Classifications

• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
  • C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents

Definitions

• the present invention relates to industrial explosives, and more particularly, to the fields of mining and industry such as civil engineering, quarrying, coal mining, and mining; It is an explosive composition to be used.
• slurry explosives and emulsion explosives. All of these stabilize the structure of the explosive component consisting of the aqueous oxidizing agent solution, combustibles and sensitizers, and the bubbles at a high concentration in the presence of the structure-imparting agent. It is detonated.
• air bubbles are often used to ensure free-flowing entrained air bubbles or chemical foams for their sensitizing function.
• the aqueous gel is composed of guar gum.
• an aqueous oxidizing agent solution and oils as combustibles form a WZO-type emulsion structure in the presence of a surfactant as a structure-imparting agent, and the air bubbles become entrained.
• Others are in the form of glass-resin microbaloons.
• a method for heating to a temperature approximately equal to the foaming temperature of the resin is described below.However, since heating is not usually required in the slurry explosive manufacturing process, resin foaming during the manufacturing process is practical. There was no. Furthermore, even if heating foaming is necessary during the manufacturing process, as will be understood from the description in JP-A-54-92614, a keen sense from the viewpoint of safety is required. After the completion of the heating and foaming at the stage where the agent was not contained, a two-stage system was inevitable to mix with the sensitizer component.
• slurry explosives have a unique gel elasticity, lack plasticity, and when used as an explosive package, the package itself is soft and rigid, making it difficult to handle and inserting into a blast hole.
• the difficulty of the blasting operation due to the difficulty of the blasting operation and the difficulty in molding and processing of the explosives may cause problems such as the difficulty in using them in the form of naked medicine excluding the medicine package. .
• An object of the present invention is to maintain extremely stable performance and good medicinal properties over a long period of time without utilizing the gel structure and the emulsion structure of a conventional hydrous explosive.
• An object of the present invention is to provide an explosive composition comprising only an oxidizing agent, water, and organic hollow microspheres.
• Another object of the present invention is to provide an explosive composition which is safe to handle, has little unexploded residue after blasting, and can reduce the harmfulness of generated gas.
• Still another purpose is low-density area, which was difficult with conventional explosives
• An object of the present invention is to provide a low-explosive explosive having stable explosive performance.
• the present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.
• a liquid phase component containing a substantially viscous component consisting mainly of an oxidizing agent and water is adsorbed and held between the surface of the organic micro air-fuel medium serving as a combustible and Z or the hollow body.
• FIG. 1 shows a microscopic photograph of the fine structure of the explosive composition according to the present invention.
• Fig. 2 (a) is a diagram schematically showing this, and (b) and (c) are diagrams schematically showing explosives and compositions according to the prior art.
• the microstructure of the explosive composition of the present invention can be observed, for example, by a micrograph.
• Typical examples Remind as in Figure 1, further c are I Do to form high density structures oxidizing agent solution 1 is attached to the periphery of the organic hollow microspheres 2 are assembled, this concept
• the explosive composition of the present invention has the structure shown in FIG. 2 (a) in which the hollow organic microstructure 2 forms the center of the structure of the explosive composition.
• the slurry explosive has entrained bubbles 5 and hollow bodies 4 dispersed in the gelled oxidizer and sensitizer phase 3 as shown in Fig. 2 (b).
• Fig. 2 (c) shows an emulsion explosive.
• a hollow body 4 such as rasmaic baloon is dispersed in the aqueous solution 6 of the oxidizing agent thus emulsified. Therefore, a comparison of the explosive composition of the present invention with conventional slurry explosives and emulsion explosives revealed that the form of air bubbles, the form of the oxidizing agent aqueous solution, and the structure of the composition were completely different. Is it. More specifically, the composition of the present invention does not require a gelling agent in conventional slurry explosives, and since air bubbles are mainly stably incorporated into the organic micro hollow body which is a combustible component, the The configuration is completely different. Also, compared to emulsion explosives, the oil phase as a combustible agent, the surfactant for forming the emulsion, and the glass microsphere for retaining bubbles are not required. Are completely different.
• the amount of the foam is practical in view of the stability and explosive performance of the explosive composition. Typically, it was about 2%.
• the gelling agent and wax and the like are obtained when the ratio of the hollow body is substantially increased in the composition substantially composed of the aqueous oxidizing agent solution and the organic fine hollow body. It has been found that a composition having stable detonation performance can be obtained without a surfactant.
• the hollow body also has a role as a combustible
• a combustible such as coal powder and aluminum powder, a sensitizer mainly composed of organic nitrate and / or inorganic nitrate, and the like are used.
• the explosive composition of the present invention has a stable structure with little separation of the liquid phase that mainly constitutes the oxidizing agent component and almost no visible oxidizing agent crystal precipitation. It can cover a wide range of explosive compositions, from those that can be detonated by primers to those that can be detonated by boosters. In particular, for example, when the average thickness of the explosive component layer around the organic micro hollow body is about 20 m or less when observed with a microscope, there is a tendency that a more stable composition is obtained.
• the oxidizing agent used in the present invention those known in the technical field of explosives can be used.
• ammonium salts, alkaline metal salts, and alkaline metal salts of inorganic acids such as nitric acid, chloric acid, and perchloric acid.
• earth metal salts which can be selected alone or in combination.
• ammonium nitrate ammonium nitrate
• the amount of the oxidizing agent is determined according to the design specification of the target explosive, and usually about 50 to 90% by weight based on the total composition.
• the amount of water used in the present invention is usually about 3 to 20% by weight based on the total composition. If this ratio is too low, The solid component of the product may increase, and stable explosive performance may not be exhibited. On the other hand, if it is too large, the detonation property is reduced, which is not preferable.
• the organic micro hollow body used in the present invention is preferably based on an organic polymer compound.
• the organic polymer compound include a phenol resin, an epoxy resin, a urea resin, and an unsaturated polymer. Ester resin, polyimide, maleic acid resin, melamine resin, cellulose, etc., as well as vinyl chloride, vinylidene chloride, atalonitrile, lacquer Linoleic acid, acrylates, acrylates, methacrylic acid, methacrylates, methacrylates, styrene, ethylene Homopolymers such as styrene, propylene, butadiene, and vinyl acetate, or copolymers of two or more, polycarbonate, poly: 5 phr, Riacetal, polyamides, polyethylene oxide, There are polyolefins, etc., each of which can be used alone or in combination of two or more.
• those having thermoplasticity include, for example, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-acrylonitrile resin
• a polyacrylic acid ester copolymer, an acrylonitrile-leuryl acrylate copolymer and the like are more preferable.
• unfoamed vinylidene chloride-acrylonitrile copolymer and methyl methyl acrylate-acrylonitrile copolymer containing low-boiling hydrocarbons Fine particles can be easily turned into fine hollow bodies by heating. Therefore, it can be used by heating and foaming after mixing with explosive components.
• the shape of the organic micro hollow body of the present invention is not particularly limited, such as a spherical shape having a hollow inside and containing gas or air, or a shape having an independent or continuous space inside the hollow body. Hollow spheres are more preferred if the object is to efficiently form a hot spot to initiate the detonation.
• the gas retained in the organic micro hollow body may be air, low-boiling-point hydrocarbon or other flammable gas, or a mixture thereof.
• the preferred particle size of the organic micro hollow body is about 1,000 / m or less, above which the number of hot spots to start detonation is reduced and stable explosion It is difficult to secure More preferably, an organic micro hollow body of 20 to 200 m can obtain a stable explosion performance without lowering the detonation speed.
• the thickness of the film constituting the organic micro hollow body may be any thickness as long as it has enough strength to provide a space for constituting the explosive composition, and is usually 0.1 to 5 ⁇ m.
• the organic polymer compound forming the organic micro hollow body has thermoplasticity, it is required that the organic polymer compound can be heated and foamed in the explosive composition. 0.1 to 2 ⁇ m is used.
• the hollow organic fine body in the explosive composition generally has a bulk density of about 0.01 to 0.3 as measured in a dry state.
• the amount of the organic micro hollow body is usually about 2 to 15% by weight based on the total composition, and the amount of the organic micro hollow body is Therefore, the density of the explosive composition can be adjusted.
• the explosive composition according to the present invention can stably obtain a composition having a density of 0.2 to 1.4 g Z cma by adjusting the degree of foaming of the organic fine hollow body.
• the detonation speed is usually about 1,500-0.5,50 Om / sec.
• One example of a method for producing the explosive composition of the present invention is a method in which a mixture of an oxidizing agent and water is heated to at least a level at which it is almost dissolved, and then uniformly mixed with an organic micro hollow body.
• the method of foaming by heating using the fusible organic microparticles is not particularly limited, but specific examples include: (1) a temperature at which the oxidizing agent, water, and the effervescent organic microparticles can be almost uniformly mixed; After heating to a mixed solution to form a mixed solution, droplets or droplets of the mixed solution are dropped or sprayed onto a heating plate or an atmosphere in which the temperature of the expandable organic microparticles is controlled to a temperature equal to or higher than the temperature at which foaming starts.
• Method by injecting the metal tube to the metal tube controlled at above the temperature to foam the foamable organic fine particles contained in the mixed solution to a mixed solvent of 3 oxidizing agent and water as the foamable organic microparticles A method in which a liquid is placed in a container, the container is heated in an external bath at a temperature not lower than the temperature at which the expandable organic microparticles start foaming, and the expandable organic microparticles contained in the mixed solution are expanded.
• the water and the foamable organic microparticles are uniformly mixed and heated to a temperature at which substantially uniform mixing can be performed to form a mixed solution. Then, the amount that allows for the volume expansion of the mixed solution is calculated using a heat-resistant film tube. After filling the tube with the air and removing the air from the film tube and sealing the tube, the tube is heated in a heating bath or oil bath at a temperature equal to or higher than the temperature at which the expandable organic microparticles start foaming.
• the foaming state can be changed arbitrarily by adjusting the temperature, and the detonator can be detonated by a booster.
• Explosives can be designed according to the purpose, even those that can be detonated by one.
• the unfoamed organic microparticles start foaming at a temperature close to the temperature at which the internal pressure rises due to heating and the organic polymer film begins to soften. It is expanded to a range of 100 times.
• the organic micro hollow body bursts due to excessive heating, It is difficult to obtain explosive performance, so it is better to stay at the temperature before overfoaming.
• the explosive composition according to the present invention takes a form such as a solid form, a powder form, a flake form, a paste form, and the like.
• Laminated paper, plastic film, laminated plastic film, paper cylinder, plastic cylinder, etc. can be used as packaging.
• the explosive composition of the present invention sufficiently satisfies the requirements as an explosive, it may be used as needed to further improve the performance, for example, a lower saturated aliphatic amine. It is also possible to add inorganic nitrate such as organic nitrate or hydrazine nitrate as a sensitizer, and to cope with the use especially in cold regions. In addition, solid combustibles such as coal powder and aluminum powder can be supplemented in consideration of blasted gas in tunnels and underground mines. In addition, an activator such as phosphoric acid ester or a decomposition inhibitor such as urea may be added.
• inorganic nitrate such as organic nitrate or hydrazine nitrate
• solid combustibles such as coal powder and aluminum powder can be supplemented in consideration of blasted gas in tunnels and underground mines.
• an activator such as phosphoric acid ester or a decomposition inhibitor such as urea may be added.
• a detonator explosive or an explosive in a wide density range can be obtained from a booster explosive, which can cover most conventional explosives.
• it is improved in terms of the dead pressure image seen in emulsion explosives, etc., in other words, it is also improved in terms of dead pressure resistance, and consumption is reduced due to the reduction of unexploded residue.
• Site safety can be further improved.
• Manufacture The method does not require advanced manufacturing techniques like conventional slurry explosives and emulsion explosives, and can be manufactured easily and safely.
• the explosive composition according to the present invention is generally used for an electric detonator, an industrial detonator, a detonator with a squib, a detonator with a gas squib, an electromagnetic detonator, a laser detonator, a radio detonator, a squib, and a detonator. It can be detonated using a known method such as a wire, but in some cases it can be detonated using a booster.o-[Example]
• primer detonation property, booster detonation property, detonation velocity, explosive transfer property in steel pipes, and dead pressure performance in sand were measured by the following methods.
• An explosive package packed in advance in a polyethylene laminating paper cylinder or a nylon 66 film tube (package diameter 2 O mm or 30 mm, drug length about 200 mm) was stored in a freezer at about -30 ° C for about 15 hours, then detonated with a No. 6 detonator while adjusting the temperature of the explosive package, and the speed at which the explosive package completely exploded was measured.
• the detonation performance was measured using a product one year after manufacture.
• a steel pipe with one longitudinal side sealed in advance JISG 3 4 5 2 3 2 A; Test explosive filled to an inner diameter of about 36 mm 0 and a length of 350 mm with a booster (No. 6 dynamite 5 Og equipped with a No. 6 detonator) It was initiated, and whether or not it was completely exploded was visually measured based on the state of steel pipe destruction. For the evaluation of aging performance, the detonation performance was measured using a product one year after manufacture.
• An explosive package filled in advance into a polyethylene laminate paper tube or Nylon 66 film tube (package diameter: 20 bandits or 30 thighs, drug length: about 300 thighs)
• a detonator was detonated by the No. 6 primer, and the detonation velocity was measured by the ion gap method.
• the detonation performance was measured using a product one year after manufacture. (Measurement of detonation velocity of steel tube filling)
• a booster No. 2 double dynamite 50 g equipped with No. 6 detonator
• an explosive previously filled in a steel pipe (JISG 345 32 32 A; inside diameter: about 36 thigh ⁇ , length: 350 mm)
• JISG 345 32 32 A inside diameter: about 36 thigh ⁇ , length: 350 mm
• the detonation velocity was measured by the ion gap method.
• the detonation performance was measured using a product one year after manufacture.
• An explosive package filled in advance into a polyethylene laminating paper cylinder or a nylon 66 film tube (package diameter: about 20 ⁇ thigh, drug length: about 150 thigh) is filled with steel pipe ( JISG 3 4 5 2 4 0 A; inner diameter about 41.6 ⁇ , pipe length 30000 0) Approximately 20 pipes are charged side by side so that they do not deform in the longitudinal direction, and then the end The explosive package was detonated with a No. 6 primer, and the length of the destroyed steel pipe was measured. For the evaluation of aging performance, the detonation performance was measured using a product one year after manufacture.
• the above explosive composition was previously sealed on one side in the longitudinal direction with a steel pipe (JISG3455232A; The inner diameter was about 36 mm ⁇ and the length was 350 mm), and when it was detonated with a booster (50 g of No. 2 double dynamite equipped with a No. 6 detonator), it completely detonated. . Furthermore, one year after the manufacture, the same test was performed, and the same performance was demonstrated.
• This explosive composition is divided into small pieces and filled with 2 Omm0 and 3 Omm0 polyethylene laminate paper (approximately 30 g to 40 g each) to form an explosive package, which has explosive performance.
• the density of the 30 band ⁇ explosives package is 0.35 g cnf, which can be detonated with a No. 6 detonator at a drug temperature of ⁇ 10 ° C, and a drug temperature of 5 ° C.
• Unfoamed organic microparticles 3 1-200 g The unfoamed organic microparticles 1 are the same as those used in Example 2, and the unfoamed organic microparticles 2 are acrylonitrile and methinomethacrylate acrylate copolymer ( The non-expanded organic microparticles 3 are a copolymer of acrylonitrile and acrylate (Matsumoto Oil & Fats Co., Ltd.). ( ⁇ ) Trade name: Micropearl F — 50).
• the explosive packaging densities of the above three explosive compositions are 20 ⁇ 3, 30 thigh ⁇ , and the explosive packaging densities are 0.23, 0.30, and 0.40, respectively.
• the ⁇ explosive package can be detonated with the # 6 detonator _, and the explosion velocity at 5 ° C at the temperature of 190 ° C is 190 ° M, 200 ° Z, and 220 ° Z. there were.
• a 2 O mm 0 explosive package was charged to a steel pipe 3 mm long with an inner diameter of 41.6 ⁇ , matching the length of the explosive package to a length of 3 m, and one side was detonated with a No. 6 primer. At that time, all the explosives charged were completely exploded, and the length of the damaged steel pipe was 3 m. Furthermore, one year after the manufacture, the same test was performed, and the same performance was shown.
• the explosive composition was subdivided into explosive packages, and the explosive performance was examined.
• the density of the 2 O mm 0 explosive package is 0.45 g_cnf, and it can be detonated with a No. 6 detonator at a drug temperature of 5 ° C, and the explosion velocity at a drug temperature of 5 ° C is 1900 m Z s.
• the explosive package was charged to a steel pipe with an inner diameter of 41.6 ⁇ , 3 m in length, matching the length of the above-mentioned explosive package to a length of 3 m. All explosives charged were completely exploded and the length of the destroyed steel pipe was 3 m.
• the two 30 mm ⁇ explosive packets were buried in parallel in a 80 cm sand at a distance of 15 cm, with a detonating No. 6 detonator on one side and 10 ms on the other. After performing the dead-pressure test in sand five times with the step-up electric detonator attached and simultaneously detonating, all exploded. Furthermore, one year after the production, the same test was performed, and the same performance was shown.
• Ammonia nitrate 15 24 g, water 28 86 g and unfoamed Organic microparticles 190 g of metal Place the mixture in a vessel and stir and mix in an external bath at about 90 ° C. to obtain a mixture at about 70 to 80 ° C. Heat the mixture to about 90 to 110 Pressure injection from one opening of a metal tube (the inner wall of the tube is made of Teflon), and a stream-like density of 1.35 g Z crf from the other opening. An explosive composition was obtained.
• the above explosive composition is filled in advance in a steel pipe (JISG345232A; inner diameter of about 36 mm0, length of 350 mm) whose one side in the longitudinal direction is sealed, and a booster (No. 6 primer)
• a steel pipe JISG345232A; inner diameter of about 36 mm0, length of 350 mm
• a booster No. 6 primer
• the unfoamed organic microparticles 2 are acrylonitrile and methionolemethacrylyl acrylate copolymer (product name of Expansel Corporation; 053 WU).
• the unfoamed organic microparticles 3 are a copolymer of acrylonitrile and acrylate (Matsumoto Yushi Co., Ltd .; Micropearl F—50).
• the densities of the above three explosive compositions were 1.38 g cm and 1.30 g / cm ⁇ 1.35 g Z cm 3 , respectively.
• Each explosive composition described above is filled in advance in a steel pipe (JISG345232A; inner diameter of about 36 mm ⁇ , length of 350 mm) with one end in the longitudinal direction sealed, and a booster ( At the time of detonation at Unit 2 dynamite (50 g) equipped with a Unit 6 detonator, each detonated completely, and the detonation speed at this time was 5500 m / .4 respectively. The values were 600 mZs and 5100 m / s. In addition, the same test was performed one year after manufacture, and the same performance was demonstrated.
• a mixture of ammonium nitrate (105 g), water (170 g), sodium nitrate (300 g) and monomethylamine nitrate (360 g) was heated and adjusted to about 70 ° C. Make a mixture.
• an organic micro hollow body (exoncell 551 DE, which is a copolymer of vinylidene chloride-acrylonitrile-methacrylic acid ester; trade name of Chemanod Corporation) 120 g
• the mixture is poured into a polyethylene bag, and after closing the opening of the bag, a force is applied from the side of the bag to mix after stirring for about 10 minutes, followed by cooling.
• An explosive composition was obtained.
• This explosive composition is divided into small pieces, filled with about 30 g to 40 g of 20-band marshal and 3 Omm0 polyethylene laminate paper cylinders to form explosive packs. Examined.
• the density of the above-mentioned explosive package is 0.35 g / cnf, and it can be detonated with a No. 6 detonator at a temperature of 20 ° C, and a temperature of 5 ° C
• the explosion speed at was 2300 ms.
• the above-mentioned explosive package of 20 marshal ⁇ was charged to a steel pipe with an inner diameter of 41.6 marauders ⁇ , 3 m in length according to the length of the above-mentioned explosive bag, 3 m.
• Example 13 In the same manner as in Example 13, the following explosive compositions were produced, and the explosive performance was examined.
• the 30 explosives in the above two explosive compositions had a density of 0.995 and 1.02, respectively, and were to be detonated with a No. 6 detonator at a chemical temperature of 0 ° C.
• the explosion speed at 5 ° C is 3 2 0 Om / s and 370 OmZs. Further, one year after the production, the same test was performed, and the same performance was shown.
• This explosive composition is subdivided and filled into polyoxyethylene laminating paper cylinders of 2 Omm0 and 3 Omm0 in approx. 30 g to 4 Og each to make explosives, and the explosive performance is improved.
• the density of the above-mentioned 30 recitation 0 explosive package is 0.80 g Z cm 3 , which can be detonated with a No. 6 detonator at a temperature of 15 ° C, and an explosion at a temperature of 5 ° C.
• the speed was 370 OmZs.
• the above-mentioned 20 thigh ⁇ explosive package was charged into a 3 m long steel pipe with an inner diameter of 41.6 mm ⁇ .
• Example 16 In the same manner as in Example 16, the following explosive compositions were produced, and the explosive performance was examined.
• the unfoamed organic microparticles 1 were the same as those used in Example 16, and the unfoamed organic microparticles 2 were used for both acrylonitrile and methacrylonitrile.
• the polymer is a polymer (product name of Expansell Co., Ltd .; 053 WU), and the unfoamed organic microparticles 3 are a copolymer of acrylonitrile and acrylate (Matsumoto Yushi ( ⁇ ) Trade name: Micropearl F — 50) 20 thigh ⁇ , 30 mm ⁇ explosive package of the above three explosive compositions
• the densities are 0.20, 0.30, and 0.45, respectively, and a 30-degree marauding ⁇ explosive package with a drug temperature of 25 ° C can be detonated with a No.
• the explosion velocity at 5 ° C was 1,900 ms, 2,300 m / s, and 2,500 mZs.
• 20 marshals 0 explosives were charged with a 31.6 mm long steel tube with an inner diameter of 41.6 mm, and the explosives were charged to match the length of 3 m. At that time, all the explosives charged were completely exploded, and the length of the broken steel pipe was 3 m. Furthermore, one year after the production, the same test was performed, and the same performance was demonstrated.
• the explosive composition according to the present invention has a structure in which an oxidizing agent, water or a sensitizing agent, an oxidizing agent, and a component composed of water are continuously held on the surface and Z or gap of an adjacent microsphere.
• the thickening agent which is indispensable for the quality preservation of the conventional wet explosive composition, is not substantially required, and the quality can be maintained for a long time. This made it possible to commercialize low-density products, which had been considered difficult. And, by lowering the specific gravity, noise and vibration at the time of blasting can be significantly reduced.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Manufacturing Of Micro-Capsules (AREA)
• Drilling And Exploitation, And Mining Machines And Methods (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)
• Compositions Of Macromolecular Compounds (AREA)
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• Disintegrating Or Milling (AREA)

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• 1993
  • 1993-06-15 KR KR1019940700435A patent/KR970004708B1/ko not_active Expired - Fee Related
  • 1993-06-15 DE DE69329271T patent/DE69329271T2/de not_active Expired - Fee Related
  • 1993-06-15 CA CA002115660A patent/CA2115660C/en not_active Expired - Fee Related
  • 1993-06-15 ES ES93913524T patent/ES2148232T3/es not_active Expired - Lifetime
  • 1993-06-15 AU AU43562/93A patent/AU657629B2/en not_active Ceased
  • 1993-06-15 EP EP93913524A patent/EP0607449B1/en not_active Expired - Lifetime
  • 1993-06-15 WO PCT/JP1993/000802 patent/WO1993025500A1/ja active IP Right Grant
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