JP2005139036A - Insensible high-power non-gunpowder crushing agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insensible high-power non-gunpowder crushing agent which has an enhanced crushing power without increasing the sensitivity in production and handling. <P>SOLUTION: The crushing agent contains a thermit agent (a metal oxidation/reduction agent) comprising an oxidant and a reductant, a gas generation agent, a desensitizer, and a binder, is not ignited nor burned down within 3 seconds in the small-gas-flame ignition test, which is the judgement test for 2nd-class combustible solids of dangerous goods of the Fire Service Law, and has a specified ballistic mortar ratio. The thermit agent contains, as the oxidant, at least one oxide selected from the group consisting of cupric oxide, ferric oxide, and metal peroxide salts; the gas generator contains at least one salt selected from the group consisting of ammonium persulfate, aluminum sulfate, and alum; and the desensitizer contains at least one compound having an average particle size of 5 μm or less and selected from the group consisting of long-chain fatty acid metal salts and long-chain fatty acids. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a non-explosive crushing drug comprising a explosive component other than the explosive component under the Explosives Control Law and containing a thermite agent and a gas generating agent as main components, and more specifically, improves the power of conventional non-explosive crushing agents. At the same time, it relates to a high-power non-explosive crushing drug that is insensitive to flames.

Conventionally, as a crushing agent composed of a non-explosive component, there is a static crushing agent mainly composed of quick lime, for example, what is called Bleister (trademark).
Moreover, as a crushing chemical | medical agent using water vapor pressure, there exists a Gunsizer (trademark), for example (for example, refer patent document 1, 2).
The mechanism of fracture of brittle bodies by crushing chemicals using water vapor pressure is that the crystal water in potassium alum, a gas generating agent, decomposes and vaporizes with high heat due to thermite reaction of the thermite in the crushing chemicals, and the gas pressure of the generated water vapor It causes tensile fracture. Therefore, the conventional crushing chemicals using this water vapor pressure have been developed to have the same level of power as black explosives with low vibration and low noise as targets. I can't wake up.

  Here, the brittle body means a material having a very high compressive strength but a small tensile strength such as rock, concrete, and stone. Generally, the tensile strength of these brittle bodies is 1/10 of the compressive strength. ~ 1/30. Therefore, the brittle body has a high yield strength against compressive fracture, but is weak against tensile fracture. Therefore, the crushing drug using water vapor pressure is in the vicinity due to the interaction between the action of the gas acting between the two adjacent holes and the stress concentration generated around the charge hole, due to the tensile stress generated between the two holes. A “tensile fracture” is caused, and a crack is formed in a predetermined direction along the two holes.

On the other hand, as with explosives, the detonation pressure of tens of thousands of atmospheres is far greater than the compressive strength of the rock mass of several hundreds Kgf / cm ² , so “compressive failure” occurs around the borehole as well as tensile failure. However, in the crushing drug using the water vapor pressure, the compression fracture hardly occurs.
Initially, this crushing agent could be made more powerful, but the products at that time were reviewed for dangerous goods by the revision of the Fire Service Act of 1990, and the Fire Service Act Dangerous Goods Class 2 Class 1 combustible solids. It became to fall under. For this reason, there has been a restriction that the specified quantity at the time of storage is less than 100 kg.
JP-A-63-319285 Japanese Patent Laid-Open No. 11-029389

In order to alleviate this restriction, the Fire Gas Act Dangerous Goods Class 2 flammable solids test method has been tried to reduce the sensitivity of small gas flame ignition, which is now cleared. It is a drug belonging to a solid. However, it is extremely difficult to increase the power while maintaining the small gas flame ignition sensitivity insensitive.
Here, the test method for the second class of dangerous goods of the Fire Service Act (purpose: small gas flame ignition test for judging the danger of ignition by flame) is a maximum of 10 seconds of flame of 70mm long city gas (butane or propane) It is a test method for assessing the risk of fire by immersing the sample in the air during the period and grasping the ignition and combustion status. Anything that ignites within 3 seconds after the start of the test and all of the sample burns and burns is considered to be very easily combustible and is judged to be easily ignitable. Judge as solid. On the other hand, those that ignite within 3 to 10 seconds after the start of the test and all the samples are burned and burned are considered to be easily combustible and judged to be ignitable. Judged as a sex solid.

Easy ignitability, other than ignitability, that is, it takes more than 10 seconds for the sample to ignite and burn out after starting the test, or even if ignited within 10 seconds, all the sample remains without burning out If it is burned while touching the flame, but the combustion is interrupted when the flame is released, it is judged as “non-ignitable” and it is judged as a non-dangerous material that does not fall under dangerous goods.
Various improvement measures have been studied so far, but the composition becomes an anti-combustible flammable solid that reduces the ignition sensitivity by flame, maintains or increases the reaction rate, or increases the gas generation amount to improve the power. In other words, no non-explosive crushing drug was obtained.

  Then, the objective of this invention is providing the high power non-explosive crushing chemical | medical agent which is insensitive to a flame while improving the power of the conventional non-explosive crushing chemical | medical agent.

In order to solve the above-described problems, the present inventor has developed a composition that does not fall under the explosives specified by the classification of the Explosives Control Law, and has aimed to increase the destruction power as much as possible. The effect of such a non-explosive crushing drug on a brittle body depends on the explosion energy possessed by the drug, that is, the generation amount of the gas product and the generation speed.
For example, sufficient reaction gas, for example, gas of 60 cc / g or more, preferably 150 cc / g or more, is generated instantaneously in a sealed space such as a bore hole in a brittle body, specifically within a few hundreds of msec. For example, the brittle body can be tensile broken.

Therefore, to return to the basics and increase the power while maintaining manufacturing and handling sensitivity, it is clear that a composition suitable for the purpose can be obtained by increasing the reaction rate (gas generation rate) or increasing the gas generation rate. It is.
However, when the reaction rate is increased, the risk gradually increases, as a matter of course for those who have knowledge of pyropharmaceuticals. If the reaction rate is increased too much, a powerful shock wave is generated, It can even be equivalent to an explosive.

Therefore, rather than increasing the reaction rate, increasing the gas generation amount without decreasing the reaction rate is a suitable method for improving the power of the crushing drug.
Therefore, what replaces potassium alum which is a gas generating agent of a conventional crushing drug is a solid in a certain particle size range, and a substance which is all gasified is preferable. For example, ammonium alum also generates some solid product and increases the amount of gas generated. Therefore, it is a candidate, but the amount of gas generated is larger when other ammonium salts are used.

Other oxidizing salts other than nitrate, perchlorate, and chlorate include hydrochloride, sulfate, oxalate, acetate, phosphate, borate, and silicate. There is.
For example, hydrochloride generates chlorine gas in the reaction product, sulfate generates sulfite gas, phosphate generates toxic gases such as phosphine, acetate and oxalate generate phosgene, etc., while borate And silicates generate solid reaction products such as boron oxide and silicon oxide.

Therefore, judging from the main purpose of decomposing the gas generating agent using the heat of reaction of the thermite composition and tensile breaking the brittle body using the gas pressure, an appropriate gas generating agent is easily decomposed thermally. In addition, it is necessary that the reaction product generates as little harmful substances as possible to the human body.
Judging from the above two points, oxalate, acetate, borate and silicate are not desirable because they are difficult to decompose and generate harmful or solid products. Since hydrochloride and phosphate generate gas harmful to the human body, it is difficult to say that they are potential candidates for gas generating agents.

Sulfate also generates sulfurous acid gas as a reaction product, but it can be determined that it is the most gentle to the human body in the above. Therefore, in order to improve the power while maintaining the non-explosive component in accordance with the Explosives Control Law, it is ideal that all sulfates become gasification components.
Examples of components that can be gasified from the above conditions include ammonium alum, ammonium persulfate, ammonium sulfate, ammonium thiosulfate, hydroxylammonium sulfate, aluminum sulfate, aluminum sulfate hydrate, calcium sulfate, chromium potassium sulfate, and hexamethylene. There are diamine and ammonium hydroxide.

The present invention has been completed based on such knowledge.
The invention according to claim 1 has a thermite agent (metal redox agent) comprising an oxidizing agent and a reducing agent, a gas generating agent, a blunting agent, and a binder. It is an insensitive, high-power non-explosive crushing agent that does not burn and burn within 3 seconds in a small gas flame ignition test, which is a test for determining a functional solid, and has a predetermined ballistic mortar ratio.

The invention according to claim 2 is an insensitive high-power non-explosive crushing agent in which the oxidizing agent of the thermite agent contains one or more selected from the group of cupric oxide, ferric oxide and metal peroxide salts. It is.
Here, as the metal peroxide salt, for example, calcium peroxide, strontium peroxide, manganese peroxide and the like can be used.

The invention according to claim 3 is the insensitive high-power non-explosive crushing drug according to claim 1 or claim 2, wherein the gas generating agent contains one or more selected from the group consisting of ammonium persulfate, aluminum sulfate and alum. It is.
For example, when a mixture of ammonium persulfate and alum is used, a crushed drug with a very static power can be obtained although it is a non-explosive component. In addition, there is an advantage that the power can be controlled arbitrarily by the mixing ratio.

The invention according to claim 4 is characterized in that the desensitizing agent includes at least one selected from the group consisting of a long-chain fatty acid metal salt having an average particle diameter of 5 μm or less and a long-chain fatty acid. The insensitive high-power non-explosive crushing drug according to any one of the above.
The invention according to claim 5 is characterized in that the long-chain fatty acid metal salt is a stearic acid metal salt such as calcium stearate, magnesium stearate, zinc stearate, and the long-chain fatty acid is stearic acid. 4. Insensitive high-power non-explosive crushing drug according to 4.

  In order to make the blunting agent a Class 2 Class 2 flammable solid of dangerous goods by reviewing the Fire Service Law, a small gas flame ignition sensitivity test, which is a confirmation test of Class 2 flammable solids of the Fire Service Law In order to prevent ignition and burning within 3 seconds, a function for delaying the combustion performance is provided. Therefore, when the crushed chemical comes into contact with the flame, the blunting agent in the component changes its state, and the melting point of the metal stearate salt or wax or the like that takes away latent heat and lowers or delays the ignitability is 2 to tens of thousands. If it is low below ℃, it has a function as a blunting agent.

Furthermore, since these blunting agents are uniformly dispersed if the particle size is small, the blunting effect is great. Specifically, it is finer than industrial reagent metal stearate, such as metal stearate for industrial use, such as metal stearate manufactured by Nippon Oil & Fats Co., Ltd. (Nissan Electol MM-2, MC-2, MZ-2). ) Is much smaller and has a much slower effect.
Here, the reason why the average particle size of the blunting agent is 5 μm or less will be described.

The smaller the particle size of the blunting agent, the larger the specific surface area of the blunting agent, and the contact of either the aluminum or cupric oxide, which is the main component of the thermite agent, or both with the coating of the blunting agent is cut off. This is because the reactivity of the thermite agent itself can be reduced.
In addition, the coating of either the main component of the thermit agent, aluminum and cupric oxide or a blunting agent for both, is simply mixing aluminum and cupric oxide in advance, either aluminum and cupric oxide or It adheres to both surfaces.

  In the invention according to claim 6, the binder is nitrocellulose, acetylcellulose, vinyl chloride, viton rubber, nitrile rubber, polyisobutylene, silicone rubber, clayton rubber, glycidyl azide polymer (GAP), bisazidomethyloxaene polymer (BAMO). And at least one selected from the group of azidomethylmethyloxaene polymer (AMMO). The insensitive high-power non-explosive crushing agent according to any one of claims 1 to 5.

Any binder may be used as long as the thermite component and the individual gas generant components are maintained in close contact with each other.
For example, in the case of an energetic binder (GAP, BAMO, AMMO, etc.), in addition to the original binding function, it itself decomposes and generates energy, which can improve the power of the crushing drug. .

  Further, a thermite composition having a good reaction rate generally has to have a very fine particle size for both the oxidizing agent and the reducing agent. Therefore, not only dust is likely to fly during production, but also there is a risk of static electricity disasters resulting from it. Therefore, in addition to the function as a binder, a binder that improves safety against static electricity is preferable. For example, when vinyl chloride is used as a binder, it is possible to improve manufacturing safety.

The invention according to claim 7 includes 25-60% thermite agent (metal redox agent), 25-75% gas generating agent, 0.2-2% blunting agent, and 0.5-15%. The insensitive high-power non-explosive crushing agent according to any one of claims 1 to 6, comprising
When the thermite composition is 25% or less, the heat source necessary for decomposing the blunting agent, the binder and the gas generating agent is insufficient, and the decomposition reaction of the gas generating agent becomes incomplete.

On the other hand, when the thermite composition is 60% or more, not only the cost increases, but also the amount of the gas generating agent is relatively reduced, so that the crushing agent has a small gas volume.
On the other hand, when the gas generating agent is 25% or less, the amount of the gas generating agent added is relatively small and the gas generating agent has a small gas volume, as described above.

On the other hand, when the amount of the gas generating agent is 75% or more, the amount of thermite agent to be added becomes small and the thermal decomposition energy is insufficient as described above, and as a result, the improvement in power cannot be achieved.
Similarly, the condition of the blunting agent 0.2 to 5% will be described. When the blunting agent is 0.2% or less, the function as a blunting agent is weak, and the test sample is completely ignited within 3 seconds according to the small gas flame ignition sensitivity test, which is a confirmation test for Class 2 flammable solids of the Fire Service Act. It burns down and falls within the category of the Fire Service Act dangerous goods Class 1 flammable solids, which is not intended. Further, since the specific surface area of the blunting agent increases as the particle diameter becomes finer, the ability to coat the surface of, for example, aluminum (or cupric oxide or both) is increased to the same extent. This is because the smaller the average particle diameter (that is, the larger the specific surface area), the smaller the amount that can be expected to achieve the same effect.

If the blunting agent is 5% or more, the blunting effect is too great, the decomposition reaction of the gas generating agent by the thermite agent is not promoted, and the reaction is interrupted.
Next, the condition that the binder is 0.5 to 15% will be described.
When the binder is 0.5% or less, the function as a binder is weakened, and it becomes impossible to maintain the uniformity of the original main crushing drug component consisting of the thermite agent component and gas generating agent component due to transport vibration, and trouble such as reaction interruption. On the other hand, if the binder is 15% or more, there is no performance problem if it is an energetic binder such as GAP, BAMO, or AMMO. When a non-reactive substance such as cellulose or polyester resin is a binder, the reaction is interrupted unless the amount is less than 15%.

The invention according to claim 8 comprises the insensitive high-power non-explosive crushing agent according to any one of claims 1 to 7 and a water-resistant substance that imparts 3% to 10% water resistance. It is an insensitive high-power non-explosive crushing agent.
Examples of water-resistant substances for imparting water resistance include gums called water-absorbing agents such as color ginnan gum, locust bean gum, guar gum, CMC (carboxymethylcellulose), and polymer water-absorbing resins such as , Polyethylene oxide, polyvinyl alcohol, sodium polyacrylate derivative, acrylic acid / vinyl alcohol copolymer, and the like. In addition, the water-resistant substance can be added after the obtained insensitive non-explosive crushing agent and then mixed to simply provide water resistance.

Gum actively absorbs water (moisture) entering from the outside and swells to form a barrier, and the swollen gums are connected to each other, and then water (moisture) enters. Is to prevent.
On the other hand, the polymer water-absorbing resin shows a slightly different form depending on the size of the particle diameter, but basically expands by absorbing water, and the volume change causes the space between the expanded particles to narrow, which appears to be a barrier-like shape. It will be in a state and subsequent invasion of water will be controlled. The individual components of the thermite agent or the gas generating agent or the entirety thereof are covered or coated with this polymer water-absorbing resin, thereby eliminating the ingress of slight moisture.

Examples of the polymer water-absorbing resin include Sumika Gel manufactured by Sumitomo Chemical Co., Ltd., Aqua Keep manufactured by Steel Chemical Industries, Ltd., Diamond Wet manufactured by Mitsubishi Oil Chemical Co., Ltd., and Sun Fresh manufactured by Sanyo Chemical Industries, Ltd.
In addition, in the case of fine-particle polymer water-absorbing resin, it is easy to absorb water and be familiar with each other. it can.

  The effect of improving water resistance can also be expected by using a mixture of a polymeric water-absorbing resin and a water-absorbing gum.

(1) According to the present invention, it is possible to improve the power by mainly increasing the amount of gas generated without increasing the reaction rate but reducing the reaction rate, and using a specific blunting agent. As a result, the sensitivity of manufacturing and handling could be reduced. As a result, in the small gas flame ignition test, which is a judgment test for the Class 2 flammable solids of the Fire Service Act, it is possible to prevent ignition and burning within 3 seconds and to have a predetermined ballistic mortar ratio. It was.
(2) By using a fine blunting agent having an average particle diameter of 5 μm or less, it was possible to reduce the sensitivity performance with a small amount of addition.
(3) Up to now, for example, 1 kg of non-explosive crushing agent was required to crush 1 m ³ rock (this is called crushing unit 1.0 kgw / m ³ ). By using this, the crushing basic unit became about 0.75 Kgw / m ³ , and the drug amount could be reduced by 25%.

In the following, the present invention will be described with reference to specific examples.
Table 1 shows the composition and performance of the following reference examples, examples and comparative examples. Table 2 shows the relationship between the amount of ammonium persulfate (or the amount of potassium ammonium alum) and the fuel speed or mortar ratio for the five reference examples in Table 1, Examples 1, 2, 3, and 4. Show.
First, the mortar ratio, which is the performance, will be described.

The power of explosives is usually displayed in terms of TNT. This is presumably because TNT has existed for a long time and is chemically stable and easily available.
There is a ballistic mortar test as a method for measuring the static power of explosives (explosives), which is also compared with relative power based on TNT. When the power of TNT is 100%, the static power of the test explosive is displayed as a percentage.

In other words, the fact that the ratio of a bullet mortar of an explosive was 140% in terms of TNT is a measure that means that the static power is 40% stronger than TNT.
Therefore, in order to make the comparison with the ballistic mortar ratio of the present invention easier to understand, a reference example is determined.
(Reference example)
1.6 parts by weight of a reagent calcium stearate having an average particle diameter of 9 μm is added to 11.5 parts by weight of aluminum, and then 15% of a 10% vinyl chloride acetone solution is added and mixed well. Add 38.5 parts by weight of cupric oxide and 50 parts by weight of potassium aluminum alum and mix well. At this time, if necessary, acetone may be further added. When the sufficiently mixed mixture becomes a soft cocoon-like shape due to the function of the binder, the mixture is passed through an 8-mesh sieve and then air-dried for 12 hours or more to remove the acetone odor.

Next, it dries for 4 hours or more in a 60 ° C. drying chamber. When this is subjected to a small gas flame ignition test, which is a test method for flammable solids of the second class of dangerous materials of the Fire Service Act, it takes 3 to 10 seconds before the sample burns and burns. It was the second kind flammable solid.
Moreover, when this was loaded into the gas pipe (SGPW20A), the loading density was 1.08 g / cc, and when the dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 360 m / s. Similarly, when a ball mill test with a dedicated igniter was performed, it was 20% (TNT ratio).

Therefore, the TNT ratio of this reference example was determined to be 100% of the ballistic mortar ratio.
(Example 1)
Add 0.8 parts by weight of industrial zinc stearate having an average particle size of 2.31 μm to 11.5 parts by weight of aluminum, and then add 15% acetone solution of 10% acetylcellulose and mix well. Add 38.5 parts by weight of cupric oxide, 25.0 parts by weight of potassium aluminum alum and 25.0 parts by weight of ammonium persulfate, and mix well. At this time, if necessary, acetone may be further added. When the mixture becomes a soft cocoon due to the function of the binder, the mixture is passed through an 8-mesh sieve and then air-dried for at least 12 hours to remove the acetone odor.

Next, it dries for at least 4 hours in a 60 degreeC drying chamber. When this was subjected to a small gas flame ignition test, which is a test method for flammable solids of the second class of dangerous materials of the Fire Service Act, the test result was 10 seconds or more before the sample burned and burned and did not correspond to a dangerous material.
Moreover, when this was loaded into the gas pipe (SGPW20A), the loading density was 1.03 g / cc, and when the dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 460 m / s. Similarly, when a ball mill test using a special igniter was performed, the power was 125% (compared to the reference example), which was 25% higher than when the reference example was taken as 100%.

(Example 2)
Add 0.6 parts by weight of industrial magnesium stearate having an average particle diameter of 2.69 μm to 11.5 parts by weight of aluminum, and then add 15% acetone solution of 10% nitrocellulose and mix well. Add 38.5 parts by weight of cupric oxide, 10.0 parts by weight of potassium aluminum alum and 40.0 parts by weight of ammonium persulfate, and mix well. At this time, if necessary, acetone may be further added. When the mixture becomes a soft cocoon due to the function of the binder, the mixture is passed through an 8-mesh sieve and then air-dried for at least 12 hours to remove the acetone odor.

Next, it dries for at least 4 hours in a 60 degreeC drying chamber. When this was subjected to a small gas flame ignition test, which is a test method for flammable solids of the second class of dangerous materials of the Fire Service Act, the test result was 10 seconds or more before the sample burned and burned and did not correspond to a dangerous material.
Moreover, when this was loaded into the gas pipe (SGPW20A), the loading density was 1.02 g / cc, and when the dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 330 m / s. Similarly, when a ball mill test using a special igniter was performed, the power was 135% (compared to the reference example), 35% higher than when the reference example was taken as 100%.

(Example 3)
Add 0.6 parts by weight of industrial calcium stearate having an average particle size of 2.41 μm to 11.5 parts by weight of aluminum, then add 15% acetone solution of 10% polyisobutylene and mix well. Add 38.5 parts by weight of cupric oxide and 50.0 parts by weight of ammonium persulfate to this and mix well. At this time, if necessary, acetone may be further added. When the mixture becomes a soft cocoon due to the function of the binder, the mixture is passed through an 8-mesh sieve and then air-dried for at least 12 hours to remove the acetone odor.

Next, it dries for at least 4 hours in a 60 degreeC drying chamber. When this is subjected to a small gas flame ignition test, which is a test method for flammable solids of the second class of dangerous materials of the Fire Service Act, it takes 3 to 10 seconds before the sample burns and burns. It was the second kind flammable solid.
Moreover, when this was loaded into the gas pipe (SGPW20A), the loading density was 1.05 g / cc, and when the dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 615 m / s. Similarly, when a ball mill test using a dedicated igniter was performed, the power was increased by 60% to 160% (compared to the reference example) compared with the reference example being 100%.

Example 4
Add 0.6 parts by weight of industrial magnesium stearate having an average particle diameter of 2.69 μm to 8.0 parts by weight of aluminum, and then add 15% acetone solution of 10% viton rubber and mix well. Add 27.0 parts by weight of cupric oxide and 65.0 parts by weight of ammonium persulfate to this and mix well. At this time, if necessary, acetone may be further added. When the mixture becomes a soft cocoon due to the function of the binder, the mixture is passed through an 8-mesh sieve and then air-dried for at least 12 hours to remove the acetone odor.

Next, it dries for at least 4 hours in a 60 degreeC drying chamber. When this is subjected to a small gas flame ignition test, which is a test method for flammable solids of the second class of dangerous materials of the Fire Service Act, it takes 3 to 10 seconds before the sample burns and burns. It was the second kind flammable solid.
Moreover, when this was loaded into the gas pipe (SGPW20A), the loading density was 1.10 g / cc, and when a dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 380 m / s. Similarly, when a ball mill test using a dedicated igniter was performed, the power was 130% (compared to the reference example), 30% higher than when the reference example was taken as 100%.

(Example 5)
0.6 parts by weight of calcium stearate having an average particle size of 2.41 μm is added to 14.5 parts by weight of magnesium, and then 15% of a 10% vinyl chloride acetone solution is added and mixed well. Add 35.5 parts by weight of cupric oxide and 50.0 parts by weight of aluminum sulfate, and mix well. At this time, if necessary, acetone may be further added. When the mixture becomes a soft cocoon due to the function of the binder, the mixture is passed through an 8-mesh sieve and then air-dried for at least 12 hours to remove the acetone odor.

Next, it dries for at least 4 hours in a 60 degreeC drying chamber. When this was subjected to a small gas flame ignition test, which is a test method for flammable solids of the second class of dangerous materials of the Fire Service Act, the test result was 10 seconds or more before the sample burned and burned and did not correspond to a dangerous material.
Moreover, when this was loaded into a gas pipe (SGPW20A), the loading density was 1.12 g / cc, and when a dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 300 m / s. Similarly, when a ball mill test using a dedicated igniter was performed, the power was increased by 20% to 120% (compared to the reference example), compared with the reference example being 100%.

(Example 6)
Add 0.6 parts by weight of industrial zinc stearate having an average particle size of 2.31 μm to 10.0 parts by weight of aluminum, then add 10% acetone solution of 10% nitrocellulose and mix well. Add 35.0 parts by weight of ferric oxide, 50.0 parts by weight of ammonium alum and 5.0 parts by weight of manganese peroxide, and mix well. At this time, if necessary, acetone may be further added. When the mixture becomes a soft cocoon due to the function of the binder, the mixture is passed through an 8-mesh sieve and then air-dried for at least 12 hours to remove the acetone odor.

Next, it dries for at least 4 hours in a 60 degreeC drying chamber. When this was subjected to a small gas flame ignition test, which is a test method for flammable solids of the second class of dangerous materials of the Fire Service Act, the test result was 10 seconds or more before the sample burned and burned and did not correspond to a dangerous material.
Moreover, when this was loaded into the gas pipe (SGPW20A), the loading density was 1.02 g / cc, and when a dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 290 m / s. Similarly, when a ball mill test using a special igniter was performed, the power was 125% (compared to the reference example), which was 25% higher than when the reference example was taken as 100%.

(Example 7)
Add 0.6 parts by weight of industrial calcium stearate having an average particle size of 2.41 μm to 12.0 parts by weight of aluminum, and then add 10% acetone solution of 10% nitrocellulose and mix well. Add 50.0 parts by weight of ammonium persulfate to this and mix well. At this time, if necessary, acetone may be further added. When the mixture becomes a soft cocoon due to the function of the binder, the mixture is passed through an 8-mesh sieve and then air-dried for at least 12 hours to remove the acetone odor.

Next, it dries for at least 4 hours in a 60 degreeC drying chamber. When this was subjected to a small gas flame ignition test, which is a test method for flammable solids of the Class 2 hazardous materials of the Fire Service Act, the result was that it was not classified as a hazardous material for 10 seconds or more before the sample burned down.
Moreover, when this was loaded into the gas pipe (SGPW20A), the loading density was 1.05 g / cc, and when the dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 420 m / s. Similarly, when a ball mortar test with a dedicated igniter was carried out, the power was 140% (compared to the reference example), 40% higher than when the reference example was taken as 100%.

(Comparative Example 1)
Here, the example of the crushing chemical | medical agent without a blunting agent is shown.
Add 15% acetone solution of 10% vinyl chloride to 11.5 parts by weight of aluminum and mix well. Add 38.5 parts by weight of cupric oxide and 50.0 parts by weight of potassium aluminum alum and mix well. At this time, if necessary, acetone may be further added. When the mixture becomes a soft cocoon due to the function of the binder, the mixture is passed through an 8-mesh sieve and then air-dried for at least 12 hours to remove the acetone odor.

Next, it dries for at least 4 hours in a 60 degreeC drying chamber. When this is subjected to the small gas flame ignition test, which is a test method for flammable solids of the Fire Service Act Dangerous Goods Class 2, it takes 3 seconds or less for the sample to burn and burn, and the Fire Service Law Dangerous Goods Class 2 Class 1 flammability Applicable to a solid.
Moreover, when this was loaded into the gas pipe (SGPW20A), the loading density was 1.21 g / cc, and when the dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 340 m / s, Similarly, when a ball mill test using a dedicated igniter was performed, the power was 115% (compared to the reference example), which was 15% higher than when the reference example was taken as 100%.

(Comparative Example 2)
To the aluminum of Comparative Example 1, as a blunting agent, a reagent calcium stearate having an average particle size of 9.0 μm is added in an amount of 2.50 parts by weight, and then 15% acetone solution of 10% nitrocellulose is added and mixed well. To this was added 35.5 parts by weight of cupric oxide and 50.0 parts by weight of potassium aluminum alum and further mixed well.

When the obtained mixture is subjected to a small gas flame ignition test, which is a test method for flammable solids of the Class 2 dangerous goods of the Fire Service Act, it takes 10 seconds or more before the sample burns and burns, resulting in a non-hazardous result. It was.
Moreover, when this was loaded into the gas pipe (SGPW20A), the loading density was 1.06 g / cc. When a dedicated igniter was attached to this and the combustion speed was measured by the optical fiber method, the combustion was interrupted. When the ballistic mortar test with the special igniter was carried out, the remaining medicine remained somewhat, and the power was 80% (compared to the reference example), which was 20% lower than when the reference example was taken as 100%.

(Comparative Example 3)
11.5 parts by weight of aluminum in Comparative Example 2 was changed to 14.5 parts by weight of magnesium, 1.60 parts by weight of industrial calcium stearate having an average particle size of 2.5 μm was added, and 15% acetone solution with 10% acetylcellulose concentration was added. Add and mix well. To this was added 35.5 parts by weight of cupric oxide and 50.0 parts by weight of potassium aluminum alum and further mixed well. When the obtained mixture is subjected to a small gas flame ignition test, which is a test method for flammable solids of the Class 2 dangerous materials of the Fire Service Act, it takes 3 seconds or more and 10 seconds or less before the sample burns down. It corresponded to thing 2nd class 2nd type flammable solid.

Moreover, when this was loaded into the gas pipe (SGPW20A), the loading density was 1.17 g / cc, and when a dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 295 m / s. Similarly, when a ballistic mortar test with a dedicated igniter was carried out, the remaining medicine remained somewhat, and the power was 85% (compared to the reference example), which was 15% lower than when the reference example was taken as 100%.
(Comparative Example 4)
To 17.7 parts by weight of aluminum, 2.0 parts by weight of industrial magnesium stearate having an average particle size of 2.65 μm is added as a blunting agent. To this, 15% of a 10% strength Viton A acetone solution is added and mixed well. Next, 59.2 parts by weight of cupric oxide and 23.1 parts by weight of ammonium persulfate are added and mixed well. At this time, if necessary, acetone may be further added. When the mixture becomes a soft cocoon due to the function of the binder, the mixture is passed through an 8-mesh sieve and then air-dried for at least 12 hours to remove the acetone odor.

Next, it dries for at least 4 hours in a 60 degreeC drying chamber. When this is subjected to a small gas flame ignition test, which is a test method for flammable solids of the second class of dangerous materials of the Fire Service Act, it takes 3 to 10 seconds before the sample burns and burns. It corresponded to the 2nd class flammable solid.
Moreover, when this was loaded into the gas pipe (SGPW20A), the loading density was 1.35 g / cc, and when a dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 320 m / s. Similarly, when a ballistic mortar test with a dedicated igniter was carried out, the remaining medicine remained somewhat, and the power was 90% (compared to the reference example), which was 10% lower than when the standard was 100%.

(Comparative Example 5)
An example is shown in which ammonium nitrate, which enters the explosive component, is used as a gas generating agent to improve power.
First, 15% acetone solution containing 10% viton rubber is added to 9.0 parts by weight of aluminum and mixed well. Next, 31.0 parts by weight of cupric oxide and 50.0 parts by weight of ammonium nitrate are added and mixed further. At this time, if necessary, acetone may be further added. When the mixture becomes a soft cocoon due to the function of the binder, the mixture is passed through an 8-mesh sieve and then air-dried for at least 12 hours to remove the acetone odor.

Next, it dries for at least 4 hours in a 60 degreeC drying chamber. If this is subjected to the small gas flame ignition test, which is a test method for flammable solids of the Fire Service Act Dangerous Goods Class 2, it takes less than 3 seconds before the sample burns and burns. Applicable to a solid.
Moreover, when this was loaded into a gas pipe (SGPW20A), the loading density was 1.35 g / cc, and when the dedicated igniter was attached to this and the burning rate was measured by the optical fiber method, it was 800 m / s. Similarly, when a ball mill test using a dedicated igniter was performed, the power was increased by 100% to 200% (compared to the reference example) compared to the reference example being 100%.

FIG. 1 shows the relationship between the ammonium persulfate amount and the fuel speed, with the horizontal axis in Table 2 representing the ammonium persulfate amount (%) and the vertical axis representing the fuel speed (m / s).
As shown in FIG. 1, as ammonium persulfate increases (conversely, potassium ammonium alum decreases), the fuel speed increases. However, when the amount exceeds 50%, the fuel speed decreases. This is because the thermite agent, which is a heat source, is relatively reduced, and the reaction is difficult to proceed due to a lack of heat.

As in FIG. 1, the horizontal axis represents the ammonium persulfate amount (%) and the vertical axis represents the mortar ratio (%), and the relationship between the ammonium persulfate amount and the mortar ratio was investigated.
As in FIG. 1, the mortar ratio increases as ammonium persulfate increases (conversely, potassium ammonium alum decreases). However, when the amount exceeds 50%, the mortar ratio also decreases. This is because the thermite agent, which is a heat source, is relatively reduced, and the amount of gas is reduced because the reaction is difficult to proceed due to insufficient heat.

In FIG. 3, the phenomenon of FIG. 1 and FIG. 2 occurs simultaneously and the power increase phenomenon is recognized. Therefore, using the principle of product, (fuel speed value) × (mortar ratio value) is taken and graphed.
In general, the power in the case of explosives is proportional to the square of the reaction speed, but here the power improvement is simply quantified by the product of the reaction speed and the fuel speed.
From this result, it is shown that if the increase in power is changed to ammonium persulfate as the gas generating agent, the value of (fuel speed) × (mortar ratio) may reach a maximum of 328%.

As described above, in both FIG. 1 and FIG. 2, when potassium ammonium alum is completely replaced by ammonium persulfate, both the fuel speed and the mortar ratio show maximum values.
Therefore, in the actual reaction in which these appear simultaneously, when potassium ammonium alum is changed to ammonium persulfate in total, its power is proportional to the value of (fuel speed) x (mortar ratio), reaching a maximum of 328%. ing.

  Until now, the bedrock has been too hard to be crushed by non-explosive crushing chemicals, and it was unavoidable to obtain a consumption permit and use explosives (industrial explosives). In addition, the use of insensitive high-power non-explosive crushing chemicals such as excavation of deep foundations, seismic exploration, and dismantling of solidified cement in cement silos expands.

It is a relationship diagram of ammonium persulfate and explosion speed. FIG. 4 is a relationship diagram of ammonium persulfate and ballistic mortar ratio. It is a relationship diagram of ammonium persulfate and total power.

Claims (8)

  Small test that has a thermite agent (metal redox agent) consisting of an oxidant and a reducing agent, a gas generating agent, a blunting agent, and a binder, and is a fire test law class 2 flammable solid judgment test Insensitive high-power non-explosive crushing agent characterized by not being ignited and burned out within 3 seconds in a gas flame ignition test and having a predetermined ballistic mortar ratio.   2. The insensitive high-power non-sensitive material according to claim 1, wherein the thermite agent contains one or more selected from the group of cupric oxide, ferric oxide, and metal peroxide salt in the oxidizing agent. Explosive crushing drug.   The insensitive high-power non-explosive crushing agent according to claim 1 or 2, wherein the gas generating agent includes one or more selected from the group consisting of ammonium persulfate, aluminum sulfate, and alum.   The said desensitizing agent contains at least 1 sort (s) chosen from the group of the long chain fatty acid metal salt and long chain fatty acid with an average particle diameter of 5 micrometers or less, The Claim 1 thru | or 3 characterized by the above-mentioned. Insensitive high-power non-explosive crushing agent.   5. The insensitive high power according to claim 4, wherein the long chain fatty acid metal salt is a stearic acid metal salt such as calcium stearate, magnesium stearate, zinc stearate, and the long chain fatty acid is stearic acid. Non-explosive crushing drug.   The binder includes nitrocellulose, acetylcellulose, vinyl chloride, viton rubber, nitrile rubber, polyisobutylene, silicone rubber, clayton rubber, glycidyl azide polymer (GAP), bisazidomethyloxaene polymer (BAMO) and azidomethylmethyloxaene. The insensitive high-power non-explosive crushing drug according to any one of claims 1 to 5, comprising at least one selected from the group of polymers (AMMO).   Having 25-60% thermite agent (metal redox agent), 25-75% gas generant, 0.2-2% blunting agent, and 0.5-15% binder. The insensitive high-power non-explosive crushing drug according to any one of claims 1 to 6.   An insensitive high-intensity comprising the insensitive high-power non-explosive crushing agent according to any one of claims 1 to 7 and a water-resistant substance imparting water resistance of 3% to 10%. Powerful non-explosive crushing drug.

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