WO2009037013A2

WO2009037013A2 - Detergents

Info

Publication number: WO2009037013A2
Application number: PCT/EP2008/058550
Authority: WO
Inventors: Nadine Warkotsch; Johannes Zipfel; Arnd Kessler; Christian Nitsch; Thomas Holderbaum
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2007-09-17
Filing date: 2008-07-03
Publication date: 2009-03-26
Also published as: ES2523920T3; WO2009037013A3; EP2188361A2; PL2188361T3; EP2188361B1; DE102007044418A1

Abstract

The invention relates to phosphate-free dishwasher detergents containing a) carboxymethyl inulin b) oxygen bleaching agents. Said invention is characterised by virtue of the fact that said dishwasher detergent contains less than 5 % in weight of phosphonate and the weight ratio of carboxymethyl inulin a) to phosphonate is greater than 2. The detergents according to the invention have good cleaning and rinsing results.

Description

cleaning supplies

The present patent application describes detergents, in particular detergents for the machine cleaning of dishes. This application relates in particular to phosphate-free automatic dishwashing detergents which contain phosphate substitutes.

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 softening and alkalizing action as a component of automatic dishwashing detergents, their use is considered environmentally problematic since a substantial portion of the phosphate enters the water via the domestic effluent, and particularly 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 alternatives 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 automatic dishwashing detergents which, in addition to a citrate, furthermore contain carbonates, bleaches and enzymes are described, for example, in European patents EP 662 117 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).

The group of complexing agents for water softening, which are used with preference in automatic dishwashing detergents, also include the organic phosphonates, as described, for example, in German patent application DE 10 2004 015 41 (Henkel KGaA).

The addition of carboxymethylinulines in combination with specific phosphonates as builders to bleach-free textile detergents is described in the European patent application EP 1 408 103 A1 (N .V. Solutia).

Despite the efforts so far, the manufacturers of automatic dishwashing agents have hitherto failed to provide phosphate-free or phosphate-reduced automatic dishwashing detergents which are comparable or even exceed the usual phosphate-containing detergents 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 substitutes in detergents, since the vast majority of end consumers will always decide against an ecologically advantageous product despite wide public discussion of environmental issues, if this is not the market standard in terms of its price and / or performance equivalent.

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

It has surprisingly been found that automatic dishwashing detergents which contain a combination of carboxymethyl inulin and oxygen bleach are suitable for achieving the abovementioned object if the amount of phosphonate used is limited in these automatic dishwashing detergents.

A first subject of this application is therefore a phosphate-free automatic dishwashing detergent containing a) Carboxymethylinulin b) oxygen bleach characterized in that the automatic dishwashing agent based on its total weight less than 5 wt .-% phosphonate and the weight ratio of carboxymethyl inulin to phosphonate is greater than 2.

The automatic dishwashing compositions according to the invention contain carboxymethyl inulin as their first essential component.

Inulin is a polysaccharide of fructose molecules stored in plants such as Jerusalem artichoke, chicory, dahlia, artichoke, dandelion or agave as a reserve substance. The chain length of these polysaccharides is up to 100 molecules. The linear fructose chains of inulins, which are usually linked by ß (2-1) bonds, are usually closed by a glucose unit. The fructose units within the chain carry 3 hydroxyl groups, which can be carboxyalkylated with ether formation. In the process products, the hydrogen of the hydroxyl group is replaced by a carboxyalkyl group, in the case of the carboxymethylinulines used according to the invention by a carboxymethyl group.

Preferred carboxymethylinulines are characterized in that 0.5 to 3 hydroxyl groups, preferably 1, 0 to 3 hydroxyl groups and in particular 2.0 to 3.0 hydroxyl groups are carboxymethylated per fructose molecule on average.

Preferred carboxymethylinulines have a molecular weight in the range from 1000 to 10,000, preferably from 1200 to 7000, preferably from 1400 to 4000 and in particular from 1500 to 3000.

The weight fraction of carboxymethylinulin in the total weight of preferred automatic dishwashing agent is, based on the total weight of the automatic dishwashing detergent, 2.0 to 40 wt.%, Preferably 2.0 to 20 wt.% And in particular 4.0 to 10 wt. ,

In addition to the carboxymethylinulines, the automatic dishwasher detergents according to the invention preferably additionally contain builders for reducing the water hardness. The builders include in particular silicates, carbonates and organic co-builders such as citrates.

With preferred machine dishwashing detergents according to the invention contain as builder crystalline layered silicates of general formula NaMSi _x O _{2x + I} ^■ y H ₂ O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9-4 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.

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

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

Particularly preferred machine dishwasher detergents according to the invention are characterized in that the dishwasher detergent, based in each case on the total weight of the dishwashing detergent, 5 to 60 wt .-%, preferably 10 to 60 wt .-% and in particular 25 to 60 wt .-% of builders from the group containing silicates, carbonates and citrates.

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, this group may in turn, the short-chain polyacrylates, the molar masses of 2000 to 10,000 g / mol, and more preferably from 3000 to 5000 g / mol, have to be preferred.

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

The content of preferred automatic dishwashing agents on (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight, in each case based on the total weight of the automatic dishwashing detergent.

Some exemplary formulations for such preferred phosphate-free automatic dishwashing detergent according to the invention can be found in the following table:

"-" means in this, as in all the following tables: the recipe is free of this ingredient

As a further essential constituent in addition to the carboxymethyl inulin, dishwasher detergents according to the invention contain an oxygen bleaching agent. Among the compounds which serve as bleaching agents 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 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also 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 dishwasher detergents are characterized in that the dishwashing agent, based in each case on the total weight of the dishwashing agent, 1, 0 to 20 wt .-%, preferably 4.0 to 18 wt .-% and in particular 8 to 15 wt .-% of a Oxygen bleaching agent, preferably 1, 0 to 20 wt .-%, preferably 4.0 to 18 wt .-% and in particular 8 to 15 wt .-% 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, 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.

With particular preference complexes of manganese in the oxidation state II, III, IV or IV are used, which preferably contain one or more macrocyclic ligand (s) 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). Examples of suitable manganese complexes are [Mn ^m ₂ (μ-O) ₁ (μ-OAc) 2 (TACN) 2] (CIO ₄ ) 2, [Mn '"Mn' ^v (μ-O) ₂ (μ-OAc) ₁ (TACN) ₂ ] (BPh ₄ ) Z, [Mn ' ^V 4 (μ-O) ₆ (TACN) 4] (CIO ₄ ) 4, [Mn "' ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (CIO ₄ ) ₂ , [Mn ^m Mn ^lv (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (CIO ₄ ) 3, [Mn ^lv ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ' ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

Automatic 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-triazacyclononan (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 exemplary formulations for preferred phosphate-free automatic dishwashing compositions can be found in the following table:

The automatic dishwashing agents according to the invention are further characterized in that they contain less than 5% by weight of phosphonate, the weight ratio of carboxymethyl inulin to phosphonate being greater than 2. Surprisingly, it was possible to improve the cleaning and rinsing action as well as the scale inhibition of the agents according to the invention by limiting the amounts of phosphonate added to amounts below 5% by weight, provided that the weight ratio of carboxymethylinulin to phosphonate in these automatic dishwashing detergents is set to values above 2. The complexing phosphonates comprise a number of different compounds such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) or diethylene triamine penta (ethylene phosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates, the 1-hydroxyethane-1,1-di-phosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (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.

In a preferred embodiment of the present invention, the weight fraction of the phosphonate (s) b) in the total weight of the automatic dishwashing agent is less than 3 wt .-%, preferably less than 2 wt .-%, preferably less than 1 wt .-% and in particular less than 0.1% by weight. Particularly preferred machine dishwasher detergents according to the invention contain no phosphonate.

Preference is furthermore given to those agents in which the weight ratio of carboxymethyl inulin to phosphonate is greater than 5, preferably greater than 10 and in particular greater than 50.

Preferred phosphate-free automatic dishwasher detergents according to the invention contain as further

Component of a copolymer, comprising i) monomers containing sulfonic acid groups, ii) further ionic and / or nonionic monomer (s).

The proportion by weight of the copolymer in the total weight of the automatic dishwashing agent is preferably 0.5 to 20 wt .-%, preferably 4 to 18 wt .-%, particularly preferably 6 to 15 wt .-% and in particular 6 to 12 wt .-%.

These copolymers, which comprise at least one other ionic or nonionic monomer in addition to a sulfonic acid group-containing monomer, 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 - (CHz) _n - with n = 0 to 4, -C00- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

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

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CHz) _n - with n = O to 4, -C00- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-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 monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 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 detergents 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.

Phosphate-free automatic dishwashing compositions containing a) carboxymethylinulin b) oxygen bleaches c) copolymer comprising i) monomers containing sulfonic acid groups)) further ionic monomers. characterized in that the automatic dishwashing agent contains less than 5 wt .-% of phosphonate based on its total weight and the weight ratio of carboxymethyl inulin to phosphonate is greater than 2, 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 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, 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.

Accordingly, phosphate-free automatic dishwashing agents containing a) carboxymethylinulin b) oxygen bleaches c) copolymer comprising i) sulfonic acid group-containing monomers ii) carboxyl-containing monomers of the formula R ¹ (R ² ) C = C (R ³ ) COOH, in 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, characterized in that the automatic dishwashing agent based on its total weight less than 5 wt .-% phosphonate and the weight ratio of carboxymethylinulin to phosphonate is greater than 2.

Particularly preferred carboxyl-containing monomers 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.

Copolymer comprising i) sulfonic acid group-containing monomers 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, or -NH ₂ , -OH or -COOH-substituted alkyl or alkenyl radicals as defined above or for -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms

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. 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.

A further preferred subject of this application is therefore phosphate-free automatic dishwashing compositions containing a) carboxymethylinulin b) oxygen bleaches c) copolymer comprising i) monomers containing sulfonic acid groups)) 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, characterized in that the automatic dishwashing agent based on its total weight contains less than 5% by weight of phosphonate and the weight ratio of carboxymethyl inulin to phosphonate is greater than 2.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1 , 4,4-Dimehtylhexan-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, meth methyl acrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Λ / (2-ethylhexyl) acrylamide, Octyl acrylate, octyl acrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, Λ / (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, Λ / - (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and Λ / - (behenyl) acrylamide or their mixtures. Some exemplary formulations for preferred phosphate-free automatic dishwashing compositions can be found in the following table:

Copolymer comprising i) sulfonic acid group-containing monomers ii) monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another represent -H, -CH ₃ or C ₂ H ₅ , X 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 with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms

Particular preference is given to copolymers which, in addition to the monomers containing sulfonic acid groups, furthermore contain both ionic and nonionic monomers. Phosphate-free automatic dishwashing detergents, characterized in that the copolymer c) i) monomers containing sulfonic acid groups ii) monomers containing carboxyl groups iii) further nonionic monomers are preferred according to the invention.

Some exemplary formulations for preferred phosphate-free automatic dishwashing detergents can be the

Copolymer comprising i) monomers containing sulfonic acid groups ii) carboxyl-containing monomers iii) other nonionic monomers

By using the above-described sulfonic acid-containing copolymers, the formation of deposits and the rinse-off result can be markedly improved in comparison to conventional polymeric or copolymeric acrylates without a sulfonic acid group.

The compositions according to the invention may furthermore contain surfactants. The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.

With particular preference, the automatic dishwashing detergents contain nonionic surfactant (s), the weight fraction of the nonionic surfactant (s) in the total weight of the automatic dishwashing agent preferably being from 1 to 10% by weight, preferably from 2 to 8% by weight. and in particular 3 to 6 wt .-% is.

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 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 an arbitrary 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 used 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 an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C _t2 - _U - alcohols with 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, C-ms alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -i ₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -i ₄ -alcohol with 3 EO and C ₁₂ -i ₈ -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 rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

With particular preference, therefore, ethoxylated nonionic surfactant selected from C ₆ - alkanols ₂ o-monohydroxy or C ₆ - ₂ o-alkyl phenols or C ₆ - ₂ o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol were used. A particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _{_16-2} alcohol), preferably a C ₁₈ alcohol obtained and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide. Of these, the so-called "narrow ranks ethoxylates" are particularly preferred.

With particular preference further combinations of one or more Taigfettalkoholen be used with 20 to 30 EO and silicone defoamers. Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) (e) with a melting point above 2O ⁰ C, preferably above 25 ⁰ C, more preferably between 25 and 6O ⁰ C and in particular from 26.6 to 43.3 ⁰ 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 Pas, preferably above 35 Pas and in particular above 40 Pas. 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.

Further 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 A 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 contains.

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 nichionic surfactants of the general formula

Ri-O- (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) - (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) -H

R2 R3

preferably, R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl; 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 usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2. Nonionic surfactants are particularly preferred In summary, the ₉ have a C .i ₅ alkyl radical 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 are each independently a straight-chain or branched, saturated or mono- or polyunsaturated C _{_2-4} o 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 (CHs) -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.

Copolymer comprising i) sulfonic acid group-containing monomers 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, or -NH ₂ , -OH or -COOH-substituted alkyl or alkenyl radicals as defined above or for -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms By using the nonionic surfactants described below having a free hydroxyl group on one of the two terminal alkyl radicals, the deposit formation and the rinse aid result can be markedly improved in comparison to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

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.

Particular preference is given to 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 denotes a linear or branched aliphatic hydrocarbon radical 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1, 5 and y for a value of at least 15.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another 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 most preferred.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ P] _x [CH ₂ I _k CH (OH) [CH ₂ ] PR ² in which R ¹ and R ² R ^{1 is} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x> 2, then each R ³ in the above R ¹ and R ² are preferably linear or branched, saturated or unsaturated, R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² . aliphatic or aromatic hydrocarbon radicals having from 6 to 22 carbon atoms, radicals having from 8 to 18 carbon atoms being particularly preferred, and the radical R ³ being H, -CH ₃ or CH ₂ CH _{3 is} 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 P] _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} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

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

Copolymer comprising i) sulfonic acid group-containing monomers 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 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 for -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 end-} capped poly (oxyalkylated) nonionic surfactant having at least one free hydroxyl group on one of the two terminal alkyl radicals

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

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

In addition to the ingredients described above such as builders or bleaches and surfactants preferred automatic dishwashing contain other ingredients, preferably active ingredients from the group of washing and cleaning active 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 particular the cationic or amphoteric polymers.

"Cationic polymers" for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain 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 acrylate and methacrylate, the vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, the quaternized polyvinyl alcohols or under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 given polymers.

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, Ci- ₃₀ linear or branched alkyl groups, aryl, aryl-substituted Ci _-30 linear or branched alkyl groups, poly alkoyxylierte 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 amino group with a positive charge. In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

H ₂ C = X ^"

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 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably 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.

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

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

X ^"

in the case of X ^' = chloride also referred to as DADMAC (diallyldimethylammonium chloride).

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

R1 HC = CR2-C (O) -NH- (CH ₂₎ -N ⁺ R3R4R5

X ^" in the R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} independently of one another 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 is} H and x is an integer between 1 and 6.

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

H ₂ C = C (CHS) -C (O) -NH- (CH ₂ ) X-N ⁺ (C HS) ₃

X ^" in the case of X ^" = chloride also referred to as MAPTAC (Methyaciylamidopropyl trimethylammonium 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 their derivatives, the allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred amphoteric polymers which can be used 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 which cationically derivatized alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferred zwitterionic polymers are from the group of acrylamidoalkyltri alkylammonium 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 of methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the Methacrylamidoalkyltrialkylammoniumchlorid / DimethyKdiallyOammoniumchlorid / 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 / dimethyldiallylammonium - Chloride / alkyl (meth) acrylic acid Copolynnere and their alkali metal and ammonium salts.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers, 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 ⁰ 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 β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae, as well as improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from β. 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 Fusahum solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

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

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

The enzymes can be used in any form known in the art. These include, for example, those obtained by granulation, extrusion or lyophilization solid preparations or, in particular in the case of liquid or gel-form compositions, solutions of the enzymes, advantageously as concentrated as possible, sparingly mixed with water and / or 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.

Preferred are one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in amounts of 0.1 to 6 wt .-%, preferably from 0.2 to 5 wt .-% and in particular of 0.4 to 5 wt .-%, each based on the total enzyme-containing agent used.

A preferred machine dishwashing detergent contains, for example, a) 4 to 35% by weight of carboxymethyl inulin b) 2 to 15% by weight of sodium percarbonate c) 2 to 8% by weight of nonionic surfactant (s) d) 0.5 to 25 % By weight of copolymer (s) comprising i) acid group-containing monomer (s) ii) further ionic and / or nonionic monomer (s) e) 1, 0 to 6 wt .-% enzyme, and is free of phosphonate.

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

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 preferred zinc salts according to the invention, preferably organic acids, particularly preferably organic carboxylic acids, ranges from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular especially below 0.01 mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all Solubilities at 2O ⁰ C water temperature). The first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the 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, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and Zinkeitrat used. 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 triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particular preference is given to using 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 present 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.

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 compositions 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, so as not to 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 detergents, characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are 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.

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.

Preference is given to using disintegration aids 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 aid-containing agent.

Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants 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. % contain. 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 cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, are present in the desintegration 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 desintegration 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 alkali metal carbonate and / or bicarbonate and an acidifier 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.

The present application further relates to a method for cleaning dishes in a dishwasher using phosphate-free automatic dishwashing detergent 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 entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher. A kit for a dishwasher comprising a) a phosphate-free automatic dishwashing detergent according to the invention; (b) instructions instructing the consumer to use the automatic dishwashing detergent without the addition of a rinse aid and / or a softening salt are another subject of this application.

As described at the outset, compositions according to the invention are distinguished from conventional automatic dishwashing agents by an improved rinsing action. An object of the present application is therefore further the use of a phosphate-free automatic dishwasher according to the invention as a rinse aid in automatic dishwashing. Examples

In a dishwasher automatic dishwashing dishes were rinsed in a dishwasher (Miele G 698) at a water hardness of 21 ° dH and a temperature of 5O ⁰ C with 21 g of the machine dishwashing detergent listed in the table below.

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):

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

Claims

claims

1. A phosphate-free automatic dishwashing detergent containing a) carboxymethylinulin b) oxygen bleaching agent, characterized in that the automatic dishwashing agent contains less than 5% by weight of phosphonate based on its total weight and the weight ratio of carboxymethylinulin to phosphonate is greater than 2.

2. Machine dishwashing detergent according to claim 1, characterized in that the dishwashing agent, based on its total weight, 2.0 to 40 wt .-%, preferably 2.0 to 20 wt .-% and in particular 4.0 to 10 wt. Contains% carboxymethylinulin.

3. Machine dishwashing detergent according to one of the preceding claims, characterized in that the dishwashing detergent, based on its total weight, 5 to 60 wt .-%, preferably 10 to 60 wt .-% and in particular 25 to 60 wt .-% builders from the Group of silicates, carbonates and citrates contains.

4. Machine dishwashing detergent according to one of the preceding claims, characterized in that the dishwashing detergent, based on its total weight, less than 3 wt .-%, preferably less than 1 wt .-%, preferably less than 0.1 wt .-% and in particular does not contain phosphonate.

5. Machine dishwashing detergent according to one of the preceding claims, characterized in that the dishwashing detergent, based on its total weight, 1, 0 to 20 wt .-%, preferably 4.0 to 18 wt .-% and in particular 8 to 15 wt. % of an oxygen bleaching agent, preferably 1, 0 to 20 wt .-%, preferably 4.0 to 18 wt .-% and in particular 8 to 15 wt .-% sodium percarbonate.

6. Machine dishwashing detergent according to one of the preceding claims, characterized in that it 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).

7. Machine dishwashing detergent according to one of the preceding claims, characterized in that the dishwashing detergent, based on its total weight, nonionic surfactant in amounts of 1 to 10 wt .-%, preferably 2 to 8 wt .-% and in particular 3 to 6 wt. - contains%.

8. Machine dishwashing detergent according to one of the preceding claims, characterized in that the automatic dishwashing agent, based on its total weight, 0.5 to 20 wt .-%, preferably 4 to 18 wt .-%, particularly preferably 6 to 15 wt. % and in particular 6 to 12% by weight of copolymer (s) comprising i) acid group-containing monomer (s) ii) further ionic (s) and / or nonionic monomer (s) ,

9. Machine dishwashing detergent according to one of the preceding claims, containing a) 4 to 35 wt .-% carboxymethyl inulin b) 2 to 15 wt .-% sodium percarbonate c) 2 to 8 wt .-% nonionic (s) surfactant (s) d) 0.5 to 25% by weight of copolymer (s), comprising i) acid group-containing monomer (s) ii) further ionic and / or nonionic monomer (s) e) 1, 0 to 6 wt .-% enzyme, characterized in that the dishwasher contains no phosphonate.

10. A method for cleaning dishes in a dishwasher, using automatic dishwashing detergent according to one of 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 dosed into the interior of the dishwasher.

A kit for a dishwashing machine, comprising a) a machine dishwashing detergent according to any one of claims 1 to 9; (b) instructions instructing the consumer to use the automatic dishwashing detergent without the addition of a rinse aid and / or a softener salt.