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WO1997012849A1 - Generateur de gaz pour airbag - Google Patents

Generateur de gaz pour airbag Download PDF

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Publication number
WO1997012849A1
WO1997012849A1 PCT/JP1996/002796 JP9602796W WO9712849A1 WO 1997012849 A1 WO1997012849 A1 WO 1997012849A1 JP 9602796 W JP9602796 W JP 9602796W WO 9712849 A1 WO9712849 A1 WO 9712849A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas generating
generating agent
combustion
agent
gas
Prior art date
Application number
PCT/JP1996/002796
Other languages
English (en)
Japanese (ja)
Inventor
Tadao Yoshida
Yasuo Shimizu
Kazuo Hara
Shiro Chijiwa
Tsukasa Maekawa
Junichi Onishi
Shigeru Sumitomo
Takashi Kazumi
Original Assignee
Otsuka Kagaku Kabushiki Kaisha
Nippon Koki Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP7353203A external-priority patent/JPH09157080A/ja
Priority claimed from JP8059405A external-priority patent/JPH09249635A/ja
Priority claimed from JP8234977A external-priority patent/JPH1077258A/ja
Priority claimed from JP8234987A external-priority patent/JPH1077259A/ja
Application filed by Otsuka Kagaku Kabushiki Kaisha, Nippon Koki Co., Ltd. filed Critical Otsuka Kagaku Kabushiki Kaisha
Priority to EP96932011A priority Critical patent/EP0801045A4/fr
Publication of WO1997012849A1 publication Critical patent/WO1997012849A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
    • C06B45/20—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an organic explosive or an organic thermic component
    • C06B45/22—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an organic explosive or an organic thermic component the coating containing an organic compound
    • 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 gas generating agent for air packs.
  • the gas generating agent for an air bag according to the present invention has an appropriate combustion performance, a low combustion temperature, a low concentration of toxic components such as CO and NOx in a gas generated by the combustion, and The concentration of released suspended particulate matter is low, the thermal stability is good, and the safety is significantly higher than conventional azide and non-azide gas generating agents. It has new characteristics.
  • the demand for airbag systems is increasing exponentially as the demands on vehicle safety increase.
  • the airbag system inflates a nylon bag (air bag) installed inside a handle or dashboard when a car crashes at high speed. This prevents the occupant from colliding with any part of the vehicle and causing death or injury, and the expansion of the knock requires the inflation in the system.
  • the gas generated by the combustion of the gas generating agent loaded in the tar (gas generating container) is used.
  • the first requirement is "showing a moderate burning rate in the inflator".
  • the impact on the vehicle is detected by a sensor, and it is determined whether or not the collision is a true collision. It ignites the gas generant inside and releases gas to inflate the airbag and protect the occupant's body, especially the head.
  • the air bag needs to be deployed in accordance with the movement of the head. Therefore, it is inappropriate if the burning rate of the gas generating agent is too fast or too slow.
  • the second requirement is “low combustion temperature”. If the combustion temperature of the gas generating agent is high, the temperature of the gas released during the bag rises and damages the bag, and furthermore, the gas leaked outside due to the damage of the bag May cause burns to the occupants.
  • solids are usually produced as a by-product, and are removed by a finolator provided between the inflator and the bag. Not included in the released gas. If the combustion temperature is high, the solids evaporate and are released together with the gas into the bag, where they condense into suspended particulate matter, damaging the bag. In some cases, it can be done.
  • the third requirement is that “the concentration of toxic components such as C • and NOx in the gas generated by combustion should be low”.
  • Airbag In the system, the bag releases some of the gas into the vehicle immediately after inflation and shrinks somewhat to reduce the impact of occupant collision with the inflated bag. High levels of components can cause occupant poisoning.
  • the fourth requirement is “good thermal stability”. Gas generants must have a long life, usually 10 years or more. It is imperative that the gas generants not decompose at temperatures to which vehicles are exposed, especially at high temperatures in summer.
  • the fifth requirement is that the raw materials, intermediates, and products be highly safe.
  • impact ignitability ignition sensitivity to impact
  • the sixth requirement is “low toxicity”. High toxicity of gas generant raw materials, intermediates and products can cause manufacturing and disposal problems.
  • an azide-based gas generating agent using azurized sodium as a gas generating base has been widely used.
  • Azide-based gas generating agents have the drawback of high force impact ignitability, which is an excellent gas generating agent that satisfies the above first to fourth requirements. Be careful with handling.
  • sodium azide is toxic and requires protective equipment during handling.
  • wastewater treatment for work using azide sodium requires special treatment equipment.
  • azide-based gas generating agents with the above-mentioned disadvantages are not preferred. Therefore, there is a strong demand for the development of a non-azide-based gas-generating base that can be used in place of azimuthized sodium.
  • a non-azide-based gas generating agent containing a nitrogen-containing organic compound such as azodicarbonamide (ADCA) and an oxidizing agent is used.
  • ADCA azodicarbonamide
  • JP-A-6-32698, JP-A-6-89 Known (JP-A-6-32698, JP-A-6-89)
  • the gas generating agent exhibits an appropriate burning rate comparable to that of a conventional azide-based gas generating agent, has a low impact ignition property, and has a remarkably low detonation property and toxicity. Further, it is desired to further reduce the combustion temperature and the concentration of active ingredients such as CO and N0X in the gas, which are sufficiently low to be practically usable. In addition, this non-azide gas generating agent is required to be further improved in terms of thermal stability.
  • Japanese Unexamined Patent Publication No. 7-300383 discloses excellent thermal stability.
  • non-azide gas generating agents bis-carba'moinolehydrazine (hydrazolic canolebon amide) and oxono-oleate are used as active ingredients.
  • the gas generants are highly detonable and dangerous.
  • chloride lime which easily becomes suspended particulate matter, is produced as a by-product during the combustion.
  • German Published Patent Application No. 195 168 188 describes viscalbamoyl hydrazine and oxidizing agents such as oxohalogenates and nitrates and III, IV, V and VI
  • a gas generating agent containing a heat reducing agent such as a sulfate hydrate, a nitrate hydrate, a carbonate, a carbonate hydrate, a hydroxide, a hydroxide hydrate, etc. of a periodic metal is described.
  • the gas generating agent does not have sufficient combustion performance, and often causes incomplete combustion.If incomplete combustion occurs, the air bag does not expand instantaneously. Serious defects.
  • One object of the present invention is to exhibit a combustion rate and combustion temperature equal to or higher than those of conventional azide-based and non-azide-based gas generating agents, and to reduce the concentration of toxic components such as CO and NOx in the gas. It is still another object of the present invention to provide a gas generating agent for airbags which is remarkably excellent in thermal stability. Another object of the present invention is to have remarkably low impact ignitability, detonation, and toxicity as compared with the above-mentioned non-azide gas generant, and to release suspended particulate matter. An object of the present invention is to provide a gas generating agent for an air pack having a low concentration of a substance.
  • Another object of the present invention is to provide a gas generating agent for an air bag which does not cause incomplete combustion.
  • biscarbamoinolehydrazine which is a gas generating base
  • oxohalogenate which is an acidifier
  • a gas generating agent for an airbag comprising a nitrate as an oxidizing agent and (4) a combustion catalyst as an active ingredient is provided.
  • the gas generating agent for an air bag of the present invention satisfies all of the above first to sixth requirements. That is, the gas generating agent for an air bag of the present invention does not cause incomplete combustion and has a combustion speed and a combustion temperature equal to or higher than those of the conventional azide and non-azide gas generating agents. Indicate CO, NOx, etc. in gas The concentration of toxic components is even lower, the impact ignitability, detonation and toxicity are remarkably low, the concentration of released suspended particulate matter is low, and the heat stability is remarkably excellent. is there.
  • Biscanoleno which is the gas generating base of the gas generating agent for airbags of the present invention, is also known as piurea or hydrazolic amide.
  • ) Is a compound that has been mainly used as a raw material for ADCA.
  • screw-power balbamoyl hydrazine is used to adjust the shape of the foamed cell when foaming a synthetic resin with high chemical resistance and heat resistance, such as vinyl chloride resin, using ADCA. It is only used as a cell nucleating agent.
  • Biskanolevamo inolehydrazine has a higher thermal stability than ADCA and a remarkably higher stability against alkali, so if the selection range of oxidizing agents and combustion catalysts is expanded, It has such advantages and contributes to remarkable improvement of the thermal stability of the gas generating agent of the present invention.
  • Biscarno's hydrazine has very low toxicity and no danger of explosion, which contributes to the safety of the gas generating agent of the present invention.
  • the particle size is not particularly limited, and may be wide depending on various conditions such as, for example, the amount of the compound, the type and ratio of other components used in combination, and the capacity of the airbag. What is necessary is just to select from a range suitably.
  • viscous rubamoyl hydrazine has a scale-like or plate-like crystal shape and a weak bonding force between the particles, which may lead to insufficient moldability during formulation. .
  • the binder described below is replaced with a non-azide gas generating agent (0.5 to 2.0 parts by weight). Or more)
  • a method of surface-treating a bismuth rubamoyl hydrazine with an inorganic surface treating agent will be described.
  • Known inorganic surface treatment agents can be used, and among them, water-soluble metal salts are preferable.
  • water-soluble metal salts for example, A 1 C] 3, C o C l 2, Z r C l 4, S n C 1 2, S n C 1 T i C 1 3, T i C 1 F e Ch,
  • One type of surface treatment agent can be used alone, or two or more types can be used in combination.
  • the amount of the surface treating agent used is not particularly limited, and the type of the surface treating agent, the type and amount of other components constituting the gas generating agent other than the modified bis-carbamoyl hydrazine, and the obtained gas generating agent
  • the force can be appropriately selected from a wide range according to the desired performance, etc., and the weight of the total weight of the visco-metal hydrazine that is normally subjected to surface treatment It may be about 0.01 to 5% by weight, preferably about 0.1 to 2% by weight.
  • the surface treatment can be performed according to a known method.
  • the pH regulator used for neutralization is not particularly limited, and known acids and alkalis can be used. Specific examples of acids Examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, oxalic acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid.
  • Al-Li are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and carbonic acid. Hydrogen potassium, ammonia, etc. can be mentioned.
  • the drying is preferably performed at about 0 to 250 ° C, considering that the thermal decomposition temperature of bis-carbocene hydrazine hydrazine is about 2 ⁇ 0 to 260 ° C. Is carried out at a temperature of about 50 to 50 ° C. Drying can also be performed under reduced pressure, which is usually performed under normal pressure. Before the surface treatment of the bismuth rubamoyl hydrazine, it can be finely pulverized or recrystallized.
  • the surface may be coated, for example, by adding the hydrophilic polymer to an aqueous solution or aqueous dispersion of biscarbamoyl hydrazine and mixing. . Since bis-hydranol hydrazine has low solubility in water, it is preferably used in the form of an aqueous dispersion in consideration of treatment efficiency and the like. During the mixing, the mixture may be heated if necessary.
  • the hydrophilic polymer compound is not particularly limited. Any known ones can be used. For example, cellulose such as ruboxymethyl cellulose, modified canoleboxyl methylcellulose, hydroxymethyl cellulose, microcrystalline cellulose, etc. And polyvinyl alcohols such as fully-genated poly-vinyl alcohol and partially-genated poly-vinyl alcohol, and starches such as soluble starch. You. One of these hydrophilic polymer compounds can be used alone, or two or more can be used in combination.
  • the hydrophilic polymer compound can be added as it is or in the form of an aqueous solution.
  • the amount of the hydrophilic polymer compound used is not particularly limited, and it can be selected from a wide range as appropriate, as well as the amount of viscanoleno to be treated normally. O About 0.1 to 5% by weight, preferably about 0.5 to 3% by weight o
  • an aqueous solution or dispersion of biscarpa'moinolehydrazine is added to a hydrophilic polymer compound or an aqueous solution.
  • the same compounds as described above can be used as the c- hydrophilic polymer compound which may be added to the mixture and heated while adding a compound and a water-soluble polymerization initiator.
  • any of those conventionally known having a polymerizable double bond can be used.
  • acrylic acid, mesylate Examples include unsaturated carboxylic acids such as acrylic acid, maleic acid, and itaconic acid, and compounds having a vinyl group such as vinyl acetate and divinylbenzene.
  • (meth) acrylic acid alkyl esters in which the alkyl portion is a linear or branched alkyl group having about 1 to 4 carbon atoms can also be used.
  • Specific examples of the alkyl (meth) acrylate include, for example, (meth) ethyl acrylate and methyl (meth) acrylate. Can be done.
  • (meth) acrylic acid aryl esters such as phenyl (meth) acrylinoleate can also be used.
  • One or more of the orifices can be used alone or in combination of two or more.
  • the use amount of the olefins is not particularly limited and can be appropriately selected from a wide range. However, it is preferably about 0.1 to 3% by weight of the amount of the bismuth rubamoyl hydrazine that is usually processed. Or about 0.5 to 1% by weight.
  • the water-soluble polymerization initiator is not particularly limited, and any conventionally known water-soluble polymerization initiator can be used.
  • hydroxyperoxides such as cumene hydroxyperoxide and water-soluble polymerization initiators; Potassium peroxosulfate, ammonium peroxosulfate, hydrogen peroxide, azobisisobutyronitrile, azobiscyclohexanocanolevonil, azobis Valeric acid, 2, 2'-azobis (2-amidinopropane) ⁇ dihydrochloride, etc.
  • the water-soluble polymerization initiator one type can be used alone, or two or more types can be used in combination.
  • the amount of the water-soluble polymerization initiator used is not particularly limited, and can be appropriately selected from a wide range.
  • the amount is about 0.01 to 5% by weight based on the amount of the ordinary olefins used. Preferably, it should be about 0.05 to 1 weight 0/6 .
  • the temperature at the time of heating is not particularly limited.
  • the force is usually about 50 to 90 ° C, preferably about 80 ° C.
  • the modified bismuth rubamoyl hydrazine may be separated by a usual separation means such as filtration or centrifugation, and dried.
  • the pulverization can be produced, for example, by processing a powder of bis-forced hydrazine hydrohydrazine with a high-pressure pulverizer.
  • a high-pressure crusher blows high-pressure air into the device from at least two directions on the side of the device to generate an air current to pulverize the powder, and floats inside the device by air pressure. It is a method of collecting the fine powder that has risen, and specifically, for example, a counter jet minole (The Netherlands, Ano Piné Co., Ltd.) Manufactured by Kurimoto Tekkosho Co., Ltd.) and Crossjet Mill (manufactured by Kurimoto Iron Works).
  • biscarbamoyl hydrazine which is finely pulverized as described above, usually has an average particle diameter of 20 zm or less and a BET specific surface area of 0.5 m 2 Zg or more. However, it is preferable to use those having an average particle diameter of 10 m or less and a BET specific surface area of 5 m 2 ng or more. The average particle size is significantly above 2 and the Z or BET specific surface area
  • the average particle diameter in the present invention was measured using a laser diffraction type particle size distribution analyzer: Horiba, Ltd.].
  • the BET specific surface area in the present invention is a BET specific surface area measuring device [manufactured by Shimadzu Corporation] It was measured using.
  • the finely powdered bismuth rubamoyl hydrazine obtained in this way can be used as it is as a gas generating base, the moldability, the formability of the obtained gas generating agent, and the like. From the viewpoint of further improving combustion performance, it is more preferable to use granules.
  • the particle size of the granules is usually about 0.05 to 1 mm, preferably about 0.1 to 0.5 mm.
  • a known method can be employed.For example, if necessary, an appropriate amount of water or hot water is added to finely powdered bis-forced rubamoyl hydrazine, followed by granulation and drying. Good.
  • granulation for example, various extrusion granulations such as a screw type, a roll type, a blade type, a self-molding type, and a ram type.
  • extrusion granulations such as a screw type, a roll type, a blade type, a self-molding type, and a ram type.
  • the method of using a machine can be mentioned.
  • a rolling granulation method, a spray-dry method, or the like may be employed.
  • a nitrate or an oxohalogenate is used alone, or a nitrate and an oxohalogenate are used. Are used together.
  • nitrate examples include alkali metal salts such as lithium nitrate, sodium nitrate, and potassium nitrate, magnesium nitrate, sodium nitrate, and sodium nitrate.
  • Alkaline such as um Examples include earth metal salts and ammonium salts such as ammonium nitrate. Of these, alkali metal salts and alkaline earth metal salts are preferred, and potassium nitrate and sodium nitrate are particularly preferred.
  • Known oxohalogenates can be used, and examples thereof include perhalogenates and halogenates.
  • perhalogenates include, for example, lithium perchlorate, potassium perchlorate, sodium perchlorate, lithium perbromate, Alkali metal salts such as potassium perbromate and sodium perbromate, magnesium perchlorate, barium perchlorate, calcium perchlorate, perbromine Alkaline earth metal salts such as magnesium acid salt, barium perbromate, and calcium perbromate; ammonia such as ammonium perchlorate and ammonium perbromate And the like.
  • the halogenates include, for example, lithium chlorate, potassium chlorate, sodium chlorate, lithium bromate, and potassium bromate.
  • Alkali metal salts such as sodium bromide, magnesium chlorate, barium chlorate, calcium chlorate, magnesium bromate, barium bromate , Alkaline earth metal salts such as calcium bromate, and ammonium salts such as ammonium chlorate and ammonium bromate.
  • Ganoic acid and perhalogenic acid Metal salts are preferred, and potassium perchlorate and chlorinated lithium are particularly preferred.
  • Nitrate and oxohalogenate can be used as they are on the market, and their shapes, particle sizes, etc. are not particularly limited. It may be appropriately selected and used according to various conditions such as the ratio and the capacity of the airbag.
  • the amount of these oxidizing agents is Normally, the stoichiometric amount may be sufficient to completely oxidize and burn the bis-powered rubamoyl hydrazine based on the oxygen amount.However, the mixing ratio of the gas generating base and the oxidizing agent may be appropriately changed. Thus, the combustion speed, the combustion temperature (gas temperature), the composition of the combustion gas, and the like can be arbitrarily adjusted, so that it is possible to appropriately select from a wide range.
  • Nitrate, oxohalogenate, or nitrate and oxohalogenate is preferably used in an amount of about 100 to 400 parts by weight based on 100 parts by weight of hydrogen hydrazine. May be blended in an amount of about 100 to 240 parts by weight.
  • the mixing ratio thereof is not particularly limited and may be appropriately selected. If the mixing ratio of oxohalogenate is higher than the above-mentioned amount, the combustion temperature becomes high. This is not preferable because a large amount of halogenated metal, such as chlorinated lithium, is generated as a result of the possibility of detonation, which becomes suspended particulate matter.
  • the combustion catalyst which is one of the active ingredients, mainly has an effect of lowering the combustion temperature and reducing the concentration of C0 and / or N0X in the gas. It is considered to have.
  • the combustion catalyst an oxide of a metal having the fourth to sixth periods of the periodic table, an oxygen-containing metal compound capable of generating the metal oxide by heating, heteropoly acid, or the like is used.
  • metal oxides of the fourth to sixth periods of the periodic table include copper oxide, nickel oxide, cobalt oxide, iron oxide, chromium oxide, manganese oxide, and oxide.
  • Zinc, calcium oxide, titanium oxide, vanadium oxide, cerium oxide, holmium oxide, ytterbium oxide, molybdenum oxide-tungsten oxide, oxide Antimony, tin oxide, titanium oxide, and the like can be given.
  • copper oxide, nickel oxide, cobalt oxide, molybdenum oxide, oxide oxide, iron oxide, tin oxide, zinc oxide, chromium oxide, and the like are preferred.
  • M o 0 3, W 0 3 , C r 2 0 a. T i O a, S n O, Z n O, F e 2 0 3 , etc. are more preferable arbitrariness.
  • These metal oxides include: The hydrate is also included. Taking a hydrate of data down Goes te emission oxide as an example, W 0 3 'H Ru 2 0 Hitoshidea. Is as a child are these metal oxides, preferred to rather than the BET specific surface area of 5 m 2 "g or more on, rather than the preferred Ri good is 1 0 m 2 Roh g or more, and still more preferred to rather than the 4 0 m 2 Roh g have good to use more.
  • M o 0, W 0 3, etc. preferred would leave that obtained simultaneously reduce the CO concentration and NOX concentration It has new characteristics.
  • the oxygen-containing metal compound capable of producing an oxide of a metal having the fourth to sixth periods of the periodic table by heating is not particularly limited, and any known compounds can be used. Taking oxygen - containing Mo Li Bude down compounds to generate a M o 0 3 Ri by the heating in Examples, mode re Bude phosphate edge Le Bok, mode re Buden dihydrogen Tsu VIII, the mode re Bude phosphate Kell such Metal salts, molybdenic acid, and molybdenum hydroxide. Also, oxygen Motota emissions Gusute emissions reduction Gobutsu that generates a W ⁇ 3 Ri by the heating, for example, Ru metal salts thereof such as Der the motor down Holdings te phosphate.
  • metal salts of tangstenic acid examples include alkali metals such as lithium tangstenate, potassium tangstenate, and sodium tangstenate. Salts, alkaline earth metal salts such as magnesium tungstate, magnesium tungstate, copper tungstate, nickel tungstate Gels, Group VIII metal salts such as iron tungstate, tangs Copper tenate and the like can be mentioned.
  • heteropolyacids include, for example, linmolibdenic acid, linguistic acid, and metal salts thereof.
  • the metal salt of heteropolyacid is not particularly limited.
  • a Group VIII metal salt such as Co salt, Ni salt, Fe salt, Mg salt, Sr salt, P salt b salt, Bi salt and the like can be mentioned, and among them, Group VIII metal salt is preferable, and Co salt is particularly preferable.
  • M o O a, W 0 3 that generates an M o 0 3 Ri by the heating including oxygen Mo Li Bude down compounds, oxygen Motota down Gusute emissions compounds which form W 0 3 Ri by the heating, re Nmo Li Bude phosphate Copa 'Le DOO, C r 20 3, T i 0 2, S n O, Z n O, F e 2 0 3 Hitoshiryoku rather specifically preferred, C o O, n i O , n i 2 O 3.
  • M 0 O 3, WO 3, Group VIII metal salt of Mo Li Bude phosphate, Linmolibdenic acid phenol is more preferred.
  • One of the above-mentioned combustion catalysts can be used alone, or two or more can be used in combination.
  • the particle size of the combustion catalyst is not particularly limited, and may be appropriately selected from a wide range according to various conditions such as the amount of the catalyst, the ratio of the catalyst to other components, and the capacity of the airbag.
  • the blending amount is 7/12849
  • the amount of the combustion catalyst varies depending on whether oxohalogenate and nitrate are used alone or in combination as oxidizing agents.
  • the gas generating base and the oxidizing agent are used from the viewpoint of achieving further reduction of both CO and NOx.
  • the gas generating base and the oxidizing agent are used from the viewpoint of achieving further reduction of both CO and NOx.
  • about 5 to 150 parts by weight preferably about 10 to 120 parts by weight, more preferably about 30 to 80 parts by weight, based on 100 parts by weight of the total amount of the agent It should be about the degree.
  • the gas generating base is considered from the viewpoint of achieving a further reduction of both CO and NOx.
  • 0.1 to 30 parts by weight preferably 0.5 to 25 parts by weight, more preferably 3 to 1 part by weight based on 100 parts by weight of the total amount of It may be about 5 parts by weight.
  • the amount of the generated metal oxide may be set so as to fall within the range specified above.
  • the airbag gas generating agent of the present invention further includes It is preferable to add an agent.
  • Combustion regulators generally lower the combustion temperature, adjust the combustion rate, and cause gas generators to become involved in fires or other impacts in the process of manufacturing, transporting, or storing gas generating agents. It is used to prevent the explosion forest from receiving fire.
  • combustion regulator examples include the following (a) to (h).
  • Alkaline earth metal carbonates and bicarbonates such as Ca, Mg, Ba, and Sr
  • Periodic table 4th to 6th periodic elements other than the above (mouth) to (c) for example, Zn, Cu, Fe, Pb, Ti, V,
  • Organic acids such as amino acids such as glycine, organic carboxylic acids such as acetic acid, and citric acid.
  • combustion regulators for example, it is preferable to use (i) to (ii) or (h), and to use a simple metal such as B, Al, Ti, Zr, or B 20. 3, a] 2 0 metal oxides such as 3, carbonate Li Ji ⁇ beam, carbonate magnesiate U beam, alkali metal and alkaline earth metal carbonates such as carbonates Kanoreshi ⁇ beam, hydroxide Aluminum two ⁇ Particularly preferred are metal hydroxides such as aluminum and amino acids such as glycine.
  • combustion regulator can be used alone, or two or more types can be used in combination.
  • Commercially available products may be used as the combustion control agents.
  • the particle size is not particularly limited, and may be appropriately selected from a wide range according to various conditions such as, for example, the compounding amount, the mixing ratio with other components, and the airbag capacity.
  • the blending amount is not particularly limited, and the mixing ratio of biscarbamoyl hydrazine and the oxidizing agent, the type of the combustion regulator itself, and the other Can be appropriately selected from a wide range according to various conditions such as the type of component of the air bag and the capacity of the air bag.
  • the amount of bismuth phenol and oxidized biscalpa molybdenum hydrazine is lower than the viewpoint of obtaining a lower combustion temperature and an appropriate combustion rate.
  • the amount is preferably about 0.5 to 5 parts by weight, and more preferably about 1 to 3 parts by weight, based on 100 parts by weight of the total amount of the agent.
  • a slag forming agent can be added.
  • the slag forming agent is an additive that solidifies the residue generated after the combustion of the gas generating agent and makes it easier to remove by the filsator inside the airbag inflator. It is.
  • a scan lag forming agent can be used known ones, for example, already silicon dioxide and Aluminum Na exemplified by the combustion modifiers, oxidation boric arsenide (especially this elevation gel B 2 0 etc.
  • the amount thereof is not particularly limited. It may be appropriately selected from a wide range according to the composition of the gas generating agent, etc.
  • the amount of the oxidizing agent is determined by the molar ratio of the oxidizing agent.
  • An appropriate value is around 1/2
  • An oxide containing an alkaline earth metal and an alkaline earth metal compound which reacts to form an oxide, such as sulfur oxide Tronium, strontium nitrate, etc. can also be used as a slag-forming agent.
  • additives conventionally used for this purpose may be blended as long as the preferable properties of the gas generating agent of the present invention are not impaired.
  • oxidizing agents other than nitrates and oxohalogenates can be used in combination as long as the preferable properties of the gas generating agent of the present invention are not impaired. Wear.
  • the oxidizing agent is not particularly limited, and may be suitably selected from those conventionally used in the art, and those which can generate and / or supply oxygen at high temperature and are preferred. Examples include nitrites, metal peroxides, superoxides, ozone compounds and the like. Examples of the nitrite include alkali metal salts such as lithium nitrite, sodium nitrite, and lithium nitrite, magnesium nitrite, and barium nitrite.
  • alkaline earth metal salts such as calcium nitrite and the like.
  • the metal peroxide include alkali metal salts such as lithium peroxide, sodium peroxide, and potassium peroxide, magnesium peroxide, and peroxide.
  • Alkaline earth metal salts such as calcium and barium peroxide can be mentioned.
  • the superoxide include alkali metal compounds such as sodium superoxide and potassium superoxide, and superoxide.
  • Alkaline earth metal compounds such as calcium oxide, super-histonium oxide, and barium superoxide, rubidium superoxide, cesium superoxide and the like. Can be done.
  • Is the o zone down compounds for example, the formula M 0 3 (wherein M is N a, K, shows the I a group element such as a R b C s.)
  • Compounds I table are exemplified up by .
  • metal sulfides such as molybdenum disulfide, bismuth-containing compounds, lead-containing compounds and the like can also be used as the oxidizing agent.
  • oxidizing agents may be used as they are commercially available, and their shape, particle size, etc. are not particularly limited.For example, the amount of the oxidizing agent, the type and the mixing ratio of each component used in combination, It may be appropriately selected and used according to various conditions such as the capacity of the air bag.
  • Preferred embodiments of the gas generating agent of the present invention described above may include a slag forming agent and other known additives.
  • the gas generating base and / or components other than the gas generating base are reduced. Both types may be surface-treated with a coupling or chelating agent.
  • the coupling agent is not particularly limited, and any known coupling agent can be used.
  • any known coupling agent can be used.
  • amide aminopropyl triethoxy Silane-based coupling agents such as lan, arginosine propylenoxy-produced methoxysilane, methyltrimethoxysilane, isopropynole Titanium-based couplings such as triisostealoinolecitaneate, etc.
  • Alminium-based capacitors such as IJ, acetate alcohol miniatures, etc. Examples include a coupling agent.
  • Known chelating agents can also be used.
  • EDTA ethylenediamine tetraacetic acid
  • EDTA.2Na salt EDTA.2K salt
  • ETDA 2Li salt EDTA / 2 ammonium salt, etc.
  • sodium getinoresitiocarbamate sodium getinoresitiocarbamate and the like.
  • the surface treatment is carried out by mixing the component to be treated with a coupling agent and / or a chelating agent in an appropriate solvent or in the absence of a solvent according to a usual method.
  • the gas generating agent of the present invention is produced by mixing bis-carbamide molybdenum hydrazine, an oxidizing agent and, if necessary, other components according to a usual method.
  • the gas generating agent of the present invention can be formulated into an appropriate form.
  • an appropriate amount of a binder may be mixed with the gas generating agent of the present invention, followed by tableting or tablet drying. At this time, it is particularly preferable to add an appropriate amount of water or hot water for safety.
  • a binder that is commonly used for such purposes. Just do it.
  • the formulation is not particularly limited, and examples thereof include pellets, discs, spheres, spheres, rods, hollow cylinders, sugary sugars, tetrapods, and the like. It can be non-porous or perforated (for example, briquette-like). Further, the pellet-shaped or disk-shaped one may have one to several projections on one or both sides.
  • the shape of the projection is not particularly limited, and examples thereof include a columnar shape, a conical shape, a polygonal pyramid shape, and a polygonal columnar shape.
  • the size of the preparation of the gas generating agent of the present invention is not particularly limited, and the particle size is selected in order to further lower the combustion temperature, which can be appropriately selected from a wide range, and to obtain a more appropriate combustion rate. It is preferable to formulate into a granule having a diameter of about 0.3 to 1.5 mm, preferably the above-mentioned particle diameter.
  • each of the components of the gas generating agent of the present invention may be formulated individually, and these may be mixed and used.
  • the gas generating agent of the present invention formulated as described above can be safely stored and transported by being filled in a synthetic resin or metal container such as polyethylene. can do.
  • the gas generating agent of the present invention is not limited to automobiles, and can be suitably used as a gas generating source of an air bag system mounted on various transportation devices.
  • BCH Biscanolenomoisolehydrazine
  • ADC Azoji Carbon Amide
  • Potassium perchlorate manufactured by Nihon Carrit Co., Ltd.
  • Silicon dioxide Nippseil NPS, trade name, manufactured by Nihon Silica Industry Co., Ltd.
  • Soluble starch First-class reagent, manufactured by Wako Pure Chemical Industries, Ltd.
  • CuO specific surface area 48 m 2 Z g and average particle size about 7.4 m. JGC Chemicals, Inc.
  • parts and % indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified.
  • the amount of perchloric acid value Li U beam was changed to 6 7.7 parts, except that use C u O l O unit in place of the ⁇ one M o 0 3, the same procedure as in Example 1 A pellet of the gas generating agent of the present invention was produced.
  • Test example 1 Example of a combustion chamber equipped with a gas exhaust hole with a diameter of 7 mm and filled with 0.8 g of Boron Z sodium phosphate as a transfer medium A 0.3 mm-thick aluminum cup filled with the gas generating agent pellets obtained in Examples 1 and 2 and Comparative Example 1 was loaded. This inflator is placed in a 60 liter tank and is operated by passing an electric current to burn the pellets of the gas generating agent. The pressure and temperature in the tank and in the 60 liter tank were measured. In addition, the gas in the 60-litre tank after combustion is sampled from a sampling hole into a 1-litre bag, and the C0 concentration and ⁇ '0X concentration in the gas are detected. It was measured using a tube. Table 1 shows the results.
  • TP max The maximum pressure (kgf Z cm 2 ) within the 60-litre tank. This parameter indicates the gas generating capacity of the gas generating agent.
  • tTPMaX Time required for the pressure in the 60 litre tank to reach its maximum (msec). A parameter that simulates the deployment speed when the airbag is deployed.
  • t TP 90 Time required for the pressure in the 60 liter tank to reach 90% of the maximum value (msec:). Airbag Parameter that simulates the deployment speed when
  • the gas generating agent of the present invention has the same combustion rate as the gas generating agent using azocarbonamide as the gas generating base, and the toxic components such as CO and NOX in the post-gas. It can also be seen that the concentration of Hb is as low as the same.
  • the gas generating agent of No. 2 had a residual weight ratio of 99.5% or more, and it was confirmed that the bismuth rubamoinolehydrazine was not substantially decomposed.
  • the residual weight ratio (%) was examined in the same manner as described above except that the storage time was set to 190 hours. The residual weight ratio was 75%. there were. Despite the storage time being less than half of the pellet of the gas generating agent of the present invention, the decomposition power of azodicarbon amide, and the fact that it has progressed considerably. I understand.
  • the gas generating agent of the present invention has much higher thermal stability than the gas generating agent using azodicarbonamide as a gas generating base. is there.
  • the combustion temperatures of the gas generating agents of Example 2 and Comparative Example 2 were measured using NASA's thermal equilibrium calculation program (B, J, McBride, 'CET89-Chemical Equilibrium with Transport Properties, 1989 Com ", COSMIC Program itLE W-15113 (1989). ), NASA, hereinafter, this program is referred to as “CET89”.) Based on the simulation calculation, the gas generating agent of Example 2 was about 210 1 The amount of the gas generating agent of Comparative Example 2 was about 2300 ⁇ .
  • the gas generating agent of the present invention is preferably azodicarbon. It can be seen that the combustion temperature is about 200 K lower than the gas generating agent using amide as the gas generating base.
  • a pellet of the gas generating agent of the present invention was produced in the same manner as in Example 1 except that the components were used in the amounts (parts) shown in Table 2 below.
  • Example 3 Using each of the pellets of the gas generating agent of the present invention obtained in Example 3, the same operation as in Test Example 1 was performed to determine the combustion performance of the gas generating agent, the C 0 concentration in the post-gas, and the N 0. The X concentration was determined.
  • the gas generating agent of the present invention has excellent combustion performance and a low C ⁇ concentration and NO X concentration in the post-gas.
  • a pellet of the gas generating agent of the present invention was produced in the same manner as in Example 1 except that the components were used in the amounts (parts) shown in Table 4 below.
  • Table 4 the gas generating agents of Nos. 1 to 18 correspond to Example 4, and the gas generating agents of Nos. 19 to 20 correspond to Comparative Example 3 (German Patent Publication No. 1995). 1618-18).
  • Example 4 Using each pellet of the gas generating agent of the present invention obtained in Example 4 and Comparative Example 3, the same operation as in Test Example 1 was carried out, and the combustion performance of the gas generating agent and the C0 concentration in the gas were used. And N ⁇ X concentration. Table 5 shows the results. Sample CPmax TPmax tTPmax tTP90 Ttemp.CO C ⁇ 2 NO x
  • Example 5 Comparative Example 4
  • Example 5 Each component was used in the amounts (parts) shown in Table 6 below.
  • the pellet of the gas generating agent of the present invention Example 5
  • the pellet of the gas generating agent described in Japanese Patent Application Laid-Open No. Hei 7-303383 was produced.
  • the following tests were performed on these gas generating agents. Table 6 shows the results.
  • thermochemical calculation temperature (adiabatic flame temperature) of the gas generant was calculated based on the NASA thermal equilibrium calculation program (CET89) and used as a guide to know the combustion temperature.
  • T DSCJ D S C exothermic decomposition onset temperature
  • T DSC thermal stability of the gas generant.
  • the thermal stability of the gas generating agent for air back is measured by maintaining the inflator loaded with the gas generating agent at 107 ° C for 400 hours and then operating the gas generator. The generation performance is evaluated based on the fact that it is the same as before heating. Force according to this method As already shown in Test Example 2, the canister was filled with a gas generating agent and kept at 107 ° C for 400 hours to reduce the amount of the gas generating agent. This is a method to evaluate weighing and thermal stability (heating loss test).
  • the present inventor has developed a correlation between the results of the weight loss test and the exothermic decomposition onset temperature (T DSC) of DSC (differential scanning calorimetry). And found that if the T DSC was 473 K or more, it passed the weight loss test on heating, and based on this finding, evaluated the thermal stability of the gas generating agent.
  • T DSC exothermic decomposition onset temperature
  • the gas generating agent was molded into a square rod-shaped strand of 7 mm in length and 3 O mm in length, and a restrictor was applied except for the upper end to prepare a sample body.
  • This sample was burned in a pressure vessel with an internal volume of about 1 liter under nitrogen pressure (70 kg Zcm 2 ), the time-pressure curve was recorded, and the linear burning rate (mmsec) was measured. It was calculated. The detonation tends to increase as the linear burning rate increases.
  • the detonation propagation of the gas generant was determined by a UN recommendation gap test.
  • a sample gas generating agent
  • a No. 6 detonator was attached, and a mild steel plate of 100 111 111 100 101 3 mm (thickness) was placed at the upper end as a proof plate.
  • the No. 6 detonator was energized to detonate the detonator and the explosive.
  • the fact that the sample propagated through the explosion forest was judged based on the fact that the steel pipe was broken.
  • the non-detonation was judged based on the fact that the steel pipe did not become fragments and the unreacted sample remained. 6
  • thermochemical calculation temperature (Tc) of the gas generator based on the thermal equilibrium calculation program (CET89) of NASA in the same way as in Example 5, and calculate the DSC exothermic decomposition temperature (Tc).
  • T DSC thermochemical calculation temperature
  • Tc DSC exothermic decomposition temperature
  • T DSC exothermic decomposition onset temperature
  • thermochemical calculation temperature was calculated based on the thermal equilibrium calculation program of NASA (CET89) and a strand test was performed in the same manner as in Example 5. The results are shown in Table 9.
  • Example 9 was repeated in the same manner as in Example 9 except that the amount of potassium perchlorate was changed to 67.7 parts and 10 parts of copper oxide was used instead of molybdenum oxide. A pellet of a gas generating agent for the invention airbag was manufactured.
  • Example 9 For comparison, operate in the same manner as in Example 9 except that unmodified bis-canolebamoinolehydrazine was used.
  • a pellet of gas generating agent (diameter 6 mm, thickness 3 mm, weight 0.15 g) was manufactured.
  • Visible Luba Moylhydrazine manufactured by Otsuka Chemical Co., Ltd., BET specific surface area: 0.20 m 2 / g, median diameter;
  • Example 11 In the same manner as in Example 11 except that the modified screw power of Reference Example 2 was replaced with that of Reference Example 3 in place of the rubamoin hydrazine hydrazine, the pelletizing agent for the airbag gas generating agent was used. A tut was manufactured.
  • a pellet of a gas generating agent for an air bag was manufactured in the same manner as in Example 11 except that untreated biscanolebacyl hydrazine was used.
  • Example 11 Pellets of three types of airbag gas generating agents obtained using 1 to 12 and untreated screw power Lubamoyl hydrazine were respectively applied to a hardness tester (product Name: HARDNESSTESTERKHT — 20 N, manufactured by Fujiwara Seisakusho Co., Ltd.), and apply a load to the pellet. The load when the pellet collapses Hardness. The hardness was measured several times and the average value was calculated. Table 11 shows the results.
  • Test example 9 Example 11 A combustion chamber equipped with a gas outlet of 7 mm in diameter and filled with 0.8 g of boron / potassium nitrate as a transfer medium was installed in an infra-red combustion chamber. 0.3 mm-thick aluminum cutlet filled with 40 g of a pellet of a gas generating agent obtained using ⁇ 12 and untreated screw-powered rubamoyl hydrazine. was loaded. This inflator is installed in a 60-litre tank, and is operated by applying an electric current to burn a pellet of the gas generating agent. Measurements of the pressure and temperature in one tank and 60 liter tank yielded similar results for all of them. After burning
  • the gas in the 60 liter tank was sampled from a sampling hole into a 1 liter driver bag, and the c0 concentration and N0X concentration in the gas were measured using a detector tube. At the same time, similar results were obtained for all of them.
  • Bi scan mosquito Runokumo Lee Sole arsenide de la di emissions (average particle size 5 2 m, BET specific surface area 0. 2 m 2 Z g, Otsuka Chemical Co., Ltd.), mosquitoes c te over di E Tsu DOO Crushed with minole.
  • the grinding conditions using a counterjet mill are air pressure 6.5 kg ⁇ / cm, rotation speed 1500 rpm, and feed rate 5 kgZ.
  • Example 13 In the same manner as in Example 13 except that the granules of Reference Example 5 were used instead of the fine powdered viscous lipa'moylhydrazine of Reference Example 4, a gas generating agent for an airpack was used.
  • Manufactured pellets For comparison, the same operation as in Example 13 was carried out except that unground pulverized bis-carbanol moist hydrazine was used in place of the finely powdered bis-rubber hydrazine hydrazine of Reference Example 4. To produce pellets of gas generating agents for air packs.
  • the pellets of the gas generating agents of Examples 13 to 14 and the pellets of the gas generating agent obtained by using the unmilled screw power Lubamoyl hydrazine were respectively used as hardness testers (products). Name: HARDNESSTESTERKHT — 20 N, manufactured by Fujiwara Seisakusho Co., Ltd.), apply a load to the pellet, and apply the load when the pellet collapses It was decided. The hardness was determined several times, and the average value was calculated. The results are shown in Table 12.
  • Examples 13 to 1 were installed in the combustion chamber of an inflator equipped with a gas outlet of 7 mm in diameter and charged with 0.8 g of boron nitrate as a transfer medium. Pellet of gas generating agent and

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)

Abstract

L'invention concerne un générateur de gaz pour airbag comprenant les ingrédients actifs suivants: (1) une biscarbamylhydrazine, constituant la base de générateur; (2) un sel d'oxacide d'halogène, comme agent oxydant; (3) un nitrate, comme autre agent oxydant; et (4) un catalyseur de combustion. Ce générateur a un rendement de combustion satisfaisant et une faible température de fusion. Il fournit un gaz à faible teneur en composants toxiques, tels que CO et NOx, et en particules suspendues émises; il a une excellente thermostabilité, et est bien plus sûr que des générateurs azide et non-azide des techniques précédentes.
PCT/JP1996/002796 1995-09-29 1996-09-27 Generateur de gaz pour airbag WO1997012849A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP96932011A EP0801045A4 (fr) 1995-09-29 1996-09-27 Generateur de gaz pour airbag

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP25330995 1995-09-29
JP7/253309 1995-09-29
JP7/353203 1995-12-29
JP7353203A JPH09157080A (ja) 1995-09-29 1995-12-29 エアバッグ用ガス発生剤
JP8/59405 1996-03-15
JP8059405A JPH09249635A (ja) 1996-03-15 1996-03-15 改質ビスカルバモイルヒドラジン及びエアバッグ用ガス発生剤
JP8/234977 1996-09-05
JP8234977A JPH1077258A (ja) 1996-09-05 1996-09-05 改質ビスカルバモイルヒドラジン及びエアバッグ用ガス発生剤
JP8/234987 1996-09-05
JP8234987A JPH1077259A (ja) 1996-09-05 1996-09-05 微粉状ビスカルバモイルヒドラジン、その顆粒化物及びエアバッグ用ガス発生剤

Publications (1)

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WO1997012849A1 true WO1997012849A1 (fr) 1997-04-10

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EP (1) EP0801045A4 (fr)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0905108A1 (fr) * 1997-09-24 1999-03-31 TRW Airbag Systems GmbH & Co. KG Mélange générateur de gaz sans particules
WO2004024652A1 (fr) * 2002-09-12 2004-03-25 Daicel Chemical Industries, Ltd. Composition de generation de gaz
US6964716B2 (en) 2002-09-12 2005-11-15 Daicel Chemical Industries, Ltd. Gas generating composition

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100381107B1 (ko) * 1998-02-25 2003-04-18 니뽄 가야쿠 가부시키가이샤 가스발생제 조성물
DE29821541U1 (de) * 1998-12-02 1999-02-18 TRW Airbag Systems GmbH & Co. KG, 84544 Aschau Azidfreie, gaserzeugende Zusammensetzung
US6523855B2 (en) 1999-09-24 2003-02-25 Breed Automotive Technologies, Inc. Air bag, method of manufacture and system therefor

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0632690A (ja) * 1992-07-13 1994-02-08 Nippon Koki Kk エアバッグ用ガス発生剤
JPH06227884A (ja) * 1993-02-05 1994-08-16 Nippon Koki Kk エアバッグ用ガス発生剤
JPH06239683A (ja) * 1993-02-15 1994-08-30 Daicel Chem Ind Ltd エアバッグ用ガス発生剤
WO1995000462A1 (fr) * 1993-06-22 1995-01-05 Automotive Systems Laboratory, Inc. Procedes et compositions generant un gaz sans azide
JPH07223890A (ja) * 1994-02-15 1995-08-22 Nippon Koki Kk ガス発生剤組成物
JPH07300383A (ja) * 1994-05-09 1995-11-14 Nippon Oil & Fats Co Ltd ガス発生剤
JPH0812481A (ja) * 1994-06-29 1996-01-16 Otsuka Chem Co Ltd エアバッグ用ガス発生剤
JPH08143388A (ja) * 1994-11-15 1996-06-04 Nippon Oil & Fats Co Ltd ガス発生剤
JPH08169792A (ja) * 1994-12-16 1996-07-02 Miyata Ind Co Ltd ガス発生剤

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0632689A (ja) * 1992-07-13 1994-02-08 Nippon Koki Kk エアバッグ用ガス発生剤
CA2115557C (fr) * 1992-07-13 2000-07-25 Tadao Yoshida Compose generant un gaz pour coussin de securite
FR2719578B1 (fr) * 1994-05-09 1996-12-20 Nof Corp Compositions de générateur de gaz comprenant un agent désoxydé et un agent oxydant.

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0632690A (ja) * 1992-07-13 1994-02-08 Nippon Koki Kk エアバッグ用ガス発生剤
JPH06227884A (ja) * 1993-02-05 1994-08-16 Nippon Koki Kk エアバッグ用ガス発生剤
JPH06239683A (ja) * 1993-02-15 1994-08-30 Daicel Chem Ind Ltd エアバッグ用ガス発生剤
WO1995000462A1 (fr) * 1993-06-22 1995-01-05 Automotive Systems Laboratory, Inc. Procedes et compositions generant un gaz sans azide
JPH07223890A (ja) * 1994-02-15 1995-08-22 Nippon Koki Kk ガス発生剤組成物
JPH07300383A (ja) * 1994-05-09 1995-11-14 Nippon Oil & Fats Co Ltd ガス発生剤
JPH0812481A (ja) * 1994-06-29 1996-01-16 Otsuka Chem Co Ltd エアバッグ用ガス発生剤
JPH08143388A (ja) * 1994-11-15 1996-06-04 Nippon Oil & Fats Co Ltd ガス発生剤
JPH08169792A (ja) * 1994-12-16 1996-07-02 Miyata Ind Co Ltd ガス発生剤

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0801045A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0905108A1 (fr) * 1997-09-24 1999-03-31 TRW Airbag Systems GmbH & Co. KG Mélange générateur de gaz sans particules
WO2004024652A1 (fr) * 2002-09-12 2004-03-25 Daicel Chemical Industries, Ltd. Composition de generation de gaz
US6964716B2 (en) 2002-09-12 2005-11-15 Daicel Chemical Industries, Ltd. Gas generating composition

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EP0801045A4 (fr) 2000-11-02

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