JPS6136189A - Aqueous 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 <Industrial Application Field> The present invention relates to a hydrous explosive composition with improved resistance to original pressure from room temperature to low temperature.

<Prior art> Unlike dynamite, hydrous explosives do not contain desiccating sensitizers such as nitroglycerin, and the best way to increase and maintain detonation sensitivity is to use foaming agents and surfactants. It is being For example, examples of using a foaming agent include a method using micro inorganic hollow bodies as in Japanese Patent Publication No. 45-25798, Japanese Patent Application Laid-open No. 54-92612, U.S. Pat.
773,573, a method using minute resin hollow spheres is used, and examples of using a surfactant include Japanese Patent Publication No. 45-34957 and Japanese Patent Application Laid-open No. 55-10.
413, Japanese Patent Publication No. 58-11400, and the like.

<Problems to be Solved by the Invention> However, although these hydrous explosives do not pose any particular problems when used for normal blasting, they do not cause any problems when used in stage blasting such as tunnel blasting in soft rock. Of course, it is difficult to prevent the generation of source pressure even at room temperature, which remains one of the remaining problems for hydrous explosives.

Although different from water-containing explosives, in the case of emulsion explosives, an example of the use of a mixture of minute inorganic hollow bodies, minute resin hollow spheres, and a surfactant is described as in JP-A-56-109890. However, the combined use of minute inorganic hollow bodies and minute resin hollow spheres in emulsion explosives is only introduced as an example of providing the effect as a sensitizer, just like when each is used alone. Also, the surfactant is W10
It provides a function as an emulsifier necessary for emulsification of a type emulsion, and the effect seen in the present invention is not described.

<Means for solving the problems> The present invention focuses on the original pressure resistance of hydrous explosives, which has been considered difficult to improve than conventional methods, and provides stable original pressure resistance even at room temperature to low temperature (approximately -5°C). As a result of various studies on hydrous explosives, the present invention was completed.

That is, the present invention provides inorganic oxide salts mainly composed of ammonium nitrate.
70% by weight, 15 to 40% by weight of a sensitizer mainly composed of organic nitrates and/or inorganic nitrates, 5 to 20% by weight of water, 0.5 to 6% by weight of gelling agent, and minute inorganic hollow bodies. 2-8
% by weight, 0.05 to 0.5 weight % of micro resin hollow spheres, and 0.05 to 0.05 weight % of a surfactant.

Inorganic oxide salts used in the present invention include alkali metal nitrates such as sodium nitrate and potassium nitrate; alkaline earth metal nitrates such as calcium nitrate and nororium nitrate; sodium chlorate, potassium chlorate, etc. Alkali metal chlorates; perchloric acid) Alkali metal perchlorates such as IJum and potassium perchlorate and ammonium perchlorate can be used alone or in combination as an auxiliary oxidizing agent. The amount of the auxiliary oxidizing agent added is 50% by weight or less based on the total inorganic oxidizing acid salt.

In the present invention, the inorganic oxide salt is 30 to 70% of the total composition.
Weight percentages are used. In other words, if it is less than 30% by weight, the oxygen flux becomes significantly negative, causing problems with the aftergas, and if it exceeds 7% by weight, there will be an excess of solid components in the explosive component, resulting in resistance to original pressure at low temperatures of -6~. It becomes difficult to secure

The sensitizing agent used in the present invention is mainly composed of organic nitrates and/or inorganic nitrates, and other sensitizing agents may be supplementarily used in combination. Organic nitrates include nitrates of saturated aliphatic amines having up to 3 carbon atoms, ethanolamine nitrate, urea nitrate, guanidine nitrate, ethylenediamine dinitrate, etc. Inorganic nitrates include hydrazine nitrate, hypradiine dinitrate, perchlorine. Examples include acid hydrazine, which can be used alone or in combination of two or more.

Among these, monomethylamine nitrate, ethanolamine nitrate, hyfurazine nitrate, etc. are particularly preferred because they allow easy preparation of explosives and provide resistance to original pressure at low temperatures.

In addition, as an auxiliary sensitizing agent, one normally used for hydrous explosives may be used. For example, when paint-grade aluminum powder is used as an auxiliary sensitizing agent, the original pressure resistance at low temperatures can be stably obtained. Low-temperature detonation sensitivity and naked detonation speed are further improved. Paint grade aluminum powder is 0
．． It is used in a proportion of 5 to 5% by weight. That is, 0.5
If it is less than 5% by weight, the effect is not achieved, and if it exceeds 5% by weight, manufacturing stability becomes a problem.

In the present invention, the sensitizer is 15 to 40% by weight based on the total composition.
used. That is, if it is less than 15% by weight, even the original pressure resistance at room temperature cannot be obtained, and if it exceeds 40% by weight, the oxygen flux becomes significantly negative, causing problems with the after-gas after blasting. Preferably, monomethylamine nitrate and/or ethanolamine nitrate and paint grade aluminum powder are used together as a sensitizing agent, with the former being 15 to 30% by weight and the latter 0.5 to 4% by weight.

The water used in the present invention is 5 to 20% by weight based on the total composition. If it is less than 5% by weight, the solid content is high and the liquid phase component necessary for detonation is insufficient, and if it exceeds 20% by weight, there is insufficient energy to destroy the rock. Preferably 8
~15% by weight is desirable.

The gelling agent of the present invention includes natural guar gum, hydroxyethyl- or hydroxyzolobil-modified guar gum, oxidized gum, hydrolyzed gum, low-molecular guar gum, natural starch, modified starch, crosslinked starch, etc. alone or in combination. . Furthermore, boron oxide, antimony oxalate, potassium pyroantimonate, etc. can be mentioned as a component for carrying out a crosslinking reaction with the above-mentioned gelling agent component. In the present invention, organic nitrates and/or inorganic nitrates are used as sensitizing agents, and are easy to manufacture due to the manufacturing process of hydrous explosives.
In order to provide storage stability, it is desirable to use guar gums, crosslinked starch, and a crosslinking agent, or to use hydroethyl- or hydroxypropyl-modified guar gum and a crosslinking agent together.

In the present invention, the gelling agent is 0.5-6% by weight and 0.5-6% by weight.
If it is less than 5% by weight, the hydrous explosive composition will separate, and I
If it exceeds f-a weight %, it will be difficult to manufacture.

Preferably, the amount is preferably 0.9 to 4% by weight based on the total components.

In the present invention, a combination of a micro inorganic hollow body and a micro resin hollow body is used. In other words, materials that contain something that is relatively strong under hydrostatic pressure, such as minute inorganic hollow bodies, exhibit pressure resistance against static pressure (for example, pressure applied underwater) and are used as underwater explosives. However, it shows almost no resistance to the original pressure against dynamic pressure (impact pressure from adjacent blast holes) such as stage blasting in tunnel construction, and microscopic resin hollow spheres do not. It also cannot withstand static and dynamic pressures. The present inventors focused on the fact that a part of the micro inorganic hollow bodies contained in the hydrous explosive that was subjected to dynamic pressure remained unbroken, and found that if there were bubbles that further increased the detonation sensitivity, it would be possible to resist the original pressure. thought it could be improved. Therefore, it is considered that the original pressure resistance was improved only by adding fine resin hollow bodies that are highly elastic and have a particle size suitable for a HotSpot.

The fine inorganic hollow bodies can be obtained from, for example, glass, shirasu, alumina, silica sand, sodium silicate, volcanic rock, nacre, obsidian, etc., and a range of 5 to 200 microns is usually sufficient. Preferably, iJ is in the range of 5 to 150 microns because it provides not only resistance to original pressure but also high detonation speed. or.

Since micro inorganic hollow bodies are generally expensive, = 10
- Shirasunonorune (for example, Hi commercially available from Idechi Kasei Co. under the trade name Winlight MOB-5011, 5021) is particularly desirable as it is economical and easily available.

On the other hand, the micro resin hollow body is a hollow sphere made of thermosetting resin or thermoplastic resin. Examples of the thermosetting resin include phenol resin, epoxy resin, urea resin, etc.; Examples include vinylidene chloride polymers such as polyvinylidene chloride, vinylidene chloride-acrylonitrile copolymer, and vinylidene chloride-methyl methacrylate copolymer; vinyl polymers such as polystyrene, polymethyl methacrylate, and polyvinyl chloride. The particle size is preferably in the range of 5 to 150 microns for the same reason as the micro inorganic hollow bodies. In addition, when using micro resin hollow spheres made of thermoplastic resin containing low boiling point hydrocarbons (for example, commercially available from Kemanord under the trade name Expancel), other micro resin hollow spheres may be used. In comparison, it has excellent resistance to original pressure, especially at low temperatures, and can also achieve high detonation speed at the same time.

In the case of micro inorganic hollow bodies, the amount of the blowing agent of the present invention added is the same as that normally added to hydrous explosives, which is 2 to 8 times the total composition. If it is less than 2% by weight, the resistance to original pressure at room temperature will be reduced rather than at low temperatures, and if it exceeds 8% by weight, the resistance to original pressure at low temperature will be reduced. On the other hand, the fine resin hollow spheres are used in an amount of 0.05 to 0.5% by weight based on the total composition. That is, if the weight ratio is less than 0.05, there is no significant difference from the case without the addition, and if it exceeds 0.5% by weight, the original pressure resistance at low temperatures is significantly reduced. Most preferably 3-6
When using micro resin hollow spheres made of thermoplastic resin containing micro inorganic hollow bodies of 0.1 to 0.4% by weight of low boiling point hydrocarbons, it provides resistance to original pressure down to the lowest temperature range. be.

The surfactant of the present invention may be one that is generally used in hydrous explosives, such as alkali metal salts of aliphatic alcohol sulfate esters (in particular, aliphatic alcohols having 8 to 14 carbon atoms), alkylvirdinium salts, Examples include Halai P (alkyl group has 8 to 24 carbon atoms), phosphoric acid esters, and the like.

Among them, phosphoric acid esters having the general formula (for example, Prysurf Jin 219B manufactured by Dai-ichi Kogyo Co., Ltd.) provide excellent resistance to original pressure at low temperatures and maintain this performance over a long period of time.

This is particularly preferable because it allows

The surfactant of the present invention is 0.05 to 0.0% based on the total composition.
5% by weight is used. In other words, if it is less than 0.05% by weight, there is no significant difference from the case without additives (if it exceeds 0.5% by weight,
When paint-grade aluminum powder is used, air bubbles adhering to the surface of the aluminum powder may be removed and the original pressure resistance at low temperatures may be lost. Preferably 0
．． It is preferable to use 1 to 0.3 gravity'X.

13- In the present invention, in addition to the above components, atomized aluminum powder, coal powder,
Giltonite powder, tire powder, sulfur powder, etc. can be added as necessary.

The method for producing the hydrous explosive composition of the present invention is no different from conventional methods. For example, a solution in which specified amounts of monomethylamine nitrate, water, and ammonium nitrate are mixed is heated to 30°C, then specified amounts of guar gum, sodium nitrate, and a blowing agent are added, and then specified amounts of paint-grade aluminum powder and crosslinking are added. This method involves uniformly mixing the ingredients.

<Effects> The hydrous explosive composition obtained according to the present invention was able to reduce the source pressure problem that tends to occur particularly at blasting sites in winter to the same level as conventional dynamite. Moreover, its performance is guaranteed for at least six months. Furthermore, it was found that compared to conventional hydrous explosives, it has a higher detonation velocity and less decrease in detonation velocity due to specific gravity.

<Example> Examples are shown below. As a method for evaluating the original pressure resistance of the present invention, the following dead pressure test in sand was conducted.

[Sand medium pressure test method]

(Dig a hole 80m deep in a mountain of sand) Attach an instantaneous electric detonator and a 10m5 electric detonator to each pre-temperature-controlled explosive package (30 charges, 1001 i'),
Explosive packages are buried parallel to m-spaces and ignited at the same time, and tested five times to see if the explosive packages equipped with XOMS electric detonators explode. In addition, in this test method, the distance between drug packages is 15 crn.
When , source pressure is most likely to occur, and 2 and 4 with dynamite at the end.
15-515 (The molecule shows its resistance to original pressure by the number of times it detonates)
It is.

Example 1 A mixed solution of 42% by weight of ammonium nitrate and 40% by weight of an aqueous monomethylamine nitrate solution (of which 15% by weight was water) was heated to 30°C, and then a blowing agent of 42% by weight of ammonium nitrate and 40% by weight of an aqueous solution of monomethylamine nitrate (of which water was 15% by weight) was added to Class/N Rune (Ijichi Kasei Co., Ltd. 5Mn-5011). ) 3.5% by weight, micro resin hollow spheres (Kemanode, Expancel 551
DE) 0.2% by weight, 1.0% by weight of hydroxypropyl-modified guar gum and 13% by weight of sodium nitrate were mixed for about 2 minutes.
Pricesurf A219B) 0.2 parts by weight, 2% by weight of cross-linked starch, 2% by weight of paint-grade aluminum powder, cross-linking agent (1 part by weight of potassium pyroantimonate for guano! muni)
%) and mixed uniformly for about 2 minutes to obtain a hydrous explosive composition.

Examples 2-8 Compositions according to the invention, summarized in Table-1, were prepared in the same manner as in Example 1.

Comparative Examples 1 and 2 As shown in Table 2, a composition using only a blowing agent was prepared in the same manner as in Example 1.

Comparative Example 3 As shown in Table 2, a composition was prepared in the same manner as in Example 1, including an excess of fine resin hollow bodies.

Comparative Examples 4 and 5 As shown in Table 2, a composition containing no surfactant was prepared in the same manner as in Example 1.

Reference example A W10 type emulsion explosive was prepared as follows.

First, 65.5% by weight of ammonium nitrate and 111% by weight of sodium nitrate were added to 13% by weight of water and heated to obtain an oxidizing agent aqueous solution at about 90°C. On the other hand, 2.5% by weight of flupitan monooleate was added to 3.5% by weight of microcrystalline wax (trade name, Wax Rex 602, Mopil Oil Co., Ltd.), and the mixture was heated and melted to form a combustible mixture at about 90°C. Obtained.

Next, first put the combustible mixture in a heat-retainable melter, and then gradually pour in the oxidizing agent solution while stirring.
A W10 type emulsion was obtained.

Next, 3.5% by weight of Glass Micro Norune (trade name, Glass Nople B 28/750.3M Company) and 1 part of a micro resin hollow body (trade name, Expancel, Kemano P Company) were added.
Add % by weight and mix uniformly to obtain emulsion explosive.

Regarding the compositions of Examples 1 to 8, Comparative Examples 1 to 5, and Reference Example, dead pressure test in sand and naked detonation speed were measured immediately after production and 6 months later, and the results are listed in Table 3.

Margin below

Claims (1)

[Claims] 1. 30 to 70% by weight of an inorganic oxide salt mainly composed of ammonium nitrate;
Sensitizer 1 mainly composed of organic nitrates and/or inorganic nitrates
5-40% by weight, water 5-20% by weight, gelling agent 0.5-40% by weight
6% by weight, micro inorganic hollow bodies 2-8% by weight, microscopic resin hollow spheres 0.05-0.5% by weight, surfactant 0.05-0
．． Hydrous explosive composition 2 characterized in that it contains 5% by weight of the inorganic oxidized acid salt mainly composed of ammonium nitrate, Claim 1 characterized in that it contains 40 to 60% by weight. The hydrous explosive composition 3 described above is characterized in that the sensitizer is a combination of 15 to 30% by weight of monomethylamine nitrate and/or ethanolamine nitrate and 0.5 to 4% by weight of paint grade aluminum powder. A hydrous explosive composition 4 according to claim 1, a hydrous explosive composition 5 according to claim 1, characterized in that water is 8 to 15% by weight, a gelling agent is 0. .9 to 4% by weight of the hydrous explosive composition 6 according to claim 1, and the content of the micro inorganic hollow bodies is 3 to 6% by weight. Hydrous explosive composition 7 according to claim 1, characterized in that the minute resin hollow spheres are 0.1 to 0.4% by weight Hydrous explosive composition 8 according to claim 1, surface active The hydrous explosive composition 9 according to claim 1, characterized in that the amount of the agent is 0.1 to 0.3% by weight, and the minute resin hollow spheres are made of a thermoplastic resin containing a low-boiling hydrocarbon. The hydrous explosive composition 10 according to claim 1, wherein the hydrous explosive composition 10 is a micro hollow body consisting of a phosphoric acid ester and has a particle size in the range of 5 to 150 microns. 40 to 60% by weight of the inorganic oxide salt mainly composed of ammonium nitrate, monomethylamine nitrate and/or ethanolamine nitrate as a sensitizer; A combination of 15-30% by weight and 0.5-4% by weight of paint grade aluminum powder, 8-15% by weight of water, 0.9-4% by weight of gelling agent, 3-6 micro inorganic hollow bodies.
% by weight, 0.1 to 0.4% by weight of micro resin hollow bodies made of thermoplastic resin containing low-boiling hydrocarbons, and the general formula is ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ n: Number of moles of ethylene oxide group added A, B: Hydrogen or R-O-(CH_2CH_2O)_n
The hydrous explosive composition according to claim 1, characterized in that R: contains 0.1 to 0.3% by weight of a phosphate ester, which is an alkyl group.