JP3019375B2 - Water-in-oil emulsion explosive composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a water-in-oil emulsion explosive (hereinafter abbreviated as W / O explosive) composition having high underwater explosion energy.

[Conventional technology]

Conventionally, among the items for evaluating the power of explosives, the degree of martyrdom, the ratio of ballistic mortars, the explosion speed, etc., have been studied, and in recent years, the research on underwater explosive energy has also been conducted.

W / O explosives containing aluminum powder include those described in JP-A-54-110308, U.S. Pat.No. 3,770,522, U.S. Pat. Uses glass microballoons (GMB) and further contains aluminum powder.

Further, as a method of increasing the underwater explosion energy of the W / O explosive composition, a method of increasing the content of an inorganic oxide such as ammonium nitrate, sodium nitrate, potassium nitrate, and the like has been considered.

[Problems to be solved by the invention]

However, the power of the W / O explosive composition of the above three conventional inventions, such as the explosion speed, the degree of marty, and the ratio of the ballistic mortar, is improved.
When GMB and aluminum powder are used together, the amount of aluminum powder is limited in terms of production, and its content is 20% by weight.
It is about. And there was a problem that it would not explode if the content of aluminum powder was increased. In addition, an increase in the content of the inorganic oxide salt has a limit in production, and therefore its effect is small.

An object of the present invention is to provide a W / O having a particularly high underwater explosion energy.
An object of the present invention is to provide an explosive composition.

[Means for solving the problem]

In order to achieve the above object, a first aspect of the present invention provides a continuous phase composed of a carbonaceous fuel component, a dispersed phase composed of an aqueous solution of an inorganic oxide salt, and a water-in-oil composed of an emulsifier, a sensitizer, and a bubble retainer. In the emulsion-type explosive composition, the cell holding agent is an organic cell holding agent, and the content thereof is 1 to 50% by volume.
Further, a means of containing 10 to 70% by weight of aluminum powder having an average particle size of 1 mm or less is employed.

Further, in the second invention, in the water-in-oil emulsion explosive composition comprising a continuous phase composed of a carbonaceous fuel component, a dispersed phase composed of an aqueous solution of an inorganic oxide salt, an emulsifier and a bubble retainer, the foam retainer is preferably used. An organic cell holding agent having an average particle diameter of 10 to 4000 μm, the content of which is 1 to 50% by volume, and the aluminum powder has an average particle diameter of 1 mm or less and a content of 10
Means of about 70% by weight.

[Detailed description of means]

Carbonaceous fuels that form a continuous phase and that have been used in conventional W / O explosives are used. For example, in the first invention, waxes such as microcrystalline wax, paraffin wax, polyethylene wax,
Fuel oils such as No. diesel oil and the like conventionally used in W / O explosives can be used, and among them, waxes are preferred from the viewpoint of chemical properties such as hardness. In the second invention, for example, paraffinic hydrocarbons, olefinic hydrocarbons, naphthenic hydrocarbons, aromatic hydrocarbons, saturated or unsaturated hydrocarbons, petroleum refined steel oil, lubricating oil, liquid paraffin, etc. Hydrocarbon derivatives such as hydrocarbons and nitrohydrocarbons;
Unrefined or refined microcrystalline wax, paraffin wax, petrolatum, etc. derived from fuel oil and / or petroleum; waxes such as montan wax which is a mineral wax; whale wax which is an animal wax such as montan wax; and beeswax which is an insect wax. And these can be used alone or as a mixture. Among these carbonaceous fuels, microcrystalline wax and petrolactam are preferable from the viewpoint of stability over time, and microcrystalline wax is particularly preferable.

In addition, a petroleum resin, a low-molecular-weight hydrocarbon polymer such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, or the like may be used in combination with the carbonaceous fuel component for adjusting the drug quality. These carbonaceous fuels are typically 1 to 10 w / o explosives.
Use by weight%.

Next, the inorganic oxyacid salt forms a dispersed phase as an aqueous solution, and includes those conventionally used in W / O explosive compositions. Examples of the inorganic oxidate include nitrates of alkali metals or alkaline earth metals such as ammonium nitrate, sodium nitrate and calcium nitrate; inorganic chlorates such as sodium chlorate, ammonium perchlorate and sodium perchlorate; and perchloric acid. Salt and the like. Usually, it is used as ammonium nitrate alone or as a mixture of ammonium nitrate and another inorganic oxide. The mixing ratio of these inorganic oxide salts is generally 5 to 90% by weight, and 70 to 80% by weight.
Is preferred.

The ratio of water in the W / O explosive composition of the present invention is 3 to 3
It is preferably 0% by weight, more preferably 7 to 30% by weight.

Next, the emulsifier plays a role of stabilizing the emulsion, and any of those conventionally used in W / O explosives can be used. For example, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan dioleate, sorbitan fatty acid esters such as sorbitan trioleate, mono- or fatty acid monoesters such as stearic acid monoglyceride Diglyceride, polyoxyethylene sorbitan fatty acid ester,
Oxazoline derivatives, imidazoline derivatives, phosphate esters, alkali metal salts or alkaline earth metal salts of fatty acids, primary, secondary and tertiary amine salts, and the like, and these are used as one kind or as a mixture of two or more kinds be able to. Of the above emulsifiers, sorbitan fatty acid esters are preferred. The mixing ratio of the emulsifier is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight.

A sensitizer enhances detonation reliability and further improves low-temperature detonation. For example, conventional W / O such as monomethylamine nitrate, hydrazine nitrate, ethylenediamine nitrate, etc.
What is used for explosives can be used,
Of these, hydrazine nitrate, which can increase the solubility of the ammonium nitrate and has a high explosion energy, is preferable. When a sharpening agent is used, its mixing ratio is preferably 1 to 40% by weight, more preferably 30% by weight or less, and particularly preferably 20% by weight or less in the W / O explosive composition. If this proportion exceeds 40% by weight, the danger in handling may increase.

In particular, when hydrazine nitrate or the like is used as a sensitizer, the use of a chelating agent such as sodium ethylenediaminetetraacetate is advantageous because decomposition of hydrazine nitrate can be prevented. The compounding ratio of this chelating agent is preferably 0.1 to 10% by weight based on the sensitizer.

The cell retainer is an organic cell retainer. This organic foam retention agent is various single minute hollow spheres, foams containing a plurality of cells, such as pitch, carbonaceous minute hollow spheres obtained from coal, etc., phenolic resin, polyvinylidene chloride, epoxy It is a synthetic resin-based micro hollow sphere obtained from a resin, a urea resin, or the like. Examples of the foam containing a plurality of cells include polymers such as olefins such as ethylene, propylene and styrene, vinyl compounds such as vinylidene chloride, vinyl alcohol, vinyl acetate, acrylic acid, methacrylic acid and esters thereof, and copolymers. Mechanical foaming, chemical foaming, microencapsulation, and volatile materials in materials consisting of coalesced polymers, modified polymers, polymer mixtures, synthetic polymers such as polyurethane, polyester, polyamide, urea resin, epoxy resin, and phenol resin. Pulverized products and particles of synthetic polymer containing air bubbles by various means such as mixing with water.

Among these organic foam retention agents, those made of polystyrene, polyethylene, polyvinylidene chloride, or the like are preferable. The organic cell holding agent does not destroy the emulsion film and maintains its stability unlike the inorganic cell holding agents such as glass and silica. Further, the organic foam retention agent is excellent in that it has a small specific gravity, does not become an inert additive, is easily available and is inexpensive, and the like.

In addition, when an organic foam-holding agent is used as the foam-holding agent, a part of the emulsion is not broken as in the case of the inorganic foam-holding agent during pumping or the like at the time of manufacturing, so that the explosion as designed does not occur. The performance can be obtained, and an explosive excellent in stability over time can be obtained.

Further, the organic foam-retaining agent is a single-cell or single-cell polymer, and any particle size can be used. In particular, in the second invention, an average particle size in the range of 10 to 4000 μm is used. I do. If the average particle size is less than 10 μm, the specific gravity increases and the amount added increases, and if it exceeds 4000 μm,
Underwater explosion energy decreases. The shape of the bubble retaining agent may be any of a shape, a cylindrical shape, a polyhedral shape, and the like.

The selection of the organic bubble retaining agent is appropriately performed according to the use of the W / O explosive. The mixing ratio is 1 to 50% by volume in the W / O explosive. If it is less than 1% by volume, there is a risk of detonating detonation and interruption of detonation. Tend to.

Next, the aluminum powder is used as a fuel to enhance the underwater explosion energy. As the aluminum powder, a commonly used aluminum powder can be used. In particular, in the second invention, the particle size is 1 mm or less, preferably in the range of 0.01 to 1 mm, more preferably in the range of 0.03 to 0.1 mm. preferable. If the particle size exceeds 1 mm, the underwater explosion energy decreases. The shape may be any shape such as a spherical shape and a neighboring piece shape.

The content of the aluminum powder can be increased conventionally, and is 10 to 70% by weight when not containing a sensitizer, preferably 20 to 70% by weight, and 10 to 70% by weight when containing a sensitizer. % By weight. If the content is less than 10% by weight, the fuel becomes insufficient and the explosion performance decreases. If the content exceeds 70% by weight, inert aluminum powder remains and the explosion performance decreases.

In the first invention, the mixing ratio of each component in the W / O explosive composition is 40 to 90% by weight of an inorganic oxidate, 7 to 30% by weight of water,
The preferred range is 0.5 to 10% by weight of carbonaceous fuel, 0.5 to 10% by weight of emulsifier, 1 to 40% by weight of sensitizer, 1 to 50% by volume of organic foam-retaining agent, and 70% by weight or less of aluminum powder. Further, in the second invention, 40 to 90% by weight of an inorganic oxide salt, 7 to 30% by weight of water, 0.5 to 10% by weight of carbonaceous fuel, 0.5 to 10% by weight of an emulsifier,
The preferred range is 1 to 40% by weight of a sharpening agent, 1 to 50% by volume of an organic cell holding agent having an average particle size of 10 to 4000 μm, and 10 to 70% by weight of aluminum powder having an average particle size of 1 mm or less.

If the content of the inorganic oxide is less than 40% by weight, the explosion performance decreases,
If it exceeds 90% by weight, its solubility decreases. 7 water
If the amount is less than 30% by weight, the solubility of the inorganic oxide salt is reduced. If the amount is more than 30% by weight, other components are relatively small and the explosion performance is apt to be reduced. If the amount of the carbonaceous fuel is less than 0.5% by weight, the emulsion cannot be made fine and the contact area is small.
If the amount exceeds 10% by weight, the mixing ratio of the inorganic oxide salt is relatively reduced. When the amount of the emulsifier is less than 0.5% by weight, the stability of the emulsion tends to decrease, and when it exceeds 10% by weight, the explosion performance is difficult to improve. When the content of the sensitizer is less than 1% by weight, the detonation reliability is low, and when the content is more than 40% by weight, the handling risk increases. If the amount of the organic bubble-retaining agent is less than 1% by volume, there is a possibility that the detonating property of the detonator and the detonation may be interrupted, and if it exceeds 50% by volume, the underwater explosion energy tends to decrease. When the aluminum powder is less than 10% by weight or more than 70% by weight, the explosion performance tends to decrease.

The W / O explosive composition of the present invention can be produced, for example, as follows.

That is, first, an inorganic oxide salt or an inorganic oxide salt, a sensitizer and a chelating agent are dissolved in warm water of about 60 to 100 ° C. to obtain an aqueous solution of an inorganic oxide salt or the like. On the other hand, a flammable mixture is obtained by melting and mixing at a temperature at which the carbonaceous fuel and the emulsifier become liquid, usually 70 to 90 ° C. Next, the aqueous solution of the above-mentioned inorganic oxide and the flammable mixture are stirred at a temperature of 60 to 90 ° C. at about 600 to 6000 rpm to obtain a W / O emulsion. Then, by mixing the organic foam retention agent and aluminum powder with this
A W / O explosive composition is obtained.

The W / O explosive composition thus obtained uses an organic foam holding agent as a foam holding agent, and further contains an aluminum powder, so that the organic foam holding agent has an emulsion compared to the inorganic foam holding agent. In particular, the underwater explosion energy is used because the organic foam holding agent has a small specific gravity compared to the inorganic foam holding agent having a large specific gravity, and therefore has a high emulsion ratio and easily enters aluminum powder. Is high.

This underwater explosion energy is equivalent to the shock energy (E
s) and bubble energy (Eb), and the ratio of Eb / Es is generally about 3. The sum of the two is the total energy of underwater explosion energy ("Explosive Encyclopedia Vol 10", 1983) Year, (America Army Armament Research and Development Command issued).

〔Example〕

Hereinafter, examples embodying the present invention will be described in comparison with comparative examples. In addition, the part in each example represents a weight part.

(Examples 1 to 6) Ammonium nitrate as an inorganic oxyacid salt, sorbitan monooleate as an emulsifier, microcrystalline wax as a carbonaceous fuel, and an average particle diameter of 300 as a foam retention agent
A W / O explosive composition was obtained by using an aggregate of single-cell polystyrene having a size of μm, hydrazine nitrate as a sensitizer, and further containing aluminum powder having an average particle size of 30 μm. The mixing ratio of each component is as shown in Tables 1 and 2 below.

In addition, the method for producing the W / O explosive composition is such that an aqueous solution of ammonium nitrate and hydrazine nitrate is dissolved at about 85 ° C., added to a mixture of microcrystalline wax and sorbitan monooleate at about 85 ° C., and stirred. The mixture was stirred with a blade and emulsified, and a foam retaining agent and aluminum powder were mixed with the emulsified mixture to obtain a W / O explosive composition. The underwater explosive energy was measured for this explosive composition. The results are shown in Tables 1 and 2.

The underwater explosion energy is measured by arranging an explosive at a depth of 4 m in an artificial pond for measuring underwater explosion energy, and using a tourmaline gauge (pressure gauge) set at an arbitrary distance at the same water depth to detect the shock pulse of the exploded explosive. Measure,
The Es and Eb were calculated. The total energy is
Eb was added, and the relative ratio to Comparative 1 was calculated by the following formula.

Here, Eso and Ebo are the values of Comparative Example 1, and Esn and Ebn are the values of the comparative example.

(Comparative example 1) Except not containing aluminum powder, it carried out similarly to Examples 1-6, and obtained the W / O explosive composition. Using this, the same items as in Example 1 were measured by the same test method. Table 3 shows the results.

(Comparative Example 2) A W / O explosive composition was obtained in the same manner as in Example 3, except that GMB having an average particle size of 50 µm, which is an inorganic foam-retaining agent, was used instead of the organic foam-retaining agent. Was. Using the same, the same items as in Examples 1 to 6 were measured by the same test method. Table 3 shows the results.

The external addition amount of the aluminum powder in Tables 1 to 3 represents% by weight based on 100 parts by weight of the W / O explosive composition other than the aluminum powder.

As can be seen from Tables 1 to 3, Examples 1 to 6 were used.
In the case of the W / O explosive composition of the present invention, the total energy of the underwater explosion energy is considerably increased to 116 to 213 when the energy of the underwater explosion is set to 100 in Comparative Example 1, and exceeds twice in Examples 5 and 6.

On the other hand, the W / O explosive composition of Comparative Example 1 contains an organic foam-retaining agent, but has low underwater explosion energy because it does not contain aluminum powder. In addition, the W / O explosive composition of Comparative Example 2 used aluminum powder in combination with GMB, which is an inorganic foam retention agent, to increase the content of aluminum powder. It exploded.

In addition, Es of the W / O explosive (standard W / O explosive composition) in Comparative Example 1 is about 0.7 MJ / kg, Eb is about 2.3 MJ / kg, and the total energy is about 2.8 MJ / kg. The total energy of the W / O explosive composition of each example was about 3.2 MJ / kg (Example 1) -6.0 MJ / kg
(Embodiment 6) It is improved to the extent of about.

(Example 7) A W / O explosive was manufactured in the following manner with the composition shown in Table 4 below.

74.4 parts of ammonium nitrate as an inorganic oxidant, 10 parts of hydrazine nitrate as a sensitizer, and 0.5 part of sodium ethylenediaminetetraacetate as a chelating agent were added to 10.5 parts of water, and completely dissolved at 90 ° C. to give an aqueous solution of an inorganic oxidate. Obtained. On the other hand, as a carbonaceous fuel,
Parts and 2.3 parts of sorbitan monooleate as an emulsifier were melt-mixed at 90 ° C. to obtain a combustible mixture. The aqueous solution of the inorganic oxide was slowly added thereto, and the mixture was stirred at 650 rpm while heating at 90 ° C. to emulsify.

After emulsification, the mixture was further stirred at 1600 rpm for 1 minute to obtain a W / O emulsion. Next, 0.7 part of an organic foam retention agent having an average particle size of 300 μm and aluminum powder were added to the W / O emulsion.
Eleven parts were mixed at 60-80 ° C to obtain a W / O explosive composition. The underwater explosion energy of this W / O explosive composition was measured. The results are shown in Table 7 below.

(Example 8) A W / O explosive composition shown in Table 4 was obtained in the same manner as in Example 7 except that the sensitizer and the chelating agent were not contained and the content of the aluminum powder was changed. Was evaluated.
The results are shown in Table-7.

As can be seen from Table 7, the explosive composition of this example has an improved overall energy ratio as compared with that of Example 7.

Example 9 A W / O explosive composition shown in Table 4 was obtained in the same manner as in Example 7 except that the content of the aluminum powder was large, and the performance was evaluated. The results are shown in Table-7.

As can be seen from Table 7, the explosive composition of this example has an improved overall energy ratio as compared with that of Example 7.

(Example 10) A W / O explosive composition shown in Table 5 was obtained in the same manner as in Example 8 except that the content of the aluminum powder was large, and its performance was evaluated. The results are shown in Table-8.

As can be seen from Table 8, the explosive composition of this example has an improved overall energy ratio as compared with that of Example 8.

Example 11 A W / O explosive composition shown in Table 5 was obtained in the same manner as in Example 9 except that the content of the aluminum powder was large, and its performance was evaluated. The results are shown in Table-8.

As can be seen from Table 8, the explosive composition of this example has an improved overall energy ratio as compared with that of Example 9.

(Example 12) A W / O explosive composition shown in Table 5 was obtained in the same manner as in Example 11 except that the content of the aluminum powder was large, and its performance was evaluated. The results are shown in Table-8.

As can be seen from Table 8, the explosive composition of this example has a slightly improved overall energy ratio as compared with that of Example 11.

(Example 13) A W / O explosive composition shown in Table-6 was obtained in the same manner as in Example 10 except that the content of the aluminum powder was large, and its performance was evaluated. The results are shown in Table-9.

As can be seen from Table-9, the explosive composition of this example has a slightly improved overall energy ratio as compared with that of Example 10.

(Example 14) A W / O explosive composition shown in Table 6 was obtained in the same manner as in Example 12 except that the content of the aluminum powder was large, and its performance was evaluated. The results are shown in Table-9.

As can be seen from Table 9, the explosive composition of this example has a slightly improved overall energy ratio as compared with that of Example 12.

(Example 15) A W / O explosive composition shown in Table 6 was obtained in the same manner as in Example 13 except that the content of the aluminum powder was large, and its performance was evaluated. The results are shown in Table-9.

As can be seen from Table-9, the explosive composition of this example has a slightly higher overall energy ratio than that of Example 13.

The abbreviations in Tables 4 to 6 below have the following meanings.

MMA nitrate: monomethylamine nitrate Hyd nitrate: hydrazine nitrate EDA nitrate: ethylenediamine nitrate EDTA: sodium ethylenediaminetetraacetate SMO: sorbitan monooleate SMG: monoglyceride stearate WAX (1): Waxrex 602 WAX (2): Microcrystalline wax 160 WAX (3): Polywax 500 GMB: Glass micro hollow sphere. Those with a particle size of 20 to 140 μm and an average particle size of 60 μm.

SMB: Shirasu micro hollow body. Particles having a particle size of 30 to 150 μm and an average particle size of 75 μm.

RMB (1): polyvinylidene chloride resin sphere. Particle size 10
100100 μm and average particle size of 30 μm.

Styrofoam (1): Styrofoam beads pre-foamed. Particle size is 180-700μm and average particle size is 30
0 μm.

Styrofoam (2): Styrofoam beads pre-foamed. Average particle size is 2500 ~ 6200μm
4100μm.

(Comparative Example 3) Example 1 except that aluminum powder was not contained.
In the same manner as described above, a W / O explosive composition shown in Table 10 was obtained, and its performance was evaluated. The results are shown in Table-16.

This explosive composition is a standard composition for each energy ratio.

(Comparative Example 4) Example 7 except that the content of aluminum powder was small.
In the same manner as described above, a W / O explosive composition shown in Table 10 was obtained, and its performance was evaluated. The results are shown in Table-16.

As can be seen from Table 16, the explosive composition of this comparative example has a smaller total energy ratio than that of Example 7.

(Comparative Example 5) A W / O explosive composition shown in Table 10 was obtained in the same manner as in Example 7 except that the content of the aluminum powder was large, and its performance was evaluated. The results are shown in Table-16. The explosive composition of this comparative example is non-explosive.

Comparative Example 6 A W / O explosive composition shown in Table 11 was obtained in the same manner as in Comparative Example 4 except that the particle size of the aluminum powder was large, and its performance was evaluated. The results are shown in Table-17. The explosive composition of this comparative example is non-explosive.

(Comparative Example 7) A W / O explosive composition shown in Table 11 was obtained in the same manner as in Comparative Example 5 except that the particle size of the aluminum powder was large, and its performance was evaluated. The results are shown in Table-17. The explosive composition of this comparative example is non-explosive.

(Comparative Example 8) A W / O explosive composition shown in Table 11 was mainly obtained in the same manner as in Example 8, except that the content of the aluminum powder was small.
Its performance was evaluated. The results are shown in Table-17.

As can be seen from Table 17, the explosive composition of this comparative example has a lower overall energy ratio than that of Example 8.

(Comparative Example 9) A W / O explosive composition shown in Table 12 was obtained in the same manner as in Example 8 except that the content of the aluminum powder was large, and its performance was evaluated. The results are shown in Table-18. The explosive composition of this comparative example is non-explosive.

(Comparative Example 10) A W / O explosive composition shown in Table 12 was obtained mainly in the same manner as in Comparative Example 8, except that the particle size of the aluminum powder was large.
Its performance was evaluated. The results are shown in Table-18. The explosive composition of this comparative example is non-explosive.

(Comparative Example 11) A W / O explosive composition shown in Table 12 was obtained mainly in the same manner as in Comparative Example 9 except that the particle size of the aluminum powder was large.
Its performance was evaluated. The results are shown in Table-18. The explosive composition of this comparative example is non-explosive.

(Comparative Example 12) Glass microballoon (GMB), which is mainly an inorganic foam holding agent instead of an organic foam holding agent as a foam holding agent
Was added in the same manner as in Example 9 except that W /
An O explosive composition was obtained and its performance was evaluated. The results are shown in Table-19.

As can be seen from Table 19, the explosive composition of this comparative example has a lower overall energy ratio than that of Example 9.

(Comparative Example 13) A W / O explosive composition shown in Table 13 was obtained in the same manner as in Example 9 except that a resin microballoon (RMB) having a small average particle size was mainly blended as a bubble retainer. The performance was evaluated. The results are shown in Table-19.

As can be seen from Table 19, the explosive composition of this comparative example has a lower overall energy ratio than that of Example 9.

(Comparative Example 14) A W / O explosive composition shown in Table 13 was obtained in the same manner as in Example 9 except that styrofoam particles having a large average particle diameter were mainly blended as a cell holding agent, and the performance was evaluated. . The results are shown in Table-19. The explosive composition of this comparative example is non-explosive.

(Comparative Example 15) Shirasu Micro Balloon (SMB), which is mainly an inorganic cell holding agent instead of an organic cell holding agent as a cell holding agent
W / shown in Table 14 in the same manner as in Example 10 except that
An O explosive composition was obtained and its performance was evaluated. The results are shown in Table-20.

As can be seen from Table 20, the explosive composition of this comparative example has a lower overall energy ratio than that of Example 10.

(Comparative Example 16) A W / O explosive composition shown in Table 14 was obtained in the same manner as in Example 10 except that a resin microballoon (RMB) having a small average particle size was mainly blended as a bubble retaining agent. The performance was evaluated. The results are shown in Table-20.

As can be seen from Table 20, the explosive composition of this comparative example has a lower overall energy ratio than that of Example 10.

(Comparative Example 17) A W / O explosive composition shown in Table 14 was obtained in the same manner as in Example 10 except that styrofoam particles having a large average particle diameter were mainly blended as a cell retainer, and its performance was evaluated. . The results are shown in Table-20. The explosive composition of this comparative example is non-explosive.

(Comparative Example 18) A W / O explosive composition shown in Table 15 was obtained in the same manner as in Comparative Example 3, except that the content of the organic foam retaining agent was increased.
Its performance was evaluated. The results are shown in Table-21. The explosive composition of this comparative example is non-explosive.

(Comparative Example 19) A W / O explosive composition shown in Table 15 was obtained in the same manner as in Comparative Example 3 except that the organic foam retaining agent was not contained, and its performance was evaluated. The results are shown in Table-21. The explosive composition of this comparative example is non-explosive.

(Comparative Example 20) A W / O explosive composition shown in Table 15 was obtained in the same manner as in Comparative Example 3, except that the content of the organic foam-retaining agent was increased, and that no sharpener was contained. Its performance was evaluated. The results are shown in Table-21. The explosive composition of this comparative example is non-explosive.

(Comparative Example 21) A W / O explosive composition shown in Table 15 was obtained in the same manner as in Comparative Example 3 except that the organic foam retaining agent was not mainly contained and the sensitizer was not contained. And evaluated its performance. The results are shown in Table-21. The explosive composition of this comparative example is non-explosive.

The abbreviations in Table-10 to Table-15 below have the following meanings.

Foamed St8μ: Styrofoam with an average particle size of 8 μm Foamed St300μ: Styrofoam with an average particle size of 300 μm Foamed St4100μ: Styrofoam with an average particle size of 4100 μm RMB (2): Polyvinylidene chloride resin sphere. Particle size is 5
〜30 μm and average particle size of 8 μm.

As can be seen from Tables 7 to 9, Examples 7 to 15 were used.
In the case of the W / O explosive composition of the present invention, the total energy of the underwater explosion energy is considerably increased to 116 to 213 when the energy of the underwater explosion is set to 100 in Comparative Example 3.

In contrast, the W / O explosive compositions of each comparative example do not explode or have low underwater explosion energy.

The total energy in Comparative Example 3 was about 2.
8 MJ / kg, whereas the total energy of each example is in the range of 3.2 MJ / kg (Example 7) to 6.0 MJ / kg (Example 14), which is considerably higher than Comparative Example 3. You can see that there is.

〔The invention's effect〕

The W / O explosive composition of the first invention of the present invention exhibits an excellent effect that the underwater explosion energy is remarkably improved, particularly by using an organic foam retention agent and aluminum powder in combination.

The W / O explosive composition of the second invention exhibits an excellent effect that the underwater explosion energy is greatly improved, especially by containing a certain amount of an organic cell holding agent having a predetermined particle size and aluminum powder having a predetermined particle size. .

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-64-52692 (JP, A) JP-A-62-207791 (JP, A) JP-A-60-51685 (JP, A) European publication 317221 (EP , A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C06B 47/14 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (2)

(57) [Claims] 1. A water-in-oil emulsion explosive composition comprising a continuous phase composed of a carbonaceous fuel component, a dispersed phase composed of an aqueous solution of an inorganic oxide, an emulsifier, a sensitizer and a foam retention agent. A water-in-oil emulsion explosive composition containing 10 to 70% by weight of an aluminum foam having an organic foam retention agent having a content of 1 to 50% by volume and an average particle size of 1 mm or less. 2. A water-in-oil emulsion explosive composition comprising a continuous phase comprising a carbonaceous fuel component, a dispersed phase comprising an aqueous solution of an inorganic oxide salt, an emulsifier and a foam-retaining agent, wherein said foam-retaining agent has an average particle size. A water-in-oil emulsion explosive composition having an organic foam retention agent having a content of 1 to 50% by volume, an aluminum powder having an average particle diameter of 1 mm or less, and a content of 10 to 70% by weight. object.