JPS6224395B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a water-in-oil emulsion explosive composition (hereinafter abbreviated as W/O emulsion explosive composition).
The present invention relates to an explosive composition containing a novel emulsifier that forms a W/O emulsion,
By using one or more selected from the group consisting of specific pentaerythritol fatty acid esters, dipentaerythritol fatty acid esters, polyoxyalkylene pentaerythritol fatty acid esters, and polyoxyalkylene dipentaerythritol fatty acid esters as an emulsifier, small diameter The present invention relates to a W/O emulsion explosive composition which has performance superior to that of conventionally known emulsifiers in terms of (25 mm diameter) and stability over time of detonation sensitivity at low temperatures. Regarding the W/O type emulsion explosive composition,
It has been researched for a long time, and the initial ones were because the morphology of the W/O emulsion was unstable (that is, the contact area between the dispersed phase and the continuous phase was relatively small), so explosive sensitizers such as nitroglycerin were used. Or non-explosive sensitizing agents such as monomethylamine nitrate (hereinafter abbreviated as sensitizing substances), or atomic number 13
Compounds of metals other than Groups 1 and 2 of the periodic table, detonation catalytic sensitizers such as water-soluble strontium compounds, or sensitizing oxidants such as ammonium or alkali metal perchlorates, etc. (hereinafter abbreviated as auxiliary sensitive substances) were added to improve the detonation sensitivity at small diameters. However, W/O type emulsion explosive compositions containing such sensitive substances or auxiliary sensitive substances, etc., may be susceptible to damage if, for example, the above-mentioned sensitive substances separate due to some factor during manufacturing or use. There was a potential danger of becoming extremely sensitive, or of the toxicity of the above-mentioned sensitive substances.
In this sense, a W/O emulsion explosive composition has also been disclosed which does not contain any of the above-mentioned sensitive substances or auxiliary sensitive substances and has improved detonation sensitivity in small diameters (enabling detonation with a detonator). For example, according to US Pat. No. 4,110,134, emulsifiers include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene ether, polyoxyalkylene oleate, polyoxyalkylene laurate, and phosphorus. Contains acid oleate, substituted oxazoline, and phosphate ester, and contains glass microscopic hollow spheres as a bubble retaining agent to complete detonation with a diameter of approximately 1.25 inches (31.8 mm) using a No. 6 detonator to a maximum tentative specific gravity of 1.25. It is stated that it will be done. Further, according to US Pat. No. 4,149,917, emulsifiers include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene (4) lauryl ether, polyoxyethylene (2) ether, polyoxyethylene ( 2) By blending stearyl ether, polyoxyalkylene oleate, polyoxyalkylene laurate, phosphoric oleate, substituted oxazoline, phosphoric ester, and mixtures thereof, it is possible to form microbubbles without containing a bubble-retaining substance. Adjust the temporary specific gravity to 0.95,
With a diameter of 1.25 inches (31.8 mm), it can be completely detonated with a No. 6 detonator even after two months have passed since manufacture (explosive temperature 21.1℃), and can be completely detonated with a No. 8 detonator even after eight months have passed (explosive temperature 21.1
°C). The number in brackets after oxyalkylene represents the number of moles of oxyalkylene group bonded to one hydroxyl group. This corresponds to the value expressed in 5 m of the emulsifier defined in the claims. same as below. It is well known that various emulsifiers are used in W/O type emulsion explosive compositions that do not contain the above-mentioned sensitizing substances or auxiliary sensitizing substances. Various emulsifiers that form emulsions are known. However, W/O emulsion explosive compositions using emulsifiers other than those described in the above-mentioned U.S. patent specifications are not as effective, as can be seen from the fact that they contain the above-mentioned sensitizing substances or auxiliary sensitizing substances. W/O
Because the mold emulsion had poor stability over time, the stability over time of detonation sensitivity at small diameters (25 mm diameter) and low temperatures was extremely poor. Furthermore, even with the W/O type emulsion explosive composition using the emulsifier described in the above-mentioned US patent specification, the stability over time of the detonation sensitivity at low temperatures is sufficiently satisfactory with a smaller diameter (25 mm diameter). It wasn't. The inventors of the present invention have conducted extensive research over a long period of time while taking into account the above-mentioned problems.
Substances that have not been considered as emulsifiers for W/O emulsion explosive compositions include ammonium nitrate or an oxidizing agent aqueous solution consisting of ammonium nitrate and other inorganic oxide salts and water, and a combustible agent consisting of fuel oil and/or waxes. It has been discovered that it can be formed into a W/O emulsion, and the W/O emulsion explosive composition thus obtained is superior to conventional known emulsifiers in terms of stability over time of detonation sensitivity at small diameters and low temperatures. It was found that this product has excellent performance, and the present invention was completed. That is, the W/O emulsion explosive composition of the present invention comprises (a) ammonium nitrate or ammonium nitrate and other inorganic oxide salts, and (b) a dispersed phase of an oxidizing agent aqueous solution consisting of water, (c) fuel oil and/or wax. (d) one type selected from the following specific pentaerythritol fatty acid esters, dipentaerythritol fatty acid esters, polyoxyalkylene pentaerythritol fatty acid esters, and polyoxyalkylene dipentaerythritol fatty acid esters; Or, it is characterized by containing two or more emulsifiers and (e) micro hollow bodies or micro bubbles. The aqueous oxidizing agent solution of the W/O emulsion explosive composition of the present invention contains ammonium nitrate as a main component and may contain other inorganic oxidizing acid salts as necessary. Here, the other inorganic oxide salts are, for example, nitrates of alkali metals or alkaline earth metals such as sodium nitrate and calcium nitrate. These inorganic oxidized acid salts may be used alone or as a mixture of two or more. The blending amount of ammonium nitrate is generally 50 to 94.7% (by weight, the same applies hereinafter) of the total, and if necessary, other inorganic oxide salts may be included at 40% or less of the total inorganic oxide salts including ammonium nitrate. Good too. If the amount of ammonium nitrate is less than the lower limit, the oxygen balance (the relationship between excess and deficiency of oxygen between the oxidizing agent and the combustible agent) will be too poor (oxygen deficiency), resulting in poor explosiveness and aftergassing. If the upper limit is exceeded, the dissolution temperature of ammonium nitrate in water becomes too high, resulting in poor productivity, and the explosive reactivity of ammonium nitrate becomes poor, resulting in poor detonation sensitivity. Regarding the other inorganic oxide salts mentioned above, by adding a small amount, the amount of oxygen supplied can be increased and the dissolution temperature in water can be lowered, improving explosiveness and manufacturability, but if the amount exceeds 40%, Since the amount of solid residue after the explosion increases, the power will be reduced and it will be disadvantageous in terms of economy. Note that the amount of water used in the oxidizing agent aqueous solution is generally 5% to 25%. If it is less than 5%, the melting temperature of ammonium nitrate or ammonium nitrate and other inorganic oxide salts becomes too high, resulting in poor productivity and poor detonation sensitivity due to poor explosive reactivity. If it exceeds 25%, productivity is improved because the melting temperature of ammonium nitrate or ammonium nitrate and other inorganic oxide salts is lowered, but the amount of gas and heat generated after the explosion is reduced, resulting in poor detonation sensitivity and low power. . Fuel oils and/or wax fuel oils include hydrocarbons, such as paraffinic hydrocarbons, olefinic hydrocarbons, naphthenic hydrocarbons, aromatic hydrocarbons, saturated or unsaturated hydrocarbons, petroleum, refined mineral oils,
Lubricants, liquid paraffin, etc. and hydrocarbon derivatives,
For example, nitrohydrocarbons. Waxes include unrefined microcrystalline wax derived from petroleum, refined microcrystalline wax,
These include paraffin wax and the like, mineral waxes such as montan wax and ozokerite, animal waxes such as spermaceti wax, and insect waxes such as beeswax. These fuel oils/waxes may be used alone or as a mixture of two or more. The amount of fuel oil and/or waxes is generally 0.1% to 10%.
%. If the fuel oil and/or wax is less than 0.1%, the stability of the W/O emulsion explosive composition will be poor, and if it exceeds 10%, the oxygen balance will be too poor, resulting in poor explosiveness and aftergassing. Specific pentaerythritol fatty acid esters, dipentaerythritol fatty acid esters, polyoxyalkylene pentaerythritol fatty acid esters, and polyoxyalkylene dipentaerythritol fatty acid esters, which are emulsifiers of the W/O emulsion explosive composition of the present invention, are as follows: Pentaerythritol fatty acids such as pentaerythritol laurate monoester, pentaerythritol stearate monoester, pentaerythritol isostearate monoester, pentaerythritol linoleate monoester, pentaerythritol oleate diester, pentaerythritol erucate diester, etc. represented by formula () Esters and polyoxyethylene (4) pentaerythritol stearate diester, polyoxyethylene (4) pentaerythritol oleate diester, polyoxypropylene (4) pentaerythritol oleate diester, polyoxyethylene (10) pentaerythritol erucate diester, etc. of polyoxyalkylene pentaerythritol fatty acids. In addition, dipentaerythritol lauric acid monoester, dipentaerythritol isostearic acid monoester, dipentaerythritol oleic acid monoester, dipentaerythritol linoleic acid monoester, dipentaerythritol erucic acid monoester, which are represented by the following general formula (), Dipentaerythritol fatty acid esters such as dipentaerythritol linolenic acid tetraester, polyoxyethylene (4) dipentaerythritol isostearate tetraester, polyoxyethylene (6) dipentaerythritol linoleic acid tetraester,
Examples include polyoxyalkylene dipentaerythritol fatty acid esters such as polyoxypropylene (10) dipentaerythritol erucic acid tetraester. [In the formula, are all A hydrogen atoms?-(R′O) _n H
group, or one RCO- group and the remaining two -(R′O) _n
Indicates H group. However, R is C _o H _2o+1 , C _o H _2o-1 ,
C _o H _2o-3 or C _o H _2o-5 , R' is -CH ₂ CH ₂ -
or

[Formula] is shown. n is 9-24; m is 2-20. ] [In the formula, Y is 1 to 3 RCO- groups and the rest are hydrogen atoms, or 3 RCO- groups and the rest -
(R′O) _n Indicates an H group. R and R' are the same as in general formula (). ] These emulsifiers may be used alone or as a mixture of two or more. The amount of emulsifier added is generally 0.1%.
~5%. Preferably it is 0.5% to 4%. If these various emulsifiers are less than 0.1%, W/O
The stability of the detonation sensitivity of the type emulsion explosive composition over time at small diameters and low temperatures is poor, and if it exceeds 5%, the oxygen balance becomes poor, resulting in poor explosiveness and aftergassing, which is also disadvantageous from an economic point of view. Further, the W/O type emulsion explosive composition of the present invention has a temporary specific gravity of 0.80 to 1.35 by using a temporary specific gravity adjusting agent.
(preferably adjusted to 1.00 to 1.15). The temporary specific gravity adjusting agent is a micro hollow sphere or a micro bubble, and the micro hollow sphere is obtained from, for example, glass, alumina, shale, shirasu, silica sand, volcanic rock, sodium silicate, borax, nacre, obsidian, etc. Inorganic minute hollow spheres, carbonaceous minute hollow spheres obtained from pitch, coal, etc., synthetic resin minute hollow spheres obtained from phenolic resin, polyvinylidene chloride, epoxy resin, urea resin, etc., and these minute hollow spheres. are used alone or as a mixture of two or more. The amount of micro hollow spheres is generally 0.1%
~10%. Microbubbles are, for example, microbubbles obtained by foaming a chemical blowing agent, or microbubbles obtained by mechanically blowing air or other gas during or after the formation of a W/O emulsion. Air bubbles, etc. 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, azodicarboxylic acid amide, azo These include organic chemical blowing agents such as bisisobutyronitrile. These chemical blowing agents may be used alone or as a mixture of two or more. The amount of chemical blowing agent added is generally 0.01% to 2%. However, regarding the above temporary specific gravity adjusting agent, the temporary specific gravity of the micro hollow spheres is less than 0.1%, the chemical blowing agent is less than 0.01%, or the W/O type emulsion explosive composition is
If the amount of air or other gas exceeds 1.35, the detonation sensitivity will be poor and the explosion will be low. If the micro hollow spheres exceed 10%, or if the chemical blowing agent exceeds 2%, or if the amount of air or other gas is such that the tentative specific gravity of the W/O emulsion explosive composition is less than 0.80. The detonation sensitivity is good, but the detonation speed is low, so the power is small. The method for producing the W/O emulsion explosive composition of the present invention is, for example, as follows. That is, an oxidizing agent aqueous solution is obtained by dissolving ammonium nitrate or a mixture of ammonium nitrate and other inorganic oxidizing acid salts in water at about 80°C to 90°C. On the other hand, the emulsifier defined in the present invention and fuel oil and/or waxes were heated at 80°C to 90°C.
A mixture (hereinafter abbreviated as combustible mixture) is obtained by melting and mixing at °C. Next, first put the combustible mixture in a heat-insulating container with a certain volume, and mix and stir for about 5 minutes at about 1600 rpm using a commonly used propeller blade stirrer while gradually adding the oxidizing agent aqueous solution. Obtain a W/O type emulsion at 85°C. Next, a W/O emulsion explosive composition is obtained by mixing micro hollow spheres or a chemical blowing agent into the W/O emulsion using a vertical mixer at about 30 rpm. In addition, when containing microbubbles made of gas such as air instead of microbubbles caused by microscopic hollow spheres or a chemical blowing agent, W/O emulsion can be mixed by stirring while blowing gas such as air into the W/O type emulsion. /O type emulsion explosive composition is obtained. Next, the W/O type emulsion explosive composition of the present invention will be specifically explained with reference to Examples and Comparative Examples. Note that all parts and percentages in each example are based on weight. Example 1 A W/O type emulsion explosive composition having the formulation shown in Table 1 was manufactured as follows. First, 381.5 parts (76.30%) of ammonium nitrate and 22.85 parts (4.57%) of sodium nitrate were added to 55.25 parts (11.05%) of water and dissolved by heating to obtain an oxidizing agent aqueous solution at about 85°C. On the other hand, a mixture of 8.75 parts (1.75%) of pentaerythritol lauric acid monoester specified in the present invention and 17.05 parts (3.41%) of unrefined microcrystalline wax was heated and melted, and the flammable agent mixture was heated to about 85°C. Obtained. Next, first put the combustible agent mixture in a heat-insulating container, then gradually add the oxidizing agent aqueous solution and mix and stir for 5 minutes at about 1600 rpm using a propeller blade stirrer to reach about 85°C. A W/O type emulsion was obtained. Next, a W/O emulsion explosive composition was prepared by mixing 14.60 parts (2.92%) of glass micro hollow spheres with an average particle size of 75μ into the W/O emulsion using a vertical mixer at approximately 30 rpm. Obtained. This W/O type emulsion explosive composition was molded to have a diameter of 25 mm, a length of 180 mm, and a drug amount of 100 gr, and was subjected to various performance tests as a medicine package wrapped in viscose-treated paper. As a performance test, (a) measurement of provisional specific gravity one day after production, (b) holding the sample cartridge at 60℃ for 24 hours, then keeping it at -15℃ for 24 hours, and repeating the temperature cycle with this as one cycle. After conducting a forced deterioration storage test, a No. 6 detonator was used to
Determine the number of temperature cycles that can cause a complete explosion when performing an explosion test at 5℃, and calculate the number of temperature cycles at room temperature (10 to 30℃).
Detonation sensitivity aging stability test estimated as the number of months of storage for complete detonation in storage (estimated from the experimental confirmation that one temperature cycle described above corresponds to approximately one month of storage at room temperature), and ( c)
Temporary specific gravity measurements were made during the detonation test described in (b) above. The results were as shown in Table 1. Examples 2 to 11 A W/O emulsion explosive composition having a composition as shown in Table 1 contains pentaerythritol isostearic acid monoester, pentaerythritol oleic ester, pentaerythritol oleic acid monoester, pentaerythritol lauric acid monoester, and pentaerythritol lauric acid monoester in Example 1. Erythritol linoleate monoester, pentaerythritol oleate diester, pentaerythritol erucate diester, polyoxyethylene (4) pentaerythritol stearate diester, polyoxypropylene (4) pentaerythritol oleate diester, polyoxyethylene (10)
It was produced according to Example 1 except that pentaerythritol erucate diester and a mixture thereof were used. Sample cartridges were prepared from these W/O emulsion explosive compositions in the same manner as described in Example 1, and performance tests were conducted on the same items. The results were as shown in Table 1. Example 12 A W/O emulsion explosive composition having the composition shown in Table 1 was prepared as in Example 1 except that N,N'-dinitrosopentamethylenetetramine was used instead of the glass micro hollow spheres. Produced according to Example 1. A sample cartridge was prepared from this W/O emulsion explosive composition in the same manner as described in Example 1, and this sample cartridge was heated in a constant temperature bath at approximately 50°C for 2 hours to blend. Chemical blowing agent (N,
The same performance tests as in Example 1 were conducted on a product whose temporary specific gravity was adjusted by decomposing and foaming N'-dinitrosopentamethylenetetramine. Example 13 A W/O type emulsion explosive composition having the formulation shown in Table 1 was produced by the following method. That is, first, a W/O type emulsion was obtained according to Example 1. Next, while blowing air into the above-mentioned W/O type emulsion through a thin nozzle, mixing and stirring was performed at approximately 1600 rpm for 2 minutes using a propeller blade type stirrer to introduce microbubbles of air. An O-type emulsion explosive composition was obtained. Sample cartridges were prepared from this W/O emulsion explosive composition in the same manner as described in Example 1, and performance tests were conducted on the same items. The results were as shown in Table 1. Examples 14 to 24 A W/O emulsion explosive composition having a composition as shown in Table 2 contains dipentaerythritol lauric acid monoester and dipentaerythritol isostearic acid in place of the pentaerythritol lauric acid monoester of Example 1. monoester,
Dipentaerythritol oleate monoester, dipentaerythritol linoleate monoester, dipentaerythritol erucate diester, dipentaerythritol linolenic acid tetraester, polyoxyethylene (4) dipentaerythritol isostearate tetraester, polyoxyethylene ( 6) Produced according to Example 1 except that dipentaerythritol linoleic acid tetraester, polyoxypropylene (10) dipentaerythritol erucic acid tetraester, and a mixture thereof were used. Sample cartridges were prepared from these W/O emulsion explosive compositions in the same manner as described in Example 1, and performance tests were conducted on the same items. The results were as shown in Table 2. Example 25 A W/O emulsion explosive composition having the composition shown in Table 2 was the same as Example 12 except that dipentaerythritol erucate diester was used in place of pentaerythritol oleate monoester. Manufactured in accordance with Sample cartridges were prepared from this W/O emulsion explosive composition in the same manner as described in Example 1, and performance tests were conducted on the same items. The results were as shown in Table 2. Example 26 A W/O emulsion explosive composition having the formulation shown in Table 2 was the same as Example 13 except that dipentaerythritol erucate diester was used in place of pentaerythritol oleate monoester. Manufactured in accordance with Sample cartridges were prepared from this W/O emulsion explosive composition in the same manner as described in Example 1, and performance tests were conducted on the same items. The results were as shown in Table 2. Comparative Examples 1 to 8 W/O emulsion explosive compositions having the formulations shown in Table 3 were manufactured according to Example 1.
This W/O type emulsion explosive composition was prepared in Example 1.
A sample medicine package was prepared using the same method as described in 2012, and performance tests were conducted on the same items. The results were as shown in Table 3. Comparative Examples 9-10 W/O emulsion explosive compositions having the formulations shown in Table 3 were produced according to Examples 12 and 13. Sample cartridges were prepared from this W/O emulsion explosive composition in the same manner as described in Example 1, and performance tests were conducted on the same items. The results were as shown in Table 3.

【table】

【table】

【table】

【table】

[Table] Examples of emulsifiers defined in the present invention include pentaerythritol laurate monoester, pentaerythritol isostearate monoester, pentaerythritol oleate monoester, pentaerythritol linoleate monoester, pentaerythritol oleate diester, and pentaerythritol erucate diester. , polyoxyethylene (4) pentaerythritol stearate diester, polyoxypropylene (4) pentaerythritol oleate diester, polyoxyethylene (10) pentaerythritol erucate diester,
Dipentaerythritol laurate monoester, dipentaerythritol isostearate monoester, dipentaerythritol oleate monoester, dipentaerythritol linoleate monoester, dipentaerythritol erucate diester, dipentaerythritol linolenic acid tetraester, polyoxyethylene (4) W/O emulsion explosive composition containing dipentaerythritol isostearate tetraester, polyoxyethylene (6) dipentaerythritol linoleate tetraester, and polyoxypropylene (10) dipentaerythritol erucate tetraester, respectively. In the case of (Examples 1 to 9 and 14 to 22), the number of months that can be stored for complete detonation at -5℃ using a No. 6 detonator is
It was between 23 and 29 months. On the other hand, in the case of W/O type emulsion explosive compositions containing known emulsifiers (Comparative Examples 1 to 7), the period was 6 to 19 months. Also, a W/O emulsion explosive composition containing sodium nitrate and calcium nitrate as inorganic oxide salts other than ammonium nitrate, liquid paraffin as a combustible agent, silica micro hollow spheres as a bubble retaining agent, and 2.50% of sorbitan monooleate as an emulsifier. In the case of Comparative Example 8, the storage period for complete detonation at -5°C using a No. 6 detonator was 24 months, but pentaerythritol oleate monoester was used as an emulsifier specified in the present invention at 2.50%.
31 months and 32 months for the W/O emulsion explosive composition containing 2.50% dipentaerythritol erucate (Example 10) and the W/O emulsion explosive composition containing 2.50% dipentaerythritol erucate diester (Example 23).
It was hot for a month. In addition, as emulsifiers defined in the present invention, pentaerythritol oleate monoester (0.80%), pentaerythritol oleate diester (0.80%), and polyoxyethylene (4) pentaerythritol oleate diester (0.90%) are used as emulsifiers.
%) and a W/O emulsion explosive composition (Example 11) containing dipentaerythritol oleate monoester (0.80%), dipentaerythritol erucate diester (0.80%), and polyoxypropylene (10). W/ containing dipentaerythritol erucic acid tetraester (0.90%)
In the case of the O-type emulsion explosive composition (Example 24), it was 33 months. In addition, W/ was prepared by adding 0.20% of N,N'-dinitrosopentamethylenetetramine as a chemical blowing agent to adjust the tentative specific gravity without adding a bubble retaining agent, and adding 1.80% of sorbitan monooleate as an emulsifier. In the case of the O-type emulsion explosive composition (Comparative Example 9), the storage period for complete detonation at -5°C using a No. 6 detonator was 14 months, but the present invention was used instead of sorbitan monooleate. A W/O emulsion explosive composition containing 1.80% pentaerythritol oleate monoester defined by (Example 12) and a W/O emulsion explosive composition containing 1.80% dipentaerythritol erucate diester ( In the case of Example 25), the period was 21 months. In addition, a W/O emulsion explosive composition in which the tentative specific gravity was adjusted by mechanically introducing microbubbles without adding a bubble retaining agent, and 1.80% of sorbitan monooleate was added as an emulsifier (Comparative Example 10) In this case, the storage period for complete detonation at -5℃ using a No. 6 detonator was 13 months, but pentaerythritol oleate monooleate was used as an emulsifier specified in the present invention instead of sorbitan monooleate. 20 months for a W/O emulsion explosive composition containing 1.80% ester (Example 13) and a W/O emulsion explosive composition containing 1.80% dipentaerythritol erucate diester (Example 26). It was hot. As explained above based on each Example and each Comparative Example, the W/O type emulsion explosive composition containing the emulsion specified by the present invention is different from the W/O type emulsion explosive composition containing the conventional emulsifier. The stability of the detonation sensitivity over time at small diameter (25mm diameter) and low temperature has been significantly improved compared to the standard.

Claims (1)

[Scope of Claims] 1. (a) a dispersed phase of an oxidizing agent aqueous solution consisting of ammonium nitrate or ammonium nitrate and other inorganic oxide salts, and (b) water, and (c) a continuous combustible material consisting of fuel oil and/or waxes. phase, (d) the following general formulas () and () [In the formula, are all A hydrogen atoms?-(R′O) _n H
group, or one RCO- group and the remaining two -(R′0) _n
Indicates H group. However, R represents C _o H _2o+1 , C _o H _2o-1 , C _o H _2o-3 or C _o H _2o-5 , and R' represents -CH ₂ CH ₂ - or [Formula]. n is 9-24 and m is 2-20. ] [In the formula, Y is 1 to 3 RCO- groups and the rest are hydrogen atoms, or 3 RCO- groups and the rest -
(R′O) _n Indicates an H group. R and R' are the same as in general formula (). ] A water-in-oil emulsion explosive composition characterized by containing an emulsifier consisting of one or more of the compounds shown below and (e) microscopic hollow spheres or microbubbles.