WO2006059460A1

WO2006059460A1 - Initiatorless electric detonator

Info

Publication number: WO2006059460A1
Application number: PCT/JP2005/020430
Authority: WO
Inventors: Yutaka Kagawa; Michiharu Arifuku; Shigeru Maeda; Hirotaka Mukunoki
Original assignee: Nippon Kayaku Kabushki Kaisha
Priority date: 2004-11-10
Filing date: 2005-11-08
Publication date: 2006-06-08
Also published as: US20080190316A1; WO2006059460A9; JP2006138510A

Abstract

An electric detonator of simple structure in which initiator and ignition charge are eliminated and secondary explosive, i.e. base charge, can be ignited directly. The detonator comprises a tubular body having one closed end, a base charge charged in the tubular body on one closed end side, and an igniter inserted from the other open end side of the tubular body and contained on the other end side and is characterized in that the igniter is a semiconductor bridge device having a laminate layer consisting of a reactive metal layer and a reactive insulator layer and an electrode pad, and the base charge is pentaerythritol tetranitrate or the like.

Description

Specification

No detonation electric detonator

Technical field

[0001] The present invention relates to an electric detonator, and more particularly to an electric detonator that does not use an explosive.

Background art

[0002] Conventional instantaneous electric detonators are metal tubes, igniters, electric igniters, plugs that seal detonators, and conductive wires loaded with explosives (primary explosives) and accessory (secondary explosives). Leg strength. Examples of primary explosives include lead azide, diazodinitrophenol (DDNP), and trinitroresorcin lead (tricinate). Examples of secondary explosives include pentaerythritol tetranitrate (PETN), cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), cyclo-1,3,5,7— Examples include tetramethylene-1,2,4,6,8-tetranitramine (HMX). In addition, a mixture of an explosive and an oxidizing agent is used as the ignition agent.

[0003] For the operation flow of the instantaneous electric detonator, the electric bridge wire (platinum wire, nichrome wire, etc.) of the electric ignition device is heated by the current supplied from the leg wire, and the ignition agent is ignited. Explosives are ignited and explode, causing the charge to explode. The secondary explosives have the property that they do not explode properly without large energy, such as the explosion caused by the primary explosive. However, igniting and explosives are very sensitive to external stimuli of heat, friction and shock compared to secondary explosives and general industrial explosives, and care must be taken during manufacturing and use. There was a need. As a countermeasure against such problems, electric detonators that do not use explosives have been developed.

[0004] Patent Document 1 discloses a detonator that does not use an explosive by mixing an oxidant with an additive that is a secondary explosive. Specifically, a detonator that functions without the use of an explosive is disclosed by mixing PETN with potassium chlorate and placing it in a metal inner tube and restraining it. However, it is necessary to use a highly sensitive igniting agent or the like for the ignition device for adding this adjunct, while the structure is complicated, such as the necessity to use a plurality of inner pipes. Similarly, Patent Document 2 discloses a method in which a flying plate is used to cause an explosion by giving an impact to an accessory medicine. Specifically, the flying plate flies toward and collides with the propellant gas ignited by the igniting agent, and the adsorbing agent explodes due to the energy at the time of the collision. In this case, the igniter for flying the flying plate uses a highly sensitive chemical such as an igniter, and a structure for flying the plate is required, which complicates the structure. Also, if it is deformed due to the influence of the adjacent holes at the time of blasting, the flying plate may not collide with the attached medicine accurately and may become unfired.

[0005] Further, with the recent development of electronic material technology, a semiconductor bridge device in which semiconductor manufacturing technology is applied to an ignition device has been developed. It is known that the semiconductor bridge device is more efficient and safer against electrical noise than the conventional platinum wire or nichrome wire bridge (Patent Document 3).

Semiconductor power bridge equipment applies a high voltage and is known for military use that explodes explosives. Application of a high voltage is unsuitable as an ignition device for industrial explosive detonators. Further, for example, the semiconductor bridge device described in Patent Document 3 is also unsuitable as an ignition device for industrial explosive detonators because of its low initiation energy.

[0006] Patent Document 1: JP-A-6-221799

Patent Document 2: JP-A-6-249594

Patent Literature 3: Special Table 2004—513319

Disclosure of the invention

Problems to be solved by the invention

[0007] Thus, if an attempt is made to omit the explosive, the structure becomes complicated and the manufacturing cost increases.

Also, since it is highly sensitive and uses igniting agents, it is necessary to pay attention to the handling during manufacturing and use. An object of the present invention is to provide an electric detonator that can directly ignite an attached charge, which is a powerful secondary explosive, with a simple structure and omitting an explosive charge and an ignition charge. Means for solving the problem

[0008] As a result of diligent investigations to solve the above problems, the present inventors have used PETN as a secondary explosive or a mixture of the PETN and a predetermined substance as an additive, and used as an ignition device. By using a semiconductor bridge (SCB) device, a simpler construction is possible without using explosives. And found that it was possible to ignite the charge directly.

That is, the present invention includes a tubular tube whose one end is closed, an additive charged in the closed one-end tube, and the other end inserted from the other open end of the tube. An ignition device housed on the side,

The igniter comprises two lands on the substrate and a bridge portion electrically connecting the two land portions, and the reactive metal layers and the reactive insulator layers stacked alternately. And an electrode pad electrically connected to at least one reactive metal layer of each of the laminate layers constituting the two land portions, and the bridge portion applied to the electrode pad. Is a semiconductor bridge device that generates plasma with a current of a certain intensity flowing through

The additive is selected from the group consisting of pentaerythritol tetranitrate or pentaerythritol tetranitrate and metal, metal oxide, metal peroxide, metal nitrate, metal chlorate, and metal perchlorate. Provide a detonator characterized by the inclusion of one or more selected agents. By providing such a structure, particularly a semiconductor bridge device that is conventionally unsuitable as a detonator for industrial explosive detonators, it can be used as an accessory without using an igniting agent or a detonating agent. It has been found that it can be ignited.

In the ignition device for a detonator of the present invention, a metal oxide can be used instead of the reactive insulator. The use of metal oxide makes it easier to manufacture the laminate layer, and the power can be ignited with low energy (low current). Even when the resistance value of the bridge is increased, good performance can be achieved, and one power source can be used. More detonators can be connected.

The reactive metal layer and the reactive insulator layer or metal oxide layer are alternately layered to form a laminate layer, and current flows through a metal pad electrically connected to the reactive metal layer. The reactive metal layer where the plasma is generated but the metal pads are electrically connected is preferably on the top layer of the laminate layer. When such a configuration is adopted, the ignition efficiency is improved. In particular, when the reactive metal layer is Ti, W, Zr, or Ni, the production is easy and the ignition efficiency is excellent. In addition, when the reactive insulator layer is B, or the metal oxide layer is SiO or TiO

2 2 If there is, it is possible to supply a stable plasma. [0010] Use of a combination of pentaerythritol tetranitrate and metal as an additive is preferable because ignition efficiency is improved. In particular, Ni, W, T, and A1 are easy to handle as metals. The invention's effect

[0011] The detonator of the present invention uses a semiconductor bridge device to directly ignite PETN, which is a simpler structure than the conventional non-detonator detonator and uses a highly sensitive igniter. It can explode and has the ability to detonate hydrous explosives, which are industrial explosives. Also, by using a PETN mixture in the detonator of the present invention, it has become possible to reduce the ignition energy compared to PETN alone.

Brief Description of Drawings

FIG. 1 is a plan view of a semiconductor bridge device.

FIG. 2 is a cross-sectional view taken along the line AA ′ of the semiconductor bridge device.

FIG. 3 is an enlarged view of a laminate layer 20.

FIG. 4 is a cross-sectional view showing a detonator detonator of Examples 2 to 4.

FIG. 5 is a cross-sectional view showing a non-detonation detonator of Example 1.

Explanation of symbols

[0013] 100 semiconductor bridge equipment

10 Silicon substrate

20 Laminate layer

22—1, 22—2, 22—3, 22—4, 22—5 Ti layer

24—1, 24—2, 24—3, 24—4, 24—5 B layer

30, 32 land part

34 Electrode pad

36 Electric Bridge

1 tube

2 Semiconductor bridge equipment

3 Embolization 6 Epoxy resin

7 Stainless steel tube

BEST MODE FOR CARRYING OUT THE INVENTION

[0014] The present invention is described in detail below.

The detonator of the present invention does not use high-sensitivity explosives that are used as igniting and detonating agents in general electric detonators.

In the detonator of the present invention, PETN is used as an attachment agent. PETN is not particularly limited in its purity as long as it is a grade generally used for detonators.

Since PETN can be ignited with lower energy than the force that can be used alone, it is preferable to use a substance that improves the sensitivity of the additive. Such additives include metals, metal oxides, metal peroxides, metal nitrates, metal chlorates, and metal perchlorates. Specifically, sodium nitrate, nitric acid or barium nitrate, etc. as metal nitrates, copper oxide, etc. as metal oxides, sodium peroxide, etc. as metal peroxides, and metal chlorates The potassium perchlorate is a potassium perchlorate, and the metal is titanium, tandastene, nickel, cobalt, iron, zinc, copper, aluminum and the like. Of these, nickel, tungsten, titanium, and aluminum are preferable from the viewpoint of sensitivity.

[0015] In order to obtain a mixture of PETN and an additive (hereinafter referred to as PETN mixture), both are put in a solvent, sufficiently mixed in a slurry state, and dried. Drying is not particularly limited as long as it is a method capable of removing the solvent, for example, at room temperature to 50 ° C for 1 day or more. As the solvent, water alcohol such as methyl alcohol and ethyl alcohol can be used, and it is sufficient to use about 50 to 200% by weight based on the total weight of the PETN mixture.

[0016] The additive is used in an amount that does not impair the power of the explosive PETN, and is usually in a ratio of about 0.:! To 50 parts by weight, preferably about 1 to 10 parts by weight with respect to 100 parts by weight of PETN. use. The particle size of the PETN used is ignited by the energy generated by the semiconductor bridge device, and in order to bring about a rapid and accelerated increase in the burning rate, the average particle size is 50 _β m or less, preferably 3 to 20 / im preferred. To obtain PETN with an average particle size in this range, For example, a recrystallization method as shown on page 310 of CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES VOLUME 4 can be employed. The particle size of the additive is usually from 0.1 to 100 xm, preferably from! To 50 xm in terms of average particle size, taking into account ignition sensitivity when mixed with PETN and manufacturing problems.

[0017] If necessary, a binder (binder) is added to make the PETN mixture easy to handle and workability is improved. Examples of the binder include rubbers such as fluorinated rubber, fibers such as nitrocellulose and ethyl cellulose, and polymers such as polybutyl alcohol. These are dissolved in a solvent in which they can be dissolved (acetone, water, etc.), added to the slurry obtained by mixing the PETN mixture and the solvent such as water or alcohol, mixed, and then dried. In general, the amount of binder added is preferably less than 5% by weight, preferably less than 1% by weight, based on the weight of the PETN mixture. The binder can also be used for the same purpose as described above when PETEN is used alone. In this case as well, a solution obtained by dissolving a binder in a predetermined solvent may be added to a slurry obtained by mixing PETN and the above-mentioned solvent such as water or alcohol and dried. The mixing order of the binder solution, PET N and solvent is not particularly limited. In this case as well, the amount of binder added is generally preferably as small as possible, and is usually 5% by weight or less, more preferably 1% by weight or less based on the weight of PETN.

[0018] A semiconductor bridge device is used as the ignition device. The semiconductor bridge device used in the present invention is shown in FIG. 1, its AA ′ cross-sectional view is shown in FIG. 2 (a), and the structure of the laminate layer 20 is shown in FIG. 2 (b). The semiconductor bridge device 100 has a laminate layer 20 and an electrode pad 34 on a substrate 10. The laminate layer 20 is composed of two lands 30 and 32 and a bridge 36 connecting the two land portions, and is alternately stacked with a reactive metal layer and a reactive insulator layer, or a reactive layer. An electrode composed of a metal layer and a metal oxide layer, electrically connected to at least one reactive metal layer of each of the laminate layers constituting the two land portions, and electrically connected to a leg wire via a pad 34; A current having a predetermined intensity flowing through the bridge portion applied to the pad 34 generates plasma. For example, a device described in Japanese Patent Application No. 2004-290993 can be used. The semiconductor bridge device is used by connecting electrode pads and leg wires with wire bonding, conductive paste, solder, etc. The In the present invention, “plasma” refers to a spark-like heat medium generated by the current flowing through the bridge.

[0019] The reactive metal layer 22- :! to 22-6 in FIG. 2 (b) includes, for example, Au, Al, Ag, Bi, C, Co, Cr, Cu, Fe, Ge, Hf, In, Ir, Mg, Mo, Nb, Ni, Pb, Pt, n-type Si, p-type Si, Sn, Ta, Ti, V, W, Zn, Zr and the like can be mentioned, and Ti, W, Zr or Ni is preferable. Reactive insulator layer 24 _ :! For _24_5, a combination that is chemically reactive with the metal is selected, and a combination with higher resistivity and lower thermal conductivity than the metal is used. Examples of reactive insulators include B, Ca, Mn or Si, and B is preferred. Examples of the metal oxide layer 2 4_ :! to 24-5 include SiO, TiO, AlO, etc.

2 2 2 3 2

TiO is preferred.

2

[0020] Reactive metal in the laminate layer 20—! At least one layer of ~ 22-6 is electrically connected to the electrical pad 34, but the reactive metal 22-6 in the uppermost layer is electrically connected to the electrical pad 34 as shown in Fig. 2 (a). Are preferred.

[0021] Fig. 3 shows an example of the present invention. In this example, the tube body 1 is a metal, and stainless steel is used in addition to copper, aluminum, and iron that are generally used as a tube of an electric detonator. it can. The shape of the tube 1 is not particularly limited, but is generally cylindrical. The inner and outer diameters, thickness, and length can be arbitrarily set according to the application and explosive amount. Inside tube 1 is a secondary explosive charge 4. Use PETN or a PETN mixture as an accessory. The amount of the charge used varies depending on the size of the tube and the desired charge density, and cannot be generally stated, but is usually 5 g or less.

[0022] Generally, the higher the charge density, the greater the power, and the smaller the charge density, the higher the ignition sensitivity. However, when a semiconductor bridge device is used, it is easier to ignite with a somewhat higher charge density. In the case of the present invention, the charge density of the additive is usually 1. Og / cm ³ or more, preferably 1.3 g / cm ³ or more. It should be noted that the charging density is gradually decreased from a position close to the semiconductor bridge device, and the charging density once reduced is increased again in consideration of ignition sensitivity. The method of charging can also be selected.

[0023] In addition to the use of PETN or a PETN mixture alone, the additive 4 can be filled in two or more layers. For example, PETN is placed in the lower layer and a semiconductor bridge The upper layer in contact with the device can also be a layer of PETN mixture.

An embolus 3 with a semiconductor bridge device 2 attached is inserted into the tube 1. The semiconductor bridge device 2 is electrically connected to the leg 5. As long as the embolus can withstand the pressure at the time of explosion, there can be used metal / resin, etc., with no particular restrictions on the material. After inserting the embolus, it may be sealed with epoxy resin or welding to further improve the sealing strength. You can also tighten the top of the tube.

Example

[0025] Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited to the examples.

[0026] Example 1

PETN2.Og (average particle diameter of about ΙΟμΐη; visually observed) recrystallized as an Additive 2 on the inside of a cylindrical tube 1 with a copper outer diameter of 8mm, a thickness of 0.8mm, and a length of 50mm. The charging was performed so that the charging density was 1.5 g / cm ³ . The plug 1 with the semiconductor bridge device was press-fitted into the charged tube 1 so that the PETN and the semiconductor bridge device were in close contact. In order to further improve the sealing performance, the upper part of the tube 1 is covered with a stainless steel tube 7 having an outer diameter of 9.5 mm and a thickness of 0.5 mm, and the inside thereof is sealed with an epoxy resin 6 to obtain the detonator of the present invention. (Fig. 4). In addition, the semiconductor bridge device is shown in FIG. 1 on a silicon substrate 10 having a side of 2 × 2 mm on a Ti (22_6 (l. Ομπι), 22-5 (0.25 xm), 22-4 (0.25 zm), 22-3 (0.25 μm), 22-2 (0.25 zm), 22-1 (0.05 μm)) and B (24-5 (0.225 μm), 24-4 (0.225 zm), 24-3 (0.225 xm) , 24-2 (0.225 zm), 24-1 (1.0 xm)) were used.

[0027] Example 2

100 parts by weight of recrystallized PETN (average particle size of about 10 zm; visually), 2.5 parts by weight of 20% acetone solution of fluoro rubber as binder and 100 parts by weight of ethyl alcohol were mixed at 40 ° C. It was dried for 1 day to obtain an attached medicine. 120 mg of the obtained additive was charged to a stainless tube 1 having an outer diameter of 8 mm, a thickness of 0.4 mm, and a length of 6 mm so that the charge density was 1.5 g / cm ³ . Next, a plug 3 attached with the same semiconductor bridge device 2 as in Example 1 was press-fitted into the charged tube 1 so that the attachment 4 and the bridge device 2 were in close contact, and the detonator of the present invention was obtained ( Fig 3 ) ₀

[0028] Example 3

Recrystallized PETN (average particle size approx. 10 / m; visually) 95 parts by weight, 5 parts by weight of W, 2.5 parts by weight of 20% acetone solution of fluorinated rubber and 100 parts by weight of ethyl alcohol were mixed. Drying was carried out at ° C for 1 day to obtain a supplement. 120 mg of the obtained additive was charged to a stainless steel tube 1 having an outer diameter of 8 mm, a thickness of 0.4 mm, and a length of 6 mm so that the charge density was 1.5 gZcm ³ . Next, a plug 3 attached with the same semiconductor bridge device 2 as in Example 1 was press-fitted into the charged tube 1 so that the attachment 4 and the bridge device 2 were in close contact with each other, and the detonator of the present invention was obtained. (Figure 3).

[0029] Example 4

95 parts by weight of recrystallized PETN (average particle size approx. 10 zm; visually) 5 parts by weight of Al (P-100, manufactured by Toyo Aluminum Co., Ltd.) And 100 parts by weight of ethyl alcohol were mixed and dried at 40 ° C for 1 day to obtain an additive. 120 mg of the obtained additive was charged into a stainless steel tube 1 having an outer diameter of 8 mm, a thickness of 0.4 mm, and a length of 6 mm so that the charge density was 1.5 g / cm ³ . Next, a plug 3 attached with the same semiconductor bridge device 2 as in Example 1 was press-fitted into the charged tube body 1 so that the attachment agent 4 and the bridge device 2 were in close contact with each other, and the detonator of the present invention was obtained. (Figure 3).

[0030] Test Example 1

The detonator obtained in Example 1 was inserted into 50 g of hydrous explosive (Nippon Kayaku Co., Ltd .; trade name: Altex). When 3J electrical energy was supplied to this detonator, the hydrous explosives detonated and exploded.

^^

Test example 2

Using the detonator obtained in Example 2 and changing the electric energy supplied to the semiconductor bridge device, the number of explosions of hydrous explosive was tested in the same manner as in Test Example 1 and the results shown in Table 1 were obtained. .

[0031] [Table 1] Energy (J) Number of explosions / tests

3 J 2/2

0. 8 J 34/37

0. 5 J 1 3/28

0. 3 J 0/6

[0032] Test Example 3

The detonator obtained in Example 3 and Example 4 was supplied with 0.3J energy to the semiconductor bridge device, and the explosion test of the hydrous explosive was conducted in the same manner as in Test Example 1. Both explosives exploded.

[0033] From the results of the test example, the detonator of the present invention has the capability of directly igniting the secondary explosive charge using a semiconductor bridge device and detonating the industrial explosive hydrous explosive. I understand that.

Claims

The scope of the claims

[1] A cylindrical tube closed at one end, and an additive charged in the closed end of the tube

An ignition device inserted from the other open end of the tube and housed in the other end,

The additive is selected from the group consisting of pentaerythritol tetranitrate or pentaerythritol tetranitrate and metal, metal oxide, metal peroxide, metal nitrate, metal chlorate, and metal perchlorate. A detonator characterized by being a supplement containing at least one selected.

[2] A cylindrical tube having one end closed, an additive charged in the closed end tube, and inserted from the other open end of the tube, And a stowed ignition device,

The igniter constitutes two lands on the substrate and a bridge portion electrically connecting the two land portions, and the reactive metal layer and the metal oxide layer stacked alternately. And an electrode pad electrically connected to at least one reactive metal layer of each of the laminate layers constituting the two land portions, and the bridge portion applied to the electrode pad. Is a semiconductor bridge device that generates plasma with a predetermined intensity of current flowing through

[3] The reactive metal layer to which the electrode pad is electrically connected is in the uppermost layer of the laminate layer. Or the detonator described in 2.

4. The detonator according to claim 1, wherein the reactive metal layer is Ti, W, Zr or Ni.

The detonator according to claim 1, wherein the reactive insulating layer is B.

The detonator according to claim 2, wherein the metal oxide layer is SiO or TiO.

twenty two

The detonator according to claim 1 or 2, wherein the accessory medicine comprises pentaerythritol tetranitrate and a metal.

The detonator according to claim 7, wherein the metal is Ni, W, T or A1.