Detergents

European).

- 1 OK II-12 / P35280PL00

EP 2 188 361 Bl

Cleaning agents

This patent application describes cleaning agents, and especially cleaning agents for machine cleaning of dishes. The subject of this application are in particular phosphate-free machine dishwashing agents that contain phosphate substitutes.

Today, machine-washed dishes are often more demanding than hand-washed ones. So, after machine cleaning, the dishes should not only be free of food residues after machine cleaning, but also not show, for example, any whitish stains due to the hardness of water or other mineral salts, which due to the lack of wetting agents come from dried water droplets.

Modern agents for machine dishwashing meet these requirements by combining cleaning, care, water softening and rinsing active substances together, and they are known to the user, e.g. as "two in one" or "three in one". As an important ingredient for the cleaning result, such as the rinse result, the machine washing agents intended for the private end user contain skeletal substances. These skeletal substances increase, first of all, the alkalinity of the cleaning bath, with the increase of alkalinity they emulsify and saponify fats and oils, and secondly, due to complexation of calcium ions contained in the water bath, they reduce the hardness of the water in the cleaning bath. Lithium phosphates have proven to be particularly effective skeletal substances, which are therefore a major component of the overwhelming number of commercially available machining agents

-2washing dishes.

While phosphates are highly valued as a component of dishwashing agents due to their softening and alkalizing effects, their use is considered problematic from the point of view of ecology, because a significant part of phosphate enters through surface sewage into surface waters, especially to surface waters stagnant waters (lakes, damming water barriers), and plays a critical role in their transportation. As a result of this phenomenon, also known as eutrophication, the use of pentasodium triphosphate in textile washing agents in some countries, e.g. in the USA, Canada, Italy, Sweden, Norway, was reduced considerably by legislation. In Germany, detergents may contain at most 20% of this skeletal substance since 1984.

In addition to nitrilotriacetic acid, sodium phosphate silicates (zeolites) are used in the laundry detergents as phosphate substitutes or replacements. However, these substances are not suitable for various reasons in machine dishwashing agents. Hence, as alternatives to alkali metal phosphates in machine dishwashing agents, a number of substitutes are discussed in the literature, of which citrates in particular should be highlighted.

Phosphate-free machine dishwashing agents which, in addition to citrate, further contain carbonates, bleaches and enzymes, are discussed, for example, in EP 662 117 BI (Henkel KGaA) and EP 692 020 BI (Henkel KGaA).

The group of complexing agents for water softening, which are preferably used in machine dishwashing agents, also includes organic phosphates such as those described e.g. in German Patent Application DE 10 2004 015 41 (Henkel KGaA).

Carboxymethylinulin addition in combination with

- 3 specific phosphonates as skeletal substances for laundry for bleaching textiles are described in European patent application EP 1 408 103 A1 (NV Solutia).

Despite the efforts made so far, producers of machine dishwashing agents have not been able to develop phosphate-free or phosphate-reduced ones, machine dishwashing agents that would be comparable in terms of their cleaning or rinsing performance, and especially their sludge inhibiting performance with ordinary phosphate-containing agents cleaners or would outweigh them altogether. However, such performance equality is a prerequisite for successful commercialization of phosphate substitutes in cleaners, since the overwhelming number of end users, despite extensive public discussion of environmental policy, are still opting for an ecologically beneficial product when its price and / or performance is not conforms to market standard.

Due to this initial situation, the task of the present invention was therefore to develop a phosphate-free or phosphate-reduced machine dishwashing agent that would be comparable with conventional phosphate-containing phosphates in both its cleaning and rinsing performance and in terms of its inhibition of deposits. cleaners or even outperform them.

Unexpectedly, it has been found that machine dishwashing agents that contain a mixture of carboxymethylinulin and an oxygen bleaching agent are suitable for solving the previously discussed task, provided that these machine dishwashing agents do not contain any phosphonate.

The first subject of this application is therefore a phosphate-free machine dishwashing agent containing

a) carboxymethylinulin,

-4b) an oxygen bleaching agent, characterized in that the machine dishwashing agent does not contain any phosphonate.

The inventive machine dishwashing agents contain carboxymethylinulin as their first essential ingredient.

Polysaccharide from fructose molecules, accumulated as storage material in plants such as Jerusalem artichoke, chicory, dahlia, artichoke, dandelion or agave, is defined as inulin. The chain length of these polysaccharides is up to 100 molecules. Linear inulin fructose chains, which are usually linked via β (2-1) bonds, are usually closed by a glucose unit. The chain fructose units contain 3 hydroxyl groups that can be carboxyalkylated to form an ether. In process products, the hydrogen of the hydroxyl group is replaced by a carboxyalkyl group, and in the case of the carboxymethylinulins used according to the invention, by a carboxymethyl group.

Preferred carboxymethylinulins are characterized in that, on average, 0.5-3 hydroxyl groups, preferably 1.0-3 hydroxyl groups, in particular 2.0-3.0 hydroxyl groups are carboxymethylated per fructose molecule.

Preferred carboxymethylinulins have a molar mass in the range of 1000-10000, preferably 1200-7000, even more preferably 1400-4000, especially 1500-3000.

The weight proportion of carboxymethylinulin in the total weight of the preferred machine dishwashing agents is 2.0-40% by weight, preferably 2.0-20% by weight and especially 4.0-10% by weight, based on the total weight of the machine dishwashing agent.

The machine dishwashing agents according to the invention contain, in addition to carboxymethylinulins, to reduce water hardness, preferably in addition skeletal substances. Skeletal substances include, in particular, silicates, carbonates and organic

- 5 builders, such as citrates.

The machine dishwashing compositions according to the invention preferably contain as skeletal material crystalline layered silicates of the general formula NaMSi_xABOUT_{2x + 1} -yH₂O, in which M is sodium or hydrogen, x is 1.9-22, preferably 1.9-4, with particularly preferred x being 2, 3 or 4, and y being 0-33, preferably 0-20 .

Amorphous sodium silicates with a Na module can also be used₂O: SiO2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8, especially from 1: 2 to 1: 2.6, which dissolve preferably with a delay and show secondary washing properties .

In the context of the present invention, preferred dishwashing agents contain 2-15% by weight, preferably 3-12% by weight and especially 4-8% by weight of silicate (s).

It is particularly preferred to use carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate, in an amount of

5-50% by weight, even more preferably 10-40% by weight, especially 15-30% by weight, based on the weight of the machine dishwashing agent in each case.

As organic co-extenders, mention may be made especially of polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic co-extenders. These substance classes are described further.

Useful organic skeletal substances are e.g. polycarboxylic acids used in the form of the free acid and / or its sodium salt, with polycarboxylic acids being understood as those carboxylic acids that contain more than one acid functional group. Examples are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), unless this type of use is questioned. ecological reasons, and mixtures thereof. In addition to their activity as an active filler, the free acids also typically have the property of an acidifying component, so they also serve to adjust the lower and milder pH value of washing or cleaning agents, and should especially mention citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and their any mixtures.

Particularly preferred machine dishwashing agents according to the invention are characterized in that, based on the total weight of the machine dishwashing agent, the dishwashing agent contains 5-60% by weight, preferably 10-60% by weight, in particular 25-60% by weight of the substance skeletal silicates, carbonates and citrates.

Polymeric polycarboxylates are further suitable as skeletal substances, e.g. alkali polyacrylic acid or methacrylic acid salts, e.g. salts with a relative molecular weight of 500-70000 g / mol.

Suitable polymers are especially polyacrylates, which preferably have a molecular weight of 2000-20000 g / mol. Due to their better solubility, short chain polyacrylates which have a molar mass of 2000-10000 g / mol, and particularly preferably 3000-5000 g / mol, may be preferred from this group.

Further suitable are copolymeric polycarboxylates, in particular copolymeric polycarboxylates of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50-90% by weight acrylic acid and 50-10 by weight have proved to be particularly suitable. % by weight maleic acid. Their relative molecular weight is generally 2000-70000 g / mol, preferably 20,000-50000 g / mol and especially 30,000-40,000 g / mol relative to free acids.

The content of (co) polymeric polycarboxylates in preferred machine dishwashing agents is preferably 0.5-20% by weight, in particular 3-10% by weight, based on the total weight of the machine dishwashing agents.

Some examples of recipes of this type of preferred phosphate-free machine dishwashing agents according to the invention can be found in the following table:

<td>Ingredient</td><td>Recipe 1 (Wt-%).</td><td>Recipe 2 (Wt-%).</td><td>Recipe 3 (Wt-%).</td>

<td>Karboksymetyloinulina</td><td> 2-15</td><td> 2-10</td><td> 4-10</td>

<td>Citrate / citric acid</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Carbonate / bicarbonate</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Oxygen bleach</td><td> 4-15</td><td> 6-15</td><td> 6-15</td>

<td>phosphonate</td><td> __*</td><td> --</td><td> --</td>

<td>Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

means in this and in all the following tables that the recipe is free from this ingredient

As a further component, the inventive machine dishwashing agents contain an oxygen bleaching agent in addition to carboxymethylinulin. Of the compounds serving as bleaching agent and providing H2O2 in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are e.g. peroxopyrophosphates, citrate perhydrates, and H2O2-providing peracid or peracid salts, such as perbenzoates, peroxophthalates, dinadazelaic acid, phthalimine peracid or dinaddodecanoic acid.

Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are peroxyacids, with examples being especially alkyl peroxy acids and aryl peroxy acids.

Preferred phosphate-free machine dishwashing agents are characterized in that the dishwashing agent contains, based on the total weight of the dishwashing agent, 1.0-20% by weight, preferably 4.0-18% by weight and especially 8-15% by weight aerobic bleaching agent, and preferably 1.0-20% by weight, even more preferably 4.0-18% by weight, especially

8-15% by weight, sodium percarbonate.

In order to achieve a better bleaching effect when cleaning at 60 ° C and below, the machine dishwashing agents according to the invention may additionally contain bleach activators. As bleach activators, compounds which give aliphatic percarboxylic acids, preferably 1-10 C atoms, especially 2-4 C atoms, and / or optionally substituted perbenzoic acid may be used under perhydrolysis conditions. Substances that contain O- and / or N-acyl groups with the above-mentioned number of C atoms and / or optionally substituted benzoyl groups are suitable. Multi-acylated alkylene diamines are preferred, with tetraacetyl ethylenediamine (TAED) being particularly preferred.

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

In addition to conventional bleach activators or instead of them so-called bleaching catalysts. These substances are bleach enhancing transition metal salts or transition metal complexes such as e.g. salen complexes or carbonyl Mn, Fe, Co, Ru or Mo complexes. As bleach catalysts, Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N tripod ligands as well as Ammin complex Co, Fe can be used,

Cu and Ru.

Manganese complexes with oxidation state II, III, IV or VI, which preferably contain one or more macrocyclic ligands with N, NR, PR, O donor functional groups, are particularly preferably used.

- 9 and / or S. Preferably, ligands which have nitrogen donor functional groups are used. It is particularly preferred to use bleach catalyst (s) in the compositions according to the invention which contain 1,4,7-trimethyl-1,4, 4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononan (macrocyclic ligands as the macrocyclic ligands). TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl1,4,7-trimethyl-1, 4,7-triazacyclononate (Me / Me-TACN) and / or 2 -methyl-1,4,7-triazacyclononan (Me / TACN). Suitable manganese complexes are, for example, [Mn^IIT2 (M-O) ₄- (μOAc) ₂ (TACN) ₂] (C1O₄)₂, [Mn^IITMn^IV (μ-O) 2 (μ-OAc) and (TACN) 2] (BPh4) 2, [Mn^IV4 (m-C) 6 (TACN) ₄] (C1O₄) 2z [No.^r2 (M-O) ₄ (Μ-OAc) ₂(Me-TACN) ₂] (CIO) ₂, [Mn^IITMn^IV (μ-O) and (μ-OAc) 2 (Me-TACN) 2] (C1O4) 3, [Mn^IV2 (m-C) 3 (Me-TACN) ₂] (PF₆)₂ and [Mn^IV2 (m-C) 3- (Me / Me-TACN) ₂] (PF₆) ₂ (OAC = OC (O) CH₃) .

Preferred according to the invention are machine dishwashing agents which are characterized in that they further comprise a bleach catalyst selected from the group of bleaching agents for transition metal salts and transition metal complexes, preferably from the group of manganese complexes with 1,4,7-trimethyl-1,4 , 7-triazacyclononaner (Me₃-TACN) or 1,2,4,7-tetramethyl-1,4, 7-triazacyclononate (Me₄-TACN), because the bleaching catalysts discussed above can, in particular, significantly improve the cleaning result.

The bleaching enhancers of transition metal complexes discussed above, especially those with central Mn and Co atoms, are used in usual amounts, preferably in an amount of up to 5% by weight, in particular 0.0025-1% by weight, particularly preferably 0.01-0, 30% by weight, in each case based on the total weight of the bleach catalyst containing agents. In special cases, however, more bleach catalysts can also be used.

Some examples of recipes of beneficial phosphate-free agents for machine washing can be found in the following table:

<td>Ingredient</td><td>Recipe 1 (Wt-%).</td><td>Recipe 2 (Wt-%).</td><td>Recipe 3 (Wt-%).</td>

<td>Karboksymetyloinulina</td><td> 2-15</td><td> 2-10</td><td> 4-10</td>

<td>Citrate / citric acid</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Carbonate / bicarbonate</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Sodium percarbonate</td><td> 4-15</td><td> 6-15</td><td> 6-15</td>

<td>Bleach activator / catalyst</td><td> 0,01-5</td><td> 0, 1-5</td><td> 1-5</td>

<td>phosphonate</td><td> —</td><td> —</td><td> —</td>

<td>Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

The dishwashing agents according to the invention are further characterized in that they do not contain any phosphonate. The cleaning and rinsing action, and the lack of phosphonate could also improve the inhibition of deposit formation in the compositions according to the invention.

Preferred phosphate-free machine dishwashing agents according to the invention contain as further component a copolymer

i) monomers containing sulfonic acid groups, ii) further ionic (s) and / or non-ionic (s) monomer (s).

The weight fraction of the copolymer in the total weight of the machine dishwashing agent is preferably

0.5-20% by weight, even more preferably 4-18% by weight, particularly preferably 6-15% by weight, especially 612% by weight.

Those copolymers which contain at least one further ionic or nonionic monomer in addition to the monomer containing sulfonic acid groups may have two, three, four or more different monomer units.

For monomers containing sulfonic acid groups, monomers of the formula are preferred

R⁵ (R⁶) C = C (R⁷) -X-SO₃H in which R⁵-R⁷ are independently -H, -CH₃, a straight or branched chain saturated alkyl radical with 2-12 carbon atoms, a straight chain or

- 11 branched, mono- or polyunsaturated unsaturated alkenyl radical with 2-12 carbon atoms, substituted with -NH₂, -OH or -COOH alkyl or alkenyl radicals or are -COOH or -COOR⁴, with R⁴ is a saturated or unsaturated, straight or branched chain hydrocarbon radical with 1-12 carbon atoms, and X is an optionally existing spacer group which is selected from - (CH₂)_n- where n = 0-4, -COO (CH₂)_k- where k = 1-6, -C (O) -NH-C (CH₃) ₂~ and -C (O) -NHCH (CH₂CH₃)

Of these monomers, monomers having formulas are preferred

H₂C = CH-X-SO₃H

H₂C = C (CH₃) -x-so₃h

HO₃SX- (R⁶) C = C (R⁷) -x-so₃h in which R⁶ and R⁷ is independently selected from -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH (CH₃)₂and X is an optionally existing spacer group which is selected from - (CH₂)_n- where n = 0-4, -COO (CH₂)_k- where k = 1-6, -C (O) -NH-C (CH₃) ₂- and -C (O) -NHCH (CH₂CH₃) - .

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, metallylsulfonic acid, allyloxybenzenesulfonic acid, metallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen-1-sulfonic acid, styrene sulfonic acid vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids or their water-soluble salts.

The sulfonic acid groups can be present in polymers in full or in partially neutralized form, which means that the acid hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali ions, especially ions sodium. According to the invention, the use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred.

The monomer distribution in the copolymers preferably used according to the invention is in copolymers which contain only monomers from groups i) and ii), preferably in each case 5-95% by weight i) or ii), particularly preferably 50-90% by weight monomer from group i) and 10-50% by weight of the monomer of group ii) in each case with respect to the polymer.

The molar mass of the sulfocopolymers used preferably according to the invention can be varied to adapt the polymer properties to the desired purpose of use. Preferred dishwashing agents according to the invention are characterized in that the copolymers have a molar mass of 2000-200000 gmol '¹, preferably 4000-25000 gmol "¹, especially 5000-15000 gmol^-1.

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

According to the invention, phosphate-free machine dishwashing agents containing

a) carboxymethylinulin,

b) oxygen bleaching agent,

c) a copolymer containing

i) monomers containing sulfonic acid groups, ii) further ionic monomers, characterized in that the machine dishwashing agent does not contain any phosphonate.

Unsaturated carboxylic acids are particularly preferably used as ionic monomers. Unsaturated carboxylic acids of formula R are particularly preferred¹ (R²) C = C (R³) COOH in which R ^ R³ independently from each other -H, -CH3, straight or branched chain,

- 13 saturated alkyl radical with 2-12 carbon atoms, straight or branched chain, mono- or polyunsaturated unsaturated alkenyl radical with 2-12 carbon atoms, substituted with -NH₂, -OH or -COOH alkyl or alkenyl radicals as previously defined or are -COOH or -COOR⁴, with R⁴ is a saturated or unsaturated straight or branched chain hydrocarbon radical with 1-12 carbon atoms.

Accordingly, phosphate-free machine dishwashing agents containing. Are particularly preferred

a) carboxymethylinulin,

b) oxygen bleaching agent,

c) a copolymer containing

i) monomers containing sulfonic acid groups, ii) carboxylic acid groups monomers of formula R¹ (R²) C = C (R³) COOH, in which R⁴-R³ are independently from each other -H, -CH3, a straight or branched, saturated alkyl radical with 2-12 carbon atoms, a straight or branched saturated, mono- or multiple unsaturated alkenyl radical with 2-12 carbon atoms, substituted with -NH2, -OH or -COOH alkyl or alkenyl radicals as previously defined or are -COOH or -COOR⁴, with R⁴ means a saturated or unsaturated, straight or branched chain hydrocarbon radical of 1-12 carbon atoms, characterized in that the dishwashing agent does not contain any phosphonate.

Particularly preferred monomers containing carboxylic acid groups are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid , methylene malonic acid, sorbic acid, cinnamic acid or mixtures thereof.

Examples of recipes of beneficial, phosphate-14 -ranran dishwashing machines can be found in the following table:

<td>Ingredient</td><td>Recipe 1 (Wt-%).</td><td>Recipe 2 (Wt-%).</td><td>Recipe 3 (Wt-%).</td>

<td>Karboksymetyloinulina</td><td> 2-15</td><td> 2-10</td><td> 4-10</td>

<td>Citrate / citric acid</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Carbonate / bicarbonate</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Sodium percarbonate</td><td> 4-15</td><td> 6-15</td><td> 6-15</td>

<td>Bleach activator / catalyst</td><td> 0,01-5</td><td> 0, 1-5</td><td> 1-5</td>

<td>copolymer¹</td><td> 4-16</td><td> 4-16</td><td> 4-16</td>

<td>phosphonate</td><td> --</td><td> --</td><td> —</td>

<td>Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

¹copolymer containing

i) monomers containing sulfonic acid groups, ii) carboxylic acid groups monomers of formula R¹ (R²) C = C (R³) COOH, in which R¹-R³ are, independently of one another, -H, -CH3, a straight or branched chain, saturated alkyl radical with 2-12 carbon atoms, a straight or branched chain, mono- or polyunsaturated unsaturated aikenyl radical with 2-12 carbon atoms, substituted with -NH2, -OH or -COOH alkyl or alkenyl radicals as previously defined or are -COOH or -COOR⁴, with R⁴is a saturated or unsaturated straight or branched chain hydrocarbon radical with 1-12 carbon atoms.

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

Preference is given to using monomers of general formula R as nonionic monomers¹ (R²) C = C (R³) -X-R⁴in which R¹R³ are independently -H, -CH₃ or -C₂H₅, X

- 15 is an optionally existing spacer group which is selected from -CH₂-, -C (0) 0- and -C (O) -NH-, and R⁴is a straight chain or branched alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms.

A further subject of this application are therefore phosphate-free, machine-washing dishes containing

a) carboxymethylinulin,

b) oxygen bleaching agent,

c) a copolymer containing

i) monomers containing sulfonic acid groups, ii) monomers of formula R¹ (R²) C = C (R³) -X-R⁴, wherein

R¹-R³ are independently -H, -CH₃ or

-C2H5, X is an optionally existing spacer group which is selected from -CH₂-, - C (O) Οι -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms, characterized in that the dishwashing agent does not contain any phosphonate.

Butene, isobutene, pentene are particularly preferred nonionic monomers. 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1,2-methylpentene-1,3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4,4-trimethiopentene-1,2,4, 4-trimethylpentene-2, 2,3-dimethylhexene-1,2,4-dimethylhexene-1,2,5-dimethylhexene-1,3,5-dimethylhexene-1,

4,4-dimethylhexene-1, ethylcyclohexin, 1-octene, α-olefins with 10 or more carbon atoms, such as e.g. 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C₂2^-α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, acrylic acid methyl ester, acrylic acid ethyl ester, propyl ester acrylic acid, acrylic acid butyl ester, acrylic acid pentyl ester, acrylic acid hexyl ester, methacrylic acid methyl ester, N- (methyl) acrylamide, acrylic acid 2-ethylhexyl ester, methacrylic acid 2-ethylhexyl ester, N- (2-ethylhexyl) acrylamide, acrylic acid octyl ester, methacrylic acid octyl ester, N- (octyl) acrylamide, acrylic acid lauryl ester, methacrylic acid lauryl ester, N- (lauryl) acrylamide, acid stearyl ester acrylic, methacrylic acid stearyl ester, N- (stearyl) -acrylamide, behenyl acrylic acid ester, methacrylic acid behenyl ester and N- (behenyl) acrylamide or mixtures thereof.

Some examples of recipes of beneficial phosphate-free agents for machine washing can be found in the following table:

<td>Ingredient</td><td>Recipe 1 (Wt-%).</td><td>Recipe 2 (Wt-%).</td><td>Recipe 3 (Wt-%).</td>

<td>Karboksymetyloinulina</td><td> 2-15</td><td> 2-10</td><td> 4-10</td>

<td>Citrate / citric acid</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Carbonate / bicarbonate</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Sodium percarbonate</td><td> 4-15</td><td> 6-15</td><td> 6-15</td>

<td>Bleach activator / catalyst</td><td> 0,01-5</td><td> 0,1-5</td><td> 1-5</td>

<td>copolymer¹</td><td> 4-16</td><td> 4-16</td><td> 4-16</td>

<td>phosphonate</td><td> --</td><td> --</td><td> --</td>

<td>Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

¹copolymer containing

i) monomers containing sulfonic acid groups, ii) monomers of general formula R¹ (R²) C = C (R³) -X20 R⁴in which Ru-R³ are independently -H, -CH₃ or -C2H5, X is an optionally existing spacer group which is selected from -CH₂-, -C (0) 0- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-12 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms.

Copolymers which, in addition to monomers containing sulfonic acid groups, further contain both ionic and nonionic monomers are particularly preferred.

According to the invention, phosphate-free machine dishwashing agents are preferred which are characterized in that copolymer c) contains

i) monomers containing sulfonic acid groups, ii) monomers containing carboxylic acid groups, iii) further nonionic monomers.

Some examples of recipes of beneficial phosphate-free agents for machine washing can be found in the following table:

<td>Ingredient</td><td>Recipe 1 (Wt-%).</td><td>Recipe 2 (Wt-%).</td><td>Recipe 3 (Wt-%).</td>

<td>Karboksymetyloinulina</td><td> 2-15</td><td> 2-10</td><td> 4-10</td>

<td>Citrate / citric acid</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Carbonate / bicarbonate</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Sodium percarbonate</td><td> 4-15</td><td> 6-15</td><td> 6-15</td>

<td>Bleach activator / catalyst</td><td> 0,01-5</td><td> 0,1-5</td><td> 1-5</td>

<td>copolymer¹</td><td> 4-16</td><td> 4-16</td><td> 4-16</td>

<td>phosphonate</td><td> --</td><td> —</td><td> --</td>

<td>Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

¹copolymer containing

i) monomers containing sulfonic acid groups, ii) monomers containing carboxylic acid groups, iii) further nonionic monomers.

By using the previously described copolymers containing sulfonic acid groups, the inhibition of deposit formation and the washing result can be clearly improved compared to traditional polymeric or copolymeric acrylates without a sulfonic acid group.

The compositions according to the invention may further comprise surfactants. Surfactants include nonionic, anionic, cationic and amphoteric surfactants.

The dishwashing agents particularly preferably contain nonionic surfactant (s), the weight proportion of surfactant (s) in the total weight of the dishwashing agent preferably being 1-10% by weight , more preferably 2-8% by weight, especially 3-6% by weight.

All nonionic surfactants known to the skilled person can be used as nonionic surfactants. Suitable nonionic surfactants are, for example, alkylglycosides of the general formula RO (G)_Xin which R corresponds to a primary, straight or branched methyl, especially branched methyl in position 2 aliphatic radical of 8-22, preferably 12-16 C atoms, and G is a symbol that represents a 5 or 6 C glucose unit, preferably glucose . The degree of oligomerization x, which reports the distribution of monoglycosides and oligoglycosides, is any number between 1-10, with x being preferably in the range of 1.2-1.4.

Aminoxide type nonionic surfactants, e.g. cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably no more than the amount of ethoxylated fatty alcohols, and in particular no more than half.

A further class of preferably used nonionic surfactants which are used either as a single nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated esters

- 19 alkyl fatty acids, preferably with 1-4 carbon atoms in the alkyl chain.

Low-foaming, non-ionic surfactants are used as preferred surfactants. Washing or cleaning agents, in particular machine dishwashing cleaners, particularly preferably contain non-ionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, even more preferably ethoxylated, especially primary alcohols, preferably with 8-18 carbon atoms and an average of 1-12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical may be linear or preferably branched in the 2-position methyl or it may contain linear and methyl branched radicals in the mixture, as they usually occur in oxo alcohol radicals. Alcohol ethoxylates having linear radicals from alcohols of natural origin with 12-18 C atoms, e.g. coconut, palm, tallow or oleyl alcohol, and on average 2-8 moles EO per mole of alcohol are especially preferred. Preferred ethoxylated alcohols include e.g.₂_and₄- alcohol with 3 EO or 4 EO CG-n-alcohol with 7 EO, C13-15 alcohol with 3 EO, 5 EO, 7 EO or 8 EO 100₁₂and g-alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of Ci₂-₁₄- alcohol with 3 EO and Ci₂-₁₈- alcohol with 5 EO. The degrees of ethoxylation given are statistical average values ​​that may correspond to an integer or fractional number for a particular product. Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used. Examples of these are tallow fatty alcohols with 14 EO, 25 EO, 30 EO or 40 EO.

Hence, ethoxylated, nonionic surfactants which are preferably obtained from Cg- are particularly preferably used.₂o-monohydroxyalkanols or Cg-₂Q-20 alkylphenols or C 1-20^_fatty alcohols and more than 12 moles, preferably more than 15 moles, especially more than 20 moles of ethylene oxide per mole of alcohol. A particularly preferred non-ionic surfactant is obtained from a straight chain fatty alcohol with 16-20 carbon atoms (Ci₆Alcohol), preferably from C18-alcohol and at least 12 moles, preferably at least 15 moles, especially at least 20 moles of ethylene oxide. Of these, the so-called "Narrow ethoxylates."

Mixtures of one or more tallow fatty alcohols with 20-30 EO and silicone anti-foam agents are further particularly preferred.

Nonionic surfactants which have a melting point above room temperature are particularly preferred. Particularly preferred is (are) the nonionic surfactant (s) with a melting point above 20 ° C, more preferably above 25 ° C, particularly preferably 25-60 ° C, especially 26.6 -43.3 ° C.

Suitable nonionic surfactants that exhibit melting or softening temperatures in the temperature range discussed are, e.g., low foaming, nonionic surfactants, which may be solid or have high viscosity at room temperature. If nonionic surfactants are used which have a high viscosity at room temperature, it is preferred that they exhibit a viscosity above 20 Pa-s, preferably above 35 Pa-s, and especially above 40 Pa-s. Depending on their purpose, nonionic surfactants which have a waxy consistency at room temperature are also preferred.

Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols, in particular from the group of nonionic surfactants of the ΕΟ-ΆΟ-21 EO type are particularly preferably used.

The room temperature solid nonionic surfactant preferably has propylene oxide units in the molecule. Such PO units preferably constitute up to 25% by weight, particularly preferably up to 20% by weight, in particular up to 15% by weight, of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene polyoxypropylene block copolymer units. The proportion of alcohol or alkylphenol in the molecules of such nonionic surfactants is preferably more than 30% by weight, particularly preferably more than 50% by weight, in particular more than 70% by weight, of the total molar mass of such nonionic surfactants. Preferred agents are characterized in that they comprise ethoxylated and propoxylated nonionic surfactants, in which the propylene oxide units constitute up to 25% by weight, preferably up to 20% by weight and especially up to 15% by weight of the total molar mass of the nonionic surfactant in the molecule.

Preferably the surfactants used come from groups of alkoxylated nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants, such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO surfactants) . Such PO / EO / PO nonionic surfactants also have good foaming control.

Further particularly preferred nonionic surfactants with a melting point above room temperature contain 40-70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer mixture which contains 75% by weight

Inverse polyoxyethylene and polyoxypropylene block copolymer with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% 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.

Low-foaming nonionic surfactants which exhibit alternating ethylene oxide and alkylene oxide units have proved to be particularly preferred nonionic surfactants in the context of the present invention. Of these, surfactants having EO-AO-EOAO blocks are again preferred, with one to ten EP or AO groups linked together before the other groups block each. Nonionic surfactants of the general formula are preferred here

R^x-O- (CH₂CH₂-ABOUT) _in- (CH₂-FOR) _x- (CH₂CH₂-ABOUT) _s- (CH₂-FOR) _from-H

R² R³ in which R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C8-24 alkyl or -alkenyl radical, each R group² be R³ is independently selected from -CH3, -CH₂CH₃, -CH₂CH₂CH₃, -CH (CH₃)₂, and the indicators w, x, y, z stand for independent integers 1-6.

Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R¹-OH and ethylene oxide or alkylene oxide. R radical¹ in the above formula may vary depending on the origin of the alcohol. If natural sources are used, the R radical¹ it has an even number of carbon atoms and is generally unbranched, with linear radicals from alcohols of natural origin having 12-18 carbon atoms, e.g. coconut, palm, tallow or oleyl alcohol, being preferred. Alcohols available from synthetic sources are, for example, guerbet alcohols or methyl branched in the 2-position or linear and branched methyl radicals in a mixture, as they are usually found in oxo alcohol radicals. Regardless of the type of alcohol used in the preparation of the nonionic surfactants contained in these agents, nonionic surfactants in which R¹ in the above formula is an alkyl radical with

6-24, preferably 8-20, particularly preferably 9-15, especially 9-11, carbon atoms.

As alkylene oxide unit, which in preferred non-ionic surfactants is alternately contained with an ethylene oxide unit, next to propylene oxide, especially butylene oxide is considered, but further alkylene oxides in which R² be R³ is independently selected from -CH2CH2-CH3 or -CH (CH3) 2. Preferably nonionic surfactants of the above formula are used in which R² be R³ are the radical -CH3, and x are independently the values ​​3 or 4, and y and y are the values ​​1 or 2 independently of each other.

In summary, nonionic surfactants that have a C9-15 alkyl radical with 1-4 ethylene oxide units followed by 1-4 propylene oxide units followed by 1-4 ethylene oxide units followed by 1-4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used particularly advantageously in accordance with the invention.

Surfactants of the general formula R are preferred according to the invention¹-CH (OH) CH2O- (AO) W (A'O) x- (A''O) y- (A '' 'O) ZR²in which R¹ and R² are independently of each other a straight or branched chain, saturated or mono- or polyunsaturated C2-4o radical^_alkyl or -alkenyl, A, A ', A' 'and A' '' are each independently a radical from the group consisting of₂ch₂, -ch₂ch₂analysis₂, -CH₂-CH (CH₃), -CHi-CH₂CH₂CH₂, -CH₂-CH (CH₃) -CH₂-, -CH₂-CH (CH2-CH3), aw, x, y and z are 24-40, whereby x, y and / or z can also be 0.

Some recipes for beneficial phosphate-free machine dishwashing preparations can be found in the following table:

<td>Ingredient</td><td>Recipe 1 (Wt-%).</td><td>Recipe 2 (Wt-%).</td><td>Recipe 3 (Wt-%).</td>

<td>Karboksymetyłoinulina</td><td> 2-15</td><td> 2-10</td><td> 4-10</td>

<td>Citrate / citric acid</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Carbonate / bicarbonate</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Sodium percarbonate</td><td> 4-15</td><td> 6-15</td><td> 6-15</td>

<td>Bleach activator / catalyst</td><td> 0,01-5</td><td> 0, 1-5</td><td> 1-5</td>

<td>copolymer¹</td><td> 4-16</td><td> 4-16</td><td> 4-16</td>

<td>Nonionic surfactant</td><td> 2-9</td><td> 3-8</td><td> 4-7</td>

<td>phosphonate</td><td> --</td><td> __</td><td> —</td>

<td>Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

¹copolymer containing

i) monomers containing sulfonic acid groups ii) carboxylic acid groups monomers of formula R¹ (R²) C = C (R³) COOH, in which R⁴-R³ are independently -H, -CH₃, a straight or branched chain, saturated alkyl radical with 2-12 carbon atoms, a straight or branched chain, single or multiple unsaturated alkenyl radical with 2-12 carbon atoms, substituted with -NH₂, -OH or -COOH alkyl or alkenyl radicals as previously defined or are -COOH or -COOR⁴, with R⁴is a saturated or unsaturated straight or branched chain hydrocarbon radical with 1-12 carbon atoms.

By using the nonionic media described below 25

Surfactants with a free hydroxyl group on one of both terminal alkyl radicals can, compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group, significantly improve the inhibition of sediment formation and the rinsing result.

Particularly closed, poly (oxyalkylated) nonionic surfactants which, according to formula R, are also preferred¹O-CH₂CH₂ABOUT]_x CH₂CH (OH) R² they show next to the R radical¹which is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical with 2-30 carbon atoms, preferably with 4-22 carbon atoms, hereinafter a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R² with 1-30 carbon atoms, x being 1-90, preferably 30-80, especially 30-60.

Surfactants of formula R are particularly preferred⁴O [CH₂CH (CH₃) ABOUT]_x [CH₂CH₂ABOUT] _sCH₂CH (OH) R.²in which R¹ is a linear or branched, aliphatic hydrocarbon radical with 4-18 carbon atoms or mixtures thereof, R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms or mixtures thereof, x is 0.5-1.5 and y is 15 or more.

Particularly preferred are poly (oxyalkylated) nonionic surfactants of formula R¹O [CH2CH2O] x [CH2CH (R³) O] y CH₂CH (OH) R²in which R¹ and R² are independently of each other a linear or branched, saturated or mono-unsaturated hydrocarbon radical with 226 carbon atoms, R³ is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH (CH3) 2, but preferably is -CH3, ax and y are independently from each other values ​​1-32, with nonionic surfactants being quite particularly preferred at R³= —CH3, x 15-32 values ​​and y values ​​0.5-1.5.

Further preferably used nonionic surfactants are terminated, poly (oxyalkylated) nonionic surfactants of formula R¹O [CH2CH (R.³) O) x [CH₂] kCH (OH) [CH₂] j OR²in which R¹ and R² are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1-30 carbon atoms, R³ is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is 1-30, stick is 1-12, preferably 1-5. When the value of xh 2, then each R³ in the above formula R ^ [CH2CH (R³) O] x [CH₂] k ~ CH (OH) [CH₂] above²may be different. R¹ and R² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 6-22 carbon atoms, with radicals having 8-18 carbon atoms being particularly preferred. In the case of the R radical³ H, -CH. are particularly preferred₃ or -CH₂CH₃. Particularly preferred values ​​for x are in the range 1-20, especially 615.

As previously described, each R³ in the above formula may be different when xh 2, whereby the alkylene oxide unit in braces may change. If x is e.g. 3, then the radical R can be selected³to form ethylene oxide units (R³ = H) or propylene oxide (R³ = CH₃) that can be connected to each other in any order, e.g. (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (OP). Value 3 is selected here as an example and can be quite larger, however the range of variability increases with increasing x values ​​and includes e.g. a large number groups (EO) in combination with a small number of groups (PO) or vice versa.

Particularly preferred, end-terminated poly (oxyalkylated) alcohols having the above formula show k = 1 and j = 1, so that the above formula is simplified to formula R¹O [CH2CH (R.³) 0] XCH₂CH (OH) CH₂OR². In the last discussed formula R¹, R² and R³ are as defined above, and x is numbers 1-30, preferably 1-27 20, especially 6-18. Surfactants in which R radicals are particularly preferred¹ and R² have 9-14 C, R atoms³ means H, ax takes values ​​of 6-15.

Some examples of recipes for particularly preferred phosphate-free machine washing agents can be found in the following table:

<td>Ingredient</td><td>Recipe 1 (Wt-%).</td><td>Recipe 2 (Wt-%).</td><td>Recipe 3 (Wt-%).</td>

<td>Karboksymetyloinulina</td><td> 2-15</td><td> 2-10</td><td> 4-10</td>

<td>Citrate / citric acid</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Carbonate / bicarbonate</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Sodium percarbonate</td><td> 4-15</td><td> 6-15</td><td> 6-15</td>

<td>Bleach activator / catalyst</td><td> 0,01-5</td><td> 0,1-5</td><td> 1-5</td>

<td>copolymer¹</td><td> 4-16</td><td> 4-16</td><td> 4-16</td>

<td>Nonionic surfactant²</td><td> 2-9</td><td> 3-8</td><td> 4-7</td>

<td>phosphonate</td><td> --</td><td> —</td><td> —</td>

<td>Different</td><td>up to 100</td><td>up to 10 0</td><td>up to 100</td>

¹ copolymer containing

i) monomers containing sulfonic acid groups ii) carboxylic acid groups monomers of formula R¹ (R²) C = C (R³) COOH, in which R²-R³ independently of each other -H, -CH3, a straight or branched chain, saturated alkyl radical with 2-12 carbon atoms, a straight or branched chain, mono- or polyunsaturated unsaturated aikenyl radical with 2-12 carbon atoms, substituted with -NH₂, -OH or -COOH alkyl or alkenyl radicals as previously defined or are -COOH or -COOR⁴, with R⁴is a saturated or unsaturated straight or branched chain radical

-28 hydrocarbon with 1-12 carbon atoms

End-closed, poly (oxyalkylated), non-ionic surfactant with at least one free hydroxyl group on one of both terminal alkyl radicals

The C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the previously discussed nonionic surfactants are statistical average values ​​that may be a whole or a fractional number for a particular product. As a result of the manufacturing processes, commercial products with the above formulas usually consist of not one individual representative, but mixtures, so that both in the case of chain lengths C and ethoxylation or alkoxylation degrees, average values ​​and hence fractional numbers may result.

The nonionic surfactants previously discussed can of course not only be used as individual substances, but also as mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of non-ionic surfactants which in their entirety correspond to one of the general formulas discussed above, but rather mixtures which contain two, three, four or more non-ionic surfactants which can be described in various from the previously described general formulas.

In addition to the above-described components, such as skeletal substances or bleaching agents and surfactants, preferred dishwashing agents also contain further components, preferably active agents from the group of polymers, enzymes, corrosion inhibitors, fragrances or dyes active in the washing or cleaning.

Active polymers for washing or cleaning include, for example, rinse polymers and / or polymers effective as emollients, especially cationic or amphoteric polymers.

"Cationic polymers" according to the present invention are polymers that have a positive charge in the polymer molecule. This charge can be accomplished, e.g., by (alkyl) ammonium species present in the polymer chain or other positively charged groups. Particularly preferred cationic polymers are derived from groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, copolymers of vinylpyrrolidone with quaternized dichloroquinolacrylacrylamidone derivatives metoimidazoliniowy, quaternized polyvinyl alcohols or polymers listed under INCI Polyąuaternium 2, Polyquaternium 17, Polyąuaternium 18 and Polyąuaternium 27.

In addition to the positively charged group in the polymer chain, "amphoteric polymers" also have negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Preferred washing or cleaning agents, especially preferred dishwashing agents, are characterized in that they contain a polymer a) which has monomeric units of formula R¹R²C = CR³R⁴in which each radical R¹, R², R³, R⁴ is independently selected from hydrogen, a derivatized hydroxyl group, linear or branched C1-6 groups₃₀alkyl, aryl, aryl substituted, linear or branched C 1-4 groups₃o-alkyl, polyalkoxylated alkyl groups, heteroatom organic groups with at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one positive charge amino group in the partial range of the pH range 2-11, or their salts, with assuming that at least one radical R¹, R², R³, R⁴ is a heteroatom organic group with at least one positive charge without a charged nitrogen, at least one quaternized N atom or at least one positive charge amino group.

Within the framework of the present application, particularly preferred cationic or amphoteric polymers contain as a monomer unit a compound of the general formula

R¹ R² R⁴

H₂C = C- (CH₂) _x-N⁺- (CH₂) _sC = CH₂ X '

R³ in which R¹ and R⁴ independently of each other H or a linear or branched hydrocarbon radical with 1-6 carbon atoms, R² and R³ are independently of each other an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl radical is linear or branched and has 1-6 carbon atoms, preferably with a methyl group, and y and y are, independently of each other, integers 1-3. X 'is a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, bisulfate, metosulfate, lauryl sulfate, dodecylbenzene sulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred R radicals¹ and R⁴ in the above formula is selected from -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH (CH₃) -CH₃, -CH₂OH, -CH₂CH₂-OH, -CH (OH) -ch₃, -CH₂CH₂CH₂-OH, -CH₂CH (OH) -CH₃, -CH (OH) -CH₂CH₃ their₂CH₂-0) _nH.

Polymers that exhibit a cationic monomer unit of the above general formula wherein R is particularly preferred¹ and R⁴ are H, R² and R³are methyl, and x and y each represent 1. A suitable monomeric unit of formula

H₂C = CH- (CH₂) -N⁺ (CH₃) ₂- (CH₂) -ch = ch₂ X 'in the case where X ~ = chloride, is also referred to as

-31 DADMAC (diallyldimethylammonium chloride).

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

R¹HC = CR²-C (O) -NH- (CH₂) _X-N⁺R³R⁴R⁵ X 'in which R¹, R², R³, R⁴ and R⁵ are independently of each other a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical with 1-6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH (CH₃) -CH₃, -CH₂OH, -CH₂CH₂-OH, -CH (OH) -CH₃, -ch₂analysis₂analysis₂OH, —CH₂—CH (OH) —CH₃, -CH (OH) -CH2-CH3 and - (CH₂CH₂-ABOUT) _nH, ax is an integer 1-6.

Polymers that exhibit a cationic monomer unit of the above general formula in which R¹ means H, R², R³, R⁴ and R⁵ are methyl, and x is 3. Suitable monomeric units of the formula

H₂C = C (CH₃) -C (O) -NH- (CH₂) _x-N⁺ (CH₃) ₃ X 'in the case where X' = chloride, is also referred to as MAPTAC (methylacrylamidopropyltrimethylammonium chloride).

Preferably, according to the invention, polymers are used which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers exhibit not only cationic groups, but also anionic monomer groups or units. Such anionic monomer units are e.g. 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 monomeric units are acrylic acid, (meth) acrylic acid, dimethylacrylic acid, ethylacrylic acid, cyanoacrylic acid,

Vinylacetic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids, such as e.g. allyloxybenzenesulfonic acid and metallylsulfonic acid or allylphosphonic acids.

Preferred amphoteric polymers used are from the group consisting of alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methyl methacrylate copolymers, alkylacrylamide / acrylic acid copolymers / alkylaminoalkyl (meth) acrylate / alkylmethylacrylate / methacrylate alkylacrylamide / methyl methacrylate / alkylaminoalkyl (meth) acrylate copolymers, alkylacrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and copolymers of unsaturated carboxylic acids, cationically derivatized, unsaturated carboxylic acids and optionally further ionic or nonionogenic monomers.

Preferably the zwitterionic polymers used are from the group consisting of acrylamidoalkyltrialkylammonium chloride copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and methacrylethylbetaine / methacrylate copolymers.

Further preferred are amphoteric polymers which, in addition to one or more anionic monomers, contain as cationic monomers methacrylamidoalkyl trialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

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

Particularly preferred are amphoteric polymers from the group of copolymers: methacrylamidopropyltrimethylammonium chloride / dimethyl (dialyl) ammonium chloride / acrylic acid, copolymers of methacrylamidopropyltrimethylammonium chloride / dimethyl (dialyl) ammonium chloride / acrylic acid and methyl methacrylate chloromethyl chloride alkyl and their alkali and ammonium salts.

In a particularly preferred embodiment of the present invention, the polymers are in pre-assembled form. Suitable for packaging polymers are, among others,

- encapsulation of polymers with water-soluble or water-dispersible coating agents, preferably with water-soluble or water-dispersible coatings, natural or synthetic polymers,

- encapsulation of polymers by means of water-insoluble, fusible coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30 ° C,

- co-granulation of polymers with inert carrier materials, preferably with carrier materials from the group of substances active in the washing or cleaning of substances, and particularly preferably from the group of active fillers (skeletal substances) or active co-fillers.

The washing or cleaning agents contain the previously discussed cationic and / or amphoteric polymers preferably in amounts of 0.01-10% by weight, each time based on the total weight of the washing or cleaning agent. Within the scope of this application, however, washing or cleaning agents are preferred in which the weight proportion of cationic and / or amphoteric polymers is 0.01-8% by weight, preferably 0.01-6% by weight, even more preferably 0.01-4% by weight in particular, preferably 0.01-2% by weight, in particular 0.01-1% by weight, based on the total weight of the machine dishwashing agent.

Enzymes can be used to increase the efficiency of washing or cleaning of washing or cleaning agents, including in particular proteases, amylases, lipases, hemicellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are essentially of natural origin and starting from natural particles are available for use in washing or cleaning agents better variants that are used preferably. Washing or cleaning agents contain enzymes preferably in total amounts from 1 x 10 "⁶ up to 5% by weight based on active protein. Protein concentration can be determined using known methods, e.g. the BCA method or the biuret method.

Of the proteases, subtilisin-type proteases are preferred and examples thereof are BPN 'and Carlsberg subtilisins and their further developed forms, PB92 proteases, subtilisin 147 and 309, alkaline proteases from Bacillus lentus, DY subtilisin and subtilisins, but not subtilisins , enzymes such as thermitase, proteinase K and proteases TW3 and TW7.

Examples of the amylases used according to the invention for use in washing and cleaning agents are oacamylases from Bacillus licheniformis, from B. amyloliaefaciens, from Aspergillus niger and A. oryzae, and better further development of the previously discussed amylases. For this purpose, further emphasize α-amylases from Bacillus sp. A

7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

According to the invention, lipases or cutinases can be further used, in particular due to their activity in the cleavage of triglycerides, and also to generate superacids in situ from the respective precursors, and include, e.g., those obtained originally from Humicola lanuginosa

-35 (Thermomyces lanuginosus) or further developed lipases, especially lipases with D96L amino acid exchange. Further, for example, cutinases that were originally isolated from Fusarium solani pisi and Humicola insolens can be used. Lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can be used further.

Further, enzymes that are included in the term hemicellulases can be used, and include, e.g., mannanases, xanthanolases, pectinolases (= pectinases), pectinesterases, pectanolases, xyloglucans (xylanases), pululanases and β-glucanases.

According to the invention, oxidoreductases, e.g. oxidases, oxidases, catalases, peroxidases, such as halo, chloro, bromo-, lignin-, glucose- or manganese-peroxidase, dioxygenase or lactase (phenoloxidases, polyphenoloxidases) can be used to increase the bleaching effect. ). Preferably, organic, especially preferably aromatic, enzyme-interacting compounds are additionally added to enhance the activity of the given oxidoreductases (enhancers) or to provide electron fluxes (mediators) with strongly different redox potentials between oxidizing enzymes and soiling.

Enzymes can be used in any form established in the art and include, for example, solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel agents, enzyme solutions, preferably as concentrated as possible, low in water and / or fixed with stabilizers .

Alternatively, the enzymes can be encapsulated in both the solid and liquid form offered, e.g. by spray drying or extrusion of the enzyme solution together with a preferred natural polymer, or in the form of capsules, e.g., capsules in which the enzymes are enclosed as in a solid gel, or core-sheath capsules in which the core containing the enzyme is coated with water, air and / or impermeable to

-36 chemicals with a protective film. Further active substances, e.g. stabilizers, emulsifiers, pigments, bleaching agents or dyes, may additionally be applied in the applied layers. Capsules of this type are applied by known methods, e.g. by screening granulation or rolling granulation or in fluidization processes. Such granules, due to the application of polymeric film-forming agents, are preferably low in dust, and due to the coating - stable during storage.

It is further possible to pack two or more enzymes together so that a single granulate has more enzymatic activities.

The protein and / or enzyme can be protected during storage against damage such as e.g. inactivation, denaturation or degradation, e.g. due to physical influences, oxidation or proteolytic cleavage. In bacterial production of proteins and / or enzymes, inhibition of proteolysis is particularly advantageous, especially when the agents also contain proteases. For this purpose, washing or cleaning agents contain stabilizers. The development of such measures is a preferred embodiment of the present invention.

Preferably, one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, are used in an amount of 0.1-6% by weight, preferably 0.2-5% by weight, in particular 0.4-5% by weight, in each case in relation to the whole agent containing the enzyme.

A preferred machine dishwashing agent comprises e.g.

a) 4-35% by weight carboxymethylinulin,

b) 2-15% by weight sodium percarbonate,

c) 2-8% by weight of the non-ionic surfactant (s),

d) 0.5-25% by weight of copolymer (s) containing

i) monomer (s) containing acidic groups, ii) further ionic (e) and / or nonionic (s) monomer (s),

-37e) 1.0-6% by weight of the enzyme, and is phosphonate free.

Some examples of recipes of beneficial phosphate-free agents for machine washing can be found in the following table:

<td>Ingredient</td><td>Recipe 1 (Wt-%).</td><td>Recipe 2 (Wt-%).</td><td>Recipe 3 (Wt-%).</td>

<td>Karboksymetyloinulina</td><td> 2-15</td><td> 2-10</td><td> 4-10</td>

<td>Citrate / citric acid</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Carbonate / bicarbonate</td><td> 10-35</td><td> 10-30</td><td> 15-30</td>

<td>Sodium percarbonate</td><td> 4-15</td><td> 6-15</td><td> 6-15</td>

<td>Bleach activator / catalyst</td><td> 0,01-5</td><td> 0, 1-5</td><td> 1-5</td>

<td>copolymer¹</td><td> 4-16</td><td> 4-16</td><td> 4-16</td>

<td>Nonionic agent surfactant</td><td> 2-9</td><td> 3-8</td><td> 4-7</td>

<td>amylase</td><td>Yes</td><td>Yes</td><td>Yes</td>

<td>protease</td><td>Yes</td><td>Yes</td><td>Yes</td>

<td>phosphonate</td><td> --</td><td> --</td><td> —</td>

<td>Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

¹ copolymer containing

i) monomers containing sulfonic acid groups ii) carboxylic acid groups monomers of formula R¹ (R²) C = C (R³) COOH, in which R¹-R³ mean independently of each other -Η, -CH₃, a straight or branched chain saturated alkyl radical

2-12 carbon atoms, straight or branched chain, mono- or polyunsaturated unsaturated alkenyl radical with 2-12 carbon atoms, substituted with -NH₂, -OH or -COOH alkyl or alkylene radicals as previously defined or are -COOH or -COOR⁴, with R⁴ is a saturated or unsaturated straight or branched chain radical

A hydrocarbon with 1-12 carbon atoms.

Glass corrosion inhibitors prevent the occurrence of clouding, streaks and cracks, as well as the irrigation of the surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts as well as magnesium and zinc complexes.

The spectrum of preferred zinc salts according to the invention, preferably organic salts, and especially preferably organic carboxylic acids, ranges from salts that are sparingly soluble or insoluble in water, and thus exhibit solubility below 100 mg / 1, preferably below 10 mg / i, and especially less than 0.01 mg / 1, for such salts which in water have a solubility above 100 mg / 1, preferably above 500 mg / 1, particularly preferably above 1 g / 1, especially above 5 g / 1 (all solubilities in water at 20 ° C). The first group of zinc salts include, e.g., zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts include, e.g., zinc formate, zinc acetate, zinc lactate and zinc gluconate.

As a glass corrosion inhibitor, it is particularly preferred to use at least one zinc salt with an organic carboxylic acid, and particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate. Zinc ricinolate, zinc abietate and zinc oxalate are also preferred.

In the context of the present invention, the zinc salt content of washing and cleaning agents is preferably 0.1-5% by weight, more preferably 0.2-4% by weight, in particular 0.4-3% by weight, or the zinc content in the oxidized form (in converted to Zn²⁺) is 0.01-1% by weight, preferably 0.02-0.5% by weight, in particular 0.04-0.5% by weight, based on the total weight of the agent containing the glass corrosion inhibitor.

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

Individual perfume compounds, e.g. synthetic products of the type esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used as perfume oils or fragrances. Preferably, however, mixtures of different aromas are used which together give a pleasant aroma. Such perfume oils may also contain natural mixtures of fragrances, such as are available from plant sources, e.g. pine oil, citrus oil, jasmine oil, patchouli oil, rose oil or ilang oil.

Fragrances can be processed directly, but it may be advantageous to apply the fragrances to carriers that provide a long-lasting fragrance due to a longer release of the fragrance. For example, cyclodectrins have proven themselves as such carrier materials, with the cyclodextrin-perfume complexes being able to be further coated with further excipients.

Preferred dyes, the selection of which is not difficult for the specialist, have a high storage stability and are insensitive to other components of the agent and to light, and have no clear affinity for substrates treated with dye-containing agents, such as textiles, glass, ceramics or dishes made of plastic so as not to tint them.

The machine dishwashing agents according to the invention can be packaged in solid or liquid form, and can also be present, e.g. as a mixture of solid and liquid forms offered.

Powders, granules, extrusion products or pressing products, in particular tablets, are particularly suitable as the solid forms offered. The liquid forms offered based on water and / or organic solvents may be in concentrated form, in the form of gel.

The compositions according to the invention can be packaged as single-phase or multiphase products. Particularly preferred are dishwashing agents having one, two, three or four phases, with dishwashing agents having the pre-existing form being particularly preferred. prepared dispensing unit with two or more phases.

The individual phases of the multi-phase agents may exhibit the same or different physical states, with machine dishwashing agents having at least two different solid phases and / or at least two liquid phases and / or at least one solid phase being particularly preferred at least one liquid phase.

Preferably, the machine dishwashing agents according to the invention are pre-packaged into dispensing units. These dispensing units preferably contain the amount of active substances necessary for the washing or cleaning process. Preferred dispensing units have a weight of 12-30 g, preferably 14-26 g, especially 15-22 g.

The volume of the previously discussed dispensing units and their spatial shape are preferably selected in such a way that the susceptibility to dispensing of the previously assembled units is ensured through the dispensing chamber of the dishwasher. Thus the volume of the dispensing unit is 10-35 ml, preferably 12-30 ml, especially 15-25 ml.

The dishwashing agents according to the invention, and especially the previously prepared dispensing units, have a particularly advantageous water-soluble casing.

In order to facilitate the disintegration and to shorten the disintegration times of previously prepared shaped products, it is possible to introduce disintegrating agents into these agents, the so-called tablet disintegrating agents.

These substances, which as a result of their action are referred to as "disintegrants", increase their volume with water access, on the one hand the own volume (swelling) increases, and on the other hand, by releasing gases a pressure can be created which allows decay tablets for smaller particles For a long time, known breakers have been, for example, carbonate / citric acid systems, other organic acids may also be used. Swelling disintegrants are e.g. 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.

Disintegrants are preferably used in amounts of 0.5-10 wt.%, Even more preferably 3-7 wt.%, Especially 4-6 wt.%, Each time based on the total weight of the disintegrant containing agent.

Preferred scavengers are cellulose based scavengers, such that the preferred washing or cleaning agents contain such a cellulose scavenger in amounts of 0.5-10% by weight, preferably 3-7% by weight, and especially

4-6% by weight. The cellulose used as a disintegrating agent is preferably not used in a fine form, but before being mixed into the pressed master batches it is made into a thicker form, e.g. granulated or pressed. The particle sizes of such disintegrating agents are generally in the range above 200 pm, and preferably at least 90 wt.% Is in the range 300-1600 pm, in particular at least 90 wt.% In the range 400-1200 pm.

Preferred disintegrating agents, preferably a cellulose based disintegrating agent, primarily in granular, co-granulated or compressed form, are included in the compositions containing the disintegrating agent in amounts of 0.5-10% by weight, preferably 3-7% by weight, in particular 4-6% by weight, in each case based on the total weight of the disintegrant containing agent.

According to the invention, further advantageous gas-evolving effervescent systems can also be used as a tablet disintegrating aid. The effervescent gas system may consist of a single substance which, on contact with water, liberates gas. Among these compounds, mention should be made of magnesium peroxide, which in contact with water releases oxygen. Preferred effervescent systems, however, consist of at least two components that react with each other to form a gas, e.g. from alkali carbonate and / or bicarbonate and an acidifying agent that is suitable for release from alkali salts in an aqueous solution of carbon dioxide. As acidifying agents which release carbon dioxide from alkaline salts in aqueous solution, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other organic salts can be used. Preferably, however, organic acidulants are used, with citric acid being a particularly preferred acidulant. In the effervescent system, acidifying agents from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof are preferred.

The subject of the present application is further a method of cleaning dishes in a dishwashing machine using the phosphate-free machine dishwashing agents according to the invention, wherein the machine dishwashing agents are dispensed into the interior space of the dishwasher preferably during a dishwashing program before starting main wash cycle or during the main wash cycle. The dispensing or introduction of the agent according to the invention into the inner space of the dishwasher can be done manually, however, the agent is preferably dispensed into the inner space of the dishwasher by means of the dispensing chamber of the dishwasher. During the cleaning process, no additional water softener or rinsing agent is preferably added to the inner space of the dishwasher. A further subject of this application is a dishwasher kit comprising

a) a phosphate-free machine dishwashing agent according to the invention,

b) an instruction that indicates to the user that the machine dishwashing agent should be used without adding rinsing agent and / or softening salt.

As described at the outset, the compositions according to the invention have a better rinsing effect compared to conventional dishwashing agents. The subject of the present application is therefore the use of a phosphate-free machine dishwashing agent according to the invention as a rinse aid for machine dishwashing.

Examples

In the machine dishwashing method, soiled dishes were washed in a dishwasher (Miele G 698) at a water hardness of 21 ° dH and at 50 ° C with the 21 g of machine dishwashing agents listed in the following table.

<td>Raw</td><td>VI (wt.%)</td><td>V2 (weight%)</td><td>V3 (weight%)</td><td>El (wt.%)</td>

<td>Phosphate</td><td> 33</td><td> —</td><td> --</td><td> --</td>

<td>Citrate</td><td> --</td><td> 30</td><td> 24</td><td> 30</td>

<td>phosphonate</td><td> 2,0</td><td> 2,0</td><td> 2,0</td><td> --</td>

<td>CMI</td><td> --</td><td> 4,0</td><td> 8,0</td><td> 4,0</td>

<td>copolymer¹</td><td> 12,0</td><td> 12,0</td><td> 12,0</td><td> 12,0</td>

<td>Soda</td><td> 28,0</td><td> 28,0</td><td> 28,0</td><td> 28,0</td>

<td>percarbonate</td><td> 10,0</td><td> 10,0</td><td> 10,0</td><td> 10,0</td>

<td>soda</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td>

<td>TAED</td><td> 2,0</td><td> 2,0</td><td> 2,0</td><td> 2,0</td>

<td>protease</td><td> 1,8</td><td> 1,8</td><td> 1,8</td><td> 1,8</td>

<td>amylase nonionic center</td><td> 5,0</td><td> 5,0</td><td> 5,0</td><td> 5,0</td>

<td>surfactant active Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

¹ Copolymer containing sulfonic acid groups

The overall picture of the items to be washed was evaluated using the rating scale given below, and the results are given in the following table (the values ​​given are the mean values ​​of 3 tests):

<td></td><td>WE</td><td>V2</td><td>V3</td><td>The</td>

<td>Creation</td><td>4.0 glass</td><td>2.2 glass</td><td>Glass 3.0</td><td>Glass 4.8</td>

<td>deposits</td><td>steel</td><td>steel</td><td>steel</td><td>steel</td>

<td></td><td>noble</td><td>noble</td><td>noble</td><td>noble</td>

<td></td><td>willing</td><td>willing</td><td>willing</td><td>willing</td>

<td></td><td> 3,2</td><td> 1, 9</td><td> 2,9</td><td> 5,0</td>

<td>Value average</td><td> 3, 6</td><td> 2, 1</td><td> 3,0</td><td> 4, 9</td>

Scale for assessing sediment formation: 10 = no sediment formation up to 0 = strong sediment formation.

Henkel AG &amp; Co. KGaA

Deputy:

MSc. Eda&gt; ar &lt;iEiiczyńsńi spokesman Palinowa

-45 OK II-12 / P35280EN00 EP 2 188 361 Pg