EP0596989A1 - Wässrige Zusammensetzungen - Google Patents

Wässrige Zusammensetzungen

Info

Publication number
EP0596989A1
EP0596989A1 EP92916635A EP92916635A EP0596989A1 EP 0596989 A1 EP0596989 A1 EP 0596989A1 EP 92916635 A EP92916635 A EP 92916635A EP 92916635 A EP92916635 A EP 92916635A EP 0596989 A1 EP0596989 A1 EP 0596989A1
Authority
EP
European Patent Office
Prior art keywords
composition
concentrate
weight
oleic acid
anionic surfactant
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Withdrawn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
EP92916635A
Other languages
English (en)
French (fr)
Inventor
Christopher 28 Wilmot Avenue Great Sankey Revell
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.)
Evonik LIL Ltd
Original Assignee
Laporte Industries Ltd
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 Laporte Industries Ltd filed Critical Laporte Industries Ltd
Publication of EP0596989A1 publication Critical patent/EP0596989A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/32—Wires, ropes or cables lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/34—Lubricating-sealants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/36—Release agents or mold release agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/38—Conveyors or chain belts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/40—Generators or electric motors in oil or gas winning field
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/42—Flashing oils or marking oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/44—Super vacuum or supercritical use
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/50—Medical uses
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • This invention is concerned with aqueous compositions. More particularly, this invention concerns aqueous compositions which are useful in or as conveyor lubricants.
  • the aqueous compositions of the present invention comprise octanoic and oleic acid soaps.
  • a clean and well lubricated conveyor surface may be required to enable progression of the bottles to be stopped during filling and capping whilst the conveyor track itself continues to move beneath the bottles. If the track surface is not clean and well lubricated, the bottles may fail to stop moving or may be knocked over, consequently resulting in disruption of the bottling line.
  • Aqueous compositions have been used as lubricants to provide the slip and detergency required on such conveyor systems.
  • an aqueous lubricant composition analysed in its concentrate form to comprise octanoic acid soap, oleic acid soap, anionic surfactant and sequestering agent, has been commercially available for this use in the United Kingdom for a number of years.
  • the lubricating compositions tend to become contaminated with bottling fluid, spilt or knocked onto the track, thereby reducing their lubricating efficiency.
  • an aqueous composition for lubricating continuously moving conveyor systems comprising octanoic acid soap and oleic acid soap and, optionally, anionic surfactant and/or sequestering agent, characterised in that the composition has a lubricant mobility height of at least 25.5cm and is obtainable by mixing 500 parts by weight water with 1 part by weight of a lubricant concentrate, wherein the lubricant concentrate is formed from 4.4% by weight KORTACID 0899 (an octanoic acid composition available from Akzo Chemicals), 10.8% by weight PRIOLENE 6900 (an oleic acid composition available from Unichema International ), 4.72% by weight AEROSOL OT100 (a dioctyl sodium sulpho succinate composition available from Cyanamid Of Great Britain ), 11.7 % by weight NERVANAID B.30 (a 30% solution of EDTA, present as its tetrasodium salt, available from Rhone-
  • the composition comprises both anionic surfactant and sequestering agent.
  • the aqueous lubricating compositions of the present invention demonstrate a surprising improvement in lubricity as evidenced by a surprising increase in lubricant mobility height, and an increased tolerance to bottling fluid contamination on PET bottling lines than commercially available conveyor lubricants.
  • the present invention provides an aqueous composition for lubricating continuously moving conveyor systems comprising octanoic acid soap, oleic acid soap, anionic surfactant, and sequestering agent and is characterised in that the anionic surfactant is a di(Cs- c 12) a .l.ky.l sulpho succinic acid or salt thereof, preferably a di(C6-C10)alkyl sulpho succinate, and most preferably a dioctyl sodium sulpho succinate.
  • the surfactant is preferably present in the composition in an amount of from 40 to 50 % by weight of the oleic acid.
  • compositions of the present invention have a lubricant mobility height of at least 25.5 cm, preferably 26 to 28cm.
  • the present invention provides a lubricant concentrate comprising octanoic acid soap, oleic acid soap, anionic surfactant and sequestering agent and is characterised in that the anionic surfactant is a di(C6- C12)alkyl sulpho succinic acid or salt thereof, preferably a di(C6-CIO)alkyl sulpho succinate, and most preferably a dioctyl sodium sulpho succinate.
  • the surfactant is present in an amount of from 40% to 50% by weight of the oleic acid.
  • a preferred lubricant concentrate is formed from 4 to 12 wt % octanoic acid, 4.5 to 15 wt % oleic acid, 1.8 to 6 wt % anionic surfactant, such as dioctyl sodium sulpho succinate, 2 to 5 wt % sequestering agent, such as EDTA, 3 to 6 wt % solubiliser, such as KOH, and the balance water.
  • the concentrate may be diluted in proportion by weight of 1:100 to 1000 with water, preferably 1:400 to 600, more preferably 1:450 to 550 and most preferably 1:500.
  • the oleic acid and/or oleic acid soap used in the lubricant concentrate may be obtained from any appropriate fatty acid source such as fatty acids of tall oil, coconut oil, sunflower oil, rape seed oil, tallow oil, soya bean oil, corn oil, cotton seed oil, palm oil and blends thereof.
  • fatty acids of tall oil, coconut oil, sunflower oil, rape seed oil, tallow oil, soya bean oil, corn oil, cotton seed oil, palm oil and blends thereof are preferred commercially available sources of oleic acid.
  • the sequestering agents which may be employed in the composition of the present invention include those disclosed in US-A-3860521, though EDTA is the most preferred.
  • a solubiliser preferably KOH
  • KOH potassium hydroxide
  • mono-, di- or tri-ethanola ine or isopropanolamine Typically, a stoichiometric excess of solubiliser is required, to maintain the pH of the concentrate above neutral.
  • the concentrate has a pH of from 8 to less than 12. Prior art compositions tend to have a pH of above 12.
  • compositions and concentrates of the present invention may also be added to the compositions and concentrates of the present invention, such as corrosion inhibitors and bacteriacides etc, without being detrimental to the advantageous properties of the composition.
  • a nonionic surfactant or an alcoholic coupling agent are not essential components of the composition of the present invention.
  • compositions, and diluted concentrates, of the present invention are particularly useful as lubricants on conveyor systems carrying PET bottles.
  • a lubricant concentrate of the present invention was prepared by mixing together the following components:
  • the concentrate was diluted in demineralised water to five hundred times dilution to form an aqueous composition of the present invention.
  • a commercially available lubricant concentrate was analysed and was found to comprise on a percent by weight basis the following components:
  • the concentrate was diluted five hundred times with demineralised water, in accordance with the manufacturers instructions.
  • the bottle is then placed onto a stainless steel plate which has been thoroughly wetted with lubricant composition.
  • an index finger an attempt is made to push the bottle smoothly along the plate.
  • the ability to push the bottle smoothly along the plate deminishes as the pushing finger is moved up the wall of the bottle.
  • the height up the bottle wall of the highest point of contact between the finger and the side of the bottle is recorded when the bottle just begins to topple instead of sliding along the plate. This recorded height is the lubricant mobility height of the composition and is believed to be a direct indication of the lubricity of the composition evaluated.
  • composition 500ml is carefully charged to a 1000ml glass measuring cylinder.
  • the volume of the liquid is measured from the side of the cylinder (Vi).
  • the composition is then agitated 30 times in 30 seconds using a perforated disk on a plunger.
  • the disk is then removed and the volume of composition and foam measured from the side of the cylinder (V2) .
  • the foam height index is calculated from V ⁇ -V ⁇ . A low foam height index is desirable.
  • the cylinder is then left stationary for 2 hours when the final volume, Vf, of the composition and foam is recorded.
  • the % defoaming is then calculated as:
  • % defoaming ( Vf-V ⁇ / ⁇ V 2 -V ⁇ ) ) x 100 A high % defoaming is desirable.
  • Compositions are contaminated with up to a few percent by weight of a carbonated soft drink (sold under the trade mark Diet Pepsi, available from Pepsi Cola) and the lubricant mobility height measured as above.
  • the recorded figure for soil tolerance is the amount of soft drink present in the composition before any reduction in lubricity is recordable. A high soil tolerance is desirable. Stress Cracking:
  • a PET bottle, as described above, is monitored for stress cracking after exposure to the composition for 24 hours.
  • An acceptable composition should record no stress cracking over this period
  • composition is visually evaluated for its clarity. An acceptable composition should be clear.
  • compositions of the present invention over the properties of the commercially available composition are surprising.
  • the stress cracking, haze, foam height index and % defoaming properties of the composition of the present invention are comparable with those of the commercially available composition and must therefore be acceptable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)
EP92916635A 1991-08-02 1992-08-03 Wässrige Zusammensetzungen Withdrawn EP0596989A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB919116776A GB9116776D0 (en) 1991-08-02 1991-08-02 Aqueous compositions
GB91167767 1991-08-02
PCT/GB1992/001425 WO1993003125A1 (en) 1991-08-02 1992-08-03 Aqueous compositions

Publications (1)

Publication Number Publication Date
EP0596989A1 true EP0596989A1 (de) 1994-05-18

Family

ID=10699462

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92916635A Withdrawn EP0596989A1 (de) 1991-08-02 1992-08-03 Wässrige Zusammensetzungen

Country Status (4)

Country Link
EP (1) EP0596989A1 (de)
AU (1) AU2379592A (de)
GB (2) GB9116776D0 (de)
WO (1) WO1993003125A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5441654A (en) * 1988-07-14 1995-08-15 Diversey Corp., A Corp. Of Canada Composition for inhibiting stress cracks in plastic articles and methods of use therefor
AU4770599A (en) * 1998-05-29 1999-12-13 Corby, Michael Peter Lubricant compositions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4274973A (en) * 1979-06-22 1981-06-23 The Diversey Corporation Aqueous water-soluble soap lubricant concentrates and aqueous lubricants containing same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9303125A1 *

Also Published As

Publication number Publication date
GB9204224D0 (en) 1992-04-08
WO1993003125A1 (en) 1993-02-18
GB9116776D0 (en) 1991-09-18
AU2379592A (en) 1993-03-02

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