JPH03122085A - Pressure-formed explosives - Google Patents

Abstract

PURPOSE:To obtain the subject comparatively economical pressure-formed explosives excellent in water resistance and capable of direct load to a bore hole by pressure forming an explosive mixture composed of an oxidizing agent and a fuel material or a mixture composed of an oxidizing agent and a water in oil type emulsion explosive. CONSTITUTION:An explosive mixture composed of an oxidizing agent consisting of one of various shaped ammonium nitrates such as a granular, powdery and porous prill-shaped one, especially preferably a granular one and a fuel material consisting of a wax and/or a resin is prepared. Or the preparation is carried out also by using a mixture composed of the above-mentioned oxidizing agent and a water in oil type emulsion explosive. The resultant prepared material is pressure formed to obtain the objective pressure-formed explosives. In addition, in case a porous prill-shaped ammonium nitrate having <=1.4mm particle size among the above mentioned porous prill-shaped ones is used, the explosiveness is most preferably improved. The amount of the oxidizing agent used in the explosive mixture is preferably within a range of 85-98 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a pressure-molded explosive used in industrial blasting operations such as quarrying, civil engineering, and mining.

(Prior art) A typical example of an explosive consisting of a mixture of an oxidizing agent and a fuel substance is an ammonium nitrate oil explosive, which is a mixture of ammonium nitrate and an oil agent.This explosive cannot be detonated with a single detonator, so ,
A booster explosive is used, but because it is a granular material with relatively insensitive characteristics and fluidity, it can be poured directly into the blasting borehole, and the entire borehole can be tightly packed. It is also well known that the unit price of the product is lower than that of other explosives, so it is widely used as an industrial blasting agent.

(Problem to be solved by the invention) Ammonium nitrate oil explosives, which are the most typical type of mixed explosives consisting of an oxidizing agent and a fuel substance, are widely used because they are safe to handle and inexpensive. However, the main component is ammonium nitrate, and when it is poured directly into a borehole and loaded, it has the disadvantage that ammonium nitrate easily dissolves in the presence of water in the borehole, making it insensitive and preventing it from exploding. Therefore, its use is restricted in boreholes with spring water and open-pit mining sites in rainy weather. As a countermeasure, a method of using ammonium nitrate explosives is used by filling water-resistant plastic cartridges with cracks. However, if the cartridge is damaged and damaged by the pore-hole wall and water enters inside, the ammonium nitrate will easily dissolve. Also, since the bulk specific gravity of the cartridge as a whole is smaller than that of water, it is necessary to take measures such as adding weight to the cartridge in order to sink it into the water hole.

Loading work becomes extremely complicated.

Alternatively, water-resistant explosives are used at such sites. Among water-resistant explosives, TNT-based explosives are used as explosives that can be poured directly. T
NT is a high-density, high-performance explosive that easily deposits in water holes, but TNT itself is explosives and must be handled with great care. Explosives cost more.

Other water-resistant explosives used include Sura IJ-explosives and dynamite, but these are cartridge-type explosives that are individually packed in a cartridge, and can be poured directly into a borehole like ammonium nitrate explosives. I can't. Therefore, a gap is created between the borehole and the loaded cartridge, making it impossible to tightly fill the entire borehole. Also, compared to ammonium nitrate explosives, the unit price is higher (which leads to an increase in blasting costs).

In addition, various studies have been conducted to improve the water resistance of ammonium nitrate explosives themselves, and one of them is a method of adding and mixing special drying ingredients to ammonium nitrate explosives. However, with this method, direct loading into the water hole is not possible, and the borehole must be drained beforehand and then loaded. If spring water occurs after loading, a special drying component interacts with the water to cause gelation, thereby preventing water from penetrating into the interior of the explosive. Therefore, the water resistance performance of this type of ammonium nitrate oil explosive cannot essentially be said to be water resistant.

As described above, a safe and inexpensive explosive consisting of a mixture of oxidizing agent and fuel material can be directly loaded into the water hole.
The big challenge was to improve it.

(Means for solving the problem) The present inventors have developed a mixed explosive consisting of an oxidizing agent and a fuel substance.
As a result of extensive research, we have developed a method that allows for direct loading into water holes, using a predetermined amount of an explosive mixture consisting of an oxidizing agent and a fuel substance, or a mixture of an oxidizing agent and a water-in-oil emulsion explosive (hereinafter referred to as W10 emulsion explosive). It was discovered that by press molding, it is possible to make an explosive that has excellent water resistance and can be directly filled into boreholes. That is, in the present invention, an explosive mixture consisting of an oxidizing agent and a fuel substance or a mixture of an oxidizing agent and a W10 type emulsion explosive is pressure-molded! #! This relates to a pressure-molded explosive with f-characteristics.

The oxidizing agent used in the present invention or the oxidizing agent in the mixed explosive mixture includes ammonium nitrate, alkali metal nitrates,
Alkaline earth metal nitrates, alkali metal chlorates,
Alkaline earth metal chlorates, alkali metal perchlorates, alkaline earth metal perchlorates, and ammonium perchlorate are used alone or in combination.

Among the oxidizing agents used in the present invention, the most economical and widely used oxidizing agent is ammonium nitrate, which is used in various forms such as powder, granules, and porous grills. Since ammonium nitrate has voids inside, it comes into close contact with the fuel material, and its detonation sensitivity is better than other ammonium nitrates.Furthermore, among porous sprill ammonium nitrates, fine porous ones with a particle size of 1.4n or less are used. The use of prill ammonium nitrate improves the explosive performance and is most preferred. In the present invention, the oxidizing agent in the explosive mixture is preferably used in the range of 85 to 98% by weight in the explosive mixture, and the oxidizing agent or the explosive mixture The oxidizing agent is preferably used in an amount of 50 to 97% by weight based on the entire pressure-molded explosive.

The fuel substances used in the explosive mixture of the present invention include hydrocarbon-containing fuel substances, including ammonium nitrate explosives, petroleum oils such as mineral oil and kerosene, and hydrophobic animal and vegetable oils, in addition to commonly used light oil. , paraffin wax, microcrystalline wax, petroleum waxes such as hetrolatum,
Animal and vegetable waxes such as wool wax and carnauba wax, and mineral waxes such as monothane wax can be used alone or in combination.

Furthermore, compatible resins can be used in combination with waxes and oils. In addition, when petroleum resin, polyisobutylene resin, butadiene resin, polyethylene wax, ethylene vinyl acetate copolymer, etc. are used as resins that can be used alone, the pressure-molded explosive of the present invention can
In particular, when the outer surface is not coated with a hydrophobic substance, it exhibits better water resistance than pressure-molded explosives using only oils or waxes, which is advantageous.

The petroleum resin used as the fuel material of the present invention is a resin obtained by polymerizing the fraction obtained in the naphtha cracking process, and includes C6 petroleum resin obtained by polymerizing a C3 fraction, C petroleum resin obtained by polymerizing a C0 fraction,
C and CO copolymerized petroleum resins obtained by copolymerizing both fractions, preferably having a molecular weight of 600 to 2,500.

The polyisobutylene resin used as the fuel material of the present invention is a polymer of high purity isobutylene, and has a molecular weight of 500C~
140,000 is preferred.

The butadiene resin used as the fuel material of the present invention is
Polymerize butadine of the general formula (CH2=CHCH=CHt) as a main component, and 1.2 bonding parts and/or
A double bond is left at the 1,4 bond, and the terminal part is [-H], (-COOHI or (-CH, -CH, O
H] with a molecular weight of 500 to 20,000
0 butadiene resin is preferred.

The polyethylene wax used as the fuel material of the present invention is an ethylene polymer represented by the general formula CCH2=CH, and preferably has a molecular weight of 1,000 to 10,000.

The ethylene-vinyl acetate copolymer used as the fuel material of the present invention is a copolymer of ethylene represented by the general formula (CH2=CH2) and vinyl acetate represented by the general formula (CH3CO0CH=CI-■2). , a melt index of 2 to 500, and a vinyl acetate content of 5
Weight percent to 50 weight percent ethylene vinyl acetate copolymer is preferred.

In addition to the oil agent of the present invention, Wanox, or a mixture of these and resins, a nitro compound such as dinitrotoluene, dinitroxylene, dinitronaphthalene, or a metal powder such as aluminum powder, magnesium powder, or silicon iron is used. It is also possible to do so.

In the present invention, the fuel substances in the explosive mixture are preferably used in the range of 2 to 15% by weight in the explosive mixture.

The WlO type emulsion explosion used in the present invention consists of an oxidizing agent aqueous solution, oils, and an emulsifier, and if necessary,
Microscopic hollow spheres can be added to form an emulsion structure in which fine droplets of an aqueous oxidizing agent solution form an internal discontinuous phase and oils form an external continuous phase are covered with a thin film by the emulsifying power of the emulsifier. are doing.

The aqueous oxidizer solution of the W10 type emuldimine explosive used in the present invention includes ammonium nitrate, alkali metal hydrochlorides,
Alkaline earth metal nitrates, alkali metal chlorates,
Alkaline earth metal chlorates, alkali metal perchlorates, alkaline earth perchlorates, and ammonium perchlorate are dissolved in water alone or in combination.

In addition, water-soluble amine nitrates such as monomethylamine nitrate, monoethylamine nitrate, hydrazine nitrate, dimethylamine dinitrate, methanolamine nitrate, ethanolamine nitrate, etc. are added to the oxidizing agent aqueous solution in the W10 emulsion explosive used in the present invention. Water-soluble alkanolamine nitrates and water-soluble ethylene glycol mononitrate can be used as co-sensitizers.

The content of filtrate in the oxidizing agent aqueous solution is preferably used within a range such that the crystal precipitation temperature of the oxidizing agent aqueous solution is 30 to 90°C, and preferably 5 to 4% per oxidizing agent aqueous solution.
0% by weight is used, more preferably 7-30% by weight.

In the oxidizing agent aqueous solution, a water-soluble organic solvent such as methyl alcohol, ethyl alcohol, homamide, ethylene glycol, glycerin, etc. can be used as an auxiliary solvent in order to lower the crystal precipitation temperature.

In the present invention, the oxidizing agent aqueous solution is preferably used in a range of 60 to 95 weight range for W10 type emulsion explosive.

The emulsifier in the W10 type emulsion explosive used in the present invention is an emulsifier normally used for producing the W10 type emulsion, such as alkali metal stearate, ammonium stearate, calcium stearate, polyoxyethylene ether, sorbitan fatty acid ester, etc. , glycerin fatty acid esters, etc. are used.

Among these emulsifiers, it is preferable to use an organic surfactant in which a hydrophobic group is formed with a long-chain unsaturated fatty acid having 10 to 24 carbon atoms.

The emulsifier in the W/0 emulsion explosive used in the present invention can be used preferably in an amount of 0.5 to 15% by weight based on the W10 emulsion explosive.

The oils used in the W10 emulsion explosive used in the present invention are hydrophobic oils that are incompatible with water, such as animal and vegetable oils, mineral oils, light oil, kerosene, mineral oil, paraffin wax, and microcrystalline wax. , petrolatum, etc. alone or in mixtures. Furthermore, it is also possible to use resins such as petroleum resins, polyisobutylene resins, butadiene resins, and ethylene-vinyl acetate copolymers alone or in combination with the above-mentioned oils.

The oil used in the W10 type emulsion explosive used in the present invention is 0.5 to 15% of the emulsion explosive.
Preferably, it is used in a range of % by weight.

Micro hollow spheres can be used in the W10 type emulsion explosive used in the pressure-molded explosive of the present invention for sensitization. In particular, when the content of emulsion explosive in the pressure-molded explosive is high, the use of micro hollow spheres is more effective for sensitization. As a micro hollow sphere, made of glass,
Alternatively, in addition to resin micro hollow spheres, shirasu balloons, perlite, etc. can be used.

The micro hollow spheres in the W10 type emulsion explosive used in the pressure-molded explosive of the present invention are preferably used in an amount of 0 to 10% by weight based on the entire emulsion explosive.

The W10 type emulsion explosive used in the pressure-molded explosive of the present invention is preferably 3 to 3% of the total pressure-molded explosive.
It is used in a range of 50% by weight.

Pressure molding of the present invention means putting a predetermined amount of a mixture of an oxidizing agent or an explosive mixture consisting of an oxidizing agent and a fuel substance and a W10 emulsion explosive into a mold, pressurizing it, and forming an aggregate of mixture particles. However, there are no particular limitations on the shape of the molded product. Depending on the shape of the formwork, cylindrical,
It can be molded into any shape such as a disc, sphere, or prism.

The weight of a single piece of the pressure-molded explosive of the present invention can be arbitrarily selected, but from the viewpoint of ease of loading into a pore hole and detonation performance of the loaded pressure-molded explosive as a whole, it is within the range of 1 g to 30 g. Something is desirable.

In addition, the density of one pressure-molded explosive depends on its settling ability in water holes and
In order to maintain adequate detonation performance, a range of 1.0 g/cc to 1.30 g/cc is preferred.

The pressure-molded explosive obtained by pressure-molding of the present invention exhibits superior water resistance performance compared to the conventional ammonium nitrate oil explosive. We have discovered that by coating the outer surface of each piece with a hydrophobic substance, water resistance can be dramatically improved.

As the hydrophobic substance for coating used in the present invention, in general, a substance that repels water can be used. Petroleum oils such as mineral oil and heavy oil, petroleum waxes such as paraffin wax, microcrystalline wax, and petrolatum, synthetic oils such as silicone oil, wool wax,
Animal waxes such as beeswax, vegetable waxes such as carnauba wax and tree wax, higher fatty acids such as myristic acid and stearic acid, higher alcohols such as cetyl alcohol and stearyl alcohol, petroleum resin, polyethylene wax, butadiene resin, polyester Individual resins such as isobutylene resin, ethylene vinyl acetate copolymer, epoxy resin,
Alternatively, a mixture of two or more types is preferably used.

Among hydrophobic substances for coating, waxes such as paraffin fuchs and microcrystalline wax, resins that are solid at room temperature, singly or in mixtures, or mixtures of the above-mentioned hydrophobic substances that are solid at room temperature. The waterproof effect is further improved by using a material exhibiting the following.

Methods for coating the outer surface of a pressure-molded explosive with a hydrophobic substance include impregnating it in a heated and melted hydrophobic substance, or in a solution prepared by diluting a hydrophobic substance in an appropriate solvent;
Alternatively, it may be carried out by spraying a molten hydrophobic substance or a hydrophobic substance diluted in a suitable solvent.

The amount of coating hydrophobic substance used in the present invention is:
0.01 g to 0.1 g per unit duram of pressure-formed explosives
It is desirable that the range be within this range.

(Function) The present inventors have developed a hydrophobic material by pressure molding an explosive mixture consisting of an oxidizing agent and a fuel substance or a mixture of an oxidizing agent and a W10 type emulsion explosive, or by further applying a hydrophobic coating to the outer surface of a pressure molded explosive. They discovered that by coating it with a chemical substance, it is possible to make an explosive that can be poured directly into water holes and exhibit sufficient water resistance.

(Example) The present invention will be described in detail below with reference to Examples.

Example 1 6 parts of No. 2 light oil (manufactured by Nippon Oil Company) were added to 94 parts of fine porous sprill ammonium nitrate (manufactured by Sumiya Kagaku Kogyo ■) with a particle size of 1.4 mm or less, and mixed thoroughly to obtain a granular explosive mixture. Ta. Next, sorbitan monooleate (Kao Co., Ltd.) was prepared by heating and dissolving an aqueous solution of an oxidizing agent consisting of 72 parts of granular ammonium nitrate (manufactured by Sumima Kagaku Kogyo Co., Ltd.), 10 parts of nitric acid (produced by Ube Industries Co., Ltd.), and 12 parts of water. The mixture was added little by little to a mixture of 2.5 parts of Rheodol 5PO-10, manufactured by Esso Oil Company, Ltd., and 3.5 parts of microcrystalline wax (Nisrax 172, manufactured by Esso Oil Company Ltd.) with stirring, to obtain a W/0 type emulsion explosive. Then, 80 parts of the granular explosive mixture and 20 parts of the WZO emulsion explosive were sufficiently mixed to obtain an explosive mixture. 5 g of this mixture was weighed, put into a cylindrical mold, and pressurized so that the density of one pressure-molded explosive became 1.15 g/cc to obtain a pressure-molded explosive.

Example 2 94 parts of fine porous sprill ammonium nitrate with a particle size of 1.4 mm or less (manufactured by Sumitomo Chemical Co., Ltd.) and 6 parts of paraffin wax (manufactured by Nippon Seiro, Ltd., 130°F paraffin wax) that had been heated and melted in advance were mixed. to destroy the granular explosive mixture. Next, this mixture 8
0 parts and W1 made with the same composition and the same manufacturing method as Example 1
20 parts of Type 0 emulsion explosive were mixed to obtain an explosive mixture. A similar pressure-molded explosive was obtained from this mixture in the same manner as in Example 1.

Example 3 94 parts of fine porous sprill ammonium nitrate having a particle size of 1.4III or less (manufactured by Sumiya Kagaku Kogyo ■) and paraffin wax (manufactured by Hiki Seiro ■, 130°F paraffin) pre-heated and melted and mixed 5.4 part and ethylene vinyl acetate copolymer (
Manufactured by Mitsui Polychemical ■, Evaflex≠250) 0.
Six parts of the mixture were mixed to obtain a granular explosive mixture. Next, 80 parts of this mixture was mixed with 20 parts of a W10 type emulsion/explosive made by the same composition and manufacturing method as in Example 1 to obtain an explosive mixture. A similar pressure-molded explosive was obtained from this mixture in the same manner as in Example 1.

Example 4 94 parts of fine porous sprill ammonium nitrate (manufactured by Sumikata Chemical Co., Ltd.) with a particle size of 1.4 cm or less and paraffin wax (manufactured by Nippon Seiso, 130°F paraffin wax 7) pre-heated and melted and mixed.
5.2 parts, 0.2 parts of petroleum resin (manufactured by Toho Oil Resin ■, Toho High Resin≠75), and ethylene-vinyl acetate copolymer (Mitsui Polychemical ■, Evaflex +
250) 0.6 part of the mixture was mixed to obtain a granular explosive mixture. Next, 64 parts of granular ammonium nitrate (manufactured by Sumikata Chemical Co., Ltd.),
Sorbitan monooleate (Rheodol 5PO-10, Kao Corporation) prepared by heating and mixing an oxidizing agent aqueous solution consisting of 5 parts of sodium nitrate (Ube Industries, Ltd.) and 10 parts of water.5.
0 parts and microcrystalline wax (Esso Oil ■
Add little by little to a mixture of 15 parts of Nisrax 172 (manufactured by Nisrax 172) with stirring, and then add 1.0 part of micro hollow spheres (Calas Bapulus C-15/250, manufactured by Sumikata 3M) and mix thoroughly to form a W10 emulsion. I got explosives. 60 parts of the above granular explosive mixture and 40 parts of W10 type emulsion explosive
The parts were mixed to obtain an explosive mixture. This mixture Log was weighed, put into a cylindrical mold, and pressurized so that the density of one pressure-molded explosive became 1.10 g/cc to obtain a pressure-molded explosive.

Example 5 94 parts of fine porous sprill ammonium nitrate having a particle size of 1.4111i1 or less (Sumikata Chemical Co., Ltd. M) and 5.4 parts of paraffin wax (Nippon Kozue Wax, 130°F Barafui 7) were heated and mixed in advance. and 0.6 parts of petroleum resin (manufactured by Toho Oil Resin ■, Tohono Iregi/+75) were mixed to obtain a granular explosive mixture. 80 parts of this mixture and 20 parts of a W10 type emulsion explosive made by the same composition and the same manufacturing method as in Example 1 were thoroughly mixed to obtain an explosive mixture.

Weigh 5g of this mixture and pressurize it to give a density of 1.15g/c.
A pressure-molded explosive of c was obtained. Furthermore, paraffin wax,
The outer surface is coated with a hydrophobic substance made of petrolatum and petroleum resin to enhance the pressure-molded explosive.

Example 6 Fine porous sprill ammonium nitrate with a particle size of 1.4fIx or less (
5. Paraffin wax (Japanese wax pear, 130°F paraffin) was heated and mixed in a mixture of 80 parts of Sumikata Chemical Industry Co., Ltd. and 14 parts of ammonium perchlorate (Hayashi Junyaku Kogyo Co., Ltd.).5. 4 parts and ethylene-vinyl acetate copolymer (Mitsui Polychemical ■Crack, Evaflex≠250) 0.6
of the mixture was added and thoroughly mixed to obtain a granular explosive mixture.

Next, 90 parts of this mixture was mixed with 10 parts of a W10 type emulsion explosive made by the same composition and the same manufacturing method as in Example 1 to obtain an explosive mixture. Weigh 5g of this mixture and place it in a cylindrical mold so that the density of one pressure-molded explosive is 1.1.
Pressure was applied to 0 g/cc to obtain a pressure-molded explosive. Furthermore, it was coated with the same hydrophobic substance as in Example 5 to obtain a pressure-molded explosive.

Example 7 80 parts of fine porous grilled ammonium nitrate having a particle size of 1.4H or less and 20 parts of a W10 type emulsion explosive made by the same composition and the same manufacturing method as in Example 1 were mixed to obtain an explosive mixture.

Weigh 5g of this mixture and pressurize it to a density of 1.08g/c.
A pressure-molded explosive of c was obtained. Furthermore, it was coated with the same hydrophobic substance as in Example 5 to obtain a pressure-molded explosive.

Example 8 A granular explosive mixture was obtained by mixing 94 parts of porous sprill ammonium nitrate (Sumikata Chemical Co., Ltd. TMFF) and 6 parts of paraffin wax (manufactured by Nippon Seiro Co., Ltd., 130°F Halafin). next,
Glycerino monooleate (Rheodor K MO-60, manufactured by Kao ■) prepared by heating and melting and mixing an oxidizing agent aqueous solution consisting of 72 parts of granular ammonium nitrate (manufactured by Sumikata Chemical Co., Ltd.) and 11 parts of water.
The mixture was added with stirring to a mixture of 3.5 parts of microcrystalline wax and 13.5 parts of microcrystalline wax (Nisrax 4+172, manufactured by Ninoso Oil Co., Ltd.), and the W10 type emulsion explosive was dissolved.

70 parts of the granular explosive mixture described above and 30 parts of W10 type emulsion explosive were sufficiently mixed to obtain an explosive mixture. Weighed 15 g of this mixture, and determined that the density of one pressure-molded explosive was 1,
Pressure was applied to 10 g/cc to obtain a pressure-molded explosive. Furthermore, a pressure-molded explosive was obtained by coating the outer surface with a hydrophobic substance consisting of paraffin wax, microcrystalline wax, and ethylene-vinyl acetate copolymer.

Example 9 A granular explosive mixture was prepared by mixing 94 parts of fine porous sprill ammonium nitrate with a particle size of 1.41 or less (manufactured by Sumima Kagaku Kogyo) and 6 parts of paraffin wax (Nippon Seiro Co., Ltd., 1300F Parafi/). Next, granular ammonium nitrate (Sukkata Chemical Co., Ltd.
f) 73.3 parts, nitric acid) IJum (manufactured by Ube Industries)
2.0 parts of sorbitan monooleate (Rheodol 5PO-10, manufactured by Kao ■), microcrystalline wax (manufactured by Ninoso Oil ■, Nislax≠), which was prepared by heating and dissolving an oxidizing agent aqueous solution consisting of 10 parts of oxidizing agent and 11 parts of water. 172
) and 0.7 parts of petroleum resin (manufactured by Toho Oil Resin ■, Toho Hi-Regi / +75) with stirring, thoroughly mixed, and then added micro hollow spheres (manufactured by Sumikata 3M ■). , Glass Bubbles C-15/250) was added and mixed uniformly to obtain a W10 type emulsion explosive. An explosive mixture was obtained by mixing 70 parts of the above-described explosive mixture and 30 parts of a W10 type emulsion explosive. This mixture was pressure molded in the same manner as in Example 8 and coated with a hydrophobic substance to obtain a pressure molded explosive.

Example 10 93 parts of powdered ammonium nitrate (manufactured by Ube Industries, Ltd.), 5.4 parts of paraffin wax (manufactured by Nippon Seiro, Ltd., 130°F paraffin wax) which had been heated and melted and mixed in advance, and petroleum resin (manufactured by Toho Oil Resin, Ltd., Tohono) - A mixture of 0.6 part of Iresin 475) was mixed uniformly, and 1.0 part of aluminum powder (manufactured by Toyo Aluminum Kiki Co., Ltd., POloo) was further added and mixed to obtain a powdered explosive mixture. 80 parts of this mixture and 20 parts of W10 type emulsion explosive made with the same composition and the same manufacturing method as in Example 1.
The parts were mixed to obtain an explosive mixture. 10 g of this mixture was weighed, put into a cylindrical mold, and pressurized so that the density of one pressure-molded explosive was 1.20 g/cc to obtain a pressure-molded explosive. Furthermore, the same hydrophobic substance as in Example 8 was coated to obtain a pressure-molded explosive.

Example 11 95 parts and 5 parts of a W/0 type emulsion explosive were mixed with a granular explosive mixture having the same composition and the same manufacturing method as in Example 3 to obtain an explosive mixture. This mixture 20
Weigh out g, put it into a cylindrical mold, and make a density of 1.05g/
The pressure was applied to cc to obtain a pressure-molded explosive. In addition, the outer surface was coated with paraffin wax to enhance the pressure-molded explosive.

Example 12 98 parts of fine porous sprill ammonium nitrate with a particle size of 1.4 fl or less (manufactured by Sumitomo Chemical Industry Co., Ltd.), paraffin wax (Japanese Seiro ■chiri, 130°F paraffin) pre-heated and melted and mixed.
1.8 parts and ethylene vinyl acetate copolymer (Mitsui Pol)
) and 0.2 parts of Evaflex+250 (manufactured by Chemical Kiki Co., Ltd.) were thoroughly mixed to obtain a granular explosive mixture. Next, 71.8 parts of granular ammonium nitrate (manufactured by Sumitomo Kagaku Kogyo Kiki) and nitric acid)
Sorbitan monooleate (Kao Kema, Rheodol 5PO-10) is prepared by heating and dissolving and mixing an oxidizing agent aqueous solution consisting of 10 parts of IJum (Ube Industries ■g) and 12 parts of water.
2.0 parts, microcrystalline wax (manufactured by Esso Oil ■, Nislax≠172), 2.5 parts, and petroleum resin (manufactured by Toho Oil Resin ■, Toho Hi-Resi/≠75) 0.
7 parts of the mixture with stirring, and further added micro hollow spheres (Dennis 3M ■Crack, Karas Hafrus C-15/25).
0) was added and thoroughly mixed to obtain a W10 type emulsion explosive. 60 parts of the granular explosive mixture described above and W1
40 parts of type 0 emulsion explosive were mixed to obtain an explosive mixture. 3 g of this mixture was weighed, put into a cylindrical mold, and pressurized to a density of 1.25 g/cc to obtain a pressure-molded explosive. Furthermore, the outer surface was coated with paraffin wax to obtain a pressure-molded explosive.

Example 13 Polyethylene wax (Sunwax 151P, manufactured by Sanyo Chemical Industries, Ltd.) 6 heated and melted in 94 parts of fine porous sprill ammonium nitrate (manufactured by Sumitomo Chemical Co., Ltd.) with a particle size of 1.4 W or less
1 part and thoroughly mixed to obtain a granular explosive mixture. 80 parts of this mixture and 20 parts of a W10 type emulsion explosive made by the same composition and manufacturing method as in Example 1 were sufficiently mixed to obtain an explosive mixture. 5 g of this mixture was weighed, put into a cylindrical mold, and pressurized to a density of 1.15 g/cc to obtain a pressure-molded explosive. Furthermore, the outer surface was coated with paraffin wax to obtain a pressure-molded explosive.

Comparative Example 1 94 parts of porous sprill ammonium nitrate (manufactured by Sumikata Chemical Co., Ltd.) and 6 parts of No. 2 light oil (manufactured by Nippon Oil Company) were mixed to obtain a granular explosive composition (ammonium nitrate explosive).

Comparative Example 2 A granular explosive composition was obtained using the same composition and the same manufacturing method as in Example 8.

Comparative example 3 A granular explosive was obtained using the same composition and the same manufacturing method as in Example 3.

Comparative Example 4 93.2 parts of fine porous sprill ammonium nitrate (manufactured by Sumikata Chemical Industry Co., Ltd.) with a particle size of 1.4 ff1l11 or less was heated and dissolved in paraffin wax (1 Nippon Seiso W, 1a).

Add 5.8 parts of 0F paraffin, mix thoroughly, and add 1 part of aluminum powder (POloo, manufactured by Toyo Aluminum Kiki).
．． 0 parts were added and thoroughly mixed to obtain a granular explosive composition.

Comparative Example 5 A granular explosive composition was obtained using the same composition and the same manufacturing method as in Example 6.

The compositions of Examples 1 to 13 and Comparative Examples 1 to 5 are summarized in Table 1.

All of these compositions were subjected to water resistance tests and comparative studies were conducted. Water resistance test: inner diameter 65III, length 10
A simulated water hole was made by filling a 00111m steel pipe with water, and the pressure-molded explosives of Examples 1 to 13 and Comparative Example 1 were placed inside the steel pipe.
~50 granular explosives were each filled, and the detonation speed performance was measured in response to the elapsed time after filling. As a method to examine detonation velocity performance, a pentolite with a diameter of 60 mm and a weight of 200 g was used as a transfer charge, detonated from the top of a steel pipe, and 15a @ and 5 (2 m of The average detonation velocity between points was measured.

These results are summarized in Table 2.

(Effects of the Invention) In contrast, the pressure-molded explosive of the present invention has a water resistance performance of 20 to 60 minutes depending on the composition without coating the outer surface with a hydrophobic substance. It is clear that water resistance is improved by pressure molding.

Moreover, when Examples 1 to 3 are compared with each other, there are differences in water resistance depending on the fuel in the granular explosive mixture. That is, the case where light oil is used has the worst water resistance, and the case where a mixture of wax and resin is used shows the best water resistance. next,
Examples 1 to 4 and Example 5. Comparing 13 to 13, it is clear that coating the outer surface of the pressure-molded explosive with a hydrophobic substance dramatically improves its water resistance.
Maintains water resistance. Next, when comparing Examples 8 and 9, it is found that the use of fine porous sprill ammonium nitrate increases the explosion velocity value, which is favorable in terms of performance.

※ 2 ※ 3 ※ 4 ※ 5 ※ 6 ※ 7 ≧ 8 ※ 9 ※ 10 Sumikata Chemical Co., Ltd. Example of particle size distribution An example of +14 meshes +16 +20 +24
+35 -35 Ube Industries ■ Seirin Pure Chemical Industries ■ Nippon Oil ■ No. 2 diesel oil Japanese wax ■ 130°F paraffin Toho oil resin ■ Split Toho Hi-Resi / ≠ 75 Mitsui Polychemical ■ Evaflex ≠ 250 Toyo PO100 made by Aluminum Kikou Sumikata Chemical Industries ■Cracked granular nitrate Ube Industries ■Reodol 5POIO manufactured by Kao ■Reodore MO-60 manufactured by Kao ■Nisrax 172 manufactured by Kotsuso Oil ■Glass Bubbles C-15/250 manufactured by Sumitomo 3M ■15/250 *16 A: Paraffin wanox/petrolatum/petroleum resin (85/1015) B: Paralye/wax/microcrystalline wax/ethylene vinyl acetate copolymer (65/3015) C: Paraffin wanox *17 Manufactured by Mitsubishi Chemical Corporation, Su/Wax 151P*
11 * 12 * 13 * 14 * 15 Procedural auxiliary device February 13, 1989

Claims (1)

[Claims] 1. A pressure-molded explosive characterized by pressure-molding an explosive mixture consisting of an oxidizing agent and a fuel substance or a mixture of an oxidizing agent and a water-in-oil emulsion explosive. 2. The pressure-molded explosive according to claim 1, wherein fine porous sprill ammonium nitrate having a particle size of 1.4 mm or less is used as the oxidizing agent. 3. Claim 1 characterized in that waxes and/or resins are used as the fuel substance of the explosive mixture
The pressure-molded explosive described in item 1 or 2. 4. The pressure-molded explosive according to claim 1 or 2, characterized in that the pressure-molded explosive is further coated with a hydrophobic substance.