EP0224952A2 - Bleichkatalysatoraggregate von mit Mangankationen imprägnierten Aluminiumsilikaten - Google Patents

Bleichkatalysatoraggregate von mit Mangankationen imprägnierten Aluminiumsilikaten Download PDF

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Publication number
EP0224952A2
EP0224952A2 EP86202015A EP86202015A EP0224952A2 EP 0224952 A2 EP0224952 A2 EP 0224952A2 EP 86202015 A EP86202015 A EP 86202015A EP 86202015 A EP86202015 A EP 86202015A EP 0224952 A2 EP0224952 A2 EP 0224952A2
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EP
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Prior art keywords
bleach catalyst
manganese
catalyst according
binder
amount
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Application number
EP86202015A
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English (en)
French (fr)
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EP0224952A3 (de
Inventor
William Martyn Karpusiewicz
Elizabeth Jean Mc Callion
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Unilever PLC
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Unilever PLC
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Publication of EP0224952A2 publication Critical patent/EP0224952A2/de
Publication of EP0224952A3 publication Critical patent/EP0224952A3/de
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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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • 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

  • the invention relates to granulated supported manganese catalysts in aggregate form which, when formulated with peroxygen compounds, promote bleaching of flexible and hard surface substrates.
  • Dry bleaching powders such as those for cleaning laundry, generally contain inorganic persalts as the active component. These persalts serve as a source of hydrogen peroxide. Normally, persalt bleach activity in aqueous solution is undetectable where temperatures are less than 100°F and delivery dosages less than 100 ppm active oxygen. The art has recognized, however, that bleaching under such mild conditions may be effectuated through the use of activators.
  • Manganese (II) salts have been reported to be exceptionally effective in activating persalts under mild conditions.
  • U.S. Patent 4,481,129 discloses bleach compositions containing manganese (II) salts in conjunction with carbonate compounds.
  • U.S. Patent 4,478,733 describes bleach compositions containing manganese (II) salts in conjunction with aluminosilicate cation-exchange materials.
  • U.S. Patent 4,488,980 reports a bleach-beneficial interaction between a condensed phosphate/alkali metal orthophosphate mixture and manganese (II) salts.
  • manganese (II) Another problem with bare cations such as manganese (II) is that, when utilized for whitening laundry, the free manganese ions deposit on the fabric. Strong oxidants, such as hypochlorites, are frequently included in laundry washes. Manganese ions will react with these strong oxidants to form highly staining manganese dioxide.
  • Another object of this invention is to provide a detergent composition containing manganese catalyst in aggregate form that exhibits improved storage stability and bleaching performance.
  • a further object of this invention is to provide an improved method for bleaching substrates, especially fabrics.
  • a bleach catalyst in aggregate form, exclusive of any peroxy compound within the aggregate, comprising:
  • the aluminosilicate support material must be one having an average particle diameter size of about 2 to 10 microns (a very fine powder). Larger diameter aluminosilicate particles would have a smaller overall surface area. These would not be as reactive. It has been herein noted that while finely powdered manganese-exchanged aluminosilicate is catalytically active in the wash, if blended as a powder it segregates in the package and adversely interacts with peroxygen compounds upon storage. Aggregation of finely powdered aluminosilicate into larger granules has solved the problem of segregation and storage instability.
  • Particle size of the catalyst aggregates has, thus, been found to be a crucial factor in overcoming the difficulties of the prior art.
  • At least 75% of the aggregates must have an average diameter ranging from at least 250 to about 2000 microns.
  • aggregate diameters should range from 500 to 1500 microns, more preferably 900 to 1200 microns.
  • synthetic zeolites are particularly suitable as the support material.
  • Preferred are those zeolites designated as A and 13X type. These zeolites are sold by the Union Carbide Corporation under the designation ZB-100 and ZB-400, respectively. ZB-100 and ZB-­400 have average pore sizes of 4 and 10 Angstroms, respectively. Additional sources of these zeolites are Crosfields Ltd, Philadelphia Quartz, Huber and Ethyl Corporations.
  • Suitable support materials of another type are the silicoalumino phosphates (SAPOs). These materials are also commercially available from Union Carbide. SAPOs have a wide range of compositions within the general formula 0-0. 3R(Si x Al y P z )O2, where x, y and z represent the mole fractions of Si, Al and P, respectively. The range for x is 0.01 to 0.­98, for y from 0.01 to 0.60, and for z from 0.01 to 0.52. R refers to the organic template that is used to develop the structure of the particular SAPO. Typical templates used in preparing SAPOs are organic amines or quaternary ammonium compounds. Included within the SAPO family are structural types such as AlPO4-16, Sodalite, Erionite, Chabazite, AlPO4-­11, Novel, AlPO4-5 and Faujasite.
  • SAPOs silicoalumino phosphates
  • the manganese used in the present invention can be derived from any manganese (II) salt which delivers manganous ions in aqueous solution.
  • manganous sulphate and manganous chloride or complexes thereof, such as manganous triacetate, are examples of suitable salts.
  • Finished catalyst will contain from about 0.1 to about 5.­5% manganese (II) per weight of solid support.
  • the amount of manganese (II) is from about 1 to about 2.5% on an anhydrous basis defined as Mn/anhydrous support + Mn.
  • the catalyst should deliver a minimum level of 0.5 ppm manganese (II) ion to the aqueous solution. For instance, if a catalyst has 1 weight % of manganese, then there is required at least 500 milligrams catalyst per litre of aqueous solution.
  • the catalyst and compositions of this invention may be applied to either flexible or hard substrates such as fabrics, dishes, dentures, tiles, toilet bowls and ceramic floors.
  • Flexible substrates specifically fabrics, will, however, be focused upon in the subsequent discussion.
  • a binder is an essential element of the catalyst aggregates. It will be present from about 0.1 to 40% by weight of the aggregate, preferably from about 5 to 20%, ideally from about 5 to 10%.
  • the binder is a water-soluble or water-dispersible material, preferably organic, and will have a pH no higher than 10.
  • Binders may be selected from organic homo-polymers or hetero-polymers, examples of which are starches, cellulose ethers, gums and sugars. Long-chain C10-C22 fatty acids and fatty acid soaps may also be suitable binders. Inorganic materials may be used as binders if they meet the pH limitation of no greater than 10, preferably less than 9.5 and more preferably less than 7, and other limitations as herein provided.
  • Illustrative of this category are the so-called glassy sodium phosphates of the molecular structure: Na2O4P[Na)3P] n PO3Na2, wherein the average value of n is from about 10 to 30. Silicates are unacceptable as binders because their pH is greater than 10.
  • Starches are preferred because of their very favourable combination of good binding and fast water-­dispersing properties. Starches usually occur as discrete particles or granules having diameters in the 2 to 115 micron range. While most starches contain from 22 to 26% amylose and 70 to 74% amylopectin, some starches, such as waxy corn starches, may be entirely free of amylose. It is intended to include within the term "starch” the various types of natural starches, including corn starch, potato starch, tapioca, cassava and other tuber starches, as well as amylose and amylopectin separately or in mixtures.
  • modified starches are particularly preferred as binders. These include Nadex 320 ®, a white corn dextrin of low viscosity, and Capsul ®, a waxy dextrin hydrophobic derivative, also of low viscosity. Nadex 320 ® and Capsul ® are commercially available from The National Starch and Chemical Company, Bridgewater, New Jersey, U.S.A.
  • Gums and mucilages are carbohydrate polymers of high molecular weight, obtainable from plants or by synthetic manufacture. Among the plant gums that are of commercial importance may be mentioned arabic, ghatti, karaya and tragacanth. Guar, linseed and locust bean are also suitable. Seaweed mucilages or gums such as agar, algin and carageenan are also within the binder definition.
  • carboxymethyl celluloses such as sodium carboxymethyl cellulose.
  • Other cellulose ethers include hydrocypropyl cellulose, methyl and ethyl celluloses, hydroxypropyl methyl cellulose and hydroxyethyl cellulose.
  • organic homo-polymers and hetero-polymers are a multiplicity of materials.
  • Commercially available water-­soluble polymers include polyvinylpyrrolidone, carboxyvinyl polymers such as the Carbopol ® sold by B.F. Goodrich Chemical Company and the polyethylene glycol waxes such as Carbowax ® sold by the Union Carbide Corporation.
  • Polyvinyl alcohol and polyacrylamides are further examples.
  • Polyvinylpyrrolidone is a particularly useful binder. Commercially, it is available from the GAF Corporation under the designation PVP K-15, K-30, K-60 and K-90. These products differ in their viscosity grades, the number average molecular weights being about 10,000, 40,000, 60,000 and 360,­000, respectively. PVP K-30 and K-60 are the preferred binders.
  • modified starches When modified starches are employed as the binder, they can be incorporated at levels up to about 40% of the total granule weight. Although acceptable granules can be obtained with modified starches at 5-10% concentration levels, it was surprisingly found that at higher binder levels the dispersion rate increased compared to the 5-10% levels. An increase in the level of these binders beyond the minimum required for granulation leads to a dramatic improvement in dispersion despite simultaneous decrease in granule porosity. The effect is similar with polyvinylpyrrolidone.
  • Binders within the definition of this invention must hold together the aluminosilicate particles in an agglomerate that is free-flowing and non-sticky. Free-flowing properties may be measured by the DFR test as outlined in U.S. Patent 4,473,485 (Greene), herein incorporated by reference. Furthermore, suitable binders are those which provide for coherent agglomerates difficult to crush under ordinary finger pressure.
  • a Dispersion Test for evaluation of this property has been devised which provides good reproducibility.
  • the percent non-dispersible particles is determined by placing 5 grams of sample agglomerate in 500 millilitres deionized water held at 40°C and at a pH of 10. After stirring for two minutes, the solution is drained through a 120 micron diameter screen. Subsequently, the screen is dried and weighed. Less than 5% by weight of the original sample should remain on the screen. Greater amounts are deemed unacceptable. Failure to adequately de-agglomerate in water means the active manganese (II) on zeolite catalyst will not, to its fullest extent, desorb and contact the peroxygen compound. Bleaching efficiency is thereby impaired.
  • II active manganese
  • Laundry bleach compositions are also disclosed by this invention.
  • a peroxide source is necessary.
  • Suitable peroxy compounds include the inorganic persalts which liberate hydrogen peroxide in aqueous solution. These may be water-soluble perborates, percarbonates, perphosphates, persilicates, persulphates and organic peroxides. Amounts of peroxy compound in the dry bleach powder should range from about 5 to about 30%. At least 30 ppm active oxygen should be delivered by the persalt to a litre of wash water. For instance, with sodium perborate monohydrate, this represents a minimum amount of 200 mg per litre of wash water.
  • the ratio of active oxygen generated by peroxy compound to manganese (II) ion in aqueous solution ranges from about 1000:1 to 1:1000, preferably 1000:1 to 1:10.
  • Phosphate salt stabilizers are suggested for combination with the dry laundry bleach powders.
  • Suitable stabilizers include the alkali metal salts of tripolyphosphate, orthophosphate and pyrophosphate.
  • Amounts of phosphate stabilizer should range from about 5% to about 35%. Preferably, they should be present from about 10% to 15%.
  • the phosphate stabilizer level should be at least 10 ppm, the ratio of stabilizer to peroxy compound being from about 10:1 to 1:10.
  • Surface-active detergents may be present in an amount from about 2% to about 50% by weight, preferably from 5% to 30% by weight. These surface-active agents may be anionic, nonionic, zwitterionic, amphoteric, cationic or mixtures thereof.
  • anionic surfactants are water-soluble salts of alkylbenzene sulphonates, alkyl sulphates, alkyl ether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulphocarboxylates and their esters, alkyl glycerol ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethoxy ether sulphates, 2-­acyloxy-alkane-1-sulphonates and beta-alkoxyalkane sulphonates. Soaps are also useful as anionic surfactants.
  • Nonionic surfactants are water-soluble compounds produced, for instance, by the condensation of ethylene oxide with a hydrophobic compound such as alcohol, alkyl phenol, polypropoxy glycol or polypropoxy ethylene diamine.
  • Cationic surface-active agents include the quaternary ammonium compounds having 1 to 2 hydrophobic groups with 8-­20 carbon atoms, e.g. cetyl trimethlyammonium bromide or chloride, and dioctadecyl dimethylammonium chloride.
  • Detergent builders may be combined with the bleach compositions.
  • Useful builders can include any of the conventional inorganic and organic water-soluble builder salts. Typical of the well-known inorganic builders are the sodium and potassium salts of the following: pyrophosphate, tripolyphosphate, orthophosphate, carbonate, bicarbonate, silicate, sesqicarbonate, borate and aluminosilicate.
  • organic detergent builders that can be used in the present invention are the sodium and potassium salts of citric acid and nitrilotriacetic acid. These builders can be used in an amount from 0 up to about 80% by weight of the composition, preferably from 10% to 50% by weight.
  • compositions of the present invention can contain all manner of minor additives commonly found in laundering or cleaning compositions in amounts in which such additives are normally employed.
  • these additives include: lather boosters, such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids; lather depressants, such as alkyl phosphates, waxes and silicones; fabric-softening agents; fillers; and, usually present in very minor amounts, fabric-­whitening agents, perfumes, enzymes, germicides and colorants.
  • a total of 5000 grams manganous chloride tetrahydride were dissolved in 100 litres of distilled water.
  • a separate vessel was charged with a slurry of 100 kilograms zeolite (Crosfields DB10) in 102 litres of water.
  • the slurry pH was adjusted to between 9.0 and 9.5 with sulphuric acid.
  • the manganese solution was fed into the zeolite slurry. Exchange was allowed for 45 minutes.
  • An Eirich Intensive Mixer (Model RV 02) was charged with 3 kilograms of the dried manganese exchanged on zeolite and with 1.153 kilograms of a 25% (by weight) aqueous PVP K-30 solution.
  • the Eirich rotor and pan were operated at 26.2 metres/sec. and 65 rpm, respectively. Water was added until a total moisture level of about 35% was reached. Agglomeration was observed to occur between about 3 to 8 minutes into the blending, the time being dependent upon the amount and timing of water addition.
  • the agglomerated product was dried in an Aeromatic STREA-1 fluid bed dryer (manufactured by the Aeromatic Corporation).
  • Target moisture level was 12.­5% water or less.
  • the original khaki colour of the starting zeolite changed to antique white after being dried to the proper moisture level.
  • Example 2 uses sodium silicate as the binder. Silicate is unacceptable because the pH is about 12, which causes manganese oxidation visually observed as brown particles. Agglomerates prepared with silicate were poorly dispersible and have unacceptable browning properties.
  • Examples 3-7 illustrate agglomerates with various modified starch binders.
  • Examples 7-9 illustrate the effect of increasing binder level on dispersion and porosity. As the binder level is increased, dispersibility increases but porosity decreases.
  • Purity Gum BE ® and 78-0059 are converted waxy starches soluble in cold water.
  • Purity Gum BE ® is a hydrophobic derivative of starch with a low-medium viscosity; 78-0059 is a stabilized starch of low viscosity; both are products of the National Starch Corporation.
  • the present Example illustrates the effects of various modified starch levels as they relate to dispersibility and bleach effectiveness.
  • Table II shows that the bleaching obtained using catalyst aggregates with 5% or less non-­dispersibles is statistically better than where the non-­dispersibles are higher than about 5%.
  • 10% starch 78-0059 gave 8.0% non-dispersibles
  • 20% and 40% of starch 78-0059 in the otherwise identical aggregate formulation gave non-dispersibles of 5.1 and 1.0%.
  • a statistically better bleaching was obtained with the 78-0059 starch formulations of 5.1 and 1.0% non-dispersibles than with 8.0% non-dispersibles.
  • Similar results were obtained in comparison of 10% and 40% binder levels using Capsul ®, Purity Gum BE ® and Nadex 320 ®.
  • a single-step heavy metal ion exchange and catalyst granulation is herein described.
  • An Eirich Intensive Mixer RV 02 was charged with 3.0 kg Crosfields DB10 zeolite powder and 1.2 kg of a 25% aqueous solution of PVP K-30 binder containing 20 g concentrated 12N sulphuric acid. The mixture was churned at a rotor tip speed of 26.2 m/s and bowl speed of 60 rpm. A manganese sulphate aqueous solution of 121 g manganous sulphate and an equal amount of water were slowly added thereto. Exchange occurred under mixing over a period of 6-8 minutes. The resultant agglomerates were dried in a fluid bed drier for about 0.5 hours at 80°C. Final product water content was between 7 and 11%.
  • Bleaching tests were conducted with a 4-pot Terg-O-Tometer from the U.S. Testing Company. Wash solutions were prepared from distilled water with hardness ions added to provide 60 ppm of calcium and magnesium (2:1),defined on a calcium carbonate basis. The wash volume was 1 litre. Temperature was maintained at 40°C. Agitation was provided throughout a 14-­minute wash period.
  • Bleaching was monitored by measuring reflectance of a dry cotton cloth (4" ⁇ 6"). Prior to bleaching, the cloth had been uniformly stained with a tea solution and washed several times in a commercial detergent. Reflectance was measured on a Gardner XL-23 Reflectometer.
  • the catalyst prepared in the one-step procedure, was blended (0.151 gram catalyst delivering 2.0 ppm manganese ion) with 1.158 grams of detergent base powder and 0.391 gram sodium perborate monohydrate.
  • the change in reflectance for the single step adsorption/­ granulation was essentially identical (about 7 units) with the two-step process outlined in Example 1. Hence, bleaching effectiveness was not impaired by eliminating one of the steps.
  • Illustrated here is the effect of the average aggregate diameter size on storage stability of sodium perborate when these components are packaged together.
  • the catalyst aggregates were formed, according to the process of Example 1, from 86.38 parts zeolite, 3.62 parts manganous chloride and 10 parts PVP K-30 binder. Catalyst (0.­151 grams) and detergent powder containing 0.391 grams sodium perborate monohydrate were blended together. A 1.7 gram sample of the detergent blend was placed in an open Petrie dish and stored at 80°F/80% relative humidity over an 8-day period. Samples were measured for percent available oxygen (Avox %) using a Kyoto Auto-Titrator. Avox measurements were taken at the beginning of the experiment and after the 8-day storage period. There were also visual inspections to note any discolouration and gross physical changes. Results of this test are shown in Table III.
  • Table III show that storage stability improves with increasing size of the agglomerated particle. Loss of available oxygen (2.87%) is significant for particle sizes of 177-250 microns. When the particles are between 500 and 2000 microns, the blend is satisfactorily stable (Avox loss _0.86%). Table III also reports that agglomerated particles in the range 177-250 microns cause the detergent blend to turn dark brown. Original granular material was observed to have turned into sludge. The larger particle size agglomerate containing detergent blend also exhibited some colour darkening. However, discolouration was not severe and the granular quality of the blend remained.

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  • Inorganic Chemistry (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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EP86202015A 1985-12-06 1986-11-17 Bleichkatalysatoraggregate von mit Mangankationen imprägnierten Aluminiumsilikaten Withdrawn EP0224952A3 (de)

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US80553085A 1985-12-06 1985-12-06
US805530 2004-03-22

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EP0224952A3 EP0224952A3 (de) 1988-09-14

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Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995030733A1 (en) * 1994-05-09 1995-11-16 Unilever N.V. Bleach catalyst composition
EP0690122A2 (de) 1994-06-30 1996-01-03 The Procter & Gamble Company Waschmittelzusammensetzungen
EP0699745A2 (de) 1994-08-31 1996-03-06 The Procter & Gamble Company Quartäre Ammoniumverbindungen als Bleiaktivatoren enthaltende Zusammensetzungen für das maschinelle Geschirrspülen sowie quartäre Ammoniumverbindungen
US5560748A (en) * 1994-06-10 1996-10-01 The Procter & Gamble Company Detergent compositions comprising large pore size redox catalysts
US5622646A (en) * 1994-04-07 1997-04-22 The Procter & Gamble Company Bleach compositions comprising metal-containing bleach catalysts and antioxidants
EP0778342A1 (de) 1995-12-06 1997-06-11 The Procter & Gamble Company Waschmittelzusammensetzungen
US5686014A (en) * 1994-04-07 1997-11-11 The Procter & Gamble Company Bleach compositions comprising manganese-containing bleach catalysts
US5703034A (en) * 1995-10-30 1997-12-30 The Procter & Gamble Company Bleach catalyst particles
US5703030A (en) * 1995-06-16 1997-12-30 The Procter & Gamble Company Bleach compositions comprising cobalt catalysts
US5705464A (en) * 1995-06-16 1998-01-06 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt catalysts
US5798326A (en) * 1995-02-02 1998-08-25 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt III catalysts
WO1999026508A1 (en) 1997-11-21 1999-06-03 The Procter & Gamble Company Product applicator
US5939373A (en) * 1995-12-20 1999-08-17 The Procter & Gamble Company Phosphate-built automatic dishwashing composition comprising 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
US6878680B2 (en) 2002-05-02 2005-04-12 Procter & Gamble Detergent compositions and components thereof
EP3075832A1 (de) 2015-03-30 2016-10-05 Dalli-Werke GmbH & Co. KG Mangan-aminosäure-verbindungen in reinigungszusammensetzungen
WO2018085300A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Methods of using leuco colorants as bluing agents in laundry care compositions
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EP3444328A1 (de) 2017-08-18 2019-02-20 The Procter & Gamble Company Reinigungsmittel
WO2020123889A1 (en) 2018-12-14 2020-06-18 The Procter & Gamble Company Foaming fibrous structures comprising particles and methods for making same
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US5686014A (en) * 1994-04-07 1997-11-11 The Procter & Gamble Company Bleach compositions comprising manganese-containing bleach catalysts
US5622646A (en) * 1994-04-07 1997-04-22 The Procter & Gamble Company Bleach compositions comprising metal-containing bleach catalysts and antioxidants
WO1995030733A1 (en) * 1994-05-09 1995-11-16 Unilever N.V. Bleach catalyst composition
US5560748A (en) * 1994-06-10 1996-10-01 The Procter & Gamble Company Detergent compositions comprising large pore size redox catalysts
EP0690122A2 (de) 1994-06-30 1996-01-03 The Procter & Gamble Company Waschmittelzusammensetzungen
EP0699745A2 (de) 1994-08-31 1996-03-06 The Procter & Gamble Company Quartäre Ammoniumverbindungen als Bleiaktivatoren enthaltende Zusammensetzungen für das maschinelle Geschirrspülen sowie quartäre Ammoniumverbindungen
US6119705A (en) * 1995-02-02 2000-09-19 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt chelated catalysts
US5968881A (en) * 1995-02-02 1999-10-19 The Procter & Gamble Company Phosphate built automatic dishwashing compositions comprising catalysts
US6020294A (en) * 1995-02-02 2000-02-01 Procter & Gamble Company Automatic dishwashing compositions comprising cobalt chelated catalysts
US5798326A (en) * 1995-02-02 1998-08-25 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt III 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
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