EP0880578A1 - Composition detergente comportant de la zeolite et une enzyme proteolytique - Google Patents

Composition detergente comportant de la zeolite et une enzyme proteolytique

Info

Publication number
EP0880578A1
EP0880578A1 EP96933913A EP96933913A EP0880578A1 EP 0880578 A1 EP0880578 A1 EP 0880578A1 EP 96933913 A EP96933913 A EP 96933913A EP 96933913 A EP96933913 A EP 96933913A EP 0880578 A1 EP0880578 A1 EP 0880578A1
Authority
EP
European Patent Office
Prior art keywords
zeolite
detergent composition
composition according
proteolytic enzyme
builder
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.)
Withdrawn
Application number
EP96933913A
Other languages
German (de)
English (en)
Other versions
EP0880578A4 (fr
Inventor
Jonathan Richard Clare
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0880578A1 publication Critical patent/EP0880578A1/fr
Publication of EP0880578A4 publication Critical patent/EP0880578A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the present invention relates to a detergent composition
  • a detergent composition comprising both zeolite as a sequestering agent for water hardness and an enzyme.
  • Detergent compositions for fabric washing conventionally contain detergency builders which lower the concentration of calcium and magnesium water hardness ions in the wash liquor and thereby provide good detergency effect in both hard and soft water.
  • inorganic phosphates such as sodium tripolyphosphate
  • alkali metal aluminosilicate ion-exchangers particularly crystalline sodium aluminosilicate zeolite A
  • crystalline sodium aluminosilicate zeolite A have been proposed as replacements for the inorganic phosphates.
  • EP 21 491 A (Procter & Gamble) discloses detergent compositions containing a building system which includes zeolite A, X or P (B) or a mixture thereof.
  • EP 384070A (Unilever) discloses specific zeolite P materials having an especially low silicon to aluminium ratio not greater than 1.33 (hereinafter referred to as zeolite MAP) and describes its use as a detergency builder, optionally with cobuilders.
  • Detergent compositions containing proteases are well-known in the art. By use of a protease in a detergent, it is possible to hydrolyze the proteins, present in stains and soil on the clothes, to such a degree that they become readily soluble in water.
  • a problem may occur when a water insoluble zeolite having a small particle size, is used as a detergency builder in a fabric laundering detergent composition containing certain protease enzymes and relatively high levels of carbonate cobuilder.
  • the problem has been found to be particularly pronounced when the zeolite builder is zeolite MAP.
  • a small particle size for a zeolite MAP component that is to say particles having a particle size, measured as a dso value, of up to 1.0 micrometres has previously been taught to be preferred in the art, as represented, for example, by EP 384070 A.
  • the problem relates to the aforementioned detergent compositions having a marked incompatibility with printed cotton fabrics.
  • the use of detergent compositions containing small particle size zeolite tends to lead to the removal of printed pigment from a printed cotton fabric surface.
  • the presence of certain proteolytic enzymes, in particular those having a high isoelectric point, and of relatively high levels of carbonate cobuilder has been found to exarcebate this effect.
  • the Applicant has surprisingly found that this problem can be ameliorated by the use in the detergent composition of proteolytic enzyme having an isoelectric point below 10.0, and by limiting the level of any carbonate cobuilder.
  • the present invention is thus based on the unexpected finding that the printed cotton fabric care profile of a detergent composition comprising zeolite of small particle size, low levels of carbonate builder and containing a protease having an isoelectric point below 10.0 is superior to that of comparable compositions containing other proteases having an isoelectric point of higher than 10.0.
  • proteases which have an isoelectric point of higher than 10.0 and which have been found not to afford such a superior printed cotton fabric care profile are Savinase (Trade Mark), which is disclosed, in EP 384070A (Unilever) Opticlean (Trade Mark), Maxacal (Trade Mark), Purafect (Trade Mark), and Esperase (Trade Mark).
  • the present invention provides a detergent composition containing
  • composition contains less than 7% by weight of the composition of carbonate builder.
  • the zeolite builder comprises zeolite P having a silcon to aluminium ratio of not greater than 1.33 (zeolite MAP).
  • the detergent composition is free of any proteolytic enzyme which has an isoelectric point greater than 10.0.
  • the detergent composition according to the invention is formulated to be especially useful in the laundering of coloured fabrics and preferably is free of bleach.
  • the composition is substantially free of an optical brightener.
  • the first essential component of the present invention is an aluminosilicate zeolite builder, optionally in conjunction with one or more cobuilders.
  • the zeolite builder is typically present at a level of from 1 % to 80%, more preferably from 15% to 40% by weight of the compositions.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(Al ⁇ 2) z (Si ⁇ 2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and mixtures thereof.
  • Zeolite A has the formula
  • Zeolite X has the formula Nas ⁇ .(Al ⁇ 2)86(Si ⁇ 2)l06-- 276 H 2 O.
  • Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • Zeolite P having a Si:AI ratio of 1.33 or less may be prepared by the following steps:
  • Preferred drying methods are spray-drying and flash-drying. It appears that oven drying at too high a temperature may adversely affect the calcium binding capacity of the product under certain circumstances.
  • Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilcate, as measured by the standard method described in GB 1473201 (Henkel).
  • the calcium binding capacity is normally 160 mg CaO/g and may be as high 170 mg CaO/g.
  • zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention amounts and percentages of zeolite are expressed in terms of the notional anhydrous material.
  • the amount of water present in hydrated zeolite MAP at ambient temperature and humidity is generally about 20 wt.%.
  • the zeolite builder used in the present invention has a particle size dso of less than 1.0 micrometres, preferably from 0.05 to 0.9 micrometres, most preferably from 0.2 to 0.7 micrometres.
  • the dso value indicates that 50% by weight of the particles have a diameter smaller than that figure.
  • the particle size may be determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope or by means of a laser granulometer.
  • Zeolite builder having the required particle size according to the present invention can, for example, be prepared by the conventional techniques as described above while adopting one or more of the following steps: -
  • the detergent composition according to the present invention essentially comprises a proteolytic enzyme of isoelectric point below 10.0, more preferably below 9.0, most preferably below 7.0.
  • Suitable proteases include proteases represented by the genus of Subtilisin Carlsberg, producible by Bacillus licheniformis.
  • Other suitable proteases include the proteases represented by the genus Subtilisin BPN', producible by Bacillus amyloliquefaciens.
  • Other suitable proteases are proteases which show a positive immunological cross-reaction with the antibody of the proteases as described hereinabove.
  • Highly preferred proteases are the proteases that are commercially sold under the tradenames Alcalase (Trade Mark), Maxatase (Trade Mark) Optimase (Trade Mark), Primase (Trade Mark) or mixtures thereof.
  • proteases according to the present invention are preferably present in an amount from 0.001% to 2%, more preferably from 0.001% to 1%, more preferably from 0.002% to 0.5% of active enzyme by weight of the detergent composition.
  • the detergent compositions may contain an organic or inorganic cobuilder.
  • Suitable organic cobuilders can be monomeric or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and/or maleic adds in neutralised form.
  • Suitable inorganic cobuilders include carbonates and amo ⁇ hous and crystalline layered silicates.
  • Suitable crystalline layered silicates have the composition:
  • M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
  • the synthetic material is commercially available from Hoechst AG as ⁇ -Na2 Si2 ⁇ s (SKS6) and is described in US Patent No. 4664830.
  • the total amount of detergency builder in the granular composition typically ranges from 10 to 80 wt.%, more preferably from 15 to 60 wt% and most preferably from 10 to 45 wt.%.
  • the level of carbonate builder that is of inorganic compound capable of releasing carbonate ions into a wash solution, is less than 7% by weight, preferably less than 4% by weight of the detergent composition. Most preferably the detergent composition is free from carbonate builder.
  • the detergent composition according to the invention may contain other detergent components such as surfactants, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
  • other detergent components such as surfactants, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
  • the detergent composition according to the invention preferably includes a surfactant selected from anionics, nonionics, zwitterionics, ampholytics and cationics.
  • the surfactant is preferably present in the detergent compositions at a level of from 1 % to 50%, preferably from 3% to 30%, most preferably from 5% to 20% by weight of the compositions.
  • anionic surfactants examples include anionic sulfates, olefm sulphonates, alkyl xylene sulphonates, dialkylsulphosuccinates, and fatty acid ester sulphonates. Sodium salts are generally preferred. Anionic sulfate surfactant
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C-
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C ⁇ -C-i ⁇ alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C ⁇ -C-is alkyl sulfate which has been ethoxylated with from 0.5 to 20, preferably from 0.5 to 5, moles of ethylene oxide per molecule.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5- C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • the nonionic surfactant is preferably a hydrophobic nonionic surfactant, particularly an alkoxylated nonionic surfactant, having a hydrophilic lipophilic balance (hlb) value of ⁇ 9.5, more preferably ⁇ 10.5.
  • hlb hydrophilic lipophilic balance
  • hydrophobic alkoxylated nonionic surfactants include alkoxylated adducts of fatty alcohols containing an average of less than 5 alkylene oxide groups per molecule.
  • alkylene oxide residues may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide residues.
  • Preferred alkylene oxide adducts of fatty alcohols useful in the present invention can suitably be chosen from those of the general formula:
  • R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably from 10 to 22 carbon atoms, y is from 0.5 to 3.5 and n is 2 or 3.
  • Preferred nonionic surfactants include primary C ⁇ ⁇
  • a particularly preferred aliphatic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol.
  • alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-C15 alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.
  • Another class of nonionic sufactants comprises alkyl polyglucoside compounds of general formula
  • Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Detergent compositions according to the invention may also contain a bleach system. Where present, this preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.
  • a bleach system preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.
  • the bleach system preferably comprises a peroxy bleach compound, preferably an inorganic persalt, optionally in conjunction with a peroxyacid bleach precursor.
  • Suitable persalts include sodium perborate monohydrate and tetrahydrate and sodium percarbonate, with sodium percarbonate being most preferred.
  • Preferred bleach precursors are peracetic acid precursors, such as tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors.
  • TAED tetraacetylethylene diamine
  • the detergent compositions are free of bleach and of particular utility in the washing of loads containing brightly coloured fabrics.
  • Preferred detergent compositions according to the invention are characterised by having a pH measured as a 1 % solution of the detergent composition in distilled water at 25°C of ⁇ I0.5, preferably ⁇ I0.4, most preferably ⁇ I0.3.
  • compositions having a low level of reserve alkalinity are advantageous in that they have a further reduced tendency to cause the removal of printed pigment from printed cotton fabrics.
  • Reserve alkalinity is expressed as g of NaOH per I00 g of composition as determined by acid titration of a sample, as 1 % solution in distilled water to a pH of 9.5.
  • Preferred values of reserve alkalinity are ⁇ 8.0 g preferably ⁇ 5.0 g, most preferably ⁇ 3.0 g NaOH per 100g of composition.
  • the detergent composition according to the invention may be of any physical type, for example powders, liquids and gels. However, granular and liquid compositions are preferred.
  • the detergent compositions of the invention may be prepared by any suitable method.
  • the particulate detergent compositions are suitably prepared by any tower (spray-drying) or non-tower process.
  • a base powder is first prepared by spray-drying a slurry and then other components unsuitable for processing via the slurry can be sprayed on or admixed (postdosed).
  • the zeolite builder is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite builder to be incorporated post-tower.
  • the crystalline layered silicate, where this is employed, is also inco ⁇ orated via a non-tower process and is preferably postdosed.
  • particulate detergent compositions in accordance win the invention may be prepared by wholly non-tower processes such as granulation.
  • the granular detergent compositions of the invention may be prepared to any suitable bulk density.
  • the compositions preferably have a bulk density of at least 400 g/l preferably at least 550 g/l, most preferably at least 700 g/l and, with particular preference at least 800 g/l.
  • powders of high bulk density for example, of 700 g/l or above.
  • Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used.
  • Processes using high-speed mixer/granulators are disclosed, for example, in EP340013A, EP 367 339A, EP 390 251 A and EP 420 317A (Unilever).
  • the detergent composition of the invention may be formulated as a liquid detergent composition which may be aqueous or anhydrous.
  • liquid used herein includes pasty viscous formulations such as gels.
  • the liquid detergent composition generally has a pH of from 6.5 to 10.5.
  • the total amount of detergency builder in the liquid composition is preferably from 5 to 70% of the total liquid composition.
  • compositions according to the present invention are presented in the following Examples.
  • the abbreviated component identifications have the following meanings:
  • TAS Sodium alkyl sulfate surfactant containing predominantly C ⁇ Q - C-j ⁇ alkyl chains derived from tallow oil.
  • SKS6 Crystalline layered silicate available from Hoechst AG as SKS6 (tradename)
  • Zeolite A Hydrated sodium aluminosilicate zeolite A having a particle size, expressed as a d o value, of 0.6 micrometres
  • MA/AA Copolymer of 1:4 maleic/acrylic acid average molecular weight about 80,000.
  • Alcalase Proteolytic enzyme sold under the tradename Alcalase by Novo Industries A/S (approx 1% enzyme activity by weight)
  • the detergent compositions according to the invention which comprise zeolite builder of larger particle size and Alcalase, show good results in stain removal and lower printed cotton fabric damage as compared with a composition comprising small particle size zeolite and Savinase.

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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)

Abstract

Cette invention concerne une composition détergente qui comprend un adjuvant sous forme de zéolite possédant une taille des particule d50 inférieure à 1,0 microns, ainsi qu'une enzyme protéolytique ayant un point isoélectrique inférieur à 10,0. Cette invention donne également un exemple d'alcalase. Cette composition contient moins de 7 % en poids de la composition d'adjuvant sous forme de carbonate, et ne comporte de préférence aucune enzyme protéolytique ayant un point isoélectrique supérieur 10,0.
EP96933913A 1995-09-26 1996-09-26 Composition detergente comportant de la zeolite et une enzyme proteolytique Withdrawn EP0880578A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9519587 1995-09-26
GBGB9519587.1A GB9519587D0 (en) 1995-09-26 1995-09-26 Detergent compositions
PCT/US1996/015451 WO1997012026A1 (fr) 1995-09-26 1996-09-26 Composition detergente comportant de la zeolite et une enzyme proteolytique

Publications (2)

Publication Number Publication Date
EP0880578A1 true EP0880578A1 (fr) 1998-12-02
EP0880578A4 EP0880578A4 (fr) 1999-01-13

Family

ID=10781271

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96933913A Withdrawn EP0880578A1 (fr) 1995-09-26 1996-09-26 Composition detergente comportant de la zeolite et une enzyme proteolytique

Country Status (5)

Country Link
EP (1) EP0880578A1 (fr)
BR (1) BR9610736A (fr)
CA (1) CA2232957A1 (fr)
GB (1) GB9519587D0 (fr)
WO (1) WO1997012026A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2901339A1 (de) * 1978-01-17 1979-07-19 Novo Industri As Detergenszusammensetzung mit einem enzymgehalt und verfahren unter deren anwendung
EP0066323A1 (fr) * 1981-05-29 1982-12-08 THE PROCTER & GAMBLE COMPANY Composition détergente enzymatique
EP0580245A2 (fr) * 1992-07-20 1994-01-26 Colgate-Palmolive Company Compositions détergentes-adoucissantes liquides aqueuses renforcées stabilisées
EP0640684A1 (fr) * 1993-08-26 1995-03-01 Colgate-Palmolive Company Composition en poudre séchée par pulvérisation contenant des enzymes pour lave-vaisselle
US5431846A (en) * 1993-05-20 1995-07-11 Lever Brothers Company, Division Of Conopco, Inc. Copolymers and detergent compositions containing them

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2001927C (fr) * 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates et detergents
GB9113675D0 (en) * 1991-06-25 1991-08-14 Unilever Plc Particulate detergent composition or component
CA2083331C (fr) * 1991-11-26 1998-08-11 Johannes H. M. Akkermans Compositions pour detergent
SK278833B6 (sk) * 1992-01-17 1998-03-04 Unilever Nv Časticová bieliaca detergentná zmes
SK278834B6 (sk) * 1992-01-17 1998-03-04 Unilever Nv Časticová bieliaca detergentná zmes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2901339A1 (de) * 1978-01-17 1979-07-19 Novo Industri As Detergenszusammensetzung mit einem enzymgehalt und verfahren unter deren anwendung
EP0066323A1 (fr) * 1981-05-29 1982-12-08 THE PROCTER & GAMBLE COMPANY Composition détergente enzymatique
EP0580245A2 (fr) * 1992-07-20 1994-01-26 Colgate-Palmolive Company Compositions détergentes-adoucissantes liquides aqueuses renforcées stabilisées
US5431846A (en) * 1993-05-20 1995-07-11 Lever Brothers Company, Division Of Conopco, Inc. Copolymers and detergent compositions containing them
EP0640684A1 (fr) * 1993-08-26 1995-03-01 Colgate-Palmolive Company Composition en poudre séchée par pulvérisation contenant des enzymes pour lave-vaisselle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9712026A1 *

Also Published As

Publication number Publication date
WO1997012026A1 (fr) 1997-04-03
BR9610736A (pt) 1999-07-13
EP0880578A4 (fr) 1999-01-13
GB9519587D0 (en) 1995-11-29
CA2232957A1 (fr) 1997-04-03

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