EP0384503B1 - Métalloporphyrines pour l'utilisation comme catalyseur de blanchiment - Google Patents

Métalloporphyrines pour l'utilisation comme catalyseur de blanchiment Download PDF

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Publication number
EP0384503B1
EP0384503B1 EP19900200228 EP90200228A EP0384503B1 EP 0384503 B1 EP0384503 B1 EP 0384503B1 EP 19900200228 EP19900200228 EP 19900200228 EP 90200228 A EP90200228 A EP 90200228A EP 0384503 B1 EP0384503 B1 EP 0384503B1
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metallo
porphyrin
formula
porphyrins
fabrics
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EP19900200228
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German (de)
English (en)
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EP0384503A1 (fr
Inventor
Marion Frances Gregory
Jean Hypolites Koek
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from GB898904062A external-priority patent/GB8904062D0/en
Priority claimed from GB898905993A external-priority patent/GB8905993D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • This invention relates to improved metallo-porphyrins for use as a bleach catalyst in the bleaching of fabrics and to compositions for the cleaning and bleaching of fabrics comprising said metallo-porphyrins.
  • metallo-porphyrins can act as an oxidation catalyst.
  • WO 88/07988 describes the use of metallo-porphyrins as catalyst in a variety of oxidative reactions.
  • U.S. Patent N o 4,077,768 describes the use of iron-porphyrins with an oxidising bleach, e.g. hydrogen peroxide and also peracids, in aqueous wash liquors for dye bleaching in solution, i.e. for inhibiting dye-transfer during the washing of fabrics.
  • an oxidising bleach e.g. hydrogen peroxide and also peracids
  • the intermediate substance can also react with a second metallo-porphyrin forming a dimeric -oxo bridged species which is ineffective as bleaching agent and quickly degrades under the oxidative conditions. Reaction of the metallo-porphyrin with hydrogen peroxide, in the absence of a substrate, results in degradation via a different pathway in which radicals are believed to play a role. It is thus necessary that careful measures should be taken to avoid the metallo-porphyrins being oxidised.
  • the invention now provides improved metallo-porphyrins as peroxyacid bleach catalysts which are more stable against oxidation by mono oxygen donor type oxydators (like peroxyacids, hypochlorite and tert.butyl hydroperoxide), than the metallo-porphyrins suggested in the art for use in the bleaching of fabrics.
  • porphyrin core formula (I) may be substituted at one or more of the remaining carbon positions indicated by the numbers 1-8, with e.g. C1-C10 alkyl, hydroxy alkyl or oxyalkyl groups.
  • the phenyl or pyridyl group (a), (b) or (c) may or may not contain other substituents, but it has been found that improved stability is only achieved if the X1 and X2 substituents are attached on the phenyl or pyridyl group at exactly the indicated places near the porphine core. X1 and X2 substituents attached on other places of the phenyl or pyridyl group such as: have no effect on stability whatsoever.
  • Preferred molecules are those in which the -(B) n -(A) m substituents on the phenyl or pyridyl groups are selected from: -CH3 ; -C2H5 ; -CH2-CH2-CH2-SO3 ⁇ ; -CH2CH(OH)CH2SO3 ⁇ and -SO3 ⁇ .
  • X1 and X2 are Cl, Br or CH3, particularly Cl or CH3.
  • Typical examples of preferred Fe(III) and Mn(III) porphyrins are thus compounds wherein the Ar-substituents are:
  • the metallo-porphyrins of the invention can be used as a catalyst for peroxyacids or peroxyacid salts for the bleaching of fabrics in the same manner as applied with the known metallo-porphyrins of the art, but it can easily be appreciated that the improved stability thereof will result in a more effective and efficient use of the catalyst.
  • a common process of using metallo-porphyrins as catalyst in the bleaching and cleaning of fabrics with peroxy acid or a peroxyacid salt is by treating the fabrics with the metallo-porphyrin compound, leaving the fabric in contact therewith for a predetermined time to effect sufficient adsorption of said compound on to the fabric, and thereafter washing the fabric with a peroxyacid bleach composition.
  • the fabrics may be treated in a bath comprising an effective amount of a dissolved or solubilised metallo-porphyrin (normally in the range of 2 to 25 ppm) for several minutes, to which bath is then added a peroxyacid bleaching agent in an amount sufficient to effect the required bleaching effect (normally at a level of about 20-1000 ppm).
  • the amount of solubilised or dissolved metallo-porphyrin in the bath and also the amount of peroxyacid bleach added thereto will depend upon the fabric wash load and the rate of staining, the adjustment thereof being within the ability of the
  • the fabrics which are treated in a bath comprising a dissolved or solubilised metallo-porphyrin may, or may not, have been manually pretreated with metallo-porphyrin as is deemed necessary.
  • the peroxyacids include any organic peroxyacids and inorganic peroxyacid salts.
  • organic peroxyacids can be represented by compounds of the general formula: wherein R is an alkylene or substituted alkylene group containing 1 to 20 carbon atoms or an arylene group containing from 6 to 8 carbon atoms, n is 0 or 1, and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution.
  • R is an alkylene or substituted alkylene group containing 1 to 20 carbon atoms or an arylene group containing from 6 to 8 carbon atoms
  • n is 0 or 1
  • Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution.
  • Such groups can include, for example: wherein M is H or a water-soluble, salt-forming cation.
  • the organic peroxyacids and salts thereof can contain either one, two or more peroxy groups and can be either aliphatic or aromatic.
  • the organic peroxyacid is aliphatic
  • the unsubstituted acid may have the general formula: wherein Y can be H, -CH3, -CH2Cl, and m can be an integer from 1 to 20.
  • compounds of this type are peracetic acid, perlauric acid and diperoxydodecanedioic acid.
  • the unsubstituted acid may have the general formula: wherein Y is, for example, hydrogen, halogen, alkyl,
  • the percarboxy or percarbonic and Y groupings can be in any relative position around the aromatic ring.
  • the ring and/or Y group (if alkyl) can contain any non-interfering substituents, such as halogen or sulphonate groups.
  • aromatic peroxyacids and salts thereof include peroxybenzoic acids m-chloroperoxybenzoic acid, p-nitro-peroxybenzoic acid, p-sulphonato-peroxybenzoic acid, diperoxyisophthalic acid and peroxy-alpha-napthoic acid.
  • inorganic peroxyacid salts is potassium monopersulphate.
  • a product comprising this compound is the triple salt, K2SO4.KHSO4.2KHSO5, available commercially under the trade-name Oxone R from E.I. Dupont de Nemours and Company.
  • the invention provides the use of a metallo-porphyrin of structural formula (I), as defined herein above, as a bleach catalyst for the bleaching of fabrics with a peroxyacid bleach system.
  • the invention also provides a fabric washing product comprising a detergent active-material, a peroxyacid bleach and said metallo-porphyrin as catalyst therefor.
  • Fabric washing products according to the invention may be presented in any form, including that of a packages washing powder comprising the metallo-porphyrin catalyst, together with a separate pack of one-wash peroxyacid containing sachets.
  • the product can be in the form of a sachet within a sachet, the inner sachet containing a peroxyacid and being provided by means of a delaying release of the contents, and the outer sachet containing a washing composition comprising the metallo porphyrin catalyst and releasing its contents fairly rapidly upon immersion in water.
  • Another product form is for example that of a washing powder comprising a peroxyacid and the metallo-porphyrin catalyst in which the peroxyacid is provided in the form of coherently coated particles. Still other product forms are feasible and those skilled in the art will have no difficulty in selecting product forms by means of existing technology.
  • the invention provides a pretreatment product for local application on to fabrics, textiles and clothes, consisting essentially of a liquid or paste-like composition comprising a dispersion or solution of a metallo-porphyrin as defined herein in a suitable liquid or semi-liquid carrier, presented in a suitable dispenser for manual application of any known form of applicators, such as an aerosol pressure container, pump-spray bottle, roller-ball capped bottle, pad applicators and the like.
  • the liquid carrier will also contain a volatile solvent which evaporates upon application, leaving the metallo-porphyrin firmly attached on to the fabric surface to absorb.
  • a suitable carrier is a mixture of a nonionic surfactant and a lower alcohol, e.g. methanol.
  • compositions comprising the metallo-porphyrins of the invention dispersed in a carrier of this type are typical for roller-ball capped bottle and pad applicators.
  • Liquid or paste-like compositions for use in a pretreatment product may contain from about 0.1-1.0 g/l metallo-porphyrin, usually from about 0.2-0.5 g/l.
  • the treating bath as well as the washing composition comprising the metallo-porphyrin catalyst can contain any of the usual components of detergent compositions in the usual amounts.
  • organic detergent-active materials of the anionic, nonionic, zwitterionic and cationic types and mixtures thereof can be present, in an amount from about 3 to about 40% by weight.
  • Suitable detergent-actives are well known in the art and examples of such suitable compounds commonly used in the art are given in "Surface Active Agents”, Vol. I, by Schwartz and Perry (Interscience 1949) and “Surface Active Agents”, Vol. II, by Schwartz, Perry and Berch (Interscience 1958).
  • Detergency builders whether inorganic or organic, phosphate or non-phosphate, water-soluble or insoluble, and other water-soluble salts and buffering agents may preferably also be present.
  • the washing composition may contain any other non-interfering ingredients normally used in detergent compositions in minor amounts, which serve to improve the bleaching and laundering characteristics of the composition or which add aesthetic appeal to the composition.
  • Such minor ingredients can include sequestering agents and co-builders (e.g. homo- and copolymers); suds control agents; soil-suspending agents and anti-redeposition agents; enzymes, particularly proteolytic and lipolytic enzymes; corrosion inhibitors, optical brightening agents, colouring agents, perfumes, clays and fillers.
  • Fabric washing compositions usable in the present invention may contain from about 3 to about 40% by weight of organic detergent active material, 0 to 60%, preferably from 5 to about 40% by weight of detergency builder, from about 1 to 10% by weight of peroxyacid, and from about 0.05 to 1.0% by weight of metallo-porphyrin. They are usable normally at a dosage of 2-10 g/l for washing fabrics at wash loads of about 4-5 kg.
  • the system is characterised by its UV/VIS, IR and FAB-mass-spectrometry.
  • This system was prepared in a manner similar to that as described for (i) above, except that now metalation was performed using FeSO4, giving the compound (ii) in a 0.3 gram (7%) yield, similary characterised as described for the manganese porphyrin.
  • Table 1 Stability values from tests with HSO5 ⁇ (3.8 x 10 ⁇ 3 mol/l) Time (min.) 0 4 8 15 30 60 T 1 ⁇ 2 TMP4 ⁇ 100 96 92 89 83 75 120.0 minutes TPP4 ⁇ 100 63 33 18 - - 5.5 minutes
  • Table 2 Stability values from tests with Per-Ac (2.4 x 10 ⁇ 3 mol/l) Time (min.) 0 5 10 30 T 1 ⁇ 2 TMP4 ⁇ 100 96 94 91 150.0 minutes TPP4 ⁇ 100 30 15 - 2.0 minutes
  • TMP4 ⁇ of the invention is more stable than TPP4 ⁇ of the art against peracetic acid and potassium monopersulphate.
  • TMP4 ⁇ is about 20 times more stable against HSO5 ⁇ and about 75 times more stable against peracetic acid than TPP4 ⁇ .

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)
  • Catalysts (AREA)

Claims (9)

  1. Utilisation en tant que catalyseur de blanchiment au peroxyacide dans le blanchiment de tissus d'une métalloporphyrine présentant la formule structurelle suivante :
    Figure imgb0020
     dans laquelle Me est un ion métallique sélectionné parmi Mn (III) et Fe (III) ; Ar est un groupe substituant sélectionné parmi les groupes composés de
    Figure imgb0021
     dans lesquels n et m sont chacun égaux à 0 ou 1 (à condition toutefois que dans la formule (b) ci-avant, si n=m=0, alors l'atome d'azote est non chargé) ; A est un groupe sulfate, sulfonate, phosphate ou carboxylate ; B est un alkyle en C₁-C₁₀ (lorsque m=0 dans la formule (c)) ou un alkylène (lorsque m=1), un polyéthoxyalkyle (lorsque m=0 dans la formule (c)) ou un alkylène (lorsque m=1), ou un hydroxyalkyle (lorsque m=0 dans la formule (c)) ou un alkylène (lorsque m=1) et X1 et X2 sont Cl, Br, CH₃, C₂H₅ ou CH₃O ;
    ou Ar est le groupe
    Figure imgb0022
  2. Utilisation selon la Revendication 1, caractérisée en ce que le groupe substituant -(B)n-(A)m est sélectionné parmi -CH₃ ; -C₂H₅ ; -CH₂-CH₂-CH₂-SO₃⁻ : -CH₂-CH(OH)-CH₂-SO₃⁻ et SO₃⁻.
  3. Utilisation selon la Revendication 1 ou 2, caractérisée en ce que X₁ et X₂ sont Cl, Br ou CH₃.
  4. Une composition pour le lavage des tissus comprenant une matière détergente active, un agent de blanchiment au peroxyacide et une métalloporphyrine présentant la formule structurelle (I) de la Revendication 1.
  5. Une composition pour le lavage des tissus selon la Revendication 4, caractérisée en ce que le groupe substituant -(B)n-(A)m est sélectionné parmi -CH₃ ; C₂H₅ ; -CH₂-CH₂-CH₂-SO₃⁻ ; -CH₂-CH(OH)-CH₂-SO₃⁻ et SO₃⁻.
  6. Une composition pour le lavage des tissus selon la Revendication 4 ou 5, caractérisée en ce que X₁ et X₂ sont Cl, Br ou CH₃.
  7. Un produit de pré-traitement pour application locale sur des tissus, textiles et vêtements, composé essentiellement d'une composition liquide ou semblable à une pâte et comprenant une dispersion ou une solution d'une métalloporphyrine présentant la formule structurelle (I) de la Revendication 1 dans un support de réaction liquide ou semi-liquide approprié, présenté dans un distributeur approprié pour une application manuelle.
  8. Un produit de pré-traitement selon la Revendication 7, caractérisé en ce que le groupe substituant -(B)n-(A)m est sélectionné parmi -CH₃ ; -C₂H₅ ; -CH₂-CH₂-CH₂-SO₃⁻ ; -CH₂-CH(OH)-CH₂-SO₃⁻ et SO₃⁻.
  9. Un produit de pré-traitement selon la Revendication 7 ou 8, caractérisé en ce que X₁ et X₂ sont Cl, Br ou CH₃.
EP19900200228 1989-02-22 1990-01-31 Métalloporphyrines pour l'utilisation comme catalyseur de blanchiment Expired - Lifetime EP0384503B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8904062 1989-02-22
GB898904062A GB8904062D0 (en) 1989-02-22 1989-02-22 Metall-porphyrins for use as bleach catalyst
GB8905993 1989-03-15
GB898905993A GB8905993D0 (en) 1989-03-15 1989-03-15 Metallo-porphyrins for use as bleach catalyst

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EP0384503B1 true EP0384503B1 (fr) 1995-06-28

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JP (1) JPH02261547A (fr)
AU (1) AU612538B2 (fr)
BR (1) BR9000786A (fr)
CA (1) CA2010271A1 (fr)
DE (1) DE69020380T2 (fr)
ES (1) ES2075132T3 (fr)
NO (1) NO900787L (fr)

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US5288746A (en) * 1992-12-21 1994-02-22 The Procter & Gamble Company Liquid laundry detergents containing stabilized glucose/glucose oxidase as H2 O2 generation system
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US5371199A (en) * 1992-08-14 1994-12-06 The Trustees Of The University Of Pennsylvania Substituted porphyrins, porphyrin-containing polymers, and synthetic methods therefor
US5622646A (en) * 1994-04-07 1997-04-22 The Procter & Gamble Company Bleach compositions comprising metal-containing bleach catalysts and antioxidants
US5686014A (en) * 1994-04-07 1997-11-11 The Procter & Gamble Company Bleach compositions comprising manganese-containing bleach catalysts
US5703030A (en) * 1995-06-16 1997-12-30 The Procter & Gamble Company Bleach compositions comprising cobalt catalysts
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US5908821A (en) * 1994-05-11 1999-06-01 Procter & Gamble Company Dye transfer inhibiting compositions with specifically selected metallo catalysts
US6020294A (en) * 1995-02-02 2000-02-01 Procter & Gamble Company Automatic dishwashing compositions comprising cobalt chelated catalysts
US6479450B1 (en) 1997-05-26 2002-11-12 Henkel Kommanditgesellschaft Auf Aktien Bleaching system
US7335629B2 (en) 2001-12-21 2008-02-26 Henkel Kommanditgesellschaft Auf Aktien Support-fixed bleaching catalyst complex compounds suitable as catalysts for peroxygen compounds

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TR26870A (tr) * 1991-10-14 1994-08-22 Procter & Gamble Yikamada boya aktarimini önleyen deterjan bilesimleri
US5445651A (en) * 1992-01-31 1995-08-29 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
US5599924A (en) * 1992-08-14 1997-02-04 Trustees Of The University Of Pennsylvania Electron-deficient porphyrins and processes and intermediates for preparing same
US5493017A (en) * 1992-08-14 1996-02-20 The Trustees Of The University Of Pennsylvania Ring-metalated porphyrins
US5817830A (en) * 1992-08-14 1998-10-06 Trustees Of The University Of Pennsylvania Pyrrolic compounds
ES2111924T3 (es) * 1993-04-08 1998-03-16 Procter & Gamble Composicion y procedimiento para inhibir la transferencia de colorante.
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US5578136A (en) 1994-08-31 1996-11-26 The Procter & Gamble Company Automatic dishwashing compositions comprising quaternary substituted bleach activators
US5968881A (en) * 1995-02-02 1999-10-19 The Procter & Gamble Company Phosphate built automatic dishwashing compositions comprising catalysts
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DE19620267A1 (de) * 1996-05-20 1997-11-27 Henkel Kgaa Katalytisch wirksame Aktivatorkomplexe mit N¶4¶-Liganden für Persauerstoffverbindungen
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AU1463799A (en) 1997-11-21 1999-06-15 Procter & Gamble Company, The Product applicator
GB9725614D0 (en) 1997-12-03 1998-02-04 United States Borax Inc Bleaching compositions
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US20070138674A1 (en) 2005-12-15 2007-06-21 Theodore James Anastasiou Encapsulated active material with reduced formaldehyde potential
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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1541576A (en) * 1975-06-20 1979-03-07 Procter & Gamble Ltd Inhibiting dye ltransfer in washing
ATE123749T1 (de) * 1987-04-17 1995-06-15 David H Dolphin Porphyrine, verfahren zu deren herstellung und verwendungen.
US4892941A (en) * 1987-04-17 1990-01-09 Dolphin David H Porphyrins
GB8720863D0 (en) * 1987-09-04 1987-10-14 Unilever Plc Metalloporphyrins

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* Cited by examiner, † Cited by third party
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EP0537381A1 (fr) * 1991-10-14 1993-04-21 The Procter & Gamble Company Compositions détergentes avec additifs pour empêcher le transfert de colorant
WO1993008324A1 (fr) * 1991-10-14 1993-04-29 The Procter & Gamble Company Compositions de detergents capables d'empecher le transfert des colorants lors du lavage
US5574003A (en) * 1991-10-14 1996-11-12 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
EP0538228A1 (fr) * 1991-10-14 1993-04-21 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
EP0553607A1 (fr) * 1992-01-31 1993-08-04 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
EP0553608A1 (fr) * 1992-01-31 1993-08-04 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
TR26405A (tr) * 1992-01-31 1995-03-15 Procter & Gamble Yikama sirasinda boya aktarilmasini engelleyen deterjan terkipleri
TR26494A (tr) * 1992-01-31 1995-03-15 Procter & Gamble Yikama sirasinda boya aktarilmasini engelleyen deterjan terkipleri
US5371199A (en) * 1992-08-14 1994-12-06 The Trustees Of The University Of Pennsylvania Substituted porphyrins, porphyrin-containing polymers, and synthetic methods therefor
EP0596186A1 (fr) * 1992-11-06 1994-05-11 The Procter & Gamble Company Compositions détergentes avec additifs pour empêcher le transfert de colorant
EP0596184A1 (fr) * 1992-11-06 1994-05-11 The Procter & Gamble Company Compositions détergentes avec additifs pour empêcher le transfert de colorant
EP0596187A1 (fr) * 1992-11-06 1994-05-11 The Procter & Gamble Company Compositions détergentes avec additifs pour empêcher le transfert de colorant
US5288746A (en) * 1992-12-21 1994-02-22 The Procter & Gamble Company Liquid laundry detergents containing stabilized glucose/glucose oxidase as H2 O2 generation system
US5622646A (en) * 1994-04-07 1997-04-22 The Procter & Gamble Company Bleach compositions comprising metal-containing bleach catalysts and antioxidants
US5686014A (en) * 1994-04-07 1997-11-11 The Procter & Gamble Company Bleach compositions comprising manganese-containing bleach catalysts
US5908821A (en) * 1994-05-11 1999-06-01 Procter & Gamble Company Dye transfer inhibiting compositions with specifically selected metallo catalysts
US5798326A (en) * 1995-02-02 1998-08-25 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt III catalysts
US6020294A (en) * 1995-02-02 2000-02-01 Procter & Gamble Company Automatic dishwashing compositions comprising cobalt chelated catalysts
US6119705A (en) * 1995-02-02 2000-09-19 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt chelated catalysts
US5705464A (en) * 1995-06-16 1998-01-06 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt catalysts
US5703030A (en) * 1995-06-16 1997-12-30 The Procter & Gamble Company Bleach compositions comprising cobalt catalysts
US5703034A (en) * 1995-10-30 1997-12-30 The Procter & Gamble Company Bleach catalyst particles
US6479450B1 (en) 1997-05-26 2002-11-12 Henkel Kommanditgesellschaft Auf Aktien Bleaching system
US7335629B2 (en) 2001-12-21 2008-02-26 Henkel Kommanditgesellschaft Auf Aktien Support-fixed bleaching catalyst complex compounds suitable as catalysts for peroxygen compounds

Also Published As

Publication number Publication date
AU612538B2 (en) 1991-07-11
AU4992790A (en) 1990-08-30
ES2075132T3 (es) 1995-10-01
DE69020380T2 (de) 1995-12-07
BR9000786A (pt) 1991-01-22
EP0384503A1 (fr) 1990-08-29
CA2010271A1 (fr) 1990-08-22
JPH02261547A (ja) 1990-10-24
DE69020380D1 (de) 1995-08-03
NO900787L (no) 1990-08-23
NO900787D0 (no) 1990-02-19

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