JPH06144983A - Explosive composition and production thereof - Google Patents

Abstract

PURPOSE:To enable to maintain stable explosion performances in the low density region and good explosive properties over a long term by making a phase consisting of an oxidizing agent and water adsorbed and retained on the surfaces of organic microballoons and/or in the spaces between the microballoons. CONSTITUTION:The explosive composition contg. no entrained bubbles can be produced by blending 2 to 15wt.% expandable organic particulates having <=1000mum particle diameter, 3 to 20wt.% water and the oxidizing agent. This composition is heated and expanded to make the phase consisting of the oxidizing agent and water adsorbed and retained on the surfaces of the organic microballoons having 0.1 to 5mum film thickness and/or in the spaces between the microballoons.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to industrial explosives, and more particularly, to the field of mining and industry such as civil engineering, quarrying, mining, mining, etc .; blasting in the fields of agriculture and forestry such as drainage, irrigation, clearing, rooting and felling. It is an explosive composition used for crushing and excavation.

[0002]

2. Description of the Related Art Slurry explosives are used as the conventional major explosives.
There are emulsion explosives. All of them hold the structure of an explosive component composed of an aqueous solution of an oxidant, a combustible substance, a sensitizer and bubbles in a stable manner at a high concentration in the presence of a structure-imparting agent, and are mainly detonated by a detonator. In slurry explosives, air bubbles are often used in the explosive structure to ensure free function of entrained air bubbles and chemical bubbles, and guar gum is used as a structure-imparting agent to form an aqueous gel. ing. In emulsion explosives, an aqueous oxidant solution and oils as a combustible agent form a W / O type emulsion structure in the presence of a surfactant as a structure-imparting agent, and air bubbles are trapped and mainly glass or resin micro It has the shape of a balloon.

Further, there is an example in which resin microballoons are used for improving the detonation property of these water-containing explosives and adjusting the density. For slurry explosives, US Pat. No. 3,773,5
73, JP-A-54-92614, and emulsion explosives in JP-A-56-100192 and JP-A-59-78994.
U.S. Pat. No. 3,773,573 discloses that when resin microballoons are applied to a wide range of explosives including slurry explosives, the foaming temperature of the resin is almost constant in the presence of unexpanded resin fine particles during the explosive manufacturing process. Although a method of heating to the same temperature is described, heating is not usually required in the manufacturing process of the slurry explosive, and thus resin foaming during the manufacturing process is not practical. Further, even if heat foaming in the production process is necessary, as understood from the description in JP-A-54-92614, heat foaming at a stage where a sensitizer is not included from the viewpoint of safety. After the above, the two-step method of mixing with the sharpening agent component had to be adopted.

These water-containing explosives do not contain highly sensitive components such as nitroglycerin in dynamite and require delicate adjustment between the explosive components and the gel structure or emulsion structure in order to maintain the detonation property. , Extremely advanced manufacturing technology is required. That is, before and after the formation of these structures, the quality behavior of the explosive component that comes into contact with and mixed with the structure is influenced, so that much time and labor must be spent on the quality control of raw materials and the control of manufacturing conditions. As a result, there are problems in that explosives of inferior quality that cannot withstand practical storage are often produced, or the explosive performance is significantly deteriorated over a long period of time. In particular, when the amount of chemical foam or foaming agent used for adjusting the density of explosive increases, it is not only difficult to obtain the desired initial performance of the explosive, but also the explosive performance deteriorates over time. It appeared more prominently.

Further, the slurry explosive has a peculiar gel elasticity, lacks plasticity, and when it is made into an explosive charge package, it is difficult to handle because it is not stiff, and it is difficult to insert it into the blast hole. This may cause problems such as reduced work efficiency and difficulty in molding explosives, making it difficult to use them in the state of naked drugs excluding the drug package. In addition, emulsion explosives may lose their explosive function by destroying the emulsion structure when they are rapidly pressurized (called dead pressure phenomenon), and non-residual residual drugs often occur during normal blasting, which is a normal blasting operation. However, it sometimes causes a problem that the subsequent processing is difficult.

[0006]

The object of the present invention is to maintain extremely stable performance and good drug properties for a long period of time without utilizing the gel structure or emulsion structure of conventional water-containing explosives. The purpose is to provide an explosive composition comprising an oxidizer / water / organic micro hollow spheres. Another object of the present invention is to provide an explosive composition which is safe to handle, has less non-residual residue after blasting, and can reduce the harmfulness of generated gas. Still another object is to provide a low explosive charge having a stable explosive performance even in a low density region which has been difficult with conventional explosives.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, a liquid phase component composed of an oxidizing agent and water as a main component and substantially not containing a viscous component is adsorbed and retained on the surface of the organic microhollow body which is a combustible agent and / or between the hollow bodies. It relates to a novel explosive composition characterized.

The microstructure of the explosive composition of the present invention can be observed, for example, by micrographs. As shown in FIG. 1, a typical example thereof has a structure in which a structure in which a high-concentration oxidant aqueous solution is attached is gathered around an organic micro hollow body. Further conceptually explaining this with a diagram, in the explosive composition of the present invention, as shown in FIG. 2, the organic microhollow body forms the center of the structure of the explosive composition, while in the case of the slurry explosive, As shown in FIG. 3, trapped air bubbles and hollow bodies are dispersed in the gelled oxidizer and sharpening agent phases. Further, in the emulsion explosive, hollow bodies such as glass microballoons are dispersed in the emulsified oxidant aqueous solution phase as shown in FIG. Therefore, when the explosive composition of the present invention is compared with the conventional slurry explosive and emulsion explosive, it is apparent that the bubble morphology, the oxidant aqueous solution morphology, the composition structure and the like are completely different. More specifically, the composition of the present invention does not require a gelling agent in a conventional slurry explosive, and bubbles are mainly incorporated into an organic micro hollow body which is a combustible agent component, so that the composition is completely different. Further, compared with the emulsion explosive, an oil phase as a combustible agent, a surfactant for forming an emulsion, a glass microballoon for retaining air bubbles, etc. are not necessary, and this point is also completely different.

Although it is known that resin microballoons are used in conventional slurry explosives, the amount of the foam is practically at most 2% from the viewpoint of stability and explosive performance of explosive compositions. It was about. In the present invention, surprisingly, when a composition comprising an aqueous solution of an oxidizing agent and an organic microhollow body is used with a high proportion of the hollow body, a gelling agent, a wax and a surfactant are not present. Also found that a composition having stable detonation performance was obtained. Further, since the hollow body also has a role of a combustible agent, coal powder, a combustible agent such as aluminum powder, or an organic nitrate and / or a sharpening agent mainly composed of an inorganic nitrate is not necessarily required, It is now possible to provide explosives with excellent performance.

Surprisingly, the explosive composition of the present invention is capable of maintaining a stable structure with almost no separation of the liquid phase which mainly constitutes the oxidizer component or visible crystallization of the oxidizer, and moreover, the detonator. It can cover a wide range of explosive compositions, from those that can be detonated to those that can be detonated by boosters. In particular, there is a tendency that a more stable composition can be obtained when the distance between the organic micro hollow bodies is calculated to be about 20 μm or less.

As the oxidizing agent used in the present invention, those known in the technical field of explosives can be used, and examples thereof include ammonium salts of inorganic acids such as nitric acid, chloric acid and perchloric acid, alkali metal salts and alkaline earth metals. Salts and the like can be selected alone or in combination. Among them, ammonium nitrate (ammonium nitrate) is an excellent oxidizing agent because it has high solubility in water and can be easily obtained. In the present invention, the amount of the oxidizer is determined according to the design specifications of the target explosive, and usually about 50 to 90% by weight is adopted with respect to the total composition. If this ratio is too small, the oxygen balance with the combustible agent will fall to the negative side and the harmfulness of the gas after blasting will increase, which is not preferable.

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 small, the solid content of the explosive composition increases, and stable explosive performance may not be exhibited. On the other hand, if it is too large, the detonation property deteriorates, which is not preferable.

The organic micro-hollow body used in the present invention is preferably based on an organic polymer compound, and examples of the organic polymer compound include phenol resin, epoxy resin,
Other than urea resin, unsaturated polyester resin, polyimide, maleic acid resin, melamine resin, celluloses, vinyl chloride, vinylidene chloride, acrylonitrile, acrylic acid, acrylates, acrylates, methacrylic acid, methacrylates, Methacrylic acid esters,
There are homopolymers of styrene, ethylene, propylene, butadiene, vinyl acetate, etc. or copolymers of two or more kinds, polycarbonate, polysulfone, polyacetal, polyamides, polyethylene oxide, polyphenylene oxide, etc. Can be mixed and used. Among these organic polymer compounds, those having thermoplasticity, such as vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-
Acrylonitrile-methacrylic acid ester copolymers, acrylonitrile-acrylic acid ester copolymers and the like are more preferable in the practice of the present invention.
In particular, unfoamed fine particles in which a vinylidene chloride-acrylonitrile copolymer contains a low boiling point hydrocarbon easily become a fine hollow body upon heating, and therefore, it can be used after being heated and foamed after being mixed with an explosive component.

Next, 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 preferable for efficiently forming hot spots for the explosive composition to initiate detonation. The gas retained in the small organic hollow body may be air, low-boiling point hydrocarbons or other heating gas, or a mixture thereof. An example of a preferable particle size of the organic micro hollow body is about 1,000 μm or less, and if it exceeds that, it becomes difficult to secure stable explosiveness because the number of hot spots for starting detonation decreases. . More preferably, the organic hollow microparticles of 20 to 200 μm can obtain stable explosion performance without reducing the detonation speed. The thickness of the film forming the organic micro hollow body is sufficient as long as it has a strength to provide a space for forming the explosive composition, and a film having a thickness of 0.1 to 5 μm is usually used. In addition, since the organic polymer compound forming the organic micro hollow body having thermoplasticity is required to be capable of being heated and foamed in the explosive composition, the thickness of the film in the foamed state is about 0.1 to 0.1. Two
The one with μm is used. The organic hollow microspheres in the explosive composition usually have a bulk density of about 0.01 when measured in a dry state.
It is about 0.3. The amount of the organic micro hollow body is usually about 2 to 15% by weight based on the whole composition, and the density of the explosive composition is also adjusted by the amount of the organic micro hollow body. Generally, if the proportion of the organic micro hollow bodies is too small, not only the detonation property deteriorates, but also it becomes difficult to maintain stable explosive performance for a long period of time, while if the proportion is too large, the power of the explosion decreases. The blasting reliability tends to be difficult to obtain.

The explosive composition according to the present invention can be stably obtained with a density of 0.2 to 1.4 g / cm ³ mainly by adjusting the organic micro hollow body. Explosion speed is usually 1,500-
It has a performance of about 5,500 m / sec. As an example of a method for producing the explosive composition of the present invention, a mixture of an oxidant and water is heated to a level at which it is almost dissolved,
A method of uniformly mixing with the organic micro hollow body is adopted.

Next, the method of heat-foaming using the expandable organic fine particles is not particularly limited, but a specific example will be given. The oxidizing agent, water and the expandable organic fine particles are made substantially uniform. After being heated to a temperature at which mixing is possible to form a mixed solution, the droplets or flying of the mixed solution are dropped onto a heating plate or in an atmosphere whose temperature is adjusted to a temperature at which the expandable organic fine particles start foaming or A method of spraying to expand the expandable organic fine particles contained in the mixed solution, heating the mixture to a temperature at which the oxidizing agent, water, and the expandable organic fine particles can be mixed almost uniformly to form a mixed solution, and then mixing the mixed solution. A method of injecting a solution into a metal tube whose temperature is controlled to be equal to or higher than the temperature at which the expandable organic microparticles start foaming to foam the expandable organic microparticles contained in the mixed solution in the metal tube, an oxidizing agent and water. Add a mixed solution of expandable organic fine particles. The vessel was heated at a temperature above the outer bath foamable organic microparticles starts foaming put in,
A method of foaming the expandable organic fine particles contained in the mixed solution, heating the oxidizer, water and the expandable organic fine particles uniformly to a temperature at which they can be mixed almost uniformly to form a mixed solution. , A heat-resistant film tube is filled with an amount in which the volume expansion of the mixed solution is expected, and after the air in the film tube is removed and sealed, the temperature is adjusted to a temperature at which the expandable organic fine particles start foaming or higher. A method of foaming the expandable organic fine particles contained in the mixed solution in a heated bath or an oil bath, in which heat is applied to a mixture of an oxidizing agent and water to dissolve most of solid salts such as the oxidizing agent There is a method of mixing a high-concentration salt solution having a temperature equal to or higher than the temperature at which the organic fine organic particles start foaming with the unexpanded organic fine particles. When water evaporates from the composition among these production methods, it is possible to predict the evaporation amount of water in advance and add excess water so as to obtain the desired explosive composition. Further, according to the method for producing the explosive composition of the present invention, the foaming state can be arbitrarily changed by adjusting the temperature, and depending on the purpose, it can be detonated by a booster to one detonated by one detonator. Explosive design is possible. By heating unexpanded organic microparticles, the internal pressure rises and the foaming starts at about the temperature at which the organic polymer film begins to soften, and expands to a range of about 20 to 100 times in volume ratio. To be done. However, if the organic micro-hollow body is ruptured by heating more than necessary, it becomes difficult to obtain the performance as an explosive. Therefore, it is preferable to stop the temperature at the temperature before the over-foaming.

The explosive composition according to the present invention is in the form of powder, flakes, paste or the like.
In consideration of properties, fields of use, and the like, conventionally known packaging materials such as paper, laminated paper, plastic film, laminated plastic film, paper cylinder, and plastic cylinder can be used as a packaged product.

The explosive composition of the present invention sufficiently satisfies the requirements as an explosive, but in order to additionally improve the performance, an organic nitrate such as a lower saturated aliphatic amine or hydrazine nitrate may be added if necessary. It is also possible to add an inorganic nitrate such as the above as a sensitizer to meet the application especially in a cold area. In addition, solid combustible materials such as coal powder and aluminum powder can be supplemented in consideration of the gas after blasting in a tunnel or an underground mine. Other activators such as phosphoric acid esters; decomposition inhibitors such as urea may be added. Examples of the above organic nitrates include nitrates of lower saturated aliphatic amines, ethanolamine nitrate, urea nitrate, guanidine nitrate, ethylenediamine dinitrate, and the like, and examples of inorganic nitrates include hydrazine nitrate, hydrazine dinitrate, hydrazine perchlorate, and the like. These may be used alone or in admixture of two or more. These are effective in imparting a stable detonation property to the explosive composition, but monomethylamine nitrate, monoethanolamine nitrate, hydrazine nitrate and the like are preferable since explosives can be easily adjusted.

According to the explosive composition of the present invention and the method for producing the same, it is possible to obtain explosives for detonator initiation, explosives for detonator initiation, and explosives in a wide density range of explosives, which can cover most conventional explosives. is there. Further, the dead pressure resistance performance found in emulsion explosives and the like has also been improved, and the reduction of non-residual residue can further improve the safety at the site of consumption. Regarding the manufacturing method, it does not require a high-level manufacturing technology such as the conventional slurry explosive or emulsion explosive, and can be manufactured simply and safely.

The explosive composition according to the invention is usually an electric detonator, an industrial detonator, a detonator with a detonator, a detonator with a gas detonator,
A known method such as an electromagnetic detonator, a laser detonator, a wireless detonator, a squib, or a detonator can be used for detonation, but in some cases, a booster can be used for detonation.

[0021]

EXAMPLES The following will describe more detailed aspects of the present invention in examples, but the present invention is not limited to these within the scope of the claims. The following methods were used to measure detonator detonation, booster detonation, detonation velocity, detonation rate in steel pipes, and dead pressure in sand.

Measurement of detonator ignitability Preliminarily polyethylene laminated paper cylinder or nylon 66 film tube (medicine package diameter 20 mm or 30 mm, drug length about 2
After storing the explosive package tightly packed in (00 mm) in a freezer at about -30 ° C for about 15 hours, detonate with No. 6 detonator while adjusting the temperature of the explosive package, and measure the temperature when the explosive package is completely detonated. did. It should be noted that one year after production was additionally measured for performance evaluation with time. Measurement of booster ignitability A steel pipe (JIS G 34
52 32A; test explosive filled in an inner diameter of about 36 mmφ and a length of 350 mm was used as a booster (2 equipped with a No. 6 detonator).
It was detonated with No. Enoki dynamite (50 g), and it was visually determined from the state of destruction of the steel pipe whether or not the explosion was complete. It should be noted that one year after production was additionally measured for performance evaluation with time. Measurement of detonation velocity of medicine package filling product Preliminarily polyethylene laminated paper tube or nylon 66 film tube (medicine package diameter 20 mm or 30 mm, medicine length about 3
(00 mm) was charged with an explosive charge packet using a No. 6 detonator, and the detonation velocity was measured by the ion gap method. It should be noted that one year after production was additionally measured for performance evaluation with time.

Measurement of Detonation Velocity of Steel Tube Filled Product Steel tube (JIS G 3452 32A; inner diameter approx. 36)
An explosive charged in mmφ and a length of 350 mm) was detonated with a booster (No. 2 enoki dynamite 50 g equipped with No. 6 detonator), and the detonation velocity was measured by the ion gap method. It should be noted that one year after production was additionally measured for performance evaluation with time. Measurement of explosive property of drug package in steel pipe Preliminarily polyethylene laminated paper tube or nylon 66 film tube (medicine package diameter of about 20φ mm, drug length of 150 mm)
The explosive package filled in the steel pipe (JIS G 3452 40
A: Inner diameter of about 41.6 mmφ, tube length of 3000 mm) About 20 pieces were arranged side by side so as not to be deformed in the longitudinal direction, and then the explosive bag at the end was detonated with a No. 6 detonator, and the length of the destroyed steel tube was measured. The steel pipe was made to be explosive. It should be noted that one year after production was additionally measured for performance evaluation with time.

Measurement of dead pressure performance in sand Two explosive sachets, which were previously filled in a polyethylene laminated paper cylinder or a nylon 66 film tube (medicine package diameter 30 mm, medicine length about 150 mm), were prepared. The electric detonator is attached to the other explosive package with a 10 ms stepped electric detonator, and the electric detonator is buried in parallel in the sand at a depth of 80 cm. Both electric detonators are connected in series and blasted. This test was repeated 5 times, and it was determined whether or not the explosive package equipped with the 10 ms step-detonated electric detonator was completely detonated to obtain the dead pressure performance in sand. It should be noted that one year after production was additionally measured for performance evaluation with time.

Example 1 805 g of ammonium nitrate and 135 g of water were mixed to obtain about 9
Adjust the temperature by 0 ℃. On the other hand, 60 g of an organic micro hollow body (Expandel 551DE, which is a vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer; trade name of Chemanode Corporation) is prepared in a polyethylene bag for weighing. Then
The above mixture was put into a polyethylene bag, the opening of the bag was closed, force was applied from the side of the bag, and the mixture was stirred and mixed for about 10 minutes and then water cooled to form an explosive having a density of 0.40 / cm ³ . A composition was obtained. The above explosive composition was exchanged by previously sealing one side in the longitudinal direction (JIS G 3452 32A;
Inner diameter of about 36 mmφ, length of 350 mm) filled, booster (No. 2 dynamite 50 g equipped with No. 6 detonator)
When I detonated, I was completely detonated. Further, the same test was performed one year after the production, and the same performance was exhibited.

Example 2 1608 g of ammonium nitrate, 310 g of water, and 82 g of unexpanded organic fine particles (a copolymer of vinylidene chloride, acrylonitrile, and methacrylic acid ester (Matsumoto Yushi Co., Ltd. trade name; Micropearl F-30)) were placed in a metal container. put in,
Stirring is performed in an external bath at about 80 ° C and mixing is performed to obtain a mixture at about 70 ° C. On the other hand, a metal plate heated to about 100 to 150 ° C. is prepared. Then, the mixture was dropped little by little onto the surface of the metal plate to obtain a coarse granular explosive composition in an extremely short time.

This explosive composition is subdivided into 20 mm
φ, 30mmφ polyethylene laminated paper cylinder approx. 30g
Explosive performance was examined by filling each of them up to 40 g to form an explosive bag. The density of the 30 mmφ explosive package was 0.35 g / cm ³ , and it was possible to detonate with a No. 6 detonator at a drug temperature of −10 ° C., and the detonation speed at a drug temperature of 5 ° C. was 1900 m / s.
In addition, the above-mentioned 20 mmφ explosive package was charged into a steel pipe with an inner diameter of 41.6 mmφ and a length of 3 m according to the length of 3 m. The explosive bag was completely detonated and the length of the destroyed steel pipe was 3 m. In addition, two of the above 30mmφ explosive packages were buried in 80cm sand at a distance of 15cm in parallel, and one of them was equipped with an explosive No. 6 detonator and the other was equipped with a 10ms stepped electric detonator. When the dead pressure test in sand was performed 5 times, all of them were completely detonated. Furthermore, the same test was performed one year after the production, and the same performance was shown. On the other hand, the conventional slurry explosive and emulsion explosive were adjusted according to the general manufacturing method, and the explosive density was adjusted. In the internal explosive charge transmission test, the detonation was interrupted near 1.2 m and the length of the destroyed steel pipe was about 1.2 m. Furthermore, in the sand dead pressure test, 10 ms
Two explosive packages equipped with the stepped electric detonator were recovered without complete explosion. Further, the same test was conducted one year after the production, but the performance was deteriorated until the detonator No. 6 could not be detonated.

Examples 3, 4, 5 The following explosive compositions were produced in the same manner as in Example 2 and their explosive properties were examined.

[Table 1]

The unexpanded organic fine particles 1 are the same as those used in Example 2, and the unexpanded organic fine particles 2 are acrylonitrile and methylmethacrylate copolymer (trade name of Expancel Co .; 053WU). The unexpanded organic fine particles 3 are copolymers of acrylonitrile and acrylic acid ester (trade name of Matsumoto Yushi Co., Ltd .; Micropearl F-
50).

20 mmφ, 3 of the above three explosive compositions
0mmφ explosive packing density is 0.23, 0.30,
It is 0.40, and the 30mmφ explosive package with a drug temperature of -10 ℃ is 6
It was possible to detonate with a No. detonator, and the detonation speed at a chemical temperature of 5 ° C was 1900 m / s, 2000 m / s, 2200 m / s. Also, a 20 mmφ explosive charge was charged into a steel pipe with an inner diameter of 41.6 mmφ and a length of 3 m according to the length of 3 m. The length of the steel pipe that was completely destroyed and destroyed was 3 m.
Further, one year after the production, the same test was performed and the same performance was shown. On the other hand, the conventional explosive explosive and emulsion explosive were adjusted according to the general manufacturing method, and the explosive density was adjusted, and the same test was carried out. In the explosive charge transfer test in the steel pipe, the detonation was interrupted in the vicinity of 0.8 to 1.6 m, and the length of the destroyed steel pipe was about 0.8 to 1.6 m. Further, the same test was conducted one year after the production, but the performance was deteriorated until the detonator No. 6 could not be detonated.

Example 6 1608 g of ammonium nitrate, 310 g of water, and 82 g of unexpanded organic fine particles (a copolymer of vinylidene chloride, acrylonitrile, and methacrylic acid ester (trade name of Matsumoto Yushi Co., Ltd .; Micropearl F-30)) in a metal container. put in,
The mixture was stirred and mixed in a water bath at about 70 ° C to obtain a mixture at about 70 ° C. The above mixture was pressure-injected from one side of a 20 mmφ metal tube (inner wall of which was made of Teflon) heated to about 100 to 150 ° C., and a continuous foamed string-like explosive composition was obtained from the other side.

This explosive composition is subdivided into explosive packages,
I investigated the explosive performance. 20mmφ explosive package density is 0.4
It is 5 g / cm ³ and can be detonated by No. 6 detonator at a drug temperature of -5 ° C, and the detonation speed at a drug temperature of 5 ° C is 1900 m.
Was / s. In addition, the explosive package was charged into a steel pipe with an inner diameter of 41.6 mmφ and a length of 3 m according to the length of 3 m, and when one of the detonators was detonated from one side, all the explosive packages were completed. The length of the steel pipe that was exploded and destroyed was 3 m. Furthermore, 2 pieces of the above 30 mmφ explosive bag are placed in 80 cm of sand for 15
It was filled in parallel with a distance of cm, and one was equipped with a No. 6 flashing detonator, and the other was equipped with a 10 ms stepped electric detonator to carry out a detonation test in sand five times. Both were completely detonated. Furthermore, the same test was performed one year after the production, and the same performance was shown.

Example 7 1524 g of ammonium nitrate, 286 g of water and 190 g of unexpanded organic fine particles (copolymer of vinylidene chloride, acrylonitrile and methacrylic acid ester (Matsumoto Yushi Co., Ltd. trade name: Micropearl F-30)) in a metal container. Approximately 70 ~ 8
A mixture at 0 ° C. is obtained. The mixture was heated to about 90 to 110 and pressure-injected through one opening of a 20 mmφ metal tube (inner wall of which was Teflon processed), and cream-like density of 1.35 g / cm ³ was obtained through the other opening. An explosive composition was obtained.

The above explosive composition was filled in a steel pipe (JIS G3452 32A; inner diameter of about 36 mmφ, length of 350 mm) whose one side in the longitudinal direction was sealed in advance, and a booster (50 g of No. 2 enoki dynamite equipped with No. 6 detonator). At the time of detonation, it completely detonated and the detonation speed at this time was 5460.
It was m / s. Further, one year after the production, the same test was performed and the same performance was shown. Examples 8, 9, and 10 The following explosive compositions were produced in the same manner as in Example 7, and the explosive properties thereof were examined.

[0035]

[Table 2]

The unexpanded organic fine particles 1 are the same as those used in Example 7, and the unexpanded organic fine particles 2 are acrylonitrile / methyl methacrylate copolymer (Expansell Co., Ltd .; trade name: 053WU). The unexpanded organic fine particles 3 are copolymers of acrylonitrile and acrylic acid ester (trade name of Matsumoto Yushi Co., Ltd .; Micropearl F-5).
0).

The densities of the above three explosive compositions are 1.38 g / cm ³ , 1.30 g / cm ³ and 1.35 g, respectively.
/ Cm ³ . Each of the above explosive compositions was formed into a steel pipe (JIS G 345) whose one side in the longitudinal direction was previously sealed.
232A; inner diameter approx. 36 mmφ, length 350 mm), and when detonated by a booster (Unit 2 dynamite 50 g equipped with No. 6 detonator), each detonated completely, and the detonation speed at this time was 5500 m / g, 460
It was 0 m / s and 5100 m / s. Further, one year after the production, the same test was performed and the same performance was shown.

Example 11 1608 g of ammonium nitrate, 310 g of water, and 82 g of unexpanded organic fine particles (copolymer of vinylidene chloride, acrylonitrile, and methacrylic acid ester (Matsumoto Yushi Co., Ltd .; Micropearl F-30) 82 g) And heated in an oil bath at about 100 ° C. to 130 ° C. with slow stirring to obtain a cream-like explosive composition.The explosive composition was divided into 20 mmφ and 30 mmφ.
About 50 g of each of the polyethylene laminated paper cylinders described above was filled into an explosive bag, and the explosive performance was examined. The density of the 30 mmφ explosive package was 0.70 g / cm ³ , and it was possible to detonate with a No. 6 detonator at a drug temperature of −5 ° C., and the detonation speed at a drug temperature of 5 ° C. was 2500 m / s. In addition, the above-mentioned 20 mmφ explosive package was charged into a steel pipe with an inner diameter of 41.6 mmφ and a length of 3 m according to the length of 3 m. The explosive bag was completely detonated and the length of the destroyed steel pipe was 3 m. Furthermore, 2 pieces of the above 30mmφ explosive package were buried in 80cm sand at a distance of 15cm in parallel, one of which was an explosive No. 6 detonator, and the other was 1
When a dead pressure test in the sand was started 5 times with a 0 ms stepped electric detonator attached, all of them were completely detonated. Furthermore, the same test was performed one year after the production, and the same performance was shown.

Example 12 1250 g of ammonium nitrate, 170 g of water, 160 g of sodium nitrate, 300 g of monomethylamine nitrate and unexpanded organic fine particles; vinylidene chloride / acrylonitrile / methacrylic acid copolymer (trade name of Matsumoto Yushi Co., Ltd .; Micropearl F- 30) 120 g is heated to about 70 ° C. to form a uniform mixed solution, and the mixed solution is divided into 20 mmφ nylon 66 film tubes in consideration of volume expansion, and the air in the space is removed to remove both ends of the nylon 66 film tube. After being bound, the mixture was placed in a heating bath at 100 to 150 ° C., the mixed solution was heated to foam the unexpanded organic fine particles contained in the mixture, and the explosive composition filled in the nylon 66 film tube. I examined the explosive performance as a thing. The density of the 20 mmφ nylon 66 film tube explosive package was 0.35 g / cm ³ , and it was possible to detonate with a No. 6 detonator at a drug temperature of −10 ° C., and the detonation speed at a drug temperature of 5 ° C. was 2200 m / s. . In addition, the 20 mmφ nylon 66 film tube explosive bag described above has an inner diameter of 41.6 mm.
φ, 3m long steel tube was charged with the above explosive package according to the length of 3m, and when one was detonated with No. 6 detonator, all explosive packages charged were completely detonated, and the steel tube length was destroyed Was 3 m. Further, the same test was performed one year after the production, and the same performance was shown.

Example 13 1050 g of ammonium nitrate, 170 g of water, 300 g of sodium nitrate and 360 g of monomethylamine nitrate were mixed and heated at about 70 ° C. to prepare a mixture. On the other hand, an organic micro-hollow body (Expandel 551D which is a vinylidene chloride-acrylonitrile-methacrylic acid ester copolymer)
E: 120 g of the product name of Chemanode Co., Ltd. is prepared for weighing in a polyethylene bag. Next, the mixture was put into a polyethylene bag, the opening of the bag was closed, and after applying force from the side surface of the bag for about 10 minutes with stirring and mixing, the mixture was cooled to obtain an explosive composition. This explosive composition is subdivided into 20 mmφ,
30mmφ polyethylene laminated paper cylinder about 30-40
Explosion performance was examined by filling each g to make an explosive bag. 3 of the above
The density of the 0 mmφ explosive package was 0.35 g / cm ³ , and it was possible to detonate with a No. 6 detonator at a drug temperature of −20 ° C., and the detonation speed at a drug temperature of 5 ° C. was 2300 m / s. In addition, the above-mentioned 20 mmφ explosive package has an inner diameter of 41.6 mmφ and a length of 3
When the above explosive sachet was charged into a 3 m steel pipe to a length of 3 m, and one was detonated with a No. 6 detonator, all explosive sachets that had been explosive were completely detonated, and the destroyed steel pipe length was 3 m. It was Furthermore, 2 pieces of the above 30 mmφ explosive bag are placed in 80 cm of sand for 15
It was buried in parallel at a distance of cm, and one of them was equipped with an explosive No. 6 detonator, and the other was equipped with a 10 ms stepped electric detonator, and a detonation test in sand was carried out five times. Both were completely detonated. Furthermore, the same test was performed one year after the production, and the same performance was shown.

Examples 14 and 15 The following explosive compositions were produced in the same manner as in Example 13 and their explosive properties were examined.

[0042]

[Table 3]

The 30 mmφ explosive packing densities of the above two explosive compositions are 0.95 and 1.02, respectively, and the drug temperature is 0.
It was possible to detonate with a No. 6 detonator at ℃, and the detonation speed at the drug temperature of 5 ℃ was 3200 m / s, 3700 m / s. Further, one year after the production, the same test was performed and the same performance was shown.

Example 16 Ammonium nitrate 1296 g, water 164 g, monomethylamine nitrate 358 g and unexpanded organic fine particles (copolymer of vinylidene chloride, acrylonitrile and methacrylic acid ester (trade name of Matsumoto Yushi Co., Ltd .; Micropearl F-3)
0) 78 g was placed in a metal container and mixed by stirring in a water bath at about 70 ° C to obtain a mixture at about 70 ° C. On the other hand, about 10
A metal plate (the surface of which is treated with Teflon) heated to 0 to 150 is prepared. Then, the mixture was dropped little by little on the surface of the metal plate to obtain a coarse-grained explosive composition in an extremely short time. This explosive composition is divided into 20 mmφ, 30
About 30 to 40 g of a polyethylene laminated paper cylinder of mmφ was filled to form an explosive bag, and the explosive performance was examined. 30m above
The density of mφ explosive package is 0.80 g / cm ³ ,
Can be detonated by No. 6 detonator at 15 ℃, drug temperature 5
The detonation velocity at ° C was 3700 m / s. In addition, the above-mentioned 20 mmφ explosive package was charged into a steel pipe with an inner diameter of 41.6 mmφ and a length of 3 m according to the length of 3 m. The explosive bag was completely detonated and the length of the destroyed steel pipe was 3 m. Furthermore, two 30 mmφ explosive sacks were buried in 80 cm sand at a distance of 15 cm in parallel, and a flashing No. 6 detonator was used on one side.
The other was subjected to a sand dead pressure test in which a 10 ms stepped electric detonator was attached and a detonation was carried out five times. All of them were completely detonated. Furthermore, the same test was performed one year after the production, and the same performance was shown.

Examples 17, 18 and 19 In the same manner as in Example 16, the following explosive compositions were produced, and their explosive properties were examined.

[0046]

[Table 4] The unexpanded organic fine particles 1 were the same as those used in Example 16, and the unexpanded organic fine particles 2 were acrylonitrile / methyl methacrylate copolymer (Expansel Co., Ltd. trade name: 053WU). The fine particles 3 are a copolymer of acrylonitrile and an acrylic acid ester (Matsumoto Yushi Co., Ltd. trade name: Micropearl F-50).

20 mmφ, 3 of the above three explosive compositions
0mmφ explosive packing density is 0.20, 0.30,
It is 0.45, and the 30mmφ explosive package with a drug temperature of -25 ° C is 6
It was possible to detonate with the No. detonator, and the detonation speed at a chemical temperature of 5 ° C was 1900 m / s, 2300 m / s, 2500 m / s. Also, a 20 mmφ explosive charge was charged into a steel pipe with an inner diameter of 41.6 mmφ and a length of 3 m according to the length of 3 m. The length of the steel pipe that was completely destroyed and destroyed was 3 m.
Further, one year after the production, the same test was performed and the same performance was shown.

Example 20 Ammonium nitrate 1346 g, water 240 g, sodium nitrate 80 g, monomethylamine nitrate 174 g and unexpanded organic fine particles (copolymer of vinylidene chloride, acrylonitrile and methacrylic acid ester (trade name of Matsumoto Yushi Co., Ltd .;
160 g of Micropearl F-30) was placed in a stainless steel container and heated in an oil bath at about 80 to 90 ° C. with slow stirring to obtain an explosive composition having an explosive density of 1.38 g / cm ³ . A steel pipe (JIS G 345232A; inner diameter of about 36 mm) in which one side in the longitudinal direction is previously sealed with the explosive composition.
(φ, length: 350 mm), and when detonated with a booster (Unit 2 dynamite 50 g equipped with a No. 6 detonator), a complete detonation occurred. The detonation speed at this time is 5600 m / s
Met. Further, one year after the production, the same test was performed and the same performance was shown.

[0049]

EFFECTS OF THE INVENTION The explosive composition according to the present invention has a structure in which a phase substantially consisting of an oxidant and water is continuously retained on the surface and / or gaps of the adjacent microspheres, whereby A low specific gravity product that has been considered difficult to put into practical use with conventional water-containing explosives, as it not only requires a thickener that is essentially indispensable for maintaining the quality of water-containing explosive compositions, but also can maintain the quality for a long time. Enabled the practical application of. Further, by reducing the specific gravity, noise and vibration at the time of blast can be significantly reduced.

[Brief description of drawings]

FIG. 1 shows a micrograph of the microstructure of an explosive composition according to the present invention.

FIG. 2 is a drawing schematically showing FIG.

FIG. 3 is a drawing schematically showing explosives and compositions according to the prior art.

FIG. 4 Same as above.

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[Procedure amendment]

[Submission date] July 20, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

Next, the method of heat-foaming using the expandable organic fine particles is not particularly limited, but a specific example will be given. The oxidizing agent, water and the expandable organic fine particles are made substantially uniform. After heating to a temperature at which mixing is possible to form a mixed solution, the droplets or droplets of the mixed solution are dropped on a heating plate or in an atmosphere whose temperature is adjusted to a temperature at which the expandable organic microparticles start foaming or A method of spraying to expand the expandable organic fine particles contained in the mixed solution, heating the mixture to a temperature at which the oxidizing agent, water, and the expandable organic fine particles can be mixed almost uniformly to form a mixed solution, and then mixing the mixed solution. A method of injecting a solution into a metal tube whose temperature is controlled to be equal to or higher than the temperature at which the expandable organic microparticles start foaming to foam the expandable organic microparticles contained in the mixed solution in the metal tube, an oxidizing agent and water. Add a mixed solution of expandable organic fine particles. The vessel was heated at a temperature above the outer bath foamable organic microparticles starts foaming put in,
A method of foaming the expandable organic fine particles contained in the mixed solution, heating the oxidizer, water and the expandable organic fine particles uniformly to a temperature at which they can be mixed almost uniformly to form a mixed solution. , A heat-resistant film tube is filled with an amount in which the volume expansion of the mixed solution is expected, and after the air in the film tube is removed and sealed, the temperature is adjusted to a temperature at which the expandable organic fine particles start foaming or higher. A method of foaming the expandable organic fine particles contained in the mixed solution in a heated bath or an oil bath, in which heat is applied to a mixture of an oxidizing agent and water to dissolve most of solid salts such as the oxidizing agent There is a method of mixing a high-concentration salt solution having a temperature equal to or higher than the temperature at which the organic fine organic particles start foaming with the unexpanded organic fine particles. When water evaporates from the composition among these production methods, it is possible to predict the evaporation amount of water in advance and add excess water so as to obtain the desired explosive composition. Further, according to the method for producing the explosive composition of the present invention, the foaming state can be arbitrarily changed by adjusting the temperature, and depending on the purpose, it can be detonated by a booster to one detonated by one detonator. Explosive design is possible. By heating unexpanded organic microparticles, the internal pressure rises and the foaming starts at about the temperature at which the organic polymer film begins to soften, and expands to a range of about 20 to 100 times in volume ratio. To be done. However, if the organic micro-hollow body is ruptured by heating more than necessary, it becomes difficult to obtain the performance as an explosive. Therefore, it is preferable to stop the temperature at the temperature before the over-foaming.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

[0046]

[Table 4] The unexpanded organic fine particles 1 were the same as those used in Example 16, and the unexpanded organic fine particles 2 were acrylonitrile / methyl methacrylate copolymer (Expansel Co., Ltd. trade name: 053WU). The fine particles 3 are a copolymer of acrylonitrile and an acrylic acid ester (Matsumoto Yushi Co., Ltd. trade name: Micropearl F-50).

Claims (2)

[Claims] 1. An oxidizer, water, and an organic micro hollow body,
An explosive composition in which a phase substantially consisting of an oxidizing agent and water is adsorbed and retained on the surface of the organic micro hollow body and / or between the hollow bodies. 2. An expandable organic fine particle 2 to 15% by weight, water 3 to 20% by weight, and a remaining component mainly consisting of an oxidizing agent are mixed to prepare a composition substantially free from entrained air bubbles, and then the composition is prepared. A method for producing an explosive composition comprising an organic microhollow body, which is substantially composed of an oxidizing agent, water, and an organic microhollow body, as a combustible component, which comprises heating and foaming the composition.