EP0247990B1 - Verfahren zur Herstellung von Explosivpatronen und danach hergestellte Explosivpatronen - Google Patents

Verfahren zur Herstellung von Explosivpatronen und danach hergestellte Explosivpatronen Download PDF

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Publication number
EP0247990B1
EP0247990B1 EP87870072A EP87870072A EP0247990B1 EP 0247990 B1 EP0247990 B1 EP 0247990B1 EP 87870072 A EP87870072 A EP 87870072A EP 87870072 A EP87870072 A EP 87870072A EP 0247990 B1 EP0247990 B1 EP 0247990B1
Authority
EP
European Patent Office
Prior art keywords
process according
hydrogen peroxide
explosive
gelling agent
stage
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.)
Expired - Lifetime
Application number
EP87870072A
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English (en)
French (fr)
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EP0247990A1 (de
Inventor
Edmond Bouillet
Jean-Claude Colery
Claude Declerck
Pierre Ledoux
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.)
Solvay Chimie SA
Original Assignee
Interox SA
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Filing date
Publication date
Application filed by Interox SA filed Critical Interox SA
Priority to AT87870072T priority Critical patent/ATE54660T1/de
Publication of EP0247990A1 publication Critical patent/EP0247990A1/de
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Publication of EP0247990B1 publication Critical patent/EP0247990B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0008—Compounding the ingredient
    • C06B21/0025—Compounding the ingredient the ingredient being a polymer bonded explosive or thermic component
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00

Definitions

  • the present invention relates to a method for manufacturing explosive cartridges containing, in a cartridge case, an explosive composition comprising hydrogen peroxide, an oxidizable organic material and a gelling agent. It relates more particularly to a process in which the gelling agent belongs to the class of macromolecular plastics.
  • the invention also relates to the explosive cartridges obtained by said process.
  • Explosive compositions have been known for a long time which contain an aqueous solution of concentrated hydrogen peroxide associated with a finely divided oxidizable combustible material and an absorbent filler (US Pat. No. 3,047,441 (AW BAKER et al) * column 2 , lines 1 to 10 and column 6, claim 1 * ).
  • absorbent fillers mention is made of the products forming gels column 2, lines 60 to 72 * ), as well as synthetic thermosetting or thermoplastic resins, such as urea-formaldehyde resins, phenol- formaldehyde or polymethyl methacrylate ( * column 2, lines 54 to 58 * ).
  • combustible materials capable of also playing the role of filling material can be used ( * column 2, lines 26 to 31 * ).
  • the present invention aims to remedy this disadvantage of known explosives, by providing a process for the manufacture of explosive cartridges which have high detonation rates, of the order of 7000 m / s and more.
  • the invention relates to a process for the manufacture of explosive cartridges containing, in a cartridge case, an explosive composition comprising hydrogen peroxide, at least one oxidizable organic material and at least one gelling agent belonging to the class of materials.
  • macromolecular plastics according to the invention, in a first step, the hydrogen peroxide, the oxidizable organic material and at least one precursor monomer of the gelling agent are mixed and, in a second step, the macromolecules of the gelling agent are synthesized in located in the socket.
  • the method according to the invention is suitable for the manufacture of cartridges, the sockets of which are produced with the materials usually used for making explosive cartridges.
  • materials are waxed paper, cardboard, metal, in particular copper, brass, bronze, zinc, aluminum, steels of various qualities and rigid plastics such as, for example, vinyl resins, polyolefins, acrylonitrile-butadiene-sytrene resins and their copolymers.
  • Composite sockets produced using several of these materials, such as sheathed metals (Cu and brass in particular), are also very suitable for the process according to the invention.
  • Hydrogen peroxide is used in the process according to the invention, in the form of a concentrated solution of hydrogen peroxide in a solvent.
  • concentrated solutions is meant solutions where the weight content of hydrogen peroxide is greater than 60%. Solutions containing at least 65% by weight and up to 99.9% by weight of hydrogen peroxide are well suited. Preferably, solutions are used which contain between 70 and 90% by weight of hydrogen peroxide.
  • the hydrogen peroxide solvent can be water or an inert organic solvent. Examples of suitable organic solvents are n-butanol, acetonitrile and chloroform. Water is the preferred solvent because of its negligible cost and the lower risks associated with its use in the presence of concentrated solutions of hydrogen peroxide.
  • the oxidizable organic material used consists of any organic product capable of rapidly oxidizing in the presence of hydrogen peroxide to a further mixture of two or more of these products. Products capable of releasing large volumes of gas after oxidation are very suitable. To limit pollution of the atmosphere after detonation, it is advantageous to select organic products containing only carbon, hydrogen and oxygen.
  • An essential characteristic of the process according to the invention is to obtain, at the end of the first stage, the most homogeneous mixture possible before proceeding to the synthesis of the macromolecules of the gelling agent.
  • organic materials are lower aliphatic alcohols such as methanol and ethanol, aliphatic diols with less than 5 carbon atoms such as ethylene glycol and sugars such as pentoses and hexoses, in particular sucrose .
  • the gelling agent is a macromolecular plastic which is synthesized in situ in the socket, in the presence of hydrogen peroxide and organic matter which can be oxidized from one or more monomers. precursors.
  • the monomer is incorporated into the mixture, at the first stage of the process.
  • monomers which are miscible and / or soluble in the hydrogen peroxide solution, at the temperature at which the two stages of the process are carried out.
  • the synthesis of the macromolecular plastic in the sockets can be carried out by any technique known per se.
  • a first technique is the chain polymerization technique.
  • a second technique consists in reacting by condensation functional groups carried by the monomer molecules in order to obtain a polycondensate within the mixture contained in the socket.
  • the plastic thus obtained can either belong to the class of thermoplastics, to that of thermosets or to that of elastomers.
  • the plastic is synthesized in the hydrogen peroxide solution.
  • the other constituents of the exposure mixture can be dispersed in the solid or liquid state in the hydrogen peroxide solution. It is preferred that they are in the dissolved state in the hydrogen peroxide solution.
  • Plastics obtainable by this technique are generally well known in themselves. They belong to the classes of resins usually produced by solution polymerization. A category of particularly suitable resins are those obtained by polymerization in aqueous solution, the hydrogen peroxide solution then being an aqueous solution. In this category, water-soluble resins are particularly interesting.
  • Examples of such resins which can be synthesized in sockets according to the process according to the invention are polyvinyl alcohol; polyacrylamides; cationic resins including polymeric amines and quaternary ammonium polymers such as polyethyleneimines, polyalkylene polyamines, poly (vinylbenzyltrimethylammonium) chlorides, poly (diallyldimethylammonium) chlorides, poly (glycidyltrimethylammonium) chlorides (2-hydroxypropyl-1,1-N-di-methylammonium); polyacrylic, polymethacrylic, poly-alpha-hydroxyacrylic acids and their alkali metal or ammonium salts; esters of polyacrylic, polymethacrylic and poly-alpha-hydroxyacrylic acids such as 2-hydroxyethyl methacrylate; polyethylene oxides known under the name of polyethers; poly (N-vinyl-2-pyrrolidone); polyvinyl ethers homopolymers of alkylvinyl ethers;
  • Epoxy resins constitute another class of resins which can be used in the context of the invention.
  • the preferred resins are those which contain only carbon, hydrogen and oxygen.
  • the gelling agent also constitutes an oxidizable material.
  • the hydrogen peroxide is mixed in the first step with the precursor monomer of the gelling agent to the exclusion of any other oxidizable organic matter.
  • the exposure obtained in the sockets at the end of the second stage has a sufficient density greater than 1.2 kg / dm 3 .
  • the best results are obtained when the density of this exhibit is greater than 1.35 kg / d m 3 .
  • a small proportion of additives are generally incorporated in the first step in the mixture, generally less than 5% by weight of this mixture.
  • the main purpose of these additives is to stabilize hydrogen peroxide against slow decomposition in water and oxygen. For this reason, the products known for a long time are used to stabilize concentrated solutions of hydrogen peroxide such as phosphates, stannates and heavy metal sequestrants of organic or inorganic type.
  • Other additives can be added to the mixture to give the explosive substance produced special properties such as reduced sensitivity to friction and impact, reduced tendency to exudate, improved mechanical properties such as plasticity, frost resistance and at low temperatures in general.
  • the proportions of the various constituents to be used in the mixture depend both on the nature of the oxidizable organic matter, on that of the precursor monomer of the plastic material constituting the gelling agent and on the solvent or solvents present. They can be easily determined by laboratory formulation tests. In general, the formulation of the mixture must be adapted so that the respective amounts of hydrogen peroxide on the one hand, of the materials liable to be oxidized (which include the oxidizable material, the plastic material and the possible arganic solvent) on the other hand, are not too far from the stoichiometric quantities corresponding to the chemical reactions of oxidation by hydrogen peroxide.
  • the explosives industry characterizes the deviation from this stoichiometry by the notion of oxygen balance expressed in% O2 and which is established as follows in the case of an explosive containing only carbon , hydrogen, oxygen and possibly also nitrogen: where c, h and o are the proportions of the carbon, hydrogen and oxygen atoms respectively in the raw chemical formula of the explosive as provided by elemental analysis.
  • the mixture produced in the first step of the process generally contains a proportion by weight of 50 to 95% of concentrated solution of hydrogen peroxide in water or in an organic solvent, 2 to 40% of oxidizable organic matter, 2 to 40% of monomer precursor of the plastic material and 0 to 5% of additives.
  • the weight proportions comprise 65 to 85% of concentrated solution of hydrogen peroxide, 5 to 30% (preferably, 5 to 20%) of oxidizable organic matter, 5 to 30% ( preferably 5 to 20%) of monomer precursor of the plastic material and at most 1% (preferably 0.2%) of additives as defined above.
  • the oxidizable organic material, the solvent, the precursor monomer of the plastic material and the respective proportions of these constituents and of hydrogen peroxide are selected so that the mixture obtained in the first step has only one homogeneous liquid phase of low dynamic viscosity, for example less than 1,500 Pa.s, preferably less than 1,000 Pa.s.
  • the first mixing step is carried out outside the sleeve, the synthesis of the macromolecules of the gelling agent is then initiated, then the mixture is introduced into the sleeve where the gelling of the explosive composition.
  • the initiation of the synthesis of macromolecules is done by all usual techniques well known in the plastics industry, for example by addition of a polymerization initiating peroxide, or by irradiation of the mixture by means of visible or ultra radiation. -purple of appropriate frequency.
  • the first mixing step can be carried out in any kind of mixing apparatus capable of homogenizing liquids and dissolving therein, if necessary, solid products, such as tanks with rotary agitators, mixers planetary, pneumatic mixing techniques or static mixers.
  • the order of introduction of the various components into the mixer must be adapted to the nature of the components and to the type of mixer. Most often, we start by mixing the oxidizable organic matter with the optional stabilizing additive. Then the hydrogen peroxide is gradually introduced into the mixer followed by the precursor monomer of the plastic.
  • the invention also relates to the explosive cartridges obtained by the method described above.
  • the explosive cartridges according to the invention find interesting uses as industrial explosives in confined atmospheres, in particular in mines and quarries. When they contain only carbon, hydrogen and oxygen, their use allows the realization of underground fire which does not pollute the ambient atmosphere and therefore increases the safety of the operating personnel while authorizing rates high firing range and therefore improved operating profitability.
  • the explosive cartridges according to the invention have a particularly low tendency to exudate.
  • the mixing was then continued for 1 hour, then the mixture was transferred into the sockets of PVC cartridges with an internal diameter of 33 mm, a wall thickness of 2 mm and a length of 310 mm.
  • the sockets contained two detectors intended to measure the detonation rate, spaced 150 mm apart, one of the detectors being 150 mm from one end of the cartridge close to the primer. These detectors were twisted copper wire sensors of 0.2 mm in diameter and covered with a thin layer of enamel, the entire sensor being placed in a PVC sheath with an external diameter of 1.5 mm having purpose of isolating it from the explosive mixture.
  • the density of the explosive material obtained after complete gelation was included for all the cartridges tested between 1.27 and 1.28 kg / dm 3 .
  • the detonation speed was measured by determining the time taken for the shock wave to travel the known distance of 150 mm separating the two detectors.
  • the measurement was carried out by hanging the cartridge horizontally 1 m from the ground.
  • the copper wires of the detectors suddenly short-circuit at the precise moment when the shock wave passes.
  • the short circuit triggers a pulse generator which delivers a steep-edge electrical pulse of sufficient amplitude to trigger an electronic chronograph.
  • the first pulse starts the chronograph, the second, coming from the second sensor, stops it.
  • Example 1R After pouring 376.2 g of the liquid mixture of stabilized methanol and hydrogen peroxide into each socket, the contents of the sockets were carefully mixed, the cartridges were closed and stored for 24 hours at room temperature during which the gelation of the mixture was completed. The same test for measuring the detonation rate was then carried out as in Example 1R.
  • the density of the explosive composition obtained was between 1.20 and 1.21 kg / dm 3 .
  • the density of the explosive composition filling the cartridges was 1.41 kg / dm 3 . No detonation speed could be measured during two repeated shots: only the first sensor short-circuited on the first shot, none of the sensors triggered on the second shot.
  • sucrose and 0.39 g of dipicolinic acid were introduced into a 1800 ml beaker. After stirring for a few minutes, 975 g of aqueous hydrogen peroxide solution containing 85% by weight of H 2 O 2 and 130 g of acid were then successively introduced into the beaker, in the form of a slow and continuous jet. acrylic monomer.
  • the density of the explosive composition contained in the cartridges was 1.38 kg / dm 3 .
  • the detonation rate was then measured.
  • the two shots fired gave rise to a high and reproducible detonation speed: 7042 m / s for the first shot and 7009 m / s for the second.
  • the cartridges prepared according to the process according to the invention are not characterized by a stable detonation ability, at high speed and endowed with a relatively high power.
  • the explosives obtained in Examples 1R, 2R and 4 were tested from the point of view of exudation under pressure.
  • the test consists in placing in a cylindrical cavity pierced with 20 holes of 0.5 mm in diameter a rod of 15 mm in diameter of the material to be tested previously wound in gauze. A pressure of 1.2 bar is then exerted on the tube by means of a piston. Note the minimum time of appearance of the first drop of exudate at the orifice of one of the holes. The test is repeated 3 times.
  • Example 4 show the clear superiority of the material obtained in Example 4 according to the method according to the invention compared to the materials obtained according to the known methods of Examples 1R and 2R.
  • the density of the explosive composition contained in the cartridges was 1.35 kg / dm 3 .
  • the two shots fired gave rise to a high and reproducible detonation speed: 6760 m / s for the first shot and 6880 m / s for the second.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Powder Metallurgy (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Driving Mechanisms And Operating Circuits Of Arc-Extinguishing High-Tension Switches (AREA)
  • Catching Or Destruction (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Air Bags (AREA)

Claims (12)

1. Verfahren zur Herstellung von Explosivpatronen, enthaltend in einer Hülse eine explosive Zusammensetzung, die Wasserstoffperoxid, wenigstens eine oxidierbares, organisches Material und wenigstens eine Geliermittel, das zur Klasse der makromolekularen Kunststoffe gehört, umfaßt, dadurch gekennzeichnet, daß in einer ersten Stufe das Wasserstoffperoxid, das oxidierbare, organische Material und wenigstens eine Vorläufer-Monomer des Geliermittels gemischt werden und, in einer zweiten Stufe, die Makromoleküle des Geliermittels in situ un der Hülse synthetisiert werden.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man für das Monomer der ersten Stufe eine Verbindung wählt, die wenigstens teilweise, ds oxidierbare organische Material bildet.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die erste Stufe außerhalb der Hülse durchführt, die Synthese der Makromoleküle des Geliermittels initiert und dann die Mischung in die Hülse einführt.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man das organische Material und das Monomer derart auswählt, daß die in der ersten Stufe erhaltene Mischung nur eine einzige homogene flüssige Phase umfaßt mit einer dynamischen Viskosität kleiner 1000 Pa.s.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Geliermittel ausgewählt ist unter den durch Kettenpolymerisation erhaltenen thermoplastischen Polymeren.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß das Geliermittel Polyacrylsäure ist.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das oxidierbare organische Material nur Kohlenstoff, Wasserstoff und Sauerstoff enthält.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß das oxidierbare organische Material Saccharose ist.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Dichte der explosiven Zusammensetzung em Ende der zweiten Stufe größer als 1,35 kg/dm3 ist.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß man der Mischung ein Stabilisierungsmittel des Wasserstoffperoxids beimengt.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß man in der ersten Stufe 65 bis 85 Gew.- % einer wässrigen Wasserstoffperoxid-Lösung zu 85 Gew.-% 5 bis 20% Saccharose, 5 bis 20% Acrylsäure und 0,01 bis 0,2% Dipicolinsäure mischt.
12. Explosivpatrone, erhalten nach dem Verfahren gemäß einem der Ansprüch 1 bis 11.
EP87870072A 1986-05-30 1987-05-21 Verfahren zur Herstellung von Explosivpatronen und danach hergestellte Explosivpatronen Expired - Lifetime EP0247990B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87870072T ATE54660T1 (de) 1986-05-30 1987-05-21 Verfahren zur herstellung von explosivpatronen und danach hergestellte explosivpatronen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8607931 1986-05-30
FR8607931A FR2599487B1 (fr) 1986-05-30 1986-05-30 Procede pour la fabrication de cartouches explosives et cartouches explosives obtenues par ledit procede

Publications (2)

Publication Number Publication Date
EP0247990A1 EP0247990A1 (de) 1987-12-02
EP0247990B1 true EP0247990B1 (de) 1990-07-18

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EP87870072A Expired - Lifetime EP0247990B1 (de) 1986-05-30 1987-05-21 Verfahren zur Herstellung von Explosivpatronen und danach hergestellte Explosivpatronen
EP87903228A Pending EP0299979A1 (de) 1986-05-30 1987-05-21 Verfahren zur herstellung von explosivpatronen und danach hergestellte explosivpatronen

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EP87903228A Pending EP0299979A1 (de) 1986-05-30 1987-05-21 Verfahren zur herstellung von explosivpatronen und danach hergestellte explosivpatronen

Country Status (11)

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US (1) US4942800A (de)
EP (2) EP0247990B1 (de)
JP (1) JPH01503057A (de)
AT (1) ATE54660T1 (de)
BR (1) BR8707709A (de)
CA (1) CA1288951C (de)
DE (1) DE3763752D1 (de)
ES (1) ES2017108B3 (de)
FR (1) FR2599487B1 (de)
GR (1) GR3000848T3 (de)
WO (1) WO1987007258A1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5465664A (en) * 1993-05-03 1995-11-14 Fey; Warren O. Fuel and explosive composition with ferric or cupric ion and reducing sugars
US6883413B2 (en) * 1999-07-19 2005-04-26 Henkel Corporation Visible and UV/visible light anaerobic curable primer mix coating
US7146897B1 (en) 1999-07-19 2006-12-12 Henkel Corporation UV/visible light and anaerobic curable composition
US6984273B1 (en) * 1999-07-29 2006-01-10 Aerojet-General Corporation Premixed liquid monopropellant solutions and mixtures
US7344610B2 (en) 2003-01-28 2008-03-18 Hodgdon Powder Company, Inc. Sulfur-free propellant compositions
FR2915479B1 (fr) * 2007-04-26 2009-08-21 Snpe Materiaux Energetiques Sa Gel pyrotechnique ; propergol solide ; chargement pyrotechnique ; procedes d'obtention
JP7646571B2 (ja) * 2019-06-07 2025-03-17 シーエムティーイー ディベロップメント リミテッド スリープタイムが改善された過酸化水素に基づく火薬
EP4086236A1 (de) 2021-05-05 2022-11-09 Hypex Bio Explosives Technology AB Sensibilisierungszusammensetzung für energetische wasserstoffperoxidemulsionen
EP4086238B1 (de) 2021-05-05 2024-01-03 Hypex Bio Explosives Technology AB Zusammensetzung zur bildung eines sprengstoffs mit einer emulsion aus wasserstoffperoxid und einem ölartigen brennstoff
EP4086237B1 (de) 2021-05-05 2025-08-06 Hypex Bio Explosives Technology AB Zusammensetzung zur formung eines wasserstoffperoxidbasierten emulsionssprengstoffs
EP4594274A1 (de) 2022-09-28 2025-08-06 Solvay SA Stabile wasserstoffperoxidgele und emulsionen zur gesteinsfragmentierung

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CH86201A (de) * 1915-03-26 1920-08-02 Chem Fab Weissenstein Ges M B Sprengstoff und Verfahren zu dessen Herstellung.
DE376160C (de) * 1915-03-26 1923-05-25 Josef Nussbaum Dr Verfahren zur Herstellung von Sprengstoffen
US3047441A (en) * 1946-04-08 1962-07-31 American Cyanamid Co Hydrogen peroxide explosives
US2452074A (en) * 1947-01-29 1948-10-26 Buffalo Electro Chem Co Peroxide-glycerol explosive
US3095334A (en) * 1957-11-06 1963-06-25 Atlantic Res Corp Thixotropic monopropellants
US3687746A (en) * 1959-06-16 1972-08-29 Exxon Research Engineering Co Rocket propellant system
US3574011A (en) * 1968-12-16 1971-04-06 Hercules Inc Aqueous slurried explosive of improved pourability containing a polyacrylamide thickener and sodium perchlorate
US3808062A (en) * 1972-12-08 1974-04-30 Nippon Kayaku Kk Liquid explosive compositions of hydrogen peroxide and an aromatic sulforic acid and process for the preparation thereof
US4033264A (en) * 1973-10-05 1977-07-05 Ici Australia Limited Explosive cartridge
FR2577548B1 (fr) * 1985-02-14 1987-03-06 Poudres & Explosifs Ste Nale Procede et installation de fabrication de blocs de propergol par la methode de moulage

Also Published As

Publication number Publication date
FR2599487A1 (fr) 1987-12-04
US4942800A (en) 1990-07-24
EP0247990A1 (de) 1987-12-02
WO1987007258A1 (fr) 1987-12-03
ES2017108B3 (es) 1991-01-01
BR8707709A (pt) 1989-08-15
CA1288951C (fr) 1991-09-17
DE3763752D1 (de) 1990-08-23
EP0299979A1 (de) 1989-01-25
FR2599487B1 (fr) 1988-08-12
ATE54660T1 (de) 1990-08-15
GR3000848T3 (en) 1991-11-15
JPH01503057A (ja) 1989-10-19

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