- or polyunsaturated sulfonic acids
   • Monomers aii) from the group of mono- or polyunsaturated carboxylic acids
   • Monomers wiii) 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 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) 4 to 14% by weight of non-hydrophobically modified copolymer B comprising
   • Monomers bi) from the group of mono- or polyunsaturated sulfonic acids
   • Monomers bii) from the group of mono- or polyunsaturated carboxylic acids
3. c) 1 to 7 wt .-% of nonionic surfactant of the general formula
   
   R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x (A "O) _y - (A"'O) _z -R ² ,
   
   in the
   • R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-21 alkyl or alkenyl radical;
   • R ² represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
   • A, A ', A "and A'" independently represent a group 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 ),
   • w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
4. d) 10 to 50 wt .-% citrate and citric acid
5. e) 2 to 15% by weight of sodium percarbonate

Some further exemplary formulations for preferred automatic dishwasher detergents according to the invention can be found in the following Table 4: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 5.0 to 60 10 to 50 10 to 50 15 to 40 carbonate 5.0 to 50 5.0 to 50 10 to 40 15 to 30 sodium 1.0 to 20 2.0 to 15 2.0 to 15 4.0 to 12 Copolymer A ¹⁾ 1.0 to 12 2.0 to 10 2.0 to 10 3.0 to 8.0 Copolymers B ²⁾ 2.0 to 16 4.0 to 14 4.0 to 14 6.0 to 12 Nonionic surfactant C ³⁾ 0.5 to B 1.0 to 7.0 1.0 to 7.0 2.0 to 6.0 bleach 0 to 8 0 to 8 0 to 8 2.0 to 6.0 bleach catalyst 0 to 5.0 0 to 1.0 0 to 1.0 0.0025 to 1.0 phosphonate 0 to 8.0 1 to 8.0 0 to 8.0 0 to 8.0 Misc Add 100 Add 100 Add 100 Add 100 ¹⁾ Copolymer A, comprising - monomers ai) from the group of mono- or polyunsaturated sulfonic acids - monomers aii) from the group of mono- or polyunsaturated carboxylic acids - monomers aiii) 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, is -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group which is selected from -CH ₂ -, - C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
²⁾ Copolymer B, comprising - monomers bi) from the group of mono- or polyunsaturated sulfonic acids - monomers bii) from the group of mono- or polyunsaturated carboxylic acids
³⁾ nonionic surfactant 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 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; - 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 ), - w, x, y and z for values between 0.5 and 120, where x, y and / or z can also be 0

An optional constituent of compositions according to the invention, apart from the dyes and fragrances, are the enzymes which are used to increase the washing or cleaning performance of detergents or cleaners. 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. Washing or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-8 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 are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309. the alkaline protease from Bacillus lentus . Subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are assigned to the subtilases, but no longer to the subtilisins in the narrower sense.

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 and improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the α-amylase from Bacillus sp . A7-7 (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, those originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further wound lipases, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium so / ani pisi and Humicola insolens . Can be used furthermore lipase, 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, kyloglucanases (= xylanases), pullulanases and β-glucanases.

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

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 such front 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 agents 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 12% by weight, preferably from 0.2 to 8% by weight and in particular of 0.5 to 8 wt .-%, each based on the total enzyme-containing agent used.

1. a) hydrophob modifiziertes Copolymer A, umfassend - Monomere ai) aus der Gruppe der ein- oder mehrfach ungesättigten Sulfonsäuren
   • Monomere aii) aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren
   • Monomere aiii) 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) nicht hydrophob modifiziertes Copolymer B, umfassend
   • Monomere bi) aus der Gruppe der ein- oder mehrfach ungesättigten Sulfonsäuren
   • Monomere bii) aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren
3. c) nichtionisches Tensid der allgemeinen Formel
   
           R¹-CH(OH)CH₂O-(AO)_w-(A'O)_x-(A"O)_y-(A"'O)_z-R²,
   
   in der
   • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
   • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
   • A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe
   • CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃) stehen,
   • w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können,
4. d) Citrat und/oder Citronensäure
5. e) Natriumpercarbonat
6. f) Bleichkatalysator und/oder Bleichaktivator
7. g) Phosphonat
8. h) Enzym

In a further particularly preferred embodiment, the phosphate-free automatic dishwasher detergents according to the invention comprise

1. a) hydrophobically modified copolymer A, comprising - monomers ai) from the group of mono- or polyunsaturated sulfonic acids
   • Monomers aii) from the group of mono- or polyunsaturated carboxylic acids
   • Monomers aiii) 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 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) non-hydrophobically modified copolymer B comprising
   • Monomers bi) from the group of mono- or polyunsaturated sulfonic acids
   • Monomers bii) from the group of mono- or polyunsaturated carboxylic acids
3. c) nonionic surfactant of the general formula
   
   R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² ,
   
   in the
   • R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
   • R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
   • A, A ', A "and A'" independently represent a group 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 ),
   • w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0,
4. d) citrate and / or citric acid
5. e) sodium percarbonate
6. f) bleach catalyst and / or bleach activator
7. g) phosphonate
8. h) enzyme

Some further exemplary formulations for preferred automatic dishwasher detergents according to the invention can be found in the following Table 5: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 5.0 to 60 10 to 50 10 to 50 15 to 40 carbonate 5.0 to 50 5.0 to 50 10 to 40 15 to 30 sodium 1.0 to 20 2.0 to 15 2.0 to 15 4.0 to 12 Copolymer A 1.0 to 12 2.0 to 10 2.0 to 10 3.0 to 8.0 Copolymer B 2.0 to 16 4.0 to 14 4.0 to 14 6.0 to 12 Nonionic surfactant C 0.5 to 8 1.0 to 7.0 1.0 to 7.0 2.0 to 6.0 bleach 0 to 8 0 to 8 0 to 8 2.0 to 6.0 bleach catalyst 0 to 5.0 0 to 1.0 0 to 1.0 0.0025 to 1.0 phosphonate 0 to 8.0 1 to 8.0 0 to 8.0 0 to 8.0 Enzyme preparation (s) 0.1 to 12 0.1 to 12 0.5 to 8.0 0.5 to 8.0 Misc Add 100 Add 100 Add 100 Add 100

A method for cleaning dishes in a dishwasher using a dishwasher detergent according to the invention is a further subject of the present application, wherein the automatic dishwashing detergent preferably metered into the interior of a dishwasher during the passage of a dishwasher, before the main wash cycle or in the course of the main wash cycle become. The metering or, the entry of the agent according to the invention in the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber of the dishwasher into the interior of the dishwasher.

Preferred methods according to the invention are characterized in that no additional water softener and no additional rinse aid are metered into the interior of the dishwasher in the course of the cleaning process.

The dishwasher detergents according to the invention exhibit their advantageous rinsing properties, in particular also in low-temperature cleaning processes. Preferred dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C.

The amount of machine dishwashing agent according to the invention used in preferred embodiments of the process according to the invention per cleaning cycle is from 12 to 26 g, preferably from 14 to 24 g and in particular from 16 to 22 g.

As mentioned above, the dishwasher detergents according to the invention are distinguished by outstanding rinsing properties. This applies in particular with regard to avoiding the formation of deposits on glass or plastic surfaces in automatic dishwashing.
A final subject of the present application is therefore the use of a machine dishwashing agent according to the invention for reducing the formation of deposits on glass surfaces or plastic surfaces in automatic dishwashing.

Claims (13)

1. A phosphate-free automatic dishwasher detergent, containing a builder, bleaching agent, and in addition

   a) hydrophobically modified copolymer A, comprising monomers ai) from the group of mono-or polyunsaturated sulfonic acids, monomers aii) from the group of mono- or polyunsaturated carboxylic acids and monomers aiii) of the general formula R¹(R²)C=C(R³)-X-R⁴, in which R¹ to R³ represent, independently of one another, -H, -CH₃ or -C₂H₅, X represents an optionally present spacer group which is selected from -CH₂-,-C(O)O- and -C(O)-NH-, and R⁴ represents a straight-chain or branched saturated alkyl functional group having 2 to 22 carbon atoms or an unsaturated, preferably aromatic functional group having 6 to 22 carbon atoms,

   b) non-hydrophobically modified copolymer B, comprising monomers bi) from the group of mono- or polyunsaturated sulfonic acids and monomers bii) from the group of mono- or polyunsaturated carboxylic acids,

   c) non-ionic surfactant C,

   d) 5 to 60 wt.% citrate and citric acid.
2. The phosphate-free automatic dishwasher detergent according to claim 1, characterized in that the percentage by weight of copolymer A is 1 to 12 wt.%, preferably 2 to 10 wt.% and in particular 3 to 8 wt.%.
3. The phosphate-free automatic dishwasher detergent according to one of the preceding claims, characterized in that the percentage by weight of copolymer B is 2 to 16 wt.%, preferably 4 to 14 wt.% and in particular 6 to 12 wt.%.
4. The phosphate-free automatic dishwasher detergent according to one of the preceding claims, characterized in that it contains a non-ionic surfactant C of the general formula
   
           R¹-CH(OH)CH₂O-(AO)_w-(A'O)_x-(A"O)_y-(A"'O)_z-R²,
   
   in which

   - R¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C_6-24 alkyl functional group or alkenyl functional group;

   - R² represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms;

   - A, A', A" and A'" represent, independently of one another, a functional group from the group -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃),

   - w, x, y and z represent values between 0.5 and 120, it being also possible for x, y and/or z to be 0.
5. The phosphate-free automatic dishwasher detergent according to one of the preceding claims, characterized in that the percentage by weight of non-ionic surfactant C is 0.5 to 8 wt.%, preferably 1 to 7 wt.% and in particular 2 to 6 wt.%.
6. The phosphate-free automatic dishwasher detergent according to one of the preceding claims, characterized in that it preferably contains 10 to 50 wt.%, and in particular 15 to 40 wt.%, citrate and citric acid.
7. The phosphate-free automatic dishwasher detergent according to one of the preceding claims, characterized in that it preferably contains 1 to 20 wt.%, preferably 2 to 15 wt.% and in particular 4 to 12 wt.%, sodium percarbonate.
8. The phosphate-free automatic dishwasher detergent according to one of the preceding claims, comprising

   a) 2 to 10 wt.% hydrophobically modified copolymer A, comprising

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

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

   - monomers aiii) of the general formula R¹(R²)C=C(R³)-X-R⁴, in which R¹ to R³ represent, independently of one another, -H, -CH₃ or -C₂H₅, X represents an optionally present spacer group selected from -CH₂-, -C(O)O and -C(O)-NH-, and R⁴ represents a straight-chain or branched saturated alkyl functional group having 2 to 22 carbon atoms or an unsaturated, preferably aromatic functional group having 6 to 22 carbon atoms

   b) 4 to 14 wt.% non-hydrophobically modified copolymer B, comprising

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

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

   c) 1 to 7 wt.% non-ionic surfactant of the general formula
   
           R¹-CH(OH)CH₂O-(AO)_w-(A'O)_x-(A"O)_y-(A'"O)_z-R²,
   
   in which

   - R¹ represents a straight-chain or branched saturated or mono- or polyunsaturated C_6-24 alkyl functional group or alkenyl functional group;

   - R² represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms;

   - A, A', A" and A'" represent, independently of one another, a functional group from the group -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-,-CH₂-CH(CH₂-CH₃);

   - w, x, y and z represent values between 0.5 and 120, it being also possible for x, y and/or z to be 0.

   d) 10 to 50 wt.% citrate and citric acid

   e) 2 to 15 wt.% sodium percarbonate.
9. The phosphate-free automatic dishwasher detergent according to one of the preceding claims, comprising

   a) hydrophobically modified copolymer A, comprising

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

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

   - monomers aiii) of the general formula R¹(R²)C=C(R³)-X-R⁴, in which R¹ to R³ represent, independently of one another, -H, -CH₃ or -C₂H₅, X represents an optionally present spacer group selected from -CH₂-, -C(O)O- and -C(O)-NH-, and R⁴ represents a straight-chain or branched saturated alkyl functional group having 2 to 22 carbon atoms or an unsaturated, preferably aromatic functional group having 6 to 22 carbon atoms

   b) non-hydrophobically modified copolymer B, comprising

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

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

   c) non-ionic surfactant of the general formula
   
           R¹-CH(OH)CH₂O-(AO)_w-(A'O)_x-(A"O)_y-(A"'O)_z-R²,
   
   in which

   - R¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C_6-24 alkyl functional group or alkenyl functional group;

   - R² represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms;

   - A, A', A" and A'" represent, independently of one another, a functional group from the group -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-,-CH₂-CH(CH₂-CH₃);

   - w, x, y and z represent values between 0.5 and 120, it being also possible for x, y and/or z to be 0.

   d) citrate and/or citric acid

   e) sodium percarbonate

   f) bleach catalyst and/or bleach activator

   g) phosphonate

   h) enzyme
10. A method for cleaning dishes in a dishwasher using an automatic dishwasher detergent according to one of the claims 1 to 9.
11. The method according to claim 10, characterized in that, in the course of the cleaning process, no additional water softener and no additional rinse aid is metered into the interior of the dishwasher.
12. The use of an automatic dishwasher detergent according to one of claims 1 to 8 for reducing the formation of scale on glass surfaces during automatic dishwashing.
13. The use of an automatic dishwasher detergent according to one of claims 1 to 8 for reducing the formation of scale on plastics surfaces during automatic dishwashing.