EP0306089A2 - Metallporphirine als Bleichkatalysator und Verfahren zum Reinigen von Wäsche - Google Patents

Metallporphirine als Bleichkatalysator und Verfahren zum Reinigen von Wäsche Download PDF

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Publication number
EP0306089A2
EP0306089A2 EP88201833A EP88201833A EP0306089A2 EP 0306089 A2 EP0306089 A2 EP 0306089A2 EP 88201833 A EP88201833 A EP 88201833A EP 88201833 A EP88201833 A EP 88201833A EP 0306089 A2 EP0306089 A2 EP 0306089A2
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EP
European Patent Office
Prior art keywords
porphyrin
metallo
iii
fabric
peroxyacid
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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.)
Withdrawn
Application number
EP88201833A
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English (en)
French (fr)
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EP0306089A3 (de
Inventor
Martin Stephenson
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0306089A2 publication Critical patent/EP0306089A2/de
Publication of EP0306089A3 publication Critical patent/EP0306089A3/de
Withdrawn legal-status Critical Current

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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
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • This invention relates to a method for using metallo-porphyrins as bleach catalyst, a process for cleaning fabrics and to products for use in carrying out the process. More particularly, the invention relates to catalytic fabric stain bleaching at low to ambient temperatures, e.g. from 10-30°C, and to products comprising metallo-porphyrins.
  • Hydrogen peroxide releasing bleaching agents such as sodium perborate, sodium percarbonate, sodium persilicate and sodium perpyrophosphate, are effective only at high washing temperatures, e.g. from 80°C up to the boil. They can be made more effective at lower temperatures by adding "activators", which are usually organic acid anhydrides, esters, amides or imides, functioning by a perhydrolysis reaction with the percompound forming organic peroxyacids which, unlike the percompound, are effective at lower temperatures.
  • activators are usually organic acid anhydrides, esters, amides or imides, functioning by a perhydrolysis reaction with the percompound forming organic peroxyacids which, unlike the percompound, are effective at lower temperatures.
  • organic peroxyacids i.e. percarboxylic acids
  • persulphates e.g. potassium monopersulphate
  • the present invention seeks to provide a method for improving the bleaching effect of peroxyacid bleach systems comprising a peroxyacid per se or formed in situ .
  • iron porphyrins can act as an oxidation catalyst.
  • US Patent N° 4,077,768 describes the application of this catalyst with an oxidising bleach, e.g. hydrogen peroxide and also peroxyacids, in aqueous wash liquors for dye bleaching in solution, i.e. for inhibiting dye-transfer.
  • the method as described in this patent comprises treating the fabrics in a bath containing a dissolved or solubilised iron porphyrin, to which bath is also supplied the oxidising bleach which is added or released slowly and in small amounts at a rate not substantially greater than that at which it is removed from said bath by reaction with the contents thereof.
  • Said rate of bleach release in or bleach addition to the bleaching bath is necessary so as to prevent catalyst decomposition.
  • Gradual introduction of hydrogen peroxide over a period of at least 5 minutes to 30 minutes is said to be suitable, and compositions comprising iron porphyrins and an oxidising bleach in a form such that it dissolves in the bath at said controlled rate are also suggested.
  • the method and compositions of this US Patent are particularly designed for inhibiting dye-­transfer but they are no good in the effective bleaching of stains on fabrics at the lower wash temperature region of e.g. between 10 and 40°C.
  • metallo-porphyrins do effectively catalyse the fabric stain bleaching action of peroxyacid bleach systems if certain conditions are fulfilled.
  • peroxyacids when adsorbed on to fabrics, can effect a catalysing action on the fabric stain bleaching of peroxyacids, making them effective for use in washing at lower temperatures.
  • peroxyacids used here includes both the organic peroxyacids, i.e. percarboxylic acids, and the inorganic peroxyacid salts, e.g. persulphates, such as potassium monopersulphate.
  • peroxyacids used here includes both the organic peroxyacids, i.e. percarboxylic acids, and the inorganic peroxyacid salts, e.g. persulphates, such as potassium monopersulphate.
  • Pre-adsorption of the metallo-porphyrin catalyst on to the fabric is a prerequisite for catalytic activity on stain bleaching. Direct mixture of catalyst and peroxyacid in solution (either slowly added or in one aliquot) or inadequate adsorption of the metallo-porphyrin on to the fabric upon per
  • the metallo-porphyrin catalyst must be pre-­adsorbed on to the fabric prior to contacting the fabric with the peroxyacid.
  • Pre-adsorption can be effected by applying the metallo-porphyrin manually upon the fabric stains or by by treating the fabric in a bath containing a dissolved or solubilised amount of metallo-porphyrin.
  • Sufficient time must be allowed for the catalyst to sufficiently adsorb on to the fabric. Generally at least 2 minutes should be allowed for the fabric to adsorb an effective amount of metallo-porphyrin from solution, preferably 5 to 30 minutes, particularly from 7-15 minutes.
  • the metallo-porphyrin is adequately adsorbed on to the fabric, for which the above-stated period of time must be allowed, it is of no benefit, rather it can be detrimental to the bleaching effect if the fabric is then treated with a bleaching bath wherein the peroxyacid is released at the controlled rate as defined in the art.
  • Treatment of the fabric in a bleaching bath comprising the full amount of peroxyacid is thus advantageous and preferred to obtain the full benefit of the metallo-porphyrin bleaching catalysis action.
  • the metallo-porphyrins usable as a catalyst in the present invention are compounds having the following structural formula: wherein M can be Fe (III), Mn (III), Ru (II/III) or Mo (V); Ar is a substituent on the meso-positions and 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; and B is C1-C10 alkyl, polyethoxyalkyl or hydroxyalkyl.
  • Preferred molecules are those in which the substituents on the phenyl or pyridyl groups are selected from the group consisting of : -CH3; -C2H5; -CH2CH2CH2SO3 ⁇ ; -CH2CH(OH)CH2SO3 ⁇ and SO3 ⁇ .
  • Preferred metallo-porphyrins are those wherein M is Fe(III) or Mn(III), the iron porphyrins and manganese poyphyrins.
  • a particularly preferred iron or manganese porphyrin is one in which the Ar substituent is 4-N-methylpyridyl:
  • Typical examples of these preferred compounds are 4-­4-TMPPFe(III) and 4-TMPPMn(III), known as: [tetra-(N-methylpyridyl)-porphyrinato-iron(III)]Cl5 and [tetra-(N-methylpyridyl)-porphyrinato-manganese(III)]Cl5, respectively.
  • Suitable metallo-porphyrins are :
  • the major determinant of catalytic activity appears to be the cationic or anionic nature of the catalyst. Since the catalyst must interact with both the oxidant and substrate, both of which are normally anionic, the advantage of a cationic catalyst is easily understood in terms of favourable electrostatic interactions. With 4-TSPPFe(III) the interaction with the substrate is electrostatically disfavoured and electron transfer to the substrate will be less able to compete with catalyst decomposition. Since most substrates in stains are likely to be anionic, a cationic metallo-porphyrin catalyst such as 4-TMPPFe(III); 4-TMPPMn(III); 2-TMPPFe(III) and 2-TMPPMn(III), would be the best choice for practical purposes.
  • the invention provides a process for cleaning and bleaching fabrics, which process comprises treating the fabric with a metallo-porphyrin compound selected from Fe(III)-, Mn(III)-, Ru(II/III)- and Mo(V)-­porphyrins, leaving the fabric in contact therewith for a predetermined time of not less than 1 minute, preferably 2 minutes, to effect sufficient adsorption of said compound on to the fabric, and thereafter washing the fabric with a peroxyacid bleach composition.
  • a metallo-porphyrin compound selected from Fe(III)-, Mn(III)-, Ru(II/III)- and Mo(V)-­porphyrins
  • the fabrics are treated in a bath comprising 2 to 25 ppm of a dissolved or solubilised metallo-porphyrin for not less than 2 minutes, normally 5-30 minutes, preferably 7-15 minutes, to which bath a peroxyacid bleaching agent is then added at a level of about 20 to 1000 ppm.
  • a peroxyacid bleaching agent is then added at a level of about 20 to 1000 ppm.
  • the amount of solubilised or dissolved metallo-porphyrin in the bath will depend upon the fabric wash load and the rate of staining, and adjusting the amount is within the ability of the skilled artisan.
  • an effective amount of metallo-porphyrin is manually applied from an applicator on to the fabric on places with stubborn or persistent stains, leaving the fabric treated therewith for at least 1 minute, preferably 2 minutes, normally 2-5 minutes, which fabric is then washed in a conventional manner with a peroxyacid bleach composition.
  • the peroxyacid includes any organic peroxyacid and inorganic peroxyacid salt.
  • organic peroxyacids can be represented by compounds of the general formula : HO-O- (O) n -R-Y 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.
  • 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 alphatic, the unsubstituted acid may have the general formula : 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 : HO-O- (O) n -C6H4-Y 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 acid, m-chloro­peroxybenzoic acid, p-nitro-peroxybenzoic acid, p-­sulphonato-peroxybenzoic acid, diperoxyisophthalic acid and peroxy-alpha-naphthoic 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® from E.I. Dupont de Nemours and Company.
  • the process of the invention may be carried out by simply preparing an aqueous bath comprising a dissolved or solubilised metallo-porphyrin, immersing in said bath the fabric with agitation for a predetermined period of not less than 2 minutes, and thereafter adding to said bath an oxidising bleaching agent in one aliquot, comprising a peroxyacid whilst further agitating the system during a normal washing/soaking time of about 10-60 minutes.
  • An essential element in the fabric bleaching (cleaning and stain removal) of the invention is that the metallo-porphyrin catalyst has already been present on the cloth upon addition of the oxidising peroxyacid. Without wishing to be bound by any theory, it is believed that this is because the catalyst is stable only in the presence of the substrate which it can oxidise; otherwise it is itself oxidised to a less active form. This can be a drawback for a potential fabric washing product where convenience is all-­important. One way around this problem would be to delay the release of the oxidant peroxyacid for 5 to 15 minutes, thereby allowing time for the majority of the catalyst to adsorb on to the fabric.
  • the invention provides a washing product comprising a peroxyacid bleach and, as catalyst therefor, a metallo-porphyrin compound, the peroxyacid being in a form such that it is released into the wash solution only 5 to 15 minutes, preferably 7 to 10 minutes, after the product has been dissolved or dispersed in water.
  • a product that will meet this requirement may be presented in the form of a packaged washing powder comprising a metallo-porphyrin, e.g.
  • 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 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 that of a washing powder comprising a peroxyacid and a metallo-porphyrin catalyst in which the peroxyacid is provided in the form of coherently coated particles. Still other product forms ar feasible and those skilled in the art will have no difficulty in selecting product forms by means of existing technology.
  • Sachets comprising the peroxyacid made of a material consisting of paper coated (at 200 g/m) with a mixture of tallow alcohol (80%) and stearic acid (20%) has proved effective in that they give a delay of release of approximately 7-10 minutes.
  • the same mixture of tallow alcohol and stearic acid can be used as the coating material for peroxyacid particles.
  • Delayed release as meant here should avoid slow and gradual leaching of the peroxyacid in the wash solution; the contents as a whole should preferably be isolated from the wash solution before the time of release.
  • 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 catalyst in a suitable liquid or semi-liquid carrier, presented in a suitable dispenser for manual application.
  • This composition may be dispensed from any known form of applicator, e.g. aerosol pressure bottles, pump-spray bottles, roller-ball capped bottles, pad applicators etc.
  • 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 metallo-porphyrins, e.g. 4-TMPPFe(III), 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 detergents of the anionic, nonionic, zwitterionic and cationic types and mixtures thereof may be present, the amount of which generally will be from about 3 to about 40% by weight.
  • Suitable detergents 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 co-­polymers); 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.
  • Detergent compositions usable in the present invention may contain from about 3 to about 40% by weight of organic detergent, 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 concentration of the peroxyacid was increased from 1 mM to about 2-3 mM to obtain the full benefit of catalysis within an hour.
  • Example bleaching experiments were carried out at 30°C on tea-stained test cloths using sachets (2.5 x 2.5 cm) made of paper coated (at 200 g/m) with a mixture of tallow alcohol (80%) and stearic acid (20%), which gave a delayed release of approximately 7-10 minutes.
  • sachets contained sufficient potassium monopersulphate to give a final concentration of 1.95 mM (0.6 g/l).
  • liquid pretreatment product was prepared: 4-TMPPFe(III) 0.2 g/l nonionic surfactant (Synperonic®A7)* 50% v/v methanol 50% v/v *C13-C15 alcohol/7 ethoxylate.
  • a sample of 4-TMPPMn(III) was prepared as a penta­(hexafluorophosphate) salt with a molecular weight of 1,300.
  • the DR 80 cloth was dyed with a red Azo-dye that resembles the substrate used for solution bleaching studies and as such represented a good comparison of homo- and heterogeneous bleaching response.
  • the EMPA 114 was prewashed before use to remove the detergible fraction. Cloths were removed at different times during the bleaching reaction and resultant reflectance measurements were corrected for contributions from uncatalysed bleaching.

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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)
  • External Artificial Organs (AREA)
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EP88201833A 1987-09-04 1988-08-29 Metallporphirine als Bleichkatalysator und Verfahren zum Reinigen von Wäsche Withdrawn EP0306089A3 (de)

Applications Claiming Priority (2)

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GB8720863 1987-09-04
GB878720863A GB8720863D0 (en) 1987-09-04 1987-09-04 Metalloporphyrins

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EP0306089A2 true EP0306089A2 (de) 1989-03-08
EP0306089A3 EP0306089A3 (de) 1990-05-09

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EP (1) EP0306089A3 (de)
JP (1) JPH0197267A (de)
AU (1) AU2167988A (de)
BR (1) BR8804531A (de)
GB (1) GB8720863D0 (de)
NO (1) NO883903L (de)

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EP0458397A2 (de) * 1990-05-21 1991-11-27 Unilever N.V. Bleichmittelaktivierung
EP0522817A1 (de) * 1991-07-11 1993-01-13 Unilever Plc Verfahren zur Herstellung von Mangan Komplexen
WO1993008324A1 (en) * 1991-10-14 1993-04-29 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
US5246612A (en) * 1991-08-23 1993-09-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing composition containing peroxygen bleach, manganese complex and enzymes
US5256779A (en) * 1992-06-18 1993-10-26 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
TR25877A (tr) * 1991-07-02 1993-11-01 Unilever Nv Peroksi bilesigi agarticilarda agartici aktivasyon icin gelistirilmis katalizör olarak gecis metali bilesiklerinin yeni kullanimi
US5280117A (en) * 1992-09-09 1994-01-18 Lever Brothers Company, A Division Of Conopco, Inc. Process for the preparation of manganese bleach catalyst
US5314635A (en) * 1991-12-20 1994-05-24 Lever Brothers Company, Division Of Conopco, Inc. Bleach activation
US5356554A (en) * 1991-11-20 1994-10-18 Lever Brothers Company, Division Of Conopco, Inc. Bleach catalyst composition, manufacture and use thereof in detergent and/or bleach compositions
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WO1995031526A1 (en) * 1994-05-11 1995-11-23 The Procter & Gamble Company Dye transfer inhibiting compositions with specifically selected metallo 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
US5622646A (en) * 1994-04-07 1997-04-22 The Procter & Gamble Company Bleach compositions comprising metal-containing bleach catalysts and antioxidants
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EP0783035A2 (de) 1996-01-04 1997-07-09 Hoechst Aktiengesellschaft Bleichmittelsysteme enthaltend Bis- und Tris-(mu-oxo)-di-Mangan-Komplexsalze
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US5908821A (en) * 1994-05-11 1999-06-01 Procter & Gamble Company Dye transfer inhibiting compositions with specifically selected metallo catalysts
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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
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US6479450B1 (en) 1997-05-26 2002-11-12 Henkel Kommanditgesellschaft Auf Aktien Bleaching system
WO2002100994A1 (en) * 2001-06-11 2002-12-19 Unilever Plc Complex for catalytically bleaching a substrate
WO2004069979A2 (en) 2003-02-03 2004-08-19 Unilever Plc Laundry cleansing and conditioning compositions
US7205267B2 (en) 2004-01-24 2007-04-17 Clariant Produkte (Deutschland) Gmbh Use of transition metal complexes as bleach catalysts in laundry detergents and cleaning compositions
US7357881B2 (en) * 2002-03-06 2008-04-15 Kao Corporation Cycloamide-transition metal complexes and bleach catalysts
DE102011010818A1 (de) 2011-02-10 2012-08-16 Clariant International Ltd. Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren in Wasch- und Reinigungsmitteln
EP2545988A2 (de) 2005-12-15 2013-01-16 International Flavors & Fragrances, Inc. Eingekapselter Wirkstoff mit reduziertem Formaldehydpotential
EP3075832A1 (de) 2015-03-30 2016-10-05 Dalli-Werke GmbH & Co. KG Mangan-aminosäure-verbindungen in reinigungszusammensetzungen
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US5153663A (en) * 1991-05-31 1992-10-06 Xerox Corporation Printing apparatus employing a compliant sheet corrugating device
DE19536358A1 (de) * 1995-09-29 1997-04-03 Heidelberger Druckmasch Ag Vorrichtung zum Bogentransport
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

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Also Published As

Publication number Publication date
AU2167988A (en) 1989-03-09
NO883903L (no) 1989-03-06
GB8720863D0 (en) 1987-10-14
EP0306089A3 (de) 1990-05-09
NO883903D0 (no) 1988-09-01
JPH0197267A (ja) 1989-04-14
BR8804531A (pt) 1989-04-04

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