EP0691317B1 - Non-azide gas generant formulations - Google Patents
Non-azide gas generant formulations Download PDFInfo
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- EP0691317B1 EP0691317B1 EP95108938A EP95108938A EP0691317B1 EP 0691317 B1 EP0691317 B1 EP 0691317B1 EP 95108938 A EP95108938 A EP 95108938A EP 95108938 A EP95108938 A EP 95108938A EP 0691317 B1 EP0691317 B1 EP 0691317B1
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- Prior art keywords
- gas
- weight
- mixture
- substance mixture
- fumaric acid
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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 invention relates to a gas-generating mixture of substances, in particular for the production of propellant gas for occupant protection devices in motor vehicles, in particular for airbag systems.
- Passive safety devices for motor vehicles such as airbag systems
- airbag systems are used in In the event of a collision of the vehicle, the vehicle occupants protect from injury.
- a Gas generator in a combustion chamber Mixture of substances in the form of tablets, pellets or granules, a propellant after electrical activation generated, which in turn inflates an airbag, thereby avoiding that the vehicle occupant, for example on the windshield, the steering wheel or the dashboard opens.
- gas-generating compositions which consist of a Alkali metal azide and a metal oxide, usually iron oxide, exist (see. DE-OS 24 59 667). These well-known However, mixtures of substances have a slow burning rate and a bad willingness to ignite.
- DE-OS 43 17 727 is a mixture of substances known from nitrocellulose and nitroglycerin.
- Such Fuel mixtures based on nitrocellulose have poor temperature stability with which Consequence of a limited lifespan and the impossibility to recycle this fabric.
- these fuel mixtures of heavy metal salts as combustion controllers, which also complicates disposal.
- the biggest disadvantage, on the other hand, is that which arises during burning enormous amounts of carbon monoxide.
- US 3 880 595 discloses Mixtures of substances based on a nitrogen-free organic Compound, such as citric acid based.
- a nitrogen-free organic Compound such as citric acid based.
- the disadvantage of these fuels is that of them low thermal stability and their high hygroscopicity as well as poor workability, especially the only with great difficulty compression to be carried out to tablets or pellets.
- the U.S. Patent 3,862,866 is considered the closest prior art viewed. It discloses a gas-generating mixture of substances, in particular to generate propellant gas for occupant protection devices in Motor vehicles, which essentially consist of a carbon, hydrogen and oxygen-containing organic compound such as Sucrose, starch, cellulose, ascorbic acid or oxalic acid, and an inorganic oxidizer from the group of perchlorates or chlorates.
- the mixture of substances contains approx. Part of the organic Compound, three parts of the inorganic oxidizer and one to four parts of metal carbonate as a coolant.
- the invention is based on the object of a gas-generating, to provide an azide-free fuel mixture that consists of non-toxic Components, high thermal and chemical stability has good workability and is not hygroscopic and finally, a sufficient burn rate as well as a has good ignitability.
- the fuel mixture according to the invention is free of heavy metals and can be manufactured with low manufacturing costs.
- An advantageous development of the mixture of substances according to the invention can also contain a metal oxide in a
- This metal oxide serves on the one hand as a coolant on the other hand u. U. as a ballistic additive.
- fumaric acid C 4 H 4 O 4
- Corresponding salts of fumaric acid in particular sodium, potassium, calcium, magnesium fumarates, can also advantageously be used as an organic compound.
- the metal oxide can be selected from the groups Al 2 O 3 , B 2 O 3 , SiO 2 , TiO 2 , MnO 2 , CuO, Fe 2 O 3 and ZnO or a mixture thereof.
- the stability test (Holland test) at a temperature of 110 ° C over a period of performed more than 70 hours.
- the well-known showed Substance mixture (reference number 1) a weight loss of almost 0.8%, while the invention Substance mixture (reference number 2) less than 0.01% weight loss having.
- the hygroscopicity test was carried out at a relative Humidity of 86% over a period of almost 100 hours.
- Figure 2 is at known mixture of substances (reference number 1) Weight gain 13%, while in the invention Substance mixture (reference number 2) no weight absorption is measurable.
- Substance mixture 2 was used to make a comparison with a further known fuel mixture (substance mixture 1) consisting of 30.8% by weight of 5-aminotetrazole, 36.1% by weight of sodium nitrate and 33.1% by weight. % Iron (III) oxide (cf. US 4,948,439).
- the fuels were burned off in a conventional gas generator.
- the fuel components were finely ground and pressed into tablets.
- the amount of gas generated and the resulting gas pressure were sufficient to fill a 65 liter sack.
- the measured harmful gas concentrations relate to a measuring volume of 60 l. The result of the test is shown in Figure 3.
- the known mixture 1 produces 15,000 ppm carbon monoxide (CO), 500 ppm nitrogen oxides (NO x ) and 3,000 ppm ammonia (NH 3 ), whereas the mixture 2 according to the invention only produces 3,000 ppm carbon monoxide, but no nitrogen oxide and no ammonia.
- a second fuel mixture according to the invention Embodiment contains 30.2% by weight of fumaric acid, 63.6% by weight of potassium perchlorate and 6.2% by weight of iron oxide. This iron oxide serves as a cooling reagent and sets the burn-up temperature is reduced by approx. 7%.
- This also according to the invention Fuel mixture generated after a burn only a harmful gas content of approx.3,000 ppm Carbon monoxide.
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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)
Description
Die Erfindung betrifft ein gaserzeugendes Stoffgemisch, insbesondere zur Erzeugung von Treibgas für Insassenschutzvorrichtungen in Kraftfahrzeugen, insbesondere für Airbag-Systeme.The invention relates to a gas-generating mixture of substances, in particular for the production of propellant gas for occupant protection devices in motor vehicles, in particular for airbag systems.
Passive Sicherheitseinrichtungen für Kraftfahrzeuge, wie beispielsweise Airbag-Systeme, dienen dazu, im Falle einer Kollision des Fahrzeuges die Fahrzeuginsassen vor Verletzungen zu schützen. Hierzu enthält ein Gaserzeuger in einem Brennraum ein gaserzeugendes Stoffgemisch in Form von Tabletten, Pellets oder Granulat, das nach einer elektrischen Aktivierung ein Treibgas erzeugt, das seinerseits einen Gassack aufbläst, wodurch vermieden wird, daß der Fahrzeuginsasse beispielsweise auf die Windschutzscheibe, das Lenkrad oder das Armaturenbrett aufschlägt.Passive safety devices for motor vehicles, such as airbag systems, are used in In the event of a collision of the vehicle, the vehicle occupants protect from injury. To do this contains a Gas generator in a combustion chamber Mixture of substances in the form of tablets, pellets or granules, a propellant after electrical activation generated, which in turn inflates an airbag, thereby avoiding that the vehicle occupant, for example on the windshield, the steering wheel or the dashboard opens.
Als gaserzeugende Stoffgemische sind verschiedene Stoffgemische bekannt. So wird beispielsweise Natriumazid als gasliefernde Hauptkomponente, Kaliumnitrat als Oxydator und Siliziumdioxyd eingesetzt, wobei das Siliziumdioxyd die bei der Reaktion des Azids mit dem Nitrat gebildeten Stoffe Natrium und Kalium als Schlacke bindet. Ein wesentlicher Nachteil der Verwendung von natriumazidhaltigen Treibstoffen liegt in deren hohen Toxizität, was besondere Maßnahmen unter anderem bei der Herstellung, dem Transport und der Entsorgung erfordert. Nachteilig sind auch die alkalisch reagierenden Verbrennungsrückstände, die eine Verätzungsgefahr hervorrufen können.There are various gas-generating mixtures Mixtures of substances known. For example, sodium azide as the main gas-supplying component, potassium nitrate used as an oxidizer and silicon dioxide, which Silicon dioxide in the reaction of the azide with the Nitrate formed substances like sodium and potassium Slag binds. A major disadvantage of use of fuels containing sodium azide lies in their high toxicity, what special measures among other things in the manufacture, transport and disposal required. Alkaline are also disadvantageous reacting combustion residues that pose a burn hazard can cause.
Ferner sind gaserzeugende Massen bekannt, die aus einem Alkalimetallazid und einem Metalloxyd, meist aus Eisenoxyd, bestehen (vgl. DE-OS 24 59 667). Diese bekannten Stoffgemische weisen jedoch eine geringe Abbrandgeschwindigkeit und eine schlechte Anzündwilligkeit auf.Furthermore, gas-generating compositions are known which consist of a Alkali metal azide and a metal oxide, usually iron oxide, exist (see. DE-OS 24 59 667). These well-known However, mixtures of substances have a slow burning rate and a bad willingness to ignite.
Weiterhin ist aus der DE-OS 43 17 727 ein Stoffgemisch aus Nitrozellulose und Nitroglyzerin bekannt. Solche Treibstoffgemische auf der Basis von Nitrozellulose weisen eine schlechte Temperaturstabilität auf, mit der Folge einer begrenzten Lebensdauer und der Unmöglichkeit diesen Stoff zu recyceln. Darüber hinaus enthalten diese Treibstoffgemische Schwermetallsalze als Abbrandregler, was zusätzlich die Entsorgung erschwert. Von größtem Nachteil dagegen sind die beim Abbrand entstehenden enormen Mengen an Kohlenstoffmonoxyd.Furthermore, DE-OS 43 17 727 is a mixture of substances known from nitrocellulose and nitroglycerin. Such Fuel mixtures based on nitrocellulose have poor temperature stability with which Consequence of a limited lifespan and the impossibility to recycle this fabric. Also included these fuel mixtures of heavy metal salts as combustion controllers, which also complicates disposal. Of The biggest disadvantage, on the other hand, is that which arises during burning enormous amounts of carbon monoxide.
Nun sind in den letzten Jahren natriumazidfreie Treibstoffmischungen vorgeschlagen worden (US 4 948 439), die als Hauptkomponente stickstoffreiche organische Verbindungen wie Tetrazole bzw. Tetrazolderivate oder Tetrazolate enthalten. Solche stickstoffhaltige, organische Treibstoffgemische besitzen dagegen den Nachteil, daß bei der Verbrennung neben Kohlenstoffmonoxyd in beträchtlichen Mengen auch nitrose Gase NOx freigesetzt werden, so daß die Gefahr einer kombinierten Vergiftung nicht ausgeschlossen werden kann.In recent years, sodium azide-free fuel mixtures have been proposed (US Pat. No. 4,948,439) which contain nitrogen-rich organic compounds such as tetrazoles or tetrazole derivatives or tetrazolates as the main component. On the other hand, such nitrogen-containing, organic fuel mixtures have the disadvantage that nitrous gases NO x are released in addition to carbon monoxide in considerable quantities, so that the risk of combined poisoning cannot be excluded.
Schließlich offenbart die Druckschrift US 3 880 595 Stoffgemische, die auf einer stickstofffreien organischen Verbindung, wie zum Beispiel Zitronensäure, basieren. Der Nachteil dieser Treibstoffe liegt in deren niedrigen thermischen Stabilität und deren hohen Hygroskopizität sowie in der schlechten Verarbeitbarkeit, insbesondere die nur unter großen Schwierigkeiten durchzuführende Verpressung zu Tabletten bzw. Pellets. Finally, US 3 880 595 discloses Mixtures of substances based on a nitrogen-free organic Compound, such as citric acid based. The disadvantage of these fuels is that of them low thermal stability and their high hygroscopicity as well as poor workability, especially the only with great difficulty compression to be carried out to tablets or pellets.
Das U.S. Patent 3 862 866 wird als nächstkommender Stand der Technik angesehen. Es offenbart ein gaserzeugendes Stoffgemisch, insbesondere zur Erzeugung von Treibgas für Insassenschutzvorrichtungen in Kraftfahrzeugen, welches im wesentlichen aus einer Kohlenstoff, Wasserstoff und Sauerstoff enthaltenden organischen Verbindung, wie beispielsweise Saccharose, Stärke, Zellulose, Ascorbinsäure oder Oxalsäure, und einem anorganischen Oxydator aus der Gruppe der Perchlorate oder Chlorate besteht. Das Stoffgemisch enthält ca. ein Teil der organischen Verbindung, drei Teile des anorganischen Oxydators und ein bis vier Teile Metallcarbonate als Kühlmittel.The U.S. Patent 3,862,866 is considered the closest prior art viewed. It discloses a gas-generating mixture of substances, in particular to generate propellant gas for occupant protection devices in Motor vehicles, which essentially consist of a carbon, hydrogen and oxygen-containing organic compound such as Sucrose, starch, cellulose, ascorbic acid or oxalic acid, and an inorganic oxidizer from the group of perchlorates or chlorates. The mixture of substances contains approx. Part of the organic Compound, three parts of the inorganic oxidizer and one to four parts of metal carbonate as a coolant.
Der Erfindung liegt demgegenüber die Aufgabe zugrunde, ein gaserzeugendes, azidfreies Treibstoffgemisch bereitzustellen, das aus ungiftigen Komponenten besteht, eine hohe thermische und chemische Stabilität aufweist, gut verarbeitbar und nicht hygroskopisch ist und schließlich auch eine ausreichende Abbrandgeschwindigkeit sowie eine gute Anzündwilligkeit besitzt.The invention is based on the object of a gas-generating, to provide an azide-free fuel mixture that consists of non-toxic Components, high thermal and chemical stability has good workability and is not hygroscopic and finally, a sufficient burn rate as well as a has good ignitability.
Diese Aufgabe wird erfindungsgemäß durch die Bereitstellung eines
gaserzeugenden Stoffgemisches gelöst, welches im wesentlichen besteht
aus:
Diese Treibstoffkomponenten sind ungiftig und preiswert sowie recyclingfähig und zudem sehr gut verarbeitbar. Ferner wird mit diesem erfindungsgemäßen Treibstoffgemisch eine hohe Abbrandgeschwindigkeit erzielt, wobei jedoch die Verbrennungsrückstände ungiftig sind. Zudem weist das Treibgas selbst nur einen minimalen Schadgasgehalt auf. Schließlich ist das erfindungsgemäße Treibstoffgemisch schwermetallfrei und ist mit geringen Herstellungskosten zu fertigen.These fuel components are non-toxic, inexpensive and recyclable and also very easy to process. Furthermore, with this fuel mixture according to the invention a high burn rate achieved, but the combustion residues are non-toxic. In addition the propellant gas itself has only a minimal harmful gas content. Finally, the fuel mixture according to the invention is free of heavy metals and can be manufactured with low manufacturing costs.
Eine vorteilhafte Weiterbildung des erfindungsgemäßen Stoffgemisches kann zusätzlich ein Metalloxid in einer An advantageous development of the mixture of substances according to the invention can also contain a metal oxide in a
Menge von höchstens 20 Gew.-% enthalten. Dieses Metalloxid dient zum einen als Kühlmittel zum anderen u. U. als ballistisches Additiv.Contain an amount of at most 20 wt .-%. This metal oxide serves on the one hand as a coolant on the other hand u. U. as a ballistic additive.
Als organische Verbindung wird erfindungsgemäß Fumarsäure (C4H4O4) eingesetzt. Auch entsprechende Salze der Fumarsäure, insbesondere Natrium-, Kalium-, Kalzium-, Magnesiumfumarate, können mit Vorteil als organische Verbindung eingesetzt werden.According to the invention, fumaric acid (C 4 H 4 O 4 ) is used as the organic compound. Corresponding salts of fumaric acid, in particular sodium, potassium, calcium, magnesium fumarates, can also advantageously be used as an organic compound.
Schließlich kann als Metalloxid eine Auswahl aus den Gruppen Al2O3, B2O3, SiO2, TiO2, MnO2, CuO, Fe2O3 und ZnO getroffen werden oder eine Mischung derselben verwendet werden.Finally, the metal oxide can be selected from the groups Al 2 O 3 , B 2 O 3 , SiO 2 , TiO 2 , MnO 2 , CuO, Fe 2 O 3 and ZnO or a mixture thereof.
Die nachfolgenden Beispiele dienen im Zusammenhang mit den Zeichnungen
der weiteren Erläuterung der Erfindung. Es zeigen:
Gemäß einem ersten Ausführungsbeispiel besteht das Stoffgemisch aus 34,4 Gew.-% Fumarsäure und 65,6 Gew.-% Kaliumperchlorat. Dieses Treibgasgemisch wurde bezüglich der thermischen Stabilität als auch der Hygroskopizität mit einem aus der schon genannten Druckschrift US 3 880 595 bekannten Stoffgemisch aus 35,3 Gew.-% Zitronensäure und 64,7 Gew.-% Kaliumperchlorat verglichen. Die Ergebnisse dieser Vergleichsversuche sind in den Figuren 1 und 2 dargestellt.According to a first embodiment, there is Mixture of 34.4% by weight of fumaric acid and 65.6% by weight Potassium perchlorate. This propellant gas mixture was regarding thermal stability and hygroscopicity with one from the publication already mentioned US 3,880,595 known mixture of 35.3 % By weight of citric acid and 64.7% by weight of potassium perchlorate compared. The results of these comparative tests are shown in Figures 1 and 2.
Nach Figur 1 wurde der Stabilitätstest (Holland-Test) bei einer Temperatur von 110 °C über eine Zeitdauer von mehr als 70 Stunden durchgeführt. Dabei zeigte das bekannte Stoffgemisch (Bezugszeichen 1) eine Gewichtsabnahme von fast 0,8 %, während das erfindungsgemäße Stoffgemisch (Bezugszeichen 2) weniger als 0,01 % Gewichtsabnahme aufweist.According to FIG. 1, the stability test (Holland test) at a temperature of 110 ° C over a period of performed more than 70 hours. The well-known showed Substance mixture (reference number 1) a weight loss of almost 0.8%, while the invention Substance mixture (reference number 2) less than 0.01% weight loss having.
Der Hygroskopizitätstest wurde bei einer relativen Luftfeuchtigkeit von 86% über eine Zeitdauer von nahezu 100 Stunden durchgeführt. Gemäß Figur 2 beträgt beim bekannten Stoffgemisch (Bezugszeichen 1) die Gewichtszunahme 13%, während bei dem erfindungsgemäßen Stoffgemisch (Bezugszeichen 2) keine Gewichtsaufnahme meßbar ist.The hygroscopicity test was carried out at a relative Humidity of 86% over a period of almost 100 hours. According to Figure 2 is at known mixture of substances (reference number 1) Weight gain 13%, while in the invention Substance mixture (reference number 2) no weight absorption is measurable.
Schließlich wurde mit dem gleichen erfindungsgemäßen
Treibstoffgemisch (Stoffgemisch 2) ein Vergleich mit
einem weiteren bekannten Treibstoffgemisch
(Stoffgemisch 1), bestehend aus 30,8 Gew.-% 5-Aminotetrazol,
36,1 Gew.-% Natriumnitrat und 33,1 Gew.-% Eisen-(III)-Oxyd
(vgl. US 4 948 439) durchgeführt. Dabei
erfolgte der Abbrand der Treibstoffe in einem üblichen
Gasgenerator. Hierzu wurden die Treibstoffkomponenten
fein aufgemahlen und zu Tabletten verpresst. Die erzeugte
Gasmenge und der entstehende Gasdruck waren ausreichend
zur Füllung eines 65 Liter-Sackes. Die gemessenen
Schadgaskonzentrationen beziehen sich dabei auf
ein Meßvolumen von 60 l. Das Ergebnis des Versuches ist
in Figur 3 dargestellt. Hiernach erzeugt das bekannte
Stoffgemisch 1 15.000 ppm Kohlenmonoxyd (CO), 500 ppm
Stickoxyde (NOx) sowie 3.000 ppm Ammoniak (NH3), wogegen
das erfindungsgemäße Stoffgemisch 2 lediglich
3.000 ppm Kohlenmonoxyd, jedoch kein Stickoxyd und kein
Ammoniak erzeugt.Finally, the same fuel mixture according to the invention (substance mixture 2) was used to make a comparison with a further known fuel mixture (substance mixture 1) consisting of 30.8% by weight of 5-aminotetrazole, 36.1% by weight of sodium nitrate and 33.1% by weight. % Iron (III) oxide (cf. US 4,948,439). The fuels were burned off in a conventional gas generator. For this purpose, the fuel components were finely ground and pressed into tablets. The amount of gas generated and the resulting gas pressure were sufficient to fill a 65 liter sack. The measured harmful gas concentrations relate to a measuring volume of 60 l. The result of the test is shown in Figure 3. Thereafter, the known
Ein erfindungsgemäßes Treibstoffgemisch als zweites Ausführungsbeispiel enthält 30,2 Gew.-% Fumarsäure, 63,6 Gew.-% Kaliumperchlorat und 6,2 Gew.-% Eisenoxyd. Dieses Eisenoxyd dient dabei als Kühlreagenz und setzt die Abbrandtemperatur um ca. 7 % herab. Auch dieses erfindungsgemäße Treibstoffgemisch erzeugt nach einem Abbrand lediglich einen Schadgasgehalt von ca. 3.000 ppm Kohlenmonoxyd.A second fuel mixture according to the invention Embodiment contains 30.2% by weight of fumaric acid, 63.6% by weight of potassium perchlorate and 6.2% by weight of iron oxide. This iron oxide serves as a cooling reagent and sets the burn-up temperature is reduced by approx. 7%. This also according to the invention Fuel mixture generated after a burn only a harmful gas content of approx.3,000 ppm Carbon monoxide.
Claims (4)
- A gas-generating substance mixture, in particular for producing propellant gas for occupant protection devices in motor vehicles, characterized in that the substance mixture consists essentially ofa) 20 to 45% by weight of fumaric acid or salts of fumaric acid;b) 55 to 80% by weight of an inorganic oxidant from the group consisting of perchlorates, chlorates, peroxides, or mixtures thereof; andc) 0 to 20% by weight of a metal oxide.
- The gas-generating substance mixture according to claim 1, characterized in that sodium, potassium, calcium, or magnesium fumarates are used as salts of the fumaric acid.
- The gas-generating substance mixture according to claim 1 or 2, characterized in that the oxidant is potassium perchlorate.
- The gas-generating substance mixture according to any of the preceding claims, characterized in that the metal oxide is selected from the group consisting of Al2O3, B2O3, SiO2, TiO2, MnO2, CuO, Fe2O3, ZnO, or mixtures thereof.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4423088A DE4423088A1 (en) | 1994-07-01 | 1994-07-01 | Gas-generating, acid-free mixture of substances |
DE4423088 | 1994-07-01 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0691317A2 EP0691317A2 (en) | 1996-01-10 |
EP0691317A3 EP0691317A3 (en) | 1997-03-05 |
EP0691317B1 true EP0691317B1 (en) | 2000-01-12 |
Family
ID=6522007
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95108938A Expired - Lifetime EP0691317B1 (en) | 1994-07-01 | 1995-06-09 | Non-azide gas generant formulations |
Country Status (5)
Country | Link |
---|---|
US (1) | US5525170A (en) |
EP (1) | EP0691317B1 (en) |
JP (1) | JP3693067B2 (en) |
KR (1) | KR100229367B1 (en) |
DE (2) | DE4423088A1 (en) |
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US3839105A (en) * | 1972-03-10 | 1974-10-01 | Thiokol Chemical Corp | Oxalyl dihydrazide compositions and use as a coolant in gas generating process |
DE2312505A1 (en) * | 1972-03-13 | 1973-09-27 | Specialty Products Dev Corp | Pyrotechnical mixture for gas development - using an oxidising agent and an organic salt |
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WO1992021636A1 (en) * | 1991-05-28 | 1992-12-10 | Daicel Chemical Industries, Ltd. | Gas generating agent |
CZ291570B6 (en) * | 1991-06-21 | 2003-04-16 | Dynamit Nobel Aktiengesellschaft | Propellant for gas generators, process of its preparation and use |
US5125684A (en) * | 1991-10-15 | 1992-06-30 | Hercules Incorporated | Extrudable gas generating propellants, method and apparatus |
FR2691706B1 (en) | 1992-06-02 | 1994-07-22 | Livbag Snc | PYROTECHNIC GAS GENERATOR PROVIDED WITH A SAFETY OPENING. |
-
1994
- 1994-07-01 DE DE4423088A patent/DE4423088A1/en not_active Withdrawn
-
1995
- 1995-05-26 US US08/452,292 patent/US5525170A/en not_active Expired - Fee Related
- 1995-06-09 DE DE59507593T patent/DE59507593D1/en not_active Expired - Lifetime
- 1995-06-09 EP EP95108938A patent/EP0691317B1/en not_active Expired - Lifetime
- 1995-06-28 JP JP19567195A patent/JP3693067B2/en not_active Expired - Lifetime
- 1995-07-01 KR KR1019950019431A patent/KR100229367B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
KR960004303A (en) | 1996-02-23 |
EP0691317A3 (en) | 1997-03-05 |
JPH0840793A (en) | 1996-02-13 |
KR100229367B1 (en) | 1999-11-01 |
DE59507593D1 (en) | 2000-02-17 |
JP3693067B2 (en) | 2005-09-07 |
US5525170A (en) | 1996-06-11 |
DE4423088A1 (en) | 1996-01-04 |
EP0691317A2 (en) | 1996-01-10 |
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