EP0763512A1 - Gasgenerator für einen airbag - Google Patents

Gasgenerator für einen airbag Download PDF

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Publication number
EP0763512A1
EP0763512A1 EP96901510A EP96901510A EP0763512A1 EP 0763512 A1 EP0763512 A1 EP 0763512A1 EP 96901510 A EP96901510 A EP 96901510A EP 96901510 A EP96901510 A EP 96901510A EP 0763512 A1 EP0763512 A1 EP 0763512A1
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EP
European Patent Office
Prior art keywords
gas generating
air bag
generating composition
gas
containing organic
Prior art date
Legal status (The legal status 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 status listed.)
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Application number
EP96901510A
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English (en)
French (fr)
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EP0763512A4 (de
Inventor
Tadao Yoshida
Tsukasa Maekawa
Shiro Chijiwa
Yasuo Shimizu
Junichi Onishi
Shigeo Daini Masuya Manshon 201 TAKAHASHI
Shigeru Sumitomo
Kazuo Hara
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Otsuka Chemical Co Ltd
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Otsuka Chemical Co Ltd
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Publication date
Priority claimed from JP7016989A external-priority patent/JPH08207695A/ja
Priority claimed from JP7020554A external-priority patent/JPH08217587A/ja
Priority claimed from JP4168895A external-priority patent/JPH08239205A/ja
Priority claimed from JP7105863A external-priority patent/JPH08301682A/ja
Priority claimed from JP7217103A external-priority patent/JPH0959082A/ja
Application filed by Otsuka Chemical Co Ltd filed Critical Otsuka Chemical Co Ltd
Publication of EP0763512A1 publication Critical patent/EP0763512A1/de
Publication of EP0763512A4 publication Critical patent/EP0763512A4/de
Withdrawn legal-status Critical Current

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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

Definitions

  • the present invention relates to an air bag gas generating composition and an air bag inflator.
  • the air bag gas generating composition of the present invention has the preferred advantages that toxic components such as CO are present at very low concentrations in a gas evolved on combustion of the composition (hereinafter referred to as "after gas"), and that the composition is far safer than conventional azide-based gas generating compositions.
  • the air bag inflator of this invention can further reduce the CO concentration in the after gas.
  • the air bag system is adapted to inflate a nylon bag (air bag) stowed in the steering wheel assembly, the dashboard of a car or the like on sensing a car crash occurring at high speed, thereby protecting the driver and other passengers from being injured or killed by the impact against the internal equipment of the car.
  • the bag is inflated with a gas evolved on combustion or decomposition of the gas generating composition held in the air bag system.
  • air bag gas generating compositions meet mainly four requirements.
  • the first requirement is that the gas generating compositions have adequate burning velocity. If the burning velocity is low, the air bag can not instantly inflate, failing to protect the passengers.
  • the second requirement is that the gas generating compositions have a low impact ignitability (ignition sensitivity to impact). High impact ignitability tends to trigger explosion or detonation in the manufacturing process as in mixing or molding, involving high risks in handling.
  • the third requirement is that the gas temperature is low. The air bag deflates by release of the gas after inflation for passengers' escape to outdoor. Yet, passengers may suffer a burn if exposed to a high temperature gas.
  • the air bag may fracture on contact with a high temperature gas, thereby becoming unfit in function or may become ignited, thereby inducing a fire.
  • the fourth requirement is that the concentrations of toxic components such as CO and NO x in the gas are low. If the gas contains toxic components at high concentrations, passengers may suffer gas poisoning in release of the gas.
  • concentrations of CO and NO x in a gas evolved on combustion of an organic compound are mutually inverse (in inverse proportion). The two components are so correlated that a decrease in the concentration of one component leads to an increase in the concentration of the other. Thus it is considered very difficult to decrease the concentrations of both components at the same time.
  • Sodium azide-based gas generating compositions which are in common use today show adequate burning velocity and gas temperature and generate nontoxic nitrogen gas for the most part but are defective in having high impact ignitability. Further, the decomposition of sodium azide used as a gas generating base may bring about a fire or may produce a toxic fume. Sodium azide reacts with an oxidizing agent to liberate toxic substances such as sodium oxide, sodium hydroxide, etc., calling for careful handling and essentially necessitating equipment for ensuring safety. Furthermore, sodium azide becomes less combustible on absorption of moisture, making it necessary to take measures against the absorption of moisture. In addition, sodium azide which is highly toxic would be likely to cause serious environmental pollution by the spread which may occur if an air bag-equipped car has fallen into a river or the sea.
  • Japanese Unexamined Patent Publications Nos.32689/1994, 32690/1994 and 227884/1994 disclose azide-free gas generating compositions proposed by the present inventors, the compositions comprising a nitrogen-containing organic compound and an oxidizing agent as active components.
  • the disclosed gas generating compositions are comparable to conventional azide-based gas generating compositions in adequate amount of generated gas, burning velocity and gas temperature. Further, the disclosed compositions are relatively low in impact ignitability and significantly low in explosion risks and toxicity, namely have the advantages which are not found in azide-based gas generating compositions. Moreover, the compositions are inexpensive. While toxic components such as CO and NO x exist at low concentrations in a gas evolved by combustion of said azide-free composition, assuring the practical use of the composition, a further reduction in the concentrations of toxic components is desired.
  • Japanese Unexamined Patent Publication No. 238867/1993 proposes the use of metallic oxides having a specific surface area of at least 5 m 2 /g (especially oxides of metals of atomic numbers 21 (Sc) to 30 (Zn)) in a gas generating composition.
  • the subject matter disclosed in the publication is a gas generating composition comprising sodium azide as a gas generating base.
  • the metallic oxide is merely added to enhance mainly the burning velocity and the ignitability.
  • a metallic oxide with its effect specifically described in the publication is only Fe 2 O 3 .
  • the inventors of the present invention conducted extensive research to overcome the foregoing problems and found that when a specific metallic oxide and/or a metallic oxide having specific properties is incorporated as a burning catalyst into an azide-free gas generating composition, the concentrations of toxic components in the after gas, especially both CO and NO x , can be markedly reduced while retaining the preferred advantages of the azide-free gas generating composition. Another finding was that the concentrations of toxic components would be further reduced if an oxidizing agent is placed on at least one part of a passage for the release of the gas within an air bag inflator. The present invention was completed based on these novel findings.
  • an air bag azide-free gas generating composition comprising a nitrogen-containing organic compound and an oxidizing agent as active components, and further containing, as a burning catalyst, at least one metallic oxide selected from the group consisting of molybdenum oxides, tungsten oxides and metallic oxides having a BET specific surface area of at least 5 m 2 /g.
  • an air bag inflator wherein an air bag gas generating composition is held in a combustion chamber and wherein an oxidizing agent for external use is disposed on at least one part of a passage for releasing into an air bag a gas evolved on combustion of the air bag gas generating composition.
  • the active components of the air bag gas generating composition according to the invention are a nitrogen-containing organic compound serving as a gas generating base, an oxidizing agent and a specific burning catalyst.
  • Organic compounds having at least one nitrogen atom per molecule can be used as the nitrogen-containing organic compound.
  • Specific examples of the nitrogen-containing organic compound to be used are amino group-containing organic compounds, nitramine group-containing organic compounds, nitrosoamine group-containing organic compounds, etc.
  • amino group-containing organic compounds that can be used are azodicarbonamide, azodicarboxylic acid and a salt thereof (alkali metal salt, alkaline earth metal salt, etc.), urea, hexamethylenetetramine, aminoguanidine bicarbonate, triaminoguanidine, biuret, cyanoguanidine, nitroguanidine, dicyandiamide, hydrazide, etc.
  • Useful hydrazides include conventional hydrazides such as acetohydrazide, 1,2-diacetylhydrazide, laurohydrazide, salicylohydrazide, oxalohydrazide, oxalodihydrazide, carbohydrazide, adipohydrazide, sebacohydrazide, dodecanediohydrazide, isophthalohydrazide, methyl carbazate, semicarbazide, formhydrazide, 1,2-diformylhydrazine and so on.
  • conventional hydrazides such as acetohydrazide, 1,2-diacetylhydrazide, laurohydrazide, salicylohydrazide, oxalohydrazide, oxalodihydrazide, carbohydrazide, adipohydrazide, sebacohydrazide, dodecaned
  • nitramine group-containing organic compounds examples include aliphatic and alicyclic compounds containing one or more nitramine groups as substituents such as dinitropentamethylenetetramine, trimethylenetrinitroamine (RDX), tetramethylenetetranitroamine (HMX) etc.,
  • nitrosoamine group-containing organic compounds examples include aliphatic and alicyclic compounds containing one or more nitrosoamine groups as substituents such as dinitrosopentamethylenetetramine (DPT), etc.
  • DPT dinitrosopentamethylenetetramine
  • nitrogen-containing organic compounds are preferred and azodicarbonamide is more preferred.
  • Such nitrogen-containing organic compounds can be used either alone or in combination. Commercially available nitrogen-containing organic compounds can be used as such.
  • the particle size of the nitrogen-containing organic compound is not specifically limited and can be suitably selected from a wide range depending on the amount of the compound, proportions with other components, volume of the air bag and other factors.
  • Useful oxidizing agents are not specifically limited and can be suitably selected from those conventionally used in the art.
  • Preferred oxidizing agents are those which can generate and/or supply oxygen at high temperatures. Examples are oxyhalogen acid salts, nitrates, nitrites, metallic peroxides, hyperoxides, ozone compounds, etc.
  • Oxyhalogen acid salts which can be used herein include conventional ones such as perhalogenates, halogenates, etc.
  • useful perhalogenates are alkali metal salts such as lithium perchlorate, potassium perchlorate, sodium perchlorate, lithium perbromate, potassium perbromate, sodium perbromate and like alkali metal salts, magnesium perchlorate, barium perchlorate, calcium perchlorate, magnesium perbromate, barium perbromate, calcium perbromate and like alkaline earth metal salts, ammonium perchlorate, ammonium perbromate and like ammonium salts, etc.
  • halogenates examples include alkali metal salts such as lithium chlorate, potassium chlorate, sodium chlorate, lithium bromate, potassium bromate, sodium bromate and like alkali metal salts, magnesium chlorate, barium chlorate, calcium chlorate, magnesium bromate, barium bromate, calcium bromate and like alkaline earth metal salts, ammonium chlorate, ammonium bromate, and like ammonium salts, etc.
  • alkali metal salts of halogen acids and oxyhalogen acids are preferred.
  • nitrates examples include lithium nitrate, sodium nitrate, potassium nitrate and like alkali metal salts, magnesium nitrate, barium nitrate, strontium nitrate and like alkaline earth metal salts, ammonium nitrates and like ammonium salts among which alkali metal salts are preferred.
  • nitrites examples include lithium nitrite, sodium nitrite, potassium nitrite and like alkali metal salts, magnesium nitrite, barium nitrite, calcium nitrite and like alkaline earth metal salts, etc.
  • metallic peroxides for use herein are lithium peroxide, sodium peroxide, potassium peroxide and like alkali metal salts, magnesium peroxide, calcium peroxide, barium peroxide and like alkaline earth metal salts, etc.
  • hyperoxides for use herein are sodium hyperoxide, potassium hyperoxide and like alkali metal compounds, calcium hyperoxide, strontium hyperoxide, barium hyperoxide and like alkaline earth metal compounds, rubidium hyperoxide, cesium hyperoxide, etc.
  • ozone compounds to be used are compounds represented by the formula MO 3 wherein M is an element of Group Ia in the periodic table such as Na, K, Rb, Cs and the like.
  • molybdenum disulfide and like metal sulfides, bismuth-containing compounds, lead-containing compounds, etc. are usable as oxidizing agents.
  • oxyhalogen acid salts nitrates, nitrites, etc. are desirable and oxyhalogen acid salts and nitrates are more desirable.
  • oxidizing agents can be used either alone or in combination.
  • the shape, particle size and other conditions of the oxidizing agent are not critical and can be selected according to, for example, the amount of the oxidizing agent, proportions with other components, and volume of air bag.
  • the amount of the oxidizing agent to be used is a stoichiometric amount sufficient to completely oxidize and burn the nitrogen-containing organic compound, calculated on the basis of the amount of oxygen.
  • the amount of the oxidizing agent can be properly selected from a wide range since the burning velocity, burning temperature (gas temperature), composition of combustible gas, etc. can be adjusted as desired by suitably changing the proportions of the nitrogen-containing organic compound and the oxidizing agent used.
  • the amount of the oxidizing agent is about 10 to about 400 parts by weight, preferably about 100 to about 240 parts by weight, per 100 parts by weight of the nitrogen-containing organic compound.
  • the gas generating composition of the invention contains, in addition to the above two components, at least one metallic oxide selected from the group consisting of molybdenum oxides, tungsten oxides and metallic oxides having a BET specific surface area of at least 5 m 2 /g.
  • the incorporation of the metallic oxide can pronouncedly reduce the concentrations of toxic components such as CO and NO x in the after gas.
  • the inventors' research has found that presumably the azide-free gas generating composition comprising, for example, azodicarbonamide as a gas generating base and oxyhalogen acid salt as an oxidizing agent undergoes a smooth reaction between the two components in nearly stoichiometric amounts since the thermal decomposition temperature of oxyhalogen acid salt is lowered closely to the thermal decomposition temperature of azodicarbonamide by the addition of the metallic oxide to the combustible reaction system although a great difference lies in the thermal decomposition temperature between the two components.
  • molybdenum oxides which can be used include conventional ones such as molybdenum oxide (VI), other oxygen-containing molybdenum compounds which can yield molybdenum oxide (VI) when heated, molybdic acid, metal salts of molybdic acid, etc.
  • Useful oxygen-containing molybdenum compounds include, for example, molybdenum hydroxides and molybdenum oxides such as MO 2 O 5 , MO 3 O 8 , MO 3 O 23 , MO 9 O 29 , etc.
  • useful metal salts of molybdic acid are cobalt molybdate, nickel molybdate and like salts of Group VIII metals, etc. Among them, molybdenum oxide (VI) and metal salts of molybdic acid are preferred, and molybdenum oxide (VI) is more preferred.
  • useful tungsten oxides include conventional ones such as tungsten oxide (VI), other oxygen-containing tungsten compounds which can yield tungsten oxide (VI) by heating, tungstic acid, metal salts of tungstic acid, etc.
  • Useful oxygen-containing tungsten compounds include, for example, tungsten oxides such as WO 2 , WO 3 , WO 3 ⁇ H 2 O, etc.
  • useful metal salts of tungstic acid are potassium tungstate, calcium tungstate, sodium tungstate, magnesium tungstate, cobalt tungstate, nickel tungstate, iron tungstate, etc. Among them, tungsten oxide (VI) and metal salts of tungstic acid are preferred, and tungsten oxide (VI) and iron tungstate are more preferred.
  • Metallic oxides having a BET specific surface area of at least 5 m 2 /g are not specifically limited insofar as they have the above-defined specific surface area and they are metallic oxides other than said molybdenum oxides and tungsten oxides.
  • metallic oxides to be used include the oxides of elements of 3rd and 4th periods in the periodic table such as copper oxide, nickel oxide, cobalt oxide, iron oxide, chromium oxide, magnesium oxide, aluminum oxide, zinc oxide, manganese oxide, etc.
  • Metallic oxides having a BET specific surface area of at least 5 m 2 /g can be used either alone or in combination.
  • Useful metallic oxides are those having a BET specific surface area of at least 5 m 2 /g, preferably at least 10 m 2 /g, more preferably at least 40 m 2 /g.
  • Metallic oxides having a large specific surface area can be prepared by conventional methods.
  • copper oxide can be prepared using copper nitrate as the starting material, as by a process comprising adding warm water of at least 60°C to basic copper nitrate to yield basic copper nitrate particles, grinding the particles and calcining the fine particles at about 300 to about 500°C (Japanese Unexamined Patent Publication No.301513/1989), a process comprising adding alkali to an aqueous solution of copper nitrate, for neutralization to give copper nitrate particles, filtering and drying the particles and calcining the particles at about 200 to about 500°C (Japanese Unexamined Patent Publication No.145422/1990), and so on.
  • Copper nitrate can be prepared also by subjecting metallic hydroxide or carbonate to low temperature plasma treatment (Japanese Unexamined Patent Publication No.26810/1990).
  • molybdenum oxides and tungsten oxides have the preferred properties of coexisting with a nitrogen-containing organic compound such as azodicarbonamide for a long term while inducing substantially no decomposition of the nitrogen-containing organic compound.
  • a nitrogen-containing organic compound such as azodicarbonamide
  • concentrations of CO and NO x in a gas evolved on combustion of the nitrogen-containing organic compound are inversely proportional to each other. That is, the concentrations of the two toxic components are so correlated that a reduction in the concentration of one component leads to an increase in the concentration of the other. Therefore it is considered very difficult to decrease the concentrations of both components at the same time.
  • Molybdenum oxides and tungsten oxides also have the favorable property of appreciably decreasing the concentrations of both components in the after gas at the same time.
  • the particle size of molybdenum oxides, tungsten oxides and metallic oxides having a BET specific surface area of at least 5 m 2 /g can be suitably selected from a wide range depending on their amounts, proportions with other components, structure of air bag, shape, volume and other factors.
  • the amount of these metallic oxides is not critical and can be properly selected from a wide range according to said conditions. Generally the amount is about 0.1 to about 50 parts by weight per 100 parts by weight of the nitrogen-containing organic compound.
  • the desired amount from the viewpoints of stabilizing the amount of generated gas and the combustibility is about 0.5 to about 30 parts by weight per 100 parts by weight of the nitrogen-containing organic compound.
  • the amount of the compound is so adjusted that the produced molybdenum oxide (VI) or the produced tungsten oxide (VI) is present in the above-specified amount range.
  • the air bag gas generating composition of the invention may contain, in addition to said three essential components, a burn modifier, an antidetonation agent, a burning velocity control catalyst and the like within the range which does not impair the properties of the composition.
  • the burn modifier is generally used to lower the burning temperature or the gas temperature.
  • specific examples of such modifier are hydroxides of aluminum and the like, carbonates, bicarbonates and oxides of alkali metals such as sodium, potassium and the like, carbonates and bicarbonates of alkaline earth metals such as calcium, magnesium, barium, strontium, etc.
  • hydroxides, carbonates and the like are preferred, and hydroxides are more preferred.
  • the amount of the burn modifier to be used is not critical and can be selected from a wide range.
  • the amount of the modifier is less than 50 parts by weight, preferably less than 20 parts by weight, per 100 parts by weight of the total amount of the nitrogen-containing organic compound and the oxidizing agent.
  • the antidetonation agent is used to avoid the detonation which would occur if the gas generating composition is wrapped in flames or subjected to great impact in the course of manufacture, transportation, storage or the like.
  • the addition of such antidetonation agent can further enhance the safety of the gas-generating composition in various stages of manufacture, transportation, storage or the like.
  • known substances can be used as the antidetonation agent.
  • metallic oxides such as bentonite, alumina, diatomaceous earth, silicon dioxide, etc. and carbonates and bicarbonates of metals such as Na, K, Ca, Mg, Zn, Cu, Al, etc. can be mentioned.
  • the amount of such antidetonation agent to be used is not critical and can be suitably selected from a broad range. Generally, the amount of the agent is about 5 to about 30 parts by weight per 100 parts by weight of the total amount of the nitrogen-containing organic compound and the oxidizing agent.
  • the burning velocity control catalyst is used chiefly to control the burning velocity.
  • Such burning velocity control catalysts include, for example, (a) the oxides, chlorides, carbonates and sulfates of elements of 4th to 6th periods in the periodic table (except for molybdenum oxides, tungsten oxides and carbonates of alkali metals or alkaline earth metals) such as zinc carbonate, iron chloride, lead oxide, titanium oxide, banadium oxide, cerium oxide, holmium oxide, calcium oxide, ytterbium oxide, etc., and (b) cellulose compounds such as carboxymethyl cellulose, hydroxymethyl cellulose, their ethers, microcrystalline cellulose particles, etc.
  • the particle size of the burning velocity control catalyst is not critical and can be suitably selected. These burning velocity control catalysts can be used either alone or in combination.
  • the amount of the burning velocity control catalyst to be used is not critical and can be suitably selected from a broad range. Generally, however, the amount of the catalyst is about 0.1 to about 50 parts by weight, preferably about 0.2 to about 10 parts by weight, per 100 parts by weight of the total amount of the nitrogen-containing organic compound and the oxidizing agent.
  • the air bag gas generating composition of the invention may contain additives conventionally used for this purpose within the range which does not impair the desirable properties of the composition.
  • the air bag gas generating composition of the invention contains, among the above-mentioned components, a compound which induces the decomposition of the nitrogen-containing organic compound, such as azodicarbonamide and the like.
  • a compound which induces the decomposition of the nitrogen-containing organic compound such as azodicarbonamide and the like.
  • such compound includes, for example, compounds containing an alkali component or those capable of liberating an alkali component on decomposition, namely compounds serving as a kind of oxidizing agent such as calcium peroxide and the like, and compounds serving as a burning catalyst such as copper oxide, chromium oxide, manganese oxide and the like.
  • decomposition-inducing compounds when used as the component of the air bag gas generating composition of the invention, it is desirable to treat the surface of the gas generating base and/or the decomposition-inducing compound.
  • a coupling agent, chelating agent or the like is used in the surface treatment.
  • Useful coupling agents include conventional coupling agents such as silane-based, titanate-based and aluminum-based coupling agents, etc.
  • silane-based coupling agents which can be used herein are ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane,N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -ureidopropyltriethoxysilane and like aminosilane-based coupling agents, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidyloxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldie
  • titanate-based coupling agents are isopropyltriisostearoyl titanate, isopropyltrisisodecylbenzenesulfonyl titanate, isopropyltris-n-decylbenzenesulfonyl titanate, isopropyltris(dioctylpyrophosphate)titanate, tetraisopropyl-bis(dioctylphosphite)titanate, tetraoctyl-bis(ditridecylphosphite)-titanate, tetra(2,2-diallyloxymethyl-1-butyl)-bis(ditridecylphos-phite)titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltrioctanoyl titan
  • Examples of useful aluminum-based coupling agents are aluminum monoacetyl acetonate-bis(ethylacetoacetate), aluminum tris(acetylacetate), acetoalkoxyaluminum diisopropylate, etc.
  • the surface treatment using a coupling agent can be done by conventional methods such as a wet method or a drying method.
  • the wet method comprises mixing the component to be treated and a solution or a dispersion of the coupling agent, separating the treated component from the mixture and drying the component.
  • the coupling agent is soluble or dispersible in water, an aqueous solution of acetic acid, methanol, ethanol, cellosolve, alkylamine, alkylolamine or like organic solvents or a mixture of these solvents.
  • the concentration of the coupling agent is not specifically limited and can be suitably selected from a wide range. But it is usually about 0.1 to about 5% by weight, preferably about 0.5 to about 2% by weight.
  • the treated component is separated by conventional methods such as filtration, centrifugation, decantation, etc.
  • the dried component When the dried component is an agglomerate, it may be ground by a conventional method.
  • a solution or a dispersion of the component to be treated is mixed with a solution or a dispersion of the coupling agent, the treated component is separated from the mixture, and the component is dried.
  • Useful solvents for dissolving or dispersing the component to be treated include the solvents exemplified above.
  • the wet method can also be performed at an elevated temperature or by heating when so required. In this case, the desired temperature is about 30 to about 100°C.
  • the drying method comprises adding a coupling agent or a solution or a dispersion of the coupling agent to a powder of the component to be treated, if necessary, with stirring and/or with preheating and mixing them (preferably at an elevated temperature).
  • the stirring and mixing can be performed using a conventional blender, preferably blenders capable of applying a shear force such as Henschel mixer or super mixer.
  • the same solution or dispersion of the coupling agent as used in the wet method can be used in the drying method.
  • the preheating and heating are effected to elevate the temperature to the range which does not cause the decomposition or degradation of the component to be treated.
  • the surface treatment can also be performed by adding the silane coupling agent or a solution or dispersion thereof when mixing together the components of the gas generating composition.
  • the amount of the coupling agent to be used can be selected from a broad range depending on the type of the coupling agent, the stability, with time, of the component to be treated and other factors. But generally the amount is about 0.01 to about 10 parts by weight, preferably about 0.1 to about 5 parts by weight, per 100 parts by weight of the component to be treated. When a solution or dispersion of the coupling agent is used, the amount of the solution or dispersion to be used is adjusted to give the foregoing proportions.
  • the chelating agent which can be used in the invention is not critical and can be selected, for example, from a broad range of conventional chelating agents which do not show alkalinity when dissolved or dispersed in water and/or an organic solvent and which can form a chelate in combination with a metal (e.g. Cu, Co, Cr, Ca, etc.) or its ions present in the compound which induces the decomposition of the gas generating base.
  • a metal e.g. Cu, Co, Cr, Ca, etc.
  • useful chelating agents are chelating reagents, photometric reagents, metal indicators, etc.
  • chelating reagents which can be used are ethylenediamine-tetraaceic acid (EDTA) and metal salts thereof (EDTA ⁇ disodium salt, EDTA ⁇ dipotassium salt, EDTA ⁇ dilithium salt, EDTA ⁇ diammonium salt, etc.), trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid ⁇ monohydrate (CyDTA), N,N-bis (2-hydroxyethyl)glycine (DHGE), 1,3-diamino-2-hydroxypropane-N,N,N'N'-tetraacetic acid (DPTA-OH), diethylenetriamine-N,N,N',N'',N'-pentaacetic acid (DTPA), ethylenediamine-N,N'-diacetic acid (EDDA), ethylenediamine-N,N'-dipropionic acid ⁇ dihydrochloride (EDDP
  • Examples of useful photometric reagents and metal indicators are 3-[N,N-bis(carboxymethyl)aminomethyl]-1,2-dihydroxyanthraquinone, 3,3'-dimethoxybenzine-N,N,N', N'-tetraacetic acid ⁇ tetrasodium salt, dimethyldithiocarbamic acid ⁇ sodium salt (DDTC), 2,7-bis(2-arsonophenylazo)-1,8-dihydroxy-3,6-naphthalene ⁇ disulfonate, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolinedisulfonic acid ⁇ disodium salt, 4,7-diphenyl-1,10-phenanthroline, 5-mercapto-3-phenyl-1,3,4-thiadiazole-2-thione ⁇ potassium salt, N-benzoyl-N-phenylhydroxyamine
  • the chelating reagent is preferred and EDTA ⁇ disodium salt is more preferred.
  • the above-exemplified chelating agents can be used either alone or in combination.
  • a chelating agent is dissolved or dispersed in a suitable solvent, and the solution or dispersion is mixed with the compound to be surface-treated. While water is chiefly used as the solvent, some chelating agents are sparingly soluble in water. When such chelating agent is used, a suitable organic solvent is used as selected from, e.g. methanol, ethanol, isopropanol, n-amyl alcohol, methyl isobutyl ketone, chloroform, carbon tetrachloride, benzene, nitrobenzene, triethanolamine, etc.
  • a suitable organic solvent is used as selected from, e.g. methanol, ethanol, isopropanol, n-amyl alcohol, methyl isobutyl ketone, chloroform, carbon tetrachloride, benzene, nitrobenzene, triethanolamine, etc.
  • the amount of the chelating agent to be used is suitably selected from a broad range depending on the type of the chelating agent, the type of the compound to be surface-treated, etc.
  • the concentration and the amount of the chelating agent are adjusted to use about 10 to about 200 parts by weight, preferably about 50 to about 150 parts by weight of the chelating agent, per 100 parts by weight of the compound to be surface-treated.
  • the mixing time is suitably selected and is usually about 0.5 to about 4 hours.
  • the surface treatment is carried out if necessary with heating, e.g. at a temperature of about 50 to about 80°C.
  • the air bag gas generating composition of the present invention can be prepared by mixing together the three essential components and other components to be optionally used. Further the air bag gas generating composition of the present invention can be molded into a suitable shape. For example, a suitable amount of a binder is admixed with the gas generating composition of the invention and the mixture is tabletted and, if necessary, dried. In this case, preferably a solvent such as water is added in a proper amount to assure safety.
  • Useful binders include, for example, those usually used for this purpose.
  • the shape of the discrete preparation is not critical and includes, for example, a pellet, disk, ball, bar, hollow cylinder, confetti and tetrapod. It may be solid or porous (e.g. honeycomb-shaped).
  • One or more projections may be formed on one or both surfaces of pellets or disks.
  • the shape of projections is not critical and includes, for example, cylinders, cones, polygonal cones, polygonal pillars, etc.
  • the size of tablets formed from the gas generating composition of the invention is not specifically limited and can be suitably selected from a broad range. However, a suitable size of tablets is about 0.3 to about 1.5 mm in diameter from the standpoints of obtaining a lower burning temperature and a more suitable burning velocity.
  • the respective components may be individually tabletted and the tablets may be used as mixed.
  • the tabletted gas generating preparation of the invention is placed into a container made of polyethylene or like synthetic resins or metals, whereby the gas generating preparation can be safely stored and transported.
  • the feature of the air bag inflator of the invention is that an oxidizer for external use is disposed on at least one part of a passage for passing the after gas into the air bag. Consequently the inflator is not specifically limited, and inflators having a known structure can be widely used.
  • Oxidizers to be externally used in the invention can be the same conventional oxidizers as used in the gas generating composition of the invention or can be other conventional species.
  • the part of the inflator for disposing the oxidizer for external use is not specifically limited insofar as it is on a passage for the after gas to pass therethrough but not on the combustion chamber.
  • the external oxidizer may be placed on a coolant, a wire netting filter, a ceramic filter, etc.
  • the number of inflator parts on which the external oxidizer is placed is not necessarily limited to one and may be two or more.
  • the external oxidizer is decomposed due to the high temperature of a gas evolved on combustion of the gas generating composition, whereby oxygen is produced and the cobalt and the like in the gas are oxidized, further reducing the CO concentration. Consequently it is desirable that the gas coming into contact with the external oxidizer be heated to a high temperature.
  • the external oxidizer is preferably placed on a coolant with which the gas released from the combustion chamber is first brought into contact.
  • the external oxidizer can be mounted on the desired inflator component, for example, by immersing a coolant, a wire netting filter, a ceramic filter or the like in an aqueous solution or dispersion, or an organic solvent solution or dispersion, of the external oxidizer, followed by drying.
  • an aqueous solution or dispersion, or an organic solvent solution or dispersion, of the external oxidizer is heated to a temperature of about 70 to about 100°C, and the inflator component is dipped into the heated solution or dispersion, which is then cooled, whereby an oxidizer layer is deposited on the surface of the inflator component. Thereafter the component is withdrawn and dried.
  • the external oxidizer may be placed on an inflator component by spraying the inflator component with a solution or dispersion of the external oxidizer and drying the coated component.
  • the external oxidizer molded in the shape of a pellet or disk may be disposed on at least one part of the passage for the release of the gas.
  • an azide-free gas generating composition is preferred, and the gas generating composition of the present invention is more preferred.
  • the gas generating composition When the gas generating composition is placed into the combustion chamber, at least one species selected from oxidizers, gas-releasing inorganic compounds and inert inorganic compounds may be accommodated together into the combustion chamber. These three types of components are hereinafter referred to as "prooxidant for combustion chamber" for the sake of expedience.
  • Oxidizers to be used among the prooxidants for combustion chamber can be any of those exemplified above. Of these examples, potassium nitrate and like nitrates, and sodium chlorate and like oxyhalogen acid salts are preferred.
  • Useful gas releasing inorganic compounds include a wide range of known compounds capable of generating a gas on thermal decomposition, e.g. sodium bicarbonate.
  • Useful inert inorganic compounds include a wide range of known compounds free of thermal decomposition, e.g. silicon dioxide.
  • potassium nitrate, sodium chlorate and like oxidizers, silicon dioxide and like inert inorganic compounds overlap some of the components for the gas generating composition of the invention.
  • these compounds are incorporated into the gas generating composition in the combined amount of the compound as the component of the gas generating composition and the compound as the prooxidant for combustion chamber, a proper burning velocity can not be attained and accordingly the CO concentration can not be lowered.
  • the prooxidant for combustion chamber can be used as a powder or as molded into any desired form selected from a pellet, disk, precipitate, granule, etc.
  • a partition means may be provided between them to separate them, such as a thin sheet of aluminum, aluminum foil, etc.
  • the air bag gas generating composition of the invention and the air bag inflator of the invention are not limited to automotive use and can be suitably used as a gas source for air bag systems to be installed in various transport means.
  • the azide-free air bag gas generating composition when a specific burning catalyst is incorporated into an azide-free air bag gas generating composition containing a nitrogen-containing organic compound as a gas generating bas, the azide-free air bag gas generating composition becomes capable of further reducing the concentrations of CO and other toxic components in the after gas while maintaining the above-mentioned desired advantages of azide-free gas generating compositions such as adequate burning velocity, amount of generated gas and gas temperature which are superior or equivalent to those of conventional azide-based gas generating compositions, lower impact ignitability than azide-based gas generating compositions, high safety, low toxicity and low costs.
  • an air bag inflator capable of further reducing the concentrations of CO and other components in the after gas.
  • the present invention further provides a method of overcoming the drawback of the azide-free gas generating composition that the nitrogen-containing organic compound such as azodicarbonamide in the composition decomposes during a long term storage after production, stated more specifically the method comprising surface treatment with a coupling agent or a chelating agent.
  • FIG. 1 schematically shows a device to be used in a burning test for testing the gas generating compositions obtained in Examples to be described later.
  • FIG. 2 is a diagrammatic section view showing an example of the inflator of the invention.
  • a 30 g quantity of the obtained pellets of the gas generating composition was charged into the combustion chamber of an inflator having a gas vent 6 mm in diameter wherein 0.8 g of boron/potassium nitrate was placed as a transfer charge.
  • the inflator was set in a 60-liter tank and operated by passing an electric current. Thereafter the gas in the tank was collected through a gas outlet in the tank into a 1-liter tedlar bag. The CO concentration in the collected gas was 0.8% when measured using a detecting tube.
  • Pellets of a gas generating composition were produced in the same manner as in Example 1 with the exception of using copper oxide (specific surface area 0.77 m 2 /g, average particle size about 4.5 ⁇ m) conventionally used for gas generating compositions.
  • Example 2 Using the obtained pellets of the gas generating composition, the same procedure as in Example 1 was repeated.
  • the CO concentration in the gas was 1.5%.
  • the catalysts Nos. 1 to 3 are all products of Nikki Kagaku K.K.
  • the gas generating compositions thus obtained were subjected to a burning test using the burning tester shown in FIG. 1.
  • Example 2 The same procedure as in Example 2 was repeated with the exception of using copper oxide alone as a burning catalyst which was conventionally employed for gas generating compositions (specific surface area 0.77 m 2 /g, average particle size about 4.5 ⁇ m), giving pellets of a gas generating composition.
  • Example 2 Gas concentration Example 2 Compar.
  • Table 2 shows that when the burning catalysts of the invention were used together with other oxidizers, a remarkable effect was produced in reducing the CO concentration.
  • Example 1 The procedure of Example 1 was repeated with the exception of using the burning catalyst No.2 of Example 2, increasing the content of potassium perchlorate to 5, 10 or 15% and using the soluble starch in an amount of 0.55 part, giving pellets of gas generating compositions according to the invention.
  • Table 3 shows that slight increases in the amount of potassium perchlorate further reduced the CO concentration.
  • the pellets of the gas generating compositions obtained above were subjected to a 60-liter tank test described below.
  • Example 4 Each of 11 types of pellets of the gas generating compositions prepared in Example 4 and Comparative Example 3 was placed into the combustion chamber of an inflator having a gas vent 7 mm in diameter and loaded with 0.8 g of boron/potassium nitrate as a transfer charge.
  • the inflator was set in a 60-liter tank and operated by passing a current to ignite the pellets of the gas generating composition. Then the pressure and the temperature in the inflator and in the 60-liter tank were measured.
  • a gas evolved by combustion in the 60-liter tank was collected through a gas outlet into a 1-liter tedlar bag, and the concentrations of CO and NO x in the gas were determined using a detecting tube. The results are shown in Table 5.
  • Table 5 shows the following.
  • the air bag gas generating compositions of the present invention can generate a suitable amount of gas and have a good combustibility.
  • the air bag gas generating compositions of the present invention containing molybdenum oxide (VI) can reduce the concentrations of CO and NO x due to the presence of the oxide at the same time to an extent equivalent to or greater than that attained in Comparative Example 3 wherein copper oxide was used.
  • Example 7 Using the pellets of the gas generating compositions prepared in Example 5, a 60-liter tank test was carried out to measure the pressure and the temperature in the inflator and the 60-liter tank and the CO and NO x concentrations in the after gas. The results are shown in Table 7. The amount of the pellets respectively charged was 40 g. Table 7 Sample No. CPmax TPmax tTPmax tTP90 Ttemp.
  • Eight kinds of pellets of the gas generating compositions prepared in Example 5 were all at least 99.5% in residual rate (%, by weight) as measured after 400-hour storage in a thermostatic container at 107°C. The data show that substantially no azodicarbonamide decomposed.
  • the pellets of the gas generating composition were placed into the combustion chamber of an inflator having a gas vent 6 mm in diameter, aluminum foil of 15 ⁇ m thickness was disposed on the pellets, and then sodium chlorate was charged into the combustion chamber.
  • the inflator was set in a 60-liter tank and a current was passed to ignite the pellets of the gas generating composition. Then the pressure in the combustion chamber and in the tank pressure was measured. A gas evolved by combustion in the tank was collected through a gas outlet into a 1-liter tedlar bag. Using a detecting tube, the collected gas was analyzed, and the CO concentration was 0.95%. The maximum combustion chamber pressure was 109 kgf/cm 2 , and the maximum tank pressure was 0.7 kgf/cm 2 .
  • Example 6 The procedure of Example 6 was repeated with the exception of using potassium nitrate in place of sodium chlorate as a prooxidant for combustion chamber.
  • the CO concentration in the after gas was 1.0%, while the maximum combustion chamber pressure was 82 kgf/cm 2 , and the maximum tank pressure was 0.8 kgf/cm 2 .
  • a burning test was performed using the pellets of the gas generating composition prepared in Comparative Example 1 and potassium nitrate as a prooxidant for combustion chamber in the amounts (part) shown in Table 8.
  • Potassium nitrate was placed into the combustion chamber of an inflator having a gas vent 7 mm in diameter. Thereafter aluminum foil of 15 ⁇ m thickness was disposed on the potassium nitrate and the pellets of the gas generating composition were deposited on the aluminum foil.
  • the inflator was set in a 60-liter tank and the same procedure as in Example 6 was repeated. The results are shown in Table 8.
  • Table 8 shows that the addition of the prooxidant for combustion chamber lowered the combustion chamber pressure and reduced the CO concentration in the after gas.
  • FIG. 2 is a diagrammatic section view of an example of the inflator according to the present invention.
  • the inflator is basically provided with a combustion chamber 1, a gas generating composition 2, a squib 3, a transfer charge 4, a gas vent 5, a coolant 6, a wire netting filter 7 and a ceramic filter 8, and has the same structure as conventional inflators except that an external oxidizer is present on the coolant 6 (not shown).
  • the squib 3 comprises a lead wire 9, a platinum electrode (not shown) and a sensitizer 10.
  • the mechanism for the generation of a gas is as follows. An electric current was passed through the lead wire 9, thereby heating the platinum electrode. Then the sensitizer 10 was electrically ignited by the heat to ignite the transfer charge 4. The ignited transfer charge 4 burned the gas generating composition 2, which then emitted a gas. The high temperature gas just generated was led to the coolant 6 via the gas vent 5, and was cooled. The CO component in the gas was oxidized to carbon dioxide by oxygen evolved on thermal decomposition of an external oxidizer disposed on the coolant 6, whereby the CO concentration was reduced. The gas flowing through the coolant 6 was passed through the wire netting filter 7 and then through the ceramic filter 8 and the filter 7 to thereby remove the solid impurities. Then the gas was finally discharged into an air bag (not shown) via an exhaust port.
  • the external oxidizer was disposed on the coolant 6 as follows.
  • the coolant 6 was dipped into a saturated aqueous solution of sodium chlorate heated to 100°C. Subsequently the aqueous solution was cooled to deposit a layer of sodium chlorate on the surface of the coolant 6. Thereafter the coolant 6 with the sodium chlorate layer thereon was withdrawn from the solution and dried by heating.
  • a wire netting of copper weighing 10 g was used as the coolant 6, and the amount of sodium chlorate deposited on the coolant 6 was 22 g.
  • the inflator was set in a 60-liter tank and operated by passing a current. Then the internal pressure in the inflator and the internal pressure in the tank were measured. After said procedure, a gas evolved in the tank was collected through a gas outlet into a 1-liter tedlar bag. The CO concentration of the gas collected in the tedlar bag was measured using a detecting tube. The results are shown in Table 9. Table 9 No. Amount of deposit CO concentration 1 5 g 1.0% 2 10 g 0.8% 3 18 g 0.6%
  • Example 11 A 60-liter tank test was conducted in the same manner as in Example 11 with the exception of using potassium chlorate (deposition amount 10 g) in place of sodium chlorate used as an external oxidizer in Example 11 with the result that the CO concentration in the after gas was 0.8%.
  • a 60-liter tank test was conducted in the same manner as in Example 11 with the exception of altering the amount of the pellets of the gas generating composition to 35 g and using potassium nitrate (deposition amount 20 g) in place of sodium chlorate as an external oxidizer with the result that the CO concentration in the after gas was 0.5%.
  • a surface-treated copper oxide was produced in the same manner as in Reference Example 1 with the exception of using ⁇ -glycidyloxypropyltrimethoxysilane (trade name: A-187, product of Nihon Unika K.K.) in place of ⁇ -aminopropyltriethoxysilane.
  • Pellets of a gas generating composition were prepared in the same manner as in the above examples with the exception of using copper oxide having an untreated surface.
  • Table 10 shows that the stability of azodicarbonamide was remarkably improved by surface-treating the copper oxide with the coupling agent.
  • the gas generating compositions of Examples 14 to 18 retained the desired advantages of azide-free gas generating compositions such as suitable burning velocity, suitable amount of generated gas, low burning temperature, low impact ignitability, high safety, low toxicity, low costs, etc.
  • a 10% aqueous solution of calcium peroxide and a 10% aqueous solution of methyltrimethoxysilane were mixed in equal amounts. The mixture was stirred at about 80°C for 2 hours, and the solids were separated by filtration, washed with water and dried, giving a surface-treated calcium peroxide.
  • Pellets of a gas generating composition were produced in the same manner as in Example 14 with the exception of using the surface-treated calcium peroxide produced in Reference Example 6 in place of the surface-treated copper oxide.
  • the obtained gas generating composition was stored in the same manner as above in a thermostatic container at 107°C for 400 hours.
  • the residual rate (%) of the azodicarbonamide was 99.5% when measured based on the decrease in the weight. Hence the decomposition was markedly inhibited due to the surface treatment.
  • Example 19 The procedure of Example 19 was repeated with the exception of using an untreated calcium peroxide, producing pellets of a gas generating composition.
  • the azodicarbonamide of the obtained pellets was completely decomposed on addition of an aqueous solution of soluble starch before a 400-hour storage test was conducted at 107°C.
  • Example 20 The procedure of Example 20 was repeated with the exception of using an untreated copper oxide, producing pellets of a gas generating composition.
  • Example 8 20 21 22 23 24 ADCA 45 45 45 45 45 45 45 45 KClO 4 55 55 55 55 55 55 KNO 3 - - 10 - - - - Metallic oxide Surface-treated copper oxide 10 10 10 - - - - Surface-treated chromium oxide - - - 10 - - Surface-treated manganese oxide - - - - 10 - Untreated copper oxide - - - - - 10 Silicon dioxide 1 1 1 1 1 1 1 Residual rate (%) 97 98 98 99 99 60
  • Table 11 shows that the surface treatment of metallic oxides with the chelating agent markedly increased the stability of azodicarbonamide.
  • the gas generating compositions of Examples 20 to 24 retained the desired advantages of azide-free gas generating compositions such as adequate burning velocity, adequate amount of generated gas, low burning temperature, low impact ignitability, high safety, low toxicity and low costs.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Air Bags (AREA)
EP96901510A 1995-02-03 1996-02-01 Gasgenerator für einen airbag Withdrawn EP0763512A4 (de)

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
JP7016989A JPH08207695A (ja) 1995-02-03 1995-02-03 エアバッグ用ガス発生剤
JP16989/95 1995-02-03
JP7020554A JPH08217587A (ja) 1995-02-08 1995-02-08 エアバッグ用ガス発生剤
JP20554/95 1995-02-08
JP4168895A JPH08239205A (ja) 1995-03-01 1995-03-01 改質された過酸化カルシウム
JP41688/95 1995-03-01
JP105863/95 1995-04-28
JP7105863A JPH08301682A (ja) 1995-04-28 1995-04-28 エアバッグ用ガス発生剤
JP217103/95 1995-08-25
JP7217103A JPH0959082A (ja) 1995-08-25 1995-08-25 エアバッグ用ガス発生剤
PCT/JP1996/000199 WO1996023748A1 (fr) 1995-02-03 1996-02-01 Agent generateur de gaz pour air-bag

Publications (2)

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EP0763512A1 true EP0763512A1 (de) 1997-03-19
EP0763512A4 EP0763512A4 (de) 2001-02-21

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997042142A1 (de) * 1996-05-02 1997-11-13 Trw Airbag Systems Gmbh & Co. Kg Gaserzeugendes, azidfreies stoffgemisch
WO1999048843A1 (de) * 1998-03-20 1999-09-30 Nigu Chemie Gmbh Gasgeneratortreibstoffe
EP0950647A1 (de) * 1998-04-15 1999-10-20 Daicel Chemical Industries, Ltd. Gaserzeugende Zusammensetzung für einen Airbag
WO2001066494A1 (fr) * 2000-03-10 2001-09-13 Nippon Kayaku Kabushiki-Kaisha Composition pour generateur de gaz destine a un airbag
US6651565B1 (en) 1998-04-20 2003-11-25 Daicel Chemical Industries, Ltd. Method of reducing NOx
WO2004065332A2 (en) * 2002-11-14 2004-08-05 Estes-Cox Corporation Composite propellant compositions
US7040657B2 (en) * 2001-04-04 2006-05-09 Daicel Chemical Industries, Ltd. Method of reducing nitrogen oxide in hybrid inflator
EP1275629A3 (de) * 2001-07-10 2010-09-22 TRW Airbag Systems GmbH & Co. KG Nitrozellulosefreie gaserzeugende Zusammensetzung
FR2949778A1 (fr) * 2009-09-10 2011-03-11 Snpe Materiaux Energetiques Composes pyrotechniques generateurs de gaz
EP2851598A1 (de) 2011-11-04 2015-03-25 Blue Gentian, LLC Erweiterbare Schlauchanordnung
CN107573203A (zh) * 2016-11-03 2018-01-12 湖北航天化学技术研究所 一种低温气体发生剂

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JPH06239683A (ja) * 1993-02-15 1994-08-30 Daicel Chem Ind Ltd エアバッグ用ガス発生剤
JPH0812481A (ja) * 1994-06-29 1996-01-16 Otsuka Chem Co Ltd エアバッグ用ガス発生剤
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US3113057A (en) * 1960-06-30 1963-12-03 Standard Oil Co Stabilized ammonium nitrate propellant
EP0607446A1 (de) * 1992-07-13 1994-07-27 Nippon Koki Co., Ltd. Gaserzeugungsmittel für airbags
DE9416112U1 (de) * 1993-10-06 1994-12-15 Contec - Chemieanlagen GmbH, 84544 Aschau Gasgeneratortreibstoff
DE4411654A1 (de) * 1993-10-20 1995-04-27 Temic Bayern Chem Airbag Gmbh Gaserzeugendes Gemisch
EP0694511A1 (de) * 1994-02-15 1996-01-31 Nippon Koki Co., Ltd. Gaserzeugende zusammensetzung, verfahren zu dessen tablettierung und verfahren zum transport
DE4442169C1 (de) * 1994-11-26 1995-12-21 Fraunhofer Ges Forschung Gaserzeugende Mischung
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997042142A1 (de) * 1996-05-02 1997-11-13 Trw Airbag Systems Gmbh & Co. Kg Gaserzeugendes, azidfreies stoffgemisch
WO1999048843A1 (de) * 1998-03-20 1999-09-30 Nigu Chemie Gmbh Gasgeneratortreibstoffe
EP0950647A1 (de) * 1998-04-15 1999-10-20 Daicel Chemical Industries, Ltd. Gaserzeugende Zusammensetzung für einen Airbag
US6468369B1 (en) 1998-04-15 2002-10-22 Daicel Chemical Industries, Ltd. Gas generating composition for air bag
US6651565B1 (en) 1998-04-20 2003-11-25 Daicel Chemical Industries, Ltd. Method of reducing NOx
WO2001066494A1 (fr) * 2000-03-10 2001-09-13 Nippon Kayaku Kabushiki-Kaisha Composition pour generateur de gaz destine a un airbag
US7040657B2 (en) * 2001-04-04 2006-05-09 Daicel Chemical Industries, Ltd. Method of reducing nitrogen oxide in hybrid inflator
EP1275629A3 (de) * 2001-07-10 2010-09-22 TRW Airbag Systems GmbH & Co. KG Nitrozellulosefreie gaserzeugende Zusammensetzung
WO2004065332A3 (en) * 2002-11-14 2005-02-17 Estes Cox Corp Composite propellant compositions
WO2004065332A2 (en) * 2002-11-14 2004-08-05 Estes-Cox Corporation Composite propellant compositions
FR2949778A1 (fr) * 2009-09-10 2011-03-11 Snpe Materiaux Energetiques Composes pyrotechniques generateurs de gaz
WO2011030071A3 (fr) * 2009-09-10 2011-05-19 Snpe Materiaux Energetiques Composes pyrotechniques generateurs de gaz
EP2851598A1 (de) 2011-11-04 2015-03-25 Blue Gentian, LLC Erweiterbare Schlauchanordnung
CN107573203A (zh) * 2016-11-03 2018-01-12 湖北航天化学技术研究所 一种低温气体发生剂
CN107573203B (zh) * 2016-11-03 2019-10-11 湖北航天化学技术研究所 一种低温气体发生剂

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