JPH03164489A - Composition for weter-in-oil emulsion explosive - Google Patents

Abstract

PURPOSE:To improve underwater explosion energy by compounding a carbonaceous fuel component, an aq. inorg. oxidized acid salt soln., an emulsifier, a sensitive agent, an org. bubble holding agent having a specific average grain size and Al powder. CONSTITUTION:The aq. soln. is prepd. by dissolving 5 to 90wt.% inorg. oxidized acid salt, such as NH4NO3 [hereafter %, the compounding ratio in the water- in-oil type emulsion explosive (hereafter W/O explosive)] and 1 to 40% total of the sensitive agent, such as hydrazine nitrate and chelating agent into hot water at 60 to 100 deg.C. On the other hand, 0.5 to 10% carbonaceous fuel, such as microcrystalline wax and 0.1 to 10% emulsifier, such as sorbitan monolaurate, are melted and mixed at 70 to 90 deg.C to form a combustible mixture. The aq. soln. of the inorg. oxidized acid salt, etc., and the combustible mixture are then stirred at a high speed to form the W/O type emulsion and in succession, 1 to 50% bubble bulding agent, such as PS foam, having 10 to 4000mu average grain size and 10 to 70% Al powder having <=1mm average grain size are mixed to obtain the W/O explosive compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a water-in-oil emulsion explosive (hereinafter abbreviated as W10 explosive) composition having high underwater explosion energy.

[Conventional technology]

Traditionally, research has been conducted on items used to evaluate the power of explosives, such as martyrdom, ballistic mortar ratio, and detonation velocity, but in recent years, research has also been conducted on underwater explosion energy.

Examples of W10 explosive containing aluminum powder include JP-A-54-110308 and U.S. Patent No. 37705.
22 and US Pat. No. 3,447,978, these use glass microballoons (GMB) as a bubble retaining agent and further contain aluminum powder.

Furthermore, as a method of increasing the underwater explosion energy of the W10 explosive composition, a method of increasing the content of inorganic oxide salts such as ammonium nitrate, sodium nitrate, potassium nitrate, etc. has been considered.

[Problem to be solved by the invention]

However, although the W10 explosive compositions of the three conventional inventions described above improve detonation speed, detonation rate, and power compared to ballistic mortar,
When using MB and aluminum powder in combination, there is a limit to the amount of aluminum powder to be blended from the viewpoint of manufacturing, and the content is about 20% by weight. Furthermore, there was a problem in that increasing the content of aluminum powder resulted in non-explosion.

In addition, increasing the content of the inorganic oxidized salt has a manufacturing limit, and therefore its effect is small.

The object of the present invention is to use W10, which has particularly high underwater explosion energy.
An object of the present invention is to provide an explosive composition.

[Means to solve the problem]

In order to achieve the above object, the first aspect of the present invention provides a continuous phase consisting of a carbonaceous fuel component, a dispersed phase consisting of an aqueous solution of an inorganic oxide salt, and a water-in-oil consisting of an emulsifier, a sensitizer, and a bubble retaining agent. In the type emulsion explosive composition, the cell retaining agent is an organic cell retaining agent and further contains aluminum powder.

Further, in a second invention, in a water-in-oil emulsion explosive composition comprising a continuous phase consisting of a carbonaceous fuel component, a dispersed phase consisting of an aqueous solution of an inorganic oxide salt, an emulsifier and a bubble retaining agent, the bubble retaining agent is It is an organic air bubble retaining agent with an average particle size of IO ~ 4000 μm, and the aluminum powder has an average particle size of L.
mm or less and the content thereof is 10 to 70% by weight.

Further, in a third invention, a method is adopted in which a sensitizing agent is blended into the water-in-oil emulsion explosive composition of the second invention.

[Detailed explanation of means]

The carbonaceous fuel forms the continuous phase and is conventionally used in W10 explosives. For example, in the first invention, waxes such as microcrystalline wax, paraffin wax, polyethylene wax, etc.
Although fuel oils conventionally used for W10 explosives, such as fuel oils such as No. Further, in the second invention and the third invention, for example, paraffinic hydrocarbons, olefinic hydrocarbons, naphthenic hydrocarbons, aromatic hydrocarbons, saturated or unsaturated hydrocarbons, refined petroleum oil, lubricating oil, Hydrocarbons such as liquid paraffin, hydrocarbon derivatives such as nitrohydrocarbons, unrefined or purified microcrystalline wax derived from fuel oil and/or petroleum, paraffin wax, petrolatum, etc., mineral wax such as Senkun wax, etc. Whale wax, which is a sex wax;
Waxes such as beeswax, which is an insect wax, can be used alone or as a mixture. Among these carbonaceous fuels, microcrystalline wax and petrolactam are preferred from the viewpoint of stability over time, and microcrystalline wax is particularly preferred.

Furthermore, for drug quality adjustment, low molecular weight hydrocarbon polymers such as petroleum resins, low molecular weight polyethylene, and low molecular weight polypropylene can also be used in combination with the carbonaceous fuel component. These carbonaceous fuels are usually used in an amount of 1 to 10% by weight based on the W10 explosive.

Next, the inorganic oxide salt forms a dispersed phase as an aqueous solution, and includes those conventionally used in W10 explosive compositions. Examples of inorganic oxide salts include alkali metal or alkaline earth metal nitrates such as ammonium nitrate, sodium nitrate, and calcium nitrate; inorganic chlorates or perchloric acids such as sodium chlorate, ammonium perchlorate, and sodium perchlorate; Salt, etc. Usually, ammonium nitrate is used alone or as a mixture of ammonium nitrate and other inorganic oxide salts. The blending ratio of these inorganic oxide salts is generally 5 to 90% by weight, and 40 to 80% by weight.
Weight percent is preferred.

Note that the proportion of water in the W10 explosive composition of the present invention is 3 to 3.
30% by weight is preferred, and 7 to 30% by weight is more preferred.

Next, the emulsifier serves to stabilize the emulsion, and any emulsifier conventionally used in W10 explosives can be used. For example, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan dioleate, and sorbitan trioleate, and fatty acids such as stearic acid monoglyceride. Mono- or diglyceride, polyoxyethylene sorbitan fatty acid ester,
Examples include oxazoline derivatives, imidacilline derivatives, phosphoric acid esters, alkali metal salts or alkaline earth metal salts of fatty acids, primary, secondary, or tertiary amine salts, and these are used alone or as a mixture of two or more. be able to. Among the above emulsifiers, sorbitan fatty acid esters are preferred.

The blending ratio of this emulsifier is preferably 0.1-10% by weight, more preferably 1-5% by weight.

Sensitizers are used to increase detonation reliability and improve low-temperature detonation properties, such as monomethylamine nitrate, hydrazine nitrate, ethylenediamine nitrate, etc.
Although it is possible to use materials used in explosives,
Among these, hydrazine nitrate is preferred since it can increase the solubility of the ammonium nitrate and has high explosive energy. Further, when a sensitizer is used, its blending ratio is preferably 1 to 40% by weight in the W10 explosive composition, more preferably 30% by weight or less, and particularly preferably 20% by weight or less. If this proportion exceeds 40% by weight,
Handling risks may increase.

Particularly, when hydrazine nitrate or the like is used as a sensitizing agent, it is advantageous to use a chelating agent such as sodium ethylenediaminetetraacetate because decomposition of the hydrazine nitrate can be prevented.

The mixing ratio of this chelating agent is 0.1 to the sensitizing agent.
~10% by weight is preferred.

The foam retaining agent is an organic foam retaining agent. The organic air bubble retaining agent is a variety of single microscopic hollow spheres, foams containing multiple bubbles, etc., such as carbonaceous microscopic hollow spheres obtained from pitch, coal, etc., phenolic resin, polyvinylidene chloride, epoxy resin, etc. These are synthetic resin microscopic hollow spheres obtained from resin, urea resin, etc. In addition, foams containing multiple cells include olefins such as ethylene, propylene, and styrene, vinylidene chloride, vinyl alcohol,
Synthetic polymers such as vinyl compounds such as vinyl acetate, acrylic acid, methacrylic acid or their esters, copolymers, modified polymers, polymer mixtures, polyurethanes, polyesters, polyamides, urea resins, epoxy resins, phenolic resins, etc. Examples include pulverized products and particles of synthetic polymers in which air bubbles are impregnated into a material made of molecules by various means such as mechanical foaming, chemical foaming, microencapsulation, and mixing of easily volatile substances.

Among these organic bubble-retaining agents, those made of polystyrene, polyethylene, polyvinylidene chloride, or the like are preferred. Unlike inorganic bubble retainers such as glass and silica, this organic bubble retainer does not destroy the emulsion film and maintains its stability. In addition, the same organic bubble-retaining agent is excellent in that it has a small specific gravity, does not become an inert additive, and is easily available and inexpensive.

In addition, when an organic cell retaining agent is used as a bubble retaining agent, there is no possibility that part of the emulsion will be destroyed during pump transportation during manufacturing, unlike inorganic foam retaining agents, so it will not explode as designed. It is possible to obtain explosives with excellent performance and excellent stability over time.

Furthermore, the organic cell retaining agent may be a single cell or an aggregate of single cells, and may have any particle size.
In particular, in the second invention and the third invention, the average particle size is 10 to 4.
000 μm range is used. This average particle size is 1
If it is less than 0 μm, the specific gravity will increase and the amount added will increase.
When the diameter exceeds 000 μm, the underwater explosion energy decreases. The shape of this bubble-retaining agent may be any one of spherical, cylindrical, polyhedral, and the like.

The selection of this organic bubble retaining agent is made as appropriate depending on the use of the W10 explosive. In addition, the blending ratio is preferably 1 to 50% by volume in the W10 explosive; if it is less than 1% by volume, there is a risk of deterioration of the detonator's detonation ability and interruption of detonation, and if it exceeds 50% by volume, the energy of underwater explosives will be reduced. There is a tendency.

Aluminum powder is then used as a fuel to improve the underwater explosion energy. As the aluminum powder, commonly used ones can be used, but particularly in the second and third inventions, the particle size is 1 mm or less, preferably in the range of 0.01 to 1 mm. , 0.03
A range of ˜0.1 mm is more preferable. When the particle size exceeds 1 mm, the underwater explosion energy decreases. The shape is spherical,
It may be in any shape such as scaly shape.

The content of aluminum powder can be increased compared to the conventional one, and is 10 to 70% by weight when not containing a sensitizer, preferably 20 to 70% by weight, and 10 to 70% when containing a sensitizer. Weight%. This content is 10
If it is less than 70% by weight, there will be insufficient fuel and the explosive performance will decrease.
If the amount exceeds 1% by weight, inert aluminum powder remains and the explosive performance deteriorates.

In the first invention, the blending ratio of each of the above components in the W10 explosive composition is 40 to 90% by weight of the inorganic oxidized salt, 7 to 30% by weight of water, 0.5 to IO% by weight of carbonaceous fuel, and 0.5% by weight of emulsifier. 5～
Suitable ranges are IO weight %, sensitizing agent 1 to 40 weight %, organic bubble retaining agent 1 to 50 volume %, and aluminum powder 70 weight % or less. In addition, in the second invention and the third invention, the inorganic oxide salt is 40 to 90% by weight, water is 7 to 30% by weight, carbonaceous fuel is 0.5 to IO, and emulsifier is 0.5 to 10% by weight.
, sensitizing agent 1 to 40% by weight, average particle size lO to 4000 μm
1 to 50% by volume of organic bubble-retaining agent, average particle size 1 mm
The following range of aluminum powder from 10 to 70% by weight is suitable.

If the inorganic oxide salt content is less than 40% by weight, the explosive performance will decrease,
If it exceeds 90% by weight, its solubility will decrease. If the water content is less than 7% by weight, the solubility of the inorganic oxide salt decreases, and the
If it exceeds 0% by weight, other components will be relatively small and the explosive performance will tend to deteriorate. If the amount of carbonaceous fuel is less than 0.5% by weight, the emulsion cannot be made fine and the contact area will be small, and if it exceeds 10% by weight, the blending ratio of the inorganic oxide salt will be relatively small. If the emulsifier content is less than 0.5% by weight, the stability of the emulsion tends to decrease (,1
If it exceeds 0% by weight, it becomes difficult to improve explosive performance. If the sensitizer content is less than 1% by weight, detonation reliability will be low, and if it exceeds 40% by weight, handling risks will increase. If the content of the organic bubble retaining agent is less than 1% by volume, there is a risk of deterioration of the detonator's detonation properties and interruption of detonation, while 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 explosive performance tends to decrease.

The W10 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 at about 60 to 100°C to obtain an aqueous solution of the inorganic oxide salt, etc.

On the other hand, the temperature at which carbonaceous fuel and emulsifier become liquid is usually 70~
Melt mix at 90°C to obtain a combustible mixture.

Next, the aqueous solution of the inorganic oxide salt, etc. and the flammable mixture are stirred at about 600 to 6000 rpm at a temperature of 60 to 90°C to obtain a W10 emulsion. Subsequently, a W10 explosive composition is obtained by mixing an organic bubble retaining agent and aluminum powder thereto.

The W10 explosive composition obtained in this way uses an organic cell retaining agent as a bubble retaining agent and also contains aluminum powder. Organic foam retainers have a lower specific gravity than inorganic foam retainers, which have a higher specific gravity, and therefore have a higher emulsion ratio, making it easier for aluminum powder to enter. It has the characteristic of being able to

This underwater explosion energy is shock energy (Es
) and bubble energy (E b), Eb/E
The ratio of s is generally about 3, and the sum of the two is the total energy of the underwater explosion.

〔Example〕

Examples embodying the present invention will be described below in comparison with comparative examples. Note that parts on each side represent parts by weight.

(Examples 1 to 6) Ammonium nitrate as an inorganic oxide salt, sorbitan monooleate as an emulsifier, microcrystalline wax as a carbonaceous fuel, and average particle size of 300 as a bubble retention agent
A W10 explosive composition was obtained by using an aggregate of single cells of polystyrene of .mu.m in diameter, hydrazine nitrate as a sensitizing agent, and further containing aluminum powder with an average particle size of 30 .mu.m.

The blending ratio of each component is as shown in Tables 1 and 2 below.

In addition, the method for producing the W10 explosive composition includes adding an aqueous solution of ammonium nitrate and hydrazine nitrate dissolved at about 85°C to a mixture of microcrystalline wax and sorbitan monooleate at about 85°C;
The mixture was stirred with a stirring blade, and the emulsified mixture was mixed with a bubble retaining agent and aluminum powder to obtain a W10 explosive composition. The underwater explosive energy of this explosive composition was measured. The results are shown in Table-1 and Table-2.

Underwater explosion energy can be measured by laying explosives at a depth of 4 meters in an artificial pond for measuring underwater explosion energy, and measuring the shock pulse of the exploded explosives using a tourmaline gauge (pressure gauge) set at an arbitrary distance at the same depth. Measure and
The above Es and Eb were calculated. The total energy was calculated by adding these Es and Eb and using the following formula as a relative ratio to Comparative Example 1.

Here, E so and E bo are the values of Comparative Example 1, and Esn and Ebn are the values of the comparative example.

(Comparative Example 1) A W10 explosive composition was obtained in the same manner as in Examples 1 to 6 except that it did not contain aluminum powder. Using this, the same items as in Example 1 were measured using the same test method. The results are shown in Table-3.

(Comparative Example 2) A W10 explosive composition was obtained in the same manner as in Example 3, except that GMB, an inorganic bubble-retaining agent, with an average particle size of 50 μm was contained instead of the organic bubble-retaining agent.

Using this, the same items as in Examples 1 to 6 were measured using the same test method.

The results are shown in Table-3.

Table 1 Table 2 Table 3 The external addition amount of aluminum powder in Tables 1 to 3 represents weight % based on 100 parts by weight of the W10 explosive composition other than aluminum powder.

As can be seen from Tables 1 to 3 above, the 'vV10 explosive compositions of Examples 1 to 6 had a total underwater explosion energy of 116 to 100 when that of Comparative Example 1 was taken as 100.
213, which is considerably higher, and in Examples 5 and 6, it is more than double.

On the other hand, the W10 explosive composition of Comparative Example 1 contains an organic bubble retaining agent but does not contain aluminum powder, and thus has a low underwater explosion energy. In addition, the W10 explosive composition of Comparative Example 2 used aluminum powder and GMB, an inorganic bubble retaining agent, to increase the content of aluminum powder, making it difficult to maintain the shape of the W10 explosive and making it non-explosive. .

In addition, the W10 explosive (standard W10 explosive composition) in Comparative Example 1 has an Es of about 0.7 MJ 7kg, an Eb of about 2.1 MJ 7kg, and a total energy of about 2.8.
MJ/kg. The total energy of the W10 explosive composition for each example is approximately 3.2 MJ/kg (Example 1) to 6
It improves to a range of about ゜OMJ/kg (Example 6).

(Example 7) A W10 explosive was manufactured in the following manner using the composition shown in Table 4 below.

74.4 parts of ammonium nitrate as an inorganic oxide salt, 10 parts of hydrazine nitrate as a sensitizing agent, 0.5 parts of sodium ethylenediaminetetraacetate as a chelating agent, and 101 parts of water.
5 parts and completely dissolved at 90° C. to obtain an aqueous solution of the inorganic oxide salt. On the other hand, 2.3 parts of Wax Rex 602 as a carbonaceous fuel 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 salt was slowly added thereto, and emulsified by stirring at 650 rpm while heating at 90°C.

After emulsification, stir at 1600 rpm for another minute and
A type 0 emulsion was obtained. Next, 0.7% of an organic bubble retaining agent with an average particle size of 300 μm was added to this W10 emulsion.
1 part and 11 parts of aluminum powder were mixed at 60 to 80°C.
10 explosive compositions were obtained. The underwater explosion energy of this W10 explosive composition was measured. The results are shown in Table 7 below.

(Example 8) Table 1 was prepared in the same manner as in Example 7 except that no sensitizing agent or chelating agent was contained and the content of aluminum powder was changed.
A W10 explosive composition shown in No. 4 was obtained and its 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 total energy ratio compared to that of Example 7.

(Example 9) A W10 explosive composition shown in Table 4 was obtained in the same manner as in Example 7 except that the content of aluminum powder was mainly increased, and its 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 total energy ratio compared to that of Example 7.

(Example 10) A W10 explosive composition shown in Table 5 was obtained in the same manner as in Example 8 except that the content of aluminum powder was mainly high, 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 total energy ratio compared to that of Example 8.

(Example 11) A W10 explosive composition shown in Table 5 was obtained in the same manner as in Example 9 except that the content of aluminum powder was mainly increased, 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 total energy ratio compared to that of example 9.

(Example 12) A W10 explosive composition shown in Table 5 was obtained in the same manner as in Example 11 except that the content of aluminum powder was mainly increased,
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 total energy ratio compared to that of Example 11.

(Example 13) A W10 explosive composition shown in Table 6 was obtained in the same manner as in Example 1O, except that the content of aluminum powder was mainly increased,
Its performance was evaluated. The results are shown in Table-9.

As can be seen from Table 9, the total energy ratio of the explosive composition of this example is slightly improved compared to that of example 10.

(Example 14) A W10 explosive composition shown in Table 6 was obtained in the same manner as in Example 12, except that the content of aluminum powder was mainly increased,
Its performance was evaluated. The results are shown in Table-9.

As can be seen from Table 9, the total energy ratio of the explosive composition of this example is slightly improved compared to that of example 12.

(Example 15) A W10 explosive composition shown in Table 6 was obtained in the same manner as in Example 13 except that the content of aluminum powder was mainly increased,
Its performance was evaluated. The results are shown in Table-9.

As can be seen from Table 9, the total energy ratio of the explosive composition of this example is slightly improved compared to 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 Nistearic acid monoglyceride WAx (1):
Wax Rex 602WAX (2): Microcrystalline Wax 160WAX (3): Polywax 500GMB Nigaras micro hollow spheres. Particle size is 20
~140 μm with an average particle size of 60 μm.

SMB Nijirus micro hollow body. Particle size is 30-150μm
with an average particle size of 75 μm.

RMB (L): Polyvinylidene chloride resin sphere. Particle size is 1
0 to 100 μm with an average particle size of 30 μm.

Styrofoam (1) Styrofoam beads pre-foamed. The particle size is 180 to 700 μm and the average particle size is 300 μm.

Styrofoam (2): Styrofoam beads that have been pre-foamed. The particle size is 2,500 to 6,200 μm and the average particle size is 4,100 μm.

Table 7 Table 9 (Comparative Example 3) A W10 explosive composition shown in Table 10 was obtained in the same manner as in Example 1 except that it did not contain aluminum powder, 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) A W10 explosive composition shown in Table 10 was obtained in the same manner as in Example 7 except that the content of aluminum powder was small, 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 lower total energy ratio than that of Example 7.

(Comparative Example 5) A W10 explosive composition shown in Table IO was obtained in the same manner as in Example 7 except that the content of aluminum powder was high, 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 W10 explosive composition shown in Table 11 was obtained in the same manner as Comparative Example 4 except that the particle size of the aluminum powder was large,
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 W10 explosive composition shown in Table 11 was obtained in the same manner as Comparative Example 5 except that the particle size of the aluminum powder was large,
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 W10 explosive composition shown in Table 11 was obtained in the same manner as in Example 8, except that the content of aluminum powder was mainly small, and 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 total energy ratio than that of Example 8.

(Comparative Example 9) A W10 explosive composition shown in Table 12 was obtained in the same manner as in Example 8 except that the content of aluminum powder was mainly increased,
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 W10 explosive composition shown in Table 12 was obtained in the same manner as Comparative Example 8, except that the particle size 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 11) Mainly due to the large particle size of the aluminum powder.A W10 explosive composition shown in Table 12 was obtained in the same manner as Comparative Example 9, and 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 bubble-holding agent instead of an organic bubble-holding agent, is used as a bubble-holding agent.
A W10 explosive composition shown in Table 13 was obtained in the same manner as in Example 9 except that the following was added, 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 total energy ratio than that of Example 9.

(Comparative Example 13) A W10 explosive composition shown in Table 13 was obtained in the same manner as in Example 9, except that resin microballoons (RMB) with a small average particle size were mainly blended as a bubble retaining agent, and its performance was evaluated. 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 total energy ratio than that of Example 9.

(Comparative Example 14) A W10 explosive composition shown in Table 13 was obtained in the same manner as in Example 9, except that expanded polystyrene particles having a large average particle size were mainly blended as a bubble retaining agent, and its 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 an inorganic bubble-holding agent, was used instead of an organic bubble-holding agent as a bubble-holding agent.
A W10 explosive composition shown in Table 14 was obtained in the same manner as in Example 10 except that the following was added, 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 total energy ratio than that of Example IO.

(Comparative Example 16) A W10 explosive composition shown in Table 14 was obtained in the same manner as in Example 10, except that resin microballoons (RMB) with a small average particle size were mainly blended as a bubble retaining agent, and its performance was evaluated. 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 total energy ratio than that of Example IO.

(Comparative Example 17) Table 14 was carried out in the same manner as in Example 1O, except that expanded polystyrene particles with a large average particle size were mainly blended as a bubble retaining agent.
A W10 explosive composition shown in was obtained 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 W10 explosive composition shown in Table 15 was obtained in the same manner as Comparative Example 3 except that the content of the organic bubble retaining agent was increased, and its performance was evaluated. -21.The explosive composition of this comparative example is non-explosive.

(Comparative Example 19) A W10 explosive composition shown in Table 15 was obtained in the same manner as Comparative Example 3 except that it did not contain an organic bubble retaining agent.
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 W10 explosive composition shown in Table 15 was obtained in the same manner as Comparative Example 3 except that the content of the organic bubble retaining agent was increased and no sensitizing agent was contained. was evaluated. The results are shown in Table-21. The explosive composition of this comparative example is non-explosive.

(Comparative Example 21) A W10 explosive composition shown in Table 15 was obtained in the same manner as in Comparative Example 3, except that it did not contain an organic bubble-retentive agent or a sensitizing agent. Performance was evaluated. The results are shown in Table-21. The explosive composition of this comparative example is non-explosive.

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

Foamed St 8μ: Styrofoam foamed St with an average particle size of 8μm Foamed St 300μ: Styrofoam foamed St with an average particle size of 300μm 4100μ: Average particle size 4100. czm
(7) Styrofoam RMB (21: Polyvinyritine resin spheres. Particle size: 5
~30 μm with an average particle size of 8 μm.

Table-10 Table-1 ■ Table-12 Table = 1 5 Table-18 Table-2 As can be seen from Tables-7 to Table-9 above, Examples 7 to 15
The W10 explosive composition has a total underwater explosion energy of 116 to 2 when that of Comparative Example 3 is taken as 100.
13, which is considerably higher, and in Examples 11, 12, and 14, it is more than double.

In contrast, the W10 explosive compositions of each comparative example were either non-explosive or had low underwater explosion energy.

In addition, the total energy in Comparative Example 3 is approximately 2.8
MJ/kg, whereas the total energy of each example is 3.2 MJ/kg (Example 7) to 660
MJ/kg (Example 14), which is considerably higher than Comparative Example 3.

〔Effect of the invention〕

The W10 explosive composition of the first aspect of the present invention exhibits an excellent effect of significantly improving underwater explosion energy, especially by using an organic bubble retaining agent and aluminum powder in combination.

The W10 explosive composition of the second invention has an excellent effect of greatly improving the underwater explosion energy, especially because it contains a certain amount of an organic bubble retaining agent of a predetermined particle size and an aluminum powder of a predetermined particle size. According to the invention, by incorporating a sensitizing agent into the W10 explosive composition of the second invention, in addition to the effects of the second invention, detonation reliability can be improved and low-temperature detonation properties can be improved. It has the effect of being able to improve.

Claims (1)

[Scope of Claims] 1. 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, a sensitizer, and a bubble retaining agent, comprising: A water-in-oil emulsion explosive composition in which the bubble retaining agent is an organic bubble retaining agent and further contains aluminum powder. 2. A water-in-oil emulsion explosive composition comprising a continuous phase consisting of a carbonaceous fuel component, a dispersed phase consisting of an aqueous solution of an inorganic oxide salt, an emulsifier and a bubble retaining agent, wherein the bubble retaining agent has an average particle size of 10 to 4000 μm. 1. A water-in-oil emulsion explosive composition, which is an organic air bubble retaining agent, and contains aluminum powder with an average particle size of 1 mm or less and a content of 10 to 70% by weight. 3. A water-in-oil emulsion explosive composition obtained by blending the water-in-oil emulsion explosive composition according to claim 2 with a sensitizer.