EP0384503A1 - Métalloporphyrines pour l'utilisation comme catalyseur de blanchiment - Google Patents
Métalloporphyrines pour l'utilisation comme catalyseur de blanchiment Download PDFInfo
- Publication number
- EP0384503A1 EP0384503A1 EP19900200228 EP90200228A EP0384503A1 EP 0384503 A1 EP0384503 A1 EP 0384503A1 EP 19900200228 EP19900200228 EP 19900200228 EP 90200228 A EP90200228 A EP 90200228A EP 0384503 A1 EP0384503 A1 EP 0384503A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metallo
- porphyrin
- porphyrins
- fabrics
- bleaching
- 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
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
- C11D3/3947—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° 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.
- the metallo - porphyrins for use as peroxyacid bleach catalyst in the bleaching of fabrics according to the invention are compounds having the following structural formula: wherein Me is a metal ion, selected from Mn(III) and Fe(III); and Ar is a substituent selected from the group consisting of and wherein n and m may be 0 or 1; A may be sulphate, sulphonate, phosphate or carboxylate groups; B is C 1 -C 10 alkyl, polyethoxy alkyl or hydroxy alkyl and X, and X 2 are Cl, Br, CH 3 , C 2 Hs or CH 3 0.
- 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. C 1 -C 10 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 X 1 and X 2 substituents are attached on the phenyl or pyridyl group at exactly the indicated places near the porphine core. X, and X 2 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:
- 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.
- groups can include, for example: or 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 unsubstituted acid may have the general formula: wherein Y can be H, -CH 3 , -CH 2 CI, or and m can be an integer from 1 to 20.
- the unsubstituted acid may have the general formula: wherein Y is, for example, hydrogen, halogen, alkyl, or
- 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, K 2 S0 4 .KHS0 4 .2KHSOs, available commercially under the trade-name Oxone 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/I metallo-porphyrin, usually from about 0.2-0.5 g/I.
- 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/I 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 FeSO 4 , giving the compound (ii) in a 0.3 gram (7%) yield, similary characterised as described for the manganese porphyrin.
- TPP 4- The oxidation stability of the substituted mangano-porphyrin of Example I (i) (TMP 4- ) against potassium monopersulphate (HSO s -) and peracetic acid (per-Ac) was determined and compared with a non-substituted mangano-porphyrin (TPP 4- ).
- Stabilities were measured by means of a UV/VIS spectroscopic method in the absence of a substrate at catalyst concentration of 10-6 mol/I.
- TMP 4 - of the invention is more stable than TPP 4 - of the art against peracetic acid and potassium monopersulphate.
- TMP 4- is about 20 times more stable against HSO 5 - and about 75 times more stable against peracetic acid than TPP 4 -.
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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)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB898904062A GB8904062D0 (en) | 1989-02-22 | 1989-02-22 | Metall-porphyrins for use as bleach catalyst |
GB8904062 | 1989-02-22 | ||
GB8905993 | 1989-03-15 | ||
GB898905993A GB8905993D0 (en) | 1989-03-15 | 1989-03-15 | Metallo-porphyrins for use as bleach catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0384503A1 true EP0384503A1 (fr) | 1990-08-29 |
EP0384503B1 EP0384503B1 (fr) | 1995-06-28 |
Family
ID=26294997
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19900200228 Expired - Lifetime EP0384503B1 (fr) | 1989-02-22 | 1990-01-31 | Métalloporphyrines pour l'utilisation comme catalyseur de blanchiment |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0384503B1 (fr) |
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) |
Cited By (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TR26870A (tr) * | 1991-10-14 | 1994-08-22 | Procter & Gamble | Yikamada boya aktarimini önleyen deterjan bilesimleri |
TR27062A (tr) * | 1991-10-14 | 1994-10-11 | Procter & Gamble | Yikamada boya aktarimini önleyen deterjan bilesimi. |
WO1994024250A1 (fr) * | 1993-04-08 | 1994-10-27 | The Procter & Gamble Company | Composition et procede d'inhibition du transfert de couleur |
EP0622447A1 (fr) * | 1993-04-26 | 1994-11-02 | The Procter & Gamble Company | Compositions détergentes pour éviter le transfer de colorant contenant des enzymes |
US5445651A (en) * | 1992-01-31 | 1995-08-29 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer in washing |
EP0690122A2 (fr) | 1994-06-30 | 1996-01-03 | The Procter & Gamble Company | Compositions détergentes |
US5493017A (en) * | 1992-08-14 | 1996-02-20 | The Trustees Of The University Of Pennsylvania | Ring-metalated porphyrins |
EP0699745A2 (fr) | 1994-08-31 | 1996-03-06 | The Procter & Gamble Company | Compositions pour lave-vaisselle automatique comprenant des composés d'ammonium quaternaire comme activateurs de blanchiment et des composés d'ammonium quaternaire |
EP0692947A4 (fr) * | 1993-04-09 | 1996-03-13 | Procter & Gamble | Procede de lavage en lave-vaisselle utilisant un catalyseur organometallique et une enzyme pour produire du peroxyde d'hydrogene |
EP0778342A1 (fr) | 1995-12-06 | 1997-06-11 | The Procter & Gamble Company | Compositions détergentes |
WO1997044430A1 (fr) * | 1996-05-20 | 1997-11-27 | Henkel Kommanditgesellschaft Auf Aktien | Complexes activateurs a action catalytique contenant des ligands de n4 pour des composes peroxydes |
WO1998008926A1 (fr) * | 1996-08-26 | 1998-03-05 | The Procter & Gamble Company | Regulation de l'activite de la cellulase par un terminateur |
US5756723A (en) * | 1992-08-14 | 1998-05-26 | The Trustees Of The University Of Pennsylvania | Metal-mediated cross-coupling with ring-metalated porphyrins |
US5817830A (en) * | 1992-08-14 | 1998-10-06 | Trustees Of The University Of Pennsylvania | Pyrrolic compounds |
US5856515A (en) * | 1992-08-14 | 1999-01-05 | Trustees Of The University Of Pennsylvania | Electron-deficient porphyrins and processes and intermediates for preparing same |
WO1999026508A1 (fr) | 1997-11-21 | 1999-06-03 | The Procter & Gamble Company | Applicateur de produit |
US5939373A (en) * | 1995-12-20 | 1999-08-17 | The Procter & Gamble Company | Phosphate-built automatic dishwashing composition comprising catalysts |
US6326342B1 (en) | 1997-12-03 | 2001-12-04 | U.S. Borax Inc. | Bleaching compositions |
WO2002100994A1 (fr) * | 2001-06-11 | 2002-12-19 | Unilever Plc | Complexe destine au blanchiment par voie catalytique d'un substrat |
WO2004069979A2 (fr) | 2003-02-03 | 2004-08-19 | Unilever Plc | Compositions de nettoyage et de conditionnement pour blanchisserie |
CN101922111A (zh) * | 2010-09-14 | 2010-12-22 | 东华大学 | 一种使用水溶性金属卟啉的低温活化漂白的方法 |
EP2545988A2 (fr) | 2005-12-15 | 2013-01-16 | International Flavors & Fragrances, Inc. | Matériau actif encapsulé avec potentiel de formaldéhyde réduit |
EP3075832A1 (fr) | 2015-03-30 | 2016-10-05 | Dalli-Werke GmbH & Co. KG | Composés d'acide aminé de manganèse dans des compositions de nettoyage |
WO2018085300A1 (fr) | 2016-11-01 | 2018-05-11 | The Procter & Gamble Company | Procédés d'utilisation de leuco-colorants en tant qu'agents d'azurage dans des compositions d'entretien du linge |
WO2018085315A1 (fr) | 2016-11-01 | 2018-05-11 | The Procter & Gamble Company | Colorants leuco utilisés comme agents d'azurage dans des compositions d'entretien du linge, conditionnement, kits et procédés associés |
WO2018140454A1 (fr) | 2017-01-27 | 2018-08-02 | The Procter & Gamble Company | Articles contenant un agent actif et ensembles de transport de produits destinés à les contenir |
WO2018140472A1 (fr) | 2017-01-27 | 2018-08-02 | The Procter & Gamble Company | Articles contenant des agents actifs présentant des propriétés d'utilisation d'articles acceptables pour le consommateur |
WO2018140431A1 (fr) | 2017-01-27 | 2018-08-02 | The Procter & Gamble Company | Articles contenant des agents actifs présentant des propriétés d'utilisation acceptables pour le consommateur |
WO2018140432A1 (fr) | 2017-01-27 | 2018-08-02 | The Procter & Gamble Company | Articles contenant des agents actifs présentant des propriétés d'utilisation acceptables pour le consommateur |
EP3444328A1 (fr) | 2017-08-18 | 2019-02-20 | The Procter & Gamble Company | Agent de nettoyage |
WO2020123889A1 (fr) | 2018-12-14 | 2020-06-18 | The Procter & Gamble Company | Structures fibreuses moussantes comprenant des particules et leurs procédés de production |
EP3719192A1 (fr) | 2012-01-04 | 2020-10-07 | The Procter & Gamble Company | Structures fibreuses comprenant des particules et leurs procédés de fabrication |
WO2021026556A1 (fr) | 2019-08-02 | 2021-02-11 | The Procter & Gamble Company | Compositions moussantes pour la production d'une mousse stable et leurs procédés de fabrication |
WO2021097004A1 (fr) | 2019-11-15 | 2021-05-20 | The Procter & Gamble Company | Articles solubles contenant des éléments graphiques et leurs procédés de fabrication |
WO2022251838A1 (fr) | 2021-05-28 | 2022-12-01 | The Procter & Gamble Company | Éléments fibreux à base de polymère naturel comprenant un tensioactif et leurs procédés de fabrication |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0553607B1 (fr) * | 1992-01-31 | 1998-03-18 | The Procter & Gamble Company | Détergents avec additifs pour éviter le transfert de colorant |
EP0553608B1 (fr) * | 1992-01-31 | 1998-06-17 | The Procter & Gamble Company | Détergents avec additifs pour éviter le transfert de colorant |
EP0596184B1 (fr) * | 1992-11-06 | 1998-04-15 | 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 |
EP0596186A1 (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 |
US5686014A (en) * | 1994-04-07 | 1997-11-11 | The Procter & Gamble Company | Bleach compositions comprising manganese-containing bleach catalysts |
EP0754218B1 (fr) * | 1994-04-07 | 1998-09-02 | The Procter & Gamble Company | Composition de blanchiment comprenant un catalyseur de blanchiment contenant un metal et des antioxydants |
US5908821A (en) * | 1994-05-11 | 1999-06-01 | Procter & Gamble Company | Dye transfer inhibiting compositions with specifically selected metallo catalysts |
DE69608541T2 (de) * | 1995-02-02 | 2001-01-18 | The Procter & Gamble Company, Cincinnati | Maschinengeschirrspülmittel zusammensetzungen mit kobalt chelatkatalysatoren |
WO1996023861A1 (fr) * | 1995-02-02 | 1996-08-08 | The Procter & Gamble Company | Compositions pour le lavage automatique de la vaisselle comprenant des catalyseurs cobalteux |
CA2224558C (fr) * | 1995-06-16 | 2003-07-15 | The Procter & Gamble Company | Compositions detergentes pour lave-vaisselle automatiques, contenant des catalyseurs au cobalt |
CA2224559A1 (fr) * | 1995-06-16 | 1997-01-03 | The Procter & Gamble Company | Compositions d'agents de blanchiment comprenant des catalyseurs au cobalt |
US5703034A (en) * | 1995-10-30 | 1997-12-30 | The Procter & Gamble Company | Bleach catalyst particles |
DE19721886A1 (de) | 1997-05-26 | 1998-12-03 | Henkel Kgaa | Bleichsystem |
DE10163331A1 (de) | 2001-12-21 | 2003-07-10 | Henkel Kgaa | Trägerfixierte Bleichkatalysatorkomplexverbindungen geeignet als Katalysatoren für Persauerstoffverbindungen |
JP5401034B2 (ja) | 2007-12-19 | 2014-01-29 | ライオン株式会社 | 漂白助剤、および該漂白助剤を含有する漂白助剤粒子 |
Citations (3)
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US4077768A (en) * | 1975-06-20 | 1978-03-07 | The Procter & Gamble Company | Inhibiting dye transfer in washing or bleaching |
WO1988007988A1 (fr) * | 1987-04-17 | 1988-10-20 | Dolphin David H | Porphyrines, leur synthese et leur utilisation |
EP0306089A2 (fr) * | 1987-09-04 | 1989-03-08 | Unilever N.V. | Porphirines de métaux comme catalyseur de blanchiment et procédé de nettoyage du linge |
Family Cites Families (1)
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---|---|---|---|---|
US4892941A (en) * | 1987-04-17 | 1990-01-09 | Dolphin David H | Porphyrins |
-
1990
- 1990-01-31 EP EP19900200228 patent/EP0384503B1/fr not_active Expired - Lifetime
- 1990-01-31 DE DE1990620380 patent/DE69020380T2/de not_active Expired - Fee Related
- 1990-01-31 ES ES90200228T patent/ES2075132T3/es not_active Expired - Lifetime
- 1990-02-16 CA CA 2010271 patent/CA2010271A1/fr not_active Abandoned
- 1990-02-19 NO NO90900787A patent/NO900787L/no unknown
- 1990-02-20 BR BR9000786A patent/BR9000786A/pt not_active IP Right Cessation
- 1990-02-20 AU AU49927/90A patent/AU612538B2/en not_active Ceased
- 1990-02-20 JP JP2039565A patent/JPH02261547A/ja active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4077768A (en) * | 1975-06-20 | 1978-03-07 | The Procter & Gamble Company | Inhibiting dye transfer in washing or bleaching |
WO1988007988A1 (fr) * | 1987-04-17 | 1988-10-20 | Dolphin David H | Porphyrines, leur synthese et leur utilisation |
EP0306089A2 (fr) * | 1987-09-04 | 1989-03-08 | Unilever N.V. | Porphirines de métaux comme catalyseur de blanchiment et procédé de nettoyage du linge |
Cited By (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TR26870A (tr) * | 1991-10-14 | 1994-08-22 | Procter & Gamble | Yikamada boya aktarimini önleyen deterjan bilesimleri |
TR27062A (tr) * | 1991-10-14 | 1994-10-11 | Procter & Gamble | Yikamada boya aktarimini önleyen deterjan bilesimi. |
US5445651A (en) * | 1992-01-31 | 1995-08-29 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer in washing |
US5856515A (en) * | 1992-08-14 | 1999-01-05 | Trustees Of The University Of Pennsylvania | Electron-deficient porphyrins and processes and intermediates for preparing same |
US5817830A (en) * | 1992-08-14 | 1998-10-06 | Trustees Of The University Of Pennsylvania | Pyrrolic compounds |
US5493017A (en) * | 1992-08-14 | 1996-02-20 | The Trustees Of The University Of Pennsylvania | Ring-metalated porphyrins |
US5756723A (en) * | 1992-08-14 | 1998-05-26 | The Trustees Of The University Of Pennsylvania | Metal-mediated cross-coupling with ring-metalated porphyrins |
WO1994024250A1 (fr) * | 1993-04-08 | 1994-10-27 | The Procter & Gamble Company | Composition et procede d'inhibition du transfert de couleur |
EP0692947A4 (fr) * | 1993-04-09 | 1996-03-13 | Procter & Gamble | Procede de lavage en lave-vaisselle utilisant un catalyseur organometallique et une enzyme pour produire du peroxyde d'hydrogene |
EP0622447A1 (fr) * | 1993-04-26 | 1994-11-02 | The Procter & Gamble Company | Compositions détergentes pour éviter le transfer de colorant contenant des enzymes |
EP0690122A2 (fr) | 1994-06-30 | 1996-01-03 | The Procter & Gamble Company | Compositions détergentes |
EP0699745A2 (fr) | 1994-08-31 | 1996-03-06 | The Procter & Gamble Company | Compositions pour lave-vaisselle automatique comprenant des composés d'ammonium quaternaire comme activateurs de blanchiment et des composés d'ammonium quaternaire |
US5968881A (en) * | 1995-02-02 | 1999-10-19 | The Procter & Gamble Company | Phosphate built automatic dishwashing compositions comprising catalysts |
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Also Published As
Publication number | Publication date |
---|---|
ES2075132T3 (es) | 1995-10-01 |
AU4992790A (en) | 1990-08-30 |
BR9000786A (pt) | 1991-01-22 |
AU612538B2 (en) | 1991-07-11 |
JPH02261547A (ja) | 1990-10-24 |
NO900787L (no) | 1990-08-23 |
EP0384503B1 (fr) | 1995-06-28 |
DE69020380T2 (de) | 1995-12-07 |
CA2010271A1 (fr) | 1990-08-22 |
NO900787D0 (no) | 1990-02-19 |
DE69020380D1 (de) | 1995-08-03 |
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