EP2329001B1 - Mélanges de catalyseurs de blanchiment contenant des sels de manganèse et de l'acide oxalique ou ses sels - Google Patents

Mélanges de catalyseurs de blanchiment contenant des sels de manganèse et de l'acide oxalique ou ses sels Download PDF

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Publication number
EP2329001B1
EP2329001B1 EP09778106A EP09778106A EP2329001B1 EP 2329001 B1 EP2329001 B1 EP 2329001B1 EP 09778106 A EP09778106 A EP 09778106A EP 09778106 A EP09778106 A EP 09778106A EP 2329001 B1 EP2329001 B1 EP 2329001B1
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Prior art keywords
manganese
oxalic acid
salts
bleach activator
weight
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EP09778106A
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German (de)
English (en)
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EP2329001A1 (fr
Inventor
Gerd Reinhardt
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Clariant Finance BVI Ltd
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Clariant Finance BVI Ltd
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/2082—Polycarboxylic acids-salts thereof

Definitions

  • the present invention relates to the use of certain manganese compounds in combination with oxalic acid or its derivatives for enhancing the bleaching effect of inorganic peroxygen compounds in bleaching colored stains on hard surfaces, and hard surface cleaners containing such combinations.
  • 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 ).
  • De-C1 19909546 describes the use of Mn-ions in combination with oxalate complexing agents for improving the enzymatic oxidation in detergents and dishwashing detergents.
  • W02001 / 045842 describes a bleach catalyst containing a macrocyclic organic ligand (TCAN), besides a water-insoluble Mn compound such as manganese oxide or manganese oxalate and a peroxide source.
  • TCAN macrocyclic organic ligand
  • the present invention has the improvement of the oxidation and bleaching action of inorganic peroxygen compounds in conjunction with Manganese compounds at low temperatures below 80 ° C, especially in the temperature range of about 15 to 45 ° C, the goal.
  • manganese compounds in combination with a persalt and oxalic acid, their salts or derivatives have a significant contribution to the cleaning performance of the peroxygen compounds against colored stains on hard surfaces, especially when used in combination with under perhydrolysis conditions peroxycarboxylic acid releasing compounds.
  • the invention relates to bleach catalyst mixtures as defined in claim 1, containing a manganese compound, oxalic acid, its salts or derivatives, and an inorganic Persaergesstoffitati.
  • the manganese compounds are manganese salts in the +2 or +3 oxidation states selected from the group consisting of manganese halides, with the chlorides being preferred, manganese sulfates, manganese acetates, manganese acetylacetonates, and manganese nitrates.
  • the oxalic acid can be used as the free acid, mono- or disalt of alkali or alkaline earth metals or ammonium salts.
  • derivatives of oxalic acid can be used, wherein at least one acid function is not derivatized, besides oxalic acid derivatives are suitable which hydrolyze under washing conditions and release oxalic acid.
  • a peracid substance compound in addition to a peracid substance compound, preferably 0.025 to 2.5% by weight, in particular 0.05 to 1.5% by weight of bleach-intensifying manganese compound and 0.025 to 2.5% by weight, in particular 0, 05 to 1.5 wt .-% of oxalic acid, their salts or derivatives.
  • 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, as 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 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.
  • the bleach formulation can be conventional bleach activators, that is, compounds which give perbenzoic acid optionally substituted under perhydrolysis conditions and / or peroxycarboxylic acids having 1 to 10 carbon atoms, especially 2 to 4 carbon atoms.
  • bleach activators that is, compounds which give perbenzoic acid optionally substituted under perhydrolysis conditions and / or peroxycarboxylic acids having 1 to 10 carbon atoms, especially 2 to 4 carbon 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 main purpose of the use is to create conditions under which a peroxidic oxidizing agent and the combination of manganese salt and oxalic acid according to the invention can react with one another in the presence of a hard surface contaminated with colored stains, 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 inventive combination of manganese salt and oxalic acid to an optionally detergent-containing solution.
  • the method is particularly advantageous using a Hard surface cleaning agent containing the inventive combination of manganese salt and oxalic acid and 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, powdery or tablet-like solids, other shaped bodies, homogeneous solutions or suspensions, may contain, in principle, all known ingredients customary in such agents, as well as the said bleach-enhancing active ingredient.
  • 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 containing from 15 to 65% by weight, in particular from 20 to 60% by weight of water-soluble builder component, from 5 to 25% by weight, in particular from 8 to 17% by weight, of oxygen-based bleach, in each case to the total agent, and 0.05% to 1.5% by weight each of manganese salt and oxalic acid.
  • 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.
  • Suitable water-soluble builder components in detergents are in principle all builders customarily employed in detergents for dishwashing, for example alkali phosphates which may be present 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 besides polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the polycarboxylate type which act as co-builders, especially in hard water regions.
  • organic polymers of the polycarboxylate type which act as co-builders, especially in hard water regions.
  • examples include polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids.
  • 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.
  • compositions 20 to 60% by weight of water-soluble organic builders, in particular alkali citrate, 3 to 20% by weight of alkali metal carbonate and 3 to 40% by weight of alkali metal disilicate are contained.
  • 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 with in each case at to 8 mol ethylene oxide and propylene 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, hafnium, cobalt or cerium salts and / or complexes in which the abovementioned 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, hydrophobized silica, the Bisfettklareamide, and other other known commercially available defoamer may be added.
  • 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 Bisfettklareamide, and other other known commercially available defoamer may be added.
  • 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 advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • 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 200 x 10 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 carried out 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. The addition is carried out 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, the use of compositions containing inventive lead activator mixtures gives a completely clean and hygienically perfect dishes.
  • 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 (III) acetate) 57% V3 (cleaner + 100 mg Mn (II) sulphate) 55% V4 (cleaner + 100 mg oxalic acid) 60% V5 (cleaner + 100 mg FeSO 4 + 100 mg oxalic acid) 53% V6 (cleaner + 100 mg Na-oxalate) 67% M1 (cleaner + 100 mg Mn (II) SO 4 + 100 mg oxalic acid) 98% M2 (cleaner + 100 mg Mn (II) acetate + 100 mg oxalic acid) 97% M3 (cleaner + 100 mg Mn (II) SO 4 + 100 mg Na-oxalate) 95% M4 (cleaner + 100 mg Mn (III) acetate + 100 mg oxalic acid) 95% M5 (cleaner + 50 mg Mn (II) SO 4 + 50 mg oxalic acid) 73% M6 (clean

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Claims (7)

  1. Mélanges d'activateurs de blanchiment contenant un sel de manganèse dans l'étage d'oxydation +2 ou +3 choisi dans le groupe constitué par les halogénures de manganèse, les sulfates de manganèse, les nitrates de manganèse, les acétates de manganèse et les acétylacétonates de manganèse, l'acide oxalique, leur mono-sel ou di-sel avec des métaux alcalins ou alcalino-terreux ou leurs sels d'ammonium ou leurs dérivés, dans lesquels au moins une fonction acide n'est pas dérivée ou leurs dérivés qui s'hydrolysent dans les conditions de lavage et libèrent de l'acide oxalique, et un composé peroxygéné inorganique.
  2. Mélanges d'activateurs de blanchiment selon la revendication 1, caractérisés en ce qu'ils contiennent comme composé peroxygéné inorganique du peroxyde d'hydrogène ou du perborate de métal alcalin monohydraté ou, selon le cas, tétrahydraté et/ou du percarbonate de métal alcalin.
  3. Mélanges d'activateurs de blanchiment selon la revendication 1 ou 2, caractérisés en ce que le composé peroxygéné inorganique contient du sodium comme métal alcalin.
  4. Mélanges d'activateurs de blanchiment selon la revendication 1, caractérisés en ce qu'ils contiennent de l'acide oxalique ou de l'oxalate de sodium.
  5. Utilisation de mélanges d'activateurs de blanchiment selon l'une quelconque des revendications 1 à 4 dans des agents de lavage ou de nettoyage ou dans des agents de blanchiment.
  6. Utilisation de mélanges d'activateurs de blanchiment selon l'une quelconque des revendications 1 à 4 dans des agents de nettoyage pour surfaces dures.
  7. Utilisation des mélanges d'activateurs de blanchiment selon la revendication 6 dans des produits vaisselle destinés aux lave-vaisselle.
EP09778106A 2008-08-30 2009-08-26 Mélanges de catalyseurs de blanchiment contenant des sels de manganèse et de l'acide oxalique ou ses sels Active EP2329001B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09778106T PL2329001T3 (pl) 2008-08-30 2009-08-26 Mieszaniny katalizatorów bielenia składające się z soli manganu i kwasu szczawiowego lub jego soli

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008045207A DE102008045207A1 (de) 2008-08-30 2008-08-30 Bleichkatalysatormischungen bestehend aus Mangansalzen und Oxalsäure oder deren Salze
PCT/EP2009/006163 WO2010022919A1 (fr) 2008-08-30 2009-08-26 Mélanges de catalyseurs de blanchiment contenant des sels de manganèse et de l'acide oxalique ou ses sels

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EP2329001A1 EP2329001A1 (fr) 2011-06-08
EP2329001B1 true EP2329001B1 (fr) 2012-10-10

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US (1) US20110146723A1 (fr)
EP (1) EP2329001B1 (fr)
JP (1) JP5469667B2 (fr)
CN (1) CN102131908B (fr)
DE (1) DE102008045207A1 (fr)
DK (1) DK2329001T3 (fr)
ES (1) ES2396414T3 (fr)
PL (1) PL2329001T3 (fr)
PT (1) PT2329001E (fr)
WO (1) WO2010022919A1 (fr)

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DE102008045215A1 (de) * 2008-08-30 2010-03-04 Clariant International Ltd. Verwendung von Mangan-Oxalatenn als Bleichkatalysatoren
DE102008064009A1 (de) 2008-12-19 2010-06-24 Clariant International Ltd. Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Metall-Komplexen
CN105369581A (zh) * 2015-11-04 2016-03-02 泉州市新宏化工贸易有限公司 一种棉织物练漂后除氧工艺及棉洁爽
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CN102131908B (zh) 2013-02-20
PT2329001E (pt) 2013-01-24
EP2329001A1 (fr) 2011-06-08
US20110146723A1 (en) 2011-06-23
ES2396414T3 (es) 2013-02-21
PL2329001T3 (pl) 2013-03-29
WO2010022919A1 (fr) 2010-03-04
DK2329001T3 (da) 2013-01-28
JP5469667B2 (ja) 2014-04-16
DE102008045207A1 (de) 2010-03-04
JP2012500871A (ja) 2012-01-12

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