EP2329000B1 - Utilisation d'oxalates de manganèse comme catalyseur de blanchiment - Google Patents

Utilisation d'oxalates de manganèse comme catalyseur de blanchiment Download PDF

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Publication number
EP2329000B1
EP2329000B1 EP09778105A EP09778105A EP2329000B1 EP 2329000 B1 EP2329000 B1 EP 2329000B1 EP 09778105 A EP09778105 A EP 09778105A EP 09778105 A EP09778105 A EP 09778105A EP 2329000 B1 EP2329000 B1 EP 2329000B1
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Prior art keywords
manganese
weight
oxalate
acid
bleaching
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German (de)
English (en)
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EP2329000A1 (fr
Inventor
Gerd Reinhardt
Michael Best
Joachim Erbes
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Clariant Finance BVI Ltd
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Clariant Finance BVI Ltd
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Priority to PL09778105T priority Critical patent/PL2329000T3/pl
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Classifications

    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • 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
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing compounds
    • 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
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds

Definitions

  • the present invention relates to the use of manganese oxalates in detergents on hard surfaces as bleach catalysts for enhancing the bleaching effect of inorganic peroxygen compounds in bleaching colored stains on hard surfaces.
  • Inorganic peroxygen compounds particularly 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 disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine and acylated glycolurils, such as tetraacetylglycoluril, also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate, sodium lauroyl-benzenesulfonate or decanoyloxybenzoic acid and acylated sugar derivatives, such as pentaacetylglucose, have become known in the literature.
  • bleach activators for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine and acyl
  • manganese / EDTA complexes as in EP 0 141 470 or manganese sulfate / picolinic acid mixtures, as in US 3,532,634 or manganese (II) or (III) salts in combination with carbonates ( EP 0 082 563 ), Fatty acids ( US 4,626,373 ), Phosphonates ( EP 0 072 166 ), Hydroxycarboxylic acids ( EP 0 237 111 ) or citric acid or its salts ( EP 0 157 483 ).
  • the invention relates to the use of manganese oxalates as bleach catalysts in cleaning agents, as defined in claim 1.
  • Manganese oxalates can be prepared in a manner known per se by reacting manganese salts with oxalic acid in water. Examples include in A. Huizing et al., Mat. Res. Bull. Vol. 12, pp. 605-6166, 1977 and Donkova et al., Thermochimica Acta, Vol. 421, pp. 141-149, 2004 ,
  • both the white manganese (II) oxalate dihydrate and the pink manganese (II) oxalate trihydrate are suitable. Although they have only a very low water solubility, these compounds surprisingly show a good bleaching performance in combination with inorganic peroxygen compounds.
  • manganese (II) sulfate manganese (II) acetate
  • manganese (III) acetate or manganese (II) chloride better storage stability in alkaline detergent and cleaner formulations.
  • the manganese oxalates according to the invention are more volume-effective bleach catalysts, which is advantageous, in particular, when used in machine dishwashing detergent tablets.
  • the cleaning agents preferably contain from 0.025 to 2.5% by weight, in particular from 0.05 to 1.5% by weight, of bleach-intensifying manganese oxalates.
  • the manganese oxalates may also be combined with oxalic acid, thereby increasing their water solubility.
  • the manganese oxalate: oxalic acid ratio in this case may correspond to 1: 0 to 1: 5 parts by weight.
  • Suitable peroxygen compounds are hydrogen peroxide, but in the first place alkali perborate or tetrahydrate and / or alkali metal percarbonate, with sodium being the preferred alkali metal.
  • the use of sodium percarbonate has particular advantages in dishwashing detergents, since it has a particularly favorable effect on the corrosion behavior of glasses.
  • the oxygen-based bleaching agent is therefore preferably an alkali percarbonate, especially sodium percarbonate.
  • the amounts of peroxygen compounds used are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm of active oxygen are present.
  • bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • bleach activators that is to say compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or peroxycarboxylic acids having 1 to 10 C atoms, in particular 2 to 4 C atoms.
  • Suitable are the customary bleach activators cited at the outset which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates , in particular nonanoyl or Isononanoyloxybenzolsulfonat, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), Pentaacetylfruktose, Te
  • bleaching is understood to mean here both the bleaching of dirt located on the hard surface, in particular tea, and the bleaching of dirt removed from the hard surface in the dishwashing liquor.
  • the use of the present invention is to create conditions on a hard surface contaminated with colored stains, under which a peroxidic oxidizing agent and the manganese oxalates can react with each other, with the aim of obtaining more strongly oxidizing secondary products.
  • Such conditions are especially present when the reactants meet in aqueous solution.
  • This can be done by separately adding the peroxygen compound and the manganese oxalate to an optionally detergent-containing solution.
  • the inventive method is particularly advantageous using a Hard surface cleaning agent containing a manganese oxalate and optionally a peroxygen-containing oxidizing agent.
  • the peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a non-oxygenated cleaner is used.
  • the cleaning agents which may be in the form of granules, powdered or tablet-form solids, other shaped bodies, homogeneous solutions or suspensions, may contain, in principle, all known ingredients customary in such agents, as well as the said manganese oxalate.
  • the compositions may in particular contain 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, additional peroxygen activators and dyes and fragrances.
  • a hard surface cleaner can contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres, and mixtures thereof.
  • Abrasives are preferably not more than 20 wt .-%, in particular from 5 to 15 wt .-%, contained in the cleaning agents.
  • An apparatus for machine dishwashing may contain from 15 to 65% by weight, especially from 20 to 60% by weight of water-soluble builder component, from 5 to 25% by weight, especially from 8 to 17% by weight of oxygen-based bleach, in each case to the total agent, and each containing 0.05 to 1.5 wt .-% manganese oxalate.
  • Such an agent is particularly low alkaline, that is, its 1-weight percent solution has a pH of 8 to 11.5, preferably 9 to 11.
  • alkali phosphates which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • alkali phosphates which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Their amounts may be in the range of up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total mean.
  • water-soluble builder components in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the type of the polycarboxylates of native or synthetic origin, which act as co-builders, in particular in hard water regions.
  • organic polymers of the type of the polycarboxylates of native or synthetic origin which act as co-builders, in particular in hard water regions.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids are suitable.
  • Commercially available products are, for example, Sokalan TM CP 5, CP 10 and PA 30 from BASF.
  • co-builder polymers of native origin include oxidized starch and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • hydroxycarboxylic acids such as mono-, dihydroxysuccinic, alpha-hydroxypropionic and gluconic acid.
  • Preferred organic builder components include the salts of citric acid, especially sodium citrate.
  • sodium citrate anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to the said co-builder salts may also be present.
  • the enzymes optionally present in the compositions include proteases, amylases, pullulanases, cutinases and / or lipases, for example proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Esperase TM and / or Savinase TM, amylases such as Termamyl TM, Amylase-LT TM, Maxamyl TM, Duramyl TM and / or Lipases such as Lipolase TM, Lipomax TM, Lumafast TM and / or Lipozym TM.
  • proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Esperase TM and / or Savinase TM
  • the enzymes used may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the cleaning agents in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, particular preference being given to using enzymes which are stabilized against oxidative degradation.
  • the machine dishwashing detergents preferably contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali metal bicarbonates.
  • Alkali silicates may be present in amounts of up to 40% by weight. in particular from 3 to 30% by weight, based on the total agent.
  • the alkali carrier system preferably used in the compositions is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be contained in an amount of up to 50% by weight, preferably 5 to 40% by weight.
  • a further agent 20 to 60 wt .-% of water-soluble organic builder in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.
  • Surfactants in particular anionic surfactants, zwitterionic surfactants and preferably weakly foaming nonionic surfactants may also be added to the compositions if appropriate, which serve to better remove greasy soilings, as wetting agents and, if appropriate, in the course of the preparation of the cleaning agents as granulation auxiliaries.
  • Their amount can be up to 20 wt .-%, in particular up to 10 wt .-% and is preferably in the range of 0.5 to 5 wt .-%.
  • extremely low-foam compounds are used in particular in detergents for use in automatic dishwashing processes.
  • C 12 -C 18 -Alkylpolyethylenglykol-polypropylene glycol ethers each with at 8 mol ethylene oxide and propylene oxide in the molecule.
  • you can also use other known low-foam nonionic surfactants such as C 12 -C 18 alkylpolyethylene glycol polybutylenglykolether with up to 8 moles of ethylene oxide and butylene oxide in the molecule, end phenomenonver totale Alkylpolyalkylenglykolmischether and the foaming, but ecologically attractive C 8 -C 14 - Alkylpolyglucoside having a degree of polymerization of about 1 to 4 and / or C 12 -C 14 alkyl polyethylene glycols having 3 to 8 ethylene oxide units in the molecule.
  • surfactants from the family of glucamides such as, for example, alkyl-N-methylglucamides, in which the alkyl moiety 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.
  • silverware inhibitors can be used in dishwashing detergents.
  • Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, Hafhium-, cobalt or cerium salts and / or complexes, in which Metals depending on the metal in one of the oxidation states II, III, IV, V or VI.
  • crystalline layered silicates and / or zinc salts are sold, for example, by the company Clariant under the trade name Na-SKS, z. Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, makatite).
  • Na-SKS-5 alpha -Na 2 Si 2 O 5
  • Na-SKS-7 beta-Na 2 Si 2 O 5 , natrosilite
  • Na-SKS-9 NaHSi 2 O 5 .H 2 O
  • Na-SKS-10 NaHSi 2 O 5 .3H 2 O, Kanemite
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 NaHSi 2 O 5
  • Na-SKS-6 delta-Na 2 Si 2 O 5
  • preferred automatic dishwashing or automatic dishwashing assistants have a weight fraction of the crystalline layered silicate of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0.4 to 10% by weight. -%, based in each case on the total weight of these funds.
  • automatic dishwashing or dishwashing auxiliaries comprise at least one zinc salt selected from the group of organic zinc salts, preferably from the group of soluble organic zinc salts, more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate , Zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.
  • group of organic zinc salts preferably from the group of soluble organic zinc salts, more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate , Zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.
  • automatic dishwashing or automatic dishwashing aids in which the proportion by weight of the zinc salt relative to the total weight of this agent is 0.1 to 10% by weight, preferably 0.2 to 7% by weight and in particular 0, are preferred , 4 to 4 wt .-% and regardless of which zinc salts are used, in particular therefore irrespective of whether organic or inorganic zinc salts, soluble or non-soluble zinc salts or mixtures thereof are used.
  • the cleaning agents may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils , Mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, bis-fatty acid amides, and other other known commercially available defoamers.
  • a foam-suppressing compound preferably from the group of silicone oils , Mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, bis-fatty acid amides, and other other known commercially available defoamers.
  • Other optional ingredients in the compositions are, for example, perfume oils.
  • organic solvents which can be used in the compositions, in particular if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers.
  • Such water-miscible solvents are preferably present in the detergents not more than 20% by weight, in particular from 1 to 15% by weight.
  • the agents can system and environmentally acceptable 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, mineral acids, in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
  • acids in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid
  • mineral acids in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
  • pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the compositions.
  • the preparation of the solid agents presents no difficulties and may be carried out in a manner known in the art, for example by spray-drying or granulation, wherein peroxygen compound and bleach catalyst are optionally added separately later.
  • Detergents in the form of aqueous or other conventional solvent-containing solutions are particularly advantageous simple mixing of the ingredients that can be added in bulk or as a solution in an automatic mixer made.
  • compositions are preferably in the form of powdered, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the like Bleaching catalyst are expected to be produced.
  • the procedure is preferably such that all ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing pressures in the range of 200x10 5 Pa to 1500x10 5 Pa pressed.
  • a tablet thus produced has a weight of 15 to 40 g, in particular from 20 to 30 g, with a diameter of 35 to 40 mm.
  • compositions in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 to 1000 g / l can be effected by subjecting the builder components with at least a proportion of liquid mixture components in a first process step Increase the bulk density of this premix and subsequently - if desired, after an intermediate drying - the other constituents of the agent, including the bleach catalyst, combined with the thus obtained premix.
  • Means for cleaning dishes can be used both in household dishwashers and in commercial dishwashers become. The addition is done by hand or by means of suitable metering devices.
  • the application concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.
  • a machine wash program is generally supplemented and terminated by a few rinses of clear water following a cleaning cycle and a rinse cycle with a common rinse aid. After drying, when using agents according to the invention, a completely clean and hygienically perfect dishes are obtained.
  • V 2 and V3 other non-inventive manganese salts or mixtures consisting of manganese salts and oxalic acid are listed as comparative examples.
  • tea cups were immersed in a 70 ° C. hot tea solution 25 times. Then each of the tea solution was added to each tea cup and the cup dried in a drying oven.
  • Table 1 test product rating V1 (cleaner) 37% V2 (cleaner + 100 mg Mn (II) sulphate) 55% V3 (cleaner + 50 mg Mn (II) SO 4 + 50 mg oxalic acid) 73% M1 (cleaner + 100 mg Mn (II) oxalate dihydrate) 80% M2 (cleaner + 100 mg Mn (III) oxalate trihydrate) 78% M3 (cleaner + 50 mg Mn (II) oxalate dihydrate) 65%

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Abstract

L'invention concerne l'utilisation d'oxalates de manganèse dans des produits de lavage et de nettoyage, notamment dans des produits de nettoyage pour surfaces dures, qui contiennent des composés peroxygène.

Claims (9)

  1. Utilisation d'oxalates de manganèse dans des produits de nettoyage pour surfaces dures, en tant que catalyseurs de blanchiment, pour l'accentuation de l'action de blanchiment de composés peroxygénés inorganiques dans le blanchiment de salissures colorées.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'oxalate de manganèse est un oxalate de manganèse(II) dihydraté ou un oxalate de manganèse (II) trihydraté.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que les composés peroxygénés inorganiques sont un perborate de métal alcalin mono- ou tétrahydraté et/ou un percarbonate de métal alcalin.
  4. Utilisation selon la revendication 3, caractérisée en ce que le métal alcalin est le sodium.
  5. Utilisation selon la revendication 1, caractérisée en ce qu'on utilise en outre de l'acide oxalique libre.
  6. Utilisation selon une ou plusieurs des revendications 1 à 5, caractérisée en ce qu'on utilise en outre de la tétraacétylènediamine.
  7. Utilisation selon une ou plusieurs des revendications 1 à 6, caractérisée en ce que le produit de nettoyage pour surfaces dures contient le composé peroxygéné et 0,025 à 2,5 % en poids d'oxalate de manganèse.
  8. Utilisation selon la revendication 7, caractérisée en ce que le produit de nettoyage pour surfaces dures contient le composé peroxygéné et 0,05 à 1,5 % en poids d'oxalate de manganèse.
  9. Utilisation selon une ou plusieurs des revendications 1 à 8, caractérisée en ce que le produit de nettoyage pour surfaces dures est un produit de lavage de la vaisselle.
EP09778105A 2008-08-30 2009-08-26 Utilisation d'oxalates de manganèse comme catalyseur de blanchiment Active EP2329000B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09778105T PL2329000T3 (pl) 2008-08-30 2009-08-26 Zastosowanie szczawianów manganu jako katalizatorów bielenia

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008045215A DE102008045215A1 (de) 2008-08-30 2008-08-30 Verwendung von Mangan-Oxalatenn als Bleichkatalysatoren
PCT/EP2009/006162 WO2010022918A1 (fr) 2008-08-30 2009-08-26 Utilisation d'oxalates de manganèse comme catalyseur de blanchiment

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EP2329000A1 EP2329000A1 (fr) 2011-06-08
EP2329000B1 true EP2329000B1 (fr) 2012-07-18

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US (1) US8927478B2 (fr)
EP (1) EP2329000B1 (fr)
JP (1) JP5667055B2 (fr)
CN (1) CN102131909B (fr)
DE (1) DE102008045215A1 (fr)
DK (1) DK2329000T3 (fr)
ES (1) ES2388234T3 (fr)
PL (1) PL2329000T3 (fr)
PT (1) PT2329000E (fr)
WO (1) WO2010022918A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008038376A1 (de) * 2008-08-19 2010-02-25 Clariant International Ltd. Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Verbindungen
DE102008045207A1 (de) * 2008-08-30 2010-03-04 Clariant International Limited Bleichkatalysatormischungen bestehend aus Mangansalzen und Oxalsäure oder deren Salze
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JP5667055B2 (ja) 2015-02-12
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US20110166055A1 (en) 2011-07-07
CN102131909A (zh) 2011-07-20
US8927478B2 (en) 2015-01-06
ES2388234T3 (es) 2012-10-11
DE102008045215A1 (de) 2010-03-04
WO2010022918A1 (fr) 2010-03-04
CN102131909B (zh) 2013-02-13
DK2329000T3 (da) 2012-10-15
EP2329000A1 (fr) 2011-06-08
PT2329000E (pt) 2012-09-17

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