EP3415593B1 - Enhanced bleaching efficiency during methods of washing and cleaning - Google Patents

Description

The present invention relates to the use of certain polyoxometalates for activating molecular oxygen in connection with the bleaching of soils when washing textiles, washing and cleaning processes in which the polyoxometalates are used, and detergents and cleaning agents which contain the polyoxometalates.

Inorganic peroxygen compounds, especially hydrogen peroxide and solid peroxygen compounds, which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes. The oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H ₂ O ₂ or alkali perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, which are able to deliver peroxocarboxylic acids under the perhydrolysis conditions mentioned and for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds, for example several times acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurononoyl anonoyl anonoyl anoxides, especially sodium phthalic acid anhydride, benzenesulfonate, O-acylated sugar derivatives, such as pentaacetyl glucose, and N-acylated lactams, such as N-benzoylcaprolactam, have become known in the literature. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the peroxide liquor alone at 95 ° C.

In the effort to save energy in washing and bleaching, application temperatures significantly below 60 ° C, in particular below 45 ° C, down to the cold water temperature have become increasingly important in recent years.

At low temperatures, the activity of the activator compounds known to date generally diminishes noticeably.

From the European patent application EP 0 761 809 A1 Bleaching agents are known which contain peroxygen compounds and polyoxometalates as bleaching catalysts, whereby the polyoxometalates must contain Mo, W, Nn, Ta and / or V and may additionally contain transition metals of the 2nd and 8th subgroups. Specifically disclosed are (Na / N (CH ₃ ) ₄ ) ₈ [MnMo ₆ O ₂₄ ], K ₄ [MnMO ₆ O ₈ (OH) ₆ ], (NH ₄ ) ₁₀ [Mn ₃ Sb ₂ W ₁₉ O ₆₈ ], Na ₁₇ [Mn ₂ Se ₆ W ₂₄ O ₉₄ Cl], Na ₂ (N (CH ₃ ) ₄ ) ₂ [Mn ₂ W ₁₂ O ₄₀ (OH) ₁₂ ] · 12H ₂ O, (Na / K) ₁₀ [Mn ₃ Se ₂ W ₁₈ O ₆₆ ], Na ₈ [MnW ₁₂ O ₄₀ (OH) ₂ ] .6H ₂ O, Na ₆ [MnW ₁₂ O ₄₀ (OH) ₂ ]. 6H ₂ O, Na ₇ [MnMo ₉ O ₃₂ ], and K ₇ [MnMo ₉ O ₃₂ ].

From the international patent application WO 97/07886 A1 peroxidic compounds and / or oxygen-activating manganese catalysts of a general formula (Q) _q (Mn _p A _a X _x Y _y M _m O _d Z _z (H ₂ O) _b ) c H ₂ O are known, in which Q represents H, Li, K, Na, Rb, Cs, Ca, Mg, Sr, Ba, AI, PR ¹ R ² R ³ R ⁴ and / or NR ¹ R ² R ³ R ⁴ with R ¹ , R ² , R ³ and R ⁴ = H or C ₁ -C ₂₀ alkyl, C ₅ -C ₈ cycloalkyl or aryl; q is in the range of 1 to 60; p ranges from 0.1 to 10; A stands for one or more transition metals of the 2nd to 8th subgroup other than Zn; X represents Ga, B, P, Si, Ge, As, F, Cl, Br and / or J; Y represents Sb, S, Se, Te or Bi; y is in the range of 0.1 to 10; M represents Mo, W, Nb, Ta and / or V; m ranges from 0.5 to 60; Z represents one or more anions; a, x and z each range from 0 to 10; d stands for the number of oxygen atoms necessary to balance the charge; and b and c are numbers in the range of 0 to 50.

The international patent application WO 99/28426 A1 relates to compositions containing a bleaching agent and as a bleaching catalyst a polyoxocobaltate with a Keggin, Dawson or Finke structure.

The international patent application WO 00/39264 A1 relates to a bleaching process using a bleaching composition containing a polyoxometalate and air as the primary source of oxygen atoms. The polyoxometalates NaWO ₄ , H ₄ SiW ₁₂ O ₄₀ , H ₃ PW ₁₂ O ₄₀ , α- and γ-K ₈ SiW ₁₁ O ₃₉ , β-Na ₁₀ SiW ₉ O ₃₄ , α-K ₇ PW ₁₁ O are specifically disclosed ₃₉ , K ₇ SiVMnW ₁₀ O ₃₉ , K ₈ [P ₂ CuW ₁₇ O ₆₂ H ₂ ], K ₈ [P ₂ CuW ₁₇ O ₆₂ H ₂ ], K ₁₀ [α-2-P ₂ W ₁₇ O ₆₁ ], Cs ₅ NbSiW ₁₁ O ₄₀ , K ₅ (NbO ₂ ) SiW ₁₁ O ₃₉ , ((CH ₃ ) ₃ NH) ₄ (NbO ₂ ) PW ₁₁ O ₃₉ , K ₇ Mo ₂ VSiW ₉ O ₄₀ , K ₇ VMnSiW ₁₀ O ₃₉ and K ₇ VCoSiW ₁₀ O ₃₉ .

The so-called polyoxomolybdate nanoball (NH ₄ ) ₄₂ [M0 ^VI ₇₂ Mo ^V ₆₀ O ₃₇₂ (CH ₃ COO) ₃₀ (H ₂ O) ₇₂ ] is in JACS 2013, 135, 10036 - 10039 and in Appl. Chem. Int. Ed. 1998, 37, 3360-3362 described.

The present invention aims to improve the oxidation and bleaching effect of liquors used in washing textiles or cleaning hard surfaces, in particular at low temperatures in the range from approximately 10 ° C. to 45 ° C.

The invention relates to the use of (NH ₄ ) ₄₂ [MO ^VI ₇₂ Mo ^V ₆₀ O ₃₇₂ (CH ₃ COO) ₃₀ (H ₂ O) ₇₂ ] and only as much H ₂ O ₂ or in water H ₂ O ₂ delivering substance that its concentration (calculated as H ₂ O ₂ ) in the liquor is 0.01 mmol / l to 0.5 mmol / l, in particular 0.06 mmol / l to 0.12 mmol / l, for activation of molecular oxygen, in particular atmospheric oxygen, when washing textiles or cleaning hard surfaces in an aqueous, in particular surfactant-containing, liquor. A second object of the invention is the use of this polyoxometalate to enhance the cleaning performance of detergents or cleaning agents in aqueous, in particular surfactant-containing liquor in the presence of a gaseous phase which is present in addition to the liquid phase of the liquor and contains molecular oxygen, in particular atmospheric oxygen.

Another object of the invention is the use of (NH ₄ ) ₄₂ [Mo ^VI ₇₂ Mo ^V ₆₀ O ₃₇₂ (CH ₃ COO) ₃₀ (H ₂ O) ₇₂ ] for bleaching color stains when washing textiles in aqueous, in particular surfactant-containing, Liquor, or in aqueous, in particular surfactant-containing, cleaning solutions for hard surfaces, in particular for dishes, for bleaching colored stains, in particular tea, in the presence of a gaseous phase which is present in addition to the liquid phase of the liquor and contains molecular oxygen, in particular atmospheric oxygen . The formulation "bleaching of soiling" is to be understood in its broadest meaning and includes both the bleaching of colored dirt present on the textile, the bleaching of colored dirt located in the wash liquor and detached from the textile, and the oxidative destruction of itself in the washing liquor textile dyes that detach from textiles under the washing conditions before they can be drawn onto textiles of a different color.

The use according to the invention essentially consists in creating conditions under which the molecular oxygen provided in particular via the dosage form air and the polyoxometalate mentioned can react with one another with the aim of obtaining secondary products having a stronger oxidizing action. Such conditions exist in particular when the polyoxometalate is present in an aqueous system and in addition to the liquid phase of this aqueous system there is a gaseous phase, for example air, which contains molecular oxygen. This can penetrate into the aqueous system through the interface with the liquid phase and form a more oxidizing secondary product there or at the interface mentioned with the polyoxometalate. By mixing the liquid and the gaseous phase, the formation of the more oxidizing secondary product can be increased. The use of air at ambient pressure and temperature is possible. However, the formation of the more oxidizing secondary product can be achieved by using a gas phase which has a higher concentration of molecular oxygen and / or a molecular oxygen containing gas phase under increased pressure, if desired, and / or accelerated. If a gas phase which is not present at normal pressure or normal ambient pressure is used, a pressure up to 100 bar, in particular in the range from 10 bar to 80 bar, is preferred. The liquor containing the polyoxometalate can also contain the usual constituents of detergents or cleaning agents which, in the usual way, originate from the introduction of such agents into the liquor. Since the bleaching effect of the liquor is enhanced by the interaction of the polyoxometalate mentioned with molecular oxygen, the detergents or cleaning agents used in the preparation of the liquor can be free of peroxygen compounds. The formation of the more oxidizing derived product can be accelerated if one starts from an optionally washing or cleaning agent containing liquor that much contains H ₂ O ₂ or in water H ₂ O ₂ -liefernder substance that the concentration of which (calculated as H ₂ O ₂ ) in the liquor is 0.01 mmol / l to 0.5 mmol / l, in particular 0.06 mmol / l to 0.12 mmol / l. The reaction with the polyoxometalate consumes the H ₂ O ₂ or the substance which supplies H ₂ O ₂ in water, but does not have to be replaced, since the more strongly oxidizing secondary product after its reaction with soils to be bleached in the sense of a cycle with the aid of molecular Oxygen is regenerated. In embodiments of the invention, the washing or cleaning agent used in addition to the polyoxometalate in the liquor is therefore free of peroxygen compounds or contains only so much H ₂ O ₂ or H ₂ O ₂ -supplying substance in water that its concentration (calculated as H ₂ O ₂ ) in the liquor is 0.01 mmol / l to 0.5 mmol / l, in particular 0.06 mmol / l to 0.12 mmol / l. Since the peroxygen compound used does not completely dissolve at the same time and the H ₂ O ₂ in the liquor can react as described, the attempt to measure the concentration of H ₂ O ₂ in the liquor used for washing or cleaning is not very useful; the concentration ranges given above therefore relate to the H ₂ O ₂ that can be arithmetically released from the total amount of added agent.

The invention further relates to a method for washing laundry and a method for cleaning hard surfaces, comprising the process steps (a) providing an aqueous liquor containing said polyoxometalate, and (b) bringing this liquor into contact with textiles to be washed or hard surfaces to be cleaned in the presence of a gaseous phase which is present in addition to the liquid phase of the aqueous liquor and contains molecular oxygen, in particular atmospheric oxygen. The contact between the aqueous liquor and the object to be washed or cleaned is preferably established at temperatures in the range from 20 ° C. to 95 ° C., in particular from 30 ° C. to 60 ° C. The object to be washed or cleaned preferably remains in contact with the aqueous liquor over a period of 15 minutes to 2.5 hours, in particular 45 minutes to 1.5 hours. The methods according to the invention can be carried out manually or using conventional devices, for example washing machines or dishwashers.

Particularly in the case of mechanical use, process steps (a) and (b) do not have to be carried out in succession, but rather occur simultaneously when the product to be cleaned is introduced into the machine and then an agent which contains the polyoxometalate is rinsed in with water. In the context of a use according to the invention and a method according to the invention, the amounts of the polyxoxometalate mentioned are selected such that their concentration in the liquor is preferably in the range from 0.05 μmol / l to 5 μm / l, in particular 0.1 μmol / l to 0 , 12 µmol / l. The above-mentioned concentrations of H ₂ O ₂ or in water in the liquor supplying H ₂ O ₂ also apply to preferred embodiments of the process according to the invention.

The liquor used in the context of the invention preferably has a pH in the range from pH 6 to pH 14, in particular from pH 8.5 to pH 12.

Another object of the invention is a washing or cleaning agent containing surfactants and (NH ₄ ) ₄₂ [Mo ^VI ₇₂ Mo ^V ₆₀ O ₃₇₂ (CH ₃ COO) ₃₀ (H ₂ O) ₇₂ ]. Solid agents which can be used in the context of the present invention are generally 0.0005% by weight to 4% by weight, preferably 0.00076% by weight to 0.4% by weight, and contain in particular 0.0015% by weight to 0.01% by weight of the polyoxometalate defined above. In liquid compositions which can be used in the context of the present invention, preference is given to 0.0005% by weight to 6% by weight, preferably 0.0006% by weight to 0.54% by weight, and in particular contain 0.001% by weight to 0.013% by weight of the polyoxometalate defined above.

Detergents and cleaning agents, which can be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or as suspensions or dispersions, can, in addition to the bleach-boosting compound and surfactants used according to the invention, in principle contain all known ingredients which are customary in such agents. The detergents and cleaning agents can in particular contain builder substances, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators and colorants and fragrances.

Suitable peroxygen compounds which may additionally be present are in particular inorganic peroxygen compounds such as hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide inclusion compounds such as H ₂ O ₂ urea adducts. Hydrogen peroxide can also be generated using an enzymatic system, i.e. an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be in the form of powders or Granules are used, which can also be coated in a manner known in principle. The peroxygen compounds can be added to the washing or cleaning liquor as such or in the form of agents which, in principle, can contain all the usual washing or cleaning agent components. Alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide is particularly preferably used in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide. If a washing or cleaning agent used in the context of the invention contains peroxygen compounds, these are preferably in amounts of from 0.1% by weight to 50% by weight, in particular from 5% by weight to 20% by weight, and are particularly preferred from 7% by weight to 17% by weight and most preferably 8% by weight to 15% by weight.

The agents contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof. Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups. Corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical are also useful.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized. The surfactants of the sulfate type which can be used include the salts of the sulfuric acid semiesters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation. The surfactants of the sulfonate type that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, as well as alpha-sulfofatty acid esters, which arise in the sulfonation of fatty acid methyl or ethyl esters.

Such surfactants are contained in the detergents used in the context of the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, while detergents for cleaning hard surfaces , in particular of dishes, preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight of surfactants.

An agent used in the context of the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid, sugar acids and carboxymethylinulins, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-dyuccinodiacetic acid and ethylenediaminodiacetic acid, methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular polycarboxylates, polymeric acrylic acids, maleic acids and malic acids, methacrylic acids, methacrylic acids and methacrylic acids Mixed polymers of these, which can also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form. The relative average molecular weight (here and hereinafter: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50 000 g / mol to 120 000 g / mol, each based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 g / mol to 100,000 g / mol. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ -carboxylic acids, with vinyl alcohol are particularly preferred. Preferred polymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% vinyl alcohol and / or vinyl acetate. Polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleinate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 are very particularly preferred , 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is substituted in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight. %, preferably 15% by weight to 25% by weight of methallylsulfonic acid or methallylsulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight, of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred. The use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.

Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate. In particular, crystalline or amorphous, water-dispersible alkali alumosilicates are used as water-insoluble inorganic builder materials, in amounts of not more than 25% by weight, preferably from 3% by weight to 20% by weight and in particular in amounts of 5% by weight to 15% by weight. -% used. Among these, the detergent-grade crystalline sodium aluminosilicates, in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X, are preferred. Amounts close to the above upper limit are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Your calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram.

In addition or as an alternative to the water-insoluble aluminosilicate and alkali carbonate mentioned, further water-soluble inorganic builder materials can be contained. In addition to the polyphosphates such as sodium triphosphate, these include in particular the water-soluble crystalline and / or amorphous alkali silicate builders. Such water-soluble inorganic builder materials are preferably contained in amounts of from 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight. The alkali silicates that can be used as builder materials preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Crystalline phyllosilicates of the general formula Na ₂ Si _x O _{2x + 1} .yH ₂ O, in which x, the so-called modulus, is a number of 1, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates. 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disitikates (Na ₂ Si ₂ O ₅ .y H ₂ O) are preferred. Practically anhydrous crystalline alkali silicates of the general formula mentioned above, in which x denotes a number from 1.9 to 2.1, can also be used, produced from amorphous alkali silicates. A crystalline layered sodium silicate with a modulus of 2 to 3, as can be produced from sand and soda, is more preferably used. Sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment of the agent. In a preferred embodiment, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.

Machine dishwashing detergents are preferably low alkaline and contain the usual alkali carriers such as alkali silicates, alkali carbonates and / or alkali hydrogen carbonates. The alkali carriers usually used include carbonates, hydrogen carbonates and alkali silicates with a molar ratio SiO ₂ / M ₂ O (M = alkali atom) of 1.5: 1 to 2.5: 1. Alkali silicates can be used in amounts of up to 30% by weight. %, based on the total, may be included. The use of the highly alkaline metasilicates as alkali carriers is preferably avoided entirely. The alkali carrier system used with preference is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which is contained in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight. Depending on which pH value is ultimately desired, the ratio of carbonate and bicarbonate used varies, but an excess of sodium bicarbonate is usually used, so that the weight ratio between bicarbonate and carbonate is generally 1: 1 to 15: 1.

In a further embodiment of the agents for cleaning dishes, these contain 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali citrate, 5% by weight to 15% by weight of alkali carbonate and 20% by weight to Contain 40 wt .-% alkali disilicate.

Enzymes which may be present in the agents are in particular those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipase and / or cellulase is particularly preferred. The proportion is preferably 0.2% by weight to 1.5% by weight, in particular 0.5% by weight to 1% by weight. The enzymes can be adsorbed onto carrier substances in a conventional manner and / or embedded in coating substances or incorporated as concentrated liquid formulations which are as anhydrous as possible.

Suitable graying inhibitors or soil release agents are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Sodium carboxymethyl cellulose and mixtures thereof with methyl cellulose are preferably used. Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of graying inhibitors and / or soil release active ingredients is generally not more than 2% by weight and is preferably 0.5% by weight to 1.5% by weight, in each case based on the composition.

Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts, for example, can be present as optical brighteners for textiles made in particular from cellulose fibers (for example cotton). For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable Instead of the morpholino group, wear a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of brighteners can also be used. Brighteners of the 1,3-diaryl-2-pyrazoline type, for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of the same structure are particularly suitable for polyamide fibers. The content of optical brighteners or brightener mixtures in the agent is generally not more than 1% by weight, preferably 0.05% by weight to 0.5% by weight.

The usual foam regulators which can be used in the compositions include, for example, polysiloxane-silica mixtures, the fine-particle silica contained therein preferably being silanized or otherwise hydrophobized. The polysiloxanes can be made from both linear compounds as well as cross-linked polysiloxane resins and mixtures thereof. Further defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, whose melting point is above 40 ° C, saturated fatty acids or soaps with in particular 20 to 22 C atoms, for example sodium behenate, and alkali metal salts of phosphoric acid mono- and / or dialkyl esters, in which the alkyl chains each have 12 to 22 carbon atoms. Among these, sodium monoalkyl phosphate and / or dialkyl phosphate with C ₁₆ to C ₁₈ alkyl groups is preferably used. The proportion of foam regulators can preferably be 0.2% by weight to 2% by weight.

The organic solvents which can be used in the compositions, especially if they are in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers derived from the compound classes mentioned. Such water-miscible solvents are present in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight, based in each case on the composition.

To set a desired pH value, which does not result from the mixture of the other components, the agents can be system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides. Such pH regulators are preferably not contained in the agents above 10% by weight, in particular from 0.5% by weight to 6% by weight.

The preparation of solid agents presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, it being possible for the polyoxometalate to be added separately later, if appropriate.

Agents in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

Examples Example 1: Preparation of (NH ₄ ) ₄₂ [M0 ^VI ₇₂ Mo ^V ₆₀ O ₃₇₂ (CH ₃ COO) ₃₀ (H ₂ O) ₇₂ ]

0.8 g of hydrazinium sulfate (6.1 mmol) was added with stirring to a solution of 5.6 g of ammonium molybdate tetrahydrate (4.5 mmol) and 12.5 g of ammonium acetate (162 mmol) in 250 ml of water. After stirring for ten minutes, 83 ml of acetic acid (50 vol.%) Were added. The deep green reaction solution was left without stirring at room temperature for four days. During this time the color of the solution changed to dark brown. The solid was filtered off and washed first with 100 ml of ethanol (90%) and then with a 1: 1 mixture of ethanol and diethyl ether and air-dried. 3 g of (NH ₄ ) ₄₂ [Mo ^VI ₇₂ Mo ^V ₆₀ O ₃₇₂ (CH ₃ COO) ₃₀ (H ₂ O) ₇₂ ] were obtained.

Claims (10)

1. The use of (NH₄)₄₂[Mo^VI ₇₂Mo^V ₆₀O₃₇₂(CH₃COO)₃₀(H₂O)₇₂] for enhancing the cleaning performance of washing or cleaning agents in aqueous, in particular surfactant-containing, liquor in the presence of a gaseous phase that is present in addition to the liquid phase of the liquor and contains molecular oxygen, in particular atmospheric oxygen.
2. The use of (NH₄)₄₂[Mo^VI ₇₂Mo^V ₆₀O₃₇₂(CH₃COO)₃₀(H₂O)₇₂] for bleaching color stains when washing textiles in aqueous, in particular surfactant-containing, liquor, or in aqueous, in particular surfactant-containing, cleaning solutions for hard surfaces, in particular for dishes, for bleaching colored stains, in particular tea, in the presence of a gaseous phase that is present in addition to the liquid phase of the liquor and contains molecular oxygen, in particular atmospheric oxygen.
3. The use of (NH₄)₄₂[Mo^VI ₇₂Mo^V ₆₀O₃₇₂(CH₃COO)₃₀(H₂O)₇₂] and only such an amount of H₂O₂ or substance that yields H₂O₂ in water that the concentration thereof (calculated as H₂O₂) in the liquor is 0.01 mmol/l to 0.5 mmol/l, in particular 0.06 mmol/l to 0.12 mmol/l, for activating molecular oxygen, in particular atmospheric oxygen, when washing textiles or cleaning hard surfaces in an aqueous, in particular surfactant-containing, liquor.
4. The use according to one of claims 1 to 2, characterized in that, in addition to the polyoxometalate, a washing or cleaning agent is used which is free of peroxygen compounds.
5. The use according to one of claims 1 to 3, characterized in that, in addition to the polyoxometalate, a washing or cleaning agent is used which contains such an amount of H₂O₂ or substance that yields H₂O₂ in water that the concentration thereof (calculated as H₂O₂) in the liquor is 0.01 mmol/l to 0.5 mmol/l, in particular 0.06 mmol/l to 0.12 mmol/l.
6. A method for washing laundry, comprising the method steps of (a) providing an aqueous liquor containing (NH₄)₄₂[Mo^VI ₇₂Mo^V ₆₀O₃₇₂(CH₃COO)₃₀(H₂O)₇₂], and (b) bringing said liquor into contact with textiles to be washed in the presence of a gaseous phase that is present in addition to the liquid phase of the aqueous liquor and contains molecular oxygen, in particular atmospheric oxygen.
7. A method for cleaning hard surfaces, comprising the method steps of (a) providing an aqueous liquor containing (NH₄)₄₂[Mo^VI ₇₂Mo^V ₆₀O₃₇₂(CH₃COO)₃₀(H₂O)₇₂], and (b) bringing said liquor into contact with a hard surface to be cleaned in the presence of a gaseous phase that is present in addition to the liquid phase of the liquor and contains molecular oxygen, in particular atmospheric oxygen.
8. The method according to claim 6 or 7, characterized in that the contact between the aqueous liquor and the object to be washed or cleaned is made at temperatures in the range of from 20 °C to 95 °C, in particular from 30 °C to 60 °C, and/or in that the object to be washed or cleaned remains in contact with the liquor over a period of 15 minutes to 2.5 hours, in particular 45 minutes to 1.5 hours.
9. The method according to one of claims 6 to 8, characterized in that such an amount of H₂O₂ or substance that yields H₂O₂ in water is introduced into the liquor that the concentration thereof (calculated as H₂O₂) is 0.01 mmol/l to 0.5 mmol/l, in particular 0.06 mmol/l to 0.12 mmol/l.
10. A washing or cleaning agent containing (NH₄)₄₂[Mo^VI ₇₂Mo^V ₆₀O₃₇₂(CH₃COO)₃₀(H₂O)₇₂] and surfactants.