EP0593651A1 - Schmierölzusammensetzung, verfahren zur herstellung und verwendungen davon, besonders als ölzusatz - Google Patents
Schmierölzusammensetzung, verfahren zur herstellung und verwendungen davon, besonders als ölzusatzInfo
- Publication number
- EP0593651A1 EP0593651A1 EP92915637A EP92915637A EP0593651A1 EP 0593651 A1 EP0593651 A1 EP 0593651A1 EP 92915637 A EP92915637 A EP 92915637A EP 92915637 A EP92915637 A EP 92915637A EP 0593651 A1 EP0593651 A1 EP 0593651A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluorinated
- polymer
- particles
- composition
- ethoxylated
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims description 11
- 239000003921 oil Substances 0.000 title description 24
- 239000000654 additive Substances 0.000 title description 7
- 230000000996 additive effect Effects 0.000 title description 5
- 239000002245 particle Substances 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000847 nonoxynol Polymers 0.000 claims abstract description 19
- 230000001050 lubricating effect Effects 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000000314 lubricant Substances 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000009738 saturating Methods 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004811 fluoropolymer Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000010687 lubricating oil Substances 0.000 description 8
- 239000012530 fluid Substances 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920006356 Teflon™ FEP Polymers 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229920002214 alkoxylated polymer Polymers 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/06—Particles of special shape or size
-
- 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
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- 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
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/06—Perfluorinated compounds
-
- 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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/02—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen and halogen only
-
- 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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/062—Polytetrafluoroethylene [PTFE]
Definitions
- Lubricating composition preparation process and applications, in particular as an additive in oils.
- the present application relates to a lubricating composition, its preparation process and its applications, in particular as an additive in oils.
- the base oils developed by petroleum companies for use as lubricants are monograde oils. Most engines such as internal combustion, petrol or diesel engines for cars, for example, use multigrade oils.
- Additives must be incorporated into these monograde oils to obtain multigrade oils after mixing.
- oils are subjected to sulfonation reactions in order to be dissolved in the oils to which they are added. With aging, the oils release acids which corrode motors, more particularly stationary motors.
- French patent application No. 2359200 describes a hybrid lubricant dilutable in a conventional fluid lubricating oil, comprising an aqueous colloidal dispersion of polytetrafluoroethylene particles, a neutralizing and stabilizing agent, a carrier fluid lubricating oil incorporated in the stabilized dispersion for forming with it an emulsion, which emulsion comprises a dispersing agent and finally a wetting agent added to 1 "emulsion endowed with affinity with respect to rubbing surfaces so as to predispose them to be impregnated by said particles and merge with them to form a surface lubricating layer.
- the hybrid lubricant uses an aqueous dispersion.
- the presence of water harms the lubrication effect of the oils, especially at the high temperatures where it is vaporized, causing circulation difficulties in its circuit.
- European patent No. 0 293 427 relates to a process for manufacturing a dispersion of polytetrafluor ⁇ ethylene for the use of lubricating oil or of additive thereto.
- a nonionic surfactant is fixed to the polytetrafluoroethylene particles by means of a heat treatment in several zones of decreasing temperature, including a first zone at very high temperature, detrimental to the quality of the oil.
- a lubricating composition for the use of lubricating oil or an additive to the latter in which particles of fluorinated (co) polymer would be perfectly miscible with the fluid in which they are in stable suspension, without any change the basic characteristics, without fear of salting out or settling of said particles in the fluid.
- the present application relates to a lubricating composition, characterized in that it contains solid particles of fluorinated (co) polymer of size less than or equal to 1 ⁇ m coated with a nonylphe ⁇ nol ethoxylated with 10 to 12 molecules of ethylene oxide and in that it is substantially anhydrous.
- compositions according to the invention are compositions characterized in that the fluorinated (co) polymer particles are coated with a stable saturating amount of ethoxylated nonylphenol.
- compositions according to the invention preference is given to those in which the fluorinated (co) polymer is polytetrafluoroethylene, as well as those in which the ethoxylated nonylphenol comprises 11 molecules of ethoxylate.
- the weight ratio of ethoxylated nonylphenol to fluorinated polymer is approximately 2 to 1 in the case of polytetrafluoroethylene, and of ethoxylated nonylphenol with 11 molecules of ethoxylate.
- the present invention also relates to a lubricant characterized in that it contains a lubricating composition as defined above.
- the present application also relates to a process for preparing a lubricating composition containing particles of fluorinated (co) polymer in suspension, characterized in that particles of substantially anhydrous fluorinated (co) polymer are treated size less than or equal to 1 ⁇ m using a substantially double volume of an ethoxylated nonylphenol with 10, 11 or 12 molecules of ethoxylate itself also substantially anhydrous, with stirring and anhydrous atmosphere, to obtain the lubricated composition ⁇ proud expected.
- the fluorinated (co) polymer may be a fluorinated resin chosen from fluorinated polymers and copolymers, perfluoroalkoxylated (co) polymers, partially fluorinated (preferably perhalogenated) (co) polymers. These (co) polymers can be used alone or as a mixture. Mention may in particular be made of Teflon R (PTFE) essentially composed of tetrafluoroethylene. Mention may also be made of Teflon FEP R , tetrafluoroethylene copolymer hexafluoropropy- lene. Mention may also be made of Teflon PRPFA R, which is a perfluorinated alkoxylated polymer.
- PTFE Teflon R
- Teflon FEP R tetrafluoroethylene copolymer hexafluoropropy- lene.
- Teflon PRPFA R which is a perfluorinated alkoxylated
- the particles of the fluorinated polymer or (co) polymer must have a small size, that is to say less than 2 ⁇ m, and preferably less than or equal to 1 ⁇ m.
- the particles must be substantially anhydrous, namely that their hygrometry must be less than 1%, in particular less than 0.5% and advantageously less than 0.2%.
- the particles can be made substantially anhydrous by carrying them for a period of time, for example 24 hours and preferably about 48 hours or more, above room temperature, for example 10 ° C above it.
- the particles used have an apparent density of approximately 0.5 preferably.
- the ethoxylated nonylphenol used is also substantially anhydrous. This anhydrous nature can be conferred by a heat treatment such as that described above for the particles of fluorinated (co) olymer.
- the bulk density of the hydrolyzant is about 1.04.
- the fluorinated (co) polymer is mixed with stirring with ethoxylated nonylphenol.
- ethoxylated nonylphenol is used per 1 volume of fluorinated (co) olymer.
- the agitation is preferably carried out in a centrifugal Vortex agitator, advantageously comprising a two-stage turbine and central bias.
- the diameter of the turbine is preferably one third that of the tank.
- the tangential speed around the turbine is preferably 15 to 30 m / s and advantageously 20 to 24 m / s.
- the radial axis of the turbine is advantageously located approximately a quarter of the bottom of the total height of the liquid.
- any operational condition allowing the particles to achieve 3 to 5 and preferably 4 revolutions per minute is usable.
- this operation is preferably carried out regularly and rapidly. For example, for a total weight of fluorinated (co) polymer and ethoxylated nonylphenol of 500 kg, the fluorinated (co) polymer is added in two minutes at a regular rate. Stirring of the mixture can be maintained from 30 minutes to an hour and preferably from 35 to 45 minutes, in particular approximately 40 minutes.
- the product obtained at the end of the process has the appearance of a thick thixotropic and adherent paste which can, for example, be lengthened using about 15% basic, neutral, monograde mineral oil. This elongated composition can be transferred.
- the transferable composition is miscible in the lubricating oil.
- the composition is not soluble in oils and therefore has the advantage of preserving the original properties of the lubricating oils without modification by adding its own.
- the transferable solution can be mixed in the lubricating oil intended for petrol, diesel, two-stroke engines, hydraulic, mechanical or automatic transmissions or even reducers, etc.
- the composition according to the present invention is particularly effective in the case of oils which circulate in a circuit.
- the usable dosage is approximately 8 grams per liter of an elongated transferable composition as indicated above (of 15% mineral oil).
- a pre-dosage which consists in mixing the transferable composition with an amount of oil.
- an amount of oil for example, 15 grams of transferable composition in solution in 0.8 liters of oil can be added to 5 liters of quality oil conforming to that recommended by an automobile manufacturer. for example.
- the fat thus modified has the advantage, as in the case of engines or transmissions, after prolonged immobilization, of avoiding the disadvantages of dry contacts between metals. The same is true of plain bearings, above all because of the small contact surfaces, for ball and roller bearings on which, during start-ups, the metal dreaded by specialists is avoided.
- the operation becomes progressively more flexible as the treatment produces its effects. Start-up becomes easier, engine wear is slowed down, certain standards are restored, in particular the compression ratios are balanced and return to normal, and the segments possibly stuck by the residues peel off and refill again their role of sealing and stoichiometric stability, avoiding the rise of oil in the combustion chambers and the projection of fuel in the oil.
- the fluorinated (co) polymer particles in particular of the polytetrafluoroethylene type, they easily pass through the oil filter without clogging.
- the polytetrafluoroethylene particles have a size less than or equal to 1 ⁇ m, these particles are miscible in all proportions both with multigrade commercial oils and with monograde oils.
- the composition contains substantially no more free ethoxylated nonylphenol, i.e. less than 0.1%
- the final density of the polytetrafluoroethylene particles is approximately 0.82 against 0.5 for the particles of original polytetrafluoroethylene.
- the above composition is diluted with 15% basic monograde mineral oil, SAE 30 to obtain a transferable composition.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
- Fats And Perfumes (AREA)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92915637A EP0593651B1 (de) | 1991-07-05 | 1992-07-06 | Schmierölzusammensetzung, verfahren zur herstellung und verwendungen davon, besonders als ölzusatz |
| GR990401675T GR3030592T3 (en) | 1991-07-05 | 1999-06-23 | Platelet activating factor antagonists. |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP91401865 | 1991-07-05 | ||
| EP91401865 | 1991-07-05 | ||
| EP92915637A EP0593651B1 (de) | 1991-07-05 | 1992-07-06 | Schmierölzusammensetzung, verfahren zur herstellung und verwendungen davon, besonders als ölzusatz |
| PCT/FR1992/000641 WO1993001262A1 (fr) | 1991-07-05 | 1992-07-06 | Composition lubrifiante, procede de preparation et applications, notamment a titre d'additif dans les huiles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0593651A1 true EP0593651A1 (de) | 1994-04-27 |
| EP0593651B1 EP0593651B1 (de) | 1999-03-31 |
Family
ID=8208591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92915637A Expired - Lifetime EP0593651B1 (de) | 1991-07-05 | 1992-07-06 | Schmierölzusammensetzung, verfahren zur herstellung und verwendungen davon, besonders als ölzusatz |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5484544A (de) |
| EP (1) | EP0593651B1 (de) |
| JP (1) | JP3159987B2 (de) |
| AT (1) | ATE178349T1 (de) |
| AU (1) | AU2327892A (de) |
| BR (1) | BR9206246A (de) |
| CA (1) | CA2112352A1 (de) |
| DE (1) | DE69228815T2 (de) |
| DK (1) | DK0593651T3 (de) |
| GR (1) | GR3030592T3 (de) |
| WO (1) | WO1993001262A1 (de) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6036945A (en) | 1997-04-11 | 2000-03-14 | Shamrock Technologies, Inc. | Delivery systems for active ingredients including sunscreen actives and methods of making same |
| US6235253B1 (en) | 1998-06-09 | 2001-05-22 | Marathon Ashland Petroleum, Llc | Recovering vanadium oxides from petroleum coke by melting |
| DE19852203A1 (de) * | 1998-11-12 | 2000-05-18 | Henkel Kgaa | Schmiermittel mit Feststoffpartikeln einer Teilchengröße unter 500 nm |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127491A (en) * | 1976-07-23 | 1978-11-28 | Michael Ebert | Hybrid lubricant including halocarbon oil |
| US5160646A (en) * | 1980-12-29 | 1992-11-03 | Tribophysics Corporation | PTFE oil coating composition |
| DE3642617C1 (de) * | 1986-12-13 | 1988-04-21 | Malte Huth | Verfahren zur Herstellung einer PTFE-Dispersion als Schmieroel oder Schmieroelzusatz |
-
1992
- 1992-07-06 CA CA002112352A patent/CA2112352A1/fr not_active Abandoned
- 1992-07-06 WO PCT/FR1992/000641 patent/WO1993001262A1/fr not_active Ceased
- 1992-07-06 BR BR9206246A patent/BR9206246A/pt not_active Application Discontinuation
- 1992-07-06 DE DE69228815T patent/DE69228815T2/de not_active Expired - Lifetime
- 1992-07-06 AT AT92915637T patent/ATE178349T1/de not_active IP Right Cessation
- 1992-07-06 US US08/170,356 patent/US5484544A/en not_active Expired - Lifetime
- 1992-07-06 DK DK92915637T patent/DK0593651T3/da active
- 1992-07-06 JP JP50203193A patent/JP3159987B2/ja not_active Expired - Fee Related
- 1992-07-06 EP EP92915637A patent/EP0593651B1/de not_active Expired - Lifetime
- 1992-07-06 AU AU23278/92A patent/AU2327892A/en not_active Abandoned
-
1999
- 1999-06-23 GR GR990401675T patent/GR3030592T3/el unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9301262A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3159987B2 (ja) | 2001-04-23 |
| ATE178349T1 (de) | 1999-04-15 |
| DE69228815T2 (de) | 1999-11-25 |
| WO1993001262A1 (fr) | 1993-01-21 |
| JPH06509129A (ja) | 1994-10-13 |
| DE69228815D1 (de) | 1999-05-06 |
| US5484544A (en) | 1996-01-16 |
| AU2327892A (en) | 1993-02-11 |
| EP0593651B1 (de) | 1999-03-31 |
| BR9206246A (pt) | 1995-10-17 |
| GR3030592T3 (en) | 1999-10-29 |
| DK0593651T3 (da) | 1999-10-18 |
| CA2112352A1 (fr) | 1993-01-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19931221 |
|
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