EP0874887B1 - Ameliorations concernant des compositions de nettoyage antimicrobiennes - Google Patents

Ameliorations concernant des compositions de nettoyage antimicrobiennes Download PDF

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Publication number
EP0874887B1
EP0874887B1 EP96938139A EP96938139A EP0874887B1 EP 0874887 B1 EP0874887 B1 EP 0874887B1 EP 96938139 A EP96938139 A EP 96938139A EP 96938139 A EP96938139 A EP 96938139A EP 0874887 B1 EP0874887 B1 EP 0874887B1
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EP
European Patent Office
Prior art keywords
alcohol
ethoxylated
compositions
nonionic surfactant
hlb
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.)
Revoked
Application number
EP96938139A
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German (de)
English (en)
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EP0874887A1 (fr
Inventor
Kenneth Leslie Rabone
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/2017—Monohydric alcohols branched
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

  • the present invention relates to the use of a specified surfactant in combination with a specific alcohol to improve the activity of the hygiene agent and to a method of treating surfaces with the said composition.
  • Hard-surface cleaning compositions generally comprise one or more surfactants, and, optionally, one or more hygiene agents and/or solvents.
  • the surfactants used in such cleaning compositions are selected-from anionic, nonionic, amphoteric and cationic surfactants. This large group of surfactants exhibit a broad range of properties. Nonionics are very commonly used due to their effectiveness on fatty soils and the ease with which their foaming can be controlled. The precise function of nonionic surfactants in cleaning compositions depends on the hydrophile/lipophile balance or 'HLB' of the surfactant chosen. In general terms, nonionic surfactants with a relatively low HLB values (7-9) are regarded as wetting agents and are used in combination with solvents where the solvent performs the cleaning function, such as in glass cleaners. Nonionic surfactants with relatively high HLB values (13-15) are regarded as detergents and themselves remove soil from surfaces.
  • Nonionic surfactants are reported as showing low biocidal activity, whereas certain anionic, cationic and amphoteric surfactants show biocidal activity under specific conditions of, for example, pH and concentration. However, the biocidal activity of surfactants is, with a few notable exceptions, low and it is commonplace to add a separate hygiene agent to compositions.
  • Typical hygiene agents include strong acids, alkali's, phenolics and oxidants such as peracids and hypohalites. These oxidants, of which a typical example is hypochlorite, are generally highly reactive species which exhibit this reactivity alone or in effective formulations in terms of one or more of, short shelf life, toxic, corrosive and irritant properties. In general, these reactive components are required at relatively high levels in formulations.
  • Other less chemically reactive hygiene agents such as 2,4,4'-trichloro-2'-hydroxy diphenyl ether (available in the marketplace as IRGASAN [RTM]), are effective at relatively low concentrations but are more expensive than simpler species and may be specific as regards their spectrum of activity.
  • a 'disinfectant' can be understood to be a hygiene agent which shows a 100,000 fold or better reduction in the number of viable micro-organisms in a specified culture when used at a level of around 0.5 wt%. This is generally known as a 'log 5 kill'. Many of the weaker hygiene agents do not achieve this level of bacterial kill, especially when present in formulations at relatively low levels.
  • APG alkyl polyglycoside
  • Alcohols such as ethanol and isopropanol (IPA), are well-known components of cleaning compositions. Generally, these are present as solvents at low levels in compositions of near neutral pH.
  • GB 1076920 (1966) relates to glass cleaners which comprise ⁇ 0.25% alkyl phenol polyoxyalkylene ether and 3.5-4% ethanol
  • GB 1403919 (1972) relates to vehicle washing compositions which comprise 3-4% nonionic surfactant (an EO/PO system is used in the examples) and 4% isopropanol
  • US 4414128 (1981) relates to hard surface cleaners with 0.5-3% Dobanol 91-8 (HLB 13.8 by calculation) and 1-2% ethanol
  • GB 2103642 (1981) relates to a spectacle-glass cleaning composition which comprises 1% ethoxylated nonionic surfactant and 10% ethanol: the preferred pH of which is 6-8.
  • GB 2167083 (1984) relates to a hard surface cleaner comprising 4% IPA and GB 2173508 (1986) relates to hard surface cleaners which comprise 1% of 3,5-dimethyl-1-hexyn-3-ol and 0.45% primary alkyl sulphate as anionic surfactant with 2-4% IPA.
  • compositions which comprise ⁇ 12% nonionic surfactants and 3% iso propyl alcohol.
  • the compositions which have a pH around 5.5, do not appear to contain alcohol ethoxylate, the surfactant being either betaine or amine oxide.
  • the antimicrobial properties of these composition arise from the known antimicrobials, such are chlorhexidine, which are incorporated in the composition.
  • EP 0478445 discloses a composition for the disinfection of surgical instruments.
  • Examples of a preferred embodiment in the cited specification relate to compositions containing 7% C13/8EO ethoxy alcohol nonionic (the HLB is around 12.8 by calculation) and 12%, ethanol/isopropanol at a pH of 8.5.
  • the compositions cited comprise 13% of didecyl dimethyl ammonium chloride, which is a known biocide and is identified as such in the specification, while the nonionic and the alcohol are optional.
  • EP 0536820 (Colgate Palmolive: 1991) discloses an acidic composition (pH 2-4) which contains nonionic surfactants (HLB 7-10 and 11) and anti-microbial disinfectants. It is mentioned in the cited patent that minor amounts of isopropyl alcohol (up to 2%) can be added to improve the anti-microbial effects (page 5, line 48ff).
  • EP 0028038 (P&G: 1979) relates to compositions which contain nonionics of HLB 10-13 and the examples contain 11.5% nonionic (HLB 12) and 1-2% ethanol.
  • the compositions have a pH of 8-13.
  • Germicides are mentioned as optional ingredients in the compositions disclosed.
  • the present invention provides for the use of 1-30%wt of a C 1 -C 5 linear or branched alcohol as a biocidal activity improving additive in a cleaning composition of pH>8 which comprises 0.01-30%wt on product of an ethoxylated nonionic surfactant other than an alkyl phenol derivative, with an HLB of 10-14.
  • ethoxylated alcohol surfactants of HLB 10-14 are inhibitors of bacterial growth but are only weakly biocidal at typical formulation pH's. In the presence of the specified alcohols, and above the normal physiological pH range, a synergy is maintained and exploited to give a product which is both an effective cleaner and biocidal. Effective cleaning and biocidal activity are desirable in a cleaning composition for hygiene purposes as it is important to both to ensure a high kill of bacteria and removal soil so as to retard reinfection and regrowth of bacterial populations. In the present invention, the important features of effective microbial kill and improved soil removal are both attained with a relatively simple and hence cost-effective formulation.
  • Nonionic, ethoxylated surfactants are present in the compositions of the invention. These surfactants are believed to engage in a synergistic interaction with both the alcohol, to improve cleaning and aid the removal of soil subsequently deposited and with the antimicrobial so as to improve the disinfecting qualities of the composition.
  • Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of ethylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound.
  • the length of the hydrophilic or polyoxyethylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements (HLB).
  • Particular examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensate having from 3 to 10 moles of ethylene oxide per mole of coconut alcohol.
  • the amount of nonionic detergent active to be employed in the composition of the invention will generally be from 0.1 to 30%wt, preferably from 1 to 20%wt, and most preferably from 3 to 10%wt for non-concentrated products. Concentrated products will generally have 10-20%wt nonionic surfactant present, whereas dilute products suitable for spraying will have 0.1-5%wt nonionic surfactant present.
  • the ethoxylated nonionic surfactant is an ethoxylated alcohol having a chain length of C 8 -C 14 and 4-10 ethoxy groups per molecule. It is however essential that the HLB of the nonionic should fall in the range 10-14. HLB can be calculated as a function of the chain length of the molecule and its degree of ethoxylation. According to Griffin (W.C. Griffin J. Soc. Cosmetic Chemists [5, 249, 1954]) the HLB of fatty alcohol ethylene oxide adducts is given as one fifth of the weight percent of oxyethylene content in the adduct.
  • CMC critical micellar concentration
  • IMBENTIN 91-35 OFA' (TM, ex. Kolb AG) a C 9-11 alcohol with, on average, five moles of ethoxylation had been found to be a suitable nonionic surfactant in compositions according to the invention.
  • This material has a calculated HLB of 11.6 and is believed to have a CMC of 1.6x10 -4 moles/litre.
  • DOBANOL 91-8 a C 9 -C 11 alcohol with on average 8 moles of ethoxylation has also been found to be a suitable material.
  • This material has a calculated HLB of 13.8 and is believed to have a CMC of 4.3x10 -4 moles/litre.
  • the alcohol is selected from the group comprising propan-2-ol, propanol, ethanol and mixtures thereof.
  • Preferred levels of alcohol are 1-25%wt on product. At these concentrations alcohols taken alone show little potential as disinfectants. Particularly preferred levels of alcohol range from 5-15%.
  • the weight ratio of the alkoxylated nonionic surfactant to the alcohol such that the alcohol is present in weight excess over the alkoxylated nonionic surfactant.
  • compositions of the invention further comprise a buffer to maintain the pH of the composition in the desired pH range upon dilution by a factor of 2-5.
  • the alkaline products according to the invention have a preferred pH of 8-11, more preferably 9.5-11. Below pH 9.5, compositions show reduced bacterial kill, whilst above pH 11, compositions are considered unacceptably hazardous for many uses.
  • Sodium bicarbonate/carbonate buffers are suitable to maintain pH in the preferred range.
  • composition according to the invention can contain other minor, unessential ingredients which aid in their cleaning performance and maintain the physical and the chemical stability of the product.
  • the composition can contain detergent builders.
  • the builder when employed, preferably will form from 0.1 to 25% by weight of the composition.
  • the composition can include one or more amphoteric surfactants, preferably betaines, or other surfactants such as amine-oxide and alkyl-amino-glycinates.
  • amphoteric surfactants preferably betaines, or other surfactants such as amine-oxide and alkyl-amino-glycinates.
  • Betaines are preferred for reasons of cost, low toxicity (especially as compared to amine oxides) and wide availability.
  • betaines in compositions according to the invention are the amido-alkyl betaines, particularly the amido-propyl betaines, preferably having an aliphatic alkyl radical of from 8 to 18 carbon atoms and preferably having a straight chain.
  • betaines are preferred as they are believed to comprise relatively low levels of nitrosamine precursors although other betaines, such as alkyl betaines, can be used in the compositions of the invention.
  • Typical levels of amphoteric range from 0.01 to 8%, with levels of 1-5wt%, particularly around 2% being preferred for normal compositions and up to four times the concentration being present in so called, concentrated products.
  • levels of 1-5wt%, particularly around 2% being preferred for normal compositions and up to four times the concentration being present in so called, concentrated products.
  • lower levels of around 0.05-1% will be employed in sprayable products and higher levels of, typically, around 4%wt in concentrates.
  • Metal ion sequestrants including ethylene-diamine-tetra-acetates, amino-poly-phosphonates (such as those in the DEQUEST R range) and phosphates and a wide variety of other poly-functional organic acids and salts, can also be employed. It is believed that the hygiene performance of the composition is improved by the presence of a metal ion sequesterant.
  • Suitable additional hydrotropes include, alkali metal toluene sulphonates, urea, alkali metal xylene and cumene sulphonates, polyglycols, >20EO ethoxylated alcohols and glycols. Preferred amongst these hydrotropes are the sulphonates, particularly the cumene, xylene and toluene sulphonates. Typical levels of additional hydrotrope range from 0-5% for the sulphonates.
  • Hydrotropes are not always required for dilute, sprayable products, but may be required if lower EO or longer alkyl ethoxylates are used or the cloud point needs to be raised considerably.
  • the cumene sulphonate is the most preferred hydrotrope.
  • compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as, further solvents, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, further bactericides, perfumes and opacifiers.
  • various other optional ingredients such as, further solvents, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, further bactericides, perfumes and opacifiers.
  • compositions according to the present invention comprise:
  • a preferred method according to the present invention comprises the step of treating a surface with a composition as disclosed herein by means of a spray.
  • Bacterial suspension was prepared as follows. Incubate bacterial culture (tryptone soya broth) for 24 hours. Spin down (50 ml tubes, Mistral 1000 centrifuge, 4100rpm, 10 min). Resuspend pellets in peptone water (20ml) and mix using a vortex mixer for 15-30 seconds. Adjust cell density with sterile peptone water to required inoculum size using a calibrated densitometer. Cell suspension is stored at 20 °C (+/- 1°C) and used within 2 hours
  • Alkaline formulations (pH 10.5) were buffered with a mixture of sodium carbonate (1.14 w/v percent decahydrate) and sodium hydrogen carbonate (0.08 w/v percent).
  • quench solution was as follows: Lecithin 0.3% Sodium thiosulphate 0.5% L-histidine 0.1% Tween 80 3.0% pH 7 buffer (see below) 10ml Distilled water to 1 litre (Prepare pH 7 buffer by dissolving 34gm potassium dihydrogen phosphate in 500ml distilled water and sterilize (autoclave, 121°C, 15 min)) After 5mins(+/-1min), 30 ⁇ l of the quenched product was serially diluted into 270 ⁇ l peptone solution using a multipipette, and mixed as previously indicated.
  • Table 1 shows that under alkaline conditions a significant increase in the biocidal activity of the composition is achieved when both the alcohol and the alcohol ethoxylate are present.
  • Example 2 further examples
  • Tables 2a and 2b below show further examples, using two nonionic surfactants and two microbes, for which the results were obtained using the method as described above in example 1.
  • the formulations contained 10% iso -propyl alcohol, 0.7% non-ionic surfactant, and were prepared at pH 11.0 Synergy with Propan-2-ol against S.aureus Nonionic surfactant Iso-propyl alcohol Log (reduction) against S.
  • Nonionic surfactant Iso-propyl alcohol Log (reduction) 0 0 1.2 0 10 5.1 Imbentin 91-35 0FA 0 5.1 Dobanol 91-5 0 3.3 Dobanol 91-8 0 4.8 Imbentin 91-35 0FA 10 >6 Dobanol 91-5 10 >6 Dobanol 91-8 10 >6

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Detergent Compositions (AREA)

Abstract

Cette invention concerne une composition nettoyante hygiénique ayant un pH inférieur à 6 ou supérieur à 8, comprenant: (a) 0,01 - 30 % en poids d'un tensioactif non ionique éthoxylé autre qu'un tensioactif dérivé d'un alkyl-phénol, ce tensioactif ayant une valeur de HLB de 10-14, ce qui correspond typiquement à un alcool éthoxylé en C8-C14 ayant 4-10 groupes éthoxy par molécule et (b) 1-30 % en poids d'un alcool en C1-C5 droit ou ramifié (choisi par exemple dans le groupe comprenant le propan-2-ol, le propanol, l'éthanol et leurs mélanges). On pense que l'utilisation de 1-30 % en poids d'un alcool en C1-C5 droit ou ramifié comme additif pour les tensioactifs non ioniques choisis améliore considérablement les propriétés biocides de la composition dans les conditions de pH spécifiées. Cette spécification concerne également un procédé de nettoyage et de désinfection d'une surface dure qui consiste à traiter cette surface avec ladite composition nettoyante.

Claims (5)

  1. Utilisation de 1 à 30% en poids d'un alcool linéaire ou ramifié en C1-5 à titre d'additif améliorant l'activité biocide dans une composition de nettoyage de pH > 8 qui comprend 0,01 à 30% en poids par rapport au produit d'un tensioactif non ionique éthoxylé autre qu'un dérivé d'alkylphénol, ledit tensioactif non ionique éthoxylé ayant une valeur I.A de 10 à 14.
  2. Utilisation selon la revendication 1, dans laquelle le tensioactif non ionique éthoxylé est un alcool éthoxylé ayant une longueur de chaíne de C8-14 et 4 à 10 groupes éthoxy par molécule.
  3. Utilisation selon la revendication 1, dans laquelle l'alcool est présent en un excès pondéral par rapport au tensioactif non ionique éthoxylé.
  4. Utilisation selon la revendication 1, dans laquelle l'alcool est choisi parmi le propanol-2, le propanol, l'éthanol et leurs mélanges.
  5. Utilisation selon la revendication 1, dans une composition qui comprend :
    a) 0,1 à 20% en poids par rapport au produit d'un alcool éthoxylé ayant une longueur de chaíne en C8-14, 4 à 10 groupes éthoxy par molécule et un I.A de 10 à 14.
    b) 1 à 30% en poids d'un alcool choisi parmi le propanol-2, le propanol, l'éthanol et leurs mélanges dans lequel l'alcool (b) est présent en un excès pondéral par rapport à l'alcool éthoxylé (a), et
    c) au moins un agent tampon pour maintenir le pH dans la gamme de 9,5 à 11.
EP96938139A 1995-12-08 1996-11-05 Ameliorations concernant des compositions de nettoyage antimicrobiennes Revoked EP0874887B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9525155.9A GB9525155D0 (en) 1995-12-08 1995-12-08 Improvements relating to antimicrobial cleaning compositions
GB9525155 1995-12-08
PCT/EP1996/004876 WO1997021795A1 (fr) 1995-12-08 1996-11-05 Ameliorations concernant des compositions de nettoyage antimicrobiennes

Publications (2)

Publication Number Publication Date
EP0874887A1 EP0874887A1 (fr) 1998-11-04
EP0874887B1 true EP0874887B1 (fr) 2000-03-22

Family

ID=10785151

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96938139A Revoked EP0874887B1 (fr) 1995-12-08 1996-11-05 Ameliorations concernant des compositions de nettoyage antimicrobiennes

Country Status (9)

Country Link
EP (1) EP0874887B1 (fr)
AU (1) AU699602B2 (fr)
BR (1) BR9611979A (fr)
CA (1) CA2235680C (fr)
DE (1) DE69607391T2 (fr)
ES (1) ES2146421T3 (fr)
GB (1) GB9525155D0 (fr)
WO (1) WO1997021795A1 (fr)
ZA (1) ZA969481B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998047635A1 (fr) * 1997-04-24 1998-10-29 Black Robert H Compositions permettant de nettoyer des surfaces dures transparentes et technique d'utilisation
WO2001044430A1 (fr) * 1999-12-14 2001-06-21 Unilever Plc Solutions antimicrobiennes
GB2393908A (en) * 2002-10-12 2004-04-14 Reckitt Benckiser Inc Thickened, abrasive containing, liquid disinfectant
WO2014082854A2 (fr) 2012-11-29 2014-06-05 Unilever N.V. Compositions de nettoyage antibactériennes douces
DE102016112163A1 (de) 2016-07-04 2018-01-04 Schülke & Mayr GmbH Getränktes textiles Flächengebilde mit effektiver Abgabe einer alkoholischen Tränkzubereitung

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4420484A (en) * 1979-08-13 1983-12-13 Sterling Drug Inc. Basic amino or ammonium antimicrobial agent-polyethylene glycol ester surfactant-betaine and/or amine oxide surfactant compositions and method of use therof
US4284532A (en) * 1979-10-11 1981-08-18 The Procter & Gamble Company Stable liquid detergent compositions
FR2667220B1 (fr) * 1990-09-28 1997-01-17 Peters Sa Composition d'agent nettoyant-decontaminant notamment pour instruments chirurgicaux.
CA2077398A1 (fr) * 1991-09-06 1993-03-07 William J. Cook Composition liquide acide, desinfectante, nettoyante, tout usage

Also Published As

Publication number Publication date
DE69607391T2 (de) 2000-07-27
DE69607391D1 (de) 2000-04-27
ES2146421T3 (es) 2000-08-01
ZA969481B (en) 1998-05-12
EP0874887A1 (fr) 1998-11-04
CA2235680A1 (fr) 1997-06-19
AU7567396A (en) 1997-07-03
BR9611979A (pt) 1999-02-17
CA2235680C (fr) 2002-03-05
WO1997021795A1 (fr) 1997-06-19
AU699602B2 (en) 1998-12-10
GB9525155D0 (en) 1996-02-07

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