EP0761809A2 - Composition de blanchiment contenant des polyoxométalates comme catalyseurs de blanchiment - Google Patents
Composition de blanchiment contenant des polyoxométalates comme catalyseurs de blanchiment Download PDFInfo
- Publication number
- EP0761809A2 EP0761809A2 EP96113058A EP96113058A EP0761809A2 EP 0761809 A2 EP0761809 A2 EP 0761809A2 EP 96113058 A EP96113058 A EP 96113058A EP 96113058 A EP96113058 A EP 96113058A EP 0761809 A2 EP0761809 A2 EP 0761809A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- stands
- bleaching
- composition according
- bleaching agent
- agent composition
- Prior art date
- 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.)
- Granted
Links
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- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000004061 bleaching Methods 0.000 title claims description 33
- 239000000203 mixture Substances 0.000 title claims description 32
- 239000002253 acid Substances 0.000 claims description 31
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- 239000003599 detergent Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 13
- 150000007513 acids Chemical class 0.000 claims description 11
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- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000012459 cleaning agent Substances 0.000 claims description 7
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- 239000000654 additive Substances 0.000 claims description 6
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- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
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- 239000000243 solution Substances 0.000 description 13
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- 238000005406 washing Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 6
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- 238000000034 method Methods 0.000 description 4
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- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 3
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- 241001122767 Theaceae Species 0.000 description 3
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 2
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- 102000004190 Enzymes Human genes 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
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- WWISPHBAYBECQZ-UHFFFAOYSA-N cyclo-L-Ala-L-Ala Natural products CC1NC(=O)C(C)NC1=O WWISPHBAYBECQZ-UHFFFAOYSA-N 0.000 description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 2
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- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
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- 125000001402 nonanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MIKSWWHQLZYKGU-UHFFFAOYSA-M sodium;2-benzoyloxybenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1OC(=O)C1=CC=CC=C1 MIKSWWHQLZYKGU-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
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
- C11D3/395—Bleaching agents
Definitions
- Active oxygen bleaching is an essential component of modern washing and cleaning agents. Its main task is to remove stubborn stains, such as tea, coffee, red wine or fruit juices, from textile fibers or solid surfaces. This is done by oxidative destruction of the chromophoric system; At the same time, adhering microorganisms are killed and adhering odor substances are neutralized.
- bleach activators are often added to them.
- these are reactive carboxylic acid esters and carboxamides.
- Preferred are tetraacetylethylene diamine (TAED), nonanoyloxy benzene sulfonate (NOBS), benzoyloxy benzene sulfonate (DADHT), pentaacetyl glucose (PAG), nonanoyl and benzoyl caprolactam, malic acid - or aryl nitriles.
- the corresponding peracids are released from the bleach activators, which usually have a broader activity spectrum than hydrogen peroxide.
- organic peroxycarboxylic acids can also be used directly as bleaching agents.
- bleach compositions that can further enhance the performance of the above compositions (i.e., bleach or bleach and bleach activator).
- bleach or bleach and bleach activator For economic and ecological reasons, catalytically active compounds are preferred.
- bleaching catalysts which react directly with the inorganic persalt in a low concentration and thus make the use of bleaching activators superfluous.
- transition metals in free or complex form catalyze the decomposition of hydrogen peroxide.
- the effectiveness of the compounds described so far is unsatisfactory in most cases.
- the addition of metal salts leads to catalytic decomposition of the hydrogen peroxide, but no bleaching effect is observed. This is usually associated with damage to the textile fabric.
- the occurrence of free transition metals during the washing and cleaning process is therefore undesirable. If the metal is used in a complexed form, the corresponding complex must be stable to hydrolysis and oxidation during storage and under conditions of use so that these side effects are suppressed.
- heteropolyacids for the oxidation of alkanes in organic solvents is known from EP-A-0 301 723.
- vanadium-doped polyoxometalates in the paper industry is described in WO-94/05849.
- J. Amer. Chem. Soc. 1991, 113, 7209-7221 and 7222-7226 describe the use of polyoxometalates for the oxidation of olefins in organic solvents.
- polyoxometalates or polyacids are outstandingly suitable as bleaching catalysts in bleaching agent compositions and are already available in low, i.e. catalytic amounts, increase the effectiveness of bleaching agents such as hydrogen peroxide, inorganic and organic peracids or caroates.
- Polyoxometalates are inorganic metal-oxygen clusters with defined oligomeric or polymeric structural units that spontaneously form under suitable conditions in an aqueous environment from simple vanadium, niobium, tantalum, molybdenum or tungsten compounds (see MT Pope, Heteropoly and Isopoly Oxometalates, Springer-Verlag, Berlin, 1983).
- Isopolyoxometalates are the simplest forms of polyoxometalates and can be described as binary oxide anions of the formula [M m O y ] p- , ie containing only metal ions and oxygen.
- Typical examples of such Isopolyoxometalates are [Mo 2 O 7 ] 2- , [W 6 O 24 ] 12 , [Mo 6 O 16 ] 2- , [Mo 36 O 112 ] 8- .
- heteropolyoxometalates contain further non-metal, semimetal and / or transition metal ions.
- Other substitutions, including different transition metal ions are known, for example [WZnMn 2 (ZnW 9 O 34 ) 2 ] 12- (J. Amer. Chem. Soc. 116, 1994, 5509).
- polyoxometalate used in the description includes both the salts of the polyacids and the corresponding polyacids.
- the polyoxometalates used according to the invention include both the aforementioned polyoxometalates of the prior art and the polyoxometalates described in the priority German application 195 30 787.9. This German patent application is expressly included here.
- q, a, x, m, y, z, b and c preferably in the ranges indicated therefor, are integers.
- these bleach catalysts are added in granular form to the bleach composition.
- they are incorporated into the bleach activator granules.
- Inorganic salts such as sodium sulfate, chloride, phosphate or silicates can be used as granulation aids.
- inorganic or organic auxiliaries can be used for granulation, film-forming materials such as surfactants, fatty acids, cellulose derivatives or polymers are preferred.
- the granules can additionally be provided with a coating, which on the one hand increases their storage stability and prevents interactions with other detergent ingredients during storage, but on the other also has a positive effect on their dissolution kinetics.
- Preferred inorganic persalts are alkali metal perborates, percarbonates, perphosphates or persulfates.
- Particularly preferred bleaches when the bleach catalysts are used in powder products are perborates, such as sodium perborate mono- or tetrahydrate, percarbonates, such as sodium percarbonate, Caro's acid or salts of Caro's acid in the form of the triple salt.
- the bleaching agents can either be used alone with the bleach catalysts according to the invention or, in a preferred embodiment, in combination with a bleach activator. As a result, the range of applications is expanded and the germicidal properties of the compositions according to the invention are enhanced.
- the bleaching agents which can be used without a bleach activator preferably include the above-mentioned organic bleaching agents.
- the use of a bleach activator is particularly advantageous for inorganic bleaching agents.
- Bleach activators are compounds which react in aqueous solutions containing hydrogen peroxide or persalts to form peracids which have a bleaching action.
- all known bleach activators are suitable as bleach activators. These include in particular the N-acylated amines, N-acylated diamines, N-acylated amides and glycolurils, as described, for example, in DE-AS-11 62 967, DE-AS-12 91 317, DE-OS-20 38 106 are known.
- tetraacetylmethylene diamine tetraacetylethylene diamine, diacetylaniline, diacetyl-p-toluidine, 1,3-diacetyl-5,5-dimethylhydantoin, tetraacetylglycoluril, tetrapropionylglycoluril, 1,4-diacetyl-2,5-diketopiacyl and 1,4 3,6-dimethyl-2,5-diketopiperazine and diacetyldioxohexahydrotriazine (DADHT).
- DADHT diacetyldioxohexahydrotriazine
- acyloxybenzenesulfonates such as nonanoyloxybenzenesulfonate (NOBS) and benzoyloxybenzenesulfonate (BOBS)
- acylated sugars such as pentaacetylglucose (PAG)
- sugar derivatives such as sugar amides
- activated carboxylic acid esters carboxylic anhydrides, such as isato, maleic, succinic and citric anhydride, lactones, acylals, acyl lactams, such as nonanoyl and benzoyl caprolactam, alkyl nitriles and aryl nitriles.
- the bleaching agent compositions according to the invention may also contain further additives from the groups of surface-active compounds, such as anionic, nonionic, zwitterionic, amphoteric or cationic surfactants, builders, cobuilders, enzymes and additives.
- surface-active compounds such as anionic, nonionic, zwitterionic, amphoteric or cationic surfactants, builders, cobuilders, enzymes and additives.
- Surfactants can be of natural or synthetic origin and are e.g. in "Surface Active Agents and Detergents" Volumes I and II by Schwartz, Perry and Berch. Examples are alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alpha-sulfofatty acid methyl esters, soaps and alkyl ether sulfonates. Nonionic surfactants such as alkyl polyglycol ethers, alkyl polyglucosides, glucamides, sugar esters and amine oxides can also be used.
- Important builder and cobuilder substances are phosphates, such as sodium polyphosphate, zeolites of the types A, X and P, alkali metal carbonates and alkali metal hydrogen carbonates, amorphous and crystalline silicates, in particular layered silicates, such as SKS-6, SKS-7, SKS-9 and SKS-10 der Hoechst AG (Germany) or disilicates such as those sold by Akzo under the trade name Britesil.
- Organic carboxylic acids such as citric acid or amino acids can be used as cobuilders, but also polymers of the polyacrylic acid type or copolymers of acrylic acid and maleic acid or its derivatives. Phosphonates or other complexing agents can also be added.
- Amylase, proteases, lipases, cellulases and peroxidases can be used as enzymes, cellulose ethers, silicones, bentonites, optical brighteners and perfume as further additives.
- the bleaching agent compositions according to the invention generally consist of 1 to 99.9995% by weight, preferably 5 to 99.999% by weight, of one or more bleaching agents, 0.0005 to 2% by weight, preferably 0.001 to 0.5% by weight, of one or more bleaching catalysts, 0 to 70% by weight, preferably 10 to 60% by weight of a bleach activator and optionally further additives to 100% by weight of the composition.
- the bleaching compositions according to the invention are used in detergents and cleaning agents, e.g. Heavy duty detergents, multi-component detergents (modular systems), stain salts, stain pretreatment agents, dishwasher detergents, detergents for hard surfaces, disinfectants and denture cleaners.
- detergents and cleaning agents e.g. Heavy duty detergents, multi-component detergents (modular systems), stain salts, stain pretreatment agents, dishwasher detergents, detergents for hard surfaces, disinfectants and denture cleaners.
- the bleaching catalysts used according to the invention also take on the function of dye transfer inhibitors.
- the polyoxometalates used according to the invention have catalytic properties and are able, in combination with one or more bleaching agents, to increase their bleaching performance several times, in particular in the washing and cleaning process, without showing fiber damage.
- Another advantage of the bleaching catalysts used according to the invention is that there are no problems with the biodegradability.
- the bleaching agent compositions according to the invention are usually used Consisting of bleaching catalyst and bleaching agent and possibly bleach activator used in the washing and cleaning agents in the following concentrations: Heavy duty detergent: 2 to 40% by weight Stain salts and laundry pretreatment agents: 20 to 100% by weight Dishwasher detergent: 1 to 30% by weight Cleaning agents for hard surfaces and disinfectants: 2 to 50% by weight Denture cleaner: 2 to 20% by weight
- the bleaching agent compositions according to the invention can be added to the washing and cleaning agents in the form of a powder or granulate.
- Example 2 Polyoxy tungstate with Mn and Se (K-2)
- Example 3 Polyoxy tungstate with Mn and Se (K-3)
- a solution of 7.5 mmol of manganese (II) nitrate and 7.5 mmol of manganese (II) acetate in 120 ml of 1-normal hydrochloric acid is added to a solution of 0.12 mol of sodium tungstate dihydrate and 15 mmol of selenic acid in 200 ml of water dripped. After stirring for 2 hours at room temperature, an excess of solid potassium chloride (3.0 g) is added, the mixture is filtered off after 24 hours and the precipitate is washed with saturated CsCl solution. After drying in 2.4 g of a brown powder are obtained under vacuum.
- Example 5 Instructions as in Example 5. In contrast to Example 5, the precipitation was carried out with 60 ml of a 1 normal KCl solution in water. Mo / Mn ratio corresponds to 9: 1, contains no selenium, no ESR signal, IR (KBr) 874, 895, 914, 930 cm-1.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19530786 | 1995-08-22 | ||
| DE19530786A DE19530786A1 (de) | 1995-08-22 | 1995-08-22 | Bleichmittelzusammensetzung enthaltend Polyoxometallate als Bleichkatalysator |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0761809A2 true EP0761809A2 (fr) | 1997-03-12 |
| EP0761809A3 EP0761809A3 (fr) | 1998-09-02 |
| EP0761809B1 EP0761809B1 (fr) | 2004-11-03 |
Family
ID=7770053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96113058A Expired - Lifetime EP0761809B1 (fr) | 1995-08-22 | 1996-08-14 | Composition de blanchiment contenant des polyoxométalates comme catalyseurs de blanchiment |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5928382A (fr) |
| EP (1) | EP0761809B1 (fr) |
| JP (1) | JP4107690B2 (fr) |
| KR (1) | KR970010940A (fr) |
| BR (1) | BR9603491A (fr) |
| CA (1) | CA2183814C (fr) |
| DE (2) | DE19530786A1 (fr) |
| ES (1) | ES2231796T3 (fr) |
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| WO1999028426A1 (fr) * | 1997-12-03 | 1999-06-10 | U.S. Borax Inc. | Compositions de blanchiment |
| WO2000039264A1 (fr) * | 1998-12-23 | 2000-07-06 | Unilever Plc | Blanchiment a l'aide de polyoxometalates et d'air ou d'oxygene moleculaire |
| WO2012000846A1 (fr) | 2010-06-28 | 2012-01-05 | Basf Se | Composition de blanchiment dépourvue de métal |
| WO2013045294A1 (fr) * | 2011-09-28 | 2013-04-04 | BSH Bosch und Siemens Hausgeräte GmbH | Appareil ménager à circulation d'eau, présentant une surface intérieure catalytiquement active, et procédé pour le faire fonctionner |
| WO2013060708A1 (fr) | 2011-10-25 | 2013-05-02 | Basf Se | Utilisation de copolymères en peigne ou séquencés comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie |
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| WO2014154432A1 (fr) * | 2013-03-26 | 2014-10-02 | BSH Bosch und Siemens Hausgeräte GmbH | Appareil ménager ayant une surface catalytiquement active ainsi que procédé pour le faire fonctionner |
| WO2017186480A1 (fr) | 2016-04-26 | 2017-11-02 | Basf Se | Composition de blanchiment sans métal |
| DE102016008185A1 (de) | 2016-07-04 | 2018-01-04 | Sven Herrmann | Salz zur Reinigung von einer Flüssigkeit und/oder einem Gas |
| EP3409757A1 (fr) | 2017-06-01 | 2018-12-05 | Henkel AG & Co. KGaA | Composition detergente blanchissante |
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| DE102017209336A1 (de) | 2017-06-01 | 2018-12-06 | Henkel Ag & Co. Kgaa | Bleichverstärkung beim Waschen und Reinigen |
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| CN114737401A (zh) * | 2022-05-18 | 2022-07-12 | 江苏金秋弹性织物有限公司 | 一种棉类织带基于POMs原位催化降解杂质的低碱前处理工艺 |
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| DE1162967B (de) | 1959-06-19 | 1964-02-13 | Konink Ind Mij Voorheen Noury | Wasch- und/oder Bleichmittel |
| DE1291317B (de) | 1958-05-09 | 1969-03-27 | Unilever Nv | Verfahren zum Bleichen von Textilien |
| DE2038106A1 (de) | 1970-07-31 | 1972-02-10 | Henkel & Cie Gmbh | Aktivatoren fuer Perverbindungen |
| EP0301723A1 (fr) | 1987-07-20 | 1989-02-01 | Sun Refining and Marketing Company | Oxydation des alcanes |
| WO1994005849A1 (fr) | 1992-08-28 | 1994-03-17 | THE UNITED STATES OF AMERICA as represented by THE SECRETARY, U.S. DEPARTMENT OF AGRICULTURE | Blanchiment oxydatif de la cellulose a l'aide de polyoxometalates a substitution vanadium |
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| DE19530787A1 (de) * | 1995-08-22 | 1997-02-27 | Hoechst Ag | Mangan enthaltende Polyoxometallate, Synthese und Verwendung |
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- 1995-08-22 DE DE19530786A patent/DE19530786A1/de not_active Withdrawn
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- 1996-08-14 EP EP96113058A patent/EP0761809B1/fr not_active Expired - Lifetime
- 1996-08-14 ES ES96113058T patent/ES2231796T3/es not_active Expired - Lifetime
- 1996-08-14 DE DE59611133T patent/DE59611133D1/de not_active Expired - Lifetime
- 1996-08-21 BR BR9603491A patent/BR9603491A/pt not_active IP Right Cessation
- 1996-08-21 CA CA002183814A patent/CA2183814C/fr not_active Expired - Fee Related
- 1996-08-21 JP JP22015196A patent/JP4107690B2/ja not_active Expired - Fee Related
- 1996-08-22 US US08/701,475 patent/US5928382A/en not_active Expired - Lifetime
- 1996-08-22 KR KR1019960034792A patent/KR970010940A/ko not_active Withdrawn
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| DE1291317B (de) | 1958-05-09 | 1969-03-27 | Unilever Nv | Verfahren zum Bleichen von Textilien |
| DE1162967B (de) | 1959-06-19 | 1964-02-13 | Konink Ind Mij Voorheen Noury | Wasch- und/oder Bleichmittel |
| DE2038106A1 (de) | 1970-07-31 | 1972-02-10 | Henkel & Cie Gmbh | Aktivatoren fuer Perverbindungen |
| EP0301723A1 (fr) | 1987-07-20 | 1989-02-01 | Sun Refining and Marketing Company | Oxydation des alcanes |
| WO1994005849A1 (fr) | 1992-08-28 | 1994-03-17 | THE UNITED STATES OF AMERICA as represented by THE SECRETARY, U.S. DEPARTMENT OF AGRICULTURE | Blanchiment oxydatif de la cellulose a l'aide de polyoxometalates a substitution vanadium |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6326342B1 (en) * | 1997-12-03 | 2001-12-04 | U.S. Borax Inc. | Bleaching compositions |
| WO1999028426A1 (fr) * | 1997-12-03 | 1999-06-10 | U.S. Borax Inc. | Compositions de blanchiment |
| WO2000039264A1 (fr) * | 1998-12-23 | 2000-07-06 | Unilever Plc | Blanchiment a l'aide de polyoxometalates et d'air ou d'oxygene moleculaire |
| EP3524347A1 (fr) | 2008-04-09 | 2019-08-14 | Basf Se | Utilisation de composés complexes hydrazides métalliques en tant que catalyseurs d'oxydation |
| WO2012000846A1 (fr) | 2010-06-28 | 2012-01-05 | Basf Se | Composition de blanchiment dépourvue de métal |
| CN103857841B (zh) * | 2011-09-28 | 2016-05-18 | Bsh家用电器有限公司 | 具有催化活性内部表面的带水运行的家用器具和用于操作该家用器具的方法 |
| WO2013045294A1 (fr) * | 2011-09-28 | 2013-04-04 | BSH Bosch und Siemens Hausgeräte GmbH | Appareil ménager à circulation d'eau, présentant une surface intérieure catalytiquement active, et procédé pour le faire fonctionner |
| CN103857841A (zh) * | 2011-09-28 | 2014-06-11 | Bsh博世和西门子家用电器有限公司 | 具有催化活性内部表面的带水运行的家用器具和用于操作该家用器具的方法 |
| US9451866B2 (en) | 2011-09-28 | 2016-09-27 | BSH Bosch und Siemens Hausgeräte GmbH | Water-using domestic appliance with a catalytically active interior surface and method for operating the same |
| WO2013060708A1 (fr) | 2011-10-25 | 2013-05-02 | Basf Se | Utilisation de copolymères en peigne ou séquencés comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie |
| WO2013060706A1 (fr) | 2011-10-25 | 2013-05-02 | Basf Se | Utilisation de copolymères d'acrylate comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie |
| US9776171B2 (en) | 2013-03-26 | 2017-10-03 | BSH Hausgeräte GmbH | Household appliance having a catalytically effective surface and method for the operation thereof |
| CN105074077A (zh) * | 2013-03-26 | 2015-11-18 | Bsh家用电器有限公司 | 具有催化有效表面的家用器具及其运行方法 |
| RU2617986C1 (ru) * | 2013-03-26 | 2017-04-28 | Бсх Хаусгерете Гмбх | Бытовой прибор с каталитически активной поверхностью и способ эксплуатации такого бытового прибора |
| WO2014154432A1 (fr) * | 2013-03-26 | 2014-10-02 | BSH Bosch und Siemens Hausgeräte GmbH | Appareil ménager ayant une surface catalytiquement active ainsi que procédé pour le faire fonctionner |
| US9790452B2 (en) | 2013-03-27 | 2017-10-17 | Basf Se | Block copolymers as soil release agents in laundry processes |
| WO2014154508A1 (fr) | 2013-03-27 | 2014-10-02 | Basf Se | Copolymères blocs comme agents de libération de la saleté dans des procédés de blanchisserie |
| US10214606B2 (en) | 2013-11-27 | 2019-02-26 | Basf Se | Random copolymers as soil release agents in laundry processes |
| WO2017186480A1 (fr) | 2016-04-26 | 2017-11-02 | Basf Se | Composition de blanchiment sans métal |
| DE102016008185A1 (de) | 2016-07-04 | 2018-01-04 | Sven Herrmann | Salz zur Reinigung von einer Flüssigkeit und/oder einem Gas |
| EP3409753A1 (fr) | 2017-06-01 | 2018-12-05 | Henkel AG & Co. KGaA | Renforcement de l'effet de blanchiment lors du lavage et du nettoyage |
| DE102017209333A1 (de) | 2017-06-01 | 2018-12-06 | Henkel Ag & Co. Kgaa | Bleichendes Wasch- oder Reinigungsmittel |
| DE102017209332A1 (de) | 2017-06-01 | 2018-12-06 | Henkel Ag & Co. Kgaa | Bleichendes Wasch- oder Reinigungsmittel |
| DE102017209335A1 (de) | 2017-06-01 | 2018-12-06 | Henkel Ag & Co. Kgaa | Bleichverstärkung beim Waschen und Reinigen |
| DE102017209336A1 (de) | 2017-06-01 | 2018-12-06 | Henkel Ag & Co. Kgaa | Bleichverstärkung beim Waschen und Reinigen |
| EP3415593A1 (fr) | 2017-06-01 | 2018-12-19 | Henkel AG & Co. KGaA | Renforcement de l'effet de blanchiment lors du lavage et du nettoyage |
| EP3409756A1 (fr) | 2017-06-01 | 2018-12-05 | Henkel AG & Co. KGaA | Composition detergente blanchissante |
| EP3409757A1 (fr) | 2017-06-01 | 2018-12-05 | Henkel AG & Co. KGaA | Composition detergente blanchissante |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0761809A3 (fr) | 1998-09-02 |
| BR9603491A (pt) | 1998-05-12 |
| KR970010940A (ko) | 1997-03-27 |
| CA2183814C (fr) | 2008-12-23 |
| JP4107690B2 (ja) | 2008-06-25 |
| JPH09118899A (ja) | 1997-05-06 |
| ES2231796T3 (es) | 2005-05-16 |
| EP0761809B1 (fr) | 2004-11-03 |
| US5928382A (en) | 1999-07-27 |
| DE59611133D1 (de) | 2004-12-09 |
| CA2183814A1 (fr) | 1997-02-23 |
| DE19530786A1 (de) | 1997-02-27 |
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