EP0845524A2 - Improved bleaching performance using tungstates and molybdates - Google Patents

Improved bleaching performance using tungstates and molybdates Download PDF

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Publication number
EP0845524A2
EP0845524A2 EP97120141A EP97120141A EP0845524A2 EP 0845524 A2 EP0845524 A2 EP 0845524A2 EP 97120141 A EP97120141 A EP 97120141A EP 97120141 A EP97120141 A EP 97120141A EP 0845524 A2 EP0845524 A2 EP 0845524A2
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EP
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Prior art keywords
weight
molybdate
cleaning
ammonium tungstate
alkali
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP97120141A
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German (de)
French (fr)
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EP0845524A3 (en
Inventor
Helmut Dipl.-Ing. Blum
Christian Dr. Dipl.-Chem. Nitsch
Siglinde Chem.-Ab. Erpenbach
Peter Dr. Dipl.-Chem. Jeschke
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0845524A2 publication Critical patent/EP0845524A2/en
Publication of EP0845524A3 publication Critical patent/EP0845524A3/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present invention relates to the use of tungstates and molybdate to enhance the bleaching effect of, in particular, inorganic peroxygen compounds when bleaching colored stains on hard Surfaces, and cleaning agents for hard surfaces, the tungstates or Molybdate included.
  • 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 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, for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic anhydrides, especially phthalic acid anhydride.
  • Carboxylic acid esters in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxybenzenesulfonate and acylated sugar derivatives, such as pentaacetyl glucose, 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.
  • the present invention has the improvement of the oxidation and bleaching effect of inorganic Peroxygen compounds at low temperatures below 80 ° C, especially in the temperature range of approx. 15 ° C to 45 ° C.
  • the invention relates to the use of alkali metal or ammonium tungstate and / or molybdate as an activator for in particular inorganic peroxygen compounds in aqueous cleaning solutions for hard surfaces, in particular for dishes.
  • the ammonium salts include those with the cation N + R 1 R 2 R 3 R 4 , in which R 1 to R 4 are independently hydrogen or a C 1-3 alkyl radical.
  • the alkali salts which can be used include in particular the sodium, potassium and lithium salts of tungstic acid and molybdic acid, alone or in mixtures.
  • bleaching refers to both the bleaching of itself on the hard Dirt, especially tea, as well as bleaching in the surface Dirt detached from the hard surface Understood.
  • the invention further relates to a method for cleaning hard surfaces, in particular of dishes using aqueous, optionally further detergent components, in particular oxidizing agents based on peroxygen, containing solution, and cleaning agents for hard surfaces, in particular cleaning agents for dishes and among these preferably those for use in mechanical cleaning processes which contain alkali metal or ammonium tungstate and / or - contain molybdate in combination with polycarboxylate and / or enzyme.
  • the use according to the invention consists essentially in the presence of a hard surface contaminated with colored stains create, among which a peroxidic oxidizing agent and the monomeric tungstates and / or molybdates can react with one another with the aim of being more oxidizing to obtain effective secondary products.
  • a peroxidic oxidizing agent and the monomeric tungstates and / or molybdates can react with one another with the aim of being more oxidizing to obtain effective secondary products.
  • Such conditions exist in particular when the reactants meet in aqueous solution. This can be done through separate Add the peroxygen compound and the tungstate and / or molybdate a solution containing detergent if necessary.
  • the method according to the invention is performed using an inventive method Detergent for hard surfaces, the alkali or Ammonium tungstate and / or molybdate in combination with polycarboxylate and / or Enzyme and optionally contains an oxidizing agent containing peroxy.
  • the peroxygen compound can also be separate, in bulk or as preferred aqueous solution or suspension, added to the solution if a peroxide-free Detergent is used.
  • the conditions can be varied widely depending on the intended use. So come in addition to purely aqueous solutions, also mixtures of water and suitable organic Solvents as a reaction medium in question.
  • the quantities of peroxygen compounds used are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5,000 ppm Active oxygen is present.
  • the amount of bleach enhancer used Tungsten or molybdate depends on the application. Depending on what you want Degree of activation, it is used in such amounts that 0.00001 mol to 0.5 mol, preferably 0.0001 mol to 0.2 mol of tungstate or molybdate per mole of peroxygen compound can be used, but in special cases these limits are also exceeded or undershot.
  • Cleaning agents according to the invention preferably contain 0.005% by weight to 5% by weight, in particular 0.05% by weight to 2% by weight of alkali metal or ammonium tungstate and / or molybdate in combination with 0.5% by weight to 60% by weight, in particular 1% by weight to 50 wt .-% monomeric and / or polymeric polycarboxylate and / or 0.01 wt .-% to 15% by weight, in particular 0.05% by weight to 10% by weight, of enzyme, in particular protease, Lipase and / or amylase.
  • the cleaning agents according to the invention in the form of granules, in powder or tablet form Solids, as other shaped bodies, homogeneous solutions or suspensions are present can, in addition to the combination mentioned, in principle all known and in such Contain common ingredients.
  • the agents according to the invention can in particular builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, foam regulators, contain additional peroxygen activators as well as colors and fragrances.
  • a cleaning agent for hard surfaces according to the invention can also abrasive components, in particular from the group comprising quartz flours, Wood flour. Plastic flours, chalks and micro glass balls and their mixtures, contain. Abrasives are preferred in the cleaning agents according to the invention do not contain more than 20% by weight, in particular from 5% by weight to 15% by weight.
  • Another object of the invention is a means for machine cleaning Tableware containing 15% to 65% by weight, in particular 20% to 60% by weight water-soluble builder component, 5% by weight to 25% by weight, in particular 8% by weight up to 17% by weight of bleaching agent based on oxygen, in each case based on the total agent, and 0.01 wt .-% to 5 wt .-% tungsten and / or molybdate contains, wherein at water-soluble builder also in combination with the tungstate and / or molybdate contained polycarboxylates.
  • Such a means is particular lower alkaline, i.e. its 1% by weight solution has a pH of 8 to 11.5, preferably 9 to 11.
  • alkali phosphates in the form their alkaline, neutral or acidic sodium or potassium salts may be present.
  • Examples include trisodium phosphate, tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Sodium hexametaphosphate and the corresponding potassium salts or mixtures from sodium and potassium salts. Their amounts can range up to about 60 wt .-%, in particular 5 wt .-% to 20 wt .-%, based on the total agent.
  • Other possible water-soluble builder components are polyphosphonates and phosphonate alkyl carboxylates, for example, organic polymers native or synthetic Origin of the type of polycarboxylates, particularly in hard water regions act as a co-builder.
  • Examples include polyacrylic acids and copolymers from maleic anhydride and acrylic acid and the sodium salts thereof Polymer acids.
  • Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • origin include oxidized starch, such as from the International patent application WO 94/05762 known, and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • the preferred builder components and preferably with tungstate or molybdate Combining polycarboxylates include the salts of citric acid, in particular Sodium citrate.
  • Trisodium citrate dihydrate can be fine or coarse crystalline Powder can be used.
  • the pH adjusted to the co-builder salts mentioned can also be used corresponding acids are present.
  • the enzymes contained in agents according to the invention include proteases, amylases, Pullulanases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
  • proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®
  • amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramy
  • the used Enzymes can, as for example in international patent applications WO 92/11347 or WO 94/23005 described, adsorbed on carriers and / or in Envelope substances are embedded to protect them against premature inactivation.
  • she are in the cleaning agents according to the invention preferably in amounts of up to Contain 10 wt .-%, in particular from 0.05 wt .-% to 5 wt .-%, being particularly preferably enzymes stabilized against oxidative degradation, for example from the international ones Patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known, can be used.
  • conventional bleach activators can be used known transition metal complexes and / or conventional bleach activators, that is Compounds that are optionally substituted under perhydrolysis conditions Perbenzoic acid and / or peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms result, are used.
  • the usual ones cited at the beginning are suitable Bleach activators, the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • acylates are preferred Alkylenediamines, especially tetraacerylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenyl sulfonates, in particular nonanoyl or isononanoyloxybenzenesulfonate, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetyl
  • the connection to tungsten and / or molybdate is preferably in the range of 1000: 1 up to 1: 4, especially from 800: 1 to 1: 1.
  • the main bleaches used are oxygen-based or alkali perborate mono tetrahydrate and / or alkali percarbonate into consideration, where sodium is the preferred alkali metal is.
  • the use of sodium percarbonate has in particular Dishwashing detergent benefits as it is particularly beneficial on the Corrosion behavior affects glasses.
  • the oxygen-based bleach is therefore preferably an alkali percarbonate, especially sodium percarbonate.
  • known peroxycarboxylic acids for example Dodecanediperic acid or phthalimidopercarboxylic acids, optionally on aromatics may be substituted.
  • the addition of small amounts known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as Magnesium sulfate may be useful.
  • the machine dishwashing detergents according to the invention preferably contain the customary alkali carriers such as, for example, alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 40% by weight, in particular 3% by weight to 30% by weight, based on the total composition, can be present.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which are contained in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight can.
  • agents according to the invention are 20% by weight to 60% by weight of water-soluble organic builder, in particular alkali citrate, 3% by weight to Contain 20 wt .-% alkali carbonate and 3 wt .-% to 40 wt .-% alkali disilicate.
  • surfactants in particular anionic surfactants, zwitterionic surfactants and preferably low-foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to better detach fatty soils, as wetting agents and, if appropriate, as granulating aids in the preparation of the cleaning agents.
  • Their amount can be up to 20% by weight, in particular up to 10% by weight, and is preferably in the range from 0.5% by weight to 5% by weight.
  • Extremely low-foaming compounds are usually used in particular in cleaning agents for use in automatic dishwashing processes.
  • C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • you can also use other known low-foaming nonionic surfactants such as C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped alkyl polyalkylene glycol mixed ethers and the foaming but ecologically attractive C 8 -C 14- alkyl polyglucosides with a degree of polymerization of about 1 to 4 (e.g.
  • surfactants from the family of glucamides such as, for example, alkyl-N-methyl-glucamides, in which the alkyl part preferably originates from a fatty alcohol with the C chain length C 6 -C 14 . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides. The presence of amine oxides, betaines and ethoxylated alkylamines is also possible.
  • silver corrosion inhibitors can be used for dishes.
  • Preferred silver corrosion inhibitor are organic sulfides like cystine and cysteine, bi- or trivalent phenols, optionally alkyl- or aryl-substituted triazoles such as Benzotriazole, isocyanuric acid, manganese, titanium, zirconium, hafnium, vanadium or Cerium salts and / or complexes in which the metals mentioned, depending on the metal, in one of the Oxidation levels II, III, IV, V or VI are present.
  • the cleaning agents for example in the presence of anionic surfactants, at the Application foam too much, they can still up to 6 wt .-%, preferably about 0.5 wt .-% to 4 wt .-% of a foam suppressing compound, preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis fatty acid amides, and other other known commercially available defoamers will.
  • a foam suppressing compound preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis fatty acid amides, and other other known commercially available defoamers will.
  • Other optional ingredients in the agents according to the invention are for example perfume oils.
  • usable organic solvents include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, Diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and their mixtures and the ethers derived from the compound classes mentioned.
  • Such water-miscible solvents are in the cleaning agents according to the invention preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight, available.
  • the agents according to the invention cannot system and pH environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, malic acid, Lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, however also mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
  • pH regulators are preferably not more than 10% by weight, in particular, in the agents according to the invention from 0.5% by weight to 6% by weight.
  • the preparation of the solid compositions according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, take place, the peroxygen compound and bleaching catalyst possibly later be added separately.
  • Cleaning agents according to the invention in the form of aqueous or other conventional Solutions containing solvents are particularly advantageous by simple Mixing the ingredients in bulk or as a solution in an automatic Mixers can be made.
  • the agents according to the invention are preferably powdered, granular or tablet-shaped preparations in a known manner, for example by Mixing, granulating, roller compacting and / or by spray drying the thermally resilient components and admixing the more sensitive components, to which in particular enzymes, bleaching agents and the bleaching catalyst are to be counted, can be produced.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with compression pressures in the range from 200 ⁇ 10 5 Pa to 1 500 ⁇ 10 5 Pa pressed.
  • conventional tablet presses for example eccentric presses or rotary presses
  • compression pressures in the range from 200 ⁇ 10 5 Pa to 1 500 ⁇ 10 5 Pa pressed.
  • unbreakable tablets are obtained which, under application conditions, dissolve sufficiently quickly, with bending strengths of normally over 150 N.
  • a tablet manufactured in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • agents according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 up to 1000 g / l can be achieved in that the Builder components with at least a portion of liquid mixture components mixed by increasing the bulk density of this premix and subsequently - if desired after intermediate drying - the other components of the agent, including the bleach catalyst, combined with the premix obtained in this way.
  • Means for cleaning dishes according to the invention can be used both in household dishwashers as used in commercial dishwashers. The addition is done by hand or by means of suitable dosing devices.
  • the application concentrations in the cleaning liquor are usually about 1 to 8 g / l, preferably 2 to 5 g / l.
  • a machine wash program is generally followed by some on the Cleaning cycle following intermediate rinse cycles with clear water and one Rinse aid supplemented with a customary rinse aid and ended. After this Drying gives a completely clean and in when using agents according to the invention hygienically perfect dishes.
  • the agent M7 was tested according to Example 1 in comparison to an agent V2 which was otherwise composed like M7 and which lacked the molybdate, an agent V3 which was otherwise composed like M7 and which lacked the amylase granules, and an agent V4 which otherwise how M7 was composed and which lacked both the molybdate and the amylase granules. It can be seen that the agent M7 according to the invention has a higher cleaning performance than would have been expected from the results of the agents V2 and V3 . Sheet removal marks medium Removal of deposits M7 17th V2 11 V3 10th V4 6

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Abstract

Activators for (preferably inorganic) peroxy compounds in aqueous detergent solutions for hard surfaces, especially crockery, comprise alkali or ammonium tungstate and/or molybdate compounds. Also claimed are (i) the use of these compounds in detergent solutions for cleaning hard surfaces, especially crockery, for bleaching coloured stains, (ii) a cleaning method for hard surfaces, especially crockery, using these aqueous detergent solutions which may also contain other cleaning agents, (iii) detergents for cleaning hard surfaces, containing combinations of these compounds with polycarboxylates and/or enzymes and (iv) the same detergents for cleaning crockery, especially for use in dishwashers.

Description

Die vorliegende Erfindung betrifft die Verwendung von Wolframaten und Molybdaten zur Verstärkung der Bleichwirkung von insbesondere anorganischen Persauerstoffverbindungen beim Bleichen von gefärbten Anschmutzungen an harten Oberflächen, und Reinigungsmittel für harte Oberflächen, die Wolframate beziehungsweise Molybdate enthalten.The present invention relates to the use of tungstates and molybdate to enhance the bleaching effect of, in particular, inorganic peroxygen compounds when bleaching colored stains on hard Surfaces, and cleaning agents for hard surfaces, the tungstates or Molybdate included.

Anorganische Persauerstoffverbindungen, insbesondere Wasserstoffperoxid und feste Persauerstoffverbindungen, die sich in Wasser unter Freisetzung von Wasserstoffperoxid lösen, wie Natriumperborat und Natriumcarbonat-Perhydrat, werden seit langem als Oxidationsmittel zu Desinfektions- und Bleichzwecken verwendet. Die Oxidationswirkung dieser Substanzen hängt in verdünnten Lösungen stark von der Temperatur ab; so erzielt man beispielsweise mit H2O2 oder Perborat in alkalischen Bleichflotten erst bei Temperaturen oberhalb von etwa 80 °C eine ausreichend schnelle Bleiche verschmutzter Textilien. Bei niedrigeren Temperaturen kann die Oxidationswirkung der anorganischen Persauerstoffverbindungen durch Zusatz sogenannter Bleichaktivatoren verbessert werden, für die zahlreiche Vorschläge, vor allem aus den Stoffklassen der N- oder O-Acylverbindungen. beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Hydrotriazine, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid. Carbonsäureester, insbesondere Natrium-nonanoyloxy-benzolsulfonat, Natrium-isononanoyloxybenzolsulfonat und acylierte Zuckerderivate, wie Pentaacetylglukose, in der Literatur bekannt geworden sind. Durch Zusatz dieser Substanzen kann die Bleichwirkung wäßriger Peroxidflotten so weit gesteigert werden, daß bereits bei Temperaturen um 60 °C im wesentlichen die gleichen Wirkungen wie mit der Peroxidflotte allein bei 95 °C eintreten.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 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, for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds. for example polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic anhydrides, especially phthalic acid anhydride. Carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxybenzenesulfonate and acylated sugar derivatives, such as pentaacetyl glucose, 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.

Im Bemühen um energiesparende Wasch- und Bleichverfahren gewinnen in den letzten Jahren Anwendungstemperaturen deutlich unterhalb 60 °C, insbesondere unterhalb 45 °C bis herunter zur Kaltwassertemperatur an Bedeutung. In the effort for energy-saving washing and bleaching processes have won in the last Years of application temperatures well below 60 ° C, especially below 45 ° C down to the cold water temperature in importance.

Bei diesen niedrigen Temperaturen läßt die Wirkung der bisher bekannten Aktivatorverbindungen in der Regel erkennbar nach. Es hat deshalb nicht an Bestrebungen gefehlt, für diesen Temperaturbereich wirksamere Aktivatoren zu entwickeln, ohne daß bis heute ein überzeugender Erfolg zu verzeichnen gewesen wäre. Ein Ansatzpunkt dazu ergibt sich durch den Einsatz von Übergangsmetallsalzen und -komplexen, wie zum Beispiel in den europäischen Patentanmeldungen EP 392 592, EP 443 651, EP 458 397, EP 544 490 oder EP 549 271 vorgeschlagen, als sogenannte Bleichkatalysatoren. Bei diesen besteht, vermutlich wegen der hohen Reaktivität der aus ihnen und der Persauerstoffverbindung entstehenden oxidierenden Intermediate, die Gefahr der Farbveränderung gefärbter Textilien und im Extremfall der oxidativen Textilschädigung. In der europäischen Patentanmeldung EP 272 030 werden Cobalt(III)-Komplexe mit Ammoniak-Liganden, die außerdem beliebige weitere ein-, zwei-, drei- und/oder vierzähnige Liganden aufweisen können, als Aktivatoren für H2O2 zum Einsatz in Textilwasch- oder -bleichmitteln beschrieben. Die internationalen Patentanmeldungen WO 96/23859, WO 96/23860 und WO 96/23861 betreffen den Einsatz entsprechender Co(III)-Komplexe in Mitteln zum automatischen Reinigen von Geschirr. Aus der europäischen Patentanmeldung EP 630 964 sind bestimmte Mangankomplexe bekannt, welche keinen ausgeprägten Effekt hinsichtlich einer Bleichverstärkung von Persauerstoffverbindungen haben und gefärbte Textilfasern nicht entfärben, aber die Bleiche von in Waschlaugen befindlichem, von der Faser abgelöstem Schmutz oder Farbstoff bewirken können. Aus der deutschen Patentanmeldung DE 44 16 438 sind Mangan-, Kupfer- und Cobalt-Komplexe bekannt, welche Liganden aus einer Vielzahl von Stoffgruppen tragen können und als Bleich- und Oxidationskatalysatoren verwendet werden sollen. Die japanische Patentanmeldung 6/041 593 A offenbart wasserlösliche Molybdän- oder Wolframverbindungen als Bleichaktivatoren für Bleichmittel auf Sauerstoffbasis zur Anwendung in der Textilwäsche.At these low temperatures, the effect of the activator compounds known to date generally diminishes appreciably. There has been no shortage of efforts to develop more effective activators for this temperature range without convincing success to date. One approach to this arises from the use of transition metal salts and complexes, as proposed, for example, in European patent applications EP 392 592, EP 443 651, EP 458 397, EP 544 490 or EP 549 271, as so-called bleaching catalysts. With these, presumably because of the high reactivity of the oxidizing intermediates formed from them and the peroxygen compound, there is a risk of color change in colored textiles and, in extreme cases, of oxidative textile damage. In European patent application EP 272 030, cobalt (III) complexes with ammonia ligands, which can also have any further one, two, three and / or tidentate ligands, are used as activators for H 2 O 2 in textile washing - or bleaches described. International patent applications WO 96/23859, WO 96/23860 and WO 96/23861 relate to the use of corresponding Co (III) complexes in agents for automatically cleaning dishes. From European patent application EP 630 964, certain manganese complexes are known which have no pronounced effect with regard to a bleaching enhancement of peroxygen compounds and which do not discolor dyed textile fibers, but which can cause the bleaching of dirt or dye which is detached from the fiber and which is detached from the fiber. German patent application DE 44 16 438 discloses manganese, copper and cobalt complexes which can carry ligands from a large number of groups of substances and are to be used as bleaching and oxidation catalysts. Japanese patent application 6/041 593 A discloses water-soluble molybdenum or tungsten compounds as bleach activators for oxygen-based bleaches for use in textile washing.

Die vorliegende Erfindung hat die Verbesserung der Oxidations- und Bleichwirkung anorganischer Persauerstoffverbindungen bei niedrigen Temperaturen unterhalb von 80 °C, insbesondere im Temperaturbereich von ca. 15 °C bis 45 °C, zum Ziel. The present invention has the improvement of the oxidation and bleaching effect of inorganic Peroxygen compounds at low temperatures below 80 ° C, especially in the temperature range of approx. 15 ° C to 45 ° C.

Es wurde nun gefunden, daß Wolframate und Molybdate einen deutlichen Beitrag zur Reinigungsleistung gegenüber gefärbten Anschmutzungen leisten, die sich an harten Oberflächen befinden, insbesondere wenn man sie in Form einer Kombination mit bestimmten weiteren Wirkstoffen einsetzt.It has now been found that tungstates and molybdates make a significant contribution to Perform cleaning performance against colored stains that adhere to hard Surfaces, especially if you combine them with certain other active ingredients.

Gegenstand der Erfindung ist die Verwendung von Alkali- oder Ammoniumwolframat und/oder -molybdat als Aktivator für insbesondere anorganische Persauerstoffverbindungen in wäßrigen Reinigungslösungen für harte Oberflächen, insbesondere für Geschirr. Zu den Ammoniumsalzen gehören solche mit dem Kation N+R1R2R3R4, in dem R1 bis R4 unabhängig voneinander Wasserstoff oder ein C1-3-Alkylrest ist. Zu den verwendbaren Alkalisalzen gehören insbesondere die Natrium-, Kalium- und Lithiumsalze der Wolframsäure beziehungsweise der Molybdänsäure, allein oder in Mischungen.The invention relates to the use of alkali metal or ammonium tungstate and / or molybdate as an activator for in particular inorganic peroxygen compounds in aqueous cleaning solutions for hard surfaces, in particular for dishes. The ammonium salts include those with the cation N + R 1 R 2 R 3 R 4 , in which R 1 to R 4 are independently hydrogen or a C 1-3 alkyl radical. The alkali salts which can be used include in particular the sodium, potassium and lithium salts of tungstic acid and molybdic acid, alone or in mixtures.

Unter dem Begriff der Bleiche wird hier sowohl das Bleichen von sich auf der harten Oberfläche befindendem Schmutz, insbesondere Tee, als auch das Bleichen von in der Geschirrspülflotte befindlichem, von der harten Oberfläche abgelöstem Schmutz verstanden.The term bleaching here refers to both the bleaching of itself on the hard Dirt, especially tea, as well as bleaching in the surface Dirt detached from the hard surface Understood.

Weiterhin betrifft die Erfindung ein Verfahren zur Reinigung von harten Oberflächen, insbesondere von Geschirr unter Einsatz von in wäßriger, gegebenenfalls weitere Reinigungsmittelbestandteile, insbesondere Oxidationsmittel auf Persauerstoffbasis, enthaltender Lösung, und Reinigungsmittel für harte Oberflächen, insbesondere Reinigungsmittel für Geschirr und unter diesen vorzugsweise solche für den Einsatz in maschinellen Reinigungsverfahren, die Alkali- oder Ammoniumwolframat und/oder - molybdat in Kombination mit Polycarboxylat und/oder Enzym enthalten.The invention further relates to a method for cleaning hard surfaces, in particular of dishes using aqueous, optionally further detergent components, in particular oxidizing agents based on peroxygen, containing solution, and cleaning agents for hard surfaces, in particular cleaning agents for dishes and among these preferably those for use in mechanical cleaning processes which contain alkali metal or ammonium tungstate and / or - contain molybdate in combination with polycarboxylate and / or enzyme.

Die erfindungsgemäße Verwendung besteht im wesentlichen darin, in Gegenwart einer mit gefärbten Anschmutzungen verunreinigten harten Oberfläche Bedingungen zu schaffen, unter denen ein peroxidisches Oxidationsmittel und die monomeren Wolframate und/oder Molybdate miteinander reagieren können, mit dem Ziel, stärker oxidierend wirkende Folgeprodukte zu erhalten. Solche Bedingungen liegen insbesondere dann vor, wenn die Reaktionspartner in wäßriger Lösung aufeinander treffen. Dies kann durch separate Zugabe der Persauerstoffverbindung und des Wolframats und/oder Molybdats zu einer gegebenenfalls reinigungsmittelhaltigen Lösung geschehen. Besonders vorteilhaft wird das erfindungsgemäße Verfahren jedoch unter Verwendung eines erfindungsgemäßen Reinigungsmittels für harte Oberflächen, das Alkali- oder Ammoniumwolframat und/oder -molybdat in Kombination mit Polycarboxylat und/oder Enzym und gegebenenfalls ein persauerstoffhaltiges Oxidationsmittel enthält, durchgeführt. Die Persauerstoffverbindung kann auch separat, in Substanz oder als vorzugsweise wäßrige Lösung oder Suspension, zur Lösung zugegeben werden, wenn ein peroxidfreies Reinigungsmittel verwendet wird.The use according to the invention consists essentially in the presence of a hard surface contaminated with colored stains create, among which a peroxidic oxidizing agent and the monomeric tungstates and / or molybdates can react with one another with the aim of being more oxidizing to obtain effective secondary products. Such conditions exist in particular when the reactants meet in aqueous solution. This can be done through separate Add the peroxygen compound and the tungstate and / or molybdate a solution containing detergent if necessary. Particularly advantageous However, the method according to the invention is performed using an inventive method Detergent for hard surfaces, the alkali or Ammonium tungstate and / or molybdate in combination with polycarboxylate and / or Enzyme and optionally contains an oxidizing agent containing peroxy. The peroxygen compound can also be separate, in bulk or as preferred aqueous solution or suspension, added to the solution if a peroxide-free Detergent is used.

Je nach Verwendungszweck können die Bedingungen weit variiert werden. So kommen neben rein wäßrigen Lösungen auch Mischungen aus Wasser und geeigneten organischen Lösungsmitteln als Reaktionsmedium in Frage. Die Einsatzmengen an Persauerstoffverbindungen werden im allgemeinen so gewählt, daß in den Lösungen zwischen 10 ppm und 10 % Aktivsauerstoff, vorzugsweise zwischen 50 ppm und 5 000 ppm Aktivsauerstoff vorhanden sind. Auch die verwendete Menge an bleichverstärkendem Wolframat beziehungsweise Molybdat hängt vom Anwendungszweck ab. Je nach gewünschtem Aktivierungsgrad wird es in solchen Mengen eingesetzt, daß 0,00001 Mol bis 0.5 Mol, vorzugsweise 0,0001 Mol bis 0,2 Mol Wolframat beziehungsweise Molybdat pro Mol Persauerstoffverbindung verwendet werden, doch können in besonderen Fällen diese Grenzen auch über- oder unterschritten werden.The conditions can be varied widely depending on the intended use. So come in addition to purely aqueous solutions, also mixtures of water and suitable organic Solvents as a reaction medium in question. The quantities of peroxygen compounds used are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5,000 ppm Active oxygen is present. Also the amount of bleach enhancer used Tungsten or molybdate depends on the application. Depending on what you want Degree of activation, it is used in such amounts that 0.00001 mol to 0.5 mol, preferably 0.0001 mol to 0.2 mol of tungstate or molybdate per mole of peroxygen compound can be used, but in special cases these limits are also exceeded or undershot.

In erfindungsgemäßen Reinigungsmitteln sind vorzugsweise 0,005 Gew.-% bis 5 Gew.-%, insbesondere 0,05 Gew.-% bis 2 Gew.-% Alkali- oder Ammoniumwolframat und/oder -molybdat in Kombination mit 0,5 Gew.-% bis 60 Gew.-%, insbesondere 1 Gew.-% bis 50 Gew.-% monomerem und/oder polymerem Polycarboxylat und/oder 0,01 Gew.-% bis 15 Gew.-%, insbesondere 0.05 Gew.-% bis 10 Gew.-% Enzym, insbesondere Protease, Lipase und/oder Amylase, enthalten. Es wurde beobachtet, daß durch die Anwesenheit des bleichverstärkenden Wirkstoffs der Beitrag des Polycarboxylats und des Enzyms zur Reinigungsleistung des Mittels verstärkt wird, während andererseits die bleichverstärkende Wirkung der Wolframate und Molybdate bei Anwesenheit von Polycarboxylat und/oder Enzym besonders ausgeprägt ist.Cleaning agents according to the invention preferably contain 0.005% by weight to 5% by weight, in particular 0.05% by weight to 2% by weight of alkali metal or ammonium tungstate and / or molybdate in combination with 0.5% by weight to 60% by weight, in particular 1% by weight to 50 wt .-% monomeric and / or polymeric polycarboxylate and / or 0.01 wt .-% to 15% by weight, in particular 0.05% by weight to 10% by weight, of enzyme, in particular protease, Lipase and / or amylase. It was observed that by the presence of the bleach-enhancing active ingredient the contribution of the polycarboxylate and the enzyme to Cleaning performance of the agent is enhanced, while the other hand bleach-enhancing effect of the tungstates and molybdates in the presence of Polycarboxylate and / or enzyme is particularly pronounced.

Die erfindungsgemäßen Reinigungsmittel, die als Granulate, pulver- oder tablettenförmige Feststoffe, als sonstige Formkörper, homogene Lösungen oder Suspensionen vorliegen können, können außer der genannten Kombination im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. Die erfindungsgemäßen Mittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, Persauerstoffverbindungen, wassermischbare organische Lösungsmittel, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie Silberkorrosionsinhibitoren, Schaumregulatoren, zusätzliche Persauerstoff-Aktivatoren sowie Farb- und Duftstoffe enthalten.The cleaning agents according to the invention, in the form of granules, in powder or tablet form Solids, as other shaped bodies, homogeneous solutions or suspensions are present can, in addition to the combination mentioned, in principle all known and in such Contain common ingredients. The agents according to the invention can in particular builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, foam regulators, contain additional peroxygen activators as well as colors and fragrances.

Ein erfindungsgemäßes Reinigungsmittel für harte Oberflächen kann darüber hinaus abrasiv wirkende Bestandteile, insbesondere aus der Gruppe umfassend Quarzmehle, Holzmehle. Kunststoffmehle, Kreiden und Mikroglaskugeln sowie deren Gemische, enthalten. Abrasivstoffe sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 5 Gew.-% bis 15 Gew.-%, enthalten.A cleaning agent for hard surfaces according to the invention can also abrasive components, in particular from the group comprising quartz flours, Wood flour. Plastic flours, chalks and micro glass balls and their mixtures, contain. Abrasives are preferred in the cleaning agents according to the invention do not contain more than 20% by weight, in particular from 5% by weight to 15% by weight.

Ein weiterer Erfindungsgegenstand ist ein Mittel zum maschinellen Reinigen von Geschirr, enthaltend 15 Gew.-% bis 65 Gew.-%, insbesondere 20 Gew.-% bis 60 Gew.-% wasserlösliche Builderkomponente, 5 Gew.-% bis 25 Gew.-%, insbesondere 8 Gew.-% bis 17 Gew.-% Bleichmittel auf Sauerstoffbasis, jeweils bezogen auf das gesamte Mittel, und 0,01 Gew.-% bis 5 Gew.-% Wolframat und/oder Molybdat enthält, wobei zum wasserlöslichem Builder auch die in Kombination mit dem Wolframat und/oder Molybdat enthaltenen Polycarboxylate gehören. Ein derartiges Mittel ist insbesondere niederalkalisch, das heißt seine 1-gewichtsprozentige Lösung weist einen pH-Wert von 8 bis 11,5, vorzugsweise 9 bis 11 auf.Another object of the invention is a means for machine cleaning Tableware containing 15% to 65% by weight, in particular 20% to 60% by weight water-soluble builder component, 5% by weight to 25% by weight, in particular 8% by weight up to 17% by weight of bleaching agent based on oxygen, in each case based on the total agent, and 0.01 wt .-% to 5 wt .-% tungsten and / or molybdate contains, wherein at water-soluble builder also in combination with the tungstate and / or molybdate contained polycarboxylates. Such a means is particular lower alkaline, i.e. its 1% by weight solution has a pH of 8 to 11.5, preferably 9 to 11.

Als wasserlösliche Builderkomponenten in erfindungsgemäßen Reinigungsmitteln kommen prinzipiell alle in Mitteln für die maschinelle Reinigung von Geschirr üblicherweise eingesetzten Builder in Frage, zum Beispiel Alkaliphosphate, die in Form ihrer alkalischen, neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können. As water-soluble builder components in cleaning agents according to the invention In principle, all come in agents for the automatic cleaning of dishes commonly used builders in question, for example alkali phosphates, in the form their alkaline, neutral or acidic sodium or potassium salts may be present.

Beispiele hierfür sind Trinatriumphosphat, Tetranatriumdiphosphat, Dinatriumdihydrogendiphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat sowie die entsprechenden Kaliumsalze beziehungsweise Gemische aus Natrium- und Kaliumsalzen. Ihre Mengen können im Bereich von bis zu etwa 60 Gew.-%, insbesondere 5 Gew.-% bis 20 Gew.-%, bezogen auf das gesamte Mittel liegen. Weitere mögliche wasserlösliche Builderkomponenten sind neben Polyphosphonaten und Phosphonatalkylcarboxylaten zum Beispiel organische Polymere nativen oder synthetischen Ursprungs vom Typ der Polycarboxylate, die insbesondere in Hartwasserregionen als Co-Builder wirken. In Betracht kommen beispielsweise Polyacrylsäuren und Copolymere aus Maleinsäureanhydrid und Acrylsäure sowie die Natriumsalze dieser Polymersäuren. Handelsübliche Produkte sind zum Beispiel Sokalan® CP 5, CP 10 und PA 30 der Firma BASF. Zu den als Co-Builder brauchbaren Polymeren nativen Ursprungs gehören beispielsweise oxidierte Stärke, wie zum Beispiel aus der internationalen Patentanmeldung WO 94/05762 bekannt, und Polyaminosäuren wie Polyglutaminsäure oder Polyasparaginsäure. Weitere mögliche Builderkomponenten sind natürlich vorkommende Hydroxycarbonsäuren wie zum Beispiel Mono-, Dihydroxybernsteinsäure, α-Hydroxypropionsäure und Gluconsäure. Zu den bevorzugten Builderkomponenten und mit Wolframat beziehungsweise Molybdat bevorzugt zu kombinierenden Polycarboxylaten gehören die Salze der Citronensäure, insbesondere Natriumcitrat. Als Natriumcitrat kommen wasserfreies Trinatriumcitrat und vorzugsweise Trinatriumcitratdihydrat in Betracht. Trinatriumcitratdihydrat kann als fein- oder grobkristallines Pulver eingesetzt werden. In Abhängigkeit vom letztlich in den erfindungsgemäßen Mitteln eingestellten pH-Wert können auch die zu den genannten Co-Builder-Salzen korrespondierenden Säuren vorliegen.Examples include trisodium phosphate, tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Sodium hexametaphosphate and the corresponding potassium salts or mixtures from sodium and potassium salts. Their amounts can range up to about 60 wt .-%, in particular 5 wt .-% to 20 wt .-%, based on the total agent. Other possible water-soluble builder components are polyphosphonates and phosphonate alkyl carboxylates, for example, organic polymers native or synthetic Origin of the type of polycarboxylates, particularly in hard water regions act as a co-builder. Examples include polyacrylic acids and copolymers from maleic anhydride and acrylic acid and the sodium salts thereof Polymer acids. Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. To the native polymers useful as co-builders For example, origin include oxidized starch, such as from the International patent application WO 94/05762 known, and polyamino acids such as polyglutamic acid or polyaspartic acid. Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic acid, α-hydroxypropionic acid and gluconic acid. The preferred builder components and preferably with tungstate or molybdate Combining polycarboxylates include the salts of citric acid, in particular Sodium citrate. Anhydrous trisodium citrate and preferably come as sodium citrate Trisodium citrate dihydrate. Trisodium citrate dihydrate can be fine or coarse crystalline Powder can be used. Depending on the ultimately in the invention The pH adjusted to the co-builder salts mentioned can also be used corresponding acids are present.

Zu den in erfindungsgemäßen Mitteln enthaltenen Enzymen gehören Proteasen, Amylasen, Pullulanasen, Cutinasen und/oder Lipasen, beispielsweise Proteasen wie BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® und/oder Savinase®, Amylasen wie Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® und/oder Lipasen wie Lipolase®, Lipomax®, Lumafast® und/oder Lipozym®. Die verwendeten Enzyme können, wie zum Beispiel in den internationalen Patentanmeldungen WO 92/11347 oder WO 94/23005 beschrieben, an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise in Mengen bis zu 10 Gew.-%, insbesondere von 0,05 Gew.-% bis 5 Gew.-%, enthalten, wobei besonders bevorzugt gegen oxidativen Abbau stabilisierte Enzyme, wie zum Beispiel aus den internationalen Patentanmeldungen WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 oder WO 95/07350, bekannt, eingesetzt werden.The enzymes contained in agents according to the invention include proteases, amylases, Pullulanases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. The used Enzymes can, as for example in international patent applications WO 92/11347 or WO 94/23005 described, adsorbed on carriers and / or in Envelope substances are embedded to protect them against premature inactivation. she are in the cleaning agents according to the invention preferably in amounts of up to Contain 10 wt .-%, in particular from 0.05 wt .-% to 5 wt .-%, being particularly preferably enzymes stabilized against oxidative degradation, for example from the international ones Patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known, can be used.

Zusätzlich zu Wolframat und/oder Molybdat können übliche als Bleichaktivatoren bekannte Übergangsmetallkomplexe und/oder konventionelle Bleichaktivatoren, das heißt Verbindungen, die unter Perhydrolysebedingungen gegebenenfalls substituierte Perbenzoesäure und/oder Peroxocarbonsäuren mit 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen ergeben, eingesetzt werden. Geeignet sind die eingangs zitierten üblichen Bleichaktivatoren, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacerylethylendiamin (TAED), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Phenylsulfonate, insbesondere Nonanoyl- oder Isononanoyloxybenzolsulfonat, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran sowie acetyliertes Sorbit und Mannit, und acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton. Auch die aus der deutschen Patentanmeldung DE 44 43 177 bekannten Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. In einer bevorzugten Ausführungsform der erfindungsgemäßen Verwendung wird gleichzeitig mit dem Wolframat und/oder Molybdat auch eine derartige unter Perhydrolysebedingungen Peroxocarbonsäure abspaltende Verbindung verwendet. In einer bevorzugten Ausführungsform erfindungsgemäßer Mittel sind zusätzlich zu Wolframat und/oder Molybdat 1 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew.-% bis 6 Gew.-% an derartiger unter Perhydrolysebedingungen Peroxocarbonsäure abspaltender Verbindung anwesend. Das Gewichtsverhältnis von unter Perhydrolysebedingungen Peroxocarbonsäure abspaltender Verbindung zu Wolframat und/oder Molybdat liegt vorzugsweise im Bereich von 1000:1 bis 1:4, insbesondere von 800:1 bis 1:1.In addition to tungstate and / or molybdate, conventional bleach activators can be used known transition metal complexes and / or conventional bleach activators, that is Compounds that are optionally substituted under perhydrolysis conditions Perbenzoic acid and / or peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms result, are used. The usual ones cited at the beginning are suitable Bleach activators, the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multiple acylates are preferred Alkylenediamines, especially tetraacerylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenyl sulfonates, in particular nonanoyl or isononanoyloxybenzenesulfonate, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose and also acetylated, optionally N-alkylated, glucamine and gluconolactone. Also the Combinations known from German patent application DE 44 43 177 conventional bleach activators can be used. In a preferred embodiment the use according to the invention is simultaneous with the tungstate and / or molybdate also such a peroxocarboxylic acid under perhydrolysis conditions splitting off connection used. In a preferred embodiment according to the invention In addition to tungsten and / or molybdate, agents are 1% by weight to 10 wt .-%, in particular 2 wt .-% to 6 wt .-% of such under perhydrolysis conditions Peroxocarboxylic acid releasing compound present. The Weight ratio of peroxocarboxylic acid releasing under perhydrolysis conditions The connection to tungsten and / or molybdate is preferably in the range of 1000: 1 up to 1: 4, especially from 800: 1 to 1: 1.

Als Bleichmittel auf Sauerstoffbasis kommen in erster Linie Alkaliperboratmonobeziehungsweise -tetrahydrat und/oder Alkalipercarbonat in Betracht, wobei Natrium das bevorzugte Alkalimetall ist. Der Einsatz von Natriumpercarbonat hat insbesondere in Reinigungsmitteln für Geschirr Vorteile, da es sich besonders günstig auf das Korrosionsverhalten an Gläsern auswirkt. Das Bleichmittel auf Sauerstoffbasis ist deshalb vorzugsweise ein Alkalipercarbonat, insbesondere Natriumpercarbonat. Zusätzlich oder insbesondere alternativ können auch bekannte Peroxycarbonsäuren, zum Beispiel Dodecandipersäure oder Phthalimidopercarbonsäuren, die gegebenenfalls am Aromaten substituiert sein können, enthalten sein. Überdies kann auch der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie beispielsweise von Phosphonaten, Boraten beziehungsweise Metaboraten und Metasilikaten sowie Magnesiumsalzen wie Magnesiumsulfat zweckdienlich sein.The main bleaches used are oxygen-based or alkali perborate mono tetrahydrate and / or alkali percarbonate into consideration, where sodium is the preferred alkali metal is. The use of sodium percarbonate has in particular Dishwashing detergent benefits as it is particularly beneficial on the Corrosion behavior affects glasses. The oxygen-based bleach is therefore preferably an alkali percarbonate, especially sodium percarbonate. In addition or in particular alternatively, known peroxycarboxylic acids, for example Dodecanediperic acid or phthalimidopercarboxylic acids, optionally on aromatics may be substituted. In addition, the addition of small amounts known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as Magnesium sulfate may be useful.

Vorzugsweise enthalten die erfindungsgemäßen maschinellen Geschirreinigungsmittel die üblichen Alkaliträger wie zum Beispiel Alkalisilikate, Alkalicarbonate und/oder Alkalihydrogencarbonate. Zu den üblicherweise eingesetzten Alkaliträgern zählen Carbonate, Hydrogencarbonate und Alkalisilikate mit einem Molverhältnis SiO2/M2O (M = Alkaliatom) von 1 : 1 bis 2,5 : 1. Alkalisilikate können dabei in Mengen von bis zu 40 Gew.-%, insbesondere 3 Gew.-% bis 30 Gew.-%, bezogen auf das gesamte Mittel, enthalten sein. Das in den erfindungsgemäßen Mitteln bevorzugt eingesetzte Alkaliträgersystem ist ein Gemisch aus Carbonat und Hydrogencarbonat, vorzugsweise Natriumcarbonat und - hydrogencarbonat, das in einer Menge von bis zu 50 Gew.-%, vorzugsweise 5 Gew.-% bis 40 Gew.-%, enthalten sein kann.The machine dishwashing detergents according to the invention preferably contain the customary alkali carriers such as, for example, alkali silicates, alkali carbonates and / or alkali hydrogen carbonates. The alkali carriers commonly used include carbonates, hydrogen carbonates and alkali silicates with a molar ratio SiO 2 / M 2 O (M = alkali atom) of 1: 1 to 2.5: 1. Alkali silicates can be used in amounts of up to 40% by weight, in particular 3% by weight to 30% by weight, based on the total composition, can be present. The alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which are contained in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight can.

In einer weiteren Ausführungsform erfindungsgemäßer Mittel sind 20 Gew.-% bis 60 Gew.-% wasserlöslicher organischer Builder, insbesondere Alkalicitrat, 3 Gew.-% bis 20 Gew.-% Alkalicarbonat und 3 Gew.-% bis 40 Gew.-% Alkalidisilikat enthalten. In a further embodiment, agents according to the invention are 20% by weight to 60% by weight of water-soluble organic builder, in particular alkali citrate, 3% by weight to Contain 20 wt .-% alkali carbonate and 3 wt .-% to 40 wt .-% alkali disilicate.

Den erfindungsgemäßen Mitteln können gegebenenfalls auch Tenside, insbesondere Aniontenside, zwitterionische Tenside und vorzugsweise schwach schäumende nichtionische Tenside zugesetzt werden, die der besseren Ablösung fetthaltiger Anschmutzungen, als Netzmittel und gegebenenfalls im Rahmen der Herstellung der Reinigungsmittel als Granulierhilfsmittel dienen. Ihre Menge kann bis zu 20 Gew.-%, insbesondere bis zu 10 Gew.-% betragen und liegt vorzugsweise im Bereich von 0,5 Gew.-% bis 5 Gew.-%. Üblicherweise werden insbesondere in Reinigungsmitteln für den Einsatz in maschinellen Geschirrspülverfahren extrem schaumarme Verbindungen eingesetzt. Hierzu zählen vorzugsweise C12-C18-Alkylpolyethylenglykolpolypropylenglykolether mit jeweils bei zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. Man kann aber auch andere bekannt schaumarme nichtionische Tenside verwenden, wie zum Beispiel C12-C18-Alkylpolyethylenglykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül, endgruppenverschlossene Alkylpolyalkylenglykolmischether sowie die zwar schäumenden, aber ökologisch attraktiven C8-C14-Alkylpolyglucoside mit einem Polymerisierungsgrad von etwa 1 bis 4 (z. B. APG® 225 und APG® 600 der Firma Henkel) und/oder C12-C14-Alkylpolyethylenglykole mit 3 bis 8 Ethylenoxideinheiten im Molekül. Ebenfalls geeignet sind Tenside aus der Familie der Glucamide wie zum Beispiel Alkyl-N-Methyl-Glucamide, in denen der Alkylteil bevorzugt aus einem Fettalkohol mit der C-Kettenlänge C6-C14 stammt. Es ist teilweise vorteilhaft, wenn die beschriebenen Tenside als Gemische eingesetzt werden, zum Beispiel die Kombination Alkylpolyglykosid mit Fettalkoholethoxylaten oder Glucamid mit Alkylpolyglykosiden. Auch die Anwesenheit von Aminoxiden, Betainen und ethoxlierten Alkylaminen ist möglich.If appropriate, surfactants, in particular anionic surfactants, zwitterionic surfactants and preferably low-foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to better detach fatty soils, as wetting agents and, if appropriate, as granulating aids in the preparation of the cleaning agents. Their amount can be up to 20% by weight, in particular up to 10% by weight, and is preferably in the range from 0.5% by weight to 5% by weight. Extremely low-foaming compounds are usually used in particular in cleaning agents for use in automatic dishwashing processes. These preferably include C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers, each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule. But you can also use other known low-foaming nonionic surfactants, such as C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped alkyl polyalkylene glycol mixed ethers and the foaming but ecologically attractive C 8 -C 14- alkyl polyglucosides with a degree of polymerization of about 1 to 4 (e.g. APG® 225 and APG® 600 from Henkel) and / or C 12 -C 14 -alkyl polyethylene glycols with 3 to 8 ethylene oxide units in the molecule. Also suitable are surfactants from the family of glucamides, such as, for example, alkyl-N-methyl-glucamides, in which the alkyl part preferably originates from a fatty alcohol with the C chain length C 6 -C 14 . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides. The presence of amine oxides, betaines and ethoxylated alkylamines is also possible.

Um einen Silberkorrosionsschutz zu bewirken, können in erfindungsgemäßen Reinigungsmitteln für Geschirr Silberkorrosionsinhibitoren eingesetzt werden. Bevorzugte Silberkorrosionsschutzmittel sind organische Sulfide wie Cystin und Cystein, zwei- oder dreiwertige Phenole, gegebenenfalls alkyl- oder arylsubstituierte Triazole wie Benzotriazol, Isocyanursäure, Mangan-, Titan-, Zirkonium-, Hafnium-, Vanadium- oder Cersalze und/oder -komplexe, in denen die genannten Metalle je nach Metall in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen. In order to provide silver corrosion protection, cleaning agents according to the invention can silver corrosion inhibitors can be used for dishes. Preferred silver corrosion inhibitor are organic sulfides like cystine and cysteine, bi- or trivalent phenols, optionally alkyl- or aryl-substituted triazoles such as Benzotriazole, isocyanuric acid, manganese, titanium, zirconium, hafnium, vanadium or Cerium salts and / or complexes in which the metals mentioned, depending on the metal, in one of the Oxidation levels II, III, IV, V or VI are present.

Sofern die Reinigungsmittel, zum Beispiel bei Anwesenheit von Aniontensiden, bei der Anwendung zu stark schäumen, können ihnen noch bis zu 6 Gew.-%, vorzugsweise etwa 0,5 Gew.-% bis 4 Gew.-% einer schaumdrückenden Verbindung, vorzugsweise aus der Gruppe der Silikonöle, Gemische aus Silikonöl und hydrophobierter Kieselsäure, Paraffine, Paraffin-Alkohol-Kombinationen, hydrophobierter Kieselsäure, der Bisfettsäureamide, und sonstiger weiterer bekannter im Handel erhältliche Entschäumer zugesetzt werden. Weitere fakultative Inhaltsstoffe in den erfindungsgemäßen Mitteln sind zum Beispiel Parfümöle.If the cleaning agents, for example in the presence of anionic surfactants, at the Application foam too much, they can still up to 6 wt .-%, preferably about 0.5 wt .-% to 4 wt .-% of a foam suppressing compound, preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis fatty acid amides, and other other known commercially available defoamers will. Other optional ingredients in the agents according to the invention are for example perfume oils.

Zu den in den erfindungsgemäßen Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylenglykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungsmittel sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 1 Gew.-% bis 15 Gew.-%, vorhanden.To those in the agents according to the invention, especially when they are in liquid or pasty form, usable organic solvents include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, Diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and their mixtures and the ethers derived from the compound classes mentioned. Such water-miscible solvents are in the cleaning agents according to the invention preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight, available.

Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die erfindungsgemäßen Mittel System- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure oder Alkalihydrogensulfate, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungsgemäßen Mitteln vorzugsweise nicht über 10 Gew.-%, insbesondere von 0,5 Gew.-% bis 6 Gew.-%, enthalten.To set a desired, by mixing the other components the agents according to the invention cannot system and pH environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, malic acid, Lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, however also mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10% by weight, in particular, in the agents according to the invention from 0.5% by weight to 6% by weight.

Die Herstellung der erfindungsgemäßen festen Mittel bietet keine Schwierigkeiten und kann in im Prinzip bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Persauerstoffverbindung und Bleichkatalysator gegebenenfalls später getrennt zugesetzt werden. The preparation of the solid compositions according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, take place, the peroxygen compound and bleaching catalyst possibly later be added separately.

Erfindungsgemäße Reinigungsmittel in Form wäßriger oder sonstige übliche Lösungsmittel enthaltender Lösungen werden besonders vorteilhaft durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt.Cleaning agents according to the invention in the form of aqueous or other conventional Solutions containing solvents are particularly advantageous by simple Mixing the ingredients in bulk or as a solution in an automatic Mixers can be made.

Die erfindungsgemäßen Mittel liegen vorzugsweise als pulverförmige, granulare oder tablettenförmige Präparate vor, die in an sich bekannter Weise, beispielsweise durch Mischen, Granulieren, Walzenkompaktieren und/oder durch Sprühtrocknung der thermisch belastbaren Komponenten und Zumischen der empfindlicheren Komponenten, zu denen insbesondere Enzyme, Bleichmittel und der Bleichkatalysator zu rechnen sind, hergestellt werden können.The agents according to the invention are preferably powdered, granular or tablet-shaped preparations in a known manner, for example by Mixing, granulating, roller compacting and / or by spray drying the thermally resilient components and admixing the more sensitive components, to which in particular enzymes, bleaching agents and the bleaching catalyst are to be counted, can be produced.

Zur Herstellung von erfindungsgemäßen Reinigungsmitteln in Tablettenform geht man vorzugsweise derart vor, daß man alle Bestandteile in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßdrucken im Bereich von 200 · 105 Pa bis 1 500 · 105 Pa verpresst. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeiten von normalerweise über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 15 g bis 40 g, insbesondere von 20 g bis 30 g auf, bei einem Durchmesser von 35 mm bis 40 mm.For the preparation of cleaning agents according to the invention in tablet form, the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with compression pressures in the range from 200 · 10 5 Pa to 1 500 · 10 5 Pa pressed. In this way, unbreakable tablets are obtained which, under application conditions, dissolve sufficiently quickly, with bending strengths of normally over 150 N. Preferably, a tablet manufactured in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.

Die Herstellung erfindungsgemäßer Mittel in Form von nicht staubenden, lagerstabil rieselfähigen Pulvern und/oder Granulaten mit hohen Schüttdichten im Bereich von 800 bis 1000 g/l kann dadurch erfolgen, daß man in einer ersten Verfahrensteilstufe die Builder-Komponenten mit wenigstens einem Anteil flüssiger Mischungskomponenten unter Erhöhung der Schüttdichte dieses Vorgemisches vermischt und nachfolgend - gewünschtenfalls nach einer Zwischentrocknung - die weiteren Bestandteile des Mittels, darunter den Bleichkatalysator, mit dem so gewonnenen Vorgemisch vereinigt.The preparation of agents according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 up to 1000 g / l can be achieved in that the Builder components with at least a portion of liquid mixture components mixed by increasing the bulk density of this premix and subsequently - if desired after intermediate drying - the other components of the agent, including the bleach catalyst, combined with the premix obtained in this way.

Erfindungsgemaße Mittel zur Reinigung von Geschirr können sowohl in Haushaltsgeschirrspülmaschinen wie in gewerblichen Spülmasehinen eingesetzt werden. Die Zugabe erfolgt von Hand oder mittels geeigneter Dosiervorrichtungen. Die Anwendungskonzentrationen in der Reinigungsflotte betragen in der Regel etwa 1 bis 8 g/l, vorzugsweise 2 bis 5 g/l.Means for cleaning dishes according to the invention can be used both in household dishwashers as used in commercial dishwashers. The addition is done by hand or by means of suitable dosing devices. The application concentrations in the cleaning liquor are usually about 1 to 8 g / l, preferably 2 to 5 g / l.

Ein maschinelles Spülprogramm wird im allgemeinen durch einige auf den Reinigungsgang folgende Zwischenspülgänge mit klarem Wasser und einem Klarspülgang mit einem gebräuchlichem Klarspülmittel ergänzt und beendet. Nach dem Trocknen erhält man beim Einsatz erfindungsgemäßer Mittel ein völlig sauberes und in hygienischer Hinsicht einwandfreies Geschirr. A machine wash program is generally followed by some on the Cleaning cycle following intermediate rinse cycles with clear water and one Rinse aid supplemented with a customary rinse aid and ended. After this Drying gives a completely clean and in when using agents according to the invention hygienically perfect dishes.

BeispieleExamples Beispiel 1example 1

Ein Reinigungsmittel (V1), enthaltend 45 Gew.-Teile Natriumcitrat, 5 Gew.-Teile Natriumcarbonat, 31 Gew.-Teile Natriumhydrogencarbonat, jeweils 1 Gew.-Teil Protease- und Amylase-Granulat, 2 Gew.-Teile nichtionisches Tensid sowie 10 Gew.-Teile Natriumperborat-Monohydrat und 4 Gew.-Teile N,N,N'N'-Tetraacetylethylendiamin (TAED) und Mittel gemäß der Erfindung (M1 bis M6), die ansonsten wie V1 zusammengesetzt waren, aber zusätzlich die in Tabelle 1 angegebenen Mengen an Wolframat beziehungsweise Molybdat enthielten, wurden folgendermaßen getestet: Zur Herstellung standardisierter Teebeläge wurden Teetassen in eine 70 °C warme Teelösung 25 mal eingetaucht. Anschließend wurde jeweils etwas der Teelösung in jede Teetasse gegeben und die Tasse im Trockenschrank getrocknet. Jeweils eine Tasse wurde bei 50 °C 30 Minuten in 3 Liter einer gerührten (Blattrührer, 80 Umdrehungen pro Minute) wäßrigen Lösung (Wasserhärte 14 °dH, Konzentration 3 g/l) des zu testenden Mittels gehängt und die Belagsentfernung anschließend visuell auf einer Skala von 0 (= unverändert sehr starker Belag) bis 10 (= kein Belag) benotet. Die in der nachfolgenden Tabelle 1 angegebenen Noten der erfindungsgemäßen Mittel M1 bis M6 liegen signifikant besser als der Wert für das Vergleichsprodukt V1. Noten für die Belagsentfernung Mittel Bleichkatalysator Belagsentfernung M1 177 ppm K2WO4 8 M2 354 ppm K2WO4 10 M3 124 ppm K2MoO4 8 M4 248 ppm K2MoO4 10 M5 372 ppm K2MoO4 10 M6 496 ppm K2MoO4 10 V1 - 4 A cleaning agent ( V1 ) containing 45 parts by weight of sodium citrate, 5 parts by weight of sodium carbonate, 31 parts by weight of sodium hydrogen carbonate, 1 part by weight of protease and amylase granules, 2 parts by weight of nonionic surfactant and 10 Parts by weight of sodium perborate monohydrate and 4 parts by weight of N, N, N'N'-tetraacetylethylene diamine (TAED) and agents according to the invention ( M1 to M6 ), which were otherwise composed like V1 , but additionally those in Table 1 contained specified amounts of tungstate or molybdate were tested as follows: To produce standardized tea coverings, teacups were immersed 25 times in a 70 ° C warm tea solution. Then some of the tea solution was added to each tea cup and the cup dried in the drying cabinet. One cup each was hung at 50 ° C for 30 minutes in 3 liters of a stirred (paddle stirrer, 80 revolutions per minute) aqueous solution (water hardness 14 ° dH, concentration 3 g / l) of the agent to be tested and the coating removal was then visually shown on a scale graded from 0 (= very thick base) to 10 (= no base). The grades M1 to M6 according to the invention given in Table 1 below are significantly better than the value for the comparative product V1 . Sheet removal marks medium Bleaching catalyst Removal of deposits M1 177 ppm K 2 WO 4 8th M2 354 ppm K 2 WO 4 10th M3 124 ppm K 2 MoO 4 8th M4 248 ppm K 2 MoO 4 10th M5 372 ppm K 2 MoO 4 10th M6 496 ppm K 2 MoO 4 10th V1 - 4th

Man erkennt, daß durch die erfindungsgemäße Wirkstoffkombination eine signifikant bessere Bleichwirkung erreicht werden kann als durch den konventionellen Bleichaktivator TAED alleine. Im wesentlichen gleiche Ergebnisse wurden erhalten, wenn man das Natriumperborat durch Natriumpercarbonat ersetzte.It can be seen that the combination of active substances according to the invention is significant better bleaching effect can be achieved than with the conventional Bleach activator TAED alone. Essentially the same results were obtained if you replaced the sodium perborate with sodium percarbonate.

Beispiel 2Example 2

In einer Geschirrspülmaschine Miele® G 590 (Dosierungen von jeweils 20 g des zu testenden Mittels, Wasserharte 16 °dH, 55 °C-Universalprogramm) wurden jeweils 8 wie in Beispiel 1 mit Teebelägen versehene Tassen gespült und die Belagsentfernung anschließend visuell auf einer Skala von 0 (= unverändert sehr starker Belag) bis 10 (= kein Belag) benotet. Eingesetzt wurden das Mittel V1 gemäß Beispiel 1 und ein Mittel M7, das wie V1 zusammengesetzt war, aber zusätzlich 0,2 Gew.-% Natriummolybdat enthielt. Die in der nachfolgenden Tabelle 2 angegebene Note des erfindungsgemäßen Mittels M7 liegt signifikant besser als der Wert für das Vergleichsprodukt V1. Noten für die Belagsentfernung Mittel Belagsentfernung M7 8 V1 4 In a Miele® G 590 dishwasher (doses of 20 g each of the agent to be tested, water hardness 16 ° dH, 55 ° C universal program), 8 cups with tea coverings, as in Example 1, were rinsed and the cover removal was then visually shown on a scale of 0 (= unchanged very thick base) to 10 (= no base) graded. Agent V1 according to Example 1 and agent M7 were used , which was composed like V1 but additionally contained 0.2% by weight of sodium molybdate. The grade of the agent M7 according to the invention given in Table 2 below is significantly better than the value for the comparative product V1 . Sheet removal marks medium Removal of deposits M7 8th V1 4th

Beispiel 3Example 3

Unter den gleichen Bedingungen wie in Beispiel 2 wurden Spülversuche mit den wie angegeben mit Teebelägen versehenen Tassen und gleichzeitig in der Geschirrspülmaschine befindlichem Geschirr, das mit Kartoffelstärke angeschmutzt worden war, ausgeführt. Die Stärkeentfernung wurde nach Anfärben mit Jod analog der Teentfernung auf einer Skala von 0 bis 10 visuell benotet. In der nachfolgenden Tabelle 3 ist die Belagsentfernungsnote als Summe der Noten für die Entfernung von Tee und für die Entfernung von Stärke angegeben. Getestet wurde das Mittel M7 gemäß Beispiel 1 im Vergleich zu einem Mittel V2, das ansonsten wie M7 zusammengesetzt war und dem das Molybdat fehlte, einem Mittel V3, das ansonsten wie M7 zusammengesetzt war und dem das Amylasegranulat fehlte, und einem Mittel V4, das ansonsten wie M7 zusammengesetzt war und dem sowohl das Molybdat als auch das Amylasegranulat fehlte. Man erkennt, daß das erfindungsgemäße Mittel M7 eine höhere Reinigungsleistung aufweist, als aus den Ergebnissen der Mittel V2 und V3 zu erwarten gewesen wäre. Noten für die Belagsentfernung Mittel Belagsentfernung M7 17 V2 11 V3 10 V4 6 Rinsing tests were carried out under the same conditions as in Example 2 with the cups provided with tea toppings and, at the same time, dishes in the dishwasher which had been soiled with potato starch. After dyeing with iodine, the starch removal was graded visually on a scale from 0 to 10 analogous to the tea removal. In Table 3 below, the deposit removal grade is given as the sum of the grades for tea removal and starch removal. The agent M7 was tested according to Example 1 in comparison to an agent V2 which was otherwise composed like M7 and which lacked the molybdate, an agent V3 which was otherwise composed like M7 and which lacked the amylase granules, and an agent V4 which otherwise how M7 was composed and which lacked both the molybdate and the amylase granules. It can be seen that the agent M7 according to the invention has a higher cleaning performance than would have been expected from the results of the agents V2 and V3 . Sheet removal marks medium Removal of deposits M7 17th V2 11 V3 10th V4 6

Claims (14)

Verwendung von Alkali- oder Ammoniumwolframat und/oder -molybdat als Aktivator für insbesondere anorganische Persauerstoffverbindungen in wäßrigen Reinigungslösungen für harte Oberflächen, insbesondere für Geschirr.Use of alkali metal or ammonium tungstate and / or molybdate as an activator for in particular inorganic peroxygen compounds in aqueous cleaning solutions for hard surfaces, especially for dishes. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die zu aktivierende Persauerstoffverbindung aus der Gruppe umfassend organische Persäuren, Wasserstoffperoxid, Perborat und Percarbonat sowie deren Gemische ausgewählt wird.Use according to claim 1, characterized in that the peroxygen compound to be activated from the group comprising organic peracids, hydrogen peroxide, Perborate and percarbonate and their mixtures is selected. Verwendung von Alkali- oder Ammoniumwolframat und/oder -molybdat in Reinigungslösungen für harte Oberflächen, insbesondere für Geschirr, zum Bleichen von gefärbten Anschmutzungen.Use of alkali or ammonium tungstate and / or molybdate in cleaning solutions for hard surfaces, especially for dishes, for bleaching stained stains. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man die Natrium-, Kalium- und Lithiumsalze der Wolframsäure beziehungsweise der Molybdänsäure einsetzt.Use according to one of claims 1 to 3, characterized in that the sodium, potassium and lithium salts of tungstic acid and the Molybdic acid is used. Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man gleichzeitig mit dem Wolframat und/oder Molybdat auch eine unter Perhydrolysebedingungen Peroxocarbonsäure abspaltende Verbindung verwendet.Use according to one of claims 1 to 4, characterized in that at the same time as the tungstate and / or molybdate, one under perhydrolysis conditions Peroxocarboxylic acid releasing compound used. Verwendung nach Anspruch 5, dadurch gekennzeichnet, daß das Gewichtsverhältnis von unter Perhydrolysebedingungen Peroxocarbonsäure abspaltender Verbindung zu Wolframat und/oder Molybdat im Bereich von 1000:1 bis 1:4, insbesondere von 800:1 bis 1:1 liegt.Use according to claim 5, characterized in that the weight ratio of compound releasing peroxocarboxylic acid under perhydrolysis conditions Tungsten and / or molybdate in the range from 1000: 1 to 1: 4, in particular from 800: 1 to 1: 1. Verfahren zur Reinigung von harten Oberflächen, insbesondere von Geschirr, dadurch gekennzeichnet, daß man Alkali- oder Ammoniumwolframat und/oder -molybdat in wäßriger, gegebenenfalls weitere Reinigungsmittelbestandteile enthaltender Lösung einsetzt. Process for cleaning hard surfaces, especially dishes, thereby characterized in that alkali metal or ammonium tungstate and / or molybdate in aqueous solution, optionally containing further detergent components starts. Reinigungsmittel für harte Oberflächen, dadurch gekennzeichnet, daß es Alkali- oder Ammoniumwolframat und/oder -molybdat in Kombination mit Polycarboxylat und/oder Enzym enthält.Detergent for hard surfaces, characterized in that it is alkali or Ammonium tungstate and / or molybdate in combination with polycarboxylate and / or enzyme contains. Reinigungsmittel für Geschirr, insbesondere für den Einsatz in maschinellen Reinigungsverfahren, dadurch gekennzeichnet, daß es Alkali- oder Ammoniumwolframat und/oder -molybdat in Kombination mit Polycarboxylat und/oder Enzym enthält.Detergent for dishes, especially for use in machine cleaning processes, characterized in that it is alkali metal or ammonium tungstate and / or molybdate in combination with polycarboxylate and / or enzyme. Mittel nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß es 0,005 Gew.-% bis 5 Gew.-%, insbesondere 0,05 Gew.-% bis 2 Gew.-% Alkali- oder Ammoniumwolframat und/oder -molybdat in Kombination mit 0,5 Gew.-% bis 60 Gew.-%, insbesondere 1 Gew.-% bis 60 Gew.-% monomerem und/oder polymerem Polcarboxylat enthält.Agent according to Claim 8 or 9, characterized in that it is from 0.005% by weight to 5 wt .-%, in particular 0.05 wt .-% to 2 wt .-% alkali or Ammonium tungstate and / or molybdate in combination with 0.5 wt .-% bis 60 wt .-%, in particular 1 wt .-% to 60 wt .-% monomeric and / or contains polymeric polycarboxylate. Mittel nach einem der Ansprüche 8 bis 10, dadurch gekennzeichnet, daß es 0,01 Gew.-% bis 15 Gew.-%, insbesondere 0,05 Gew.-% bis 10 Gew.-% Enzym, insbesondere Protease, Lipase und/oder Amylase, enthält.Agent according to one of claims 8 to 10, characterized in that it 0.01% by weight to 15% by weight, in particular 0.05% by weight to 10% by weight of enzyme, in particular protease, lipase and / or amylase. Mittel nach einem der Ansprüche 8 bis 11, dadurch gekennzeichnet, daß zusätzlich zu Alkali- oder Ammoniumwolframat und/oder -molybdat 1 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew.-% bis 6 Gew.-% unter Perhydrolysebedingungen Peroxocarbonsäure abspaltende Verbindung anwesend ist.Agent according to one of claims 8 to 11, characterized in that in addition to Alkali metal or ammonium tungstate and / or molybdate 1% by weight to 10% by weight, in particular 2% by weight to 6% by weight under perhydrolysis conditions peroxocarboxylic acid splitting off connection is present. Mittel nach Anspruch 12, dadurch gekennzeichnet, daß das Gewichtsverhältnis von unter Perhydrolysebedingungen Peroxocarbonsäure abspaltender Verbindung zu Wolframat und/oder Molybdat im Bereich von 1000:1 bis 1:4, insbesondere von 800:1 bis 1:1 liegt.Agent according to claim 12, characterized in that the weight ratio of compound releasing peroxocarboxylic acid under perhydrolysis conditions Tungsten and / or molybdate in the range from 1000: 1 to 1: 4, in particular from 800: 1 to 1: 1. Mittel nach einem der Ansprüche 8 bis 13, dadurch gekennzeichnet, daß es 15 Gew.-% bis 65 Gew.-%, insbesondere 20 Gew.-% bis 60 Gew.-% wasserlösliche Builderkomponente, 5 Gew.-% bis 25 Gew.-%, insbesondere 8 Gew.-% bis 17 Gew.-% Bleichmittel auf Sauerstoffbasis und 0,01 Gew.-% bis 5 Gew.-% Wolframat und/oder Molybdat enthält.Agent according to one of Claims 8 to 13, characterized in that it is 15% by weight up to 65% by weight, in particular 20% by weight to 60% by weight of water-soluble builder component, 5% by weight to 25% by weight, in particular 8% by weight to 17% by weight Oxygen-based bleach and 0.01% to 5% by weight tungsten and / or Contains molybdate.
EP97120141A 1996-11-27 1997-11-18 Improved bleaching performance using tungstates and molybdates Withdrawn EP0845524A3 (en)

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