JPS6154757B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hydrous explosive composition with improved sensitivity by adding a surfactant. More specifically, it relates to the use of a surfactant in hydrous explosives that has both the properties of foaming and foam stability. A method of improving the sensitivity of a hydrous explosive by adding a surfactant to a hydrous explosive composition is known, as disclosed in Japanese Patent Application Laid-open No. 50-88205 and 1988-88206. this is,
The content of this technology was to utilize the foaming properties of surfactants to significantly lower the specific gravity of hydrous explosives, and to improve sensitivity by introducing effective bubbles that would serve as hot spots into the hydrous explosives. However, these surfactants have a problem with foam stability, and unless the specific gravity is lowered, the effective bubbles that improve sensitivity cannot be retained in the hydrous explosive, resulting in a decrease in the sensitivity of the hydrous explosive containing the sensitizing agent. There has also been only moderate success in improving the In order to solve the above problems,
121412 uses a foaming surfactant and a foam-stabilizing surfactant in combination to improve the stability of the bubbles introduced into the hydrous explosive and improve its sensitivity.
However, when using these two types of surfactants,
The two surfactants had to be uniformly present at the bubble interface, making it difficult to maintain reproducibility and causing problems in manufacturability. The present invention has been made to solve the above problems. That is, the present inventors did not use a foaming surfactant and a foam-stable surfactant together, but instead used a surfactant that had both of these characteristics and introduced it into a hydrous explosive. As a result of intensive research aimed at stabilizing bubbles and improving sensitivity,
The alkylpyridinium halide is further added to a sensitizing agent containing at least one of an inorganic oxygen-supplying salt such as ammonium nitrate, water, a flammable substance, a thickener, a crosslinking agent, and a water-soluble organic nitrate or its ester or a finely divided aminium. When added to a hydrous explosive composition containing a porous specific gravity adjuster, the introduced air bubbles were stabilized, and a highly sensitive hydrous explosive composition with a high specific gravity range could be obtained. The hydrous explosive composition of the present invention comprises an inorganic oxygen supplying salt,
A composition to which a sensitizer consisting of at least one of water, a flammable substance, a thickener, a crosslinking agent, a water-soluble organic nitrate or its ester, or flaky aluminum, and a porous specific gravity adjuster are added. In contrast, 0.05 to 5% by weight of alkylpyridinium halide is further blended. The inorganic oxygen-supplying salt is, for example, a salt of an inorganic acid such as nitric acid, chloric acid, perchloric acid, etc., with ammonium, alkali metal, or alkaline earth metal, and is constituted singly or in combination. The thickener may be one or a combination of two or more of natural or synthetic polymer compounds such as guar gum, locust bean gum, guar gum derivatives, locust bean gum derivatives, xanthan gum, and polyacrylamide. In particular, in the mixture of thickeners, a crosslinking agent is required which reacts with at least one of the thickeners. This is because a hydrous explosive composition to which no crosslinking agent is added deteriorates in sensitivity at low temperatures. For example, the combination of a thickener and a crosslinking agent may include a thickener comprising at least one of guar gum, locust bean gum, a guar gum derivative, a locust bean gum derivative, and at least one of antimonate, chromate, and borate. A crosslinking agent containing one. Derivative gums include hydroxyethyl gum, hydroxypropyl gum, carboxymethyl gum, and low molecular weight gums. Combustibles include solid combustibles such as coal powder and aluminum powder, or liquid combustibles such as ethylene glycol. Examples of sensitizers include alkylamine nitrates,
Alkanolamine nitrates can be used. In particular, the composition obtained from monomethylamine nitrate has good detonation properties. When organic nitrates, particularly monomethylamine nitrate, are used as sensitizing agents, the use of ammonium nitrate or sodium nitrate as oxygen supplying salts significantly increases the solubility, which is particularly effective because high solubility is maintained even at low temperatures. Aluminum flakes are made of 90% 325 mesh.
A path granularity is better. Also, as a specific gravity adjuster, the bulk specific gravity is 0.02~
0.1 substance can be used. In particular, expanded nacre is advantageous due to its good bubble entrainment properties. This is because the air bubbles between the particles of the specific gravity adjuster are involved in the hydrous explosive, thereby adjusting the specific gravity well and introducing microbubbles. Particularly when using the foaming properties of surfactants to introduce air bubbles into hydrous explosives, it is important to note that specific gravity is difficult to control. Known chemical gas treatment methods may also be used to introduce the gas bubbles into the hydrous explosive. The hydrous explosive composition contains 5 to 50% by weight of a sensitizer;
20-80% by weight inorganic oxygen-providing salt, 5-20% by weight water, 0.5-8.0% by weight thickener, 0.005-1.0% by weight
of crosslinking agent, 0.1 to 7% by weight of combustibles, and even 0
~5% by weight of a specific gravity adjuster. In the present invention, the above-mentioned components include alkylpyridinium halide. It is characterized by containing. The number of carbon atoms in the alkyl group R is 8 to 24, preferably 12 to 18 from the viewpoint of the balance between lipophilic groups and hydrophilic groups.
X represents halogen, such as chlorine and bromine.
A suitable example is laurylpyridinium chloride. The amount of alkylpyridinium halide added is 0.05 to 100 parts by weight of hydrous explosive.
The amount is 5 parts by weight, preferably 0.1 to 2.0 parts by weight. The lower limit of the blending amount seems to be determined by the amount of surfactant adsorbed at the bubble interface necessary to stabilize the bubbles introduced into the hydrous explosive, and the upper limit depends on the properties of the surfactant. Therefore, the crosslinking reaction between the thickener and the crosslinking agent is inhibited, thereby limiting the amount of water used. The method for producing the hydrous explosive composition of the present invention is as follows. Put the sensitizer, inorganic oxygen supply salt, and water into a mixing tank.
Stir at 30-50° C., maintain the solution temperature at an appropriate point in the temperature range, and add and stir the residual inorganic oxygen-providing salt and premixed thickener therein. As the remaining inorganic oxygen supplying salt, sodium nitrate is preferable. Then, a combustible material and a specific gravity adjuster are added, an alkylpyridinium halide is further added and stirred, and a crosslinking agent is further added and stirred to obtain a hydrous explosive composition. In the sensitizing agent, aluminum can be added even after adding the thickener. Also, the specific gravity adjuster, combustible material, and alkylpyridinium halide may be added before the thickener is added.
The timing of addition is flexible. The resulting composition is then filled into a tube made of synthetic polymer.

[Table] Leave it alone.
Table 1 shows the foam stability of the surfactants. Among these, laurylpyridinium chloride shows remarkable stability in a single surfactant solution. When hydrous explosives were produced using these surfactants, it was found that the compositions to which laurylpyridinium chloride was added had good detonation sensitivity. The hydrous explosive composition of the present invention has the following properties. In other words, when a hydrous explosive composition containing a foaming surfactant has a specific gravity of 1.0 or more, it can be detonated at a low temperature of -10°C even with a single No. 6 electric detonator when the diameter of the explosive is 50 mm. I can't let you. In contrast, the hydrous explosive composition of the present invention has −
It can be detonated at 10℃, and this sensitivity is 3 after manufacture.
No decline was observed even after several months.
In this case, it was observed that even if the specific gravity was increased to 1.10 or higher, it detonated at -5°C or higher. Furthermore, when a hydrous explosive composition to which flaky aluminum sensitizer was added was detonated at -5°C using a No. 6 electric detonator with a diameter of 25 mm, the one to which laurylpyridinium halide was added was -5. It was possible to detonate it at ℃. Next, the effects of the present invention will be explained with reference to Examples and Table 2. Examples and Reference Examples In a hydrous explosive composition having the compounding ratio shown in Table 2, monomethylamine nitrate, ammonium nitrate,
Water is placed in a mixing tank and stirred and dissolved at 40°C, a preliminary mixture of sodium nitrate and hydroxypropyl guar gum is added and stirred, and expanded pearlite and combustible materials are added. If aluminum is to be added, it is added at this point. Laurylpyridinium chloride was added thereto, stirred for 5 to 7 minutes, and finally a crosslinking agent was added and stirred to obtain a hydrous explosive composition of an example. This composition was placed in a polyethylene tube with a thickness of 0.1 mm and an explosion test was conducted. The hydrous explosive composition containing laurylpyridinium chloride has a dense appearance with uniform fine bubbles, and the gelled composition filled in a 50 mm polyethylene tube has a tentative specific gravity of 1.0 or more after 7 days of manufacture. Ta. When this gelled hydrous explosive composition was detonated using one No. 6 electric detonator, -10
The results showed complete explosion at ℃. These hydrous explosive compositions showed no change in appearance even after 3 months,
It was possible to detonate the bomb at -10°C using a single No. 6 electric detonator. On the other hand, the slurry explosive composition shown in the reference example also had a provisional specific gravity of 1.0 or more after 7 days of production, but it could not be detonated at -10°C using a single No. 6 electric detonator, and the interface Even hydrous explosive compositions containing no activator could only be detonated at -5°C.
A hydrous explosive composition containing no foaming surfactant could not be detonated at -5 DEG C. even with a single No. 6 electric detonator after three months of manufacture. In addition, a hydrous explosive composition containing aluminum flakes was heated to -5°C using a No. 6 electric detonator with a diameter of 25 mm.
The explosive composition to which laurylpyridinium chloride was added was able to be detonated when detonated at As described above, compared to hydrous explosives containing foaming surfactants, the hydrous explosive composition of the present invention has a tentative specific gravity of 1.0 or higher, which is sufficient for practical use.
It is so sensitive that it can be detonated at -10℃ using a book.
It also has good stability over time.

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Claims (1)

[Scope of Claims] 1. A composition comprising an inorganic oxygen-supplying salt, water, a combustible material, a thickener, a crosslinking agent, and a sensitizing agent according to the following formula [formula] (where R is a carbon number of 8 to 24). A water-containing explosive composition, characterized in that it contains 0.05 to 5.0 weight of alkylpyridinium halide represented by the following (alkyl group, X represents halogen) per 100 weight of the above composition. 2. The hydrous explosive composition according to claim 1, wherein the inorganic oxygen-supplying salt is composed of an ammonium, alkali metal, or alkaline earth metal salt of an inorganic acid such as nitric acid, chloric acid, or perchloric acid. 3. The hydrous explosive composition according to claim 1, wherein the combustible material is a solid combustible material such as coal powder or aluminum powder, or a liquid combustible material such as ethylene glycol. 4. The water-containing product according to claim 1, wherein the thickener is one or a combination of two or more natural or synthetic polymer compounds such as guar gum, locust bean gum or derivatives thereof, xanthan gum, and polyacrylamide. explosive composition. 5. The hydrous explosive composition according to claim 1, wherein the crosslinking agent comprises at least one of antimonate, chromate, and borate. 6. The hydrous explosive composition according to claim 1, wherein the sensitizer comprises at least one of a water-soluble organic nitrate or its ester, and flaky aluminum. 7. A composition consisting of an inorganic oxygen supplying salt, water, a combustible material, a thickener, a crosslinking agent, a sensitizing agent, and a specific gravity adjuster is prepared using the following formula [formula] (where R is an alkyl group having 8 to 24 carbon atoms). , X represents halogen. 8. The hydrous explosive composition according to claim 7, wherein the alkyl group in the alkylpyridinium halide has 8 to 24 carbon atoms. 9. The hydrous explosive composition according to claim 7, wherein the inorganic oxygen-supplying salt is composed of an ammonium, alkali metal, or alkaline earth metal salt of an inorganic acid such as nitric acid, chloric acid, or perchloric acid. 10 Claim 7 in which the combustible material is a solid combustible material such as coal powder or aluminum powder, or a liquid combustible material such as ethylene glycol.
The hydrous explosive composition described in . 11. The water-containing liquid according to claim 7, wherein the thickener is one or a combination of two or more of natural or synthetic polymer compounds such as guar gum, locust bean gum or derivatives thereof, xanthan gum, and polyacrylamide. explosive composition. 12. The hydrous explosive composition according to claim 7, wherein the crosslinking agent comprises at least one of antimonate, chromate, and borate. 13. The hydrous explosive composition according to claim 7, wherein the sensitizing agent comprises at least one of a water-soluble organic nitrate or its ester, and flaky aluminum. 14. The hydrous explosive composition according to claim 7, wherein the specific gravity adjuster is made of expanded nacre.