JPS5957983A - Water-in-oil type emulsion explosive composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a water-in-oil emulsion desiccant composition (hereinafter referred to as W10).
Regarding the type emulsion [abbreviated as ii composition], W1
The present invention relates to a desiccant composition containing a novel emulsifier for forming a type 0 emulsion, which is a type W10 emulsion with improved stability over time and resistance to dead pressure at small diameters (95 mm) and low temperatures. The present invention relates to a composition.

W10 type emulsion desiccant compositions have been studied for a long time, and the early ones used nitroglycerin because the W10 type emulsion had an unstable morphology (that is, the contact area between the dispersed phase and the continuous phase was relatively small). Explosives such as AIJ or non-explosives such as monomethylamine nitrate (hereinafter abbreviated as desensitizing substances, etc.), or those with an atomic number of 18 or higher and other than Groups 2 and 2 of the periodic table. or explosive catalytic sensitizers such as water-soluble strontium compounds, or desensitizing oxidizing agents such as ammonium or alkali metal perchlorates, chlorine #I salts, etc. (hereinafter abbreviated as auxiliary mirror-sensitizing substances, etc.) ) was added to improve the size of small-mouthed calves: gauze IN, '3 f'l.

However, this (first acute HT3 substance or auxiliary desensitization
For example, a W10 type emulsion explosive composition containing 2 liters of /l substance! I'! ! At 1M, if the above-mentioned desensitizing substances are separated for some reason during use, it may become extremely sharp 11C, or there is a potential danger such as the toxicity of the above-mentioned loose desensitizing substances. Ta.

In this sense, several W10 type emulsion explosive compositions have been disclosed which do not contain any desensitizing substances or auxiliary desensitizing substances and have improved detonation sensitivity in small diameters (capable of being detonated by detonators).

For example, according to U.S. Pat. No. 4,110,134, emulsifiers include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene ether, polyoxyalkylene oleate ester, and polyoxyalkylene lauryl. Acid ester, phosphate oleate ester, substituted oxazoline, and phosphoric acid ester are blended, and glass microballoons are blended as a bubble retaining agent to produce approximately 1.2
Made with a leaf diameter of 5 inches (31.8 fim)? Gara 18~
It is stated that after 24 hours, it will be completely detonated with a No. 6 detonator to a maximum tentative specific gravity of 1.25 (medicinal water 21.1°C to 26.7°C).

Also, according to U.S. Patent No. 4,149,917,
As an emulsifier, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene (4) lauryl ether, polyoxyethylene (2) ether, polyoxyethylene (2) stearyl ether, polyoxyalkylene oleate, By blending polyoxyalkylene lauryl ester, phosphoric oleate, substituted oxazoline, phosphoric ester, and mixtures thereof, the tentative specific gravity is 0.95 due to microbubbles without containing a bubble-retaining substance.
θ11 was adjusted to
1.1'c), it is stated that even after s months, a complete detonation occurs with a No. 8 detonator (temperature: 21.1°C).

Also, Japanese Patent Application Laid-open No. 55-75993, 55-7599Φ
According to Japanese Patent Publication No. 55-75995, W1 containing an imidacillin derivative, a mercaptan, and an oxyethylene oxypropylene block copolymer as an emulsifier
The type 0 emulsion explosive composition also showed a temperature of -10° even after 80 temperature cycles (one cycle of 4 hours at 0°C and 7 hours at 40°C) without adding a desensitizing substance or an auxiliary desensitizing substance. A complete explosion occurred with a No. 6 detonator at temperatures between -20°C.

However, the W10 type emulsion explosive composition using the emulsifier described in the above-mentioned U.S. special consideration specification and W's publication at the time of publication,
A temperature cycle test (2Φ hours at 60°C and a 24-hour cycle at -15°C) conducted by the inventors at room temperature (10°C to 80°C) that well reflects the passage of time (No. 8 detonator at -5°C) (1 cycle corresponds to approximately 1 month of aging at room temperature), it is 6 to 26 cycles (6 to 26 months), and is stable over time. Considering the usage situation in Japan. There were some things that I was satisfied with. However, W10 type emulsion explosives are inherently thermodynamically unstable, so they are destroyed by many factors other than time, and the detonation sensitivity decreases as the degree of detonation deteriorates, eventually resulting in a thunderbolt. Among these, the most problematic phenomenon is the drying phenomenon (generally called the dead pressure phenomenon) caused by the destruction of the emulsion form due to the action of bombardment waves and combustion gas from adjacent holes. be. In that sense, the temperature cycle test mentioned above
26 cycles (6 to 26 months) is still insufficient considering the stability of the W10 type emulsion's morphology and the drying phenomenon (primary pressure phenomenon).
5 fin diameter) and stability over time of detonation sensitivity at low temperature and W10
A mold emulsion with strong resistance to dead pressure was desired.

As a result of intensive research over a long period of time while taking into account the above-mentioned problems, the present inventors have found that a W10 type emulsion desiccant composition obtained by using a new specific emulsifier has a small diameter and a low temperature. It has been found that this emulsifier has better performance than conventionally known emulsifiers in terms of stability over time of detonation sensitivity and resistance to dead pressure, and the present invention has been completed.

That is, the W10 type emulsion explosive composition of the present invention contains ammonium nitrate or ammonium nitrate and other inorganic N oxide.
In a water-in-water emulsion explosive composition consisting of a dispersed phase of an oxidizing agent aqueous solution consisting of % In and water, a continuous phase of combustible material consisting of fuel oil and/or waxes, an emulsifier and microscopic hollow spheres or microbubbles, an emulsifier or This is a 1 tll water-in-water type dried mulberry composition characterized by containing maltitol fatty acid ester and/or polyoxyalkylene maltitol fatty acid ester.

The aqueous oxidizing agent solution of the W10 type emulsion explosive composition of the present invention contains ammonium nitrate as a main component and optionally contains other oxidized acid salts. Here, other inorganic oxide salts include, for example, alkaline salts such as fi)'1tn sodium and calcium nitrate, or nitrates of alkaline earth metals. In addition, auxiliary mirror-sensitizing substances such as alkali metal or alkaline earth metal persalt cumulative salts and chlorates, or desensitizing substances such as monomethylamine nitrate, are not essential components in terms of stability over time of detonation sensitivity and dead pressure resistance. There is no such thing, but it is not safe to mix it. 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 46% to 94.69% (by weight, hereinafter the same) of the total amount, and if necessary, other inorganic oxide salts may be added to 40% or less of the total amount of inorganic oxide salts including ammonium nitrate. It may also be included.

If the amount of ammonium nitrate is less than the lower limit, the oxygen balance (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 low gas. If the upper limit is exceeded, the minimum dissolution temperature of ammonium nitrate in water becomes too high, resulting in poor articulation, and the explosive reactivity of ammonium nitrate becomes poor, resulting in poor detonation sensitivity.

Regarding the other non-oxidized acid salts mentioned above, by adding them in small amounts, the oxygen supply can be increased and the minimum dissolution temperature in water can be lowered, so that the pk development and cleavage properties can be improved. If it exceeds %, the amount of solid residue after the explosion will increase, resulting in a decrease in power and a disadvantage in terms of economics.

In addition, as a general rule, the water used for the oxidizing agent aqueous solution is 5% to 2%
It is 5%.

If it is less than 5%, the minimum melting temperature of ammonium Iil'fate or ammonium monosulfate and other inorganic oxide salts will become too high, resulting in poor control performance and poor detonation sensitivity due to poor explosive reactivity. .

If it exceeds 25%, I+fQ (lfl) The minimum melting temperature of ammonium or ammonium nitrate and other inorganic oxide salts will decrease, so the productivity will be improved, but the amount of gas produced after the explosion and the amount of heat will decrease, resulting in detonation. Poor sensitivity and low power.

Fuel oils and/or waxes are hydrocarbons, such as paraffinic hydrocarbons, olefinic hydrocarbons, naphthenic hydrocarbons, aromatic hydrocarbons, saturated or unsaturated hydrocarbons, petroleum, refined mineral oil, lubricants. , liquid paraffin, etc., and hydrocarbon rust conductors, such as nitrohydrocarbons. Waxes include microcrystalline wax derived from petroleum, petrolatum, paraffin wax, etc., mineral waxes such as montan wax and osichelite, animal waxes such as spermaceti wax, and insect waxes such as beeswax. be. These fuel oils and waxes are 1
Use as a seed or a mixture of two or more. The blending amount of fuel oil and/or waxes is generally 0.1% to IO%.

W1 if fuel oil and/or waxes are less than 0.1%
The stability of the type 0 emulsion explosive composition is poor, and if it exceeds 10%, the oxygen balance becomes too poor, resulting in poor explosiveness and aftergassing.

Maltitol fatty acid ester and polyoxyalkylene maltitol fatty acid ester, which are new specific emulsifiers that can be used in the W10 type emulsion desiccant composition of the present invention, are, for example, maltitol or polyoxyalkylene maltitol and fatty acid chloride. The reaction to,
It is a compound that can be converted into aa by a dehydration reaction between maltitol or polyoxyalkylene maltitol and a fatty acid, and is represented by the following general formula. ) ester, maltitol oleic monoacid (mono, diotri, tetra, penta, hexa) ester, maltitol isostearic acid (mono.

diotri, tetra, penta, hexa) ester, maltitol linoleic acid (mono, diotri, tetra, penta,
hexa) ester, maltitol erucic acid (mono, diotri, tetra, penta, hexa) ester, maltitol erucic acid (mono.

Diotri, tetra, penta, hexa) esters and the like can be mentioned.

X = ROO- or H(R'O)m-Y = H(R
'O)m- R”CnH2n+110nH2n-110nH2n-8
1CnH2n-1i (n-'~24)R'=-OH2
0H2- or -0H-OH, -H8 m-o ~ 20 These new specific emulsifiers are used alone or as a mixture of two or more. The amount of emulsifier added is generally 0.1%.
~7%. Preferably it is 0.5% to 4%.

If these various emulsifiers are less than 0.1%, the W10 type emulsion explosive composition will have poor detonation sensitivity, stability over time and dead pressure resistance at small diameters and low temperatures, and if it exceeds 7%, the oxygen balance will be poor and no light will be produced. The speed and speed become arbitrary, and it is also disadvantageous in terms of economy.

Further, the W10 type emulsion explosive composition of the present invention has its temporary specific gravity adjusted to 0.80 to 1.35 (preferably 1.00 to 1.20) by using a temporary specific gravity adjuster.

The tentative specific gravity is a micro hollow sphere or micro bubble, and a hollow sphere is, for example, glass, alumina, shale, whitebait, silica sand, volcanic rock, sodium silicate, borax, nacre, obsidian, etc. There are inorganic fiber-covered small hollow spheres obtained from carbon TIj-based micro hollow spheres obtained from pitch, coal, etc., synthetic resin-based micro hollow spheres obtained from phenolic resin, polyvinylidene poly(4M), epoxy resin, urea resin, etc. These microscopic hollow spheres may be used alone or as a mixture of two or more. The amount of micro hollow spheres is generally 0.
．． It is 1% to 10%. Microbubbles are microbubbles obtained by foaming, for example, containing a chemical foaming agent, or W1
These are microbubbles etc. obtained by mechanically blowing air or other gas during or after forming the type 0 emulsion. 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. Chemical blowing agent formulation 1. ↓ is generally 0.0
It is 1% to 2%.

Therefore, regarding the temporary specific gravity adjuster, less than 0.1% of micro hollow spheres or less than 0.01% of chemical foaming agent or W1
If the amount of air or other gas is such that the tentative specific gravity of the Type 0 emulsion explosive composition exceeds 1.36, the detonation sensitivity will be poor and the detonation velocity will be low even in the absence of light.

If the micro hollow spheres exceed 10% or the chemical blowing agent
%, or when the amount of air or other gas is such that the tentative specific gravity of the W10 type emulsion explosive composition is less than 0.80, the detonation sensitivity is good but the detonation velocity is low and the power is small. .

The method for preparing the W10 type emulsion explosive composition of the present invention is, for example, as follows. That is, ammonium nitrate or a mixture of ammonium nitrate and other non-oxidized acid salts
An aqueous solution of the oxidizing agent dissolved in water is obtained at 0°C to 95°C. On the other hand, a mixture (hereinafter abbreviated as combustible mixture) is obtained by melt-mixing the emulsifier defined in the present invention and fuel oil and/or wax at 90°C to 95°C. Next, put the fuel mixture for massaging into a heat-insulating container with a certain volume, and gradually add the oxidizing agent aqueous solution, using the normally used propeller blade method (using a stirrer, at about 160 Or:pm). 5
Mix and stir for a minute to obtain a W10 emulsion at about 90"C. Next, add micro hollow spheres or a chemical blowing agent to the W/
o Using a vertical kneading machine for the qv emulsion, approx.
A W10 type emulsion composition is obtained by mixing at rpm. In addition, when containing microbubbles made of gas such as air instead of microbubbles caused by micro hollow spheres or chemical foaming, W10 type emulsion can be created by stirring while blowing gas such as air into the W10 type emulsion.
A type emulsion explosive composition is obtained.

Next, the W10 type emulsion explosive composition of the present invention will be specifically explained using Examples and Comparative Examples.

Note that all parts and percentages in each example are based on weight.

Example 1 A W10 type emulsion explosive composition having the composition shown in Table 1 was reduced to -0 as follows.

First, 3.81.5 parts of 61% ammonium acid (6,30
%) 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 90°C.

On the other hand, a mixture of 18.75 m (1,75%) of maltitol lauric acid sieste specified in the present invention and 17.05 parts (8,41%) of microcrystalline wax (Wax Rex 602 manufactured by Tatemobile Oil) was heated. The mixture was melted to obtain a combustible mixture at about 90°C.

Next, first put the combustible mixture in a heat-insulating container, and then gradually add the oxidizing agent aqueous solution and mix and stir for 5 minutes at about 160 Orpm using a propeller blade stirrer. A W10 type emulsion was obtained. Next, average particle size 75 μ0), f 5 Sfil small hollow spheres (8
15/250 (manufactured by 3M) 14.60 copies (2,92%)
was mixed with the W10 emulsion described above using a vertical kneading machine at about 8 Orpm to obtain a W10 emulsion desiccant composition. This W10 type emulsion desiccant composition was molded to have a diameter of 25 mm, a thickness of approximately 170 mm, and a weight of 100 g, and was subjected to an n-eye test for each sex with a medicine package covered with viscose-treated paper. Performance tests include (a) measurement of provisional specific gravity one day after manufacturing, and (b) temperature cycle in which the sample drug package was kept at 60°C for 24 hours and then kept at -15°C for 24 hours, with this as one cycle. We conducted a forced deterioration storage test in which the detonation test was carried out using a No. 6 detonator at 15°C. ) Detonation sensitivity aging stability test estimated as the number of months of storage for complete detonation when stored unattended (estimated from the experimental confirmation that the 1-part cycle described above corresponds to approximately 1 month when stored at room temperature); (c) Temporary specific gravity measurement during the detonation test in (b) above and
o9) and 507 dynamite at a certain distance #1f111
! After completely detonating 50 g of dynamite, the test mulberry was detonated one second later, and a dead field resistance test was conducted by converting the maximum underwater pressure (kg/Cm'') for complete detonation from the minimum distance for complete detonation. The results were as shown in Table 1.

Examples 2 to 11 W10 type emulcimin (with the formulation shown in Table 1)
In the IJ composition, maltitol oleate diester, maltitol isostearate triester, maltitol linoleate tetraester, maltitol linoleate pentaester, maltitol erucate hexaester, Polyoxyethylene (4) maltitol balmitate tetraester, polyoxyethylene (6) maltitol stearate pentaester, polyoxypropylene (■
Examples 2 to 1 shown in Table 1 except that o) maltitol oleate hexaester and mixtures thereof were used.
It was produced according to Example 1 with a blending composition of 11. Sample cartridges were prepared from these W10 type 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 W10 type emulsion desiccant composition having the formulation shown in Table 1 was prepared by using N in place of the glass imitation small hollow spheres in Example 1.
, N'-dinitrosopentamethylenetetramine was used in accordance with Example 1. A sample cartridge was prepared from this W10 type emulsion explosive composition in the same manner as described in Example 1, and the sample cartridge was held at an angle of about 50°.
A chemical blowing agent (N
, N'-dinitrosopentamethylenetetramine) was decomposed and foamed to adjust the tentative specific gravity, and the same performance tests as in Example 1 were conducted.

Example 18 A W10 type emulsion Takuwa composition having the formulation shown in Table 1 was produced by the following method. That is, first, a W10 type emulsion was obtained according to Example 1. Next, air was blown into the W10 emulsion through a thin nozzle and heated to about 160 O using a propeller blade stirrer.
Mixing and stirring was carried out at rpm for 2 minutes to introduce microbubbles of air, thereby obtaining a W10 type emulsion explosive composition having the desired tentative specific gravity.

Sample cartridges were prepared from this W10 type 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.

Comparative Examples 1 to 11 W with a formulation using a known emulsifier as shown in Table 2
A Type 10 emulsion explosive composition was prepared according to Example 1. Example 1 This W10 type emulsion Bakumou composition
A sample medicine package was prepared using the same method as described in 2013, and performance tests were conducted on the same items. The results were as shown in Table 2.

Comparative Examples 12 to 18 W with a formulation using a known emulsifier as shown in Table 2
A Type 10 emulsion explosive composition was loaded according to Examples 12 and 18. A sample cartridge was prepared from this W10 type 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.

As the emulsifier defined in the present invention, maltitol monolauric acid monoester, maltitol oleic acid diester, maltitol isostearic acid triester, maltitol linoleic acid tetraester, maltitol lylunic acid pentaester, maltitol erucic acid hexaester, W10 type blended with polyoxyethylene (Φ) maltitol palmitate tetraester, polyoxyethylene (6) maltitol stearate pentaester, polyoxypropylene (4o) maltitol oleate hexaester, and a mixture of these. In the case of the emulsion kettle compositions (Examples 1 to 9), the storage period for complete explosion at -6°C using a No. 6 detonator is 86 months to 39 months, and the maximum pressure for complete explosion is 105 kg/cm2. ~124kg
It was 70m2. On the other hand, W10 containing a known emulsifier
In the case of type emulsion explosive compositions (Comparative Examples 1 to 10), the storage time for complete detonation at -5°C using a No. 6 detonator is 6 to 6 months.
26 months and the maximum pressure for complete explosion is 40 kg7Cm2~7
5 kg/cm".

In addition, sodium nitrate and calcium nitrate are used as inorganic oxide salts other than ammonium nitrate, liquid paraffin is used as an additive, silica micro hollow spheres (Silica Balloon NLi manufactured by Kushiro Coal Dry Distillation) are used as a bubble retaining agent, and polyoxyethylene (6) is used as an emulsifier. In the case of the W10 type emulsion Takuwa composition (Comparative Example 11) containing 2.50% sorbitol oleate tetraester, a No. 6 detonator was used to
The storage period for complete detonation at °C was 28 months, and the maximum pressure for complete detonation was 97 kg/cm. The W10 type emulsion explosive composition (Example 10) had a power of 41 months and a maximum pressure of 19
It was 2 kg/cm2. Further, as emulsifiers specified in the present invention, maltitol oleate diester and maltitol lylphate pentaester are each 0.8%, and polyoxyethylene (6) maltitol stearate pentaester is 0.9%. The blended W10 type emulsion explosive composition (Example 11) had a power of 40 months and a maximum pressure of 170 kg7Cm.The bubble retaining agent was added as a chemical blowing agent during the compounding process, such as N, N' - 0.2% dinitrosopentamethylenetetramine was added to adjust the tentative specific gravity, and polyoxyethylene (
6) Sorbitol oleate tetraester 1.80
% W10 emulsion explosive composition (Comparative Example 1)
In the case of 2), the storage period for complete detonation at -5°C using a No. 6 detonator is 9 months, and the maximum detonation pressure G; i 88 k
g/cm” but polyoxyethylene> (6) Unexploded QI instead of sorbitol oleate tetraester
Maltitol oleate diester defined by J
．． 8 (W10 type emulsion explosive composition containing 1% (
In Example 12), the force is 81, and the maximum pressure for complete explosion is 7.
9/Cm”.

In addition, a W10 type emulsion was prepared in which the tentative specific gravity was adjusted by mechanically introducing microbubbles without adding a bubble retaining agent, and 1.8% of polyoxyethylene (6) sorbitol tetraf oleate, f# was added as an emulsifier. In the case of the SM composition (Comparative Example 13), the storage time for complete detonation at -5°C using a No. 6 detonator is 8 months, and the maximum pressure for complete detonation is 88~/
cm2, but polyoxy, ethylene (61) W10 type emulsion explosive composition (Example 18) containing 1.8% maltitol oleate diester as an emulsifier defined in the present invention instead of sorbitol oleate tetraester. It is 82 months and what is the maximum pressure for complete explosion?
, Okg, Am”.

As described above based on each Example and each Comparative Example, the maltitol fatty acid ester and/or
The W10 type emulsion explosive composition, which does not contain an emulsifier such as a polyoxyalkylene maltitol fatty acid ester, has a smaller diameter (g5 mm diameter) and lower temperature than the W10 type emulsion explosive composition which contains a conventional known emulsifier. The stability of detonation sensitivity over time and resistance to dead pressure have been significantly improved.

Claims (1)

[Scope of Claims] L A dispersed phase of an oxidizing agent aqueous solution consisting of ammonium Il'l acid or ammonium ra acid, another inorganic oxidizing acid salt, and water, a continuous phase of a combustible material consisting of fuel oil and/or waxes, A water-in-oil emulsion desiccant composition comprising an emulsifier and microscopic hollow spheres or microbubbles, wherein the emulsifier is a maltitol fatty acid ester or a polyoxyalkylene maltitol fatty acid ester. explosive composition. 2. The water-in-oil emulsion explosive composition according to claim 1, wherein the proportion of the emulsifier is 0.1 to 7% by weight based on the total amount of the water-in-oil emulsion desiccant composition.