EP0761809B1 - Composition de blanchiment contenant des polyoxométalates comme catalyseurs de blanchiment - Google Patents

Composition de blanchiment contenant des polyoxométalates comme catalyseurs de blanchiment Download PDF

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Publication number
EP0761809B1
EP0761809B1 EP96113058A EP96113058A EP0761809B1 EP 0761809 B1 EP0761809 B1 EP 0761809B1 EP 96113058 A EP96113058 A EP 96113058A EP 96113058 A EP96113058 A EP 96113058A EP 0761809 B1 EP0761809 B1 EP 0761809B1
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Prior art keywords
weight
bleaching
group
acids
acid
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EP96113058A
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German (de)
English (en)
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EP0761809A2 (fr
EP0761809A3 (fr
Inventor
Gerd Dr. Reinhardt
Vera Friderichs
Bernd Dr. Scharbert
Rolf Peter Dr. Schulz
Bernt Prof. Dr. Krebs
Rainer Dl. Böhner
Christian Dl. Thülig
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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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
    • C11D3/395—Bleaching agents

Definitions

  • Active oxygen bleaching is an essential part of modern Detergents and cleaning agents. Your main job is removing stubborn Soiling, such as tea, coffee, red wine or fruit juices, from textiles Fibers or solid surfaces. This is done by oxidative destruction of the chromophoric system; at the same time become adherent microorganisms killed and adhering odors neutralized.
  • Hydrogen peroxide, organic, are usually used as bleaching or oxidizing agents or inorganic peracids used.
  • powdered washing and Detergent is usually a persalt as a source of hydrogen peroxide used.
  • TAED Tetraacetylethylenediamine
  • NOBS Nonanoyloxibenzenesulfonate
  • BOBS benzoyloxibenzenesulfonate
  • DADHT Diacetyldioxohexahydrotriazine
  • PAG pentaacetylglucose
  • Nonanoyl and benzoyl caprolactam isatoic, maleic, amber and Citric anhydrides and acylated sugar or sugar derivatives, next to it Alkyl or aryl nitriles.
  • the bleach activators corresponding peracids released, which usually have a broader spectrum of action exhibit as hydrogen peroxide.
  • transition metals in free or complex form catalyze the decomposition of hydrogen peroxide.
  • the Most of the compounds described so far are effective Cases unsatisfactory.
  • the addition of metal salts leads to one catalytic decomposition of the hydrogen peroxide, however, a bleaching effect not observed. This is usually with damage to the textile fabric connected.
  • the appearance of free transition metals during washing and Cleaning process is therefore undesirable.
  • the metal becomes more complex Form used, the corresponding complex must be used during storage and under Conditions of use be stable to hydrolysis and oxidation, so this Side effects are suppressed.
  • heteropolyacids for the oxidation of alkanes in organic solvents are known from EP-A-0 301 723.
  • the use of Vanadium-doped polyoxometalates in the paper industry is described in WO-94/05849 described.
  • J. Amer. Chem. Soc. 1991, 113, 7209-7221 and 7222-7226 describes the use of polyoxometalates for the oxidation of Olefins described in organic solvents.
  • the invention thus relates to the use of heteropolyoxometalates as bleaching catalysts in peroxide containing Detergents, cleaning agents, disinfectants and denture cleaners.
  • Polyoxometalates are inorganic metal-oxygen clusters with defined oligomeric or polymeric structural units that spontaneously come under suitable Conditions in an aqueous environment from simple vanadium, niobium, tantalum, Form molybdenum or tungsten compounds (see M.T. Pope, Heteropoly and Isopoly Oxometalates, Springer-Verlag, Berlin, 1983).
  • the polyoxometalates are divided into iso- and heteropolyoxometalates.
  • Isopolyoxometalates are the simplest forms of polyoxometalates and can be described as binary, ie only metal anions and oxygen-containing oxide anions of the formula [M m O y ] p- .
  • 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.
  • transition metal ion A By substituting M m O y structural units both in iso- and in heteropolyoxometalates for a transition metal ion A, it is possible to introduce redoxative transition metal ions of type A into the solid-state structures.
  • the term used in the description includes Polyoxometalate both the salts of the polyacids and the corresponding ones Polyacids.
  • q, a, x, m, y, z, b and c mean in the ranges specified therefor, preferably whole numbers.
  • these bleaching catalysts are in granular form Bleach composition added. In a preferred application form they are incorporated into the bleach activator granulate.
  • a granulating aid can be inorganic salts, such as sodium sulfate, chloride, phosphate or silicates be used.
  • inorganic or organic auxiliaries are used, preferred are film-forming materials, such as surfactants, fatty acids, Cellulose derivatives or polymers.
  • the granules can also with a Coating should be provided, which on the one hand increases their storage stability and Interactions with other detergent ingredients during the Storage can be prevented, but also their dissolution kinetics is positively influenced.
  • Preferred inorganic persalts are alkali metal perborates, percarbonates, perphosphates or persulfates.
  • Particularly preferred bleaching agents are if the bleaching catalysts are used in powder products, 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 bleaching 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
  • Suitable bleach activators are state of the art 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, amber and Citric anhydride, lactones, acylals, acyl lactams, such as nonanoyl and Benzoyl caprolactam, alkyl nitriles and aryl nitriles.
  • Acyloxybenzenesulfonates such as nonanoyloxybenzenesulfonate (NOBS) and Benzoyloxybenzenesulfonate (BOBS)
  • acylated sugars such as pentaacetylgluco
  • the bleaching compositions according to the invention still further additives from the groups of surface-active compounds, such as anionic, non-ionic, zwitterionic, amphoteric or cationic surfactants, builders, Contain cobuilders, enzymes and additives.
  • surface-active compounds such as anionic, non-ionic, zwitterionic, amphoteric or cationic surfactants, builders, Contain 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 described. Examples are alkyl sulfates, alkyl sulfonates, Alkylarylsulfonates, alpha-sulfofatty acid methyl esters, soaps and Alkyl ether. Nonionic surfactants, such as alkyl polyglycol ethers, Alkyl polyglucosides, glucamides, sugar esters and amine oxides can also be used 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, as further additives cellulose ethers, silicones, bentonites, optical brighteners and Perfume can be used.
  • 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 Washing and cleaning agents, e.g. Heavy-duty detergents, Multi-component detergents (modular systems), stain salts, Stain pretreatment agents, dishwasher detergents, cleaning agents for hard surfaces, disinfectants and denture cleaners.
  • Washing and cleaning agents e.g. Heavy-duty detergents, Multi-component detergents (modular systems), stain salts, Stain pretreatment agents, dishwasher detergents, cleaning agents for hard surfaces, disinfectants and denture cleaners.
  • bleaching catalysts used according to the invention also the function of dye transfer inhibitors.
  • the polyoxometalates used according to the invention have catalytic ones Properties and are able to be combined with one or more Bleaching agents whose bleaching performance, especially in washing and Cleaning process to increase several times without fiber damage demonstrate.
  • Another advantage of the used according to the invention Bleaching catalysts is that there are no problems with the biological Degradability result.
  • the bleaching agent compositions according to the invention consisting of bleaching catalyst and bleaching agent and optionally bleach activator, are usually used in the washing and cleaning agents in the following concentrations: Vollwaschsch 2 to 40% by weight Stain removers and laundry pretreatment agents 20 to 100% by weight Automatic dishwasher detergents 1 to 30% by weight Hard surface cleaner and disinfectant cleaner 2 to 50% by weight denture cleaners 2 to 20% by weight
  • the bleaching compositions according to the invention can be used for washing and Detergents in the form of a powder or granules can be added.
  • Example 2 Polyoxy tungstate with Mn and Se (K-2)
  • Example 3 Polyoxy tungstate with Mn and Se (K-3)
  • 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 9: 1, no selenium, no ESR signal, IR (KBr) 874, 895, 914, 930 cm-1.
  • Bleaching catalysts are capable of even in low concentrations Increase bleaching performance of various bleaching agents at 20 ° C.

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  • 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)

Claims (8)

  1. Utilisation d'hétéropolyoxométallates de formule générale (Q)q(AaXxMmOyZz(H2O)b-cH2O dans laquelle les symboles Q, A, X, M, Z, q, a, x, m, y, z, b et c ont les significations suivantes:
    Q représente un ou plusieurs cations choisis dans le groupe formé par H, Li, K, Na, Rb, Cs, Ca, Mg, Sr, Ba,
    Al, PR1R2R3R4 et NR1R2R3R4, où R1, R2, R3 et R4 sont identiques ou différents et représentent un atome d'hydrogène, un groupe alkyle en C1 à C20, cycloalkyle en C5 à C8 ou aryle en C6 à C24 ;
    q représente un nombre de 1 à 60, en particulier de 1 à 40 et désigne en même temps, pour des contre-cations monovalents, la charge de l'unité anionique ;
    A représente un ou plusieurs métaux de transition des sous-groupes 2 et 8, de préférence Mn, V, Ti, Fe, Co, Cu, Zn, Ni et, de manière plus particulièrement préférée, Mn, V, Ti, Fe, Co et Zn ;
    a représente un nombre de 1 à 10, de préférence de 1 à 8 ;
    X représente un ou plusieurs atomes choisis dans le groupe formé par Sb, S, Se, Te, Bi, Ga, B, P, Si, Ge, F, Cl, Br et I ; de préférence P, B, S, Sb, Bi, Si, F, Cl, Br et I ;
    x représente un nombre de 1 à 10, de préférence de 0 à 8 ;
    M représente Mo ou W ;
    m représente un nombre de 0,5 à 60, de préférence de 4 à 10 ;
    Z représente un ou plusieurs anions choisis dans le groupe formé par OH-, F-, Cl-, Br-, I-, N3 -, NO3 -, ClO4 -, NCS-, SCN-, PF6 -, RSO3 -, RSO4 -, CF3SO3 -, BR4 -, BF4 -, CH3COO-, où R représente un atome d'hydrogène, un groupe alkyle en C1 à C20, cycloalkyle en C5 à C8 ou aryle en C6 à C24 ;
    z représente un nombre de 0 à 10, de préférence de 1 à 8 ;
    O représente un atome d'oxygène ;
    y représente le nombre d'atomes d'oxygène nécessaire pour l'équilibre structure/charge et
    b et c représentent, indépendamment l'un de l'autre, des nombres de 0 à 50, de préférence de 0 à 30,
    en tant que catalyseurs de blanchiment dans des détergents, des produits nettoyants, des désinfectants et des produits nettoyants pour appareils dentaires contenant des peroxydes.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'on met en oeuvre, en tant qu'agent de blanchiment, le peroxyde d'hydrogène, des peracides organiques, des peracides inorganiques, des persels organiques, des persels inorganiques, l'acide de Caro et les caroates.
  3. Utilisation selon l'une quelconque des revendications 1 ou 2, caractérisée en ce que les peracides organiques ou leurs sels sont choisis dans le groupe formé par les acides monoperoxycarboxyliques, les acides diperoxycarboxyliques, les acides peroxycarboxyliques avec une liaison amide dans la chaíne hydrocarbonée, les acides sulfonylperoxycarboxyliques, les acides phtaloylaminoperoxycarboxyliques de formule
    Figure 00250001
    dans laquelle R représente un atome d'hydrogène, de chlore, de brome, un groupe alkyle en C1 à C20, alcényle en C1 à C20, aryle, de préférence un groupe phényle ou alkaryle, de préférence un groupe (alkyle en C1 à C4) phényle et n représente un nombre entier de 1 à 20.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que les persels inorganiques sont choisis dans le groupe formé par les perborates de métaux alcalins, les percarbonates de métaux alcalins, les perphosphates de métaux alcalins ainsi que les persulfates de métaux alcalins.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que l'on met en oeuvre en outre un ou plusieurs activateurs de blanchiment.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que l'activateur de blanchiment est choisi dans le groupe formé par les amines N-acylées, les diamines N-acylées, les amides N-acylés, les glycoluriles, les acyloxybenzènesulfonates, les glucides acylés, les dérivés de glucides, les esters d'acides carboxyliques activés, les amides d'acides carboxyliques activés, les anhydrides d'acides carboxyliques, les lactones, les acylales, les acyllactames, les alkylnitriles et les arylnitriles.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on met en oeuvre des adjuvants supplémentaires.
  8. Utilisation selon l'une quelconque des revendications 1 à 7, dans laquelle les agents nettoyants ou les produits nettoyants pour appareils dentaires se composent de
    1% à 99,9995% en poids, de préférence de 5% à 99,999% en poids d'un ou de plusieurs agents de blanchiment,
    0,0005% à 2% en poids, de préférence de 0,001% à 0,5% en poids d'un ou de plusieurs catalyseurs de blanchiment,
    0% à 70%, de préférence de 10% à 60% en poids d'un ou de plusieurs activateurs de blanchiment et
       éventuellement d'adjuvants supplémentaires jusqu'à 100% en poids de la composition.
EP96113058A 1995-08-22 1996-08-14 Composition de blanchiment contenant des polyoxométalates comme catalyseurs de blanchiment Expired - Lifetime EP0761809B1 (fr)

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

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EP0761809A2 EP0761809A2 (fr) 1997-03-12
EP0761809A3 EP0761809A3 (fr) 1998-09-02
EP0761809B1 true EP0761809B1 (fr) 2004-11-03

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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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DE102011083572A1 (de) 2011-09-28 2013-03-28 BSH Bosch und Siemens Hausgeräte GmbH Wasserführendes Haushaltsgerät mit einer katalytisch wirksamen inneren Oberfläche sowie Verfahren zu seinem Betrieb
DE102013205302A1 (de) 2013-03-26 2014-10-16 BSH Bosch und Siemens Hausgeräte GmbH Hausgerät mit einer katalytisch wirksamen Oberfläche sowie Verfahren zu seinem Betrieb
DE102015224832A1 (de) 2015-12-10 2017-06-14 BSH Hausgeräte GmbH Flüssigkeitsspeichersystem für ein flüssigkeitsführendes Haushaltsgerät

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US8809392B2 (en) 2008-03-28 2014-08-19 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
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ES2651319T3 (es) 2010-06-28 2018-01-25 Basf Se Composición blanqueadora libre de metales
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KR102004562B1 (ko) 2011-10-25 2019-07-26 헨켈 아게 운트 코 카게아아 세탁 과정에서의 오염 재부착방지제 및 방오제로서의 빗살형 또는 블록 공중합체의 용도
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KR970010940A (ko) 1997-03-27
JP4107690B2 (ja) 2008-06-25
CA2183814C (fr) 2008-12-23
ES2231796T3 (es) 2005-05-16
CA2183814A1 (fr) 1997-02-23
BR9603491A (pt) 1998-05-12
JPH09118899A (ja) 1997-05-06
DE19530786A1 (de) 1997-02-27
EP0761809A2 (fr) 1997-03-12
EP0761809A3 (fr) 1998-09-02
DE59611133D1 (de) 2004-12-09

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