EP0369678A2 - Composition de blanchiment - Google Patents

Composition de blanchiment Download PDF

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Publication number
EP0369678A2
EP0369678A2 EP19890311590 EP89311590A EP0369678A2 EP 0369678 A2 EP0369678 A2 EP 0369678A2 EP 19890311590 EP19890311590 EP 19890311590 EP 89311590 A EP89311590 A EP 89311590A EP 0369678 A2 EP0369678 A2 EP 0369678A2
Authority
EP
European Patent Office
Prior art keywords
alkanol
oxidase
bleach
aldehyde
hydrogen peroxide
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
EP19890311590
Other languages
German (de)
English (en)
Other versions
EP0369678B1 (fr
EP0369678A3 (fr
Inventor
Adrianus Cornelis Maria Appel
Johan Haverkamp
Jiri Hora
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0369678A2 publication Critical patent/EP0369678A2/fr
Publication of EP0369678A3 publication Critical patent/EP0369678A3/fr
Application granted granted Critical
Publication of EP0369678B1 publication Critical patent/EP0369678B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • 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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase

Definitions

  • the present invention relates to a bleach composition and to its use in detergent compositions. More particularly, it relates to a bleach composition comprising a hydrogen peroxide precursor which comprises a C1-C4 alkanol oxidase and a C1-C4 alkanol.
  • Such bleach compositions are described in British patent application 2,101,167. They are advantageously used in detergent compositions for fabric washing in which they may effectively provide a low-temperature enzymatic bleach system.
  • the alkanol oxidase enzyme catalyses the reaction between dissolved oxygen and the alkanol to form an aldehyde and hydrogen peroxide.
  • the hydrogen peroxide In order to obtain a significant bleach effect at low wash temperatures, e.g. 15-55°C, the hydrogen peroxide must be activated, using a bleach activator.
  • the preferred bleach activator used to that end is tetraacetyl ethylene diamine (TAED), which yields peracetic acid upon reacting with the hydrogen peroxide, the peracetic acid being the actual bleaching species.
  • TAED tetraacetyl ethylene diamine
  • catalase contamination may be overcome by using a catalase-free micro-organism as the source of alkanol oxidase. This approach has been described in European patent application 244,920.
  • the drawbacks of the known enzymatic bleach compositions containing a C1-C4 alkanol oxidase and a C1-C4 alkanol may be overcome by the bleach composition of the present invention, which is characterised in that it further comprises a C1-C4 aldehyde oxidase, the K m of the aldehyde oxidase for the aldehyde resulting from oxidation of the alkanol being lower than the K m of the alkanol oxidase for the alkanol.
  • Aldehyde oxidases (EC 1.2.3.1) are known in the art. They catalyse the reaction between an aldehyde, oxygen and water to form a carboxylic acid and hydrogen peroxide. Aldehyde oxidases of animal origin not only act upon aldehydes, but also upon various nitrogen-containing aromatic heterocyclic compounds. For the purpose of the present invention, aldehyde oxidases having a greater substrate specificity are preferred. Such aldehyde oxidases can be obtained from bacteria, for example, described in the European patent application 091,810 which is incorporated herein by reference.
  • the aldehyde oxidase must also be essentially free of catalase activity, since this enzyme would efficiently decompose any hydrogen peroxide formed.
  • the enzyme can be purified according to known methods, for instance as described in the British patent application 2,101,167.
  • the enzyme could be produced from a genetically modified or engineered catalase-free micro-organism.
  • the aldehyde oxidase enzyme improves the performance of a detergent composition comprising an alkanol, an alkanol oxidase and a bleach activator by preventing the build-up of inhibiting concentrations of aldehyde.
  • Supportive for this idea is the finding that certain chemical compounds which are known to react with aldehydes, such as semicarbazide, are also capable of improving the performance of the known alkanol oxidase based bleaching compositions.
  • the addition of catalytic amounts of aldehyde oxidase according to the present invention is much to be preferred to the addition of substantial amounts of a highly reactive chemical compound like semicarbazide.
  • the bleach compositions according to the present invention are advantageously used in detergent compositions, which may be in any suitable physical form.
  • the detergent composition is most often an aqueous or non-aqueous liquid, paste or gel.
  • the bleach composition can contain the usual compounds of a detergent composition, such as surfactants, builders, other enzymes, such as proteolytic, amylolytic, cellulolytic and lipolytic enzymes, perfumes and the like.
  • a detergent composition such as surfactants, builders, other enzymes, such as proteolytic, amylolytic, cellulolytic and lipolytic enzymes, perfumes and the like.
  • Suitable surfactants or detergent-active compounds are soap or non-soap anionics, nonionics, cationics, amphoteric or zwitterionic compounds. Examples thereof are given in the British patent application 2,101,167.
  • the quantity of alkanol oxidase to be employed in compositions according to the invention should be at least sufficient to provide, after dilution or dissolution of the composition with water and interaction with the alkanol, sufficient hydrogen peroxide to bleach standard tea-stained fabric.
  • the detergent composition according to the invention will contain from 10 to 1000, preferably from 20 to 500 units alkanol oxidase per g or ml of the detergent composition, a unit of enzyme activity being defined as the quantity required to convert 1 ⁇ mole of substrate per minute under standard conditions.
  • the medium will contain from 0.1 to 10, preferably from 0.2 to 5 units of enzyme per ml which, on interaction with the alkanol substrate also present, will produce sufficient hydrogen peroxide to bleach standard tea-stained fabric.
  • the amount of aldehyde oxidase will equally depend on its specific activity and purity.
  • the detergent composition according to the present invention contains from about 10 to 1000, preferably from about 20 to 500 units aldehyde oxidase per g or ml of the composition. Upon dissolution or dilution 100 times by addition of water, the wash medium will then contain from about 0.1-10, preferably 0.2-5 units/ml.
  • the bleach composition of the present invention comprises a C1-C4 alkanol, preferably a primary alkanol.
  • the especially preferred alkanol is ethanol.
  • the quantity of the alkanol to be employed should be at least sufficient to provide, after dilution of the composition with water and interaction with the alkanol oxidase, sufficient hydrogen peroxide to bleach standard tea-stained fabric.
  • a suitable quantity of alkanol forms from 2 to 25%, preferably 5 to 20% and most preferably 5 to 12% by weight of the composition.
  • the quantity of hydrogen peroxide precursor containing alkanol oxidase, aldehyde oxidase and the alkanol in the composition should be such that, when the composition is diluted with 100 times its weight of water, the enzyme and substract will reaction, at a temperature of 40°C and a pH of 9, to yield hydrogen peroxide at a concentration of at least 2 mM.
  • the alkanol oxidase, aldehyde oxidase and the alkanol are present in sufficient quantity to yield under these conditions hydrogen peroxide at a concentration of at least 5 mM, most preferably 20 mM or even higher.
  • compositions according to the invention will also preferably contain a bleach activator to enable hydrogen peroxide generated at a low temperature of for example 15°-55°C to bleach soiled fabric.
  • Bleach activators are conventionally organic compounds having one or more acyl reactive acyl residues, which at relatively low temperatures react with hydrogen peroxide causing the formation of organic peracids, the latter providing for a more effective bleaching action at lower temperatures than hydrogen peroxide itself.
  • the best known organic activator of practical importance is N,N,N′,N′-tetraacetyl ethylenediamine (TAED).
  • organic bleach activators are other N-acyl substituted amines, for example tetraacetyl methylene diamine, carboxylic acid anhydrides, for example succinic, benzoic and phthalic anhydrides; carboxylic acid esters, for example sodium acetoxy benzene sulphonate, sodium p-sulphonated phenyl benzoate; acetates, such as glucose pentaacetate and xylose tetraacetate, and acetyl salicylic acid.
  • carboxylic acid anhydrides for example succinic, benzoic and phthalic anhydrides
  • carboxylic acid esters for example sodium acetoxy benzene sulphonate, sodium p-sulphonated phenyl benzoate
  • acetates such as glucose pentaacetate and xylose tetraacetate, and acetyl salicylic acid.
  • Organic bleach activators can be employed in compositions according to the invention at a concentration of from 0.1 to 10%, preferably from 0.5 to 5% by weight.
  • bleach activators heavy metal ions of the transition series, such as cobalt, which catalyse peroxide decomposition, optionally together with a special type of chelating agent for said heavy metal such as are described in U.S. patent 3,156,654.
  • compositions according to the present invention might comprise an enzymatic bleach activator system in the form of an esterase and/or lipase enzyme, capable of generating peracids from glycerides and hydrogen peroxide, such as described in the European patent application 253,487, for example.
  • liquid detergent compositions according to the present invention were tested using a liquid detergent having the following formulation: wt.% Linear Alkyl Sulphonate 7.4 Groundnut Fatty Acid 0.8 C13-C15 7EO Nonionic 2.2 Caustic Soda 1.2 KOH 0.4 Glycerol 5.6 Sodium Tetraborate.10 aq 3.1 Sodium Tripolyphosphate 23.0 Sodium Carboxymethylcellulose 0.1 Enzyme - Alcalase 2.34 L 0.5 Minors 0.6 Water to 100.0
  • a wash liquid was prepared by dissolving 10 g of the above formulation in 1 litre water of 14°FH and supplementing the solution with the following additives to the given concentrations: ethanol (20 mM), TAED (0.8 mM) and borax 10 (10 mM).
  • the enzyme or enzyme combinations given in Table I were added to a series of closed 250 ml polyethylene flasks containing 25 ml wash liquor and a piece of 5 x 5 cm of BC-1 test cloth. The flasks were incubated for 45 minutes at 40°C in a shaking bath at a frequency of 5 Hz. After the wash, the BC-1 test cloth reflection was measured at 450 nm and compared with a control cloth washed in the absence of bleaching enzymes.
  • the methanol oxidase used was completely free from catalase activity, as described in European patent application 0,244,920. It was obtained by harvesting yeast cells cultured as described in EP 0,244,920, centrifuging the cells and freeze-drying the material of the centrifuge pellet. The result of this procedure is rather generally suitable for adding to the compositions of the invention, and the dry composition can have an activity level of e.g. 0.7U/mg or more.
  • Aldehyde oxidase as described in European patent application 0,091,810 was obtained from Kyowa Hakko Kogyo Co. Ltd. It was produced from a Pseudomonas sp. No. 6233 FERM P-6467.
  • the enzyme was separated from accompanying catalase activity by selective precipitation with polyethyleneimine (J. Jendrisak, J. Cell. Bioch., Suppl. 11c, 116 (1987)), followed by affinity chromatography (IMAC method, E. Sulkowski, Trends in Biotechnology 3 , 1-7 (1985)).
  • the ratio of catalase units/aldehyde oxidase units of the final preparation was lower than 0.1.
  • the methanol oxidase used here had a Km for methanol of about 7.2 mM, while the Km of the aldehyde oxidase for acetaldehyde was about 0.12 mM.
  • Table II confirms the results which are shown in Table I for a phosphate-containing detergent composition.
  • the addition of aldehyde oxidase effects a clear increase in bleaching performance of the zolite-containing liquid detergent composition.

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  • Chemical & Material Sciences (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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
EP89311590A 1988-11-11 1989-11-09 Composition de blanchiment Expired - Lifetime EP0369678B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8826401 1988-11-11
GB888826401A GB8826401D0 (en) 1988-11-11 1988-11-11 Bleach composition

Publications (3)

Publication Number Publication Date
EP0369678A2 true EP0369678A2 (fr) 1990-05-23
EP0369678A3 EP0369678A3 (fr) 1991-08-28
EP0369678B1 EP0369678B1 (fr) 1996-05-01

Family

ID=10646694

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89311590A Expired - Lifetime EP0369678B1 (fr) 1988-11-11 1989-11-09 Composition de blanchiment

Country Status (5)

Country Link
EP (1) EP0369678B1 (fr)
JP (1) JPH0735519B2 (fr)
DE (1) DE68926381T2 (fr)
ES (1) ES2087084T3 (fr)
GB (1) GB8826401D0 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0538228A1 (fr) * 1991-10-14 1993-04-21 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
EP0553607A1 (fr) * 1992-01-31 1993-08-04 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
EP0553608A1 (fr) * 1992-01-31 1993-08-04 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
TR26870A (tr) * 1991-10-14 1994-08-22 Procter & Gamble Yikamada boya aktarimini önleyen deterjan bilesimleri
WO1995007972A1 (fr) * 1993-09-17 1995-03-23 Unilever N.V. Composition enzymatique de blanchiment
US5445651A (en) * 1992-01-31 1995-08-29 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
EP0692947A1 (fr) * 1993-04-09 1996-01-24 The Procter & Gamble Company Procede de lavage en lave-vaisselle utilisant un catalyseur organometallique et une enzyme pour produire du peroxyde d'hydrogene
WO2004024859A1 (fr) * 2002-09-13 2004-03-25 Kimberly-Clark Worldwide, Inc. Procede ameliorant les vehicules de nettoyant et vehicules de nettoyant utilisant ce procede
WO2006131503A2 (fr) * 2005-06-10 2006-12-14 Novozymes A/S Detergents comprenant des systemes d'adjuvant et de blanchiment enzymatiques
US7476047B2 (en) 2004-04-30 2009-01-13 Kimberly-Clark Worldwide, Inc. Activatable cleaning products

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4026814A (en) * 1974-09-09 1977-05-31 Lever Brothers Company Oxido-reductase in soap
GB2101167A (en) * 1981-07-07 1983-01-12 Unilever Plc Bleach composition comprising hydrogen peroxide precursor
EP0173378A2 (fr) * 1984-07-27 1986-03-05 Unilever N.V. Procédé de préparation d'un polypeptide par culture des micro-organismes transformés, micro-organisme correspondant et séquences d'ADN utiles pour la préparation d'un tel micro-organisme.
EP0242007A1 (fr) * 1986-11-24 1987-10-21 Unilever N.V. Procédé de préparation de levure contenant une oxidase exempte de catalase et son utilisation
EP0244920A1 (fr) * 1986-06-05 1987-11-11 Unilever N.V. Procédé de préparation d'une oxydase exempte de catalase et d'une levure contenant une oxydase exempte de catalase et leur emploi

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4026814A (en) * 1974-09-09 1977-05-31 Lever Brothers Company Oxido-reductase in soap
GB2101167A (en) * 1981-07-07 1983-01-12 Unilever Plc Bleach composition comprising hydrogen peroxide precursor
EP0173378A2 (fr) * 1984-07-27 1986-03-05 Unilever N.V. Procédé de préparation d'un polypeptide par culture des micro-organismes transformés, micro-organisme correspondant et séquences d'ADN utiles pour la préparation d'un tel micro-organisme.
EP0244920A1 (fr) * 1986-06-05 1987-11-11 Unilever N.V. Procédé de préparation d'une oxydase exempte de catalase et d'une levure contenant une oxydase exempte de catalase et leur emploi
EP0242007A1 (fr) * 1986-11-24 1987-10-21 Unilever N.V. Procédé de préparation de levure contenant une oxidase exempte de catalase et son utilisation

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0538228A1 (fr) * 1991-10-14 1993-04-21 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
EP0537381A1 (fr) * 1991-10-14 1993-04-21 The Procter & Gamble Company Compositions détergentes avec additifs pour empêcher le transfert de colorant
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.
US5574003A (en) * 1991-10-14 1996-11-12 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
AU664716B2 (en) * 1991-10-14 1995-11-30 Procter & Gamble Company, The Detergent compositions inhibiting dye transfer in washing
EP0553607A1 (fr) * 1992-01-31 1993-08-04 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
EP0553608A1 (fr) * 1992-01-31 1993-08-04 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
TR26405A (tr) * 1992-01-31 1995-03-15 Procter & Gamble Yikama sirasinda boya aktarilmasini engelleyen deterjan terkipleri
TR26494A (tr) * 1992-01-31 1995-03-15 Procter & Gamble Yikama sirasinda boya aktarilmasini engelleyen deterjan terkipleri
US5445651A (en) * 1992-01-31 1995-08-29 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
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
EP0692947A1 (fr) * 1993-04-09 1996-01-24 The Procter & Gamble Company Procede de lavage en lave-vaisselle utilisant un catalyseur organometallique et une enzyme pour produire du peroxyde d'hydrogene
WO1995007972A1 (fr) * 1993-09-17 1995-03-23 Unilever N.V. Composition enzymatique de blanchiment
US5601750A (en) * 1993-09-17 1997-02-11 Lever Brothers Company, Division Of Conopco, Inc. Enzymatic bleach composition
WO2004024859A1 (fr) * 2002-09-13 2004-03-25 Kimberly-Clark Worldwide, Inc. Procede ameliorant les vehicules de nettoyant et vehicules de nettoyant utilisant ce procede
US7476047B2 (en) 2004-04-30 2009-01-13 Kimberly-Clark Worldwide, Inc. Activatable cleaning products
WO2006131503A2 (fr) * 2005-06-10 2006-12-14 Novozymes A/S Detergents comprenant des systemes d'adjuvant et de blanchiment enzymatiques
WO2006131503A3 (fr) * 2005-06-10 2007-09-07 Novozymes As Detergents comprenant des systemes d'adjuvant et de blanchiment enzymatiques

Also Published As

Publication number Publication date
EP0369678B1 (fr) 1996-05-01
DE68926381D1 (de) 1996-06-05
DE68926381T2 (de) 1996-09-05
GB8826401D0 (en) 1988-12-14
EP0369678A3 (fr) 1991-08-28
JPH0735519B2 (ja) 1995-04-19
JPH02182794A (ja) 1990-07-17
ES2087084T3 (es) 1996-07-16

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