Classifications

• • 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
  • C06B33/04—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 nitrogen-oxygen salt
• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
  • C06C9/00—Chemical contact igniters; Chemical lighters
• • 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

Definitions

• the present invention relates to a novel explosive composition that can be used as an enhancer agent (fire transfer agent) used in a gas generator of an airbag device for a vehicle.
• the present invention is characterized by having an auto-ignition property while maintaining a high calorific value.
• Airbag devices are occupant protection devices that have been widely adopted in recent years to improve the safety of vehicle occupants.
• the principle is that when a sensor detects a collision, it emits an electric signal, activates the gas generator, deploys the airbag, and reduces the impact of the occupant collision.
• the sequence in which the gas generator operates is as follows: the igniter that has received the signal from the sensor first ignites, then transmits the heat to the enhancer, and then ignites the gas generator.
• the role of the enhancer is to ignite the entire surface of each gas generating agent within a predetermined time.
• the gas generator exhibits its original performance as calculated and without any ignition delay.
• the so-called “boron saltpeter” mainly containing boron and potassium nitrate has been generally used as an enhancer agent.
• This enhancer is frequently used because of its advantages such as instantaneous combustion and high calorific value, generation of heat particles of boron metal, and promotion of ignition.
• the generated gas mole number per 100 g of this boron saltpeter is less than 0.4, which is less than that of the gas generating agent with poor ignitability.
• the material of the gas generator container As the material of the gas generator container, it has become popular to use aluminum instead of conventional stainless steel (SUS) in order to reduce the weight of the gas generator.
• the sus product has excellent high-temperature strength, so even when the temperature rises in a vehicle fire or incineration of a gas generator, the internal gas generating agent can be burned without destroying the container. It is.
• the gas generator vessel is made of aluminum, the strength at high temperatures is significantly reduced.
• the gas generator is exposed to a flame due to a vehicle fire and the internal gas generating agent burns, if the strength of the aluminum container itself is reduced by the flame, the container cannot withstand the combustion pressure of the gas generating agent. Bursts. Fragments of the ruptured container can splatter around and damage the occupants and the people around them.
• an explosive composition that automatically ignites at a temperature lower than the temperature at which the strength of aluminum is reduced is provided in a container made of an anodized aluminum separately from the gas generating agent Janhansa. Therefore, it is proposed that the gas generating agent be burned in the aluminum container before the strength of the aluminum container is reduced so that there is no danger such as the rupture of the aluminum container.
• the auto-ignition property of an auto-igniting explosive means that it ignites in the range of 180 ° C or more and 210 ° C or less, which is lower than the reduction in strength of aluminum at high temperatures. Temperature.
• WO 97207686 discloses an auto-ignition enhancer agent.
• this enhancer has a calorific value of 3400 ⁇ 8 , which is lower than the calorific value of boron nitrate of 6700 JZg, and contains almost no metal particles. Therefore, there is a problem that the gas generator may ignite or output may be insufficient.
• the conventional boron nitrite enhancer has an ignition point of about 470 ° C, and does not exhibit the auto-ignition function described here.
• the present invention has been made in view of the above problems, and an object of the present invention is to provide an enhancer composition having an auto-ignition property and having a high calorific value. It is in. Disclosure of the invention
• the inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, by defining the composition of the enhancer-agent, the auto-ignition is developed, and the ignition of the gas-generating agent has a high calorific value. And found that the present invention It has been completed.
• the enhancer agent preferably has the following characteristics i to iii. In this sense, the calorific value is low and the amount of generated gas is increased.
• the present invention has been made based on the understanding that the pursuing gas generating agent is an explosive composition having a fundamentally different purpose. It is ideal that the enhancer agent has all of the following characteristics i to iii. However, it is possible to function as an enhancer agent only by the following characteristic i.
• the gas generating agent must have the number of generated gas moles to generate an appropriate gas flow to ignite the entire surface of the gas generating agent.
• the self-igniting enhancer composition of the present invention comprises the following components, and has a heat value of 450 J / g or more, preferably 600 J / g or more.
• the self-igniting enhancer composition of the present invention is obtained by adding an oxidizing agent such as potassium nitrate, sodium nitrate and strontium nitrate and molybdenum trioxide in addition to 5-aminotetrazole and metal powder.
• an oxidizing agent such as potassium nitrate, sodium nitrate and strontium nitrate and molybdenum trioxide
• auto-ignition property means that ignition occurs in a range of 180 ° C. to 210 ° C., which can be said to be a necessary temperature range from the viewpoint of a decrease in strength of aluminum at high temperatures.
• the self-igniting enhancer composition of the present invention has a high calorific value of 450 J / g or more while having auto-ignition properties, and thus has properties that are preferable as an enhancer composition. .
• those having a calorific value of 600 J / g or more are most suitable as an enhancer composition.
• the self-igniting enhancer agent composition of the present invention enables the gas generator to have auto-ignitability without complicating the structure of the gas generator.
• the self-igniting enhancer composition of the present invention is characterized in that, in addition to the above characteristics, the number of moles of generated gas per 100 g is from 0.5 niol to 2.0 mol.
• the number of moles of the generated gas per 100 g is 0.5 raol or more and 2.0 Omol or less, an amount of the generated gas flow suitable for igniting the gas generating agent can be supplied.
• Such a self-igniting enhancer composition of the present invention achieves stable and good ignition performance by combining a high calorific value and an appropriately generated gas flow in a well-balanced manner.
• the auto-ignitable enhancer composition of the present invention also exhibits auto-ignitability while maintaining superior heat transfer properties to general boron saltpeter enhancers.
• the metal powder may be a powder of an alloy, but is preferably at least one selected from the group consisting of aluminum, magnesium, magnalium, boron, titanium and zirconium.
• the composition ratio of the self-igniting enhancer agent composition is the following I, more preferably ⁇ I.
• I 5- aminotetrazole 3 wt 0/0 to 25 wt% or less
• Such a self-igniting enhancer composition of the present invention is different from other explosive compositions containing a large amount of nitrogen-containing organic compounds, in that nitrogen-containing organic compounds, That is, the content of 5-aminotetrazole is as low as 25% by weight or less, more preferably as low as 15% by weight, and the content of metal powder is in the range of 5% by weight or more and 30% by weight or less, more preferably 16% by weight or more and 25% by weight. It is contained in large amounts in the range of not more than% by weight. As a result, the gas generating agent is ignited directly by a large number of metal thermal particles, so that there is little temperature dependence and stable ignition performance can be obtained.
• FIG. 1 is a diagram of an ignition waiting test apparatus used in each of the examples and comparative examples.
• FIG. 2 is a schematic cross-sectional view of a main part showing a structure of a gas generator used in each of Examples and Comparative Examples.
• FIG. 3 is a graph showing the combustion state of a 60 L tank test obtained by operating a gas generator using the autoignitable enhancer agent composition of the present invention, as a function of time and pressure.
• FIG. 4 is Table 1 showing the results of the measurement test. BEST MODE FOR CARRYING OUT THE INVENTION
• the self-igniting enhancer agent composition of the present invention contains the following components, and has a heat generation amount of 450 J / g or more, preferably 600 J / g or more.
• the number of moles of generated gas per 1 g is preferably 0.5 mol or more and 2.0 O mol or less.
• the 5-aminotetrazole is contained as a fuel component.
• the nitrogen-containing organic compounds 5-aminotetrazole is extremely easy to handle, including stability and safety, and inexpensive, and is a preferable substance for the present invention.
• the content of 5-aminotetrazole is preferably from 3% by weight to 25% by weight, more preferably from 5% by weight to 15% by weight.
• the content of 5-aminotetrazole may be the minimum amount to have auto-ignition property. If the content is more than 25% by weight, the calorific value of the enhancer agent composition is reduced, and the amount of metal heat particles is reduced. Decrease, ie, shortage of heat transfer power. On the other hand, if the content is less than 3% by weight, auto-ignition property is not exhibited, which is not preferable.
• At least one selected from the group consisting of nitric acid, sodium nitrate and strontium nitrate is contained as an oxidizing agent.
• Other nitrates alone do not exhibit auto-ignition and are not preferred.
• nitric acid are selected from the group consisting of lime, sodium nitrate and strontium nitrate. When used in combination with at least one of them, auto-ignition can be exhibited.
• potassium nitrate is preferable because it has no hygroscopicity and is easy to handle.
• the content of the oxidizing agent 5 0 wt% or more 8 5 weight 0/0 hereinafter well, still more preferably 6 0 wt% or more 8 0 wt% or less. If the content of the oxidizing agent is less than 50% by weight, the oxygen supply becomes insufficient, and harmful CO is generated due to incomplete combustion. If it is more than 85% by weight, the calorific value decreases and the heat transfer power becomes insufficient.
• the metal powder include aluminum, magnesium, magnalium, boron, titanium and zirconium. Boron is particularly preferred because of low handling risk and low price.
• the calorific value increases, and the amount of heat particles increases.
• the content is preferably 5% by weight or more and 30% by weight or less, more preferably 16% by weight or more and 25% by weight or less. If the content is less than 5% by weight, the calorific value will decrease and the amount of metallic hot particles will decrease. On the other hand, if the content is more than 30% by weight, the content of other components is relatively reduced, and the auto-ignition property is not exhibited.
• the content of the molybdenum trioxide is preferably from 0.2% by weight to 10% by weight, more preferably from 1% by weight to 7% by weight.
• the content of molybdenum trioxide may be the minimum amount at which auto-ignition occurs, and if it is less than 0.2% by weight, auto-ignition does not occur and more than 10% by weight was added. In such a case, a significant decrease in the calorific value is caused.
• the self-igniting enhancer composition of the present invention when the number of generated gas moles is less than 0.5 mol, ignition may be unstable due to a small flow of generated gas. When the number of moles of generated gas is larger than 2. Since the calorific value is low, the performance as an enhancer agent may not be sufficiently exhibited. .
• additives can be added as needed.
• additives that can be used include a binder, an anti-caking agent, and a molding aid.
• binder include hydrotalcites and nitrocellulose.
• anti-caking agent include silicon nitride and silicon carbide.
• molding aid include magnesium stearate and zinc stearate. it can.
• the content of these additives with respect to the enhancer composition of the present invention is preferably from 0.1% by weight to 5% by weight.
• the preferred composition ratio of each component is 5% to 25% by weight of 5-aminotetrazole, 5% to 30% by weight of boron, 50% to 85% by weight of nitric acid rim. , Molybdenum trioxide 0.2 weight. / 0 or more and 10% by weight or less.
• 5-aminotetrazole is 5% to 15% by weight
• boron is 16% to 25% by weight
• potassium nitrate is 60% to 80% by weight
• molybdenum trioxide is 1% by weight.
• the calorific value is adjusted so as to be at least 450 J / g or more, more preferably 600 J or more within this composition ratio range.
• the calorific value is preferably higher from the viewpoint of ignitability, but is preferably set to 7500 g or less from the viewpoint of heat resistance of the aluminum container used for the gas generator.
• the shape of the self-igniting enhancer composition of the present invention may be any of powder, granule and pellet, and the kneaded drug may be cast or extruded. ,.
• Examples of the shape that can be molded include a tablet shape, a single-hole circular shape, a porous cylindrical shape, and the like.
• the self-igniting enhancer composition of the present invention can be carried out by any of press molding and extrusion molding. By performing heat treatment after molding, the auto-igniting enhancer composition can be sufficiently dried to prevent ignition delay caused by moisture and improve environmental resistance.
• an anti-caking agent is added to a fuel component and an oxidizing agent, and the mixture is mixed by a V-type mixer and then pulverized.
• Predetermined amounts of pulverized fuel components, pulverized oxidizing agent, and molding aids are measured and uniformly mixed with a V-type mixer, and then charged into a press molding machine for heat treatment.
• the obtained molded article is used as an enhancer one-part composition.
• extrusion molding similarly, fuel components and oxidizers are powdered, each component is weighed into a spiral mixer, water is added in a range of 8 to 25% by weight, kneaded well, and the viscosity is reduced. Make it a moisturizer. Then, it is extruded into a desired shape using a vacuum kneading extruder, cut as appropriate, and then subjected to heat treatment. The extruded product thus obtained is used as a one-part composition.
• the preferred particle size of each component is as follows at a 50% particle size.
• 5-aminotetrazole 1 ⁇ or more and 30 ⁇ or less
• potassium nitrate 20 ⁇ or more and 100 / m or less
• boron 0.5 m or more and 20 m or less
• molybdenum trioxide 1 ⁇ m or more and 40 ⁇ m or less.
• More preferred particle sizes are as follows at 50% particle size.
• 5-aminotet Lasol 10 m or more and 20 m or less
• potassium nitrate 40 ⁇ m or more and 70 ix m or less
• boron 1 ⁇ m or more and 15 ⁇ m or less
• molybdenum trioxide 5 // m or more 2 5 ⁇ or less.
• the calorific value was measured using a bomb calorimeter. 1.0 g of the self-igniting enhancer composition of the present invention was weighed into a closed container made of SUS, and the lid was closed with the nichrome wire in contact. This was charged into a water-filled insulated container, and the nichrome wire was energized to completely burn the enhancer agent composition therein. The calorific value was calculated from the raised water temperature and specific heat.
• a bath 10 with an automatic temperature controller shown in FIG. 1 was filled with silicone oil 11 and an iron cylinder 12 with an inner diameter of 2 cm and a length of 20 cm was installed. The temperature was maintained at 20 CTC by the heater 13 and the thermometer 14. After 0.2 g of the autoignitable enhancer agent composition of the present invention was charged into iron steel 12, the time until ignition or sounding was measured. If ignition or pronunciation was confirmed within 1 minute, it was defined as having auto-ignition property.
• the gas generator 1 shown in FIG. 2 Using the gas generator 1 shown in FIG. 2, a 60 L tank test was conducted to examine the ignitability of the enhancer composition for the gas generating agent.
• the gas generator 1 has a central ignition chamber 7 in which an ignition device 2 and a transfer charge 3 are arranged. 04074
• this gas generator 1 was operated and the pressure was measured.
• pi is the maximum ultimate pressure in the container
• t1 is the time from the energization of the ignition device to the operation of the gas generator 1
• t2 is the time of the gas generator 1.
• the ignition performance of the enhancer agent composition is required to have a time t1 of 4 ms or less. If the time exceeds this range, the gas generator 1 will be delayed in operation and will not exhibit sufficient performance.
• the time t 1 from the energization of the ignition device 2 to the operation of the gas generator 1 is shown.
• the gas generating agent 4 in the gas generator 1 used in the 60 L tank test was prepared as follows.
• 5-aminotetrazole and guanidine nitrate were prepared as fuel components, strontium nitrate as an oxidizing agent component, silicon nitride as a slag forming agent, and synthetic hydrotalcite as a binder in the following composition ratio.
• Each component was prepared in the following composition ratio.
• 5-aminotetrazole (15 ⁇ m at 50% particle size): 19.5 parts by weight Boron fine powder (9 mm at 50% particle size): 8.0 parts by weight Molybdenum trioxide (1% at 50% particle size) 7 ⁇ m): 8.0 parts by weight Potassium nitrate (60 ym at 50% particle size): 64.5 parts by weight Isoamyl acetate solution of nitrocellulose: 50.0 parts by weight
• Table 1 in Fig. 4 shows the measurement results in each of the above tests using this sample.
• Each component was prepared in the following composition ratio.
• the 5-aminotetrazole, the boron fine powder, and the molybdenum trioxide were dry-mixed using a V-type mixer. Then, the solution of diisoamyl acid in the above-mentioned ditrocellulose was added and mixed in a mortar until a slurry was obtained. To this, the potassium nitrate was added and mixed until uniform. Thereafter, the isoamyl acetate was evaporated and passed through a 1 mm mesh to obtain granules. This was dried at 11 for 5 hours to obtain the self-igniting enhancer composition of the present invention.
• Table 1 in Fig. 4 shows the measurement results in each of the above tests using this sample.
• Each component was prepared in the following composition ratio.
• Table 1 in Fig. 4 shows the measurement results in each of the above tests using this sample.
• polon nitrite generally used as an enhancer composition was prepared by the following procedure.
• Each component was prepared in the following composition ratio.
• Table 1 in Fig. 4 shows the measurement results in each of the above tests using this sample.
• Example 2 an auto-ignitable composition disclosed as Example 1 in W097 / 20786, republished, was prepared by the following procedure.
• Each component was prepared in the following composition ratio.
• 5-aminotetrazole 34.2 parts by weight Potassium nitrate: 56.8 parts by weight
• Molybdenum trioxide 4.5 parts by weight
• Synthetic hydrotalcite 4.5 parts by weight
• the 5-aminotetrazole, the potassium nitrate, The molybdenum trioxide and the synthetic hydrotalcite were dry-mixed by a V-type mixer. Then, water is added as a solvent, wet granulation is performed, and a 1 mm mesh is To give granules. This was dried with 11 O for 5 hours to obtain the autoignitable composition.
• Each component was prepared in the following composition ratio.
• the sucrose, the potassium chlorate, and the magnesium oxide were dry-mixed using a V-type mixer. To this, silicon resin was added, kneaded, and granulated through a 1 mm mesh. This was left to cure for 48 hours to obtain the auto-ignitable composition.
• the self-igniting enhancer composition of the present invention (Examples 1 to 3) has a self-igniting property while having a calorific value of 450 jZg or more. No ignition delay is observed in the 60 L tank test.
• the self-igniting enhancer composition of the present invention has a high calorific value and is therefore most suitable as an enhancer composition. Furthermore, since the present invention is a one-part composition having an auto-ignition property, the auto-ignition property can be imparted to the anore-minimum gas generator without complicating the structure of the aluminum gas generator. .

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• Chemical & Material Sciences (AREA)
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• Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

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• 2000
  • 2000-07-06 JP JP2000204591A patent/JP4131486B2/ja not_active Expired - Fee Related
  • 2000-07-07 US US09/926,815 patent/US6562087B1/en not_active Expired - Lifetime
  • 2000-07-07 CZ CZ2002-75A patent/CZ304826B6/cs not_active IP Right Cessation
  • 2000-07-07 KR KR10-2001-7016921A patent/KR100450704B1/ko not_active Expired - Fee Related
  • 2000-07-07 WO PCT/JP2000/004536 patent/WO2001004074A1/ja not_active Ceased
  • 2000-07-07 EP EP00944325A patent/EP1205458B1/en not_active Expired - Lifetime
  • 2000-07-07 DE DE60045843T patent/DE60045843D1/de not_active Expired - Lifetime

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