JP6893722B2 - Non-explosive crushing composition - Google Patents

Description

The present invention relates to a non-explosive crushing composition for crushing brittle bodies such as rocks, rocks and concrete.

The non-explosives crushing composition is a composition composed of components other than explosives specified by the Explosives Control Act. This non-explosive fracture composition is a pyrolysis gas generated by a thermite reaction caused by perforation of rock, bedrock, concrete, etc. (hereinafter referred to as a brittle body), a so-called bore hole, which is filled and closed, and ignition combustion after the blockage. The brittle body is instantly tensilely crushed (broken) by using the gas pressure (steam gas, carbon dioxide gas, etc.).

The non-explosive crushing composition described above has good fluidity, a large amount of gas generated, and has product stability even at high temperatures, for example, a thermite agent composed of cupric oxide and aluminum, a polycarbonate resin, or the like. A gas generator made of a plastic powder (petroleum-based synthetic resin) of a polyacetal resin is mixed, and an organic binder is further mixed to granulate the mixture (see Patent Document 1). In addition to a thermite agent, a gas generating agent consisting of potassium alum or ammonium alum, and an organic binder, a desensitizing agent made of calcium stearate was mixed to improve safety against open flames. (See Patent Document 2).

Japanese Patent No. 58055565 Japanese Patent No. 3688855

As is well known, the non-explosive crushing composition utilizes the thermal decomposition of the gas generating agent by the thermite reaction heat. For example, in the case of the non-explosive crushing composition disclosed in Patent Document 1, the non-explosive crushing composition Incomplete decomposition and incomplete combustion of plastic powder contained in objects are likely to occur. Especially in a non-explosive crushing composition using a polyacetal resin, when incomplete decomposition or incomplete combustion of a gas generating agent occurs, toxic and flammable formaldehyde is likely to be generated at a high concentration, so that a place where gas is likely to stay. Great care should be taken when using non-explosive crushing compositions in. Further, the polycarbonate resin or polyacetal resin is a synthetic resin material derived from petroleum, and is not a substance that is decomposed by, for example, microorganisms (a substance having biodegradability). Therefore, if the non-explosive crushing composition remains in the soil in an incompletely burned or unburned state, the plastic powder contained in the non-explosive crushing composition remains in the soil for a long period of time, leading to an environmental load.

Further, in the case of the non-explosive crushing composition disclosed in Patent Document 2, in addition to water vapor, sulfur oxides such as sulfurous acid gas are generated at a relatively high concentration during ignition combustion. Sulfur oxides are highly toxic and are likely to pose a danger to animals and plants. Therefore, even in the case of the non-explosive crushing composition disclosed in Patent Document 2, great care must be taken when using the non-explosive crushing composition in a place where gas tends to stay. In addition to this, there is a risk that air pollution and acid rain may occur due to the generation of sulfur oxides, which may adversely affect the surrounding environment.

The present invention has been made in order to meet such a demand, and reduces the generation of toxic gas and highly flammable gas while maintaining the crushing performance in the non-explosive crushing composition, and further, the non-explosive crushing. It is an object of the present invention to provide a non-explosive crushing composition capable of suppressing an environmental load by preventing the composition from remaining in the soil in an incompletely burned or unburned state.

In order to solve the above-mentioned problems, the non-explosive crushing composition of the present invention comprises a thermite agent that causes a thermite reaction during combustion, one kind of biodegradable material, two or more kinds of biodegradable materials, or two or more kinds of biodegradable materials. The raw material in a non-explosive crushing composition comprising any of the alloys made of a biodegradable material, a granular gas generating agent that generates a thermal decomposition gas in response to the thermite reaction of the thermite agent during combustion. The degradable material is a biodegradable resin, and the biodegradable resin is either a full-scale biomass raw material plastic, a partial biomass raw material plastic, or a petroleum raw material plastic, and the thermite agent and the gas generating agent are used. The compounding composition (weight ratio: wt%) is characterized in that the thermite agent: the gas generating agent = 40:60 to 90:10 .

Further, the non-explosive crushing composition of the present invention comprises a thermitt agent that causes a thermit reaction during combustion, a granular gas generating agent that generates a pyrolysis gas in response to the thermit reaction of the thermit agent during combustion, and the thermit agent. In a non-explosive crushing composition comprising a binder for binding the gas generating agent and the gas generating agent, the gas generating agent and the binder are one kind of biodegradable material, two or more kinds of biodegradable materials, or two or more kinds. The biodegradable material is a biodegradable resin, and the biodegradable resin is a full-scale biomass raw material plastic, a partial biomass raw material plastic, or a petroleum raw material. It is one of the plastics, and the compounding composition (weight ratio: wt%) of the thermit agent and the gas generating agent is in the range of the thermit agent: the gas generating agent = 40:60 to 90:10. It is a feature.

Further, the biodegradable material is a monomer, a homopolymer or a copolymer containing no sulfur element and a halogen element, and is a repeating unit of the monomer, the homopolymer or the copolymer. The repeating unit preferably has one or more structures of at least one of ester, ether, ketone and hydroxyl group.

Further, the biodegradable material is preferably any one of an aliphatic polyester, an aliphatic polyether, an aliphatic polyhydric alcohol or a sugar, which does not contain sulfur elements and halogen elements.

Further, the ratio of the number of oxygen atoms to the number of carbon atoms contained in the monomer, the homopolymer or the copolymer is preferably 1/3 or more based on the number of carbon atoms.

The biodegradable material is any of polylactic acid, polyglycolic acid, polyvinyl alcohol, poly [lactic acid / glycolic acid], starch, starch acetate, cellulose, trehalose, maltose, maltitol, sucrose, glucose, fructose or sorbitol. It is preferable that it is.

Further, the biodegradable material is characterized in that it has a particle size range of 45 μm or more and less than 5600 μm.

The biodegradable material preferably has a particle size range of 45 μm or more and less than 250 μm. Further, the biodegradable material preferably has a particle size range of 250 μm or more and less than 2000 μm.

According to the present invention, the generation of toxic gas and highly flammable gas is reduced while maintaining the crushing performance of the non-explosive crushing composition, and the non-explosive crushing composition is incompletely burned or unburned. It is possible to reduce the environmental load by preventing it from remaining in the soil.

It is a figure which shows the result of the performance test of the non-explosive crushing composition using polylactic acid having a different particle size range as a gas generating agent. It is a figure which shows the result of the performance test of the non-explosive crushing composition produced by changing the compounding ratio of a thermite agent and a gas generating agent. It is a figure which shows the result of the performance test of the non-explosives crushing composition using different gas generating agents. It is a figure which shows the result of the evaluation test of the gas generated when the non-explosive crushing composition using different gas generating agents is burned.

Hereinafter, the non-explosive crushing composition of the present invention will be described in detail.

The non-explosive crushing composition of the present invention is obtained by mixing and granulating a thermite agent and a gas generating agent. Hereinafter, a non-explosive crushing composition obtained by mixing and granulating a thermite agent and a gas generating agent will be described as an example, but the surface of the granulated gas generating agent is coated with the thermite agent. May be good.

The thermite agent is composed of an oxidizing agent and a reducing agent, and causes a thermite reaction when burned. As the oxidizing agent, for example, one kind of metal oxide of cupric oxide, ferric oxide, ferric oxide, nickel oxide (II) or molybdenum oxide (VI), or two or more kinds of metal oxides. Is used. Further, as the reducing agent, for example, aluminum, magnesium, manganese, titanium and the like are used. In consideration of the amount of heat generated during the thermite reaction, the production cost of the thermite agent, and the like, a combination of cupric oxide and aluminum is generally used as the combination of the oxidizing agent and the reducing agent used as the thermite agent.

Here, the compounding composition of the oxidizing agent and the reducing agent in the thermite agent differs depending on the type of metal oxide or metal used. For example, the compounding composition (weight ratio: wt%) when producing a thermite agent using cupric oxide and aluminum is in the range of cupric oxide: aluminum = 90: 10 to 60:40. A more preferred range of weight ratios of cupric oxide and aluminum is the range of cupric oxide: aluminum = 88: 12-64: 36, and a more preferred range is cupric oxide: aluminum = 81.6 :. It is in the range of 18.4 to 77:23. Copper oxide uses particles having a particle size range of 0.5 to 10 μm, and aluminum uses particles having a particle size range of 10 to 100 μm.

As is well known, the non-explosive crushing composition composed of the thermite agent and the gas generating agent utilizes the thermal decomposition reaction of the gas generating agent by the heat of formation during the thermite reaction. Therefore, in order to improve the composition of the gas generated by the non-explosive crushing composition, it is important to select a gas generating agent in consideration of the thermal decomposition characteristics.

Therefore, in the present embodiment, as the non-explosive crushing composition, either one kind of biodegradable material, two or more kinds of biodegradable materials, or an alloy composed of two or more kinds of biodegradable materials is used.

For example, the biodegradable material is either a biodegradable resin, a biodegradable oligomer or a biodegradable monomer. The biodegradable material is a monomer, a homopolymer, or a copolymer that does not contain sulfur elements and halogen elements, and is a repeating unit of the monomer, the homopolymer, or the copolymer. The repeating unit has one or more structures of at least one of ester, ether, ketone and hydroxyl group.

In addition, the biodegradable material is either an aliphatic polyester, an aliphatic polyether, an aliphatic polyhydric alcohol or a sugar, which does not contain sulfur elements and halogen elements. Examples of carbohydrates include monosaccharides, oligosaccharides, polysaccharides, and inducible sugars.

In the above-mentioned monomers, homopolymers, and copolymers, the ratio of the number of oxygen atoms to the number of carbon atoms contained therein (the number of oxygen atoms / the number of carbon atoms) is preferably 1/3 or more. The above ratio may be 1/2 or more, or 2/3 or more.

The biodegradable resin described above is either a full-scale biomass raw material plastic, a partial biomass raw material plastic, or a petroleum raw material plastic.

Specific examples of the biodegradable resin and the biodegradable oligomer include polyaspartic acid, polyhydroxybutyrate, poly [hydroxybutyrate / hydroxyhexanoate], poly-D-lactic acid, poly-L-lactic acid, and poly-. DL-lactic acid, poly [lactic acid / butylene succinate], [polylactic acid / polybutylene succinate] block polymer, poly [lactic acid / glycolic acid], polydioxanone, polycaprolactone, poly [caprolactone / butylene succinate], polybutylene Succinate, poly [butylene succinate / adipate], poly [butylene succinate / carbonate], poly [ethylene terephthalate / succinate], poly [butylene adipate / terephthalate], poly [tetramethylene adipate / terephthalate], polyethylene succinate, Polyester, polyether and polyhydric alcohols such as polyvinyl alcohol, polyglycolic acid, polyethylene oxide (polyethylene glycol), polypropylene oxide (polypropylene glycol), starch, esterified starch (starch acetate, sodium octenyl succinate starch, phosphorylated starch) ), Ethereated starch (vidroxypropyl starch, carboxymethyl starch, carboxypropyl starch) Cross-linked starch (glycerol distarch, acetylated adipic acid cross-linked starch, acetylated phosphoric acid cross-linked starch, hydroxypropylated phosphoric acid cross-linked starch, phosphoric acid Monoesterified phosphoric acid cross-linked starch, phosphoric acid cross-linked starch), grafted starch, pregelatinized starch, solubilized starch, oxidized starch dextrin, cellulose, cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose , Ethyl cellulose, chitin, chitosan, glycogen, dextrin, glucan, fructo-oligosaccharide, galactooligosaccharide, mannan oligosaccharide, acarbose, starch, meregitos, raffinose, meregitos, maltotriose, sucrose, lactose, maltose, maltol, fructan, trehalose, Examples thereof include polysaccharides such as starch and cellobiose, oligosaccharides, trisaccharides and disaccharides.

Specific examples of biodegradable monomers include glucelaldehyde, erythrose, treose, ribose, lixose, xylose, arabinose, allose, talose, glucose, altrose, mannose, galactose, idose, and dihydroxyacetone. Examples include monosaccharides such as elittlerose, xylose, ribulose, psicose, fructose, sorbose, tagatose, α-methylgluxide, D sorbitol, glucosamine, deoxyribose, psicose, growth, fucose, fuclos, ramnorse, sedhepturose.

As these biodegradable materials, anhydrides or hydrates can be used. In the case of hydrate, the flammable gas concentration tends to increase as the amount of crystalline water increases, so it is necessary to select the amount of hydrate in consideration of the gas composition.

When the above-mentioned biodegradable materials remain in the ground, they are completely consumed by microorganisms and produce natural by-products such as carbon dioxide, methane, water and biomass. Therefore, even if the gas generating agent is incompletely decomposed or incompletely burned during combustion with the thermite agent and remains in the soil, it does not give an environmental load. In addition, since the biodegradable material has a high oxygen content, the toxicity and flammability of the generated gas are reduced.

When a biodegradable material is used as a gas generator, the particle size range of the biodegradable material is any one of 5600 μm or more, 2000 μm or more and less than 5600 μm, 250 μm or more and less than 2000 μm, 45 μm or more and less than 250 μm, or 45 μm or more and less than 5600 μm. It is preferably in the diameter range. Here, when a range in which the particle size range is 45 μm or more and less than 5600 μm is used, the same amount of biodegradable materials in each range of the above-mentioned particle size range may be mixed, or at a predetermined ratio. It may be a mixture. The method for adjusting the particle size of the biodegradable material is not particularly limited, but usually, powders and granules are pressure-molded, crushed using a room temperature crusher or a low temperature crusher, and then a classifier or the like is used. Classify.

In the case of the performance test method according to the embodiment of the present invention, it is preferable that the gas generation pressure during combustion by the thermite reaction is 8 MPa or more. Therefore, among the above-mentioned particle size ranges, the particle size range is 250 μm or more and less than 2000 μm, and the particle size. It is preferable to use any biodegradable material having a range of 45 μm or more and less than 250 μm.

In the particle size range of the biodegradable material, if the particle size of the biodegradable material becomes large, the heat generated when the thermite agent burns is not sufficiently transferred to the center of the particles, and the biodegradable material is incompatible. Prone to complete decomposition and incomplete combustion. In this case, the pressure generated by the gas generated by the thermal decomposition and combustion of the biodegradable material is low, and the amount of gas generated is also low. However, when biodegradable materials become incompletely decomposed and incompletely burned and remain in the soil, they are consumed by microorganisms and produce natural by-products. Therefore, the particle size range of the biodegradable material described above is set to 5600 μm as an example of the upper limit.

The compounding composition of the thermite agent and the gas generating agent described above will be described. When the content of the gas generating agent is less than 5 wt% in the compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent in the non-explosive crushing composition, the gas generating agent is completely decomposed and burned. The pressure generated by the gas generated by the decomposition and combustion of the gas generating agent is low. On the other hand, when the content of the gas generating agent exceeds 60 wt%, the gas generating agent tends to be incompletely decomposed and burned, and the pressure of gas generated by the decomposition and combustion of the gas generating agent is lowered. Therefore, the compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent is preferably in the range of the thermite agent: gas generating agent = 40:60 to 90:10.

Next, a method for preparing the non-explosive crushing composition will be described. As an example of the biodegradable material, the case where polylactic acid is used will be described. The ratio of the number of oxygen atoms to the number of carbon atoms of polylactic acid is 2/3 based on the number of carbon atoms. When other biodegradable resins, biodegradable oligomers and monosaccharides are used as the gas generating agent, they are also prepared according to the following method.
1) Polylactic acid is pulverized with a pulverizer (MX1200XTM manufactured by Waring Co., Ltd.) while controlling the temperature so as not to rise above the melting point. The temperature of polylactic acid during crushing is controlled by using a thermocouple attached to the crushing container. For example, when the surface temperature rises to about 45 ° C., the crusher is stopped and allowed to cool.
2) Using the sieve specified in JIS Z 8801-1 (Test Sieve-Part 1: Metal Net Sieve), pulverize by the sieving method specified in JIS K 0069 (Chemical Sieve Test Method). Classify the machine-crushed polylactic acid.
When classifying the crushed polylactic acid, the powder sifted by the 3.5 Tyler mesh stop is made into a powder having a particle size range of 5600 μm or more. The powder sifted through 3.5 Tyler mesh and 8.6 Tyler mesh stop is made into a powder having a particle size range of 2000 μm or more and less than 5600 μm. Further, the powder that is sifted through the 8.6 Tyler mesh and stopped at the 60 Tyler mesh is defined as a powder having a particle size range of 250 μm or more and less than 2000 μm. Further, the powder that is sifted through the 60 Tyler mesh and stopped at the 330 Tyler mesh is defined as a powder having a particle size range of 45 μm or more and less than 250 μm.
3) 2.5 parts by weight of calcium stearate as a desensitizing agent was placed in the same container with respect to 11.5 parts by weight of aluminum powder, mixed so that the powder was not biased, and then 38.5 parts by weight of cupric oxide. Is added and mixed to produce a thermite agent.
4) Add a preset amount of the classified polylactic acid to the thermite agent and mix them. At this time, if it is desired to adjust the cohesiveness, bulk density, etc. of the finally obtained non-explosive crushing agent composition powder, a biodegradable resin (polylactic acid, polyvinyl alcohol, etc.) is used as a solvent such as acetone or ethanol. About 6 parts by weight of the melted biodegradable resin binder may be added, kneaded and dried.

Below, the performance test results of the non-explosive crushing composition using polylactic acid having a different particle size range as a gas generating agent are shown in FIG. As shown in FIG. 1, the non-explosive crushing composition of Example 1 uses polylactic acid having a particle size range of 5600 μm or more, and the non-explosive crushing composition of Example 2 uses polylactic acid having a particle size range of 2000 μm or more and less than 5600 μm. Is used. Further, the non-explosive crushing composition of Example 3 uses polylactic acid having a particle size range of 250 μm or more and less than 2000 μm, and the non-explosive crushing composition of Example 4 uses polylactic acid having a particle size range of 45 μm or more and less than 250 μm. There is. Further, the non-explosive crushing composition of Example 5 uses polylactic acid having a particle size range of 45 μm or more and less than 5600 μm. In each of the non-explosive crushing compositions shown in Examples 1 to 5, the compounding composition (weight ratio: wt%) of the thermite agent and polylactic acid is the thermite agent: gas generating agent = 50: 50. is there.

Performance tests include measurement test of gas generation amount during combustion of non-explosive crushing composition, measurement test of gas generation pressure during combustion of non-explosive crushing composition, JIS drop sensitivity test, BAM type friction sensitivity test and small gas. It is a flame ignition test.

<Measurement test of gas generation during combustion>
The measurement test of the amount of gas generated during combustion was carried out according to the following procedure.
1) 0.8 g of the crushing agent blended in the blended compositions of Examples 1 to 5 is filled in an aluminum tube having a diameter of about 7 mm and a wall thickness of 0.1 mm.
2) A specimen is produced by caulking after attaching a leg wire with a platinum wire to which 0.2 g of a boron-copper oxide igniter capsule is attached to a tube body.
3) After fitting the generated specimen into the jig, fill the gap between the specimen and the jig with epoxy resin as a measure to prevent gas leakage.
4) Screw the specimen into the 1.93cc closed tank.
5) Energize the leg wire, ignite the ignition charge, crush the tube, and collect the gas that has flowed into the air hose connected to the 1.93cc airtight tank by water replacement, and the amount of combustion gas collected. To measure.

<Measurement test of gas generation pressure during combustion>
The measurement test of the gas generation pressure during combustion was carried out according to the following procedure.
1) 0.8 g of the crushing agent blended in the blended compositions of Examples 1 to 5 is filled in an aluminum tube having a diameter of about 7 mm and a wall thickness of 0.1 mm.
2) A specimen is produced by attaching a leg wire with a platinum wire equipped with 0.2 g of boron-copper oxide igniter capsule to the tube body and then caulking it.
3) After fitting the generated specimen into the jig, fill the gap between the specimen and the jig with epoxy resin as a measure to prevent gas leakage.
4) Screw the specimen into a 10cc closed tank equipped with a strain gauge (PGM-200KE manufactured by KYOWA).
5) By energizing the leg wire and igniting the ignition charge, the pressure of the combustion gas released into the inside of the 10 cc closed tank by crushing the tube is measured with a strain gauge.

<JIS Hammer Sensitivity Test>
As is well known, in the JIS hammer sensitivity test, a sample non-explosive crushing composition is sandwiched between two cylindrical rollers placed on the bottom of a tester, and then the iron hammer is dropped and dropped. This is a test to examine the sensitivity of explosives from the relationship between the height of the mallet and the state of the explosion. This JIS hammer sensitivity test is carried out according to JIS K 4810 2003. In the JIS drop sensitivity test, for example, a test of dropping an iron mallet weighing 5 kg onto about 0.1 ml of a sample is performed 6 times at the same height, and the height is estimated to explode only once or only once. (1/6 explosion point) is obtained, and the grade is determined based on the height of the 1/6 explosion point.

<BAM type friction sensitivity test>
As is well known, the BAM type friction sensitivity test is a non-explosive crushing composition that serves as a sample between a porcelain friction rod and a friction plate attached to a friction sensitivity tester developed by the German Material Testing Laboratory (BAM). This is a test to examine the sensitivity of a sample from the relationship between the load and the success or failure of the explosion by performing a frictional motion with the load applied. In the BAM type friction sensitivity test, a test of applying friction to a sample with the same load is performed 6 times with the same load, and a load (1/6 explosion point) estimated to explode only once or explode only once is applied. Obtain and determine the grade based on the load at the 1/6 explosion point.

<Small gas flame ignition test>
The small gas flame ignition test is a test based on the Fire Service Act dangerous goods evaluation test. This small gas flame ignition test is a test for determining the type of dangerous substance (flammable solid) under the Fire Service Act from the time until ignition, and specifically, for evaluating "flammability" from the time until ignition. The test method is as follows. ^{A 3 cm 3} sample is placed on an inorganic heat insulating plate having a thickness of 10 mm or more. Here, the sample used is stored in a desiccator containing silica gel for drying at a temperature of 20 ° C. for 24 hours or more. Here, when the sample is powdery or granular, the sample is placed hemispherically on the inorganic heat insulating material. Bring the flame of liquefied petroleum gas into contact with the sample for 10 seconds. Here, the flame of the liquefied petroleum gas is a diffusing flame of an ignition device having a rod-shaped tip, and the length of the flame is adjusted to be 70 mm with the mouth of the ignition device facing upward. Further, as a condition for bringing the flame into contact with the sample for 10 seconds, for example, the contact area between the flame and the sample is 2 cm ² , and the contact angle is 30 °. Measure the time from when the flame is brought into contact with the sample until the sample ignites, and observe whether the sample continues to burn (including the state where it burns without raising the flame). If all of the sample burns while the flame is in contact with the sample, if all of the sample burns within 10 seconds after the flame is released, or if it continues for 10 seconds or more after the flame is released. When the sample burns, it is assumed that the burning is continued.

As shown in FIG. 1, in the non-explosive crushing composition of Example 1, the amount of gas generated during combustion was 92.5 cc / 0.8 g, and the gas generation pressure was 6.89 MPa. Further, in the non-explosive crushing composition of Example 2, the amount of gas generated during combustion was 87.5 cc / 0.8 g, and the gas generation pressure was 7.05 MPa. In the non-explosive crushing composition of Example 3, the amount of gas generated during combustion was 175.5 cc / 0.8 g, and the gas generation pressure was 9.49 MPa. Further, in the non-explosive crushing composition of Example 4, the amount of gas generated during combustion was 153.6 cc / 0.8 g, and the gas generation pressure was 9.85 MPa. Further, in the non-explosive crushing composition of Example 5, the amount of gas generated during combustion was 121.5 cc / 0.8 g, and the gas generation pressure was 8.26 MPa.

In the non-explosive crushing composition disclosed in Patent Document 2 described above, in other words, the non-explosive crushing composition using potassium alum or ammonium alum as a gas generating agent, the amount of gas generated during combustion is 170 cc / 0.8 g, and the gas is generated. The generated pressure was 8.45 MPa.

In the item of "Performance as a crushing agent (generated pressure standard)" in FIG. 1, when the gas generating pressure when the non-explosive crushing composition in Patent Document 2 is burned is 8.45 MPa or more, "◎", patent. When the pressure is 6.76 MPa or more and less than 8.45 MPa, which is 80% of the gas generation pressure when the non-explosive crushing composition in Document 2 is burned, "○" is given, and the non-explosive crushing composition in Patent Document 2 is designated. When it is less than 6.76 MPa, which is 80% of the gas generation pressure at the time of combustion, it is marked with "Δ".

It was found that the non-explosive crushing compositions of Examples 1, 2 and 5 were inferior in the performance of the non-explosive crushing composition disclosed in Patent Document 2. On the other hand, it was found that the non-explosive crushing compositions of Examples 3 and 4 had performance comparable to the performance of the non-explosive crushing composition disclosed in Patent Document 2. As described above, it is said that the generation pressure of the gas generated at the time of combustion of the non-explosive crushing composition is preferably 8 MPa. From this, it was found that the performance of the non-explosive crushing composition of Example 3 and Example 4 was good.

In each of the above-mentioned Examples 1 to 5, the result of the JIS hammer sensitivity test is grade 8, the result of the BAM type friction sensitivity test is grade 7, and the result of the small gas flame ignition test is class 2 flammable. It turned out to be a sex solid.

Therefore, the non-explosive crushing compositions of Examples 3 and 4 have excellent performance in that they exceed the gas generation pressure in the non-explosive crushing composition disclosed in Patent Document 2. On the other hand, the non-explosive crushing compositions of Examples 1, 2 and 5 are capable of satisfying 80% of the gas generation pressure in the non-explosive crushing composition disclosed in Patent Document 2. all right. The non-explosive crushing compositions of Examples 1, 2 and 5 are inferior to the non-explosive crushing compositions disclosed in Patent Document 2 in terms of gas generation pressure, but the gas generating agent is incompletely decomposed. In the case of incomplete combustion, considering that it is consumed in the ground, in other words, the environmental load is low, the non-explosive crushing compositions of Examples 1, 2 and 5 are crushed with non-explosives. It can be used as a composition. Considering the results of these performance tests, the particle size range of the gas generating agent is any one of 5600 μm or more, 2000 μm or more and less than 5600 μm, 250 μm or more and less than 2000 μm, 45 μm or more and less than 250 μm, or 45 μm or more and less than 5600 μm. It was found that any of 250 μm or more and less than 2000 μm and 45 μm or more and less than 250 μm is particularly preferable.

Next, FIG. 2 shows the performance test results of the non-explosive crushing composition in which the blending ratio of the thermite agent and the gas generating agent was changed. The particle size range of the gas generating agent used in each of the examples shown in FIG. 2 is 250 μm or more and 2000 μm. Here, the compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent in the non-explosive crushing composition shown in FIG. 2 is the thermite agent: gas generating agent = 95: 5 in Example 6. In Example 7, the thermite agent: gas generator = 90:10, in Example 8, the thermite agent: gas generator = 80:20, and in Example 9, the thermite agent: gas generator = 70:30. Further, in Example 10, the thermite agent: gas generating agent = 60:40, and in Example 11, the thermite agent: gas generating agent = 40:60. Further, in Example 12, the thermite agent: gas generating agent = 30:70. Here, as Comparative Example 1, a performance test was also conducted in the case of the thermite agent: gas generating agent = 20:80.

In the non-explosive crushing composition of Example 6, the amount of gas generated during combustion was 150.0 cc / 0.8 g, and the gas generation pressure was 6.55 MPa. Further, in the non-explosive crushing composition of Example 7, the amount of gas generated during combustion was 176.7 cc / 0.8 g, and the gas generation pressure was 9.45 MPa. In the non-explosive crushing composition of Example 8, the amount of gas generated during combustion was 176.7 cc / 0.8 g, and the gas generation pressure was 9.39 MPa. Further, in the non-explosive crushing composition of Example 9, the amount of gas generated during combustion was 178.0 cc / 0.8 g, and the gas generation pressure was 8.96 MPa. Further, in the non-explosive crushing composition of Example 10, the amount of gas generated during combustion was 170.0 cc / 0.8 g, and the gas generation pressure was 9.63 MPa. Further, in the non-explosive crushing composition of Example 11, the amount of gas generated during combustion was 145.0 cc / 0.8 g, and the gas generation pressure was 8.50 MPa. In the non-explosive crushing composition of Example 12, the amount of gas generated during combustion was 120.0 cc / 0.8 g, and the gas generation pressure was 6.69 MPa. On the other hand, the result was obtained that the non-explosive crushing composition of Comparative Example 1 did not burn.

In FIG. 2, as in FIG. 1, the item of "performance as a crushing agent (generated pressure standard)" is provided. In this item, "◎" is given when the gas generation pressure when the non-explosive crushing composition in Patent Document 2 is burned is 8.45 MPa or more, and when the non-explosive crushing composition in Patent Document 2 is burned. "○" when it is 6.76 MPa or more and less than 8.45 MPa, which is 80% of the gas generation pressure, is 80% of the gas generation pressure when the non-explosive crushing composition in Patent Document 2 is burned. When it is less than 6.76 MPa, it is marked with "Δ".

It was found that in each of Examples 3 and 6 to 12 described above, the result of the JIS hammer sensitivity test was grade 8 and the result of the BAM type friction sensitivity test was grade 7. At the same time, the results of the small gas flame ignition test in Examples 6 to 8 are the type 1 flammable solid, and the results of the small gas flame ignition test in Examples 9 to 12 are the type 2 flammable solid. It turned out to be.

Therefore, in the non-explosive crushing compositions of Examples 3 and 7 to 11, the gas generation pressure exceeds the gas generation pressure of the non-explosive crushing composition disclosed in Patent Document 2, and Patent Document 2 It was found that the performance was comparable to the performance of the non-explosive crushing composition disclosed in. On the other hand, in the non-explosive crushing compositions of Examples 6 and 12, the gas generation pressure is 80% or less of the gas generation pressure of the non-explosive crushing composition disclosed in Patent Document 2, and Comparative Example 1 is ignited. Since it does not burn, it was found that Examples 6, 12 and Comparative Example 1 are non-explosive crushing compositions inferior in the performance of the non-explosive crushing composition disclosed in Patent Document 2.

Considering the results of these performance tests, the compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent is such that the thermite agent: gas generating agent = 40 (wt%): 60 (wt%) to 90 (wt%). %): It was found that the range of 10 (wt%) is preferable.

Next, FIG. 3 shows the performance test results when the non-explosive crushing composition using different gas generating agents was burned. The particle size range of the gas generating agent used in each of the examples shown in FIG. 3 is 250 μm or more and 2000 μm. The compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent in the non-explosive crushing composition shown in FIG. 3 is the thermite agent: gas generating agent = 70:30.

Here, the gas generating agents used in the non-explosive crushing compositions in Examples 13 to 24 are as follows.

The gas generating agent used in the non-explosive crushing composition in Example 13 is polyglycolic acid, and the ratio of the number of oxygen atoms to the number of carbon atoms is 1/1 of the number of oxygen atoms / the number of carbon atoms. The gas generating agent used in the non-explosive crushing composition in Example 14 was poly [lactic acid / glycolic acid] (lactic acid / glycolic acid = 50/50), and the ratio of the number of oxygen atoms to the number of carbon atoms was oxygen. The number of atoms / the number of carbon atoms = 5/6. The gas generating agent used in the non-explosive crushing composition in Example 15 is polyvinyl alcohol, and the ratio of the number of oxygen atoms to the number of carbon atoms is oxygen atom number / carbon atom number = 1/2. The gas generating agent used in the non-explosive crushing composition in Example 16 is starch, and the ratio of the number of oxygen atoms to the number of carbon atoms is oxygen atom number / carbon atom number = 5/6. The gas generating agent used in the non-explosive crushing composition in Example 17 was starch acetate, and the ratio of the number of oxygen atoms to the number of carbon atoms was 2/3 to 3/4 of the number of oxygen atoms / carbon atoms. is there. The gas generating agent used in the non-explosive crushing composition in Example 18 is cellulose, and the ratio of the number of oxygen atoms to the number of carbon atoms is oxygen atom number / carbon atom number = 5/6.

The gas generating agent used in the non-explosive crushing composition in Example 19 was trehalose dihydrate, and the ratio of the number of oxygen atoms to the number of carbon atoms was 13/12. Is. The gas generating agent used in the non-explosive crushing composition in Example 20 is trehalose anhydride, and the ratio of the number of oxygen atoms to the number of carbon atoms is oxygen atom number / carbon atom number = 11/12. The gas generating agent used in the non-explosive crushing composition in Example 21 was D (+)-maltose monohydrate, and the ratio of the number of oxygen atoms to the number of carbon atoms was equal to the number of oxygen atoms / the number of carbon atoms. It is 1/1. The gas generating agent used in the non-explosive crushing composition in Example 22 was D (+)-glucose, and the ratio of the number of oxygen atoms to the number of carbon atoms was 1/1 of the number of oxygen atoms / carbon atoms. is there. The gas generating agent used in the non-explosive crushing composition in Example 23 is D (-)-fructose, and the ratio of the number of oxygen atoms to the number of carbon atoms is 1/1 of the number of oxygen atoms / carbon atoms. is there. The gas generating agent used in the non-explosive crushing composition in Example 24 is D (-)-sorbitol, and the ratio of the number of oxygen atoms to the number of carbon atoms is 1/1 of the number of oxygen atoms / carbon atoms. is there. The gas generating agent used in the non-explosive crushing composition in Example 25 was a mixture of D (+)-glucose and D (-)-fructose in a ratio of 50:50 (weight ratio), and had an oxygen atom number and carbon. The ratio to the number of atoms is the number of oxygen atoms / the number of carbon atoms = 1/1.

Here, the polyglycolic acid used in the gas generating agent of Example 13 is obtained by encapsulating trioxane, chlorosulfuric acid and dichloromethane in a stainless steel autoclave based on, for example, US Pat. No. 6,027,415, and the internal pressure becomes 55 kg / cm ² . After introducing carbon monoxide and reacting at 180 ° C. for 2 hours under stirring, unreacted carbon monoxide in the container was removed, and the product was filtered with acetone, washed, and dried.

Further, the trehalose (anhydrous) used in the gas generating agent of Example 20 was adjusted by drying the trehalose dihydrate in a vacuum dryer at 50 ° C. for 48 hours.

The gas generating agents in Examples 13 to 15 described above are freeze-crushed by a freeze-mill (TPH-01 manufactured by ASONE) and then JIS Z 8801-1 (test sieve-Part 1: metal mesh sieve). Using the sieve specified in the above, the resin that was freeze-milled by the sieving method specified in JIS K 0069 (chemical sieving test method) was classified, and among the classified resins, the particle size range was 250 μm or more and less than 2 mm. Particles are used.

Further, the gas generating agents in Examples 16 to 24 are pellet-molded with a pressure molding machine, and after crushing the pellets with an agate mortar, JIS Z 8801-1 (test sieve-Part 1: metal net). Using the sieve specified in (Sieve), the pellets crushed by the sieving method specified in JIS K 0069 (Sieve test method for chemicals) are classified, and among the classified pellets, the particle size range is 250 μm or more and less than 2 mm. Particles are used.

Hereinafter, the results of the performance test of the non-explosive crushing composition in Examples 13 to 24 will be described. Since it is assumed that the gas generating agents used in the non-explosive crushing compositions of Examples 15 to 23 generate a large amount of water in thermal decomposition, the amount of gas generated by water replacement is not measured. ..

As shown in FIG. 3, in the non-explosive crushing composition of Example 13, the amount of gas generated during combustion was 181.3 cc / 0.8 g, and the pressure of the generated gas (gas generation pressure) was 9.13 MPa. .. In the non-explosive crushing composition of Example 14, the amount of gas generated during combustion was 153.9 cc / 0.8 g, and the gas generation pressure was 8.51 MPa.

The non-explosive crushing composition of Example 15 had a gas generation pressure of 8.49 MPa. The non-explosive crushing composition of Example 16 had a gas generation pressure of 8.72 MPa. The non-explosive crushing composition of Example 17 had a gas generation pressure of 8.89 MPa. The non-explosive crushing composition of Example 18 had a gas generation pressure of 8.61 MPa. The non-explosive crushing composition of Example 19 had a gas generation pressure of 9.01 MPa. The non-explosive crushing composition of Example 20 had a gas generation pressure of 9.22 MPa. The non-explosive crushing composition of Example 21 had a gas generation pressure of 8.68 MPa. The non-explosive crushing composition of Example 22 had a gas generation pressure of 9.03 MPa. The non-explosive crushing composition of Example 23 had a gas generation pressure of 8.88 MPa. The non-explosive crushing composition of Example 24 had a gas generation pressure of 8.85 MPa. The non-explosive crushing composition of Example 25 had a gas generation pressure of 8.41 MPa.

In FIG. 3, as in FIGS. 1 and 2, the item of "performance as a crushing agent (generated pressure standard)" is provided. In this item, "◎" is given when the gas generation pressure when the non-explosive crushing composition in Patent Document 2 is burned is 8.45 MPa or more, and when the non-explosive crushing composition in Patent Document 2 is burned. "○" when it is 6.76 MPa or more and less than 8.45 MPa, which is 80% of the gas generation pressure, is 80% of the gas generation pressure when the non-explosive crushing composition in Patent Document 2 is burned. When it is less than 6.76 MPa, it is marked with "Δ".

It was found that in each of Examples 13 to 25 described above, the result of the JIS hammer sensitivity test was grade 8 and the result of the BAM type friction sensitivity test was grade 7. At the same time, it was found that the results of the small gas flame ignition test in Examples 13 to 25 were Class 2 flammable solids.

Therefore, in each of the non-explosive crushing compositions of Examples 13 to 25, the gas generation pressure exceeds the gas generation pressure of the non-explosive crushing composition disclosed in Patent Document 2, and Patent Document 2 states. It was found to have performance comparable to the disclosed non-explosive crushing composition.

Considering the results of the performance test shown in FIG. 3, it was found that it is preferable to use a biodegradable material typified by a biodegradable resin, a polysaccharide, a monosaccharide or the like as a gas generating agent.

Finally, a composition analysis test of the gas generated when the non-explosive crushing composition was burned was conducted. The result of the composition analysis test of the generated gas is shown in FIG. In the gas composition analysis test, for example, the gas generated when the composition is burned is analyzed to obtain an index of toxicity.

The gas composition analysis test was carried out according to the following procedure.
1) In addition to Example 3, Example 9, Example 14, Example 16, Example 20, and Example 22, 0.8 g of a crushing agent blended in the blended compositions of Comparative Examples 2 to 4 was added in diameter. It is filled in an aluminum tube having a wall thickness of about 7 mm and a wall thickness of 0.1 mm.

Here, in the non-explosive crushing composition of Example 3, polylactic acid is used as a gas generating agent, and the compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent is used as the thermite agent: gas generating agent = 50 :. It is a non-explosive crushing composition blended as 50. In Example 3, the ratio of the number of oxygen atoms to the number of carbon atoms in the gas generating agent is the number of oxygen atoms / the number of carbon atoms = 2/3. In the non-explosive crushing composition of Example 9, polylactic acid is used as a gas generating agent, and the compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent is compounded as the thermite agent: gas generating agent = 70:30. It is a non-explosive crushing composition. In Example 9, the ratio of the number of oxygen atoms to the number of carbon atoms in the gas generating agent is the number of oxygen atoms / the number of carbon atoms = 2/3.

Further, in the non-explosive crushing composition of Example 14, poly [lactic acid / glycolic acid] (lactic acid / glycolic acid = 50/50) was used as a gas generating agent, and the compounding composition (weight ratio) of the thermite agent and the gas generating agent. : Wt%) as a thermite agent: gas generating agent = 70:30, which is a non-explosive crushing composition. In Example 14, the ratio of the number of oxygen atoms to the number of carbon atoms in the gas generating agent is the number of oxygen atoms / the number of carbon atoms = 5/6. In the non-explosive crushing composition of Example 16, starch was used as a gas generating agent, and the compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent was blended as the thermite agent: gas generating agent = 70:30. It is a non-explosive crushing composition. In Example 16, the ratio of the number of oxygen atoms to the number of carbon atoms in the gas generating agent is the number of oxygen atoms / the number of carbon atoms = 5/6.

In the non-explosive crushing composition of Example 20, trehalose (anhydrous) was used as a gas generating agent, and the compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent was used as the thermite agent: gas generating agent = 70 :. It is a non-explosive crushing composition blended as 30. In Example 20, the ratio of the number of oxygen atoms to the number of carbon atoms in the gas generating agent is the number of oxygen atoms / the number of carbon atoms = 11/12. In the non-explosive crushing composition of Example 22, D (+)-glucose is used as a gas generating agent, and the compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent is used as the thermite agent: gas generating agent = 70. It is a non-explosive crushing composition blended as: 30. In Example 22, the ratio of the number of oxygen atoms to the number of carbon atoms in the gas generating agent is the number of oxygen atoms / the number of carbon atoms = 1/1.

On the other hand, in the non-explosive crushing composition of Comparative Example 2, polylactic acid and polypropylene were used as gas generating agents, and a compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent polylactic acid and polypropylene was used as the thermite agent. : Polylactic acid: Polypropylene = 70:15:15 is a non-explosive crushing composition. In Comparative Example 2, the ratio of the number of oxygen atoms to the number of carbon atoms in the gas generating agent is the number of oxygen atoms / the number of carbon atoms = about 1/4. Further, in the non-explosive crushing composition of Comparative Example 3, potassium alum was used as a gas generating agent, and the compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent was used as the thermite agent: gas generating agent = 50:50. It is a non-explosive crushing composition formulated in. Further, in the non-explosive crushing composition of Comparative Example 4, polyacetal was used as a gas generating agent, and the compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent was blended with the thermite agent: polyacetal = 50:50. It is a non-explosive crushing composition. In Comparative Example 4, the ratio of the number of oxygen atoms to the number of carbon atoms in the gas generating agent is the number of oxygen atoms / the number of carbon atoms = 1/1.

The non-explosive crushing composition shown in Comparative Example 3 is the non-explosive crushing composition disclosed in Patent Document 2, and the non-explosive crushing composition shown in Comparative Example 4 is the non-explosive crushing composition disclosed in Patent Document 1. It is a thing.
2) A specimen with a platinum wire attached with 0.2 g of boron-copper oxide igniter capsule is attached to the tube body and crimped to generate a specimen.
3) After fitting the generated specimen into the jig, fill the gap between the specimen and the jig with epoxy resin as a measure to prevent gas leakage.
4) Screw the specimen into the 1.93cc closed tank.
5) Energize the leg wire, ignite the ignition charge, crush the tube, and suck 50 cc of the combustion gas poured into the 1 L gas sampling bag connected to the 1.93 cc closed tank with a gas tight syringe, and use another gas. Dilute 10-fold in a sampling bag. The combustion gas is diluted with air.
6) Measure the diluted combustion gas with a gas detector (MultiRAE Lite and MiniRAE3000 manufactured by RAE systems), and record the composition data of the combustion gas.

As shown in FIG. 4, in the gas composition analysis test described above, the total VOC (Volatile Organic Compounds) value and the flammable gas concentration are measured. Here, the total VOC value is a value converted to acetaldehyde. The concentration of flammable gas is a value converted to hydrogen. The unit of concentration of flammable gas, "% LEL (% Lower Explosive Limit)", indicates the lower explosive limit concentration, and is the lowest concentration that causes an explosion due to ignition when the flammable gas is mixed with air. Is shown. For example, since the lower explosive limit of hydrogen is 4 vol%, the lower explosive limit concentration in terms of hydrogen is 100% LEL. Further, when 1 vol% of hydrogen is contained, the value is 1/4 of the above lower explosive limit, so that the flammable gas concentration can be indicated by 25% LEL.

In the non-explosive crushing composition of Example 3, the total VOC value of the gas generated during combustion was 2120 ppm, and the concentration of the flammable gas was 88% LEL. Further, in the non-explosive crushing composition of Example 9, the total VOC value of the gas generated during combustion was 1140 ppm, and the concentration of the flammable gas was 79% LEL.

In the non-explosive crushing composition of Example 14, the total VOC value of the gas generated during combustion was 1050 ppm, and the concentration of the flammable gas was 76% LEL. Further, in the non-explosive crushing composition of Example 16, the total VOC value of the gas generated during combustion was 1520 ppm, and the concentration of the flammable gas was 85% LEL.

In the non-explosive crushing composition of Example 20, the total VOC value of the gas generated during combustion was 1470 ppm, and the concentration of the flammable gas was 79% LEL. Further, in the non-explosive crushing composition of Example 22, the total VOC value of the gas generated during combustion was 1280 ppm, and the concentration of the flammable gas was 83% LEL.

Further, in the non-explosive crushing compositions of Examples 3, Example 9, Example 14, Example 16, Example 20 and Example 22, hydrogen sulfide and sulfur oxides in the generated gas were below the detection limit. In other words, it was found that it was hardly contained in the generated gas.

In the non-explosive crushing composition of Comparative Example 2, the total VOC value of the gas generated during combustion was 2630 ppm, and the concentration of the flammable gas was 90% LEL. In the non-explosive crushing composition of Comparative Example 3, the total VOC value of the gas generated during combustion was 3040 ppm, and the concentration of the flammable gas was 92% LEL. The gas generated when the non-explosive crushing composition of Comparative Example 3 is burned is derived from hydrogen generated by the thermal decomposition of water of crystallization in addition to the thermal decomposition gas of the desensitizing agent and the binder. In the non-explosive crushing composition of Comparative Example 4, the total VOC value of the gas generated during combustion was 5870 ppm, and the concentration of the flammable gas was 99% LEL or more.

Further, it was found that in the non-explosive crushing compositions of Comparative Example 2 and Comparative Example 4, hydrogen sulfide and sulfur oxides in the generated gas were not included in the generated gas below the detection limit, in other words, in the generated gas. On the other hand, in the non-explosive crushing composition of Comparative Example 3, hydrogen sulfide and sulfur oxides were contained in the generated gas, and it was found that their concentrations were 200 ppm or more.

Comparing the results of the gas composition analysis test of the non-explosive crushing composition of Example 3 and Example 9, it was found that the VOC increased as the compounding ratio of polylactic acid contained in the non-explosive crushing composition increased. At the same time, it was found that the flammable gas concentration also increased. The non-explosive crushing compositions of Examples 3 and 9 have lower VOC values and flammable gas values than the non-explosive crushing compositions of Comparative Examples 2 to 4, and hydrogen sulfide and sulfur oxides are generated. I found that I didn't.

Similarly, the non-explosive crushing compositions of Examples 14, 16, 20, and 22 have higher VOC values and flammable gases than the non-explosive crushing compositions of Comparative Examples 2 to 4. The value was low, and it was found that hydrogen sulfide and sulfur oxides were not generated.

Therefore, considering the results of the performance tests shown in FIGS. 2, 3 and 4, it is possible to maintain the same crushing performance as the conventional non-explosive crushing composition, and a toxic gas or a highly flammable gas at the time of combustion. It is possible to reduce the occurrence of.

The compounding substances used in producing the non-explosive crushing composition are shown below.
・ Aluminum: Toyo Aluminum Co., Ltd. Product name PF0100S
・ Calcium stearate: Kanto Chemical Co., Inc. Reagent deer first grade ・ Copper oxide: Nissin Kemco Co., Ltd. N-10
・ Potassium alum: Wako Pure Chemical Industries, Ltd. First-class reagent ・ Polylactic acid: Unitika Ltd. Terramac (registered trademark) TE2000
・ Polypropylene: Asahi Kasei Corporation (Telpet 560F)
-Poly [lactic acid / glycolic acid]: Sigma-Aldrich Co LLC reagent Resomer RG503H
-Polyvinyl alcohol: Wako Pure Chemical Industries, Ltd. Reagent special grade (Mw = 133000)
・ Starch: Wako Pure Chemical Industries, Ltd. First-class reagent (derived from corn)
・ Starch acetate: Sansho Kogyo Co., Ltd. SB GUM-R
・ Cellulose: Wako Pure Chemical Industries, Ltd. First-class reagent (microcrystal)
・ Trehalose dihydrate: Wako Pure Chemical Industries, Ltd. Reagent special grade ・ D (+)-Maltose monohydrate: Wako Pure Chemical Industries, Ltd. Reagent first grade ・ D (+)-Glucose: Wako Pure Chemical Industries, Ltd. Reagent First grade D (+)-Fructose: Wako Pure Chemical Industries, Ltd. Reagent special grade D (-)-Sorbitol: Wako Pure Chemical Industries, Ltd. Reagent first grade

Claims (9)

A thermite agent that causes a thermite reaction during combustion,
It is composed of either one type of biodegradable material, two or more types of biodegradable material, or an alloy composed of two or more types of biodegradable material, and is subjected to the thermite reaction of the thermite agent during combustion to cause a pyrolysis gas. Granular gas generators that generate
In a non-explosive crushing composition having
The biodegradable material is a biodegradable resin.
The biodegradable resin is either a full-scale biomass raw material plastic, a partial biomass raw material plastic, or a petroleum raw material plastic.
The compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent is a non-explosive crushing composition in the range of the thermite agent: the gas generating agent = 40:60 to 90:10. Stuff. A thermite agent that causes a thermite reaction during combustion,
A granular gas generator that generates a pyrolysis gas in response to the thermite reaction of the thermite agent during combustion.
A binder that binds the thermite agent and the gas generating agent,
In a non-explosive crushing composition having
The gas generating agent and the binder are composed of either one type of biodegradable material, two or more types of biodegradable materials, or an alloy composed of two or more types of biodegradable materials.
The biodegradable material is a biodegradable resin.
The biodegradable resin is either a full-scale biomass raw material plastic, a partial biomass raw material plastic, or a petroleum raw material plastic.
The compounding composition (weight ratio: wt%) of the thermite agent and the gas generating agent is a non-explosive crushing composition in the range of the thermite agent: the gas generating agent = 40:60 to 90:10. Stuff. In the non-explosive crushing composition according to claim 1 or 2.
It said biodegradable materials do not contain sulfur element and a halogen element, an alone polymer or copolymer,
Before SL homopolymer repeat unit or repeat units of the copolymer of the ester, ether, non-explosive fracturing composition, characterized in that one or more have at least one kind of structure of the ketone and hydroxyl. In the non-explosive crushing composition according to claim 1 or 2.
It said biodegradable materials do not contain sulfur element and a halogen element, a non-explosive fracturing composition characterized in that an aliphatic polyester or aliphatic polyether Le. In the non-explosive crushing composition according to claim 3.
Before SL homopolymers or ratio of the number of oxygen atoms and number of carbon atoms said copolymer having, upon the basis of the number of carbon atoms, non-explosive fracturing composition characterized in that it is 1/3 or more .. In the non-explosive crushing composition according to claim 4 or 5.
A non-explosive crushing composition, wherein the biodegradable material is any one of polylactic acid, polyglycolic acid, polyvinyl alcohol or poly [lactic acid / glycolic acid ]. In the non-explosive crushing composition according to any one of claims 1 to 6.
The biodegradable material is a non-explosive crushing composition having a particle size range of 45 μm or more and less than 5600 μm. In the non-explosive crushing composition according to any one of claims 1 to 6.
The biodegradable material is a non-explosive crushing composition having a particle size range of 45 μm or more and less than 250 μm. In the non-explosive crushing composition according to any one of claims 1 to 6.
The biodegradable material is a non-explosive crushing composition having a particle size range of 250 μm or more and less than 2000 μm.

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