TW200301236A - Explosive agent - Google Patents

Abstract

This invention proposes a water drip in oil type emulsion explosive, containing an ethylene vinyl acetate copolymer. The explosive agent exhibits an excellent stability over a long line span, such that a long time storage of one year under load will not lead to a deterioration of explosive performance or hardening of the agent, except a partial hardening that can be relieved easily, and the explosive agent can be loaded with a loading machine. The explosive agent also exhibits an excellent resistance to water and can be used for blasting in water.

Description

200301236 V. Description of the invention (l) [Technical field to which the invention belongs] The present invention relates to explosives. Further details are related to dripping emulsion explosives in oil used in industrial explosive operations such as tunnel digging, quarrying and mining. [Previous Technology] Industrial explosives used in explosive operations and the like are known as dynamite, water-containing explosives, ammonium nitrate explosives, ammonium nitrate fuel explosives (hereinafter referred to as ANFO (Ammonium Nitrate Fuel Oil) explosives), and the like. The water-containing explosives in the above-mentioned explosives are widely used as industrial explosives because they do not contain gunpowder components and are safer than traditionally used dana explosives. Such aqueous explosives can be largely divided into two types: slurry (s 1 u r r y) explosives and emulsified (e m u 1 s i ο η) explosives. Among them, emulsified explosives have the characteristics of excellent moldability and weather resistance. And this type of emulsified explosive is a drop-type emulsified explosive in oil, which has been improved after being published in U.S. Pat. Nos. 3, 16 1 and 5 51. At present, there are products that are superior to traditional explosives in water resistance and safety. . On the other hand, from the point of view of simplification of explosive charging operation or ensuring safety of explosives during operation and use at the opening site, mechanization of explosive charging operations has been urgently expected. In order to carry out the mechanical filling operation of explosives, the explosives used must be safer. The method of loading ANF0 explosives by mechanical means such as a loader has been put into practical use in mines or quarries. However, compared with the drop-type emulsion explosives in oil, after the explosion, A N F 0 explosives must be equipped with sufficient exhaust devices due to the residual gas components. In addition, if there is water in the blasting hole, A N F 0 explosive is dissolved in water, so that the explosive performance cannot reach the predetermined one, which causes trouble in use. Therefore, it is used for blasting holes with water or

314281.ptd Page 5 I. Description of the invention (2) Sometimes when the water outlet is complicated, it is necessary to take complicated methods, for example, removing the water in the blast hole before inserting it into the polyethylene pipe, and then filling the polyethylene pipe with ANFO. Explosives. In addition, regarding water droplet emulsion explosives in oil, as described in the "Effective Tunnel Technology Review Report" issued by the Japan Tunnel Technology Association, mohno-pumps driven by air will be called It is a batch of emulsified (bu 1 k emu 1 si on) explosive oil-type emulsion explosives in oil directly filled directly into the openings. The method known as a batch of emulsion explosive systems has been put into practice. However, because the batch (bu 1 k) emulsion explosive system uses a high viscosity oil-type drop emulsion emulsion, the cleaning operation after the charging operation or the management of residual explosives may be complicated, which may lead to high prices. In addition, in order to ensure safety when filling emulsion explosives, expensive filling machines must be used. Because of this, it is expected that it can be filled with relatively simple machinery such as an air loader, and can also be used for explosives with high water blast holes and high safety explosives. A method for solving the above problems is, for example, the development of a water-drop type emulsion explosive in granules or granular oils described in JP-A No. 7-2 2 3 8 8 8 or JP 1-2-7 8 9 7 5 etc. processing. However, the method described in the above publication for granulating or granulating a water-drop type emulsion explosive in oil is to crystallize Θ by an aqueous solution of an inorganic oxidant in the emulsion, and then granulate the emulsion structure. It is generally known that "the oxidant aqueous solution of the drop-type emulsion explosive in oil is crystallized", and the crystallization part of the emulsion begins to disintegrate. As a result, the sensitivity or performance of the explosive cannot be maintained. It is well known that even in this state, as long as the on-site mixing method is used, Or similar, because it ’s made from explosives

314281.ptd Page 6 V. Description of the Invention (3) There is only a short period of several hours or days before use, so no major problems occur. However, the period from manufacture to use of explosives is usually several months, a little longer than half a year or even nearly a year. Therefore, droplet-type emulsion explosives in granular or granular oils are also required to prevent the oxidant aqueous solution from crystallizing and maintain stability for several months. In particular, a drop-in-oil emulsion explosive with high stability and long-term properties suitable for mechanical filling is expected. In addition, the explosives formed in the form of granules are agglomerated by the load during long-term storage or mechanical loading, resulting in the explosives not being able to be dispersed uniformly, which may cause difficulties in use. Therefore, droplet-type emulsion explosives in granular oils are also expected to be able to be stored for a long period of time, and they will not agglomerate even if they are loaded due to load during mechanical filling, and they will easily spread evenly. [Summary of the Invention] In order to solve the above problems, the inventors of the present invention, through careful research, found that all or part of the continuous phase components of the droplet-type emulsion in oil were made with ethyl acetate polymer (E thy 1 ene) V iny 1 A cetatep 1 ymer) instead of or including it in the continuous phase component, when made into a water droplet emulsion emulsion in oil, it can maintain moderate strength and solid solid explosives stable for several months to complete the present invention. That is, the present invention relates to the following explosives: (1) A water-drop type emulsion explosive in oil, characterized in that ethylene-vinyl acetate copolymer is contained in a continuous phase. (2) An emulsified explosive as described in the above item (1), characterized in that it contains 0.2 to 8% by mass of an ethylene-vinyl acetate-based copolymer. «Μ. _

Hi 111 secret 丨

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20030123G V. Description of the invention (4) (3) —A kind of oil-drop emulsion explosive in oil, which is characterized by containing oxidizing agent, oil, ethylene-vinyl acetate polymer, emulsifier and micro hollow sphere. (4) The emulsified explosive according to the above item (3), wherein the micro hollow sphere is a glass micro balloon or a resin micro balloon. (5) The emulsified explosive as described in the above item (3), wherein the proportion of the ethylene-vinegar-acid-based copolymer is 30% by mass or more of the total amount of the oil and the ethylene vinyl acetate-based copolymer. (6) The emulsified explosive according to the above item (3), wherein the melt flow rate (m e 1 t f 1 〇 w r a t e) of the ethylene-vinyl-ethylene copolymer is 10 g / 10 m i n or more. (7) The emulsified explosive according to the above item (3), wherein the number average molecular weight of the ethylene-vinyl acetate copolymer is 100 to 5000. (8) The emulsified explosive according to any one of (1) to (7) above, which is a solid. (9) The explosive as described in the above item (8), which is formed into a column shape having a diameter of 3 to 20 mm and a length of 1 to 30 mm. [Embodiment]-The following is a detailed description of the present invention. In addition, if the "Ministry" and "Lu%" appearing below are not specifically noted, the quality is used as the benchmark. The continuous phase of the water-drop type emulsion explosive in the oil of the present invention is an oil phase (fuel-phase), and usually a mixture of an oil-containing type and an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA; f-seal) is preferred. In the present invention, the oil phase of the continuous phase does not contain oil depending on the situation, and is made of EVA resin or a mixed resin with other resins.

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5. Description of the invention (5) It is also possible. EVA resin has the property of being hardened or reduced in viscosity due to heat. It is preferred that the mixture be mixed with an oxidizing agent, water, emulsifier, and small hollow spheres with an oil to be injection-molded. More specifically, the number-average molecular weight used is usually in the range of 1,000 to 600,000, and preferably about 1,000 to 50,000. The molecular weight is more than 200, and it is better to be more than loooo, and less than 400. The E V A resin used in the present invention may contain other copolymer components in addition to the ethylene vinyl acetate copolymer as the main component. When the EVA resin is a copolymer containing other copolymerization components, the ethylene-vinyl acetate copolymer is preferably 30 to 100% of the total amount of the EVA resin, more preferably 50 to 100%, and more preferably 70 To / 10 0% is even better. The most preferred is an ethylene vinyl acetate copolymer containing no other copolymerization component. If it is an ethylene-vinyl acetate copolymer, the ratio of ethylene acetate to ethyl acetate is not particularly concerned, but usually the molar ratio is based on ethyl acetate: Otome-1 · 9 to 1:15. Once the explosive content of the ethylene-vinyl acetate copolymer of the explosives is sufficient, the effect of the present invention is only required, and 0.2% to ^ w of each is better, η βο / η L It ’s better to go above $ 0.4%, more than 0.4%, and more than 1% to 6%, better than 8%, and less than 8%, and less than 4% to be a civil engineering site. * / G is better from below, The content of Ma Ran's animals varies depending on the type of vinyl acetate, pain / ± n, and the best range for the general extraction of m-items in different places is about 0.6 to 3〇 / 〇. The continuous phase of this Maoming explosive is I as a mixture of the following oil-containing fish copolymers. The resin containing 2 continuous acid phase in the continuous phase is also acceptable, but as long as it can travel +, it is only one other than the EVA resin copolymer; the effect of Mao Ming 'contains ethylene vinyl acetate-based secret fat. Other resins are lipophilic or oily

314281.ptd Page 9 200301236 V. Description of the Invention (6) Compatibility is better. The other resins include thermosetting resins, thermoplastic resins, and synthetic rubbers. Specifically, there are: vulcanized rubber, petroleum resin, phenol resin, AAS resin, ABS resin, PET resin, urea resin, melamine resin, bad oxygen resin, unsaturated polyresin resin, polyamine resin, and polyethylene Polyvinyl acetate, polyamidoamine resin, polyamidoimide resin, polyethylene resin, etc .; In order to maintain the stability of water-drop type emulsion in oil, resins that do not react with other ingredients are preferred. In addition, heat-hardening resins that are liquid or low melting point at room temperature or fluid heat / plastic resins that are fluid after heating at room temperature as solids are #. Specific examples are: phenol resin, petroleum resin, polyethylene, polypropylene, polybutene, polyisobutylene, ethylene vinyl acetate copolymer resin, polybutadiene, styrene butadiene rubber, etc., among which petroleum resin or ethylene acetic acid Ethylene copolymer resins are preferred. In addition, the above petroleum resin can be used with or without added water, for example, it can be used. An aliphatic or C 5 petroleum resin based on the C fraction in the distillation component of the decomposed oil; an aromatic or C based petroleum resin in the C fraction; or C 5C copolymerized petroleum resin etc. using both as raw materials. Among the above petroleum resins, resins that use C fractions as raw materials, such as copolymers of isoprene, isoprene, 2-methylbutene-1, and 2, and most of the conjugated diolefins have a cyclic structure. A person with the following formula is a representative example. CH3 / -CH2 — C a CH — CH2 —

HC CHCH3 ^ / CH-CH2

314281.ptd Page 10 η 2003 V. Description of the invention (7) r \ --CH2 — CH--

I ίΓ

CH

I, CH3 J n (where m and n in the formula represent the number of superimposed structures) In addition, the resin using C fraction as the raw material is copolymerized with, for example, styrene, vinyltoluene, α-methylstyrene, and indene as main components. It has the following structures as its representative examples.

(Where η is the number of repeated structures in the formula) Unless otherwise specified, the terms "oil mixture" appearing in this specification are EVA resin and oil mixture or / and EVA resin. The continuous phase of the explosive of the present invention is formed from an oil mixture. The proportion of EVA resin in the total amount of oil and EVA resin is not particularly limited as long as it can exert the effects of the present invention, but it is usually preferably 10% or more, more preferably 20% or more, and sometimes the entire mixture is EVA haw f Fat is also available. However, it is more preferable that the E V A resin accounts for 30 to 80% of the total amount of the oil mixture. When used in combination with other resins, it is better to control the content of EVA resin within the above range. The optimal content of EVA resin varies according to the molecular weight of EVA; f sealant is different, it is preferred that the content is slightly lower at high molecular weight, and that the content is slightly higher at low molecular weight.

314281.ptd Page 11 20030123 V. Description of Invention (8) " " " '~~-Potential. For example, when the number average molecular weight is more than 10,000, it is preferably 12,000 or more, more preferably 20,000 or more, and the content is preferably 60% or less of the total amount, preferably 25. To / 0% is better. The low molecular weight EVA resin having a number average molecular weight of about 2,000 to 3,000 has a content of more than 50%, more preferably about 60 to 80%. In addition, since the EVA resin is generally used in a melted state in the process of the emulsion-type emulsion explosive in oil of the present invention, it is preferable that the EVA resin melts at the manufacturing temperature. For example, when measured using the "Flow Test Method for Thermoplastic Plastics" described in j 丨 s κ 7 2 1 0, the melt flow rate is above 10 g / 10 m 丨 n. It is expected to be used at 15 g. / 10 mi η or more EVA resin. When a resin other than EVA resin is used in combination, its characteristics should be the same as those of EVA resin. The number average molecular weight of the resin can be measured by gel permeation chromatography or the like. The explosives of the present invention usually contain oils. Oils commonly used in oil-drop emulsion explosives can be used. Oils can improve the emulsification of emulsions: EVA resins together form a continuous phase. Oils are: petroleum oils such as light oil, kerosene, mineral oil, lubricating oil, and heavy oil; petroleum waxes such as paraffin and microcrystalline wax; other hydrophobic vegetable oils, vegetable waxes, animal oils, animal waxes, etc. Or mix two or more types. The content of the oil-containing oil mixture in the present invention is generally 20% ', preferably in the range of from 1% to 10%. Furthermore, one of the preferred consistent application states of the present invention is that when using a fat having a number average molecular weight of 1000 to 50000, the amount of oil mixture used is usually 0.005% or more 0.5% of the total explosive amount. More than% is better, more than 1% is better, and more than 1.5% is best. Use cap soil

V. Description of the invention (9) Often about 10%, and preferably less than 7%. The optimal use range is approximately 2 to 5%. The emulsifier used in the explosive of the present invention is an emulsifier which is usually used in oil-type emulsion explosives in oil, for example, carbons such as alkali metal stearate, ammonium stearate or calcium stearate are about 15 to Fatty acid salts of 30 (preferably alkali metal salts, alkaline earth metal salts, and ammonium salts, etc.), polyvinyl ethers, fatty acid esters, and fatty acid esters with carbons of 15 to 30 are preferred, for example: Sorbitol anhydride fatty acid ester, sorbitol fatty acid ester and the like. These emulsifiers can be used alone or in combination of two or more. The content of emulsifier accounts for more than 0.1% of the total explosive amount, 0.5% is better, and 1% is better. The upper limit is usually about 10%, 7% is better, and 5% is better. The oxidant used in the explosive of the present invention is preferably used as its aqueous solution. Examples of the oxidant include nitrate and perchlorate. Specific examples include alkali metal nitrates such as sodium nitrate, alkaline earth metal nitrates such as calcium nitrate, alkali metal chlorates such as ammonium nitrate and sodium chlorate, and alkaline earth such as calcium chlorate. Alkali earth metal perchlorates such as metal chlorate, If such as perchloric acid, If, etc. Such oxidants can be used alone or in combination. Among such oxidants, ammonium nitrate and sodium nitrate are particularly preferred. The content of the oxidant in the oxidant solution is preferably adjusted to 30 to 90 ° C according to the purpose of use. Therefore, depending on the type of oxidant, it is usually 60 to 9 5%, 70 to 93% is preferable, and 85 to 92% is more preferable. In addition, in the oxidant aqueous solution used in the present invention, water-soluble amine nitrates such as monomethylamine nitrate, monoethylamine nitrate, hydrazine nitrate, and dimethylamine dinitrate can be added as needed; methanolamine nitrate, ethanolamine nitrate, etc. Water-soluble alkanolamine nitrates and water-soluble auxiliary monosensitizers such as ethylene glycol mononitrate.

314281.ptd Page 13 200301236 V. Description of the invention (10) The oxidant aqueous solution used in the present invention can appropriately adjust the crystallization temperature at 30 to 90 ° C. The water content of the oxidant solution is usually 5 to 40% of the total amount of the water solution, preferably 7 to 30%, and most preferably 8 to 15%. In order to reduce the crystallization temperature of the oxidant aqueous solution, auxiliary solvents such as water-soluble organic solvents such as methanol, ethanol, formamide, ethylene glycol, and glycerin can be used. In the explosives of the present invention, the oxidant aqueous solution (which may also contain auxiliary solvents) is used to remove the remainder of other components, and it is preferably 60 to 97% of the total amount, and it is in the range of 80 to 95%. better. In the oil-in-water emulsified explosive of the present invention, an appropriate amount of the low-density #volume agent is preferably a fine hollow sphere, so that the sensitivity of the explosive can be adjusted within a wide range from the detonator initiation to the detonator initiation. The density of the low-density extender is usually below 0 · 8 g / cc, preferably 0.5 g / cc, and preferably below 0 · 3 g / cc; when using an organic density extender, it is 0. lg / cc or less 0,5 g / cc or less as appropriate. The low-density extender may be an inactive low-density one, and fine hollow spheres are preferred for stable explosive performance. Examples of fine hollow spheres are: one or more mixtures of inorganic hollow spheres such as glass micro balloons, white sand balloons, and organic hollow spheres such as expanded styrene and resin micro balloons; glass micro balloons or resin micro balloons are preferred And glass micro balloons are better. 8 g / cc or more, 0 · 9 g / cc or more is better, 1 g / cc or more is better; 1 · 4 g / cc or less, and even 1.3 g / cc or less is better. The ideal range of the blending amount is about 0.1 to 10%, preferably 1 to 8%, more preferably 1 to 6%,

314281.ptd Page 14 2ϋ030Π3δ 5. Description of the invention (11) The most suitable range is 2 to 5% depending on the situation. In a preferred embodiment of the present invention, when a glass microballoon is used, the 'preferred blending amount is 1% or more', as appropriate, 2% or more, 8% or less, and more preferably 5% or less. Metal powders such as aluminum powder and magnesium powder, wood powders, and organic powders such as starch can also be added to the oil-drop emulsified explosive in oil of the present invention. The content of such powders is usually in the range of 0 to 10% of the total explosive, depending on the type and purpose of addition. The explosive of the present invention is produced, for example, by the following method. That is, the aforementioned oxidant is supplemented with an auxiliary sensitizer as needed and dissolved in water at about 85 to 95 ° C to obtain an oxidant aqueous solution. In addition, oil mixture components (such as EVA resins and oils, if necessary, use resins other than EVA resins) and emulsifiers are heated and melted thoroughly to obtain oil mixtures containing emulsifiers. Next, the oil mixture is heated to about 85 to 95 ° C, and the above-mentioned oxidant aqueous solution is slowly added while thoroughly stirring to obtain a water-drop type emulsion base in oil. Then, maintaining the temperature, adding a low-density extender such as a fine hollow sphere and other additives as required, and mixing them with a kneader to obtain the water-drop type emulsion explosive in oil of the present invention. The obtained explosive can be in a fluid state or can be cooled to room temperature and then transferred to a molding machine for molding. This is the explosive of the present invention after molding. In addition, when a water-in-oil emulsion is obtained here, it is also possible to add a part of the oil mixture component when adding fine hollow spheres. For example, oils and emulsifiers are first mixed to form a water droplet emulsion in oil, and EVA resin is added when fine hollow spheres are added, or EVA ^ Ii grease is first mixed with an emulsifier to form a water droplet emulsion in oil. When adding fine hollow spheres, it is also possible to add oil; however, it is usually mixed with the oil mixture as described above.

314281.ptd Page 15 200301236 V. Description of the invention (12) * Emulsifier, water-drop type emulsion in oil containing emulsifier oil mixture is obtained. Among them, it is better to add fine hollow spheres. The water-drop type emulsion explosive in oil of the present invention obtained as described above is preferably used by molding in an appropriate shape by a conventional method. The shape of the explosive of the present invention after molding is not particularly specified, and it can be formed into any shape such as a spherical shape, a cylindrical shape, a disc shape, and a corner pillar shape by a common molding machine. However, its size is the longest in its shape. The part (length or maximum diameter of the longest side) is preferably less than 30 mm, more preferably 20 mm or less, and the shortest part (length or shortest diameter of the shortest side) is preferably 1 mm or more, and more preferably 3 mm or more. # The method for manufacturing the explosive of the present invention includes: an extruder generally used, or a pulverizer for pulverizing a water-drop type emulsion explosive in oil, and then granulating the pellet with a granulator. However, since the latter process is complicated, the extrusion molding method is preferred. Specifically, for example, the water droplet emulsion explosive in oil is extruded through an orifice plate or a curtain to shape the water droplet emulsion explosive in oil into a rod shape, and then cut into an appropriate length with a knife or a steel wire to make it columnar. Molding. If the shaped article of the explosive of the present invention is made too large, the porosity will be increased when the shaped article of explosive is filled in the explosion hole, which will cause the explosive transmission of the explosive to be reduced. Therefore, the size of the shaped article of the explosive is 3 to 20 mm in diameter, and the length is 1 to 30 mm, preferably about 5 to 1 Onn in diameter and 3 to 20 mm in length. ® The explosive of the present invention, which is formed into a cylindrical shape, can be manufactured in a simple manner to the same degree as a conventional drop-type emulsion explosive in oil. -[Examples] Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples.

314281.ptd Page 16 V. Description of the invention (13) Implementation exemption] ι will be composed of 95.0 parts by weight of ammonium nitrate, 4.8 parts by weight of sodium nitrate, and 10.6 parts by weight of water (TC oxidant aqueous solution is added Based on 1.5 parts by weight of microcrystalline wax, an ethylene vinyl acetate copolymer resin (manufactured by Mitsui DuPont Polymer Co., Ltd., trade name: EVAF LEX P- 2 8 0 7, number average molecular weight 2 0 0 0 0 to 3 0 0 0 0, melt flow rate I5g / 10min) 1.4 parts by weight, 1.4 parts by weight of sorbitol oleic acid ester, and after stirring thoroughly, a water-drop type emulsion in oil can be obtained. Then added as a fine hollow The glass micro-balloons of a sphere are mixed with 3.8 parts by weight (specific gravity: 0.25g / cc) to obtain the water-drop emulsified explosive in oil of the present invention. The water-drop emulsified explosive in oil is extruded with a mold having a diameter of 8 mm. After the machine is formed, cut with a knife into a length of 10 to obtain the explosive of the present invention. Its specific gravity is 1.1. Example 2 will be from 75.0 parts by weight of rucid acid, 4.8 parts by weight of sodium nitrate, water 1 10. 6 parts by weight of a 90 ° C oxidant aqueous solution was added to the microcrystalline butterfly containing 1.5 parts by weight, ethylene acetate Ethylene copolymer resin (manufactured by TOSOH, trade name: Ni po ilex 7 2 0, number average molecular weight 3 7 0 0 0, melt flow rate 1 50 g / 1 0 mi η) 1 · 4 parts by weight, Yamanashi 25g / cc) In a mixture of 2.9% by weight of sugar oleic acid ester, a water-emulsion emulsion in oil can be obtained by thorough stirring. Glass microballoons as fine hollow spheres are added 3.8 parts by weight (specific gravity 0.25g / cc) The water-drop type emulsion explosive in oil of the present invention is obtained after stirring and mixing. This water-drop type emulsion explosive in oil is formed by an extrusion molding machine equipped with a 8-diameter mold, and then cut into a length of 10 mm with a knife to obtain the explosive of the present invention. Its specific gravity is 1.17.

3l428l.ptd Page 17 V. Description of the invention (14) Comparative queue 1 will be composed of 75.0 parts by weight of wall acid, 4.8 parts by weight of sodium oxalate, and 0.90 parts by weight of water 10. C oxidant aqueous solution was added to a mixture containing 3.8 parts by weight of microcrystalline wax and 2.0 parts by weight of sorbitan oleate, and a water-emulsion emulsion in oil was obtained after sufficient stirring. 3.8 parts by weight (specific gravity: 0.25 g / cc) of glass microballoons, which are the same as in the examples, were added as fine hollow spheres, and the mixture was stirred and mixed to obtain the oil-in-water emulsion emulsion explosive of the present invention. The water-drop type emulsion explosive in oil was formed on an extrusion molding machine equipped with a mold with a diameter of 8 mm, and then cut with a knife to a length of 10 mm to obtain a comparative explosive. Its specific gravity is 1. 1 7. # Table 1 shows the composition of the water-drop type emulsion explosive in each oil obtained in Examples 1 to 3 and Comparative Example 1. Table 1 Compound composition ratio Example 1 Example 2 Comparative example 1 Ammonium nitrate 75.0 75.0 75.0 Sodium nitrate 4. 8 4. 8 4. 8 Water 10. 6 10.6 10. 6 Microcrystalline wax 1.5 5 1.5 3. 8 Sorbitan oleate 2. 9 2. 9 2. 0 #AFLEX P- 2 8 0 7 1. 4 — — Nipoflex 720-1. 4-Glass micro balloon test example 3. 8 3.8 3.8 will be made from Example 1 To 2 and Comparative Example 1

314281.ptd Page 18 20031236 V. Description of the invention (15) Charged into a steel pipe with an inner diameter of 48mm, a length of 1mm, and a thickness of 5mm, using an aqueous explosive (trade name: ALTEX) made by Japan Chemical Co., Ltd. After 50g is the detonation tube, the detonation velocity is measured by Dautorishe's method. In addition, after the steel pipe is filled with water in advance, each explosive is charged with an air loader in the same manner as described above, and the detonation velocity in the water hole is measured. For further testing with time, the obtained shaped explosive was placed in a PE plastic bag to a thickness of about 15 to 20 cm, and stored at room temperature for 6 months and one year after measurement in a dry manner. Detonation speed of holes and water holes. The results are shown in Table 2. In addition, in order to investigate whether the drop-type emulsion explosive in oil is solidified under load and easily dispersed after curing, the explosives obtained in Examples 1 to 2 and Comparative Example 1 were actually packaged into 20 Kg (the explosive packaging bag was stored in a cardboard box) , Stored at room temperature for 6 months and one year. Observe and evaluate the explosives stored for 6 months and one year. The test results are shown in Table 2.

314281.ptd Page 19m V. Description of the invention (16) Table 2 Performance test results Example 1 Example 2 Comparative Example 1 Dry hole after time explosion manufacturing ~ 2824, a rebate _______---------- --- 2970 ---------------------- 3120 Blasting holes 3110 3210 3430 Drying the holes after 6 months of speed 2970 ----______------** · --— 2890 Unable to measure the degree of water holes 3280 3190 Unable to measure the dry holes after 1 year 2930 3030 Unable to measure (m / s) Water holes 3220 3300 Unable to measure the solids after a period of 6 months Partially solidified Partially slightly cured pellets After 1 year of sexuality ......... h Part # Xiaowei curing part After picking up the micro-cure pellets, the elapsed time — months and f 6 months later --- ---- 、 Easy Gu Yi ------- One difficulty% One Yi after ^ _____ Gu Yi Difficult performance test results: as shown in Table 2, too; "ΒΒ-重 况 保 #! It will not be cured after years; the non-charged i at room temperature, the performance of the explosive of the comparative example is measured immediately after production. In contrast to the fact that 6 'can be measured in a non-loaded state at room temperature, the detonation speed cannot be measured, as shown in Table 2. "Break the integrated block" Therefore, if it is about the solidification under load, a little solidification can be observed after 1 year. The explosive of Ming Ming is easily dispersed after 6 months, and it is also compatible with the loading machine. Just a slight impact can'j, ..., any difficulty. But comparative example

314281.ptd 200301236 V. Description of the invention (17) The explosives after 6 months and 1 year became pellets, because it is difficult to disperse them from the solidified state, and it is also difficult to fill them with a filling machine. Example 3 A 90 ° C oxidant aqueous solution composed of 75.0 parts by weight of nitric acid, 4.8 parts by weight of sodium phosphonate, and 1.0 part by weight of water was added to a microcrystalline wax containing 2.0 parts by weight of ethylene. A vinyl acetate copolymer resin (manufactured by TOSOH Corporation, trade name: Nipoflex 722, melt flow rate 400g / 10min) 0.9 parts by weight, 2.9 parts by weight of sorbitan oleate, which can be obtained by sufficient stirring Drop type emulsion in oil. Then, 3.8 parts by weight (specific gravity: 0.25 g / cc) of glass micro-air spheres as fine hollow spheres were added, and the mixture was stirred and mixed to obtain the oil-in-water type emulsion explosive of the present invention. The water-drop type emulsion explosive in the oil is formed by an extrusion molding machine equipped with a mold with a diameter of 8 in m, and then cut into a length of 10 m with a knife to obtain the explosive of the present invention. Its specific gravity is 1. 1 7. The obtained explosive was the same as the test example described below, and the detonation speed, curing, and ease of dispersion after curing were tested. The results are shown in Table 3.

314281.ptd Page 21 200301236 V. Description of the invention (18) Table 3 Dry holes after time explosion production 2862 Water holes 3005 Dry holes after 6 months 2789 Degree water holes 2990 Dry holes 2978 (m / s) Water hole 3129 After curing for 6 months, the part is slightly cured. After 1 year, the part is slightly cured and dispersed. After 1 year, it is easy to be cured after 1 year. [Possibility of industrial use] Water droplet type in the oil of the present invention Emulsion explosives are not easy to deform and coagulate due to the load. After long-term storage under load for half a year to 1 year, only a little solidification occurs, and they can be easily dispersed, and have long-term stability and excellent water resistance. Therefore, when the explosive of the present invention is appropriately formed, a filling machine such as air filling can be used, and the explosive hole can be easily filled, and the performance of the explosive will not be reduced even when used in a water hole. In addition, the composition of residual gas after the explosion Also better than ANFO explosives.

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Claims (1)

η 2003 6. Scope of patent application 1. A water-drop type emulsion explosive in oil, characterized in that it contains ethylene-vinyl acetate copolymer in continuous phase. 2. The emulsified explosive according to item 1 of the scope of patent application, characterized in that it contains 0.2 to 8% by mass of ethylene vinyl acetate copolymer. 3. —Drop-type emulsion explosives in oil, which are characterized by those containing oxidants, oils, ethylene-vinyl acetate polymers, emulsifiers, and tiny hollow spheres. 4. The emulsified explosive of item 3 of the patent application, wherein the micro hollow spheres are glass micro-balloons or resin micro-balloons. The emulsified explosive such as the item 3 of the scope of patent application is called for, in which the proportion of ethylene-vinyl acetate copolymer is 30% by mass or more of the total amount of oil and ethylene-vinyl acetate copolymer. 6. The emulsified explosive according to item 3 of the patent application scope, wherein the melt flow rate of the ethylene-vinyl acetate copolymer is 10 g / 100 m i η or more. 7. The emulsion explosive according to item 3 of the patent application range, wherein the number average molecular weight of the ethylene-vinyl acetate copolymer is 100 to 5 0 0 0. 8. Emulsified explosives as claimed in any of claims 1 to 7 are solid. 9. For example, the explosives under the scope of patent application No. 8 are formed into pillars with a diameter of 3 to 20 mm in and a length of 1 to 30 m. 314281.pid Page 24