EP0905108B1 - Particle-free gas generating mixture - Google Patents
Particle-free gas generating mixture Download PDFInfo
- Publication number
- EP0905108B1 EP0905108B1 EP98118023A EP98118023A EP0905108B1 EP 0905108 B1 EP0905108 B1 EP 0905108B1 EP 98118023 A EP98118023 A EP 98118023A EP 98118023 A EP98118023 A EP 98118023A EP 0905108 B1 EP0905108 B1 EP 0905108B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixture
- mixture according
- nitrate
- ammonium nitrate
- ammonium
- 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.)
- Expired - Lifetime
Links
Classifications
-
- 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 particle-free, gas-generating mixture for use in gas generators for safety devices, in particular in gas generators for vehicle occupant restraint systems.
- Gas generators for safety devices usually contain a solid fuel based on sodium azide as a gas supplier Main component.
- sodium azide is toxic and can become easily with heavy metals forming extremely dangerous and violent implement reacting connections. Therefore, both in manufacturing the gas-generating mixtures as well as in the disposal Defective or unused gas generators require special measures.
- blowing agents containing sodium azide also a range of solids through suitable filter devices removed from the gas flow in the gas generator or in the gas generator have to be held back. There have therefore been attempts to Production of blowing agents which burn off essentially without residues made.
- US-A-5 545 272 describes a gas generating composition; which consists essentially of 35 to 55 wt .-% nitroguanidine and about 45 to 65 wt .-% phase-stabilized ammonium nitrate.
- phase stabilizing agents e.g. Potassium nitrate and potassium perchlorate, but also potassium dichromate, Potassium oxalate and mixtures thereof in an amount from 5 to about 25 % By weight, preferably 10 to 15%.
- the gas generating composition of US-A-5 545 272 can due to the relatively high proportion of phase stabilizing additives not residue-free for the ammonium nitrate, i.e. without solid combustion residues, burn down.
- this fuel burns up thus smoke formation caused by filter devices in the gas generator can only be suppressed incompletely.
- the known mixture is difficult to ignite and has a relative low burning rate.
- the high proportion of ammonium nitrate also leads to high hygroscopicity, which Storage and use in the gas generator an increased Effort requires an undesirable change in the fuel mixture to prevent.
- DE 195 05 568 A1 discloses a propellant for gas generators, the fuel as at least one compound from the group Tetrazoles, triazoles, triazines, cyanic acid, urea, their derivatives, Descendants or their salts, at least three as oxidizing agents Compounds from the group of peroxides, nitrates, chlorates or Perchlorate, as well as combustion moderators and the proportion of toxic Contains gas reducing supplements. Can be used as urea derivatives Biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, Aminoguanidine nitrate, thiourea and triaminoguanidine nitrate be used.
- EP 0 659 712 A1 describes a gas-generating pyrotechnic composition, which essentially consists of an oxygen-containing thermoplastic Elastomer as a binder, based on a high-energy plasticizer of polyglyzidyl azide, an inorganic oxidizer and control additives burn rate, with the oxidizer at least 85 % By weight is ammonium nitrate. Binder and plasticizer form about 5 to 15 % By weight of the composition.
- additives to control the burning rate is a mixture of ammonium perchlorate and potassium nitrate used, the potassium nitrate about 7% by weight and the ammonium perchlorate forms between 4 and 6% by weight of the composition.
- the invention accordingly provides an acid-free, particle-free burning, gas generating mixture for use in a gas generator ready for a safety device, which consists of a high-energy Fuel with an oxygen value of not less than -35%, with an oxidizer mixture of ammonium nitrate and ammonium perchlorate an ammonium nitrate content of 35 to 50 wt .-% and an ammonium perchlorate content of between 3 and 10% by weight, based in each case on the Total weight of the mixture, possibly a phase stabilizing one Additive for the ammonium nitrate in a proportion of at most 5% by weight, based on the weight of the ammonium nitrate, Burning moderators in a proportion of 0 to 3 wt .-%, based on the Total weight of the mixture and processing aids in one Proportion of 0 to 5% by weight, based on the total weight of the mixture, consists.
- the total water content of the gas-generating mixture is at most 0.3%.
- the ammonium nitrate content is preferably between 40 and 50%, particularly preferably between 40 and 45%.
- the ammonium perchlorate content is preferably in the range between 3 and 7% by weight.
- the high-energy fuel is preferably from guanidine nitrate, Nitroguanidine, triaminoguanidine nitrate, urea nitrate, Nitro urea, nitropenta, nitrotriazalon, hexogen, octogen or their mixtures selected existing group. Particularly preferred is the fuel guanidine nitrate and / or nitroguanidine. The latter is the most preferred fuel.
- the ammonium nitrate used in the invention can be small amounts contain phase stabilizing additives to increase storage stability, those made of copper oxide, zinc oxide, complex zinc compounds or mixtures of existing groups are selected. It it has been found that, in contrast to those in US-A-5 545 272 required amounts of 10 to 15% of potassium compounds for phase stabilization in the application according to the invention at most 5% of the mentioned additives are needed. Surprisingly, it was found that while controlling the water content of the overall mixture the proportion of phase-stabilizing additives reduced to zero can be. While phase stabilizing at water contents of 0.1 to 0.3% Additions of 3 to 5% to ensure storage stability can be used if the water content is below 0.1% phase-stabilizing additives are completely dispensed with. All in all this results in a reduction in solid emissions compared to US Pat. No. 5,545,272 by the mixture according to the invention from 50 to 100%.
- the compounds known in the art can be used as the combustion moderator. These include transition metal compounds and carbon black.
- the transition metal compounds can be selected from the group of transition metal oxides, hydroxides, nitrates, carbonates and organometallic compounds of the transition metals. Exemplary examples of this are iron oxides, copper oxides, chromium oxides, zinc oxide, copper chromite, basic copper nitrate, zinc carbonate, copper resorcylate and ferrocene.
- carbon black as a combustion moderator, optionally in a mixture with transition metal compounds, is preferred, however, because carbon black is inexpensive on the one hand and burns off without residue with the formation of CO 2 .
- processing aids are added, which from the from the Pressing aids, trickling aids or lubricants existing group selected are.
- processing aids are Polyethylene glycol, cellulose, methyl cellulose, graphite, wax, magnesium stearate, Zinc stearate, boron nitride, talc, bentonite, silicon dioxide or molybdenum sulfide.
- Ammonium nitrate content ensures that the inherently unfavorable properties, such as. the low structural stability, hygroscopicity, the poor willingness to ignite and the slow burning rate of mixtures containing ammonium nitrate through the addition of ammonium perchlorate can be compensated.
- an ammonium perchlorate content of less than 3% there is no significant improvement with regard to the willingness to ignite and the burning rate of the Fuel.
- An ammonium perchlorate content of above 10% by weight leads to the formation of free hydrogen chloride, which is due to the strict toxicity requirements for propellant gases for occupant protection systems is undesirable.
- ammonium perchlorate leads also in the small proportion of 3 to 10% by weight Increase in the willingness to ignite and burning rate of the invention Propellant. Due to the higher oxygen content of Ammonium perchlorate can also the ammonium nitrate in the Mixture can be reduced more.
- the invention thus creates a gas yield of up to 100 percent burning gas-generating mixture from which an essentially particle-free gas mixture is released and that physiologically is harmless.
- the use of an oxidizer mixture Ammonium nitrate and ammonium perchlorate also ensure good Willingness to ignite and a high burning rate. At the same time points the mixture according to the invention has high thermal and chemical stability on.
- a temperature storage test at 110 ° C. was also carried out with the mixture carried out over 400 h.
- the measured weight loss was below 0.8%; the mixture is therefore sufficiently stable.
- a thermal shock test was also carried out on tablets with different moisture contents.
- the tablets were first dried in vacuo ( ⁇ 1 mbar) at 100 ° C for 18 hours, then part of it was in a desiccator over 8 hours at 45% rel. Moisture again moistened in a defined way.
- the H 2 O content of the dried tablets was 0.08%, the H 2 O content of the moistened tablets was 0.30%.
- the tablets were hermetically sealed in an aluminum container and subjected to a temperature change between - 35 ° C and + 85 ° C (56 cycles). While the tablets with the increased moisture content swelled strongly after the test, were partially broken and thus had become unusable for the intended use, the dry tablets showed no change in their mechanical properties.
- the tablets with a moisture content of 0.20% were the in Example 1 subjected to thermal cycling. To The tablets showed no change when the stress was complete their mechanical properties.
- Example 1 Tablets processed and ignited in a gas generator 51.5 g dried nitroguanidine, 40.0 g dried ammonium nitrate, 8.0 g of dried ammonium perchlorate, 2 g of copper chromite and 0.5 g of carbon black was added in the manner described in Example 1 Tablets processed and ignited in a gas generator.
- the average burning rate at 200 bar was 23 mm / s.
Landscapes
- 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 partikelfrei abbrennendes gaserzeugendes Gemisch zur Verwendung in Gasgeneratoren für Sicherheitseinrichtungen, insbesondere in Gasgeneratoren für Fahrzeuginsassen-Rückhaltesysteme.The invention relates to a particle-free, gas-generating mixture for use in gas generators for safety devices, in particular in gas generators for vehicle occupant restraint systems.
Gasgeneratoren für Sicherheitseinrichtungen enthalten üblicherweise einen Festtreibstoff auf der Grundlage von Natriumazid als gasliefernde Hauptkomponente. Natriumazid ist jedoch giftig und kann sich leicht mit Schwermetallen unter Bildung extrem gefährlicher und heftig reagierender Verbindungen umsetzen. Daher sind sowohl bei der Herstellung der gaserzeugenden Gemische als auch bei der Entsorgung defekter oder unverbrauchter Gasgeneratoren besondere Maßnahmen erforderlich.Gas generators for safety devices usually contain a solid fuel based on sodium azide as a gas supplier Main component. However, sodium azide is toxic and can become easily with heavy metals forming extremely dangerous and violent implement reacting connections. Therefore, both in manufacturing the gas-generating mixtures as well as in the disposal Defective or unused gas generators require special measures.
Bei der Verbrennung von natriumazidhaltigen Treibmitteln entstehen zudem eine Reihe von Feststoffen, die durch geeignete Filtereinrichtungen im Gasgenerator aus dem Gasstrom entfernt bzw. im Gasgenerator zurückgehalten werden müssen. Es wurden daher bereits Versuche zur Herstellung von im wesentlichen rückstandsfrei abbrennenden Treibmitteln unternommen. Combustion of blowing agents containing sodium azide also a range of solids through suitable filter devices removed from the gas flow in the gas generator or in the gas generator have to be held back. There have therefore been attempts to Production of blowing agents which burn off essentially without residues made.
In der US-A-5 545 272 ist eine gaserzeugende Zusammensetzung beschrieben; die im wesentlichen aus 35 bis 55 Gew.-% Nitroguanidin und etwa 45 bis 65 Gew.-% phasenstabilisiertem Ammoniumnitrat besteht. Der Zusatz von phasenstabilisierenden Mitteln zu dem Ammoniumnitrat wird als notwendig erachtet, da eine in reinem Ammoniumnitrat bei 32,3°C auftretende Strukturänderung mit einer Volumenzunahme verbunden ist, die gemäß der genannten Patentschrift verhindert werden soll. Als phasenstabilisierende Zusätze werden Kaliumsalze, wie z.B. Kaliumnitrat und Kaliumperchlorat, aber auch Kaliumdichromat, Kaliumoxalat und deren Mischungen in einer Menge von 5 bis etwa 25 Gew.-%, bevorzugt 10 bis 15%, genannt.US-A-5 545 272 describes a gas generating composition; which consists essentially of 35 to 55 wt .-% nitroguanidine and about 45 to 65 wt .-% phase-stabilized ammonium nitrate. The Addition of phase stabilizing agents to the ammonium nitrate considered necessary because one in pure ammonium nitrate at 32.3 ° C occurring structural change is associated with an increase in volume, which is to be prevented according to the cited patent. As phase stabilizing additives are potassium salts, e.g. Potassium nitrate and potassium perchlorate, but also potassium dichromate, Potassium oxalate and mixtures thereof in an amount from 5 to about 25 % By weight, preferably 10 to 15%.
Die gaserzeugende Zusammensetzung der US-A-5 545 272 kann jedoch aufgrund des relativ hohen Anteils an phasenstabilisierenden Zusätzen für das Ammoniumnitrat nicht rückstandsfrei, d.h. ohne feste Verbrennungsrückstände, abbrennen. Beim Abbrand dieses Treibstoffs tritt somit eine Rauchbildung ein, die durch Filtereinrichtungen im Gasgenerator nur unvollständig unterdrückt werden kann. Zudem ist die bekannte Mischung nur schlecht anzündbar und weist eine relativ geringe Abbrandgeschwindigkeit auf. Der hohe Anteil an Ammoniumnitrat führt überdies zu einer hohen Hygroskopizität, die bei der Verarbeitung, Lagerung und dem Einsatz im Gasgenerator einen erhöhten Aufwand erfordert, um eine unerwünschte Veränderung des Treibstoffgemischs zu verhindern.However, the gas generating composition of US-A-5 545 272 can due to the relatively high proportion of phase stabilizing additives not residue-free for the ammonium nitrate, i.e. without solid combustion residues, burn down. When this fuel burns up thus smoke formation caused by filter devices in the gas generator can only be suppressed incompletely. In addition, the known mixture is difficult to ignite and has a relative low burning rate. The high proportion of ammonium nitrate also leads to high hygroscopicity, which Storage and use in the gas generator an increased Effort requires an undesirable change in the fuel mixture to prevent.
Die DE 195 05 568 A1 offenbart ein Treibmittel für Gasgeneratoren, die als Brennstoff wenigstens eine Verbindung aus der Gruppe Tetrazole, Triazole, Triazine, Cyansäure, Harnstoff, deren Derivate, Abkömmlinge oder deren Salze, als Oxidationsmittel wenigstens drei Verbindungen aus der Gruppe der Peroxide, Nitrate, Chlorate oder Perchlorate, sowie Abbrandmoderatoren und den Anteil der toxischen Gase reduzierende Zuschläge enthält. Als Harnstoffderivate können Biuret, Guanidin, Nitroguanidin, Guanidinnitrat, Aminoguanidin, Aminoguanidinnitrat, Thioharnstoff und Triaminoguanidinnitrat eingesetzt werden. Als Oxidationsmittel werden, unabhängig voneinander, unter anderem Ammoniumnitrat oder Ammoniumperchlorat genannt. Die DE 195 05 568 A1 enthält jedoch keinerlei Angaben zum Anteil der Feststoffe in der nach dem Abbrand der Treibmittel freigesetzten Gasmischung.DE 195 05 568 A1 discloses a propellant for gas generators, the fuel as at least one compound from the group Tetrazoles, triazoles, triazines, cyanic acid, urea, their derivatives, Descendants or their salts, at least three as oxidizing agents Compounds from the group of peroxides, nitrates, chlorates or Perchlorate, as well as combustion moderators and the proportion of toxic Contains gas reducing supplements. Can be used as urea derivatives Biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, Aminoguanidine nitrate, thiourea and triaminoguanidine nitrate be used. As an oxidizer, become independent from each other, including ammonium nitrate or ammonium perchlorate called. However, DE 195 05 568 A1 does not contain any information on Proportion of solids in the after the propellant burns released gas mixture.
Die EP 0 659 712 A1 beschreibt eine gaserzeugende pyrotechnische Zusammensetzung, die im wesentlichen aus einem sauerstoffhaltigen thermoplastischen Elastomer als Binder, einem hochenergetischen Weichmacher auf der Grundlage von Polyglyzidylazid, einem anorganischen Oxidator und Additiven zur Steuerung der Abbrandgeschwindigkeit besteht, wobei der Oxidator zu mindestens 85 Gewichts-% Ammoniumnitrat ist. Binder und Weichmacher bilden etwa 5 bis 15 Gewichts-% der Zusammensetzung. Als Additive zur Steuerung der Abbrandgeschwindigkeit wird insbesondere ein Gemisch aus Ammoniumperchlorat und Kaliumnitrat verwendet, wobei das Kaliumnitrat etwa 7 Gewichts-% und das Ammoniumperchlorat zwischen 4 und 6 Gewichts-% der Zusammensetzung bildet.EP 0 659 712 A1 describes a gas-generating pyrotechnic composition, which essentially consists of an oxygen-containing thermoplastic Elastomer as a binder, based on a high-energy plasticizer of polyglyzidyl azide, an inorganic oxidizer and control additives burn rate, with the oxidizer at least 85 % By weight is ammonium nitrate. Binder and plasticizer form about 5 to 15 % By weight of the composition. As additives to control the burning rate is a mixture of ammonium perchlorate and potassium nitrate used, the potassium nitrate about 7% by weight and the ammonium perchlorate forms between 4 and 6% by weight of the composition.
Es besteht daher weiterhin Bedarf an physiologisch unbedenklichen Treibmitteln für Gasgeneratoren, die unter Bildung eines im wesentlichen partikelfreien, ungiftigen Verbrennungsgases mit bis zu hunderprozentiger Gasausbeute abbrennen und eine ausreichend hohe Abbrandgeschwindigkeit sowie eine gute thermische und chemische Stabilität aufweisen.There is therefore still a need for physiologically harmless Propellants for gas generators, which form an essentially particle-free, non-toxic combustion gas burn with up to 100% gas yield and one sufficiently high burn rate and good thermal and have chemical stability.
Die Erfindung stellt demgemäß ein azidfreies, partikelfrei abbrennendes, gaserzeugendes Gemisch zur Verwendung in einem Gasgenerator für eine Sicherheitseinrichtung bereit, welches aus einem energiereichen Brennstoff mit einem Sauerstoffwert von nicht unter -35%, einem Oxidatorgemisch aus Ammoniumnitrat und Ammoniumperchlorat mit einem Ammoniumnitratanteil von 35 bis 50 Gew.-% und einem Ammoniumperchloratanteil von zwischen 3 und 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Gemischs, gegebenenfalls einem phasenstabilisierenden Zusatz für das Ammoniumnitrat in einem Anteil von höchstens 5 Gew.-%, bezogen auf das Gewicht des Ammoniumnitrats, Abbrandmoderatoren in einem Anteil von 0 bis 3 Gew.-%, bezogen auf das Gesamtgewicht des Gemischs und Verarbeitungshilfsmittel in einem Anteil von 0 bis 5 Gew.-%, bezogen auf das Gesamtgewicht des Gemischs, besteht. Der Gesamtwassergehalt des gaserzeugenden Gemischs beträgt höchstens 0,3%. Der Ammoniumnitratanteil liegt bevorzugt zwischen 40 und 50%, besonders bevorzugt zwischen 40 und 45%. Der Ammoniumperchloratanteil liegt bevorzugt im Bereich zwischen 3 und 7 Gew.-%.The invention accordingly provides an acid-free, particle-free burning, gas generating mixture for use in a gas generator ready for a safety device, which consists of a high-energy Fuel with an oxygen value of not less than -35%, with an oxidizer mixture of ammonium nitrate and ammonium perchlorate an ammonium nitrate content of 35 to 50 wt .-% and an ammonium perchlorate content of between 3 and 10% by weight, based in each case on the Total weight of the mixture, possibly a phase stabilizing one Additive for the ammonium nitrate in a proportion of at most 5% by weight, based on the weight of the ammonium nitrate, Burning moderators in a proportion of 0 to 3 wt .-%, based on the Total weight of the mixture and processing aids in one Proportion of 0 to 5% by weight, based on the total weight of the mixture, consists. The total water content of the gas-generating mixture is at most 0.3%. The ammonium nitrate content is preferably between 40 and 50%, particularly preferably between 40 and 45%. The ammonium perchlorate content is preferably in the range between 3 and 7% by weight.
Der energiereiche Brennstoff ist vorzugsweise aus der aus Guanidinnitrat, Nitroguanidin, Triaminoguanidinnitrat, Harnstoffnitrat, Nitroharnstoff, Nitropenta, Nitrotriazalon, Hexogen, Oktogen oder deren Mischungen bestehenden Gruppe ausgewählt. Besonders bevorzugt ist der Brennstoff Guanidinnitrat und/oder Nitroguanidin. Letzteres ist der am meisten bevorzugte Brennstoff.The high-energy fuel is preferably from guanidine nitrate, Nitroguanidine, triaminoguanidine nitrate, urea nitrate, Nitro urea, nitropenta, nitrotriazalon, hexogen, octogen or their mixtures selected existing group. Particularly preferred is the fuel guanidine nitrate and / or nitroguanidine. The latter is the most preferred fuel.
Das erfindungsgemäß verwendete Ammoniumnitrat kann geringe Mengen phasenstabilisierender Zusätze zur Erhöhung der Lagerstabilität enthalten, die aus der aus Kupferoxid, Zinkoxid, komplexen Zinkver-bindungen oder deren Gemische bestehenden Gruppe ausgewählt sind. Es hat sich herausgestellt, daß im Gegensatz zu den in der US-A-5 545 272 benötigten Mengen von 10 bis 15% an Kaliumverbindungen zur Phasenstabilisierung im erfindungsgemässen Anwendungsfall höchstens 5% der genannten Zusätze benötigt werden. Überraschenderweise wurde gefunden, daß bei gleichzeitiger Kontrolle des Wassergehaltes der Gesamtmischung der Anteil an phasenstabilisierenden Zusätzen bis auf Null reduziert werden kann. Während bei Wassergehalten von 0,1 bis 0,3% phasenstabilisierende Zusätze von 3 bis 5% zur Gewährleistung der Lagerstabilität eingesetzt werden, kann bei Wassergehalten von unter 0,1% auf phasenstabilisierende Zusätze völlig verzichtet werden. Insgesamt ergibt sich so gegenüber der US-A-5 545 272 eine Reduktion der Feststoffemissionen durch das erfindungsgemässe Gemisch von 50 bis 100%.The ammonium nitrate used in the invention can be small amounts contain phase stabilizing additives to increase storage stability, those made of copper oxide, zinc oxide, complex zinc compounds or mixtures of existing groups are selected. It it has been found that, in contrast to those in US-A-5 545 272 required amounts of 10 to 15% of potassium compounds for phase stabilization in the application according to the invention at most 5% of the mentioned additives are needed. Surprisingly, it was found that while controlling the water content of the overall mixture the proportion of phase-stabilizing additives reduced to zero can be. While phase stabilizing at water contents of 0.1 to 0.3% Additions of 3 to 5% to ensure storage stability can be used if the water content is below 0.1% phase-stabilizing additives are completely dispensed with. All in all this results in a reduction in solid emissions compared to US Pat. No. 5,545,272 by the mixture according to the invention from 50 to 100%.
Als Abbrandmoderator können die in der Technik bekannten Verbindungen eingesetzt werden. Unter anderem zählen hierzu Übergangsmetallverbindungen und Ruß. Die Übergangsmetallverbindungen können ausgewählt werden aus der Gruppe der Übergangsmetalloxide, -hydroxide, -nitrate, -carbonate und metallorganischer Verbindungen der Übergangsmetalle. Exemplarische Beispiele hierfür sind Eisenoxide, Kupferoxide, Chromoxide, Zinkoxid, Kupferchromit, basisches Kupfernitrat, Zinkcarbonat, Kupferresorcylat und Ferrocen. Eine Verwendung von Ruß als Abbrandmoderator, gegebenenfalls im Gemisch mit Übergangsmetallverbindungen, wird jedoch bevorzugt, da Ruß zum einen kostengünstig ist und zum anderen unter Bildung von CO2 rückstandsfrei abbrennt.The compounds known in the art can be used as the combustion moderator. These include transition metal compounds and carbon black. The transition metal compounds can be selected from the group of transition metal oxides, hydroxides, nitrates, carbonates and organometallic compounds of the transition metals. Exemplary examples of this are iron oxides, copper oxides, chromium oxides, zinc oxide, copper chromite, basic copper nitrate, zinc carbonate, copper resorcylate and ferrocene. The use of carbon black as a combustion moderator, optionally in a mixture with transition metal compounds, is preferred, however, because carbon black is inexpensive on the one hand and burns off without residue with the formation of CO 2 .
Schließlich können dem gaserzeugenden Gemisch in bekannter Weise auch Verarbeitungshilfsmittel beigegeben werden, die aus der aus den Preßhilfen, Rieselhilfen oder Gleitmittel bestehenden Gruppe ausgewählt sind. Beispiele für derartige Verarbeitungshilfsmittel sind Polyethylenglykol, Zellulose, Methylzellulose, Graphit, Wachs, Magnesiumstearat, Zinkstearat, Bornitrid, Talkum, Bentonit, Siliziumdioxid oder Molybdänsulfid.Finally, the gas-generating mixture in a known manner also processing aids are added, which from the from the Pressing aids, trickling aids or lubricants existing group selected are. Examples of such processing aids are Polyethylene glycol, cellulose, methyl cellulose, graphite, wax, magnesium stearate, Zinc stearate, boron nitride, talc, bentonite, silicon dioxide or molybdenum sulfide.
Der erfindungsgemäß unter 50 Gew-%, bevorzugt unter 45%, liegende Ammoniumnitratanteil gewährleistet, daß die an sich ungünstigen Eigenschaften, wie z.B. die geringe Strukturstabilität, Hygroskopizität, die schlechte Anzündwilligkeit und die niedrige Abbrandgeschwindigkeit von Ammoniumnitrat enthaltenden Gemischen durch den Zusatz von Ammoniumperchlorat kompensiert werden können. Bei einem Ammoniumperchloratanteil von unter 3% tritt aber keine wesentliche Verbesserung bezüglich der Anzündwilligkeit und der Abbrandgeschwindigkeit des Treibstoffs ein. Ein Ammoniumperchloratanteil von oberhalb 10 Gew.-% führt zu einer Bildung von freiem Chlorwasserstoff, was aufgrund der strengen Toxizitätsanforderungen an Treibgase für InsassenschutzSysteme unerwünscht ist. Überraschenderweise wurde gefunden, daß eine Verwendung von Ammoniumperchlorat in Anteilen zwischen 3 und 10 Gew.-% im praktischen Einsatz nicht zur Bildung von Chlorwasserstoff führt oder die Chlorwasserstoffkonzentration in der Gasmischung, vermutlich aufgrund von Absorptionseffekten oder einer Niederschlagung mit Wasserdampf, wesentlich geringer ist als nach theoretischen Berechnungen erwartet. Das erfindungsgemäße gaserzeugende Gemisch kann daher als physiologisch unbedenklich eingestuft werden.That according to the invention is less than 50% by weight, preferably less than 45% Ammonium nitrate content ensures that the inherently unfavorable properties, such as. the low structural stability, hygroscopicity, the poor willingness to ignite and the slow burning rate of mixtures containing ammonium nitrate through the addition of ammonium perchlorate can be compensated. With an ammonium perchlorate content of less than 3% there is no significant improvement with regard to the willingness to ignite and the burning rate of the Fuel. An ammonium perchlorate content of above 10% by weight leads to the formation of free hydrogen chloride, which is due to the strict toxicity requirements for propellant gases for occupant protection systems is undesirable. Surprisingly, it was found that a Use of ammonium perchlorate in proportions between 3 and 10% by weight does not lead to the formation of hydrogen chloride in practical use or the concentration of hydrogen chloride in the gas mixture, presumably due to absorption effects or precipitation Water vapor, is significantly lower than according to theoretical calculations expected. The gas-generating mixture according to the invention can therefore can be classified as physiologically harmless.
Darüber hinaus führt aber die Verwendung von Ammoniumperchlorat auch in dem geringen Anteil von 3 bis 10 Gew-% zu einer wesentlichen Steigerung der Anzündwilligkeit und Abbrandgeschwindigkeit des erfindungsgemäßen Treibmittels. Durch den höheren Sauerstoffgehalt von Ammoniumperchlorat kann überdies der Ammoniumnitratanteil in dem Gemisch stärker vermindert werden.In addition, the use of ammonium perchlorate leads also in the small proportion of 3 to 10% by weight Increase in the willingness to ignite and burning rate of the invention Propellant. Due to the higher oxygen content of Ammonium perchlorate can also the ammonium nitrate in the Mixture can be reduced more.
Die Erfindung schafft somit ein mit bis zu hundertprozentiger Gasausbeute abbrennendes gaserzeugendes Gemisch, aus dem ein im wesentlichen partikelfreies Gasgemisch freigesetzt wird und das physiologisch unbedenklich ist. Die Verwendung eines Oxidatorgemischs aus Ammoniumnitrat und Ammoniumperchlorat gewährleistet zudem eine gute Anzündwilligkeit und eine hohe Abbrandgeschwindigkeit. Zugleich weist das erfindungsgemäße Gemisch eine hohe thermische und chemische Stabilität auf.The invention thus creates a gas yield of up to 100 percent burning gas-generating mixture from which an essentially particle-free gas mixture is released and that physiologically is harmless. The use of an oxidizer mixture Ammonium nitrate and ammonium perchlorate also ensure good Willingness to ignite and a high burning rate. At the same time points the mixture according to the invention has high thermal and chemical stability on.
Die Erfindung wird nachfolgend anhand bevorzugter Ausführungsbeispiele beschrieben, die jedoch nicht in einem einschränkenden Sinn zu verstehen sind. The invention is described below using preferred exemplary embodiments described, but not in a restrictive sense are to be understood.
51,5 g getrocknetes Nitroguanidin, 43,0 g getrocknetes Ammoniumnitrat, 5,0 g getrocknetes Ammoniumperchlorat und 0,5 g Ruß wurden gemeinsam in einer Kugelmühle homogenisiert und anschließend zu Treibstofftabletten verpresst. Die so hergestellten Tabletten wurden in einem Gasgenerator zur Zündung gebracht. Der im Gasgenerator erzielte Verbrennungsdruck betrug 350 bar, die Abbranddauer lag im für den vorgesehenen Anwendungszweck benötigten Bereich von 30 ms. Die Schwadenzusammensetzung des so gezündeten Gemischs erwies sich als vollständig partikelfrei. Der Chlorwasserstoffgehalt in der Schwadenzusammensetzung lag mit <50 ppm unterhalb physiologisch bedenklicher Werte.51.5 g dried nitroguanidine, 43.0 g dried Ammonium nitrate, 5.0 g dried ammonium perchlorate and 0.5 g carbon black were homogenized together in a ball mill and then added Compressed fuel tablets. The tablets so produced were ignited in a gas generator. The one in the gas generator achieved combustion pressure was 350 bar, the burn time was in the the intended application range of 30 ms. The The vapor composition of the mixture thus ignited turned out to be completely particle-free. The hydrogen chloride content in the vapor composition was less than 50 ppm below physiologically questionable Values.
Mit dem Gemisch wurde ebenso ein Temperaturlagertest bei 110°C über 400 h durchgeführt. Der gemessene Gewichtsverlust betrug unter 0,8%; das Gemisch ist damit ausreichend stabil.A temperature storage test at 110 ° C. was also carried out with the mixture carried out over 400 h. The measured weight loss was below 0.8%; the mixture is therefore sufficiently stable.
Ferner wurde ein Temperaturwechselbelastungstest mit Tabletten unterschiedlicher Feuchtegehalte durchgeführt. Die Tabletten wurden zunächst im Vakuum (<1 mbar) bei 100°C 18 Stunden getrocknet, anschließend wurde ein Teil hiervon im Exsikkator über 8 Stunden bei 45% rel. Feuchte wieder definiert befeuchtet. Der H2O-Gehalt der getrockneten Tabletten betrug 0,08%, der H2O-Gehalt der befeuchteten Tabletten 0,30%. Die Tabletten wurden in einem Aluminiumbehälter hermetisch versiegelt und einer Temperaturwechselbelastung zwischen - 35°C und +85°C (56 Zyklen) unterworfen. Während die Tabletten mit dem erhöhten Feuchtegehalt nach dem Test stark aufquollen, teilweise zerbrochen und damit für den vorgesehenen Einsatzzweck unbrauchbar geworden waren, zeigten die trockenen Tabletten keine Änderung ihrer mechanischen Eigenschaften.A thermal shock test was also carried out on tablets with different moisture contents. The tablets were first dried in vacuo (<1 mbar) at 100 ° C for 18 hours, then part of it was in a desiccator over 8 hours at 45% rel. Moisture again moistened in a defined way. The H 2 O content of the dried tablets was 0.08%, the H 2 O content of the moistened tablets was 0.30%. The tablets were hermetically sealed in an aluminum container and subjected to a temperature change between - 35 ° C and + 85 ° C (56 cycles). While the tablets with the increased moisture content swelled strongly after the test, were partially broken and thus had become unusable for the intended use, the dry tablets showed no change in their mechanical properties.
51,5 g getrocknetes Nitroguanidin, 43,0 g Ammoniumnitrat, das mit 4% ZnO als Phasenstabilisator versehen war, 5,0 g getrocknetes Ammoniumperchlorat, und 5,0 g Ruß wurden in der im Beispiel 1 beschriebenen Weise zu Tabletten verarbeitet. 51.5 g dried nitroguanidine, 43.0 g ammonium nitrate, which with 4% ZnO was provided as a phase stabilizer, 5.0 g dried Ammonium perchlorate, and 5.0 g of carbon black were in the in Example 1 described way processed into tablets.
Die Tabletten mit einem Feuchtegehalt von 0,20% wurden der in Beispiel 1 beschriebenen Temperaturwechselbelastung unterzogen. Nach abgeschlossener Belastung zeigten die Tabletten keine Veränderung ihrer mechanischen Eigenschaften.The tablets with a moisture content of 0.20% were the in Example 1 subjected to thermal cycling. To The tablets showed no change when the stress was complete their mechanical properties.
51,5 g getrocknetes Nitroguanidin, 40,0 g getrocknetes Ammoniumnitrat, 8,0 g getrocknetes Ammoniumperchlorat, 2 g Kupferchromit und 0,5 g Ruß wurden in der in Beispiel 1 beschriebenen Art und Weise zu Tabletten verarbeitet und in einem Gasgenerator zur Zündung gebracht. Die mittlere Abbrandgeschwindigkeit bei 200 bar betrug 23 mm/s.51.5 g dried nitroguanidine, 40.0 g dried ammonium nitrate, 8.0 g of dried ammonium perchlorate, 2 g of copper chromite and 0.5 g of carbon black was added in the manner described in Example 1 Tablets processed and ignited in a gas generator. The average burning rate at 200 bar was 23 mm / s.
51,5 g getrocknetes Nitroguanidin, 40,0 g getrocknetes Ammoniumnitrat, 8,0 g getrocknetes Ammoniumperchlorat, 2 g Eisenoxid (γ-Fe2O3) und 0,5 g Ruß wurden in der in Beispiel 1 beschriebenen Art und Weise verarbeitet und einem Temperaturlagertest bei 110°C unterworfen. Der Gewichtsverlust nach 400 h lag bei 0,13%.51.5 g of dried nitroguanidine, 40.0 g of dried ammonium nitrate, 8.0 g of dried ammonium perchlorate, 2 g of iron oxide (γ-Fe 2 O 3 ) and 0.5 g of carbon black were processed in the manner described in Example 1 and subjected to a temperature storage test at 110 ° C. The weight loss after 400 h was 0.13%.
Claims (13)
- An azide-free, gas-generating mixture burning off in a particle-free manner for use in a gas generator for a safety device, in particular for a vehicle occupant restraint system, with a total water content of the gas-producing mixture of at most 0.3%, consisting of:a) an energy-rich fuel with an oxygen value of not less than -35%;b) an oxidant mixture of ammonium nitrate and ammonium perchlorate, wherein the ammonium nitrate is contained in a proportion of 35 to 50 wt.% and the ammonium perchlorate in a proportion of 3 to 10 wt.%, each as related to the total weight of the mixture;c) optionally a phase-stabilising additive for the ammonium nitrate in a proportion of at most 5 wt.% as related to the weight of the ammonium nitrate;d) 0 to 3 wt.% combustion moderators, as related to the total weight of the mixture; ande) 0 to 5 wt.% processing aids, as related to the total weight of the mixture.
- The mixture according to claim 1, characterized in that the fuel is selected from the group consisting of guanidine nitrate, nitroguanidine, triaminoguanidine nitrate, urea nitrate, nitrourea, pentaerythritol tetranitrate, nitrotriazolon, hexogen, octogen or mixtures thereof.
- The mixture according to claim 2, characterized in that the fuel is guanidine nitrate and/or nitroguanidine.
- The mixture according to claim 3, characterized in that the fuel is nitroguanidine.
- The mixture according to any one of claims 1 to 4, characterized in that the phase-stabilising additive is selected from the group consisting of copper oxide, zinc oxide, a complex zinc compound or mixtures thereof
- The mixture according to any one of claims 1 to 5, characterized in that the combustion moderator is soot.
- The mixture according to any one of claims 1 to 5, characterized in that the combustion moderator is a transition metal compound, preferably in a mixture with soot.
- The mixture according to claim 7, characterized in that the transition metal compound is selected from the group of transition metal oxides, hydroxides, nitrates, carbonates and organo-metallic compounds of the transition metals.
- The mixture according to any one of claims 1 to 8, characterized in that the processing aids are selected from the group consisting of the compression aids, flowing aids or lubricants.
- The mixture according to claim 9, characterized in that the processing aids are selected from the group consisting of polyethylene glycol, cellulose, methyl cellulose, graphite, wax, magnesium stearate, zinc stearate, boron nitride, talcum, bentonite and molybdenum sulfide and mixtures thereof.
- The mixture according to any one of claims 1 to 10, characterized in that the total water content of the mixture is 0.1 to 0.3 wt.% and the proportion of phase-stabilising additives for the ammonium nitrate is 3 to 5%.
- The mixture according to any one of claims 1 to 10, characterized in that the total water content of the mixture is less than 0.1 wt.% and the ammonium nitrate is free of phase-stabilising additives.
- The mixture according to claim 1, characterized in that the mixture is composed of:51.5 wt.% nitroguanidine;43.0 wt.% ammonium nitrate;5.0 wt.% ammonium perchlorate;0.5 wt.% soot.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19742203A DE19742203A1 (en) | 1997-09-24 | 1997-09-24 | Particle-free gas-generating mixture |
DE19742203 | 1997-09-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0905108A1 EP0905108A1 (en) | 1999-03-31 |
EP0905108B1 true EP0905108B1 (en) | 2002-11-27 |
Family
ID=7843508
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98118023A Expired - Lifetime EP0905108B1 (en) | 1997-09-24 | 1998-09-23 | Particle-free gas generating mixture |
Country Status (3)
Country | Link |
---|---|
US (1) | US5989367A (en) |
EP (1) | EP0905108B1 (en) |
DE (2) | DE19742203A1 (en) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6296724B1 (en) * | 1998-07-21 | 2001-10-02 | Trw Inc. | Gas generating composition for an inflatable vehicle occupant protection device |
US6132538A (en) * | 1998-07-30 | 2000-10-17 | Autoliv Development Ab | High gas yield generant compositions |
JP2000086375A (en) * | 1998-09-09 | 2000-03-28 | Daicel Chem Ind Ltd | Gas generator composition |
JP2000086376A (en) * | 1998-09-14 | 2000-03-28 | Daicel Chem Ind Ltd | Gas generator composition |
DE29821544U1 (en) | 1998-12-02 | 1999-02-18 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azide-free, gas generating composition |
DE29821541U1 (en) | 1998-12-02 | 1999-02-18 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azide-free, gas generating composition |
US6017404A (en) * | 1998-12-23 | 2000-01-25 | Atlantic Research Corporation | Nonazide ammonium nitrate based gas generant compositions that burn at ambient pressure |
US6143102A (en) * | 1999-05-06 | 2000-11-07 | Autoliv Asp, Inc. | Burn rate-enhanced basic copper nitrate-containing gas generant compositions and methods |
US6176950B1 (en) * | 1999-05-17 | 2001-01-23 | James C. Wood | Ammonium nitrate and paraffinic material based gas generating propellants |
US6149746A (en) * | 1999-08-06 | 2000-11-21 | Trw Inc. | Ammonium nitrate gas generating composition |
US6361630B2 (en) * | 1999-08-17 | 2002-03-26 | Trw Inc. | Cool burning gas generating composition |
US20030066584A1 (en) * | 2000-03-01 | 2003-04-10 | Burns Sean P. | Gas generant composition |
US6550808B1 (en) * | 2000-11-17 | 2003-04-22 | Autoliv Asp. Inc. | Guanylurea nitrate in gas generation |
US6547900B2 (en) * | 2001-01-24 | 2003-04-15 | Breed Automotive Technology, Inc. | Method of stabilizing the density of gas generant pellets containing nitroguanidine |
US6589375B2 (en) | 2001-03-02 | 2003-07-08 | Talley Defense Systems, Inc. | Low solids gas generant having a low flame temperature |
US6875295B2 (en) | 2001-12-27 | 2005-04-05 | Trw Inc. | Cool burning gas generating material for a vehicle occupant protection apparatus |
DE10230402B4 (en) * | 2002-07-05 | 2007-01-11 | Trw Airbag Systems Gmbh & Co. Kg | Process for the preparation of a gas generating composition |
US7758709B2 (en) * | 2006-06-21 | 2010-07-20 | Autoliv Asp, Inc. | Monolithic gas generant grains |
US9193639B2 (en) * | 2007-03-27 | 2015-11-24 | Autoliv Asp, Inc. | Methods of manufacturing monolithic generant grains |
US8057611B2 (en) * | 2007-08-13 | 2011-11-15 | Autoliv Asp, Inc. | Multi-composition pyrotechnic grain |
WO2009126182A1 (en) * | 2008-04-10 | 2009-10-15 | Autoliv Asp, Inc. | Monolithic gas generants containing perchlorate-based oxidizers and methods for manufacture thereof |
US8815029B2 (en) | 2008-04-10 | 2014-08-26 | Autoliv Asp, Inc. | High performance gas generating compositions |
US8808476B2 (en) | 2008-11-12 | 2014-08-19 | Autoliv Asp, Inc. | Gas generating compositions having glass fibers |
US9051223B2 (en) | 2013-03-15 | 2015-06-09 | Autoliv Asp, Inc. | Generant grain assembly formed of multiple symmetric pieces |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3708357A (en) * | 1971-04-21 | 1973-01-02 | Us Army | Oxidizers with improved thermal stability and method of making same |
US4111728A (en) * | 1977-02-11 | 1978-09-05 | Jawaharlal Ramnarace | Gas generator propellants |
CA1147593A (en) * | 1979-08-24 | 1983-06-07 | Michael S. Ady | Model rocket propulsion system including a solid propellant grain with a cylindrical burning port adjacent the throat section of a nozzle |
US4552597A (en) * | 1984-08-17 | 1985-11-12 | Megabar Explosives Corporation | Soft composite explosives and process for making same |
US4604151A (en) * | 1985-01-30 | 1986-08-05 | Talley Defense Systems, Inc. | Method and compositions for generating nitrogen gas |
KR100411997B1 (en) * | 1993-08-04 | 2004-04-03 | 오토모티브 시스템즈 라보라토리, 인코포레이티드 | Low Residual Azide-Glass Gas Generator Compositions |
FR2713632B1 (en) * | 1993-12-07 | 1996-01-12 | Poudres & Explosifs Ste Nale | Pyrotechnic compositions generating clean and non-toxic gases, containing a thermoplastic elastomer binder. |
DE4435524C2 (en) * | 1994-10-05 | 1996-08-22 | Fraunhofer Ges Forschung | Solid fuel based on pure or phase-stabilized ammonium nitrate |
DE4435523C1 (en) * | 1994-10-05 | 1996-06-05 | Fraunhofer Ges Forschung | Solid fuel based on phase-stabilized ammonium nitrate |
DE19505568A1 (en) * | 1995-02-18 | 1996-08-22 | Dynamit Nobel Ag | Gas generating mixtures |
US5545272A (en) * | 1995-03-03 | 1996-08-13 | Olin Corporation | Thermally stable gas generating composition |
US5780768A (en) * | 1995-03-10 | 1998-07-14 | Talley Defense Systems, Inc. | Gas generating compositions |
DE19531130A1 (en) * | 1995-08-24 | 1997-02-27 | Bayern Chemie Gmbh Flugchemie | Granulated or pelleted gas generating substance, suitable for use in airbags |
WO1997012849A1 (en) * | 1995-09-29 | 1997-04-10 | Otsuka Kagaku Kabushiki Kaisha | Gas generator for air bag |
US5827996A (en) * | 1995-09-29 | 1998-10-27 | Otsuka Kagaku Kabushiki Kaish | Air bag gas generating composition |
JPH09328387A (en) * | 1996-06-03 | 1997-12-22 | Daicel Chem Ind Ltd | Gas producing agent composition |
-
1997
- 1997-09-24 DE DE19742203A patent/DE19742203A1/en not_active Withdrawn
-
1998
- 1998-09-23 EP EP98118023A patent/EP0905108B1/en not_active Expired - Lifetime
- 1998-09-23 DE DE59806422T patent/DE59806422D1/en not_active Expired - Lifetime
- 1998-09-24 US US09/159,917 patent/US5989367A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
US5989367A (en) | 1999-11-23 |
DE59806422D1 (en) | 2003-01-09 |
DE19742203A1 (en) | 1999-03-25 |
EP0905108A1 (en) | 1999-03-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0905108B1 (en) | Particle-free gas generating mixture | |
EP0949225B1 (en) | Non-azide gas generating composition | |
DE69730202T2 (en) | AZIDFREE, GAS-CREATING COMPOSITIONS | |
DE69001893T2 (en) | Composition and method for inflating a safety air bag. | |
DE69423626T2 (en) | GAS-GENERATING RESIDUE-FREE AZID-FREE COMPOSITION | |
DE4412871C2 (en) | Gas generator compositions | |
DE69609791T2 (en) | CATALYST-CONTAINING, AZID-FREE GAS GENERATING COMPOSITIONS | |
DE69531935T2 (en) | GAS GENERATING FUEL | |
EP0691317B1 (en) | Non-azide gas generant formulations | |
EP0519485A1 (en) | Propellant for gas generators | |
DE69609793T2 (en) | Heterogeneous gas-generating propellant charges | |
DE69413372T2 (en) | Gas generating compositions using dicyanamide salts as fuel | |
DE69323410T2 (en) | GAS GENERATOR FOR AIRBAGS | |
EP0716058B1 (en) | Gas generating mixture | |
EP1345872B1 (en) | Gas generator fuel composition | |
DE4411654C2 (en) | Gas generating mixture | |
DE29722912U1 (en) | Azide free gas generating composition | |
EP1162183B1 (en) | Ignition mixture for use in gas generators | |
WO1998017607A1 (en) | Azide-free, gas-generating solid mixture | |
DE19730872A1 (en) | Propellant useful in munitions and gas generator | |
DE19840993B4 (en) | Use of a gas-generating mixture as ignition mixture in a gas generator | |
EP0914305B2 (en) | Temperature fuse | |
DE102020104119A1 (en) | GAS GENERATING COMPOSITION AND ITS USE IN A GAS GENERATOR | |
DE19925442A1 (en) | Gas generating composition for car gas bag system contains organic fuel, ammonium nitrate stabilized with alkali or alkaline earth metal salt and ammonium halide, sulfate or sulfamate as coolant | |
DE19617538C1 (en) | Gas-generating, acid-free mixture of substances |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR NL SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17P | Request for examination filed |
Effective date: 19990420 |
|
AKX | Designation fees paid |
Free format text: DE FR NL SE |
|
17Q | First examination report despatched |
Effective date: 20010125 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20021127 |
|
REF | Corresponds to: |
Ref document number: 59806422 Country of ref document: DE Date of ref document: 20030109 |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: TRW AIRBAG SYSTEMS GMBH |
|
NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: TRW AIRBAG SYSTEMS GMBH |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20030828 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20060906 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20060908 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070924 |
|
EUG | Se: european patent has lapsed | ||
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20080531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20071001 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20140930 Year of fee payment: 17 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 59806422 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160401 |