JPH02133385A - Water-in-oil type emulsion explosive composition - Google Patents

Abstract

PURPOSE:To harden the chemical nature of the compsn. without impairing the stability of initiating sensitivity at a small diameter and low temp. with age and to facilitate loading at the time of blasting by incorporating specific carbonaceous fuel, aq. inorg. oxidizing acid salt soln., emulsifier, and bubble holding agent. CONSTITUTION:The water-in-oil type emulsion explosive compsn. having 0.80 to 1.35 tentative sp. gr. and 10 to 20mm penetration hardness is obtd. by mixing the aq. soln. contg. 36 to 95wt.% inorg. oxidizing acid salt soln. (e.g.: hydrazine sulfate), 0.1 to 7wt.% emulsifier (e.g.: sorbitan fatty acid ester) and 0.01 to 10wt.% bubble holding agent (e.g.: microhollow spherical bodies of glass) with 1 to 10wt.% carbonaceous fuel consisting of >=5wt.% low-mol. wt. PE which has 40 to 120 deg.C m.p. or softening point, 350 to 1000 numbers average mol. wt., and 0.90 to 0.96g/cc density and has no polar groups at the terminal and <=95wt.% one or >=2 kinds of waxes selected from a mineral system, animal and plant system, petroleum system, and synthetic system having >=10wt.% isoparaffin content.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a water-in-oil type (hereinafter referred to as type-10) emulsion explosive composition, which contains a specific carbonaceous fuel to achieve 1. This invention relates to a W10 type emulsion explosive composition that has improved handling properties such as hardening of the substance without compromising the stability over time of detonation sensitivity at small diameter (25 mm diameter) and low temperature, and facilitating loading during blasting.

(Conventional technology)! A10 type emulsion explosive is disclosed in U.S. Patent No. 31615.
Since it was first published in No. 51, various W10 emulsion explosives have been proposed depending on the purpose.

The type 170 emulsion explosive that has been proposed so far is
Basically, it comprises a continuous phase consisting of a carbonaceous fuel, a dispersed phase consisting of an aqueous solution of an inorganic oxide salt, an emulsifier and a bubble retaining agent.

In order to improve the stability over time of the detonation sensitivity of W10 emulsion explosives at small diameters and low temperatures, it is known to use a specific emulsifier, for example, a mixture of sorbite fatty acid ester, sorbitan fatty acid ester, and sorbitol fatty acid ester in a specific ratio. (Japanese Unexamined Patent Publication No. 59-207889). The carbonaceous fuel specifically used here is a hydrocarbon oil obtained by refining a petroleum wax such as microcrystalline wax or a lubricating oil fraction such as liquid paraffin.

In addition, as a 匈10 emulsion explosive with improved stability over time, we have added a specific emulsifier, such as an emulsifier whose hydrophobic group is made of a long-chain unsaturated fatty acid such as sorbitan monooleate, and 30% or more of a urea-free component. It is also known to use it in combination with a petroleum wax such as microcrystalline wax or paraffin wax (Japanese Patent Publication No. 8998/1989).

In addition, as a W10 type emulsion explosive with improved stability over time of detonation sensitivity, the carbonaceous fuel contains a polymer selected from epoxy resin, unsaturated polyester resin, polybutene, isobutylene, petroleum resin, and butadiene resin without containing oil. It has also been proposed to use the
Publication No. 892).

The petroleum resin used here is a resin obtained by polymerizing the fraction obtained in the naphtha decomposition process, and is a C6 petroleum resin or a C1 petroleum resin, and preferably has a molecular weight of 1000 to 1400.

Furthermore, for the same purpose as above, a carbonaceous fuel using poly(7-) selected from α-olefin polymers and their copolymers, pentadiene polymers and their copolymers, and alicyclic hydrocarbon resins has also been proposed. (Unexamined Japanese Patent Publication No. 61-4
Publication No. 0893).

The α-olefin polymer used here has 6 carbon atoms.
~14, which is a polymer mainly polymerized with an α-olefin represented by general 2CH2=Cl1-R (R is an alkyl group), and preferably has a molecular weight of 300 to 100.000, and more preferably has a molecular weight of 300 to 100.000. 3.000 and is liquid at room temperature. Even in a specific example,
Only an α-olefin polymer with a molecular diameter of about 700 (manufactured by Lion Oil Co., Ltd., trade name “Rivolup 70”, pour point -55°C) is shown, and this is an α-olefin oligomer that is liquid at room temperature.

In addition, as a type 10 emulsion explosive with improved stability over time, it can be combined with oil such as gear oil and the average molecular i! 500
~5.000 polyethylene wax, average molecular ffi
Polypropylene with an average molecular weight of 5,000 or less or 1
5. It has also been proposed to use it as a carbonaceous fuel in combination with one type of active polypropylene polymer having the following properties (Japanese Unexamined Patent Publication No. 149893/1989).

The polyethylene wax disclosed in the specific example of this publication has an average molecular weight of 300.500.2000°500.
0.8000, but there is no mention of its melting point, density, or end groups, nor is there any mention of the product name used.

On the other hand, in order to harden the medicinal substance without impairing its stability over time, it contains a specific emulsifier, that is, a specific amount of fatty acids and fatty acid soap, and a specific ratio of sorbite fatty acid ester, sorbitan fatty acid ester, and sorbitol fatty acid ester. It is also known to use a mixture consisting of (JP-A-62462685). The carbonaceous fuel specifically used here is petroleum wax such as microcrystalline wax or paraffin wax, or liquid paraffin.

(Problems to be Solved by the Invention) In the conventional W10 type emulsion explosive, those using a specific emulsifier or a specific emulsifier in combination with a specific petroleum wax improve the stability over time, but have poor drug quality. The problem was that it was not hard enough.

Further, carbonaceous fuels using specific polymers have high viscosity and high stickiness, which poses problems in terms of the productivity of W10 type emulsion explosives. Furthermore, even if the manufactured explosives were improved in terms of storage stability, there was a problem in that the chemical properties were not sufficiently hard.

In addition, carbonaceous fuels using α-olefin oligomers that are liquid at room temperature have the same problem of stickiness and drug properties that are not sufficiently hard, even though the stability of detonation sensitivity over time can be improved. The problem was that it didn't.

In addition, even if polyethylene wax is used in combination with oil as a carbonaceous fuel, if the number average molecular weight is less than 350,
There was no effect of improving drug quality, and if it exceeded 1000, there was a problem that the stability of detonation sensitivity over time decreased. Further, even with polyethylene waxes having an average molecular weight of 350 to 1000, emulsification is difficult depending on the terminal polar group, for example, when the terminal is a carboxyl group, and there are problems in terms of productivity.

Furthermore, when using an emulsifier that contains a specific amount of fatty acids or fatty acid soap and is a mixture of a specific ratio, there is a problem in that it is difficult to always obtain stable performance because the emulsifier is not a single component. In addition, there was also the problem that there were limitations in terms of pharmacological properties, and that the drug was not yet sufficient.

As carbonaceous fuel, it is possible to produce hard medicinal fuels to some extent by blending large amounts of oils and emulsifiers with high melting points or high softening points, or by adjusting their ratio, but There was a problem in that increasing the amount of emulsifier deteriorated the stability of detonation sensitivity over time.

If the W10 type emulsion explosive has a soft charge, it may deform during transportation or deform when loaded into a borehole, making it difficult to load, especially in small-caliber products, making it difficult to handle, and the blasting effect may be poor. It was also a cause of unexploded explosions.

On the other hand, 10-type emulsion explosives take up to 6 months to 1 year after manufacture until they are used.
It must have good stability over time.

However, a Type 10 emulsion explosive that fully satisfies both properties has not yet been proposed, and this is becoming a major problem to be solved.

Therefore, in consideration of manufacturability, product stability, etc., the present inventors focused on carbonaceous fuel, and as a result of long-term research on various waxes and polymers, the inventors found that specific low molecular weight polyethylene could be used as carbonaceous fuel. The present invention was completed based on the knowledge that the above technical problem can be solved by using the present invention.

(Means for Solving the Problems) The present invention provides a type 10 emulsion explosive comprising a continuous phase consisting of a carbonaceous fuel, a dispersed phase consisting of an aqueous solution of an inorganic oxide salt, an emulsifier and a bubble retaining agent, The carbonaceous fuel has a melting point or softening point of 40 to 120°C, a number average molecular weight of 350 to 1000, a carbon number of 20 to 80, and a density of 0.90 to 0.96 g/cc. , is low molecular weight polyethylene that does not have a polar group at the end,
Or one or two types selected from the group consisting of mineral-based, animal and plant-based, petroleum-based, and synthetic waxes containing 5% by weight or more of low molecular weight polyethylene and 10% by weight or more of isoparaffin with a melting point of 40°C or higher. 9 or more wax
This is a water-in-oil emulsion explosive composition, characterized in that it contains 5% by weight or less.

The carbonaceous fuel used in the present invention is a specific low molecular weight polyethylene as described above or a combination of this low molecular weight polyethylene and a specific natural wax and/or synthetic wax.

This low molecular weight polyethylene is completely different from the conventionally known oligomers mainly composed of α-olefins represented by the general formula ((CO,=CH-R) where R is an alkyl group), and is solid at room temperature. It is.

In the present invention, the melting point or softening point of the low molecular weight polyethylene exceeds 120°C or the number average molecular weight is 10
00 (carbon number 80) or density is 0.96
If it exceeds g/cc, the viscosity becomes high and a hard medicinal product can be obtained, but on the other hand, the stability of the detonation sensitivity over time deteriorates, and the productivity also deteriorates.

In addition, its melting point or softening point is less than 40°C, its number average molecular weight is less than 350 (carbon number 20), or its density is 0.
If it is less than 90, the viscosity is low and therefore the productivity is good, but the medicinal substance becomes soft, the physical strength as a continuous phase becomes weak, and the stability of the detonation sensitivity over time also deteriorates. Especially small diameter (
25■) The stability over time of detonation sensitivity at low temperatures deteriorates. Here, the melting point or softening point is preferably 60 to 100°C in consideration of manufacturability and hardness of the medicinal substance.

Furthermore, even if low molecular weight polyethylene satisfies the above conditions,
If the terminal has a polar group, such as a carboxyl group, emulsification is difficult and it is not possible to obtain a type 10 emulsion explosive with excellent stability over time.

Note that the melting point, softening point, number average molecular weight, and density of low molecular weight polyethylene are measured by commonly used methods.

First about low molecular weight polyethylene used in the present invention
Although specific examples are shown in the table, it goes without saying that the invention is not limited to these commercially available products.

None of these low molecular weight polyethylenes has a polar group at the end.

In addition, in the present invention, a specific wax may be used in combination with the low molecular weight polyethylene, but the melting point of each of the mineral, animal and plant, petroleum and synthetic waxes is 4.
If it is less than 0°C, the viscosity is low, so the productivity is good, but the medicinal substance becomes soft, the physical strength as a continuous phase becomes weak, and the stability over time becomes poor.

In addition, if the isoparaffin content is less than 10% by weight, there will be many chain components such as normal paraffins, resulting in high crystallinity and hardening of the medicinal substance, but the connection with the emulsifier will be weak and it will not function as a continuous phase. Physical strength becomes weaker and stability over time becomes worse.

Specific examples of mineral waxes, animal and vegetable waxes, petroleum waxes, and synthetic waxes used in the present invention are shown in Table 2, but it goes without saying that the waxes are not limited to these commercially available products.

The low molecular weight polyethylene used in the present invention is one or two types.
It is used as a mixture of more than one type, and mineral-based, animal- and plant-based, petroleum-based, and synthetic waxes are also used as one type or a mixture of two or more types.

The proportion of mineral, animal and vegetable, petroleum and synthetic waxes added to low molecular weight polyethylene is usually 5 to 95% (by weight, the same applies hereinafter), preferably 20 to 80%.
The range is as follows.

If the blending ratio of mineral, animal/vegetable, petroleum, or synthetic waxes to low molecular weight polyethylene exceeds 95%, the medicinal substance becomes soft.

Carbonaceous fuel consisting of low molecular weight polyethylene used in the present invention, or one or two types selected from the group consisting of mineral waxes, petroleum waxes, and synthetic waxes added to the low molecular weight polyethylene.
Carbonaceous fuel W containing 95% or less of wax
The blending ratio in the type 10 emulsion explosive composition is usually 1
-10%, preferably 2-5%.

If the blending amount of the carbonaceous fuel of the present invention is less than 1χ, the stability over time of the detonation sensitivity of the W10 type emulsion explosive at small diameters and low temperatures tends to deteriorate, and the drug quality tends to deteriorate. On the other hand, if it exceeds 10%, the oxygen balance tends to deteriorate, resulting in poor explosiveness and aftergassing.

The aqueous solution of the inorganic oxide salt used in the present invention contains conventionally known ammonium nitrate as a main component and contains other inorganic oxide salts as necessary. Other inorganic oxide salts are alkali metal or alkaline earth metal nitrates. Furthermore, perchlorates and chlorates of alkali metals or alkaline earth metals, water-soluble amine nitrates and methanolamine nitrates such as monomethylamine nitrate, monoethylamine nitrate, hydrazine nitrate, dimethylamine dinitrate, and ethylenediamine dinitrate. ,
Water-soluble alkanolamine nitrates such as ethanolamine nitrate, water-soluble ethylene glycol nitrates, and the like can be used as auxiliary sensitizers.

A particularly preferred co-sensitizer is hydrazine sulfate, which is highly effective in promoting the dissolution of inorganic oxidized salts.

By using an auxiliary sensitizer, detonation reliability can be improved and low-temperature detonation properties can be improved.

The amount of ammonium nitrate is generally 36 to 95% of the total.
%, and if necessary, other inorganic oxide salts etc. can be contained in an amount of 40% or less of the total inorganic oxide salts containing ammonium nitrate. Furthermore, when an auxiliary sensitizer is used, the amount of -a to be blended is 40% or less, preferably 30% or less, particularly preferably 20% or less of the total amount. 40%
Exceeding this may increase handling risks.

Note that the amount of water used for the aqueous solution of the inorganic oxide salt is usually 5 to 2.
It is 5%.

The emulsifier used in the present invention is one of the conventionally known emulsifiers.
110 are all emulsifiers that form emulsions.

For example, sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, oxazoline derivatives, imidacillin derivatives, phosphoric acid esters, alkali metal salts or alkaline earth metal salts of fatty acids, -class, secondary and tertiary amines, These include their nitrates or acetates. These emulsifiers are used singly or as a mixture of two or more.

The amount of emulsifier added is generally 0.1 to 7%.

Preferably it is 0.5 to 4%.

Further, the tentative specific gravity of the W10 emulsion explosive composition of the present invention is adjusted to 0.80 to 1.35 (preferably 1.00 to 1.20) using a bubble retaining agent.

The bubble retaining agent includes conventionally known micro hollow spheres, microbubbles, and bubble aggregates in which a large number of bubbles aggregate to form primary particles (see JP-A-60-90887).

Examples of micro hollow spheres include glass, shirasu, silica sand,
Inorganic micro hollow spheres obtained from sodium silicate etc., carbonaceous micro hollow spheres obtained from coal etc., synthetic resin micro hollow spheres obtained from phenol resin, polyvinylidene chloride etc., or those whose surfaces have been treated. It is. The amount of micro hollow spheres is generally 0.01 to 10%. Examples of microbubbles include microbubbles obtained by foaming containing a chemical blowing agent, or microbubbles obtained by mechanically blowing air or other gas during or after the formation of the W10 emulsion. It is.

Chemical blowing agents include, for example, inorganic chemical blowing agents such as alkali metal boron hydrides, those using a combination of sodium nitrite and urea, or N,N'-dinitrosopentamethylenetetramine, azobisisobutyronitrile. and other organic chemical blowing agents. The amount of the chemical blowing agent is generally 0.01 to 2%.

As the bubble aggregate, polystyrene and ABS are used.

Thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, cellulose acetate, acrylic resins, rubbers such as natural rubber and synthetic rubber, and/or resins copolymerized or modified with these various resins, inorganic foaming agents and organic foaming agents. It refers to a cell aggregate having a cell-like or sponge-like cell structure by adding various blowing agents such as foaming agents, low-boiling point hydrocarbons, etc. The content of the cell aggregate is generally 0.05 to 15%. These micro hollow spheres, chemical blowing agents, and bubble aggregates may be used alone or as a mixture of one or more of them.

In the present invention, when a bubble aggregate is used as a bubble retaining agent, there is no possibility that a part of the bubble will be destroyed during pump transportation during manufacturing, unlike inorganic microscopic hollow spheres, so the explosion will occur as designed. It is possible to obtain explosives with excellent performance and excellent stability over time.

Further, if micro hollow spheres and bubble aggregates are used together as a bubble retaining agent, the problem of destruction of the micro hollow spheres can be solved.

In addition to the above ingredients, conventionally known emulsion stabilizers,
For example, water- and oil-insoluble powders of 1 μm or less can be added. (Refer to Japanese Patent Publication No. 58-15467). In addition, water-soluble phosphate (Japanese Unexamined Patent Publication No. 59-789
(see Japanese Patent No. 95), a chelating agent can also be added depending on the above-mentioned components.

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

Furthermore, when used for coal mining, conventionally known halides such as sodium chloride can also be added.

A manufacturing example of the above type 10 emulsion explosive will be briefly described. An aqueous solution of an inorganic oxide salt is dissolved at 90°C, a specific carbonaceous fuel and an emulsifier are melted and mixed at 90"C, and the oxidized salt aqueous solution and the carbonaceous fuel are stirred and emulsified under heating at 90°C to form bubbles. A retaining agent is added to obtain a W10 type emulsion explosive.

The W10 type emulsion explosive of the present invention thus obtained has a penetration hardness of 10 to 20 mm. Here, the penetration hardness is the penetration depth when a 133 g conical (30'') iron cone is dropped from a height of 45 mm.

(Effects of the Invention) Since the W10 type emulsigone explosive composition of the present invention contains a specific carbonaceous fuel, the conventional -1 emulsigone explosive composition that does not contain it
Compared to the Type 0 engineered Marsillon explosive composition, it has a smaller diameter (25 mm).
Diameter) It has the effect of hardening the medicinal substance without impairing its stability over time at low temperatures, and it can improve handling properties such as making it easier to load during blasting. In addition, when the specific carbonaceous fuel of the present invention is used, the viscosity and stickiness during production are low, and the productivity is excellent.
Furthermore, compared to type 10 emulsion explosives in which specific emulsifiers are mixed in specific ratios to improve drug quality, the present invention has the advantage that a product of constant quality can be obtained because a single emulsifier is used.

(Example) Next, the present invention will be specifically explained by using Examples and Comparative Examples.

Note that the present invention is not limited to the following examples. All parts in each example are by weight.

Example 1 A W10 type emulsion explosive having the composition shown in Table 3 was manufactured as follows.

75.5 parts of ammonium nitrate and 5.0 parts of sodium nitrate were added to 12.2 parts of water and completely dissolved at 90°C to obtain an aqueous inorganic oxidizing agent solution. On the other hand, 3.0 parts of low molecular weight polyethylene (manufactured by Mitsubishi Chemical Industries, Ltd., Dialene 30) as a carbonaceous fuel specified in the present invention and 1 to 1.7 parts of sorbitan monooleate as an emulsifier were melt-mixed at 90°C. A mixture of flammable agents was obtained. To this, 92.7 parts of the oxidizing agent aqueous solution was slowly added, and stirring and emulsification was performed at 650 rpm while heating at 90°C. After emulsification, the mixture was further stirred at 1800 rpm for 3 minutes to obtain 97.4 parts of W10 type emulsion. Glass micro hollow spheres (manufactured by The PQ Co., Ltd., glass micro hollow spheres Q-ce111500) as a bubble retaining agent 2.6
60 to 8 parts and 9764 parts of the above-mentioned revised type 0 emulsion.
After mixing and kneading at 0℃, weigh 100g each to make a diameter of 25mm.
It was molded into a cylindrical shape and wrapped in viscose paper to obtain a W10 type emulsion explosive.

Performance tests include (a) measurement of provisional specific gravity one day after production, (b) keeping the test drug packet at -40℃ for 2 hours, and then heating it to +3℃.
After conducting a forced deterioration storage test in which the specimen was kept at 0°C for 22 hours and repeated temperature cycles, one cycle was followed by an detonation test at -15°C using a No. 6 detonator to determine the number of temperature cycles that would allow a complete explosion. Detonation sensitivity stability test over time determined (c)
The sample cartridge was kept at 50"C for 72 hours, and then returned to room temperature (0~
(30℃) Low temperature detonation sensitivity test to determine the temperature at which detonation occurs at low temperature after storage (1 year), (d) Penetration hardness (mm)
) measurement, i.e. 133g iron cone (30°)
The depth of penetration (mm) when dropped from the height of the bar was measured.

The results of the various tests mentioned above are shown in Table 3.

Examples 2 to 10 Based on Example '1, -10 type emulsion explosives were obtained using the formulations shown in Table 3. -10 of each
The same tests as in Example 1 were conducted on type emulsion explosives. The test results are shown in Table 3.

Comparative Examples 1-8 Example 1. Based on the above, W10 type emulsion explosives were obtained using the formulations shown in Comparative Examples 1 to 8 in Table 3. The same performance tests as in Example 1 were conducted for each type 10 emulsion explosive. The test results are shown in Table 3.

In Table 3, the carbonaceous fuels are shown below.

[Phase] Wax Rex 602: Microcrystalline wax, melting point 81°C (manufactured by Mobil Oil Company).

■ Hi-Mic 2045: Microcrystalline wax, melting point 60°C (manufactured by NOF Corporation).

■ Diasin 208: Low molecular weight polyethylene, melting point or softening point 38°C, B average molecule 1318 (carbon number 2
3), density 0.96 g/cc (manufactured by Mitsubishi Chemical Industries, Ltd.)
.

[Phase] Hiwax 200: low molecular weight polyethylene,
Melting point or softening point 113℃ 1 number average molecular ff1200
0 (carbon number 143), density 0.97 g/cc (manufactured by Mitsui Petrochemicals).

■ Polywax 2000: low molecular weight polyethylene,
Melting point or softening point 125℃ Number average molecular weight 2000 (
carbon number 143), density 0.96 g/cc (manufactured by Petrolite).

■ Polybis 1ON = polybutene, number average molecular weight 100
0 (manufactured by NOF Corporation).

■ Evaflex 210: Vinyl acetate copolymer, containing 40x vinyl acetate, softening point 85°C (manufactured by Mitsui Polychemical Co., Ltd.).

■ Rivoloop 7 former α-olefin oligomer number average molecule 1700 (manufactured by Lion Oil Co., Ltd.).

In Table 3, the bubble retaining agents are shown below.

@l GMB (Q-cel1500) Nigaras micro hollow sphere (manufactured by The PQ Co., Ltd.).

@ SMB (SPW-7) Nijirus micro hollow body (manufactured by Kushiro Coal Carbonization Co., Ltd.).

@ RMB (Expancel DB): Polyvinylidene chloride resin sphere (manufactured by Kemanode Plastics).

0 Styrofoam pre-expanded beads: Styrofoam beads made by Mitsubishi Yuka Pardish Co., Ltd. that are pre-expanded with a size of 0.2 or less (bulk specific weight: .3, average particle size: 0)
．． 6) From the relationship between the above examples and comparative examples, the W10 type emulsion explosive compositions (Examples 1 to 10) using a specific number molecular weight polyethylene as the carbonaceous fuel are the W10 type emulsion explosive compositions not using it. Compared to the compositions (Comparative Examples 1 to 8), it was confirmed that the compositions became pharmacologically hard without impairing stability over time.

Examples 11 to 18 Based on Example 1, W10 type emulsion explosives were obtained using the formulations shown in Table 4. The same test as in Example 1 was conducted for each W10 type emulsigon explosive. The test results are shown in Table 4.

Comparative Examples 9 to 15 Based on Example 1, W10 type emulsion explosives were obtained using the formulations shown in Table 4. The same tests as in Example 1 were conducted for each Type 10 emulsion explosive. The test results are shown in Table 4.

In Table 4, the carbonaceous fuels are as follows.

The same numbers as in Table 3 indicate the same items.

■ 115°F Paraffin: Paraffin wax, melting point 46°C, isoparaffin content 10% (manufactured by Nippon Seiro Co., Ltd.) @OX-ed.5SEN-8: Low molecular weight polyethylene,
Softening point: 84°C, number average molecular weight: 950 (carbon number: 67), density: 0.94 g/ccs, carboxyl group at the end (manufactured by Nippon Seirosha) In Table 4, the bubble retaining agent is the same as in Table 3. shows.

From the relationship between the above Examples and Comparative Examples, the -70 type emulsion formula is a carbonaceous fuel in which 95% or less of specific mineral, animal/vegetable, petroleum, or synthetic waxes are blended with specific low molecular weight polyethylene. Compared to the Type 10 emulsion explosive compositions (Comparative Examples 9 to 14) that do not use the same, the emulsion explosive compositions (Examples 1 to 1B) do not have poor stability over time and do not become pharmacologically hard. confirmed.

Furthermore, it was confirmed that even low molecular weight polyethylene as a carbonaceous fuel cannot be emulsified if its end has a polar group such as a carboxyl group (Comparative Example 15).

Patent applicant: NOF Corporation

Claims (1)

[Scope of Claims] 1. A water-in-oil emulsion explosive comprising a continuous phase consisting of a carbonaceous fuel, a dispersed phase consisting of an aqueous solution of an inorganic oxide salt, an emulsifier and a bubble retainer, wherein the carbonaceous fuel is , 4
It has a melting point or softening point of 0 to 120°C, a number average molecular weight of 350 to 1000, a carbon number of 20 to 80, a density of 0.90 to 0.96 g/cc, and a polar group at the end. 1. A water-in-oil emulsion explosive composition, characterized in that it is a low molecular weight polyethylene that does not contain any of the following. 2. A water-in-oil emulsion explosive comprising a continuous phase consisting of a carbonaceous fuel, a dispersed phase consisting of an aqueous solution of an inorganic oxide salt, an emulsifier and a bubble retaining agent, wherein the carbonaceous fuel
It has a melting point or softening point of ~120°C, a number average molecular weight of 350 to 1000, a carbon number of 20 to 80, a density of 0.90 to 0.96 g/cc, and a polar group at the end. One or two types selected from the group consisting of 5% by weight or more of low molecular weight polyethylene and 10% by weight or more of isoparaffin with a melting point of 40°C or higher, mineral-based, animal-vegetable-based, petroleum-based, or synthetic waxes. More than 95% of wax
A water-in-oil emulsion explosive composition, characterized in that it contains not more than % by weight of: