JP2000178093A - Waterdrop-in-oil (w/o) type emulsion explosive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance explosive power of an explosive composition without reducing its performance with respect to low-temperature initiation sensitivity and sympathetic detonation sensitivity and also without adversely affecting its aging stability by controlling the degrees of oxygen excess/shortage of emulsion base materials before and after the addition of a metallic heat-generating agent within their respective specified ranges. SOLUTION: This w/o type emulsion explosive composition comprises: a discontinuous phase consisting of ammonium nitrate, another oxidizing salt(s), water and an organic amine oxidizing salt(s); a continuous phase consisting of petroleum hydrocarbons and an emulsifier suitable for forming a w/o type emulsion; a specific-gravity adjusting agent; and 3-20 wt.% of a metallic heat-generating agent, wherein the explosive composition contains water (or water content) in a 5-20 wt.% ratio of the water to the whole explosive composition, and also, the degree of oxygen excess/shortage of an emulsion base material having a composition before the addition of the metallic heat-generating agent, is adjusted to -5.00 to +3.00 g/100 g and the degree of oxygen excess/shortage of another emulsion base material having a composition after the addition of the metallic heat-generating agent, is adjusted to -20.00 to -4.00 g/100 g, and further, as the metallic heat-generating agent, a powdery or flaky metallic heat-generating agent having a particle size distribution such that the weight ratio of the particle fraction passing through a sieve of the sieve designation 149 μm specified in JIS or other equivalent standards) to the total weight of all the particles is >=90 wt.%, is preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a discontinuous phase comprising ammonium nitrate and other nitrates, water and / or an organic amine oxidizing salt (such as a monoethanolamine oxidizing salt), a petroleum hydrocarbon fuel and an emulsifier. The present invention relates to a high-power emulsion explosive composition comprising a continuous phase, a specific gravity adjusting agent, and a metal exothermic agent such as aluminum, which has excellent stability over time and excellent post-gas.

[0002]

2. Description of the Related Art Generally, industrial explosives contain ammonium nitrate as a main component and water of at least 5% by weight in order to enhance safety, in addition to explosives which have been well known, such as dynamite and carlit. There are two types of explosives: water-containing explosives and extremely low-cost ANFO explosives. In addition, the water-containing explosive contained a slurry explosive in which a fuel component was mixed in an aqueous phase, and the oil explosive in which the fuel component was included in the oil phase, as opposed to the slurry explosive, contained a discontinuous phase of fine droplets which was an aqueous phase component. Emulsion explosive compositions. In recent years, highly explosive hydrous explosives have been
It is composed of components that are not explosives themselves, and contains water in the components. The density is slightly lower than that of dynamite, so the explosive concentration effect is inferior. However, the handling sensitivity is extremely insensitive, and No. 6 It is an industrial explosive that can be detonated with just one electric detonator.

Various techniques for improving the explosive power by adding a metal exothermic agent such as aluminum to an emulsion explosive composition have hitherto been known, but they have been known for several months to ten and several months after production. In Japan, which is often stored in gunpowder storage, the stability over time is impaired during storage, causing problems such as non-explosion. It has recently been resolved.

[0004] To increase the power of this hydrous explosive, the measures taken so far have been, among experts in the art, to raise the explosion reaction temperature by adding a known metal exothermic agent such as aluminum. It is a way to increase the power of the explosion. The technology of adding a metal powder such as aluminum to a water-containing explosive has been used since the development of slurry explosives in the 1970s. Addition), JP-A-3-164489 (improvement of underwater explosion energy by adding aluminum), JP-A-6-128071 (measurement of underwater explosion energy), U.S. Pat. No. 3,447,978 (Detonation) Aluminum as a component sensitive to properties or a component useful as a fuel), US Pat. No. 3,770,522
Specific gravity as described in U.S. Pat. No. 4,110,134 (up to 15 wt% reserve fuel such as aluminum). In addition to the use as a sensitizer similar to a hollow microsphere as a regulator, the use of aluminum is basically disclosed for further improving the explosive power.

[0005] Recent water-containing explosives are high-security explosives in which the explosive substance, which is an explosive or explosive by itself, is not contained in the components but contains 5% by weight or more of water or moisture and pursues safety. This includes slurry explosives and emulsion explosives, and the principle of maintaining explosive performance, including explosion and explosion propagation, is due to adiabatic compression of bubbles in the components. In such explosives, when the volume ratio of air bubbles in the explosive decreases, the specific gravity of the explosive increases, the proportion of hot spots that should serve as an adiabatic compression source decreases, and the sensitivity of the explosive to low-temperature detonation or blasting on sand is reduced. Explosive performance is significantly reduced. On the other hand, if the proportion of the bubbles in the explosive volume is too large, the explosive density will decrease and the sensitivity will increase, but not only will the explosive power decrease, but the proportion of the bubbles in the total explosive volume will be 80%.
Above this, the proportion of reactive substances to be exploded becomes insufficient and the stability of the explosion is gradually impaired, eventually resulting in a non-explosion. The volume ratio of bubbles for exhibiting a stable explosion phenomenon is approximately 15%.
Experiments have confirmed that the range is ８０80%.

[0006]

The technique of increasing the power by adding a metal exothermic agent such as aluminum to the emulsion explosive composition is a known technique as described above. There was a problem that the reaction gradually progressed between the water in the explosive and the added metal exothermic agent such as aluminum, and the stability with time deteriorated, and eventually the explosive property was sometimes lost.

Therefore, in order to prevent the metal exothermic agent such as aluminum added for increasing the power from reacting with the moisture in the emulsion composition in an atmosphere of normal temperature and normal pressure, the surface of the metal exothermic agent such as aluminum is reduced. May be coated with a lipophilic substance which is compatible with the emulsion atmosphere or an inert substance with respect to the discontinuous phase.

Commonly known coatings are, for example,
There are fatty acid salts such as calcium or aluminum salts of stearic acid. As an oxidizing salt other than ammonium nitrate used as a component for improving the power, particularly an emulsion explosive composition containing an organic amine oxidizing salt (for example, monoethanolamine oxidizing salt),
Even if fine-grained aluminum surface-treated with a generally known coating agent such as stearic acid or a salt thereof is added, a sufficient temporal stability effect cannot be obtained.

Further, when a metal exothermic agent such as aluminum or magnesium is added to the emulsion explosive composition,
If the explosive energy increases and the amount of added metal heating agent increases, the explosive energy will increase
JP-A-3-164489, JP-A-6-12807
Although it is disclosed in Japanese Patent Application Publication No. 1 (1993), there is no known material which aims at the maximum explosive energy increasing effect by adding a minimum amount of a metal exothermic agent.

An emulsion explosive composition made by Nippon Koki Co., Ltd., to which no metal exothermic agent such as aluminum is added, has a low-temperature detonation sensitivity of -35 ° C. under a constant condition of an explosive specific gravity of about 1.10. And the JIS explosion speed is about 565
It is an industrial explosive with a very high performance of 0 m / sec. However, the martyr explosion sensitivity (a value of the martyr explosion test specified in JIS K 4810 (explosives performance test method) and an index of the responsiveness expressed by a multiple of the test explosive diameter) and the mortar ratio [Index indicating explosive power of explosives specified in JIS K 4810 (Explosives performance test method), expressed as a ratio (%) to TNT. ] Are about 2 times diameter and about 100 times, respectively.
% And slurry explosives manufactured by Nippon Koki Co., Ltd.
Diameter, not far below 115%. In general, mixed explosives contain water explosives, and when the specific gravity increases, both the low-temperature detonation sensitivity and the blast explosion sensitivity decrease, while the explosion speed increases to a specific gravity of about 1.28, but when the specific gravity increases, it increases. , Falls sharply and no longer explodes.

That is, the explosive sensitivity decreases as the explosive specific gravity increases, and the reaction rate correspondingly decreases. further,
In general, the borehole at the actual blasting site often has water, and the specific gravity of the water is 1.10 or more because it is muddy water mixed with milling powder. In such muddy water, even if the explosive is charged, it floats and is difficult to charge, and if the specific gravity of the explosive is low, the concentration effect of the explosive is poor, and hard rock or a hole with severe restraint conditions Near the bottom or in the tunnel blast, the hole butt remains, and it is notorious that the power of the explosion is weak.

All of these prior arts aim at improving the explosive power mainly by adding a metal exothermic agent such as aluminum to the emulsion explosive composition. Metal exothermic agents such as aluminum, magnesium, and magnalium in the emulsion explosive composition, when reacted, generate high temperatures and contribute significantly to an increase in explosive temperature. In general, there are various methods of expressing power, but there is a factor f called a force of explosives in static power usually obtained from thermodynamic calculations.

This is expressed by f∝PVT, and the explosive power f
The static power represented by (atm · l / kg) increases in proportion to the detonation pressure P (atm), the gas generation amount V (1 / Kg), and the explosion temperature T (゜ K). Therefore, it is obvious that if a metal exothermic agent such as aluminum is added to the components of the emulsion explosive composition, the explosion temperature T increases and the static power increases.

[0014] However, these prior inventions mention the amount of addition of a metal heating agent such as aluminum or the excess or deficiency of oxygen in order to increase the explosive energy of explosives.
Few have described the effect of particle size of metal exothermic agents such as aluminum. However, G. Bjarnholt and R. Ho
lmberg's "Explosive expansion work in underwater d
etonation "Proceeding of Sixth Symposium on Detona
tion, San Diego, 549 (1976), in the case of slurry explosives, the particle size of aluminum was changed from 120 μm to 600 μm.
m, the underwater explosion energy (total expansion work per unit weight of explosive) is reduced.

JP-A-3-164489 states that those having a content of 10 to 70% by weight and an average particle diameter of 1 mm or less, particularly 30 to 100 μm, are effective. Japanese Patent Publication No. 128071 describes that it is effective to use aluminum having an average particle diameter of 20 to 100 μm. The emulsion explosive composition wraps a discontinuous phase composed of an oxidizing agent solution with a continuous phase which is a fuel such as wax, and an inert substance which is a fine hollow sphere such as a glass microballoon which is a specific gravity regulator in these two phases. Is interposed.

If a substance which is not inert to the discontinuous phase, for example, a solid substance which reacts or dissolves with water, such as nitrate, perchlorate or aluminum, magnesium, sucrose, is added to these two phases, the stability with time will be increased. Is greatly impaired. This is caused by the reaction or state change of the liquid components, especially water or moisture, in the discontinuous phase with the solid substances. If the substance to be added is a substance inert to a liquid component such as water or moisture in a discontinuous phase such as a glass microballoon, the stability with time is not impaired.

Therefore, the present inventor has sought to increase the stability over time by inactivating the metal exothermic agent such as aluminum which is a solid substance added for increasing the explosive power of the emulsion explosive composition. As a result of intensive research, a metal heating agent such as aluminum having a particle diameter of 1 to 105 μm coated with a wax which is a substance inert to a discontinuous phase in an amount of 2 to 5% by weight based on the total weight of the metal heating agent such as aluminum added. By using up to 20% by weight, it is extremely effective and practical for improving the stability over time and increasing the power of underwater explosions, and even if the excess or deficiency of oxygen is large and negative, it is harmful to the human body, especially CO, small emulsion explosive composition of NO _X generation could be obtained. In particular, microcrystalline wax was found to be the most effective as an inert substance effective for an emulsion composition containing an organic amine oxidizing salt.

The present invention has been made based on such knowledge, and in order to eliminate the disadvantage that the specific gravity of explosives is low, the specific gravity of explosives is set at 1.18 ± 0.03, and a metal exothermic agent such as aluminum is used. With the aim of increasing the explosive power represented by underwater explosive energy without significantly deteriorating the stability over time of explosives while maintaining the low-temperature detonation sensitivity and the blast explosion sensitivity more than before by adding It is an object of the present invention to provide a water-in-oil emulsion explosive composition.

[0019]

According to the first aspect of the present invention, there is provided a discontinuous phase comprising ammonium nitrate, another oxidizing salt, water and / or an organic amine oxidizing salt, a petroleum hydrocarbon and a water-in-oil emulsion. A continuous phase composed of an emulsifier suitable for the above, a specific gravity regulator, and 3 to 20% by weight of a metal exothermic agent.
In a water-in-oil emulsion explosive composition containing 0% by weight, the excess / deficiency of oxygen in the emulsion base material in the mixing ratio before the addition of the metal exothermic agent is -5.00 to +3.00 g / 100.
g, oxygen excess / deficiency after adding the metal exothermic agent is -20.0
0 to -4.00 g / 100 g.

According to a second aspect of the present invention, there is provided the water-in-oil type emulsion explosive composition according to the first aspect, wherein the metal exothermic agent is in the form of powder or scale that passes 90% by weight or more of JIS sieve nominal (μ) 149. It is characterized by the shape.

According to a third aspect of the present invention, in the water-in-oil type emulsion explosive composition according to the second aspect, the metal exothermic agent is in the form of powder or scale that passes 90% by weight or more of JIS sieve nominal (μ) 105. It is characterized by the shape. According to a fourth aspect of the present invention, in the water-in-oil type emulsion explosive composition according to any one of the first to third aspects, the metal exothermic agent includes a substance that is inactive in the discontinuous phase. It is characterized by being in the form of powder or scale coated with 2 to 5% by weight of the agent.

According to a fifth aspect of the present invention, in the water-in-oil type emulsion explosive composition according to any one of the first to fourth aspects, the organic amine oxidizing salt is a monoethanolamine oxidizing salt. And it is characterized by containing 3-5% by weight.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A conventional means for improving performance such as low-temperature detonation sensitivity or explosive power of a water-containing explosive has been to use a nitrate or a perchlorate as an organic amine oxidizing salt. And a method using a compound having an explosive property such as hydrazine nitrate, urea nitrate, and guanidine nitrate. Well-known organic amine oxidizing salts include monomethylamine nitrate, monoethanolamine nitrate, monoethylene glycol nitrate, ethylenediamine nitrate and the like, and these perchlorates are sometimes used.

The above-mentioned hydrazine nitrate, urea nitrate,
The method of using a compound having explosive properties such as guanidine nitrate and the method of using a compound having three or more nitro groups, which is an explosive per se, may be used as long as these additives are easily water-soluble. By dissolving in an oxidizing agent solution and using it in the same manner as in the method using an oxidizing salt, an emulsion explosive composition having good stability over time can be obtained. Therefore, when the above-mentioned components are added as one raw material of the sensitizer or the energy enhancer of the emulsion explosive composition, it is generally desirable that the raw material itself is water-soluble.

If the content of the above-mentioned organic amine oxidizing salt is about 3% by weight or more, a corresponding effect can be obtained. However, in a water-in-oil emulsion explosive composition containing a wax and an emulsifier, if too much oxygen is added to the organic amine having a negative oxygen excess and deficiency, the oxygen excess and deficiency of the finally obtained explosive will be greatly negative, and the explosive performance will be reduced. Not only does it decrease, but when it explodes, it generates a large amount of gas harmful to the human body, making it difficult to use in sites where ventilation facilities are insufficient, such as tunnel blasting.

Therefore, when the oxygen excess / deficiency of the obtained explosive is designed to be as close to zero as possible, the above-mentioned organic amine to be added is inevitably added in an amount of about several percent by weight. With this amount, the effect of increasing the explosive power is almost obtained. I can't. However, among these, monoethanolamine is net 3-5% by weight.
It was found that even a small addition amount was effective in improving the explosive power.

Here, the knowledge obtained regarding the relationship between the excess and deficiency of oxygen and the post-gas is specified. In general, industrial explosives
In order to maintain reactivity and reduce the amount of harmful gas generated to the human body after the explosion, oxygen excess / deficiency is adjusted to almost zero. Heretofore, this concept has been recognized as being the same for both slurry explosives and emulsion explosives, but the situation is different for emulsion explosive compositions.

In an emulsion explosive, the conventional concept of oxygen balance, in which aluminum obtains oxygen from an oxidizing agent in the explosive to become aluminum oxide, requires a new concept that cannot be explained. That is, in the emulsion explosive composition, the contact area between the oxidizing agent and the fuel is very large because the oxidizing agent droplets are very fine, several μm or less.

This is why the reaction rate is extremely high and the explosion velocity is also high. When a fine metal exothermic agent such as aluminum is added to the emulsion explosive composition having such a high reaction rate, the metal exothermic agent such as aluminum acts as a reducing agent during the high temperature and high pressure detonation reaction, and water in the explosive is used. Alternatively, since the water undergoes an oxidation-reduction reaction using an oxidizing agent, the excess or deficiency of oxygen in the composition (emulsion base material) before the addition of a metal exothermic agent such as aluminum is substantially −5.00 to +5.0.
It is calculated by the conventional method of the emulsion explosive composition by controlling the range of 3.00 g / 100 g and further setting the maximum amount of the metal exothermic agent such as aluminum to the amount of water or moisture contained in the emulsion explosive composition. would oxygen deficiency is large negative that is, but after never harmful to the human body gas, especially CO, nO _X was found not to increase.

When a metal exothermic agent such as aluminum is added to the emulsion explosive composition, the explosive performance,
In particular, the increase in static power is described in US Pat.
No. 70,522 and U.S. Pat. No. 4,110,1.
No. 34, and is well known in the art of slurry explosive manufacturing. Nevertheless, in Japan, 10 years after the launch of emulsion explosives
Only after a few years has the aluminum explosive composition containing aluminum been on the market means that it has been difficult to ensure stability over time.

The present inventor has also conducted intensive studies to develop a high-performance explosive while improving the stability over time of an emulsion explosive composition containing a metal exothermic agent such as aluminum. By coating a metal exothermic agent such as aluminum itself with an active lipophilic substance, an emulsion explosive composition having good stability over time and a large explosion energy can be developed, which has led to the present invention.

Various techniques for coating the surface of a metal exothermic agent such as aluminum with an inert substance are known irrespective of the technical field of industrial explosives. For example, as a technique for coating an aluminum surface with a water-repellent stearic acid and / or a stearic acid salt, Japanese Patent Laid-Open No. 6-1280 discloses a technique.
No. 71 discloses this. Further, as a two-component flowable explosive composition mainly composed of sodium perchlorate, US Pat. No. 5,007,973 describes octyltrimethoxy (or ethoxy) silane as an aluminum coating agent. .

These are intended to improve the stability over time by suppressing the reaction between aluminum added to the explosive and a solvent such as water which is a component of the industrial explosive. Aluminum is inactivated by reaction with water as shown below. _{2Al + 6H 2 O → 2Al (} OH) 3 + 3H 2 ··· (1) 2Al (OH) 3 → Al 2 O 3 + 3H 2 O ··· (2) While the presence of water in the explosive system, The reaction of the formula (1) proceeds gradually, and the surface of aluminum becomes aluminum hydroxide and changes to white crystalline, and the aluminum becomes stable.
The emulsion itself is destroyed, leading to lower sensitivity for low temperature detonation.

At the stage of the formula (1), the metal exothermic agent such as aluminum loses the function and effect as a reducing agent (exothermic agent), and also the emulsion structure itself is partially destroyed. As a result, the low-temperature detonation sensitivity decreases. Further, it is supposed that the reaction of the formula (2) hardly occurs because aluminum hydroxide itself is very stable. Therefore, at least for two years during the product warranty period, the reaction of the equation (1) is performed so that the reaction as shown in the equation (1) does not occur, or even if it occurs, the performance does not significantly deteriorate. It is to suppress.
For this reason, as a result of intensive research, it has been found that the problem can be solved by coating a surface of a metal exothermic agent such as aluminum on a discontinuous phase such as a specific wax with an inert substance or a lipophilic substance.

[0035] Among the lipophilic substances or other inert substances having high compatibility with the continuous phase component used in the emulsion composition, heat is generated from a metal such as aluminum by using microcrystalline wax, for example, Hi-mic 2095 manufactured by Nippon Seiwa Co., Ltd. The coating on the surface of the agent constitutes a form in which fine oxidant droplets, which are a discontinuous phase, are individually wrapped with petroleum hydrocarbon fuel, which is a continuous phase.
Even if a metal exothermic agent coated with a coating agent such as microcrystalline wax having the same properties as the continuous phase component is interposed between the discontinuous phases, during storage, the metal exothermic agent and water or water in the emulsion composition may not react. It is understood that the reaction is suppressed and the stability effect with time is increased.

In order to increase the explosive power with the minimum amount of a metal exothermic agent such as aluminum, the use of a fine particulate metal exothermic agent having a particle diameter of 1 to 105 μm is used. In this way, even if the amount of the metal exothermic agent is the same, an industrial explosive with the largest underwater explosion energy can be obtained, and even if the excess or deficiency of oxygen by the conventional calculation method becomes significantly negative, CO, NO _X It has been found that an emulsion explosive composition in which the gas does not increase after an explosion harmful to the human body, such as that described above, can be obtained.

That is, in view of cost and effect, by adding a metal exothermic agent such as aluminum having a particle size range of 1 to 105 μm, which can be produced at the current industrial technology level, to the emulsion explosive composition, the specific gravity of the explosive can be reduced. Despite the increase by 0.02 or more, it was found that the low-temperature detonation sensitivity was improved, or that the underwater explosion energy was highest even with the same amount of metal exothermic agent such as aluminum. For metal exothermic agents such as fine aluminum,
In addition to the particulate metal heating agent, there is also a flaky metal heating agent,
When compared only from aluminum from the viewpoint of underwater explosion energy, particulate aluminum exhibits slightly higher performance.

This is because, as described above, the droplet diameter of the discontinuous phase solution comprising the oxidizing agent constituting the emulsion explosive composition is as small as several μm or less, and the surface thereof is formed of a continuous phase such as wax as fuel. Is present in a wrapping state. Therefore, the composition in which the contact area between the fuel and the oxidizing agent is extremely large is obtained, and once the detonation reaction starts, it propagates with high efficiency.

However, if a metal exothermic component such as aluminum, which is larger than the particle diameter of the oxidant droplet, is present, the metal exothermic agent such as aluminum itself is also a fuel component, but the particle size is much larger than that of the oxidant droplet. Because
The reaction efficiency decreases. As a phenomenon supporting this, an emulsion explosive composition containing a metal heating agent such as aluminum having a particle size much larger than the oxidant droplet particle size,
The bomb speed always decreases. Although it is impossible with the current technology, if a metal exothermic agent such as fine-particle aluminum having an oxidant droplet particle size or less can be used, the explosion velocity will not decrease.

As in the above discussion, it can be interpreted that flaky aluminum has a larger average particle diameter than fine-grained aluminum, so that the reaction efficiency is reduced and the explosion energy is reduced. This indicates that the smaller the particle size of aluminum, the easier it is to react, and that the energy increasing effect is enormous. Industrial explosives generally adjust oxygen deficiency to near zero. This is because gases generated after the explosion are harmful to humans, such as CO, NO.
_This is to suppress the occurrence of _X and the like.

As described above, when a metal exothermic agent such as aluminum is added to an emulsion explosive composition having a high reaction efficiency, a metal exothermic agent such as aluminum is used as a reducing agent in a high-temperature and high-pressure detonation reaction. The water or moisture in the water functions as an oxidizing agent. For example, when the metal exothermic agent is aluminum, the reaction as shown in equation (3) proceeds.

2Al + 3H ₂ O → Al ₂ O ₃ + 3H ₂ (3) Therefore, in the emulsion explosive composition containing a metal exothermic agent such as aluminum, the oxygen of the emulsion explosive composition in the absence of a metal exothermic agent such as aluminum is used. Excess or deficiency is -5.
If it is designed to be almost zero at 00 to +3.00 g / 100 g, by adding a metal exothermic agent such as aluminum,
Even if the excess or deficiency of oxygen by the conventional calculation method becomes significantly negative, water is reduced to an oxidizing agent and a metal heating agent such as aluminum is reduced to the vicinity of the addition amount of a metal heating agent such as aluminum in the same weight ratio as water or moisture in the explosive. Since it causes an oxidation-reduction reaction as an agent, components harmful to the human body such as CO,
NO _X, etc. came to found the present invention that does not increase.

That is, when a metal exothermic agent such as aluminum having a chemical equivalent or more represented by the formula (3) is added, the oxidizing agent for the metal exothermic agent such as aluminum becomes insufficient,
The redox reaction occurs with oxygen in the explosive system, and the amount of post-gas harmful to the human body gradually increases due to lack of oxygen in the entire explosive. The chemical equivalent means that the atomic weight of aluminum is 27 and the molecular weight of water is 18 when the formula (3) is viewed in terms of weight ratio, so that 2 × 27/3 × 18 = 1, and water or moisture in the explosive system is That is the same amount.

Therefore, in the present invention, the excess or deficiency of oxygen in the emulsion explosive composition (emulsion base material) before the addition of a metal exothermic agent such as aluminum is determined to be −5.00 to +5.0.
After adjusting to the range of 3.00 g / 100 g, the maximum amount of the metal exothermic agent such as aluminum is adjusted to be about the water or moisture contained in the emulsion explosive composition by weight ratio, so that the oxygen expenditure of the emulsion explosive composition is Although the shortage would be greatly negative, it was found that the gas would never increase after harm to the human body.

Among the lipophilic substances which are highly compatible with the petroleum hydrocarbon fuel component used in the emulsion composition and which are inactive with respect to the discontinuous phase component constituting the oxidizing agent solution, microcrystalline wax, For example, when a surface of a metal exothermic agent such as aluminum is coated using Hi-mic 2095 manufactured by Nippon Seiro Co., Ltd., it is inactive with fine oxidizing agent droplets which are a discontinuous phase, while enclosing it. Petroleum hydrocarbon fuels, such as Hi-mic 2065
Not only does not adversely affect the stability over time of the emulsion explosive composition, but also suppresses the reaction between a metal exothermic agent such as aluminum and water or moisture in the emulsion explosive composition during storage. It is understood that the aging stability effect is enhanced.

The metal exothermic agent in the total explosive is 3 to 20.
If it is less than 3% by weight, even if a very fine metal exothermic agent having a size of 45 μm or less is added, the effect of improving the explosive power by adding the metal exothermic agent cannot be obtained. If the amount exceeds 10% by weight, the explosive power is improved, but the explosive power is not linearly increased in proportion to the added amount, so that it is disadvantageous in terms of cost and effect.

Further, the coating amount of the substance inert to the discontinuous phase is as described in claim 4, and this coating amount is the total amount of the metal exothermic agent such as aluminum added to the explosive. When the amount is less than 2% by weight, the effect of the coating agent is weakened and the stability over time is impaired. On the other hand, when the amount of the coating agent exceeds 5% by weight, the emulsion explosive without a metal exothermic agent such as aluminum is used. The oxygen excess / deficiency of the composition becomes smaller than -5.00 g / 100 g, the amount of post-gas harmful to the human body increases, and at the same time, the reactivity of the added aluminum for the thickness of the coating material decreases, so that the explosion power Decrease.

As the inert substance for coating the metal exothermic agent such as aluminum, there are various kinds such as fatty acid salts, phosphates, polymer resins, and waxes. Of these, waxes are the most easy to handle and have good stability over time. It is.
More preferably, it is a microcrystalline wax, and among them, a microcrystalline wax having a high melting point exhibits a better temporal stability effect.

In claim 3, the particle size of the metal exothermic agent such as aluminum, which can be further recommended, is as follows.
The use of a fine particulate metal exothermic agent of 05 μm. If a metal exothermic agent having this particle size range is used, even if the same amount of metal exothermic agent is added, even if the explosion energy is the largest, and even if oxygen excess or deficiency is large and negative, a post-gas harmful to the human body, for example, CO 2 the emulsion explosive composition which generation amount of the nO _X does not increase can be obtained.

That is, by adding a metal exothermic agent such as aluminum having this particle size range to the emulsion explosive composition, the explosive specific gravity is increased by about 0.02 or more, but the low temperature detonation sensitivity is also improved, or even the addition amount of the metal heating agent, such as the same aluminum, the underwater explosion energy is highest, even more negative large oxygen excess or deficiency, the gas after harmful to the human body, for example CO, of the NO _X It was found that an emulsion whose generation amount did not increase could be obtained.

Here, the coating on the metal exothermic agent will be further described. The term "without deteriorating the explosive performance of an emulsion explosive" means not only deteriorating explosive performance but also deteriorating various properties such as stability over time and handling or manufacturability. Generally, by adding a metal heating agent such as aluminum into an emulsion explosive,
As mentioned earlier, increasing the explosive power is a known technique.

However, simply adding a metal exothermic agent such as aluminum or magnesium greatly improves explosive performance, but greatly impairs stability over time or manufacturing safety, and makes it very difficult to commercialize the product. In order to solve this problem, a means for coating the surface of a metal heating agent added to increase the power of the emulsion explosive composition, for example, a metal heating agent such as aluminum, so as not to react with the emulsion explosive composition is adopted. did.

The particle size range of the metal heating agent to be added is 105 μm.
If it exceeds m, the ballistic mortar ratio, which is one indicator of the static power of explosives, is greatly improved. However, the ballistic mortar test has a small amount of reagent and is not appropriate as an energy evaluation method for explosives. In the energy evaluation method by underwater explosion, which is a typical energy evaluation method that overcomes the above, no large increase in energy is recognized.

Therefore, from the viewpoint of developing an explosive having a large energy value evaluated by an underwater explosion that matches well with the actual explosive use situation, the static power evaluation method of the conventional simple ballistic mortar test shows a high value. However, it turned out that some of them have low underwater explosion energy values. When investigating the relationship between the aluminum particle size to be added and the underwater explosion energy, for aluminum of 105 μm or less,
Even with the same amount of aluminum added, the smaller the particle size of aluminum, the greater the effect of increasing explosive energy. Therefore, the aluminum used is more effective as the particles are finer, but on the other hand, the production risk such as dust explosion is increased, or the productivity is reduced due to electrostatic damage, etc.
The end result is expensive aluminum, and a particle size of less than 1 μm cannot be selected from the viewpoint of cost effectiveness.

The metal exothermic agent such as fine aluminum is not only in particulate form but also in flake form. However, from the viewpoint of underwater explosion energy, a metallic exothermic agent such as particulate aluminum has slightly higher performance. is there. This is because, as described above, the particle diameter of the droplet of the oxidizing agent solution constituting the emulsion is as very small as several μm or less, and the surface of the oxidizing agent solution exists in a state in which the wax as the fuel is wrapped.

Therefore, the composition has a very large contact area between the fuel and the oxidizing agent, and once the detonation reaction starts, it propagates with high efficiency. However, if a metal exothermic component such as aluminum that is larger than the particle diameter of the oxidant droplet composed of several μm is interposed, the metal exothermic agent such as aluminum itself is also a fuel component. Due to the large particle size, the contact between the oxidant and the fuel is cut off, and the reaction efficiency is reduced. As a phenomenon supporting this, fine granular aluminum that is currently available on a commercial basis, which is aluminum with an average particle size equal to or larger than the oxidizer droplet particle size, the emulsion explosive composition to which this is added always has a detonation speed. descend.

Although it is impossible with the current technology, if a metal exothermic agent such as aluminum fine particles having a particle diameter equal to or less than the oxidant droplet particle diameter can be used, the explosion speed will be maintained at substantially the same value. In addition, from the viewpoint of cost-effectiveness or handling risk, there is a limit in reducing the particle size of the metal heating agent. Similarly to the above discussion, it can be interpreted that flaky aluminum has a larger average particle diameter than particulate aluminum, so that the reaction efficiency is reduced and the explosion energy is reduced. This indicates that the reaction is easy if the particle size of the metal exothermic agent such as aluminum is small, and the effect of increasing the energy is enormous.

Here, the method of evaluating the explosion energy and the particle size range of the metal exothermic agent will be further described. To increase the maximum explosion energy effect by adding a small amount of metal heating agent means that adding a metal heating agent such as aluminum can increase the explosion power as described above, or increase the explosion power according to the amount Knowing that
As described above, when a large amount of metal exothermic agent is added, not only does the amount of the coating agent that does not contribute to the explosion reaction increase, but also the factor of increasing the unit cost of explosives.

Therefore, it is desirable to aim at the maximum effect of increasing the explosion energy by adding as little metal exothermic agent as possible. Therefore, when the characteristics of metal exothermic agents such as aluminum and the explosive power were studied diligently, as a test method for comparing the power increasing effect of explosives, a simple test such as a ballistic mortar test was used so far, This method has a small amount of test explosive and is therefore unsuitable for power judgment or comparison scale because of the possibility that the explosive itself has not reached a steady detonation and the relative comparison with the reference explosive TNT.

For this reason, the inventor of the present invention compares and examines the absolute energy amount of explosives by an underwater explosion test which can be performed in a state of explosive cartridges having a diameter of 30 mm and a drug amount of 200 g, which is a form actually consumed by the user. I decided that. As a result, various effects were found that could not be understood by the ballistic mortar test, which is a simple test method that has been implemented so far.

That is, even if the ratio of the ballistic mortar is large, the underwater explosion test does not always show a large explosion energy value. Furthermore, even if the mortar ratio is almost the same,
Explosion energy values from underwater explosion tests have significant changes. Based on this result, the explosion energy increasing effect was examined, and as a result, the particle diameter of a metal heating agent such as aluminum was in the range of 1 to 105 μm, more preferably 45 μm or less, the dramatic increase in the ballistic mortar ratio. Even though there was no effect, it was found that the underwater explosion energy was greatly increased, and this measure was adopted. The lower limit of 1 μm does not need to be particularly restricted, but cannot be made infinitely small in consideration of handling, manufacturing safety and unit cost of raw materials.

Industrial explosives generally adjust the oxygen excess / deficiency to near zero. This is harmful gases to the human body in a gas product generated after explosion, for example CO, in order to suppress the occurrence of NO _X. As described above, when a metal exothermic agent such as aluminum is added to an emulsion explosive composition having a high reaction efficiency, the metal exothermic agent such as aluminum acts as a reducing agent in a high-temperature and high-pressure state of the detonation reaction. The water or moisture therein functions as an oxidizing agent, and the reaction proceeds as described in the equation (3) as described above.

Therefore, in the emulsion explosive composition containing a metal exothermic agent such as aluminum, the excess or deficiency of oxygen in the emulsion base in the absence of a metal exothermic agent such as aluminum is -5.00 to +3.00 g as described in claim 1. / 100
g, if the excess or deficiency of oxygen becomes significantly negative due to the addition of a metal heating agent such as aluminum,
It was found that the gas components harmful to the human body in the gas after the explosion did not increase up to the vicinity of the amount of the metal exothermic agent such as aluminum or the like in which the weight ratio of water or water in the explosive was about equal.

Therefore, the emulsion explosive composition of the present invention
Of water or water content depends on stability over time and
The range was 5 to 20% by weight due to the packing problem. According to the present invention
Gold such as aluminum in emulsion explosive compositions
The amount of the genus exothermic agent should be equal to or more than the chemical equivalent represented by the formula (3).
When it does not contain metal exothermic agents such as aluminum
The excess or deficiency of oxygen in the emulsion base material is -5.00 to +3.0.
Since it is adjusted to 0 g / 100 g, it is expressed by the equation (3).
Metal such as aluminum added in excess of the chemical equivalent
Explosives, because the heating agent consumes oxygen of the oxidizing agent other than water
As a whole, it is large, oxygen excess and deficiency become negative, and eventually the human body
Harmful to CO, NO _xAfter that, the gas increases.

Therefore, in the present invention, after adjusting the oxygen excess / deficiency of the emulsion base before adding the metal exothermic agent such as aluminum to the range of -5.00 to +3.00 g / 100 g, the maximum of water is adjusted. By adding a metal exothermic agent such as aluminum having a content (% by weight) such as aluminum, generation of post-gas harmful to the human body is suppressed. The excess or deficiency of oxygen in the emulsion base without the metal exothermic agent is-
If it is less than 5.00 g / 100 g,
Also NO _X is reduced as the explosion after gas, at the same time CO is increased, explosive performance typified by low detonation sensitivity and detonation velocity is lowered.

On the other hand, if this value exceeds +3.00 g / 100 g, CO decreases as gas after explosion, but NO _x
At the same time, the low-temperature detonation sensitivity and especially the explosion speed drop sharply. In addition, the excess or deficiency of oxygen in the emulsion explosive composition after adding the metal exothermic agent was -20.0 g / 100.
If it is less than g is to role insufficient water or moisture with as an oxidizing agent for aluminum at high temperature and high pressure of detonation reaction, and at the same time increases both the CO and NO _X as explosive gas after detonation velocity is reduced come.

Similarly, this oxygen excess / deficiency is -4.00 g /
If it exceeds 100 g, in particular, NO _X increases, and the explosion speed sharply decreases. When the amount of water or water is less than 5% by weight, not only does the definition of a water-containing explosive deviate from the definition, but the resulting emulsion explosive composition becomes extremely hard, which causes difficulty in filling the paper cylinder, and the stability over time is extremely poor. turn into.

On the other hand, if the content exceeds 20% by weight, the explosive itself becomes soft and difficult to use, and in addition, detonation energy is deprived of evaporating these moistures at the time of explosion, resulting in lower explosion energy. . Here, the correlation between the post-gas, the oxygen balance, and water or moisture will be further described.

As to the explosion performance of the coating on the metal exothermic agent, industrial explosives use different types of explosives depending on the place of use. In an era when only dynamite, carlit, and ANFO explosives are the only options, underground blasting, such as tunnel blasting, is an explosive that generates less harmful gas out of the gases generated after the explosion (referred to as “post-gas”), for example, 2 No. Enoki dynamite has been mainly used.

However, in recent years, hydrous explosives, which are composed of components that are not explosives themselves, and have an excellent rear gas appearance,
Furthermore, with the technical improvement and enlargement of ventilation equipment, there is no longer a need to examine gas much. Such a water-containing explosive generally adjusts the oxygen balance to near zero in order to maintain high explosion performance while taking into account post-gas.

However, in the emulsion explosive composition to which a metal exothermic agent such as aluminum is added to increase the explosive power of the explosive as in the present invention, the contact efficiency between the oxidizing agent solution and the fuel is extremely high, and At the time of the reaction, the added metal exothermic agent such as aluminum and water or moisture in the emulsion composition cause an oxidation-reduction reaction as in the formula (3) in which the metal exothermic agent is a reducing agent and water is an oxidizing agent, and the explosive is used. The detonation reaction is completed with little consumption of oxygen in the system.

This is more effective as the particle size of the metal heating agent to be added is smaller. Therefore, by adding a metal heating agent such as fine aluminum and a foaming agent to an emulsion composition having no aluminum and almost no oxygen excess / deficiency, even if the oxygen excess / deficiency is greatly negative, the It has been found that an emulsion explosive composition having a high explosive power, in which CO and NO _X harmful to the human body increase rather than increase, can be obtained.

To satisfy this, the oxygen balance of the emulsion base without a metal exothermic agent such as aluminum was
In the range of 5.00 to +3.00 g / 100 g, preferably, a metal exothermic agent such as fine aluminum having a particle diameter of 45 μm or less is added to water or water in the explosive system by 20% by weight.
In the following range, and the oxygen excess / deficiency of the final product is -20.0
It was designed to be -4.00 g / 100 g, and a means of adding a foaming agent to obtain an emulsion explosive composition was employed.

[0074]

Hereinafter, comparative examples and examples of the present invention will be described based on tables. First, Table 1 corresponding to claim 1 will be described. In Comparative Example 1, the emulsion base was prepared using 70% monoethanolamine (organic amine oxidizing salt).
An emulsion explosive composition in which B was -8.4, which did not contain aluminum, and which was added with 2.4% by weight of glass bubbles K-15 manufactured by Sumitomo 3M Co., Ltd. as a specific gravity adjuster. .

Comparative Example 2 has the same composition as Comparative Example 1, except that OB of the emulsion base material was -17.9 and 2.0% by weight of Glass Bubbles K-15 was added.
Comparative Examples 3 and 4 are emulsion explosive compositions in which the base OB of the emulsion explosive using an organic amine oxidizable salt was -7.4, -16.3, respectively, as in Comparative Example 1. Particle size JIS sieve nominal (μ) 10 for increase
5 Flake aluminum (PF) with 90% by weight or more
100S) was added in an amount of 5% by weight, and the same K-15 as that of Comparative Example 1 was used as a specific gravity regulator.

In Comparative Examples 3 and 4, each of the emulsion base materials contained 7.1 monoethanolamine as an amine.
13.6% by weight, and 4.9% by weight of metal heating agent
This is a blended sample. As described above, Comparative Examples 1 and 2
The oxygen balance of the emulsion base material is -5.0 g / 100
In Comparative Examples 3 and 4, the oxygen balance of the emulsion base material was adjusted to a negative value from −5.0 g / 100 g, and a metal exothermic agent was added to adjust the oxygen balance of the emulsion explosive composition to − 4.0 to -20.0 g / 10
The sample was 0 g.

Example 1 is an emulsion explosive composition in which the OB of the emulsion base material without using an organic amine oxidizing salt was +2.0. The same Grass Havulus K-1 as Comparative Example 1 was used.
5, 2.5% by weight, and the same amount (5% by weight) of flake aluminum PFS100S as in Comparative Examples 3 and 4. Examples 2 to 6 are emulsion explosive compositions in which the OB of an emulsion base using an organic amine oxidizable salt was -5 or more, and the specific gravity regulator glass bubbles (K-25) was 6.0% by weight to 7%. 0.02% by weight. Further, in Examples 2 and 3, atomized aluminum AB1700 having a particle size of JIS sieve nominal (μ) 105 and a transmittance of 90% by weight or more was added. JIS sieve nominal (μ) 149 Atomized aluminum AC0780 having a pass ratio of 90% by weight or more was added.

As described above, in Examples 1 to 6, the oxygen balance of the emulsion base material was -5.0 to +3.0 g / 10
0 g, and a metal exothermic agent was added to adjust the oxygen balance of the emulsion explosive composition from -20.0 to -4.0 g / 10.
The sample was 0 g. <Discussion> Even if the oxygen balance of the emulsion explosive composition is the same, the oxygen balance of the emulsion base material is −5.
0- + 3.0 g / 100 g of the sample of the example, and -5.0.
g / 100 g, the sample of the example has a higher low-temperature detonation sensitivity, a higher ratio of ballistic mortar and underwater explosion energy, and is a harmful component in gas generated by the explosion. The generation amount of certain CO (carbon monoxide) is small and good.

In particular, comparing the sample of Example 3 in which the oxygen balance of the emulsion explosive composition is about -20.0 g / 100 g with the sample of Comparative Example 4, the oxygen balance of the emulsion base material was -4.4 g / In Example 3 of 100 g, the oxygen balance of the emulsion base material was -16.3 g / 100.
g compared with Comparative Example 4, the Example 3 having the low-temperature detonation sensitivity, the underwater explosion energy, and the performance of the ballistic mortar ratio was extremely excellent, and the content of CO in the product gas after the explosion was extremely small. Has become.

Here, the post-gas detonates 500 g of a sample in a pit having a length, width, and height of about 4 × 4 × 2.5 m, and data obtained by the Kitazawa-type detector of the gas collected within one minute. is there. Example 4 is a sample in which 4.3% by weight of monoethanolamine was added as an amine to the emulsion base material.

Thus, Example 4 is different from Comparative Examples 3, 4,
As compared with Table 9 (Table 2), it can be seen that the underwater explosion energy, the low-temperature detonation sensitivity, and the ratio of the ballistic mortar are large, and good performance can be obtained by mixing 3 to 5% by weight of monoethanolamine.

[Table 1] Details of each material in Table 1 are as follows.

The 67% nitric acid in the column of oxidizing agent is industrial grade manufactured by Nippon Kasei Co., Ltd., sodium acetate is industrial grade manufactured by Daito Chemical Co., Ltd., and ammonium nitrate is industrial granular ammonium nitrate, sodium nitrate grade manufactured by Mitsubishi Kasei Corporation. Is an industrial product manufactured by Mitsubishi Kasei Corporation. Also, Hi-mic2 in the wax column
065 is a microcrystalline wax manufactured by Nippon Seiro Co., Ltd.

In the emulsifier column, emmatol NS is sorbitan polyol manufactured by Nippon Emulsifier Co., Ltd., Reodol AO-15 is sorbitan sesquiolate manufactured by Kao Corporation, and rheodol SP-010 is sorbitan monooleate manufactured by Kao Corporation. It is. In addition, G in the specific gravity adjusting agent column
MB K-15 is a glass bubble made by Sumitomo 3M Co., Ltd. (true specific gravity 0.15 ± 0.02, pressure resistance 300 ps.
i, floating rate 96 vol%), GMB K-25 is glass bubbles manufactured by Sumitomo 3M Co., Ltd. (true specific gravity 0.25 ±
0.02, compressive strength 750psi, floating rate 96vol
%).

Further, PF0100S in the aluminum column
Is flake aluminum manufactured by Toyo Aluminum Co., Ltd. (particle size JIS sieve nominal (μ) 105;
Above, 50% particle size 15μ by laser diffraction particle size measurement
m), AB1700 is atomized aluminum manufactured by Toyo Aluminum Co., Ltd. (particle size JIS sieve nominal (μ) 1
05, 90% by weight or more, 50% particle size 34 μm by laser diffraction particle size measurement), AC0780 is atomized aluminum manufactured by Toyo Aluminum Co., Ltd. (particle size JIS sieve nominal (μ) 149, 90% by weight or more, laser 50% particle size by diffraction particle size measurement 144 μm).

Next, Table 2 corresponding to claims 2 and 3 will be described. Comparative Examples 5 and 9 are emulsion explosive compositions using no organic amine oxidizing salt.
Indicates that no aluminum was added, and Comparative Example 9
Is the particle size JIS sieve nominal (μ) 149, 40% by weight
The following atomized aluminum AC0270 was added.

Comparative Examples 6 to 8 and 10 to 12 are emulsion explosive compositions using an organic amine oxidizing salt.
Indicates that no aluminum was added, and Comparative Examples 7, 8 and 11 had a particle size of JIS sieve nominal (μ) 149
Atomized aluminum AC0220 / A of not more than% by weight
B0110 was added, and Comparative Examples 10 and 12 had a particle size JI
S sieve nominal (μ): 149 Atomized aluminum with a passage rate of 40% by weight or less was added.

As described above, Comparative Examples 5 to 12 and Examples 7 to 17 are samples in which the oxygen balance of the emulsion base material was -5.0 to +3.0 g / 100 g.
Comparative Examples 5 and 6 are samples that do not contain a metal exothermic agent.
Comparative Examples 7 to 12 are samples in which a metal exothermic agent having a passing rate of JIS sieve nominal (μ) 149 of less than 90% by weight was mixed.

Comparative Example 9 is a sample containing no amines in the emulsion base material and containing 4.9% by weight of a metal exothermic agent. Example 7 is an emulsion explosive composition not using an organic amine oxidizing salt, in which 2.3% by weight of a resin balloon (2) was added to a specific gravity adjusting agent, and a particle diameter was JIS sieve nominal (μ) 149.
Atomized aluminum VA1 with a passing rate of 90% by weight or more
520 was added by 4.9% by weight.

Examples 8 to 10 and 12 to 17 are emulsion explosive compositions using an organic amine oxidizing salt, wherein a glass balloon as a specific gravity modifier was added in a range of 2.5 to 7% by weight, In addition, 4.9% by weight of aluminum to 19.
In Examples 8 and 9, the atomized aluminum VA1520 having a particle size of JIS sieve nominal (μ) 149 and a passage ratio of 90% by weight or more was added. Atomized aluminum AB1700 with JIS sieve nominal (μ) 105 passing rate of 90% by weight or more
In Examples 14 to 16, flake aluminum PF100S having a particle size of JIS sieve nominal (μ) 105 and a transmittance of 90% by weight or more was added, and in Example 17, magnesium M-1002 was added instead of aluminum. Things.

Example 11 is an emulsion explosive composition using an organic amine oxidizing salt, in which 0.5% by weight of a resin balloon (3) was added to a specific gravity regulator, and the particle diameter passed through a JIS sieve nominal (μ) 105. Atomized aluminum AB1700 having a ratio of 90% by weight or more was added by 4.9% by weight. As described above, Examples 7 to 17 are samples in which a metal exothermic agent having a passing rate of JIS sieve nominal (μ) 149 of 90% by weight or more was blended.

Further, Examples 10 to 16 are samples in which a metal exothermic agent having a passing rate of JIS sieve nominal (μ) 105 of 90% by weight or more was blended. <Consideration> Samples of Comparative Examples 7 to 10 in which a 4.9 to 5.0% by weight of a metal heating agent having a passing rate of less than 90% by weight of a JIS sieve nominal (μ) 149 were blended do not contain a metal heating agent. The mortar ratio is 9 to 20 compared to the underwater energy of Examples 5 and 6.
%growing.

However, the underwater explosion energies were 2.5 to 2.6 kJ / k for Comparative Examples 5 and 6, which did not contain a metal exothermic agent.
g, whereas Comparative Examples 7 to 12 were 2.7 kJ / kg,
Comparative Example 1 did not show much effect of adding a metal exothermic agent.
In Nos. 1 and 12, the mixing ratio of the metal exothermic agent was 9.8% by weight,
Although the sample was increased to 6% by weight, its underwater explosion energy was 2.7 to 2.9 kJ / kg, and even if the mixing ratio of the metal exothermic agent was increased, little effect was observed.

The passing rate of JIS sieve No. (μ) 149 is 90
In Examples 7 to 17 in which 2.9 to 19.6% by weight of a metal heating agent was blended in an amount of at least 3.1% to 4.6 kJ, the underwater explosion occurred.
Comparative Examples 5 and 6 containing no metal exothermic agent
Underwater explosion energy is greater than that of Comparative Examples 7 to 12 in which a metal exothermic agent having a pass ratio of IS sieve nominal (μ) 149 of less than 90% by weight is blended.

Further, comparing Comparative Examples 7 to 12 and Examples 7 to 17 with the same compounding ratio of the metal exothermic agent,
It is clear that the sample of the example in which a metal exothermic agent having a passing rate of JIS sieve nominal (μ) 149 of 90% by weight or more is blended has an effect of increasing the underwater explosion energy. Further, Examples 10 to 16 are samples containing a metal heating agent that passes 90% by weight or more of JIS sieve nominal (μ) 105,
When compared with the samples of Comparative Examples 7 to 12 having the same compounding ratio of the metal exothermic agent, it can be seen that the underwater explosion energy greatly increased.

[Table 2] Details of the sample column in Table 2 are as follows. However, Table 1
Excluding those described in. GMB Z- in specific gravity modifier
25 is glass bubbles manufactured by Tokai Rika Co., Ltd. (true specific gravity 0.25 ± 0.03, pressure resistance 727 psi, floating rate 9
8.5 vol%), resin balloon (1) is BJO-0930 (Euka phenolic micro balloon) manufactured by Union Carbide Japan Co., Ltd., resin balloon (2)
Is MFL-100CA (acrylonitrile-based plastic balloon) manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.
13 ± 0.03, pressure resistance 200 kg / cm ² or more, average particle diameter 100 μm), and the resin balloon (3) is Expancel 551DE80 manufactured by Expancel (true specific gravity 0.025 ± 0.003, average particle diameter). Diameter 68-80μ
m).

VA1520 in the aluminum column is as follows:
Atomized aluminum manufactured by Yamaishi Metal Co., Ltd. (particle size: JIS sieve nominal (μ): 149, transmission rate: 90% by weight or more, 50% particle size by laser diffraction type particle size measurement: 137 μm), A
C0270 is atomized aluminum manufactured by Toyo Aluminum Co., Ltd. (particle size: JIS sieve nominal (μ): 149, passage rate: 40% by weight or less, laser diffraction particle size: 50%).
% Particle size 376 μm), Cap420A is commercially available
o Alumi. Ltd. Atomized aluminum manufactured by Toyo Aluminum Co., Ltd. (particle size: JIS sieve (μ) 149, passage rate of 50% by weight or less), and Atomized aluminum manufactured by Toyo Aluminum Co., Ltd. (particle size: JIS sieve: (μ) 1)
AB1010 is an atomized aluminum manufactured by Toyo Aluminum Co., Ltd. (particle size: JIS sieve nominal (μ) 149, passing rate 10% by weight or less). is there.

Also, M-1002 in the magnesium column is
Fine powdered magnesium manufactured by Cerac (particle size: JIS sieve nominal (μ) 105, transmissivity of 90% by weight or more, 50% particle size by laser diffraction type particle size measurement 11 μm). Next, Table 3 corresponding to claim 4 will be described. Comparative Examples 13 to
Reference numeral 15 denotes an emulsion explosive composition using an organic amine oxidizing salt, Comparative Example 13 does not include aluminum, and Comparative Examples 14 and 15 each have a particle size of JIS sieve nominal (μ) 149, and a passing rate of 10% by weight. % Or less of atomized aluminum AC0220 / AB0110, which is not coated with a coating agent.

As described above, Comparative Example 13 is a sample containing no metal exothermic agent. Comparative Examples 14 and 15 are samples in which the metal exothermic agent was blended without coating. Example 18
21 to 21 are emulsion explosive compositions using an organic amine oxidizing salt, and Examples 18, 20, and 21 have particle diameters of J.
A coating agent (microcrystalline wax) was coated and added to atomized aluminum AB1700 having an IS sieve nominal (μ) 105 passing rate of 90% by weight or more. In Example 19, a particle size JIS sieve nominal (μ) 149 passing rate of 90% by weight was used. The above-mentioned atomized aluminum AC0780 is obtained by coating and adding a coating agent (microcrystalline wax).

[0098] As described above, Examples 18 to 21 are samples in which a metal heating agent is coated with a coating agent and blended. <Discussion> Comparative Example 13 in which the metal exothermic agent was not mixed was 2
Low temperature detonation sensitivity of -15 after 4 and 36 cycles
At 5 ° C., the low-temperature detonation sensitivity is lower by 5 ° C. than at −20 ° C. after production.

In Comparative Examples 14 and 15, the low temperature explosion sensitivity after the 24th cycle and the 36th cycle was −10 ° C. in the temperature cycle test, which was lower than the −25 ° C. during production by 15 ° C. By adding a metal heating agent,
It can be seen that the low-temperature detonation sensitivity after the temperature cycle test was deteriorated. Examples 18 to 21 are samples mixed with a metal exothermic agent coated with a coating agent. The low-temperature detonation sensitivity after 24 cycles and 36 cycles is −20 ° C., which is 5 ° C. lower than −25 ° C. after production. Although the detonation sensitivity is lowered, the temperature is the same as that of Comparative Example 13 in which the metal exothermic agent is not blended. For this reason, it is clear that if the metal exothermic agent is coated with a coating agent, the temperature range in which the low-temperature detonation sensitivity decreases with the passage of the temperature cycle can be reduced.

[Table 3] Details of the sample column in Table 3 are as follows. However, Table 1
Excluding those described in. Hi- in the column of coating agent
mic2095 is a microcrystalline wax manufactured by Nippon Seiwa Co., Ltd., Hi-mic2045 is a microcrystalline wax manufactured by Nippon Seirosu Co., Ltd., Luva
x2191 is a microcrystalline wax manufactured by Nippon Seiro Co., Ltd.

The production methods of Examples and Comparative Examples shown in Tables 1 to 3 are the same as those of Examples 1 and 7 containing no amines and Comparative Examples 5 and 9 because the production methods are the same. 1 and Examples containing amines (Examples 1 and 7 and Examples other than Comparative Examples 5 and 9 and Comparative Examples) are the same as those in Example 2. Example 21 will be described as a representative example among Examples 18 to 21 in which is coated.

[Production method of Example 1] Emulsions were prepared by mixing the components of the oxidizing agent, heating and dissolving the components in water to form an oxidizing agent solution, and mixing and emulsifying with a wax and an emulsifier. Obtain a substrate. This emulsion base material 9
An emulsion explosive composition was obtained by simultaneously adding 2.5% by weight of a specific gravity regulator (K-15) and 5% by weight of a metal heating agent (aluminum PF100S) to 2.5% by weight.

[Production method of Example 2] In advance, 3.9% by weight of monoethanolamine and 3.7% by weight of nitric acid were reacted in an aqueous solution of ammonium nitrate to produce monoethanolamine nitrate. Other components are blended to form an oxidizing agent solution, and a wax and an emulsifier are blended and emulsified to obtain an emulsion base material. Emulsion explosive composition was obtained by simultaneously adding 6.0% by weight of specific gravity regulator (K-25) and 9.8% by weight of metal exothermic agent (Aluminum AB1700) to 84.2% by weight of this emulsion base material.

[Production Method of Example 21] First, 0.4% by weight of a coating agent (wax Hi-mic 2095) was added to 19.6% by weight of a metal exothermic agent (Aluminum AB1700), and the mixture was stirred while heating, followed by coating. Stir at a temperature above the melting point of the wax for 5 minutes. afterwards,
Turn off the heat and slowly stir until the temperature is 10 ° C. below the melting point of the coating wax.

20% by weight of the coated aluminum thus obtained was simultaneously added to 76.5% by weight of the emulsion base material and 3.5% by weight of the specific gravity regulator (K-15) to obtain an emulsion composition.

[0105]

As described above, claims 1 to 5 are described.
In the invention according to the above, the maximum explosive energy effect can be increased by adding a small amount of metal exothermic agent without lowering the explosive performance of the emulsion explosive.

According to the invention of claim 1, high sensitivity and high power are maintained, and explosive gas harmful to the human body is not increased. According to the invention according to claim 2, the underwater explosion property is improved.
According to the invention according to claim 3, the underwater explosion energy can be greatly increased. According to the invention according to claim 4, the stability over time can be improved. According to the fifth aspect of the present invention, the effect of the underwater explosion can be sufficiently exhibited even with a small addition amount of monoethanolamine of 3 to 5% by weight.

Claims (5)

[Claims] 1. A discontinuous phase comprising ammonium nitrate and another oxidizing salt and water and / or an organic amine oxidizing salt; a continuous phase comprising a petroleum hydrocarbon and an emulsifier suitable for a water-in-oil emulsion; And a water-in-oil emulsion explosive composition comprising 3 to 20% by weight of a metal exothermic agent and containing 5 to 20% by weight of water or moisture in the total explosive, wherein the mixing ratio of the metal exothermic agent before addition is The excess / deficiency of oxygen in the emulsion base material was −5.00 to +3.00 g / 100 g, and the excess / deficiency of oxygen after adding the metal heating agent was −20.00 to
A water-in-oil type emulsion explosive composition characterized by having a weight of -4.00 g / 100 g. 2. The water-in-oil type emulsion explosive composition according to claim 1, wherein the metal exothermic agent is in the form of powder or scale which passes 90% by weight or more of JIS sieve nominal (μ) 149. And a water-in-oil emulsion explosive composition. 3. The water-in-oil type emulsion explosive composition according to claim 2, wherein the metal exothermic agent is in the form of powder or scale which passes 90% by weight or more of JIS sieve nominal (μ) 105. And a water-in-oil emulsion explosive composition. 4. The water-in-oil type emulsion explosive composition according to any one of claims 1 to 3, wherein the metal exothermic agent is a substance which is inactive in the discontinuous phase with respect to the metal exothermic agent. A water-in-oil type emulsion explosive composition, which is in the form of a powder or scale coated with 2 to 5% by weight. 5. The water-in-oil emulsion explosive composition according to any one of claims 1 to 4, wherein the organic amine oxidizing salt is a monoethanolamine oxidizing salt, A water-in-oil type emulsion explosive composition characterized by containing by weight.