KR970004708B1 - Explosive composition and production thereof - Google Patents

Abstract

None.

Description

[Name of invention]

Explosive composition and preparation method thereof

[Brief Description of Drawings]

1 is a micrograph of the microstructure of the explosive composition of the present invention.

2 (a) is a schematic diagram of the above structure, and (b) and (c) are schematic diagrams of a conventional powder composition.

Detailed description of the invention

[Technical Field]

The present invention relates to industrial explosives. More specifically, the mining industry, such as civil engineering construction, quarrying, coal mining, mining; It relates to explosive compositions that can be used for various destructive operations, such as blasting, crushing, excavating, etc. in the agricultural and forestry fields, including drainage, irrigation, clearing and logging.

[Background]

The main major water explosives are slurry explosives and emulsion explosives. In the explosives, active explosive components and bubbles containing aqueous oxidizing agent, flammables and sensitizers maintain the structure at high concentrations and stably in the presence of a structurant, and the explosives are usually detonated by a primer. In slurry explosives, air bubbles or chemical bubbles are typically present in the explosive composition to perform a preliminary function, and guar rubber is used as a structuring agent to form an aqueous gel. In emulsion explosives, oils acting as oxidizing agents and flammables are combined to form W / O emulsions in the presence of surfactants acting as structurants. The bubbles in the explosive contain glass or resinous microballoons in addition to the air bubbles.

The use of hollow single-cell thermoplastic thermoplastic microparticles for improving the detonation or density control of explosives is described in US Patent No. 3,773,573 and Japanese Patent Application No. 54-92614 for slurry explosives and for emulsion explosives. Are described in Japanese Patent Application No. 56-100192 and Japanese Patent Application No. 59-78994. U.S. Patent No. 3,773,573 discloses the use of hollow mono-bubble thermoplastic microparticles in a wide variety of explosives, including slurry explosives. The explosive composition is heated in the presence to a temperature substantially equal to the foaming temperature of the thermoplastic microparticles. However, heating in the production of slurry explosives is usually unnecessary, so resin foaming during the manufacturing process is practically of little importance. In addition, even when foaming by heating is necessary during the manufacturing process, as the understanding of the description of Japanese Patent Application No. 54-92614, the pre-heating agent is finished after the heating foaming in the step of not adding the pre-treatment agent in terms of stability. There is no choice but to employ a two-step method of mixing.

The water-containing explosives do not contain highly sensitive components such as nitroglycerin in dynamite and require minute adjustment of the explosives and the gel or emulsion structure to maintain detonation, and such adjustments require a high level of skill. do. Therefore, in the production of water-containing explosives, explosive detonation is affected by the quality and aspect of the explosive component through the process of forming the structure, so much time and effort is required for quality control of raw materials and / or management of explosive manufacturing conditions. . As a result, serious problems such as poor quality explosives are frequently manufactured, which are not resistant to storage and explosive performance deteriorates significantly over time. In particular, when the amount of the chemical bubble or the foaming agent used in the density composition of the explosive composition is increased, not only it becomes more difficult to obtain the desired initial explosive performance, but also the problem of lowering the explosive performance over time becomes more serious.

In addition, slurry explosives have a characteristic gel elasticity and lack of plasticity, and when they are filled into a cartridge, the medicine itself is soft and dull, difficult to handle, and difficulty in inserting the medicine into the blasting hole. Therefore, the work efficiency of the blasting work is reduced. Further, due to the poor moldability of the explosives of the above kind, it is difficult to use the explosives in the form as it is without using the medicine.

In the case of emulsion explosives, sudden pressure on them can destroy the emulsion structure and cause the explosive function to be lost (this phenomenon is called dead pressure). Its post-processing problem is difficult.

[Initiation of invention]

An object of the present invention consists of an explosive composition consisting essentially of an oxidizing agent, water and organic microspheres, having extremely stabilized explosive properties and long-term weakness without the gel or emulsion structure found in conventional hydrous explosives. To provide.

It is another object of the present invention to provide an explosive composition which is low in volatile residue after blasting, can reduce the harmfulness of generated gas and can be handled safely.

It is still another object of the present invention to provide a low explosion rate explosive having a stable explosive performance even in a low density region, which is difficult to obtain with a conventional explosive.

The present inventors have made a thorough study to overcome the above problems of conventional water explosives and have completed the present invention.

Accordingly, the present invention is a novel explosive composition characterized in that a liquid component composed mainly of an oxidizing agent and water, wherein the liquid component substantially free of the viscous component is adsorbed and retained between the organic microhollow body surface and / or the hollow body as the combustor component. To provide.

Best Mode for Carrying Out the Invention

The microstructure of the explosive composition of the present invention can be confirmed, for example, from micrographs.

As shown in FIG. 1, which is a representative micrograph showing the structure of the explosive composition of the present invention, the composition comprises an organic micro hollow body 2 having a high concentration of an oxidizing agent aqueous solution 1 attached to the periphery of the organic micro hollow body 2. It is a collection of microparticles | fine-particles each containing. The conceptual diagram of the structure is shown in FIG. 2 (a), from which it can be seen that the organic micro-hollow bodies 2 constitute the structural center of the composition in the explosive composition of the present invention. This is in contrast to the composition structure of conventional slurry explosives in which air bubbles 5 and hollow bodies 4 are dispersed in the gelling oxidant / sensitizer phase 3 as shown in FIG. 2 (b). In the emulsion explosive, as shown in FIG. 2 (c), the hollow body 4 such as the glass microballoon is dispersed in the emulsified oxidant solution phase 6. Therefore, it is apparent that the explosive composition of the present invention is very different from the conventional slurry explosives and emulsion explosives in the form of bubbles, the form of an oxidizing agent aqueous solution and the structure of the composition. More specifically, the composition of the present invention does not require the gelling agent required for conventional slurry explosives and, unlike the conventional slurry explosives, has a structure in which bubbles are mixed in a stable form in an organic micro-hollow body which is a combustible component. . In addition, the compositions of the present invention as compared to emulsion explosives do not require an oil phase as a flammable component, a surfactant for emulsion formation and a free microbalun to hold bubbles, which is in stark contrast to conventional emulsion wilderness.

It is known to use hollow monofoam thermoplastic microparticles in conventional slurry explosives, but the amount of bubbles has been practically limited to about 2% or less in view of the storage stability and explosive performance of the explosive composition. In the present invention, surprisingly, by increasing the proportion of the organic microhollows in the composition consisting essentially of the oxidizing agent solution and the organic microhollowers, an explosive composition having stable explosive performance even when no gelling agent, wax or surfactant is used is obtained. Can be obtained. In addition, the micro-hollow bodies can simultaneously act as a combustor component, so that an explosive having excellent performance can be provided without necessarily using a flame retardant composed mainly of a combustor such as carbon or aluminum powder and an organic nitrate and / or an inorganic nitrate. Can be.

In the explosive composition of the present invention, the separation of the liquid phase constituting mainly the oxidant component does not occur, and crystal precipitation of the oxidant is not visually observed, and a stable structure can be maintained. It is very noteworthy that it can be used in various explosives, from to explosives.

It is noted that the composition may be further stabilized, especially when the average thickness of the explosive compound layer near the organic microhollows is about 20 μm or less when viewed under a microscope.

The oxidant used in the present invention may be selected from those known in the art of explosives. Examples of such oxidants include ammonium salts, alkali metal salts and alkaline earth metal salts of inorganic acids such as nitric acid, chloric acid, perchloric acid, and the like, and the oxidants can be used alone or in combination. Of these oxidizing agents, ammonium nitrate is particularly recommended because of its high solubility in water and its availability. The oxidant content in the composition of the present invention is determined according to the specification of the explosive to be prepared, but is usually in the range of 50 to 90% by weight based on the whole composition. If this oxidant content is less than the above-mentioned range, the balance value between the coral and the combustor is inclined toward the negative toward oxygen, thereby increasing the hazard of the gas released after the blasting. On the other hand, if the content exceeds the above range, the blasting reactivity is lowered, detonation propagation is inhibited.

The water content in the composition of the present invention is typically in the range of 3 to 20% by weight, based on the total composition. When the water content is less than the above range, the solid content of the explosive composition is increased so that its stable explosive performance is not exerted, whereas when the water content is too high, the detonation is deteriorated.

The organic micro hollow bodies used in the present invention are preferably produced by using an organic high molecular compound as a base material. Examples of the organic polymer compound usable in the present invention include waste resin, epoxy resin, urea resin, unsaturated polyester resin, polyimide, maleic acid resin, melamine resin, cellulose, vinyl chloride, vinylidene chloride, acrylonitrile, acrylic acid, and acrylic acid. Salts, acrylic acid esters, methacrylic acid, methacrylic acid salts, methacrylic acid esters, homopolymers or copolymers such as styrene, ethylene, propylene, butadiene, vinyl acetate, polycarbonates, polysulfones, polyacetals, Polyamides, polyethylene oxide, polyphenylene oxide and the like. The compounds may be used alone or in combination. Among the organic polymer compounds, an organic polymer compound having thermoplasticity such as vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer, acrylonitrile-acrylic acid ester copolymer, and the like is the present invention. Particularly preferred for use in carrying out the process of. The unfoamed fine particles of the vinylidene chloride-acrylonitrile copolymer or methylmethacrylate-acrylonitrile copolymer mixed with the low boiling hydrocarbon are easily prepared into micro hollow bodies by heating, and then mixed with the explosive composition. It is noted that it can be used in the form of a heating announcement.

The organic micro hollow bodies used in the composition of the present invention are not particularly limited; Although it may be a spherical hollow containing gas or air inside the cavity or a hollow body having an independent or continuous space therein, a spherical hollow body is preferable in order to efficiently form a hot spot when the explosive starts to detonate. . The gas stored in the organic spherical hollow body may be air, low boiling hydrocarbons, other flammable gases, or mixtures thereof. The preferred particle size of the organic micro hollow body is about 1000 μm in diameter or less. When the particle size exceeds the above range, the number of hot spots for initiation of explosion decreases, making it difficult to obtain stable explosiveness. More preferably, the organic micro hollow body has a particle diameter of 20 to 200 µm, which is a particle diameter capable of providing stable explosive performance without lowering the detonation speed. The film thickness of the organic micro hollow body is not important; The film may be appropriately selected within a range having sufficient strength to provide space for constituting the explosive composition. Usually the film thickness is 0.1-5 micrometers. When the organic high molecular compound forming the organic micro hollow bodies has thermoplasticity, they are required to be heat-foamable in the explosive composition, and thus, micro hollow bodies having a film thickness of about 0.1 to 2 m are used. The organic micro hollow bodies in the explosive composition of the present invention typically have a bulk density of about 0.01 to 0.3 as measured in the dry state. The amount of organic micro hollow bodies in the composition is typically about 2-15% by weight, based on the total composition. The density of the explosive composition can be controlled by the amount of organic microhollows. In general, when the ratio of the organic microhollows in the composition is too low, the explosion efficiency is lowered and it is difficult to maintain the stabilized explosion performance for a long time. On the other hand, when the ratio of the said organic micro hollow body is too high, there exists a tendency for explosion force to fall and blasting reliability is not obtained.

According to the invention, it is possible to obtain explosive compositions having a density of 0.2 to 1.4 g / cm ³ by a stabilized method of adjusting the degree of foaming of the organic microhollows. The detonation velocity of the explosive composition of the present invention is usually about 1,500 to 5,500 m / s.

In the preparation method of the explosive composition of the present invention, the mixture of the oxidizing agent and water is heated to the extent that the mixture is substantially dissolved, and thereafter, the organic micro hollow bodies are uniformly mixed therein.

The method of heat-expanding the organic microhollows is not specified in the present invention, but the following methods may be mentioned as preferred examples:

① The oxidizing agent, water, and the expandable organic microparticles are heated to a temperature at which the materials are mixed substantially uniformly to form a mixed solution, which is then adjusted to a temperature at or above which the microparticles begin to foam. Dropping or spraying on a heating plate or in the air to foam the organic fine particles contained in the mixed solution;

(2) heat the oxidant, water and effervescent organic microparticles to a temperature at which the materials are mixed substantially uniformly to form a mixed solution, and then heat the solution to a temperature at or above which the microparticles begin to foam; Injecting into the metal tube to foam the organic fine particles contained in the mixed solution;

(3) putting a mixed solution of an oxidizing agent, water, and expandable organic microparticles into a container, and heating the container in an external bath at a temperature at which foaming of the microparticles occurs, thereby foaming the organic microparticles contained in the mixed solution;

④ Uniformly mix the oxidizing agent, water, and expandable organic microparticles and heat it to a temperature at which the materials are mixed substantially uniformly to produce a mixed solution, and then heat the predetermined amount of the solution determined in consideration of volume expansion (heating). After filling into a film tube and removing the air from the film tube and closing it, it is placed in a heating bath or an oil bath heated to a temperature above the temperature at which the microparticles begin to foam and the organic rice contained in the mixed solution. Foaming small particles;

(5) Heat the mixture of oxidant and water to dissolve most of the solid salts to prepare a highly concentrated salt solution, and then heat the solution to a temperature above the temperature at which foaming of the expandable organic microparticles occurs, and mix the organic microparticles with the solution. How to.

In the above methods, when water is evaporated from the composition, excess water is added to determine the amount of water that can be evaporated to obtain the desired explosive composition. In addition, according to the explosive composition preparation method of the present invention, it is possible to arbitrarily change the foaming conditions by adjusting the temperature, and various explosives ranging from the kind to be detonated by the buster to the kind to be detonated by one primer. Can be obtained. The unfoamed organic microparticles increase in internal pressure by heating, and start to foam when heated near the temperature at which the organic polymer film starts to soften, and expand in a volume ratio of about 20 to 100 times. However, when the organic micro hollow bodies are ruptured by heating more than necessary, they are no longer functioning as active ingredients of explosives, so it is preferable to stop heating before reaching a temperature at which overfoaming can occur.

The explosive composition of the present invention can be prepared in various forms such as solid form, powder form, flake, paste and the like, and is selected from paper, laminate paper, plastic film, laminated plastic according to the composition form, its characteristics, purpose of use and other factors. It can be packaged in known packaging materials such as films, paper tubes, plastic tubes and the like, and can therefore be marketed in the form of packages.

Although the explosive composition of the present invention can sufficiently satisfy the quality requirements for explosives, in order to further improve the explosive performance, organic nitrates such as lower saturated aliphatic amines or inorganic nitrates such as nitrate hydrazine are added as a preservative in cold areas. It can correspond to the use of. In addition, in consideration of the gas discharge after the blast in a tunnel or underground light, it is possible to supplementally add solid combustibles such as coal powder or aluminum powder. Other suitable ingredients, for example activators such as phosphate esters, degradation inhibitors such as urea and the like, can be added safely as needed.

By using the explosive composition of the present invention and a method for producing the same, a wide range of explosives and dead pressure densities ranging from booster explosives to primer explosives can be obtained. The present invention can be applied to the formulation of almost all kinds of conventional explosives. In addition, the explosive composition of the present invention has been improved in the dead-pressure phenomenon appearing in the emulsion explosive, that is, improved in terms of the internal pressure resistance performance, the workplace safety can be further improved due to the reduction of the unintentional residual mixture. The production method of the present invention does not require the advanced manufacturing techniques such as those required for the manufacture of conventional slurry explosives and emulsion explosives, and can produce explosives of the desired type simply and safely.

The explosive composition of the present invention is usually an electric primer, an industrial primer, a primer attached to a gas pipe, a primer attached to a gas conduit, an electromagnetic bomber, a laser bomber, a radio detonator, a wire detonator, a wire detonator, etc. It can be initiated by using various known methods. In some cases, the explosive composition can be initiated by using a buster.

Example

Although the present invention is described in more detail with reference to examples, the examples are for illustrative purposes only and should not be understood as limiting the scope of the invention. In addition, tube explosion, boot ride explosion, detonation velocity, steel tube chemical resistance and sand pressure performance in sand are measured by the following method.

Determination of Primer Atrophy

The explosives are packed in polyethylene laminate paper tubes or nylon 66 film tubes (medicine diameter: 20 mm or 30 mm; drug length: about 200 mm) and stored in a freezer at about -30 ° C for about 15 hours. Next, the temperature-controlled explosives are detonated with a # 6 primer, and the temperature at which the explosives explode completely is measured. To assess quality integrity, the same detonation performance is measured for the same explosives stored for one year after manufacture.

Busta Detonation Measurement

Test explosives filled in steel pipes (JIS G 3452 32A; inner diameter: 36mm, length: 350mm) sealed in the longitudinal direction by Busta (Enoki Dynamite 50g on # 2 with # 6 primer attached) Detonate and visually observe the burst state of the steel pipe to determine whether a complete explosion has occurred. To assess quality integrity, the same detonation performance is measured for the same explosive stored for one year after manufacture.

Measurement of detonation speed of medicine packing

The explosives (medicine diameter: 20 mm or 30 mm; drug length: 300 mm) filled in a polyethylene laminate paper tube or nylon 66 film tube are detonated by # 6 primer, and the detonation velocity is measured by the ion gap method. To assess quality integrity, detonation performance is measured for the same explosive stored for one year after manufacture.

Measurement of detonation speed of steel pipe filling

An explosive filled in a steel pipe (JIS G 3452 32A; inner diameter: about 36 mm Φ; length: 350 mm) is detonated by a booster (50 g of # 2 enoki dynamite with a # 6 primer) and the detonation velocity is measured by an ion gap method. . To assess quality integrity, the same detonation performance is measured for the same explosive stored for one year after manufacture.

Full width test by medicine in steel pipe

Fill the explosives into a polyethylene laminate paper tube or nylon 66 film tube (medicine diameter: approx. 200 mmΦ; drug length: 150 mm), and apply about 20 chemicals to the steel pipes (JIS G 3452 40A; internal diameter: about 41.6) to prevent longitudinal deformation. mm; length: 3,000 mm) Next, the explosives of the distal end are detonated with a # 6 primer, and the width of the rupture portion of the steel pipe is measured to determine the total width of the steel pipe. To assess quality integrity, the same detonation performance is measured for the same explosives stored for one year after manufacture.

Measurement of Internal Pressure Performance in Sand

The explosives are filled into polyethylene laminate paper tubes or nylon 66 film tubes (medicine diameter: 30 mm; drug length: about 150 mm). Two medicines are prepared. One medicine is equipped with a quick # 6 electric primer and the other medicine is equipped with a single 10 ms electric primer. Arranged in parallel and buried 80 cm deep in the sand. Explosives are explosive by directly connecting two electric primers and electric shock. Repeat this test five times and examine whether the explosives equipped with a single 10 ms electric primer are stiff and measure the penetration performance in sand.

To assess quality integrity, the same tests are performed on the same explosives stored for one year after manufacture.

Example 1

805 g ammonium nitrate and 135 g water are mixed and heated to about 90 ° C. On the other hand, organic micro hollow bodies (EXPANCEL) 60 g of 551DE (vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer), made by Experience AB) is weighed and placed in a polyethylene bag. The mixture is then introduced into a polyethylene bag. Next, the bag material is stirred and mixed for about 10 minutes by closing the opening of the bag and applying a force to the side of the bag, followed by cooling with water to obtain an explosive composition having an explosive density of 0.40 g / cm ³ . This explosive composition is filled into a closed steel pipe (JIS G 3452 32A; inner diameter: about 36 mm; length: 350 mm) at one end in the longitudinal direction and detonated with a booster (50 g of # 2 enoki dynamite with a # 6 primer). Completely exploded. Similar results are obtained when the same test is performed with the same explosive composition stored for 1 year after preparation.

Example 2

1608 g of ammonium nitrate, 310 g of water, and 82 g of unfoamed organic microparticles (MATSUMOTO MICROSPHERE F-30, manufactured by vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer) manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. Stirring and mixing in an external bath at 80 ° C yields a mixture of about 70 ° C. In addition, a metal plate heated to about 100 ~ 150 ℃ is produced. The mixture is added dropwise in small portions onto the surface of the metal plate to obtain a granulated explosive composition in a very short time.

The explosive composition is divided into small portions and filled into polyethylene laminate paper tubes having diameters of 20 mm and 30 mm to prepare explosives containing 30 to 40 g of the composition, respectively, and then the detonation performance is investigated. The density of the 30 mm-diameter explosives is 0.35 g / cm ³ , which can be detonated by a # 6 primer at −10 ° C. At a temperature of 5 ° C., the detonation velocity is 1,900 m / s. A 2 mm-diameter explosive is loaded into a steel pipe 41.6 mm in diameter and 3 m long and detonated from one end by a # 6 primer. As a result, all explosives were stiffened and the length of the ruptured steel pipe portion was 3 m. In addition, the two 30mm diameter explosives were buried in the sand parallel to each other at a distance of 15 cm, one explosive was equipped with a quick # 6 primer, and the other explosive was equipped with a single 10 ms electric primer, and then electrocuted by the primer. Detonate and perform dead-pressure test in sand. This test is carried out five times and two explosives are blunted with each test. Similar results are obtained when the same test is performed with the same explosives stored for one year after manufacture. On the other hand, no explosives can be detonated by the # 6 primer at temperatures below 0 ° C. when the same test is carried out using conventional slurry and emulsion explosives prepared by conventional methods and suitably adjusted in explosive density. Also, in the steel pipe explosive test, the explosion is stopped at 1.2m near the end of the explosion and the length of the pipe rupture area is about 0.8 ~ 1.6m. In the sand pressure test, two explosives equipped with a single 10 ms electric primer were not stiff and recovered as incomplete explosives. When the same test was performed using the same explosives stored for one year after manufacture, they all found that the detonation performance was so low that they could not be detonated by the # 6 primer.

Examples 3-5

In the same manner as in Example 1, the following explosive composition was prepared to investigate explosive performance.

Unfoamed organic microparticles 1 are the same as those used in Example 2. Unfoamed organic microparticles 2 is made of acrylonitrile-methyl methacrylate copolymer (Expancel AB 053WU) and unfoamed organic microparticles 3 is acrylonitrile-acrylic acid ester copolymer (MATSUMOTO MICROSPHERE F-30, Matsumoto Yusi -Made by Seiyaku Co., Ltd.).

The 20 mm-diameter and 30 mm-diameter explosive densities of the three explosive compositions are 0.23, 0.30 and 0.40, respectively. 30 mm-diameter explosives at −10 ° C. may be detonated by a # 6 primer. The explosive velocities of the three explosive compositions at a temperature of 5 ° C. are 1,900 m / s, 2,000 m / s and 2,200 m / s, respectively. When a 20mm-diameter explosive is secured in a steel pipe of 41.6mm in inner diameter and 3m in length and detonated from one end, all explosives are stiffened and the rupture portion of the steel pipe is 3m in length. Similar results are obtained when the same test is performed with the same explosive composition stored for one year after preparation. On the other hand, no explosives can be detonated below 0 ° C. when the same test is carried out using conventional slurry and emulsion explosives prepared by conventional methods and with appropriately adjusted explosive density. In addition, in the full width test of the explosives within the steel pipe, the explosion is stopped at 0.8 ~ 1.6m near the detonated end, and the length of the rupture portion of the steel pipe is about 0.8 ~ 1.6m. The same test is further performed with the same explosive composition stored for 1 year after preparation, but all compositions are degraded to the extent that they cannot be detonated by the # 6 primer.

Example 6

1608 g of ammonium nitrate, 310 g of water, and 82 g of unfoamed organic microparticles (MATSUMOTO MICROSPHERE F-30, manufactured by vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer) manufactured by Matsumoto Yusi-Seiyaku Co., Ltd. Stirring and mixing in a water bath at about 70 ° C yields a mixture at about 70 ° C. The mixture is injected from one end of a 20 mm-diameter metal tube (inner wall is Teflon coated) heated to about 100 to 150 ° C., and a continuous foamed explosive composition is obtained from the other end.

Dividing the explosive composition obtained as described above little by little to prepare the explosive cloth by the above-described method and to measure the explosion performance. The density of 20mmΦ explosives is 0.45 / cm This explosive can be detonated by a # 6 primer at a temperature of -5 ° C. The detonation velocity at 5 ° C. is 1,900 m / s. When the explosives cut into 3m lengths are secured in steel pipes of 41.6mm in diameter and 3m in length and detonated from one end by a # 6 primer, all explosives are slack and the length of the rupture portion of the steel pipe is 3m. In addition, the two 30mm Φ explosives are buried at a depth of 80 cm in the sand parallel to each other at 15 cm intervals, one of which is fitted with a quick # 6 primer and the other with a single 10 ms electric primer, which detonates both primers at the same time. The sand pressure test is then performed. Perform this test five times. Each explosive gun is stiffened every test. Similar results are obtained when the same test is performed with the same explosive composition stored for one year after preparation.

Example 7

1,524 g of ammonium nitrate, 286 g of water, and 190 g of unfoamed organic microparticles (MATSUMOTO MICROSPHERE F-30, vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer, manufactured by Matsumoto Yusi-Seiyaku Co., Ltd) were placed in a metal container. Inject and stir and mix in an external bath of about 90 ° C. to obtain a mixture of about 70 ° C. to 80 ° C. The mixture is injected from one end opening of a 20 mmΦ metal tube (inner wall is Teflon coated) heated to about 90-110 ° C., with a density of 1.35 g / cm from the opening of the other end. A phosphorous explosive composition is obtained.

When the explosive composition is introduced into a closed steel pipe (JIS G 3452 32A; inner diameter: 36mm; length: 350mm) in one longitudinal direction and detonated by busbust (50g of anodized dynamite in # 2 equipped with # 6 primer) , The composition is narrow and the detonation speed is 5460 m / s. Similar results are obtained when the same test is performed with the same explosive composition stored for 1 year after preparation.

Examples 8-10

The method of Example 7 was followed to produce the following explosive composition and to measure the explosive performance.

Unfoamed organic microparticles 1 are the same as those used in Example 1, and unfoamed organic microparticles 2 are made of acrylonitrile-methyl methacrylate copolymer (O53WU Expancel AB). Unfoamed organic microparticles 3 is composed of acrylonitrile-acrylic acid ester copolymer (MATSUMOTO MICROSPHERE F-50, manufactured by Mastumote Yusi-Seiyaku Co., Ltd.).

The densities of the three explosive compositions are 1.38 g / cm each. And 1.35 g / cm to be. The explosive composition is filled into steel pipes (JIS G 3452 32A; inner diameter: about 36 mm; length: 350 mm) each closed in one longitudinal direction and detonated by busbust (50 g of # 2 enoki dynamite with # 6 primer). . As a result, the explosive composition is stiffened, respectively, and the detonation speeds are 5,500 m / s, 4,600 m / s and 5,100 m / s, respectively. Similar results are obtained when the same test is performed on the same explosive composition stored for one year after preparation.

Example 11

1608 g of ammonium nitrate, 310 g of water, and 82 g of unfoamed organic microparticles (MATSUMOTO MICROSPHERE F-30, vinylidene-acrylonitrile-methacrylic acid ester copolymer, manufactured by Mastsumoto Yusi-Soiyaku Co., Ltd.) are placed in a stainless steel container. Place and heat with gentle stirring in an oil bath at about 100-130 ° C. to obtain a creamy explosive composition. The explosive composition is divided into small portions and filled into 20 mm Φ and 30 mm Φ polyethylene laminate paper tubes to prepare explosives containing about 50 g of the composition, respectively, and the explosive performance is measured. The density of 30mmΦ explosives is 0.70g / cm This explosive can be detonated by a # 6 primer at -5 ° C. The detonation velocity at 5 ° C. is 2,500 m / s. A 20 mm Φ explosive is loaded into a steel pipe having an internal diameter of 41.6 mm and a length of 3 mm, and detonated from one end by a # 6 primer. All explosives are stiff and the rupture area of the steel pipe is 3m long. In addition, two 30mm Φ explosives were buried at a depth of 80 cm in the sand parallel to each other at 15 cm intervals, one explosive was equipped with a # 6 electric primer, and the other explosive was equipped with a single 10 ms primer to detonate the primer by electric shock. A sand pressure test is performed. Perform this test five times. Two explosives are stiffened every test. Similar results are obtained when the same test is performed on the same explosive composition stored for 1 year after preparation.

Example 12

1250 g of ammonium nitrate, 170 g of water and 160 g of sodium nitrate, 300 g of monomethylamine nitrate and 120 g of unfoamed organic microparticles (MATSUMOTO MICROSPHERE F-30, vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer) The mixture was heated by heating to prepare a homogeneous mixture. A certain amount of the solution determined in consideration of possible swelling on heating is filled in a 20 mmΦ nylon 66 film tube. After degassing the tube, both ends are closed, and the tube is placed in a thermal bath at 100-150 ° C. to heat the mixed liquor to produce organic microparticles contained in the mixture, and the explosives filled in the nylon 66 film tube. The explosive performance is measured as a composition. The density of the explosives in the 20 mm Φ nylon 66 film tube was 0.35 g / cm This explosive can be detonated by a # 6 primer at -10 ° C. The detonation velocity at 5 ° C. is 2,200 m / s. In addition, the explosives are loaded into a steel pipe having a diameter of 4.16 mm and a length of 3 m and detonated from one end by a # 6 primer. As a result, all explosives are stiff and the rupture area of the steel pipe is 3m long. Similar results are obtained when the same test is performed on the same explosive composition stored for 1 year after preparation.

Example 13

A mixture was prepared by heating and mixing 1,050 g of ammonium nitrate, 170 g of water, 300 g of sodium nitrate, and 360 g of monomethylamine nitrate at about 70 ° C. On the other hand, organic micro hollow bodies (EXPANCEL) 551DE, vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer, 120 g of Expancel AB) is weighed and placed in a polyethylene bag. Next, after the mixture is injected into the bag and the opening is closed, a force is applied from the side of the bag, stirred for about 10 minutes to mix the material in the bag, and then cooled to obtain an explosive composition. The explosive composition is divided into small portions and filled into 20 mm Φ and 30 mm Φ polyethylene laminate tubes to prepare explosives containing 30 to 40 g of the composition, respectively, and investigate the explosion performance. The density of the 30 mm Φ explosive is 0.35 g / cm ³ , which can be detonated by a # 6 primer at -20 ° C. The detonation velocity at 5 ° C. is 2,300 m / s. A 20 mm Φ explosive is 41.6 mm in diameter and is loaded into a 3 m long steel tube and recorded from one end by a # 6 primer. As a result, all explosives were stiffened and the length of the bursting portion of the steel pipe was 3m. In addition, two 30mm Explosive Explosives were buried at a depth of 80 cm in the sand parallel to each other at a distance of 15 cm, one explosive was equipped with a quick # 6 primer, and the other explosive was equipped with a single 10 ms electric primer to shock the primer. Simultaneously detonating, sand pressure test is performed. This test is carried out five times and two explosives are blunted for each test. Similar results are obtained when the same test is performed with the same explosive composition stored for one year after preparation.

Examples 14 and 15

By performing the method of Example 13, the following explosive composition is prepared and the explosive performance is investigated.

The 30mmΦ explosives density of the two explosives compositions is 1.02 and 0.95, respectively, and the explosives can be detonated by a # 6 primer at 0 ° C. The detonation speeds at 5 ° C. were 3,700 m / s and 3,200 m / s, respectively. Similar results are obtained when the same test is performed on the same explosive composition stored for 1 year after preparation.

Example 16

1,296 g ammonium nitrate, 164 g water, 358 g monomethylamine nitrate, and unfoamed organic microparticles (MATSUMOTO MICROSPHERE F-30, vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer, Mastumoto Yusi-Seiyaku Co., Ltd. I) 78 g is placed in a metal container and mixed by stirring the vessel in a water bath of about 70 ° C. to obtain a mixture of about 70 ° C. On the other hand, a metal plate (inner wall is Teflon coated) is heated to about 100 ~ 150 ℃. The mixture is added dropwise in small portions onto the surface of the hot metal plate to obtain a granulated explosive composition in a very short time.

The explosive composition is divided into small portions and filled into 20 mm Φ and 30 mm Φ polyethylene laminate tubes to prepare explosives containing about 30 to 40 g of the composition, respectively, and investigate explosive performance. The density of 30mmΦ explosives is 0.80g / cm And this explosive can be detonated by # 6 primer at -15 ℃. The detonation velocity at 5 ° C. is 3,700 m / s. A 20 mm Φ explosive is loaded into a steel pipe with an internal diameter of 41.6 mm and a length of 3 m and detonated from one end by a # 6 primer. As a result, all explosives are stiffened and the length of the bursting portion of the steel pipe is 3 m. Also, buried two 30mm Φ explosives at a depth of 80 cm in the sand parallel to each other at 15 cm intervals, and one explosive is equipped with a revolving # 6 primer and the other explosive is equipped with a single 10 ms electric primer. Detonate and perform a dead pressure test in sand. This test is carried out five times, and two explosives are fully tested and blasted. Similar results are obtained when the same test is performed on the same explosive composition stored for 1 year after preparation.

Examples 17-19

The following explosive composition was prepared according to the method of Example 16 and the explosive performance was investigated.

Unfoamed organic microparticles 1 are the same as those used in Example 16, and unfoamed organic microparticles 2 are made of acrylonitrile-methyl methacrylate copolymer (O53WU, Expancel AB). Unfoamed organic microparticles 3 is composed of acrylonitrile-acrylic acid ester copolymer (MATSUMOTO MICROSPHERE F-50 Matsumoto Yusi-Seiyaku Co., Ltd).

The 20mmΦ and 30mmΦ explosive densities of the three explosive compositions are 0.20, 0.30 and 0.45, respectively. 30mmΦ explosives of -25 ℃ can be detonated by # 6 primer. The detonation speeds at 5 ° C. are 1,900 m / s, 2,300 m / s and 2,500 m / s, respectively. The 20mm Φ explosive is loaded into a 41.6mm diameter steel pipe with a length of 3m and detonated from one direction by a # 6 primer. All injected explosives are stiffened and the length of the rupture portion of the steel pipe is 3m. Similar results are obtained when the same test is performed on the same explosive composition stored for 1 year after preparation.

Example 20

1346 g of ammonium nitrate, 240 g of water, 80 g of sodium nitrate, 174 g of monomethylamine nitrate, and 160 g of unfoamed organic microparticles (MATSUMOTO MICROSPHERE F-30) are placed in a stainless steel container and heated with slow stirring in an oil bath at about 80 to 90 ° C. Explosive density of 1.38 g / cm A phosphorus explosive composition is obtained. When the explosive composition is filled with a closed steel pipe (JIS G 3452 32A; inner diameter: 36 mm; length: 350 mm) in one longitudinal direction and detonated by busbust (50 g of # 2 enoki dynamite with a # 6 primer), The explosive composition is full. The detonation speed is 5,600 m / s. Similar results are obtained when the same test is performed on the same explosive composition stored for 1 year after preparation.

Industrial availability

The explosive composition according to the present invention, due to the unique structure in which the oxidizing agent and water or the active ingredient containing the preservative, the oxidizing agent and the water are continuously maintained on the surface and / or space of the adjacent microspheres, the quality preservation of the conventional hydrous explosive composition The use of a critical agent, which is indispensable, is practically unnecessary, and the quality can be preserved for a long time, and the practical use of low-weight goods, which has been difficult to use with conventional water-containing explosives, becomes possible. Due to the reduction in specific gravity, the loudness and vibration generated during blasting can be significantly reduced.

Claims (28)

An explosive composition containing an oxidant, water and an organic micro hollow body, wherein the phase composed of an oxidizing agent and water is adsorbed and held between the organic micro hollow body surface or between the organic micro hollow body and the organic micro hollow body surface. The explosive composition according to claim 1, wherein the organic micro hollow body is spherical. The thermoplastic explosive composition according to claim 1 or 2, wherein the organic micro hollow body is a thermoplastic explosive composition. The explosive composition according to claim 1 or 2, wherein the thermoplastic organic micro hollow body is a vinylidene chloride-acrylonitrile copolymer. The explosive composition according to claim 1 or 2, wherein the thermoplastic organic micro hollow body is a vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer. The explosive composition according to claim 1 or 2, wherein the thermoplastic organic micro hollow body is an acrylonitrile-acrylic acid ester copolymer. An explosive composition containing an oxidant, water and organic micro hollow bodies is packed into a packaging material, in which a phase composed of an oxidizing agent and water is adsorbed and held between the organic micro hollow bodies or between organic micro hollow bodies and between and. Package in explosive composition. Characterized by mixing the remaining components consisting of 2 to 15% by weight of effervescent organic fine particles, 3 to 20% by weight of water, mainly an oxidizing agent, to prepare a composition containing no air bubbles, and then heating the composition to form the composition, A process for producing an explosive composition composed of an oxidant, water and an organic micro hollow body used as a combustible component. The method according to claim 8, wherein the expandable organic microparticles are spherical. 10. The process according to claim 8 or 9, wherein the expandable organic microparticles are thermoplastic. The production method according to claim 8 or 9, wherein the thermoplastic expandable organic microparticles are vinylidene chloride-acrylonitrile copolymer. 10. The process according to claim 8 or 9, wherein the thermoplastic expandable organic microparticles are vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer. The process according to claim 8 or 9, wherein the thermoplastic expandable organic microparticles are acrylonitrile-acrylic acid ester copolymers. Effervescent organic microparticles are prepared by mixing 2-15% by weight of water, 3-20% by weight of water, and a residual component consisting mainly of an oxidizing agent to prepare a composition containing no air bubbles, and then heating the composition. The explosive composition packaged product which packaged the explosive composition manufactured by the manufacturing method of the explosive composition consisting of the organic microhollow body used as an oxidizing agent, water, and a combustible component in a packaging material. An explosive composition containing an oxidant, water and organic micro hollow bodies, in which a phase composed of a pre-sensing agent, an oxidizing agent and water is adsorbed and held between the organic micro hollow body surface or between the organic micro hollow body and the organic micro hollow body surface, and between, The explosive composition according to claim 15, wherein the organic micro hollow body is spherical. The explosive composition according to claim 15 or 16, wherein the organic micro hollow body is thermoplastic. The explosive composition according to claim 15 or 16, wherein the thermoplastic organic micro hollow body is a vinylidene chloride-acrylonitrile copolymer. The explosive composition according to claim 15 or 16, wherein the thermoplastic organic micro hollow body is a vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer. The explosive composition according to claim 15 or 16, wherein the thermoplastic organic micro hollow body is an acrylonitrile-acrylic acid ester copolymer. A packaging material containing an explosive composition containing an oxidant, water and an organic micro hollow body, wherein a phase composed of a preliminary agent, an oxidizing agent and water is adsorbed and held between an organic micro hollow body surface or between an organic micro hollow body and an organic micro hollow surface. The packaged product in the explosive composition packaged in the inside. 2-15% by weight of effervescent organic microparticles, 3-20% by weight of water, a residual component consisting mainly of a preservative and an oxidizing agent is mixed to prepare a composition containing no air bubbles, and then the composition is characterized by heating and foaming. The manufacturing method of the explosive composition comprised from a preservative, an oxidizing agent, water, and an organic micro hollow body. The method of claim 22, wherein the expandable organic microparticles are spherical. The process according to claim 22 or 23, wherein the expandable organic microparticles are thermoplastic. The production process according to claim 22 or 23, wherein the thermoplastic organic microparticles are vinylidene chloride-acrylonitrile copolymer. The production process according to claim 22 or 23, wherein the thermoplastic expandable organic microparticles are vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer. The process according to claim 22 or 23, wherein the thermoplastic expandable organic microparticles are acrylonitrile-acrylic acid ester copolymers. Effervescent organic microparticles are prepared by mixing 2-15% by weight of water, 3-20% by weight of water, and a residual component consisting mainly of a preservative and an oxidizing agent to prepare a composition containing no vented air bubbles, and then An explosive composition packaged article containing the explosive composition prepared by the method for producing an explosive composition comprising a presensitizer, an oxidizing agent, water, and an organic micro-hollow body in a packaging material.