WO2012008161A1 - 点火器用点火薬組成物 - Google Patents
点火器用点火薬組成物 Download PDFInfo
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- WO2012008161A1 WO2012008161A1 PCT/JP2011/004023 JP2011004023W WO2012008161A1 WO 2012008161 A1 WO2012008161 A1 WO 2012008161A1 JP 2011004023 W JP2011004023 W JP 2011004023W WO 2012008161 A1 WO2012008161 A1 WO 2012008161A1
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- igniter
- powder
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/06—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being an inorganic oxygen-halogen salt
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
- C06C9/00—Chemical contact igniters; Chemical lighters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
- B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
- B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
- B60R21/26—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow
- B60R2021/26029—Ignitors
Definitions
- the present invention relates to an igniter composition for an igniter and an igniter using the igniter composition, and more specifically, an igniter composition for an igniter used for an electric detonator or an airbag installed in an automobile, and the like.
- TECHNICAL FIELD The present invention relates to an igniter using an igniter composition (so-called squib), and more particularly to an igniter composition for an igniter having reduced friction sensitivity while satisfying a required current ignition sensitivity, and an igniter using the igniter composition. Is.
- various igniters have been developed as igniters mounted on gas generators used in automobile safety devices such as airbags and seat belt pretensioners.
- Such an igniter is generally loaded with an igniting agent that ignites with minute electric energy, and the igniting agent responds quickly to thermal energy converted from an electric signal, and functions to ignite and activate a gas generator.
- a mixture of zirconium powder and potassium perchlorate (ZPP), a mixture of zirconium powder, tungsten powder, and potassium perchlorate (ZWPP) is used as the igniter composition for the igniter.
- ZPP zirconium powder and potassium perchlorate
- ZWPP potassium perchlorate
- various igniting agents have been developed in order to meet the demands for improving the performance of safety devices and the safety of manufacturing processes for gas generator igniters.
- Patent Document 1 discloses a technique characterized by adding titanium hydride or the like as a combustion accelerator to an explosive composition of a mixture of zirconium powder and an oxidizing agent.
- Patent Document 1 is a single-prime charge containing zirconium as an essential component in a single-prime charge, and relates to obtaining an igniter composition that secures a sufficient amount of heat in ignition. It is not intended to reduce the friction sensitivity of the igniting agent.
- Patent Document 2 discloses an igniter for an igniter containing potassium perchlorate and potassium nitrate in metal powder. It is described that the composition is an igniter with reduced friction sensitivity. That is, the invention described in Patent Document 2 reduces the friction sensitivity by adding potassium nitrate to the conventional igniter.
- Patent Document 3 discloses a technique for suppressing a decrease in safety during handling while maintaining current ignition sensitivity by making the shape of the metal particles forming the metal powder into a scale shape. Is disclosed. However, this technique requires the metal powder to have a special shape, and has the disadvantages that the production control of the metal powder is difficult and the production cost is increased.
- An object of the present invention is to provide an igniter composition for an igniter capable of solving the above-described problems of the prior art and reducing friction sensitivity while satisfying required current ignition sensitivity.
- the metal hydride (A) is one or more selected from the group consisting of tungsten powder, molybdenum powder, aluminum powder, titanium powder, and magnesium powder.
- the friction sensitivity is reduced while satisfying the required current ignition sensitivity of the igniter composition for an igniter.
- the present invention has been completed.
- the present invention relates to the contents according to the following (1) to (8).
- An igniter composition for an igniter is (1)
- the igniter composition for an igniter according to the present invention can provide an igniter for an igniter with reduced friction sensitivity while satisfying the current ignition sensitivity required as the igniter.
- By reducing the friction sensitivity it is possible to prevent an accidental accidental ignition of the igniting agent due to friction, which has been a problem at the time of manufacturing the igniting agent and the igniter. Therefore, the safety of the igniter manufacturing process can be improved, and an igniter having quick response can be manufactured.
- a gas generator for a seat belt pretensioner using an igniter loaded with such an igniter composition for an igniter, and a gas generator for an air bag can be provided.
- the igniter composition for an igniter according to the present invention includes a metal hydride (A); one or more metal powders (B) selected from the group consisting of tungsten powder, molybdenum powder, aluminum powder, titanium powder, and magnesium powder. And perchlorate (C).
- the metal hydride (A) used in the present invention functions as a combustion component. That is, in the ignition process, it generates heat by receiving an oxidation action, and also has a function of providing metal hot particles and hot gas.
- Examples of the metal hydride (A) used in the present invention include zirconium hydride, titanium hydride, aluminum hydride, magnesium hydride, calcium hydride and the like. These metal hydrides (A) may be used individually by 1 type, and may mix and use 2 or more types.
- the particle size of the metal hydride (A) affects the current ignition sensitivity related to quick ignition response, and is appropriately set according to the required performance of the igniter.
- the particle size used is preferably 1 to 10 ⁇ m.
- the content of the metal hydride (A) in the igniter composition for an igniter of the present invention is preferably 10 to 50% by mass. More preferably, it is in the range of 10 to 40% by mass. If the content of the metal hydride (A) is less than 10% by mass, sufficient output cannot be obtained, and if it exceeds 50% by mass, the current ignition sensitivity required for the igniter composition for an igniter may not be satisfied. .
- the metal powder (B) used in the present invention functions as a combustion component.
- the metal powder (B) used in the present invention is a metal powder (B) selected from tungsten powder, aluminum powder, magnesium powder, titanium powder, and molybdenum powder. These metal powders (B) may be used individually by 1 type, and 2 or more types may be mixed and used for them.
- the metal powder (B) has a function of generating metal heat particles while part of or the entire content is subjected to an oxidizing action to generate heat.
- As the metal powder (B) it is preferable to use tungsten powder or molybdenum powder from the viewpoint of reducing the friction sensitivity of the igniter composition for an igniter and facilitating handling during production. Is more preferable.
- the spherical shape formed by a well-known method is used suitably for metal powder (B).
- the particle size of the metal powder (B) affects the current ignition sensitivity related to quick ignition response, and is appropriately set according to the required performance of the igniter.
- the particle size of the metal powder (B) used is preferably 0.01 to 5 ⁇ m.
- the content of the metal powder (B) used in the igniter composition for igniters of the present invention is preferably in the range of 10 to 50% by mass, and in the range of 15 to 45% by mass in the igniter composition for igniters. More preferably it is. If the content of the metal powder (B) is less than 10% by mass, the required current ignition sensitivity may not be satisfied. On the other hand, if it exceeds 50% by mass, the output may decrease.
- a perchlorate (C) is used in the igniter composition for an igniter of the present invention, and this perchlorate (C) functions as an oxidant, and the metal hydride (A) and metal powder (B). It has a function to oxidize.
- the perchlorate (C) include alkali metal perchlorate, alkaline earth metal perchlorate, and ammonium perchlorate. In particular, alkali metal perchlorate is preferable, and potassium perchlorate and sodium perchlorate are preferably used.
- the content of perchlorate (C) in the igniter composition for an igniter is preferably 20 to 70% by mass, and more preferably 25 to 60% by mass. If the content of perchlorate (C) is less than 20% by mass, sufficient output cannot be obtained. On the other hand, if it exceeds 70% by mass, the current ignition sensitivity required for the igniter composition for an igniter is not satisfied. There is a fear.
- the igniter composition for an igniter according to the present invention has a metal hydride (A) of 10 to 50% by mass, a metal powder (B) of 10 to 50% by mass, and a perchlorate (C) of 20 to 70% by mass.
- the metal hydride (A) is preferably in the range of 10 to 40% by mass
- the metal powder (B) is in the range of 15 to 45% by mass
- the perchlorate (C) is in the range of 25 to 60% by mass. More preferably.
- the metal hydride (A) is zirconium hydride and / or titanium hydride
- the metal powder (B) is tungsten powder or molybdenum powder
- Acid salt (C) is potassium perchlorate.
- particularly preferable igniter compositions include compositions containing zirconium hydride, tungsten, and potassium perchlorate. In this case, a composition containing 10 to 50% by mass of zirconium hydride, 10 to 50% by mass of tungsten, and 20 to 70% by mass of potassium perchlorate is preferable.
- Another preferred embodiment includes a composition containing titanium hydride, tungsten, and potassium perchlorate. In this case, a composition containing 10 to 50% by mass of titanium hydride, 10 to 50% by mass of tungsten, and 20 to 70% by mass of potassium perchlorate is preferable.
- the igniter composition for an igniter according to the present invention may further contain other metal powders, other oxidizing agents, basic substances, binders, compounding agents and the like as optional components.
- metal powder (B) in addition to the metal powder (B), other metal powders can be arbitrarily added and used as a mixed metal powder.
- other metal powders zirconium powder, magnalium powder, copper powder, beryllium powder and the like can be applied.
- the addition amount of another metal powder is 10 mass% or less in the igniter composition for igniters.
- the igniter composition for an igniter of the present invention can optionally contain other oxidizing agent in addition to perchlorate (C).
- oxidizing agents include potassium nitrate, sodium nitrate, strontium nitrate, basic nitric acid cylinder, magnesium nitrate, nitrates such as ammonium nitrate, sodium chlorate, potassium chlorate, magnesium chlorate, calcium chlorate, chlorine Examples include chlorates such as strontium acid and ammonium chlorate.
- These other oxidizing agents may be used alone or in combination of two or more.
- mixed oxidizers of perchlorates (C) and nitrates are expected to have both a function of maintaining current ignition sensitivity and a function of reducing friction sensitivity, and the effect of the igniter composition according to the present application. This is preferable because an improvement effect is expected.
- the content rate of another oxidizing agent is 30 mass% or less in the ignition agent composition for igniters.
- the igniter composition for an igniter of the present invention preferably further contains an arbitrary basic substance.
- blending this basic substance the corrosion of the metal part of an igniter can be suppressed.
- metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide , Lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, zinc oxide, thallium oxide, cesium oxide and other metal oxides, lithium peroxide, sodium peroxide, Metal peroxide such as potassium peroxide, rubidium peroxide, cesium peroxide, magnesium peroxide, calcium peroxide, strontium peroxide, barium peroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, carbonic acid Magnesium ,
- these basic substances may be used individually by 1 type, and 2 or more types may be mixed and used for them. Further, these basic substances may be water-soluble or water-insoluble. Of these, metal oxides are preferable, and magnesium oxide is particularly preferable. In addition, it is preferable that the content rate of a basic substance is 10 mass% or less in the igniter composition for igniters. Considering the balance of the igniter composition, it is more preferably 5% by mass or less.
- the igniter composition for an igniter of the present invention preferably further contains a binder.
- a binder When the igniter composition for an igniter is formed into a molded body by blending the binder, the fracture strength and other mechanical properties can be improved.
- These binders may be used individually by 1 type, and 2 or more types may be mixed and used for them.
- the content rate of a binder is 5 mass% or less in the igniter composition for igniters.
- the binder may be used as it is by mixing it with the igniter composition, or a method of adding an appropriate solvent to the binder and mixing it with the igniter composition may be used. If the said solvent is inert with respect to a binder and is excellent in a dispersibility, or shows a good solubility, it can be used without a problem in particular. On the other hand, physical properties that are easily volatilized in the drying process are preferable in the manufacturing process, and volatile organic solvents such as hydrocarbons, esters, and ketones are preferably used.
- the igniter composition for an igniter of the present invention is blended by mixing various optional components appropriately selected as necessary with the metal hydride (A), metal powder (B), and perchlorate (C).
- A metal hydride
- B metal powder
- C perchlorate
- a powdered igniter for an igniter can be manufactured.
- the mixture of each composition component can be granulated and the ignition agent for igniters can also be manufactured as a granule molding.
- the metal hydride (A), the metal powder (B), the perchlorate (C), and optional components are mixed in a mixer.
- a mixture of these can be obtained.
- a binder dissolved in a solvent is added to a mixture obtained by adding other optional components such as metal powder to a mixture of metal hydride (A) and metal powder (B), and this is mixed with a mixer. Mix with.
- the method of adding perchlorate (C) and arbitrary other oxidizing agents, a basic substance, etc., and further mixing and obtaining these mixtures is mentioned.
- the granulation method examples include a method in which a binder component is added and the mixture obtained through the mixing step is air-dried on a pallet and then passed through a sieve to obtain granules.
- the particle size of the granules to be obtained is determined by the size of the sieve mesh used.
- the particle size is preferably in the range of 1.0 mm or less, 0.8 mm The following range is more preferable.
- the mesh size should be determined taking this into account.
- the igniter composition for an igniter according to the present invention has physical properties that have reduced friction sensitivity, greatly improve handling safety in the production process, and have a remarkably excellent effect.
- the igniter composition for an igniter of the present invention can achieve a reduction in friction sensitivity while maintaining current ignition sensitivity. Therefore, it has the effect of improving the safety of the igniter preparation process, and by adopting the igniter in the igniter, it ensures the safety in the igniter manufacturing process while ensuring quick response as the igniter. It is possible to do that. Therefore, the present invention includes an igniter using the above-described igniter composition for an igniter.
- the igniter of the present invention is not particularly limited except that the igniter composition for an igniter is used, and can be manufactured by a known method.
- FIG. 1 is a cross-sectional view of an example of an igniter according to the present invention.
- a cup body 6 for storing an ignition agent 2 a cover body 9 for storing the cup body 6, and electrode pins 8 for electrical connection to the outside are fixed by an insulator 4.
- a bridge wire 3 connected between the electrode pins 8 and in contact with the igniting agent 2.
- the junction between the embolus 7 and the cup body 6 and the junction between the embolus 7 and the electrode pin 8 are covered and protected by the insulating resin 5.
- the igniter 1 of this invention can be further equipped with the well-known components normally used for an igniter.
- the igniter 1 of the present invention needs to use the igniter composition for an igniter of the present invention described above or an igniter that is a molded body thereof as the igniter 2.
- the igniter 1 in FIG. 1 When a sensor (not shown) detects a vehicle collision, a signal is sent to a control unit (actuator; not shown), and the electrode pin 8 is energized from the control unit that has detected this signal.
- the bridge wire 3 emits Joule heat by this energizing current, and the igniting agent 2 contacting the bridge wire 3 is ignited by this heat, and the cup body 6 is broken by the generated heat energy and the generated pressure, and the flame is ignited by the igniter. 1 functions as an igniter by being discharged to the outside. That is, the igniting agent 2 is required to have an ignition sensitivity performance that ignites quickly by the heat generated by the bridge 3.
- the igniter 1 in which the electrode pin 8 and the bridge 3 are mounted on the embolus 7 is inserted into the cup body 6 filled with the ignition agent 2 and fixed. Thereafter, the igniter 1 can be manufactured by covering the outer periphery of the cup body 6 with the cover body 9 and mold-fixing with the insulating resin 5.
- the igniter 2 is manufactured through the physical movement and mechanical contact friction process in the metering process, the loading process to the cup body 6, the embolus assembly inserting process, and the embolus fixing process.
- the igniter composition for an igniter of the present invention maintains a current ignition sensitivity equivalent to that of a conventionally used igniter and has quick ignition characteristics.
- the friction sensitivity is reduced, which is a physical property that greatly improves the handling safety in the manufacturing process of the igniter. That is, by employing the igniter composition of the present invention in an igniter, it is possible to provide an igniter that can improve manufacturing safety and satisfy specified performance in igniter sensitivity.
- the present invention includes a gas generator using the igniter.
- the said gas generator is used suitably as a small gas generator used for starting of a seatbelt pretensioner. Moreover, it is used suitably as a gas generator for airbag deployment.
- the gas generator of the present invention will be described in detail with reference to FIG.
- FIG. 2 is a cross-sectional view of an example of a gas generator for a seat belt pretensioner using the igniter of the present invention.
- a gas generator 11 shown in FIG. 2 includes a cup body 13 that stores a gas generating agent 12 that generates gas by combustion, and an electrode pin 16 that is disposed inside the cup body 13 and electrically connected to the outside.
- the gas generator 11 can further be equipped with well-known components normally used for a gas generator.
- the operation of the gas generator 11 in FIG. 2 will be described.
- a sensor (not shown) senses a collision
- a signal is sent to a control unit (actuator) (not shown), and the electrode pin 16 is energized from the control unit that senses this signal.
- the electric bridge wire existing in the igniter 14 generates heat, and the igniting agent loaded in the igniter 14 is ignited by this heat, and the flame is released to the inside of the cup body 13 of the igniter 14. Due to this flame, the gas generating agent 12 burns to generate a large amount of gas.
- a large amount of the generated gas is introduced into a seat belt pretensioner (not shown), and the pressure in the seat belt pretensioner is increased to operate the seatbelt pretensioner and tighten the seatbelt.
- FIG. 3 is a cross-sectional view of an example of a gas generator for an air bag using the igniter of the present invention.
- an outer shell is formed by a housing upper 22 made of a metal container in which a plurality of gas ejection holes 26 are installed, and an igniter 23 and a filter 25 according to the present invention are installed therein. ing.
- the internal space is filled with a gas generating agent 24, and an enhancer chamber is installed in the vicinity of the igniter 23. In the case of a normal gas generator configuration, an ignition flame generated from the igniter 23 is reduced.
- An enhancer agent (fire transfer agent) 27 that transmits to the gas generating agent 24 is filled in the enhancer chamber.
- the gas generator 21 can be equipped with the well-known components normally used for a gas generator.
- the enhancer agent 27 a known material that is usually used can be used.
- a so-called disk type gas generator having a short cylindrical shape is shown and described in FIG. 3, the gas generator for deploying an airbag according to the present invention is not limited to this, and a cylinder type gas generator having a long cylindrical shape,
- the igniter of the present invention should be applied to a hybrid gas generator including an ignitable pyrotechnic preparation and a high-pressure gas cylinder.
- the operation of the gas generator 21 in FIG. 3 will be described.
- a sensor (not shown) detects a vehicle collision
- a signal is sent to a control unit (actuator) (not shown), and an energization signal is sent to the igniter 23 from the detected control unit.
- the igniter 23 generates heat in the existing bridge, and the igniting agent loaded in the igniter 23 is ignited by this heat, and the flame is released into the enhancer chamber of the igniter 23.
- the enhancer agent loaded in the enhancer chamber is ignited by the flame, and a more powerful flame and high-temperature high-pressure gas are delivered to the gas generating agent 24 to burn the gas generating agent 24 and generate a large amount of gas.
- a large amount of the generated gas passes through the filter 25 and is introduced into the airbag from the gas ejection hole 26 to deploy the bag.
- Example 1 Nitrocellulose was dissolved as a binder in isoamyl acetate to prepare an isoamyl acetate solution having a binder concentration of 2% by mass. Next, 8.55 g of zirconium hydride (particle size: 2.5 ⁇ m), 9.6 g of tungsten powder (particle size: 0.6 to 0.8 ⁇ m) and 11.85 g of potassium perchlorate (particle size: 12 to 18 ⁇ m) ) After adding 1.5 g of the above-mentioned binder isoamyl acetate solution (binder concentration: 2 mass%) to a mixture of 0.15 g of magnesium oxide, 11 g of isoamyl acetate was further added and mixed in a mixer.
- Examples 2-4 Furthermore, the composition ratios of the respective components were changed as shown in Table 1, and igniters for igniters of Examples 2 to 4 were prepared by the same preparation method as in Example 1.
- Table 1 shows the compositions of the igniters for the igniters of Examples 1 to 4 and the comparative example.
- a compounding quantity is a mass ratio on the whole composition basis.
- Friction sensitivity test (Test method according to JIS K 4810) A friction sensitivity test was performed by sandwiching the ignition powder of the example or the comparative example between the friction rod made of porcelain attached to the BAM type friction sensitivity tester and the friction plate, and moving the friction plate horizontally with the load applied. It was. The degree of friction sensitivity is examined from the relationship between the load and the success or failure of the explosion. The degree of friction sensitivity is estimated to be one or only one explosion after six consecutive tests at the same load. Judgment was made by determining the load at 1/6 explosion point.
- the ignition agents of Examples 1 to 4 were found to have a 1/6 explosion point load of 5600 to 10800 gf.
- the comparative example which is a conventional igniter, caused two explosions at a load of 75 gf and no explosion at a load of 50 gf. Therefore, a load of 1/6 explosion point exists between the loads of 50 to 75 gf. I decided.
- the igniter compositions for the igniters of Examples 1 to 4 had a load of 1/6 explosion point larger than that of the igniter composition for the igniter of the comparative example, and the friction sensitivity decreased significantly. It can be seen that it is insensitive.
- Examples 1 to 4 the values of the minimum ignition current and the maximum misfire current were almost equal in Examples 1 to 4 and the comparative example which is a conventional igniting agent. It can be seen that Examples 1 to 4 have no problem in using the igniter for the igniter and satisfy the required current ignition sensitivity.
- Example 5 6.3 g of titanium hydride (particle size: 8.0 ⁇ m), 9.6 g of tungsten powder (particle size: 0.6 to 0.8 ⁇ m), and 14.1 g of potassium perchlorate (particle size: 12 to 18 ⁇ m)
- Example with the same preparation method as in Example 1 magnesium oxide: 0.15 g, adding 1.5 g of isoamyl acetate solution of nitrocellulose (binder concentration: 2% by mass) as a binder
- the composition ratio was charged 5 igniters for the igniter were prepared.
- Example 6 2.782 g of titanium hydride (particle size: 8.0 ⁇ m), 6.572 g of tungsten powder (particle size: 0.6 to 0.8 ⁇ m), 10.646 g of potassium perchlorate (particle size: 12 to 18 ⁇ m), and 7 g of isoamyl acetate was added and mixed with a mixer. After mixing was completed, the resulting mixture was spread on a pallet and air-exposed. After air exposure, granulation is carried out through a sieve of 24 mesh (aperture approximately 0.8 to 0.6 mm), and the granulated product is put into a dryer and dried at 60 ° C. An explosive (about 20 g) was obtained.
- Table 3 shows the compositions of the igniters for the igniters of Examples 5 to 6.
- a compounding quantity is a mass ratio on the whole composition basis.
- Examples 5 to 6 were confirmed to ignite under the condition that a current of 1.2 A was applied at an energization time of 2 msec, and there was no problem when used as an igniter composition for an igniter. I was able to confirm.
- the igniter composition for an igniter according to the present invention achieves performance with reduced friction sensitivity while satisfying the required current ignition sensitivity. That is, it is an igniting agent having a sensitivity that can be surely ignited by a minute current, and has a remarkably excellent effect that safety in the manufacturing process is improved by reducing and desensitizing the friction sensitivity.
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Abstract
Description
このような問題に対して、特許文献3には、金属粉末を形成する金属粒子の形状を鱗片形状とすることで、電流発火感度を維持しつつ、取り扱い時の安全性の低下を抑制する技術が開示されている。しかしながらこの技術は、金属粉末を特殊な形状とすることが必要であり、金属粉末の製造制御が困難であるとともに、製造コストが高くなるという欠点がある。
(1)金属水素化物(A);タングステン粉末、モリブデン粉末、アルミニウム粉末、チタン粉末、及びマグネシウム粉末からなる群から選択される1種以上である金属粉末(B);並びに過塩素酸塩(C)を含有する点火器用点火薬組成物。
(2)前記金属水素化物(A)が、水素化ジルコニウム及び/又は水素化チタンを含有する前記(1)に記載の点火器用点火薬組成物。
(3)前記金属粉末(B)が、タングステン粉末を含有する前記(1)または(2)のいずれかに記載の点火器用点火薬組成物。
(4)前記金属水素化物(A)を10~50質量%含有することを特徴とする前記(1)~(3)のいずれかの一項に記載の点火器用点火薬組成物。
(5)前記金属水素化物(A)を10~50質量%、前記金属粉末(B)を10~50質量%、並びに前記過塩素酸塩(C)を20~70質量%含有してなることを特徴とする前記(1)~(4)のいずれか一項に記載の点火器用点火薬組成物。
(6)前記(1)~(5)のいずれか一項に記載の点火器用点火薬組成物を用いることを特徴とする点火器。
(7)前記(6)に記載の点火器を用いたことを特徴とするシートベルトプリテンショナー用ガス発生器。
(8)前記(6)に記載の点火器を用いたことを特徴とするエアバッグ用ガス発生器。
本発明に使用される金属水素化物(A)は、燃焼成分として機能するものである。すなわち点火過程において酸化作用を受け発熱すると共に、金属熱粒子及び熱ガスを供する機能を担う。
本発明に用いられる金属水素化物(A)としては、水素化ジルコニウム、水素化チタン、水素化アルミニウム、水素化マグネシウム、水素化カルシウム等が挙げられる。これら金属水素化物(A)は、1種単独で使用してもよいし、2種以上を混合して使用してもよい。点火薬組成物としての安定性、取り扱い容易性の観点から、水素化ジルコニウム及び/又は水素化チタンが好ましく、特に水素化ジルコニウムが好ましい。
当該金属水素化物(A)の粒径は、迅速な着火応答性に関する電流発火感度に影響するものであり、点火器の要求性能に応じ適宜設定されるものである。用いる粒径は1~10μmであることが好ましい。
本発明の点火器用点火薬組成物における金属水素化物(A)の含有率は、10~50質量%が好ましい。より好ましくは10~40質量%の範囲である。金属水素化物(A)の含有量が10質量%未満では、十分な出力が得られず、50質量%を超えると、点火器用点火薬組成物に要求される電流発火感度を満たさないおそれがある。
本発明の点火器用点火薬組成物に用いる金属粉末(B)の含有率は、点火器用点火薬組成物中、10~50質量%の範囲であることが好ましく、15~45質量%の範囲であることが更に好ましい。金属粉末(B)の含有率が10質量%未満では、要求される電流発火感度を満たさないおそれがあり、一方、50質量%を超えると、出力が下がるおそれがある。
当該点火器用点火薬組成物中における過塩素酸塩(C)の含有率は、20~70質量%が好ましく、25~60質量%の範囲であることが更に好ましい。過塩素酸塩(C)の含有率が20質量%未満では、十分な出力が得られず、一方、70質量%を超えると、点火器用点火薬組成物に要求される電流発火感度を満たさないおそれがある。
本発明の点火器用点火薬組成物は、より好ましくは、金属水素化物(A)が水素化ジルコニウム及び/又は水素化チタンであり、金属粉末(B)がタングステン粉末またはモリブデン粉末であり、過塩素酸塩(C)が過塩素酸カリウムである。
当該点火薬組成物として特に好ましい具体例としては、水素化ジルコニウム、タングステン、過塩素酸カリウムを含有する組成物が挙げられる。この場合、水素化ジルコニウム10~50質量%、タングステンを10~50質量%、過塩素酸カリウムを20~70質量%を含有する組成物とすることが好ましい。また別の好ましい態様としては、水素化チタン、タングステン、過塩素酸カリウムを含有する組成物が挙げられる。この場合、水素化チタン10~50質量%、タングステンを10~50質量%、過塩素酸カリウムを20~70質量%を含有する組成物とすることが好ましい。
なお、塩基性物質の含有率は、点火器用点火薬組成物中、10質量%以下であることが好ましい。点火薬組成物のバランスを考慮すると、5質量%以下であることが更に好ましい。
なお、バインダの含有率は、点火器用点火薬組成物中、5質量%以下であることが好ましい。
本発明において、バインダはそのまま当該点火薬組成物に混用して用いてもよく、バインダに適当な溶剤を添加し、当該点火薬組成物に混用する方法を用いてもよい。上記溶剤は、バインダに対して不活性であり、分散性に優れるもの、又は良溶解性を示すものであれば特に問題なく使用することができる。一方、乾燥工程において揮散しやすい物性が製造工程上で好ましく、炭化水素類、エステル類、ケトン類等の揮発性の有機溶剤が好適に用いられる。
図1は、本発明の点火器の一例の断面図である。図1に示した点火器1は、点火薬2を格納するカップ体6と、カップ体6を格納するカバー体9、外部と電気的に接続するための電極ピン8が絶縁体4により固定された塞栓7と、各電極ピン8間に接続され点火薬2に接する電橋線3とを備える。塞栓7とカップ体6の接合部、及び塞栓7と電極ピン8の接合部は絶縁樹脂5により覆われて保護されている。なお、本発明の点火器1は、更に点火器に通常用いられる公知の部品を備えることができる。ここで、本発明の点火器1は、点火薬2に、上述した本発明の点火器用点火薬組成物、またはその成形体である点火薬を用いることを要する。
塞栓7に電極ピン8及び電橋線3等を装着した塞栓組立て体を、点火薬2を充填したカップ体6に挿入して固定する。その後、カップ体6の外周にカバー体9を被せ、絶縁樹脂5でモールド固定することにより当該点火器1が製造することができる。点火薬2は、計量工程、カップ体6への装填工程、塞栓組立て体の挿入工程、及び塞栓固定工程において、物理的移動及び機械的接触摩擦過程を経由して、当該点火器1が製造される。
本発明の点火器用点火薬組成物は、従来汎用されている点火薬と同等の電流発火感度が維持されており、迅速な点火特性を有する。更に摩擦感度が低減されており、点火器の製造工程における取扱い安全性において大いに向上する物性である。すなわち、本発明の点火薬組成物は、点火器に採用することにより、製造安全性が向上すると共に、点火器感度において規定の性能を満たす点火器を提供できるものである。
図2を参照して本発明のガス発生器を詳細に説明する。図2は、本発明の点火器を用いたシートベルトプリテンショナー用ガス発生器の一例の断面図である。図2に示したガス発生器11は、燃焼によりガスを発生するガス発生剤12を格納するカップ体13と、カップ体13の内側に配置され、外部と電気的に接続するための電極ピン16を備え、通電によりガス発生剤12を着火させる点火器14と、カップ体13と点火器14を固定するホルダー15とを備える。なお、ガス発生器11は、更にガス発生器に通常用いられる公知の部品を備えることができる。
図3は、本発明の点火器を用いたエアバッグ用ガス発生器の一例の断面図である。図3に示したガス発生器21は、ガス噴出孔26が複数個設置された金属製容器によるハウジングアッパー22により外殻が形成され、その内部に本発明の点火器23とフィルター25が装備されている。その内部空間にはガス発生剤24が充填されており、前記点火器23の近接部にはエンハンサー室が設置されおり、通常のガス発生器構成の場合、点火器23から発生される点火炎をガス発生剤24に伝達するエンハンサー剤(伝火薬)27がエンハンサー室に充填されている。なお、ガス発生器21は、更にガス発生器に通常用いられる公知の部品を備えることができる。エンハンサー剤27は、通常用いられる公知の材料を用いることができる。
図3において短尺円筒形状のいわゆるディスク型ガス発生器を示し説明したが、本発明に係るエアバッグ展開用ガス発生器はこれに限定されず、長尺円筒形状のシリンダー型ガス発生器、少量の発火性火工製剤と高圧ガスボンベを備えたハイブリッド型ガス発生器においても同様に、本発明の点火器は適用されるべきものである。
酢酸イソアミル中にバインダとしてニトロセルロースを溶解し、バインダ濃度2質量%の酢酸イソアミル溶液を調製した。次に、水素化ジルコニウム(粒径:2.5μm)8.55g、タングステン粉末(粒径:0.6~0.8μm)9.6g及び過塩素酸カリウム11.85g(粒径:12~18μm)、酸化マグネシウム0.15gの混合物に、上記バインダの酢酸イソアミル溶液(バインダ濃度:2質量%)1.5gを添加した後、さらに酢酸イソアミル11gを添加し、混合機にて混合した。混合を終了した後、得られた混合物をパレット上に広げ、風晒した。風晒した後、24メッシュ(目開き約0.8~0.6mm)の篩を通して造粒を行い、その造粒物を乾燥機に入れ、60℃で乾燥させ、実施例1の点火器用点火薬(約30g)を得た。
さらに、それぞれの成分の組成比を、表1に示すように変更して、実施例1と同様の調製方法で実施例2~4の点火器用点火薬を調製した。
酢酸イソアミル中にバインダとしてニトロセルロースを溶解し、バインダ濃度1.3質量%の酢酸イソアミル溶液を調製した。次に、ジルコニウム(粒径: 2μm)150g、タングステン粉末(粒径:0.6~0.8μm)175gの混合物に、上記酢酸イソアミル溶液(バインダ濃度:1.3質量%)45gを添加した後、さらに酢酸イソアミル50gを添加し、混合機にて混合した。その後、過塩素酸カリウム175g、及び酸化マグネシウム2.5g、さらに酢酸イソアミル60gを添加し、混合機にて混合した。混合を終了した後、得られた混合物をパレット上に広げ、風晒した。風晒した後、24メッシュの篩を通して造粒を行い、その造粒物を乾燥機に入れ、60℃で乾燥させ、点火器用点火薬(約500g)を得た。
BAM式摩擦感度試験機に取り付けた磁器製の摩擦棒と摩擦板の間に、実施例または比較例の点火薬をはさみ、荷重をかけた状態で摩擦板を水平に動かすことにより、摩擦感度試験を行った。荷重と爆発の成否との関係から摩擦感度の度合いを調べるが、その度合いについては、同一荷重で連続して試験を6回行い、1回だけ爆発するか、又は1回だけ爆発すると推定される1/6爆点の荷重を求めることにより、判断した。
最小発火電流、及び最大不発火電流を計算するための統計的な手法として、ブルーストーン法を用い、電流発火感度を評価した。簡単に説明すると、図1に示す点火器に、実施例1~4及び比較例の点火薬を215mg装填して、試験点火器を作製した。これに対し、通電電流について等間隔で分けた複数のレベルを設定し、通電による試料の発火、不発火に応じて通電電流のレベルを変えていく。これを40回行い、最終的に統計処理をして最小発火電流及び最大不発火電流の平均値及び標準偏差を算出し、そこから所望の信頼度における最小発火電流及び最大不発火電流を求めた。なお、最小発火電流及び最大不発火電流の信頼水準を95%とし、信頼度を99.9999%とした。
一方、電流発火感度については、実施例1~4と従来品の点火薬である比較例は、最小発火電流、及び最大不発火電流の値はほぼ同等であった。実施例1~4は点火器用点火薬の使用に際して問題はなく、要求される電流発火感度を満たしていることがわかる。
水素化チタン(粒径:8.0μm)6.3g、タングステン粉末(粒径:0.6~0.8μm)9.6g、および過塩素酸カリウム(粒径:12~18μm)14.1gの組成比率にて仕込んだ以外は、実施例1と同様の調製方法(酸化マグネシウム:0.15g、バインダとしてニトロセルロースの酢酸イソアミル溶液(バインダ濃度:2質量%)1.5gを添加)で実施例5の点火器用点火薬を調製した。
水素化チタン(粒径:8.0μm)2.782g、タングステン粉末(粒径:0.6~0.8μm)6.572g、過塩素酸カリウム(粒径:12~18μm)10.646g、及び酢酸イソアミル7gを添加し、混合機にて混合した。混合を終了した後、得られた混合物をパレット上に広げ、風晒した。風晒した後、24メッシュ(目開き約0.8~0.6mm)の篩を通して造粒を行い、その造粒物を乾燥機に入れ、60℃で乾燥させ、実施例6の点火器用点火薬(約20g)を得た。
図1に示す点火器に、実施例5~6の点火器用点火薬215mgを点火薬2として装填して、試験用点火器を作製した。電極ピン8に、電流1.2Aを通電時間2msecにて印加して発火の有無を確認した。
2 点火薬
3 電橋線
4 絶縁体
5 絶縁樹脂
6,13 カップ体
7 塞栓
8,16 電極ピン
9 カバー体
11,21 ガス発生器
12,24 ガス発生剤
15 ホルダー
22 ハウジングアッパー
25 フィルター
26 ガス噴出孔
27 エンハンサー剤
Claims (8)
- 金属水素化物(A)、
タングステン粉末、モリブデン粉末、アルミニウム粉末、チタン粉末、及びマグネシウム粉末からなる群から選択される1種以上である金属粉末(B)、並びに
過塩素酸塩(C)
を含有する点火器用点火薬組成物。 - 前記金属水素化物(A)が、水素化ジルコニウム及び/又は水素化チタンを含有する請求項1に記載の点火器用点火薬組成物。
- 前記金属粉末(B)が、タングステン粉末を含有する請求項1または2に記載の点火器用点火薬組成物。
- 前記金属水素化物(A)を10~50質量%含有することを特徴とする請求項1~3のいずれか一項に記載の点火器用点火薬組成物。
- 前記金属水素化物(A)を10~50質量%、
前記金属粉末(B)を10~50質量%、並びに
前記過塩素酸塩(C)を20~70質量%
含有してなることを特徴とする請求項1~4のいずれか一項に記載の点火器用点火薬組成物。 - 請求項1~5のいずれか一項に記載の点火器用点火薬組成物を用いることを特徴とする点火器。
- 請求項6に記載の点火器を用いたことを特徴とするシートベルトプリテンショナー用ガス発生器。
- 請求項6に記載の点火器を用いたことを特徴とするエアバッグ用ガス発生器。
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- 2011-07-14 MX MX2013000536A patent/MX2013000536A/es not_active Application Discontinuation
- 2011-07-14 JP JP2012524456A patent/JP5819829B2/ja active Active
- 2011-07-14 CN CN201180034704.5A patent/CN103052609B/zh not_active Expired - Fee Related
- 2011-07-14 US US13/810,120 patent/US20130305952A1/en not_active Abandoned
- 2011-07-14 WO PCT/JP2011/004023 patent/WO2012008161A1/ja active Application Filing
- 2011-07-14 EP EP11806494.8A patent/EP2594545B1/en not_active Not-in-force
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014028731A (ja) * | 2012-07-31 | 2014-02-13 | Chugoku Kayaku Kk | 電気雷管用の点火剤 |
CN103980073A (zh) * | 2014-04-30 | 2014-08-13 | 北京理工大学 | 一种含氢化铈高热量炸药的制备方法 |
CN103980073B (zh) * | 2014-04-30 | 2016-07-06 | 北京理工大学 | 一种含氢化铈高热量炸药的制备方法 |
WO2023127359A1 (ja) | 2021-12-27 | 2023-07-06 | 日本化薬株式会社 | 点火薬、およびそれを含む点火器 |
Also Published As
Publication number | Publication date |
---|---|
MX2013000536A (es) | 2013-07-29 |
EP2594545A1 (en) | 2013-05-22 |
CN103052609B (zh) | 2015-10-07 |
CN103052609A (zh) | 2013-04-17 |
US20130305952A1 (en) | 2013-11-21 |
EP2594545B1 (en) | 2015-09-09 |
SG186824A1 (en) | 2013-02-28 |
JPWO2012008161A1 (ja) | 2013-09-05 |
JP5819829B2 (ja) | 2015-11-24 |
EP2594545A4 (en) | 2014-01-22 |
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