EP0143491A2 - Reinigungsmittelzusammensetzung - Google Patents

Reinigungsmittelzusammensetzung Download PDF

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Publication number
EP0143491A2
EP0143491A2 EP84201655A EP84201655A EP0143491A2 EP 0143491 A2 EP0143491 A2 EP 0143491A2 EP 84201655 A EP84201655 A EP 84201655A EP 84201655 A EP84201655 A EP 84201655A EP 0143491 A2 EP0143491 A2 EP 0143491A2
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EP
European Patent Office
Prior art keywords
copper
detergent composition
dye
peracid
weight
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
Application number
EP84201655A
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English (en)
French (fr)
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EP0143491B1 (de
EP0143491A3 (en
Inventor
Anthony Henry Clements
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority to AT84201655T priority Critical patent/ATE41672T1/de
Publication of EP0143491A2 publication Critical patent/EP0143491A2/de
Publication of EP0143491A3 publication Critical patent/EP0143491A3/en
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Publication of EP0143491B1 publication Critical patent/EP0143491B1/de
Expired legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3932Inorganic compounds or complexes

Definitions

  • This invention relates to fabric-washing detergent compositions which are especially, but not exclusively, designed for the washing of coloured or mixed coloured and white fabric loadings.
  • Hitherto fabric-washing detergent compositions of two types were available, i.e. (1) washing products of a non-bleaching type for coloured fabrics, which, although safe for the fabric dyes themselves, are not effective to prevent the tendency of some coloured fabrics to release into the wash liquor dyes which are then transferred during the washing process onto other fabrics being washed therewith; and (2) a bleach- containing fabric-washing product type which can inhibit dye transfer to a certain extent but at the same time will cause bleaching and fading of the colours of the fabrics.
  • washing products of a non-bleaching type for coloured fabrics which, although safe for the fabric dyes themselves, are not effective to prevent the tendency of some coloured fabrics to release into the wash liquor dyes which are then transferred during the washing process onto other fabrics being washed therewith
  • a bleach- containing fabric-washing product type which can inhibit dye transfer to a certain extent but at the same time will cause bleaching and fading of the colours of the fabrics.
  • dye-transfer-inhibiting compositions which comprise a peroxygen compound, e.g. an organic peroxyacid, combined with rather complex aldehyde or ketone compounds as bleach activator.
  • a peroxygen compound e.g. an organic peroxyacid
  • aldehyde or ketone compounds rather complex aldehyde or ketone compounds
  • compositions having dye-transfer inhibitory effects are disclosed in European Patent 0024367 (based on the activation of organic peracids with bromide ions) and European Patent Application 0024368 (based on a system comprising an organic peracid precursor and a bromide activator). Still, the main drawback of these compositions is that they too exert a rather strong direct fabric bleaching, tending to cause fading of the coloured fabrics.
  • European Patent Application 0058444 describes washing compositions useful for the reduction of dye transfer in fabric washing at lower temperatures, comprising a bleach system consisting essentially of an organic peracid or an organic peracid precursor in conjunction with a water-soluble iodide salt.
  • a bleach system consisting essentially of an organic peracid or an organic peracid precursor in conjunction with a water-soluble iodide salt.
  • iodide catalyst There are some snags in the use of iodide catalyst, i.e. 1) the risk of staining due to iodine formation and 2) the effect of direct fabric dye bleaching.
  • transition metal ions can catalyse dye bleaching in solution by oxygen bleaches. So hydrogen peroxide or hydrogen peroxide adducts, inorganic persalt/bleach activator systems and peroxyacids per se can all be activated by copper ions. However, it has been found that copper-catalysed peracid bleach systems were much more effective than copper-catalysed hydrogen peroxide systems (e.g. sodium perborate) .
  • transition metal ions are well known to interact with peroxide compounds as in Route B above, thus inducing decomposition to radicals or radical species which are known to have high oxidation potential and are capable of oxidizing most unsaturated molecules, no other transition metals are as effective for dye transfer inhibition as copper.
  • Cupric ion being the smallest divalent transition metal ion, with the highest charge density, most readily forms stable complexes.
  • Cobalt III and chromium III complexes of dyes are also very stable, but apparently they are kinetically inert and, in contrast to copper, severe conditions are generally necessary to introduce cobalt III and chromium III into dye structures.
  • manganese which is known to be very useful for catalysing stain bleaching, especially with hydrogen peroxide bleaches in the presence of a carbonate, has proved to be ineffective for dye transfer inhibition. Experiments have even shown that under practical conditions manganese can inhibit the catalytic effect of copper, and so the presence of manganese ions in the system of the invention should preferably be avoided.
  • cupric ion concentration The influence of cupric ion concentration on an experiment of dye transfer inhibition is shown in the following Table II for the peracid bleaches monopersulphate (Oxone®), diperisophthalic acid (SuproxA and magnesium monoperphthalate, with and without sodium perborate.
  • the detergent base used in the experiments had the following composition :
  • the influence of pH on dye transfer inhibition with copper-catalysed monopersulphate bleach systems is shown in Table III.
  • the diperisophthalic acid used was a commercial product "Suprox”; monopersulphate used was a commercial product “Oxone”; and the peracetic acid used was pretreated with catalase to remove H 2 0 2 .
  • the apparatus consists of a Beckman DB spectrophotometer fitted with a 1 cm silica flow cell, a water bath to maintain the temperature of the bulk liquor and a p H stat to control the pH.
  • the cell is connected to the solution with small-bore silicon rubber tubing and the liquor is circulated by a Watson Marlow flow inducer. This is fitted on the return tube from the cell to the bulk solution to prevent accidental flooding of the cell compartment.
  • the silicon rubber tubes enter the cell compartment of the spectrophotometer through small holes in the lid. The small amount of light which must enter here does not affect readings in the visible range.
  • the silica flow cell has a path length of 1 cm. Its stopper has a glass entry tube almost reaching the bottom of the cell and set to one side out of the light path. A short exit tube takes the solution from the top of the cell through the pump and back to the bulk solution.
  • a 0.04% w/v stock solution of dye was diluted with demineralised water to give 250 ml of 0.004% solution. This was poured into a 600 ml beaker set in the water bath preheated to 40°C and the pH was adjusted. The solution was then pumped through the cell at a rate of 40 ml per minute. This gives a good flow through the cell without turbulence causing bubbles. The per cent transmission at max for the dye was monitored on the recorder.
  • a further 250 ml of demineralised water containing 1.137 x 10 -4 m of peracid was warmed to 40°C and the pH adjusted. This was added to the dye solution and the change in % transmission was recorded for one hour. During this time, the solution was stirred constantly and, at various time intervals, 50 ml aliquots were taken for titration with M/200 sodium thiosulphate.
  • Bleaches were compared at equal active oxygen concentrations.
  • the dye solution was scanned from 700 nm to 400 nm to find the maximum absorption wavelength. Then an absorption (at ⁇ max) vs concentration (% w/v) graph was plotted and the slope calculated.
  • Test fabrics with different dye types are used. One 17.5 cm x 17.5 cm square of dyed test cloth was used in each wash.
  • the fabrics for dye pick-up were white mercerised, de- sized cotton shirting and white bulked nylon 66, both non-fluorescent. One 12 cm x 12 cm square of each of these was put into the wash, regardless of the dye type, to keep the liquor to cloth ratio the same.
  • the sets of test cloths were washed in the Terg-O-Tometer for 30 minutes at a constant 40°C and 100 rpm.
  • the product concentration was 0.4% w/v in 18° hard water with a liquor to cloth ratio of 50:1.
  • Each set of cloths was rinsed separately with three 600 ml portions of cold 18° hard water.
  • the sets of cloths from each pot were put into separate 600 ml portions of cold 18° hard water.
  • the rinses were then continued, each set of cloths being rinsed three times in 600 ml portions of cold 18° hard water.
  • the reflectance of the cloths was measured at the maximum absorbence wavelength of the dye using a Beckmann DB-GD grating spectrophotometer fitted with a diffuse reflectance attachment. Barium sulphate was used to standardise the instrument and as a reference when measuring the cloths.
  • composition of the invention should preferably contain at least 0.002% by weight of copper, i.e. equivalent to about 0.1 ppm in solution, should preferably have a 5 g/1 solution pH of from about 7 to about 11, and should preferably contain a hydrogen peroxide adduct at molar ratios to peracid which can be as low as about 1:100 up to about 2:1, most preferably from 1:25 to 1:1.
  • the upper limit of the copper concentration can be set at about 2.5% by weight based on the total composition.
  • any copper salt can be used in the practice of the invention, for example copper sulphate, copper carbonate, copper chloride, copper phosphate etc.
  • sequestration of copper by strong sequestrants should be minimized so as to favour dye/copper interaction and the production of radicals from the bleach, but on the other hand excessive bleach decomposition must be avoided during storage of the powder.
  • a relatively weak sequestrant such as ethylene diamine tetra-acetates (EDTA) can be tolerated in the present invention at levels usually below 0.2% by weight, preferably up to about 0.1% by weight, based on the total composition.
  • the level of sequestrant tolerated will depend on the level of copper added.
  • a higher level of copper in the formulation is required.
  • a preferred level of copper in such formulations will in general be at least about 0.02% by weight.
  • stain chromophores on fabrics which are generally quinonoid in character, are unlikely to behave very differently to dyes in bleaching reactions.
  • Dyes of different types e.g. azo, quinonoid and indigoid, have all been found to respond to transition metal ion catalysis in solution.
  • dyes can be bleached in solution (i.e. a homogeneous reaction)
  • the bleach in order to bleach dye on the cloth, the bleach must transfer from the solution phase into (or onto) the substrate phase.
  • a surprising feature of the present invention is that generally no positive catalysis of dye or stain bleaching on the fabric is observed from copper added to the wash solution.
  • the effect of copper in solution is likely to deplete the concentration of transferable bleach species (bleach anion ROO - and especially undissociated ROOH) in solution and thus to reduce the amount of bleach available to undergo phase transition into the dye or stain on the fabric, thus reducing direct fabric bleaching.
  • transferable bleach species bleach anion ROO - and especially undissociated ROOH
  • peracids are also applicable to peracid precursor systems which form organic peracids in aqueous media by hydrolysis or perhydrolysis.
  • the organic peracids which can be used in the present invention are known in the art. They can be either aliphatic or aromatic and have the general formula: wherein R is an alkylene group containing from 1-16 carbon atoms or an arylene group containing from 6-8 carbon atoms and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution, for example: wherein M is hydrogen or a water-soluble salt-forming cation.
  • aliphatic peracids are peracetic acid, monoperazelaic acid, diperazalaic acid, diperadipic acid, diperoxy dodecanoic acid and decyl butane diper- oxoic acid.
  • aromatic peracids are monoperoxy phthalic acid, perbenzoic acid, m-chloro-perbenzoic acid, diperisophthalic acid or mixtures thereof.
  • peracid salts examples include magnesium monoperphthalate, potassium monopersulphate, and peroxymonophosphate. Mixtures of peracids (with or without a hydrogen peroxide adduct) may be useful in practice.
  • the peracid in situ from its precursor or precursors, can be formed from the combination of an organic peracid precursor, so-called “persalt activator” and a persalt of the peroxyhydrate type, e.g. sodium perborate, by perhydrolysis, or from a precursor which generates peracid by hydrolysis.
  • an organic peracid precursor so-called “persalt activator”
  • a persalt of the peroxyhydrate type e.g. sodium perborate
  • perhydrolysis e.g. sodium perborate
  • various peracid precursors will fall within the scope of use in the compositions of the invention.
  • these include benzoyl peroxide and diph- thaloyl peroxide, both of which are capable of generating peracids, i.e. perbenzoic acid and monoperoxyphthalic acid, respectively.
  • Precursors which generate peracid on perhydrolysis are known in the art and include esters, such as those described in British Patents 836,988 and 970,950, including glycerol penta-acetate and tetra-acetyl xylose; acyl amides, such as N,N,N',N'-tetra-acetyl ethylene diamine (TAED), tetra-acetyl glycoluril, N,N'-diacetyl acetoxy methyl malonamide and others described in British Patents 907,356; 855,735; 1,246,339 and US Patent 4,128,494; acyl azoles, such as those described in Canadian Patent 844,481; acyl imides, such as those described in South African Patent 68/6344; and triacyl cyanurates, such as described in US Patent 3,332,882.
  • the amount of peracid compound in the composition of the invention will be in the range generally of
  • peracid compounds are applicable to organic peracids, peracid salts as well as precursors which generate peracids by hydrolysis or perhydrolysis.
  • the organic peracid precursor will advantageously be used in stoichiometric ratio to the persalt, though higher ratios of persalt to organic precursors can also be used, particularly if a persalt bleach scavenger, such as catalase, is present.
  • Preferred persalts are sodium perborate and sodium percarbonate.
  • Precursors which generate peracids on perhydrolysis are therefore usable at levels of about 0.5-25% by weight, preferably 1-15% by weight, in conjunction with a persalt at levels of about 0.5-50% by weight, preferably 0.5-30% by weight of the composition.
  • the invention therefore provides an improved fabric-washing composition especially but not exclusively designed for the washing of mixed coloured fabrics, comprising from 0.5 to 25% by weight of a peracid or a peracid precursor as hereinbefore defined and at least 0.002% by weight of a copper cation in the absence or substantial absence of a powerful sequestrant which complexes strongly with copper.
  • the washing composition of the instant invention contains a surfactant.
  • the surfactant can be anionic, nonionic, cationic, semi-polar, ampholytic or zwitterionic in nature, or can be mixtures thereof.
  • Anionics/nonionics and cationics/nonionics are typical basic surfactant mixtures.
  • These surfactants can be used at levels from about 5% to about 50% of the composition by weight, preferably at levels of about 10% to 35% by weight.
  • Typical anionic non-soap surfactants are the alkylbenzene sulphonates having from 8-16 carbon atoms in the alkyl group, e.g. sodium dodecyl benzene sulphonate; the aliphatic sulphonates, e.g.
  • C 8 -C 18 alkane sulphonates the olefin sulphonates having from 10-20 carbon atoms, obtained by reacting an alpha-olefin with gaseous diluted sulphur trioxide and hydrolysing the resulting product; the alkyl sulphates, such as tallow alcohol sulphate; and further the sulphation products of ethoxylated and/or propoxylated fatty alcohols, alkyl phenols with 8-15 carbon atoms in the alkyl group, and fatty acid amides having 1-8 moles of ethylene oxide or propylene oxide groups.
  • Other anionic surfactants usable in the present invention are the alkali metal soaps (e.g. of C 8 -C 22 fatty acids).
  • Typical nonionic surfactants are the condensation products of alkyl phenols having 5-15 carbon atoms in the alkyl group with ethylene oxide, e.g. the reaction product of nonyl phenol with 6-30 ethylene oxide units; the condensation products of higher fatty alcohols, such as tridecyl alcohol and secondary C 10 -C 15 alcohols, with ethylene oxide, known under the trade-name of "Tergitols”®, supplied by Union Carbide; the condensation products of fatty acid amine with 8-15 ethylene oxide units and the condensation products of polypropylene glycol with ethylene oxide.
  • Typical cationic surfactants include the conventional quaternary ammonium compounds and the C 10 -C 25 alkyl imidazolinium salts.
  • Preferred quaternary ammonium compounds are the di(C 16 -C 20 alk y l)di(C 1 - C 4 alkyl) ammonium salts such as ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methylsulphate; dihydrogenated tallow dimethyl ammonium chloride or methyl sulphate; dioctadecyl dimethyl ammonium chloride; dicoconut alkyl dimethyl ammonium chloride.
  • Also suitable are the single long chained quaternary ammonium compounds wherein the long chain is a C 10 -C 22 alkyl or alkenyl group.
  • a preferred member of the class of C 10 -C 25 alkyl imidazolinium salts believed to be the 1-methyl-2- tallow-3-(2-tallow amide ethyl) imidazolinium chloride, is sold under the trade-name of Varisoft 455 or 457 (Ashland Chemical Company) or Stemoquat M 5040/H (Chemische Werke Rewo).
  • a washing composition of the invention will also include one or more detergency builders and alkaline materials.
  • the total amount of detergency builders in a detergent composition of the invention will be from about 5 to about 70% by weight of the detergent composition.
  • Many detergency builders are known, and those skilled in the art of formulating fabric-washing detergent compositions will be familiar with these materials.
  • detergency builders are sodium triphosphate; sodium orthophosphate; sodium pyrophosphate; sodium trimetaphosphate; sodium carbonate; sodium silicate; sodium oxydi- acetate; sodium salts of long-chain dicarboxylic acids, for instance straight-chain (C 10 to C 20 ) succinic acids and malonic acids; sodium salts of alpha-sulphonated long-chain monocarboxylic acids; sodium salts of polycarboxylic acids, i.e.
  • acids derived from the (co)polymerisation of unsaturated carboxylic acids and unsaturated carboxy acid anhydrides such as maleic acid, acrylic acid, itaconic acid, methacrylic acid, crotonic acid and aconitic acid, and the anhydrides of these acids, and also from the copolymerisation of the above acids and anhydrides with minor amounts of other monomers, such as vinyl chloride, vinyl acetate, methyl methacrylate, methyl acrylate and styrene; and modified starches such as starches oxidized, for example using sodium hypochlorite, in which some anhydroglucose units have been opened to give dicarboxyl units.
  • Another class of suitable builders is the insoluble aluminosilicates as described in British Patents 1 429 143, 1 470 250 and 1 529 454, e.g. zeolite A.
  • a detergent composition of the invention may contain any of the conventional detergent composition ingredients in any of the amounts in which such conventional ingredients are usually employed therein.
  • additional ingredients are lather boosters, such as coconut mono-ethanolamide and palm- kernel mono-ethanolamide; lather controllers, inorganic salts, such as sodium sulphate and magnesium sulphate; anti-redeposition agents, such as sodium carboxymethylcellulose; and, usually present only in minor amounts, perfumes, colorants, fluorescers, corrosion inhibitors and germicides.
  • the washing composition of the present invention can suitably be used in relatively short washes as well as in relatively longer soak-washings under room temperature conditions up to 60°C for coloured fabrics, with a minimal risk of dye transfer and without the risk of serious direct fabric bleaching.
  • the invention can also be formulated as a washing or bleach adjunct to improve the performance of existing detergent compositions, e.g. fine wash products.
  • the system will essentially consist of a dry mixture of 0.5 to 25 parts by weight of a peracid compound and 0.002 to 2.5 parts by weight of a copper catalyst, e.g. cupric sulphate or cupric chloride, and optionally an inert filler such as sodium sulphate.
  • washing compositions of the invention are preferably particulate, either as flowable powders or aggregates.
  • They can be prepared using any of the conventional manufacturing techniques commonly used or proposed for the preparation of particulate detergent compositions, such as dry-mixing, or slurry-making followed by spray- drying or spray-cooling and subsequent dry-dosing of sensitive ingredients, e.g. the solid organic peroxyacid compound, the peroxyacid precursor and the inorganic peroxyhydrate salt.

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Detergent Compositions (AREA)
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EP84201655A 1983-11-23 1984-11-15 Reinigungsmittelzusammensetzung Expired EP0143491B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84201655T ATE41672T1 (de) 1983-11-23 1984-11-15 Reinigungsmittelzusammensetzung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8331278 1983-11-23
GB838331278A GB8331278D0 (en) 1983-11-23 1983-11-23 Detergent composition

Publications (3)

Publication Number Publication Date
EP0143491A2 true EP0143491A2 (de) 1985-06-05
EP0143491A3 EP0143491A3 (en) 1985-10-30
EP0143491B1 EP0143491B1 (de) 1989-03-22

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Application Number Title Priority Date Filing Date
EP84201655A Expired EP0143491B1 (de) 1983-11-23 1984-11-15 Reinigungsmittelzusammensetzung

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EP (1) EP0143491B1 (de)
JP (1) JPS60138000A (de)
AT (1) ATE41672T1 (de)
AU (1) AU550759B2 (de)
BR (1) BR8405950A (de)
CA (1) CA1234456A (de)
DE (1) DE3477397D1 (de)
DK (1) DK556184A (de)
FI (1) FI844531L (de)
GB (2) GB8331278D0 (de)
GR (1) GR80988B (de)
IN (1) IN161099B (de)
NO (1) NO163964C (de)
PH (1) PH20525A (de)
PT (1) PT79540A (de)
TR (1) TR22429A (de)
YU (1) YU196684A (de)
ZA (1) ZA849117B (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0369841A2 (de) * 1988-10-25 1990-05-23 S.A. Camp Fabrica De Jabones Textilbleichmittel, wirksam bei niedrigen Temperaturen
WO1995027775A1 (en) * 1994-04-07 1995-10-19 The Procter & Gamble Company Bleach compositions comprising metal-containing bleach catalysts
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
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
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

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8508010D0 (en) * 1985-03-27 1985-05-01 Unilever Plc Liquid bleaching compositions
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

Citations (5)

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Publication number Priority date Publication date Assignee Title
FR1515237A (fr) * 1967-01-20 1968-03-01 Colgate Palmolive Co Composition de nettoyage à effet de blanchiment amélioré
FR2253823A1 (de) * 1973-12-11 1975-07-04 Colgate Palmolive Co
DD141844A1 (de) * 1978-12-28 1980-05-21 Rudolf Opitz Bleichmittel
EP0025608A2 (de) * 1979-09-18 1981-03-25 Süd-Chemie Ag Katalysator zur kontrollierten Zersetzung von Peroxoverbindungen, seine Herstellung und Verwendung; Wasch- oder Bleichmittel und Verfahren zur Herstellung eines Peroxoverbindungen enthaltenden Wasch- oder Bleichmittels
EP0072166A1 (de) * 1981-08-08 1983-02-16 THE PROCTER & GAMBLE COMPANY Bleichkatalysatorzusammensetzungen, deren Verwendung bei Wäschebleich- und Detergenszusammensetzungen und Verfahren zum Bleichen damit

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL266614A (de) * 1960-07-07
NL276367A (de) * 1961-03-24

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1515237A (fr) * 1967-01-20 1968-03-01 Colgate Palmolive Co Composition de nettoyage à effet de blanchiment amélioré
FR2253823A1 (de) * 1973-12-11 1975-07-04 Colgate Palmolive Co
DD141844A1 (de) * 1978-12-28 1980-05-21 Rudolf Opitz Bleichmittel
EP0025608A2 (de) * 1979-09-18 1981-03-25 Süd-Chemie Ag Katalysator zur kontrollierten Zersetzung von Peroxoverbindungen, seine Herstellung und Verwendung; Wasch- oder Bleichmittel und Verfahren zur Herstellung eines Peroxoverbindungen enthaltenden Wasch- oder Bleichmittels
EP0072166A1 (de) * 1981-08-08 1983-02-16 THE PROCTER & GAMBLE COMPANY Bleichkatalysatorzusammensetzungen, deren Verwendung bei Wäschebleich- und Detergenszusammensetzungen und Verfahren zum Bleichen damit

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 94, no. 1 , May 1981, pages 108-109, no. 141604c, Columbus, Ohio, US; & DD-A-141 844 (R. OPITZ et al.) 21-05-1980 *
Lindner's Tenside-Textilhilfsmittel-Waschrohstoffe, vol. I, pp. 462-466 (1964) *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0369841A3 (de) * 1988-10-25 1991-01-16 S.A. Camp Fabrica De Jabones Textilbleichmittel, wirksam bei niedrigen Temperaturen
EP0369841A2 (de) * 1988-10-25 1990-05-23 S.A. Camp Fabrica De Jabones Textilbleichmittel, wirksam bei niedrigen Temperaturen
WO1995027775A1 (en) * 1994-04-07 1995-10-19 The Procter & Gamble Company Bleach compositions comprising metal-containing bleach catalysts
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
US5968881A (en) * 1995-02-02 1999-10-19 The Procter & Gamble Company Phosphate built automatic dishwashing compositions comprising catalysts
US6119705A (en) * 1995-02-02 2000-09-19 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt chelated 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
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
US5703034A (en) * 1995-10-30 1997-12-30 The Procter & Gamble Company Bleach catalyst particles
US5939373A (en) * 1995-12-20 1999-08-17 The Procter & Gamble Company Phosphate-built automatic dishwashing composition comprising catalysts

Also Published As

Publication number Publication date
JPS60138000A (ja) 1985-07-22
FI844531A0 (fi) 1984-11-19
GR80988B (en) 1985-02-27
NO163964C (no) 1990-08-15
ZA849117B (en) 1986-07-30
DE3477397D1 (en) 1989-04-27
PT79540A (en) 1984-12-01
IN161099B (de) 1987-10-03
EP0143491B1 (de) 1989-03-22
NO844648L (no) 1985-05-24
DK556184A (da) 1985-05-24
GB8331278D0 (en) 1983-12-29
CA1234456A (en) 1988-03-29
GB2150944B (en) 1987-12-02
JPH0352519B2 (de) 1991-08-12
AU3569784A (en) 1985-05-30
GB2150944A (en) 1985-07-10
GB8429496D0 (en) 1985-01-03
DK556184D0 (da) 1984-11-22
EP0143491A3 (en) 1985-10-30
YU196684A (en) 1986-12-31
PH20525A (en) 1987-02-04
NO163964B (no) 1990-05-07
TR22429A (tr) 1987-06-02
ATE41672T1 (de) 1989-04-15
BR8405950A (pt) 1985-09-10
FI844531L (fi) 1985-05-24
AU550759B2 (en) 1986-04-10

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