EP1006096B1 - Non-azide gas generating composition - Google Patents

Non-azide gas generating composition Download PDF

Info

Publication number
EP1006096B1
EP1006096B1 EP99123906A EP99123906A EP1006096B1 EP 1006096 B1 EP1006096 B1 EP 1006096B1 EP 99123906 A EP99123906 A EP 99123906A EP 99123906 A EP99123906 A EP 99123906A EP 1006096 B1 EP1006096 B1 EP 1006096B1
Authority
EP
European Patent Office
Prior art keywords
weight
proportion
nitrate
composition according
guanidine
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
Application number
EP99123906A
Other languages
German (de)
French (fr)
Other versions
EP1006096A1 (en
Inventor
Siegfried Zeuner
Achim Hofmann
Roland Schropp
Karl-Heinz Rödig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZF Airbag Germany GmbH
Original Assignee
TRW Airbag Systems GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TRW Airbag Systems GmbH filed Critical TRW Airbag Systems GmbH
Publication of EP1006096A1 publication Critical patent/EP1006096A1/en
Application granted granted Critical
Publication of EP1006096B1 publication Critical patent/EP1006096B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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 present invention relates to an acid-free, gas-generating Composition, in particular for use in security devices for motor vehicles.
  • Gas generating compositions used in safety devices used for motor vehicles mostly consist of a fuel based on sodium azide and an oxidizing agent. However, due to the toxicity of sodium azide, it was premature started looking for alternatives to the azide-containing gas generators To look for mixtures.
  • US-A-5 608 183 describes a gas generating mixture containing between about 30 and 85 percent by weight of a fuel and between about 15 and about 70 percent by weight of an oxidizing agent.
  • At least 60% by weight of the fuel consists of the nitrate of an acidic polyamine or a C 2 -C 3 -alkyldiamine, such as, for example, the nitrates of urea, guanidine, aminoguanidine, diaminoguanidine, semicarbazide, ethylenediamine, 1,3-propanediamine or 1, 2-propanediamine, or mixtures thereof.
  • the oxidizing agent comprises at least 60% by weight of basic copper nitrate and / or cobalt triamine trinitrate. The mixture is processed in a wet process.
  • the gas generating mixture known from US-A-5 608 183 has however, an insufficient willingness to ignite and a too low Burn-up speed. Due to the high proportion of basic Copper nitrate is also an increased proportion of toxic gases in the released Detectable gas mixture. Processing the mixture in A wet process requires additional drying stages and is therefore expensive.
  • The. German utility model No. 298 06 504 represents a gas generating Composition ready, the one of at least two components existing fuel mixture in a proportion of 20 to 60 wt .-% and an oxidizer mixture consisting of at least three components in a proportion of 40 to 80% by weight, based in each case on the total composition, includes.
  • the fuel mixture of the known composition is from 5 to 95% by weight of a guanidine compound, 5 to 95 % By weight of a heterocyclic organic acid, for example Cyanuric acid, as well as 0 to 20% by weight of other fuels.
  • the oxidizer mixture of the known composition consists of one or more transition metal oxides in a proportion of 20 to 70% by weight and 10 to 50% by weight of basic copper nitrate and 2 to 30 % By weight metal chlorate, metal perchlorate, ammonium perchlorate, alkali nitrate, Alkaline earth nitrate or mixtures thereof.
  • an additional fuel such as However, cyanuric acid
  • the Composition is therefore for use in gas generators for the Driver's side unsuitable because of the shorter distance between high burn-up speeds for the vehicle occupant and the vehicle internals to be favoured.
  • the additional fuels used must have a lower oxygen balance than guanidine nitrate also a higher proportion of oxidizer to balance the mixture and to achieve an optimally reduced harmful gas emission be used.
  • the higher proportion of oxidizer leads to a increased solids content in the gas mixture and thus to an increased Particulate emissions.
  • the present invention provides such a composition ready, the one consisting of one or more components Fuel in a proportion of 20 to 60 wt .-% and one of at least three components consisting of an oxidizer mixture in a proportion of 40 up to 80 wt .-%, each based on the total composition.
  • the composition is characterized in that the fuel a guanidine compound in a proportion of at least 95% by weight and another fuel component in a proportion of 0 to less than 5 wt .-%, each based on the fuel.
  • the oxidizer mixture consists of one or more transition metal oxides in a proportion of 20 to 80 wt .-%, basic copper nitrate in a proportion of 0 to 50% by weight, metal chlorate, metal perchlorate, Ammonium perchlorate or mixtures thereof in a proportion of 1 to 15 % By weight and alkali nitrate, alkaline earth nitrate or mixtures thereof a proportion of 1 to 15 wt .-%, each based on the oxidizer mixture.
  • Preferred guanidine compounds are guanidine carbonate, guanidine nitrate, Guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, Triaminoguanidine nitrate, nitroguanidine or mixtures thereof used.
  • the further fuel component is preferably an organic one Compound that has an oxygen balance of more than -90%.
  • Cyanuric acid is particularly preferred as a further fuel component, Urea, oxamide, urazole, alloxan, alloxantin and parabanic acid or mixtures thereof.
  • oxygen balance is to be understood as the amount of oxygen in percent by weight which is released when a compound or a mixture is completely converted to CO 2 , H 2 O, Al 2 O 3 , B 2 O 3 , etc. (O 2 overbalancing) , If the available oxygen is not sufficient for this, the shortfall necessary for complete conversion is given with a negative sign (O 2 under-balancing).
  • the transition metal oxide present as a component of the oxidizer mixture can be selected from the group consisting of Cr 2 O 3 , MnO 2 , Fe 2 O 3 , Fe 3 O 4 , CuO, Cu 2 O or mixtures thereof.
  • the oxidizer mixture preferably contains a mixture of Fe 2 O 3 and CuO, in addition to the other components of the oxidizer mixture.
  • the Fe 2 O 3 is preferably present in a proportion of at least 4% by weight, particularly preferably in a proportion of at least 9%, based on the overall composition.
  • the simultaneous use of Fe 2 O 3 and CuO enables a further reduction in the proportion of toxic gases in the combustion products.
  • the composition may also include conventional processing aids a proportion of up to 5% by weight, based on the total composition, included, the processing aids preferably from the consisting of the flow aids, pressing aids and / or lubricants Group are selected.
  • a preferred composition according to the invention consists of 30 to 60% by weight guanidine nitrate, 0 to 3.15% by weight cyanuric acid, 15 to 30% by weight CuO, 15 to 30% by weight basic copper nitrate, 1 to 5% by weight. -% ammonium perchlorate and 1 to 5 wt .-% alkali and / or alkaline earth metal nitrate, each based on the total composition.
  • Part of the CuO can preferably be replaced by Fe 2 O 3 .
  • compositions according to the invention stand out the previously known mixtures due to improved combustion behavior, and in particular through an extremely low particle emission in combination with a high burning rate. they are therefore particularly suitable for use in driver airbag systems.
  • the improved burning behavior of the compositions according to the invention is achieved through the use of at least one organic compound favored as a fuel from the group of guanidine compounds.
  • the use of guanidine nitrate is particularly preferred because of its favorable oxygen balance of - 26.2%. Compared to others organic compounds or their mixtures with guanidine nitrate less oxidizer is thus required to balance the mixture. This measure therefore already results in lower particle emissions reached.
  • the proportion of basic copper nitrate in the oxidizer mixture should in any case be at most 50% by weight, based on the oxidizer mixture.
  • the mixture In addition to a high combustion rate and extremely low carbon monoxide and NO x emissions, the mixture is easy to ignite and has excellent retention properties with regard to solid combustion residues. A higher proportion of basic copper nitrate is undesirable since this would in particular increase the NO x proportions in the gas inadmissibly.
  • a particularly preferred gas generating according to the invention Mixture consists of 40 to 55% by weight guanidine nitrate, 0 to 2.9% by weight Cyanuric acid, each 15 to 30 wt .-% copper oxide and basic copper nitrate as well as 1 to 5% by weight of ammonium perchlorate and alkali or Alkaline earth metal. This composition ensures due the low proportion of cyanuric acid is one for driver airbag systems sufficient burning rate.
  • a mixture of 47.1 parts guanidine nitrate and 52.9 parts basic copper nitrate was prepared according to the procedure described in Example 1 of US-A-5,608,183. The mixture showed poor ignitability and only a slow burning rate. The NO x portion of the gas generated measured in the test jug was 1300 ppm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Air Bags (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Die vorliegende Erfindung betrifft eine azidfreie, gaserzeugende Zusammensetzung, insbesondere zur Verwendung in Sicherheitseinrichtungen für Kraftfahrzeuge.The present invention relates to an acid-free, gas-generating Composition, in particular for use in security devices for motor vehicles.

Gaserzeugende Zusammensetzungen, die in Sicherheitseinrichtungen für Kraftfahrzeuge verwendet werden, bestehen meist aus einem Brennstoff auf der Grundlage von Natriumazid sowie einem Oxidationsmittel. Aufgrund der Toxizität von Natriumazid wurde aber schon frühzeitig damit begonnen, nach Alternativen zu den azid-haltigen gaserzeugenden Gemischen zu suchen.Gas generating compositions used in safety devices used for motor vehicles mostly consist of a fuel based on sodium azide and an oxidizing agent. However, due to the toxicity of sodium azide, it was premature started looking for alternatives to the azide-containing gas generators To look for mixtures.

Die US-A-5 608 183 beschreibt ein gaserzeugendes Gemisch, welches zwischen etwa 30 und 85 Gew.-% eines Brennstoffs und zwischen etwa 15 und etwa 70 Gew.-% eines Oxidationsmittels enthält. Wenigstens 60 Gew.-% des Brennstoffs bestehen aus dem Nitrat eines sauren Polyamins oder eines C2-C3-Alkyldiamins, wie beispielsweise den Nitraten von Harnstoff, Guanidin, Aminoguanidin, Diaminoguanidin, Semicarbazid, Äthylendiamin, 1,3-Propandiamin oder 1,2-Propandiamin, oder deren Mischungen. Das Oxidationsmittel umfaßt wenigstens 60 Gew.-% basisches Kupfernitrat und/oder Kobalttriamintrinitrat. Die Verarbeitung des Gemischs erfolgt in einem Naßprozess. US-A-5 608 183 describes a gas generating mixture containing between about 30 and 85 percent by weight of a fuel and between about 15 and about 70 percent by weight of an oxidizing agent. At least 60% by weight of the fuel consists of the nitrate of an acidic polyamine or a C 2 -C 3 -alkyldiamine, such as, for example, the nitrates of urea, guanidine, aminoguanidine, diaminoguanidine, semicarbazide, ethylenediamine, 1,3-propanediamine or 1, 2-propanediamine, or mixtures thereof. The oxidizing agent comprises at least 60% by weight of basic copper nitrate and / or cobalt triamine trinitrate. The mixture is processed in a wet process.

Das aus der US-A-5 608 183 bekannte gaserzeugende Gemisch weist allerdings eine unzureichende Anzündwilligkeit sowie eine zu niedrige Abbrandgeschwindigkeit auf. Aufgrund des hohen Anteils an basischem Kupfernitrat ist zudem ein erhöhter Anteil an toxischen Gasen im freigesetzten Gasgemisch feststellbar. Die Verarbeitung des Gemischs in einem Naßprozess erfordert zusätzliche Trocknungsstufen und ist daher kostenintensiv.The gas generating mixture known from US-A-5 608 183 has however, an insufficient willingness to ignite and a too low Burn-up speed. Due to the high proportion of basic Copper nitrate is also an increased proportion of toxic gases in the released Detectable gas mixture. Processing the mixture in A wet process requires additional drying stages and is therefore expensive.

Das. deutsche Gebrauchsmuster Nr. 298 06 504 stellt eine gaserzeugende Zusammensetzung bereit, die ein aus mindestens zwei Komponenten bestehendes Brennstoffgemisch in einem Anteil von 20 bis 60 Gew.-% und ein aus mindestens drei Komponenten bestehendes Oxidatorgemisch in einem Anteil von 40 bis 80 Gew.-%, jeweils bezogen auf die Gesamtzusammensetzung, umfaßt. Das Brennstoffgemisch der bekannten Zusammensetzung ist aus 5 bis 95 Gew.-% einer Guanidinverbindung, 5 bis 95 Gew.-% einer heterozyklischen organischen Säure, beispielsweise Cyanursäure, sowie 0 bis 20 Gew.-% weiteren Brennstoffen zusammengesetzt. Das Oxidatorgemisch der bekannten Zusammensetzung besteht aus einem oder mehreren Übergangsmetalloxiden in einem Anteil von 20 bis 70 Gew.-% sowie 10 bis 50 Gew.-% basischem Kupfernitrat und 2 bis 30 Gew.-% Metallchlorat, Metallperchlorat, Ammoniumperchlorat, Alkalinitrat, Erdalkalinitrat oder deren Mischungen.The. German utility model No. 298 06 504 represents a gas generating Composition ready, the one of at least two components existing fuel mixture in a proportion of 20 to 60 wt .-% and an oxidizer mixture consisting of at least three components in a proportion of 40 to 80% by weight, based in each case on the total composition, includes. The fuel mixture of the known composition is from 5 to 95% by weight of a guanidine compound, 5 to 95 % By weight of a heterocyclic organic acid, for example Cyanuric acid, as well as 0 to 20% by weight of other fuels. The oxidizer mixture of the known composition consists of one or more transition metal oxides in a proportion of 20 to 70% by weight and 10 to 50% by weight of basic copper nitrate and 2 to 30 % By weight metal chlorate, metal perchlorate, ammonium perchlorate, alkali nitrate, Alkaline earth nitrate or mixtures thereof.

Die Verwendung eines zusätzlichen Brennstoffs, wie beispielsweise Cyanursäure, in einem Anteil von mehr als 5% hat jedoch eine deutlich verringerte Abbrandgeschwindigkeit der Zusammensetzung zur Folge. Die Zusammensetzung ist daher für den Einsatz in Gasgeneratoren für die Fahrerseite ungeeignet, in denen wegen der kürzeren Distanz zwischen dem Fahrzeuginsassen und den Fahrzeugeinbauten hohe Abbrandgeschwindigkeiten bevorzugt werden. Da die zusätzlich verwendeten Brennstoffe eine niedrigere Sauerstoffbilanz als Guanidinnitrat aufweisen, muß außerdem ein höherer Anteil an Oxidator zur Ausbilanzierung des Gemisches und zum Erzielen einer optimal reduzierten Schadgasemission verwendet werden. Der höhere Oxidatoranteil führt aber zu einem erhöhten Feststoffanteil im Gasgemisch und damit zu einem erhöhten Partikelausstoß. The use of an additional fuel, such as However, cyanuric acid, in a proportion of more than 5%, has a clear reduced burning rate of the composition. The Composition is therefore for use in gas generators for the Driver's side unsuitable because of the shorter distance between high burn-up speeds for the vehicle occupant and the vehicle internals to be favoured. Because the additional fuels used must have a lower oxygen balance than guanidine nitrate also a higher proportion of oxidizer to balance the mixture and to achieve an optimally reduced harmful gas emission be used. The higher proportion of oxidizer leads to a increased solids content in the gas mixture and thus to an increased Particulate emissions.

Es besteht daher weiterhin ein Bedarf an verbesserten azidfreien, gaserzeugenden Zusammensetzungen zur Verwendung in Sicherheitseinrichtungen für Kraftfahrzeuge, mit denen eine hohe Abbrandgeschwindigkeit bei gleichzeitig niedrigem Partikelausstoß erzielt werden kann.There is therefore still a need for improved azide-free, gas generating compositions for use in security devices for motor vehicles with a high burning rate can be achieved with low particle emissions at the same time.

Die vorliegende Erfindung stellt eine derartige Zusammensetzung bereit, die einen aus einer oder mehreren Komponenten bestehenden Brennstoff in einem Anteil von 20 bis 60 Gew.-% und ein aus mindestens drei Komponenten bestehendes Oxidatorgemisch in einem Anteil von 40 bis 80 Gew.-%, jeweils bezogen auf die Gesamtzusammensetzung, umfaßt. Die Zusammensetzung ist dadurch gekennzeichnet, daß der Brennstoff aus einer Guanidinverbindung in einem Anteil von mindestens 95 Gew.-% und einer weiteren Brennstoffkomponente in einem Anteil von 0 bis weniger als 5 Gew.-%, jeweils bezogen auf den Brennstoff, besteht. Ferner besteht das Oxidatorgemisch aus einem oder mehreren Übergangsmetalloxiden in einem Anteil von 20 bis 80 Gew.-%, basischem Kupfernitrat in einem Anteil von 0 bis 50 Gew.-%, Metallchlorat, Metallperchlorat, Ammoniumperchlorat oder deren Mischungen in einem Anteil von 1 bis 15 Gew.-% und Alkalinitrat, Erdalkalinitrat oder deren Mischungen in einem Anteil von 1 bis 15 Gew.-%, jeweils bezogen auf das Oxidatorgemisch.The present invention provides such a composition ready, the one consisting of one or more components Fuel in a proportion of 20 to 60 wt .-% and one of at least three components consisting of an oxidizer mixture in a proportion of 40 up to 80 wt .-%, each based on the total composition. The composition is characterized in that the fuel a guanidine compound in a proportion of at least 95% by weight and another fuel component in a proportion of 0 to less than 5 wt .-%, each based on the fuel. Further the oxidizer mixture consists of one or more transition metal oxides in a proportion of 20 to 80 wt .-%, basic copper nitrate in a proportion of 0 to 50% by weight, metal chlorate, metal perchlorate, Ammonium perchlorate or mixtures thereof in a proportion of 1 to 15 % By weight and alkali nitrate, alkaline earth nitrate or mixtures thereof a proportion of 1 to 15 wt .-%, each based on the oxidizer mixture.

Als Guanidinverbindung werden bevorzugt Guanidincarbonat, Guanidinnitrat, Guanidinperchlorat, Aminoguanidinnitrat, Diaminoguanidinnitrat, Triaminoguanidinnitrat, Nitroguanidin oder deren Mischungen verwendet.Preferred guanidine compounds are guanidine carbonate, guanidine nitrate, Guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, Triaminoguanidine nitrate, nitroguanidine or mixtures thereof used.

Die weitere Brennstoffkomponente ist bevorzugt eine organische Verbindung, die eine Sauerstoffbilanz von mehr als -90 % aufweist. Besonders bevorzugt werden als weitere Brennstoffkomponente Cyanursäure, Harnstoff, Oxamid, Urazol, Alloxan, Alloxantin und Parabansäure oder deren Mischungen eingesetzt.The further fuel component is preferably an organic one Compound that has an oxygen balance of more than -90%. Cyanuric acid is particularly preferred as a further fuel component, Urea, oxamide, urazole, alloxan, alloxantin and parabanic acid or mixtures thereof.

Unter der "Sauerstoffbilanz" ist diejenige Sauerstoffmenge in Gewichtsprozent zu verstehen, die bei vollständiger Umsetzung einer Verbindung oder eines Gemischs zu CO2, H2O, Al2O3, B2O3, etc. frei wird (O2-Überbilanzierung). Reicht der vorhandene Sauerstoff hierzu nicht aus, so wird die zum vollständigen Umsatz notwendige Fehlmenge mit negativen Vorzeichen angegeben (O2-Unterbilanzierung).The “oxygen balance” is to be understood as the amount of oxygen in percent by weight which is released when a compound or a mixture is completely converted to CO 2 , H 2 O, Al 2 O 3 , B 2 O 3 , etc. (O 2 overbalancing) , If the available oxygen is not sufficient for this, the shortfall necessary for complete conversion is given with a negative sign (O 2 under-balancing).

Das als Bestandteil des Oxidatorgemischs vorhandene Übergangsmetalloxid kann aus der aus Cr2O3, MnO2, Fe2O3, Fe3O4, CuO, Cu2O oder deren Mischungen bestehenden Gruppe ausgewählt sein.The transition metal oxide present as a component of the oxidizer mixture can be selected from the group consisting of Cr 2 O 3 , MnO 2 , Fe 2 O 3 , Fe 3 O 4 , CuO, Cu 2 O or mixtures thereof.

Das Oxidatorgemisch enthält bevorzugt eine Mischung aus Fe2O3 und CuO, neben den weiteren Komponenten des Oxidatorgemisches. Das Fe2O3 ist bevorzugt in einem Anteil von wenigstens 4 Gew.-%, besonders bevorzugt in einem Anteil von wenigstens 9%, bezogen auf die Gesamtzusammensetzung, enthalten. Durch die gleichzeitige Verwendung von Fe2O3 und CuO kann eine weitere Reduzierung des Anteils toxischer Gase in den Verbrennungsprodukten erreicht werden.The oxidizer mixture preferably contains a mixture of Fe 2 O 3 and CuO, in addition to the other components of the oxidizer mixture. The Fe 2 O 3 is preferably present in a proportion of at least 4% by weight, particularly preferably in a proportion of at least 9%, based on the overall composition. The simultaneous use of Fe 2 O 3 and CuO enables a further reduction in the proportion of toxic gases in the combustion products.

Die Zusammensetzung kann ferner übliche Verarbeitungshilfen in einem Anteil von bis zu 5 Gew.-%, bezogen auf die Gesamtzusammensetzung, enthalten, wobei die Verarbeitungshilfen bevorzugt aus der aus den Rieselhilfen, Preßhilfsmitteln und/oder Gleitmitteln bestehenden Gruppe ausgewählt sind.The composition may also include conventional processing aids a proportion of up to 5% by weight, based on the total composition, included, the processing aids preferably from the consisting of the flow aids, pressing aids and / or lubricants Group are selected.

Eine bevorzugte erfindungsgemäße Zusammensetzung besteht aus 30 bis 60 Gew.-% Guanidinnitrat, 0 bis 3,15 Gew.-% Cyanursäure, 15 bis 30 Gew.-% CuO, 15 bis 30 Gew.-% basischem Kupfernitrat, 1 bis 5 Gew.-% Ammoniumperchlorat und 1 bis 5 Gew.-% Alkali- und/oder Erdalkalimetallnitrat, jeweils bezogen auf die Gesamtzusammensetzung. Bevorzugt kann ein Teil des CuO durch Fe2O3 ersetzt sein.A preferred composition according to the invention consists of 30 to 60% by weight guanidine nitrate, 0 to 3.15% by weight cyanuric acid, 15 to 30% by weight CuO, 15 to 30% by weight basic copper nitrate, 1 to 5% by weight. -% ammonium perchlorate and 1 to 5 wt .-% alkali and / or alkaline earth metal nitrate, each based on the total composition. Part of the CuO can preferably be replaced by Fe 2 O 3 .

Die erfindungsgemäßen Zusammensetzungen zeichnen sich gegenüber den bisher bekannten Gemischen durch ein verbessertes Abbrandverhalten, und insbesondere durch einen äußerst niedrigen Partikelausstoß in Kombination mit einer hohen Abbrandgeschwindigkeit, aus. Sie sind damit besonders geeignet für die Verwendung in Fahrerairbagsystemen. Das verbesserte Abbrandverhalten der erfindungsgemäßen Zusammensetzungen wird durch die Verwendung von mindestens einer organischen Verbindung aus der Gruppe der Guanidinverbindungen als Brennstoff begünstigt. Besonders bevorzugt ist der Einsatz von Guanidinnitrat wegen seiner günstigen Sauerstoffbilanz von - 26,2%. Im Vergleich mit anderen organischen Verbindungen oder deren Gemischen mit Guanidinnitrat wird somit zur Ausbilanzierung des Gemischs weniger Oxidator benötigt. Durch diese Maßnahme wird daher bereits ein geringerer Partikelausstoß erreicht.The compositions according to the invention stand out the previously known mixtures due to improved combustion behavior, and in particular through an extremely low particle emission in combination with a high burning rate. they are therefore particularly suitable for use in driver airbag systems. The improved burning behavior of the compositions according to the invention is achieved through the use of at least one organic compound favored as a fuel from the group of guanidine compounds. The use of guanidine nitrate is particularly preferred because of its favorable oxygen balance of - 26.2%. Compared to others organic compounds or their mixtures with guanidine nitrate less oxidizer is thus required to balance the mixture. This measure therefore already results in lower particle emissions reached.

Bekannt ist, daß der Zusatz von weiteren Brennstoffkomponenten, wie beispielsweise Cyanursäure, zu den Guanidinverbindungen einen günstigen Einfluß auf die Kohlenmonoxid- und NOx-Anteile im freigesetzten Heißgas ausübt. Überraschenderweise wurde jedoch gefunden, daß der Anteil an weiteren Brennstoffkomponenten unterhalb von 5 Gew.-%, bezogen auf die Gesamtmenge an Brennstoff, gehalten werden muß, um die Abbrandgeschwindigkeit ausreichend hoch zu halten und gleichzeitig den Partikelausstoß zu minimieren. Höhere Anteile an weiteren Brennstoffkomponenten haben eine unzulässige Verringerung der Abbrandgeschwindigkeit und Erhöhung der emittierten Partikelmenge zur Folge. Je nach den an die gaserzeugende Zusammensetzung gestellten Anforderungen kann auf den Zusatz der weiteren Brennstoffkomponente auch ganz verzichtet werden.It is known that the addition of further fuel components, such as cyanuric acid, to the guanidine compounds has a favorable influence on the carbon monoxide and NO x components in the hot gas released. Surprisingly, however, it was found that the proportion of further fuel components must be kept below 5% by weight, based on the total amount of fuel, in order to keep the rate of combustion sufficiently high and at the same time to minimize particle emissions. Higher proportions of other fuel components result in an impermissible reduction in the rate of combustion and an increase in the amount of particles emitted. Depending on the requirements placed on the gas-generating composition, the addition of the further fuel component can also be dispensed with entirely.

Der Anteil an basischem Kupfernitrat im Oxidatorgemisch sollte auf jeden Fall höchstens 50 Gew.-%, bezogen auf das Oxidatorgemisch, betragen. Neben einer hohen Abbrandgeschwindigkeit und äußerst niedrigen Kohlenmonoxid- und NOx-Emissionen werden so eine gute Anzündwilligkeit des Gemischs sowie eine ausgezeichnete Rückhaltefähigkeit hinsichtlich der festen Verbrennungsrückstände erreicht. Ein höherer Anteil an basischem Kupfernitrat ist unerwünscht, da hierdurch insbesondere die NOx-Anteile im Gas unzulässig ansteigen würden.The proportion of basic copper nitrate in the oxidizer mixture should in any case be at most 50% by weight, based on the oxidizer mixture. In addition to a high combustion rate and extremely low carbon monoxide and NO x emissions, the mixture is easy to ignite and has excellent retention properties with regard to solid combustion residues. A higher proportion of basic copper nitrate is undesirable since this would in particular increase the NO x proportions in the gas inadmissibly.

Ein gemäß der Erfindung besonders bevorzugtes gaserzeugendes Gemisch besteht aus 40 bis 55 Gew.-% Guanidinnitrat, 0 bis 2,9 Gew.-% Cyanursäure, jeweils 15 bis 30 Gew.-% Kupferoxid und basischem Kupfernitrat sowie jeweils 1 bis 5 Gew.-% Ammoniumperchlorat und Alkalioder Erdalkalimetallnitrat. Diese Zusammensetzung gewährleistet aufgrund des geringen Anteils an Cyanursäure eine für Fahrerairbagsysteme ausreichende Abbrandgeschwindigkeit. Das gleichzeitige Vorhandensein von Ammoniumperchlorat und Alkali- bzw. Erdalkalimetallnitrat in einem molaren Verhältnis von etwa 1:1 (Alkali) bzw. 2:1 (Erdalkali) hat sich als besonders günstig für eine weitere Reduktion des Partikelausstoßes erwiesen, da durch diese Kombination verglichen mit Mischungen der anderen Oxidatoren, zur Erzielung gleicher Oxidationsäquivalente, die geringsten Mengen an festen Verbrennungsrückständen erzeugt werden. Gleichzeitig wird das Entstehen von HCl als toxischem Verbrennungsprodukt verhindert. Der Zusatz von geringen Mengen an Ammoniumperchlorat und Metallnitrat hat zudem einen günstigen Eintluß auf die Abbrandgeschwindigkeit.A particularly preferred gas generating according to the invention Mixture consists of 40 to 55% by weight guanidine nitrate, 0 to 2.9% by weight Cyanuric acid, each 15 to 30 wt .-% copper oxide and basic copper nitrate as well as 1 to 5% by weight of ammonium perchlorate and alkali or Alkaline earth metal. This composition ensures due the low proportion of cyanuric acid is one for driver airbag systems sufficient burning rate. The simultaneous existence of ammonium perchlorate and alkali or alkaline earth metal nitrate in one molar ratio of about 1: 1 (alkali) or 2: 1 (alkaline earth) as particularly favorable for a further reduction in particle emissions proven that by this combination compared to mixtures of other oxidizers, to achieve the same oxidation equivalents, the smallest amounts of solid combustion residues are generated. At the same time, the formation of HCl as a toxic combustion product prevented. The addition of small amounts of ammonium perchlorate and metal nitrate also has a favorable impact on the Burning rate.

Die Erfindung wird nachfolgend anhand von besonders bevorzugten Ausführungsbeispielen beschrieben, welche jedoch nicht einschränkend zu verstehen sind.The invention is based on particularly preferred Described embodiments, which, however, are not restrictive are to be understood.

Ausführungsbeispiel 1Embodiment 1

473 g mikronisiertes Guanidinnitrat, 20 g gemahlene Cyanursäure, je 231 g Kupferoxid und basisches Kupfernitrat sowie 26 g Ammoniumperchlorat und 19 g Natriumnitrat wurden gemeinsam in eine Kugelmühle eingewogen, drei Stunden lang gemahlen und miteinander vermischt. Das erhaltene Gemisch wurde ohne weitere Verarbeitungsschritte direkt zu Tabletten verpreßt. Testversuche ergaben eine sehr gute Anzündwilligkeit bei einer Abbrandgeschwindigkeit von 17 mm/s. Der Feststoffanteil im freigesetzten Gasgemisch betrug 1,7%.473 g micronized guanidine nitrate, 20 g ground cyanuric acid, 231 g copper oxide and basic copper nitrate as well as 26 g ammonium perchlorate and 19 g of sodium nitrate were put together in a ball mill weighed, ground for three hours and mixed together. The The mixture obtained was added directly without further processing steps Tablets pressed. Test trials showed very good willingness to ignite at a burn rate of 17 mm / s. The solids content in the released gas mixture was 1.7%.

Ausführungsbeispiel 2Embodiment 2

493 g mikronisiertes Guanidinnitrat, je 231 g Kupferoxid und basisches Kupfernitrat sowie 26 g Ammoniumperchlorat und 19 g Natriumnitrat wurden gemeinsam in eine Kugelmühle eingewogen. Zum Ansatz wurden noch 5 g Calciumstearat zugefügt und wie im Ausführungsbeispiel 1 aufgearbeitet. Beim Beschuß der erhaltenen Tabletten ergab sich eine gute Anzündwilligkeit und eine Abbrandgeschwindigkeit von 17 mm/s, bei einem Feststoffanteil im erzeugten Gas von 1,8%. Der NOx-Gehalt des erzeugten Gases, gemessen in einer 60 l-Testkanne, betrug 550 ppm.493 g of micronized guanidine nitrate, 231 g of copper oxide and basic copper nitrate as well as 26 g of ammonium perchlorate and 19 g of sodium nitrate were weighed together in a ball mill. 5 g of calcium stearate were added to the batch and worked up as in Example 1. When the tablets obtained were bombarded, there was good ignitability and a burning rate of 17 mm / s, with a solids content in the gas produced of 1.8%. The NO x content of the gas produced, measured in a 60 l test can, was 550 ppm.

Vergleichsbeispiel 1Comparative Example 1

29,5 g mikronisiertes Guanidinnitrat, 12,8 g Cyanursäure, jeweils 25,65 g Kupferoxid und basisches Kupfernitrat sowie 6,4 g Kaliumperchlorat wurden, wie im Ausführungsbeispiel 1 beschrieben, in einer Kugelmühle vermischt und zu Tabletten verpreßt. Das Gemisch zeigte in Testversuchen eine nur mäßige Anzündwilligkeit, die Abbrandgeschwindigkeit betrug 10 mm/s. Der Feststoffanteil im Gasgemisch betrug 3,1%. Der in einer 60 l-Testkanne bestimmte NOx-Gehalt lag bei 550 ppm.29.5 g of micronized guanidine nitrate, 12.8 g of cyanuric acid, in each case 25.65 g of copper oxide and basic copper nitrate and 6.4 g of potassium perchlorate were mixed in a ball mill, as described in exemplary embodiment 1, and compressed into tablets. The mixture showed only moderate willingness to ignite in test trials, the burn-off rate was 10 mm / s. The solids content in the gas mixture was 3.1%. The NO x content determined in a 60 l test can was 550 ppm.

Vergleichsbeispiel 2Comparative Example 2

Ein Gemisch aus 47,1 Teilen Guanidinnitrat und 52,9 Teilen basischem Kupfernitrat wurde nach der in Beispiel 1 der US-A-5 608 183 beschriebenen Vorschrift hergestellt. Das Gemisch zeigte eine schlechte Anzündwilligkeit und eine nur geringe Abbrandgeschwindigkeit. Der in der Testkanne gemessene NOx-Anteil des erzeugten Gases betrug 1300 ppm.A mixture of 47.1 parts guanidine nitrate and 52.9 parts basic copper nitrate was prepared according to the procedure described in Example 1 of US-A-5,608,183. The mixture showed poor ignitability and only a slow burning rate. The NO x portion of the gas generated measured in the test jug was 1300 ppm.

Ausführungsbeispiel 3Embodiment 3

1147 g mikronisiertes Guanidinnitrat, 612 g basisches Kupfernitrat, 316 g Kupferoxid, 242 g Eisenoxid, 103 g Ammoniumperchlorat, 75 g Natriumnitrat sowie 5 g Calciumstearat wurden gemeinsam in eine Kugelmühle eingewogen und analog dem Ausführungsbeispiel 1 aufgearbeitet. Die Testversuche ergaben ebenfalls eine gute Anzündwilligkeit und eine Abbrandgeschwindigkeit von ca. 15 mm/s.1147 g micronized guanidine nitrate, 612 g basic copper nitrate, 316 g copper oxide, 242 g iron oxide, 103 g ammonium perchlorate, 75 g of sodium nitrate and 5 g of calcium stearate were combined in one Ball mill weighed and processed analogously to embodiment 1. The test trials also showed good willingness to ignite and a burning rate of approx. 15 mm / s.

Die Analyse der toxischen Komponente der Verbrennungsgase ergab, daß die Kombination von Eisenoxid (Fe2O3) und Kupferoxid (CuO) als Metalloxid-Komponente im Treibmittelgemisch einen besonders günstigen Einfluß auf die Emissionen von Kohlenmonoxid (CO) und Ammoniak (NH3) hat.The analysis of the toxic component of the combustion gases showed that the combination of iron oxide (Fe 2 O 3 ) and copper oxide (CuO) as a metal oxide component in the blowing agent mixture has a particularly favorable influence on the emissions of carbon monoxide (CO) and ammonia (NH 3 ) ,

Folgende Gasemissionen wurden beim Beschluß von Gasgeneratoren mit für die Beifahrerseite typischen Leistungen (ca. 2,3 bar in einer 146 Kanne) enthalten: CO-Konzentration [ppm] NH3-Konzentration [ppm] Gasgenerator mit 150 g Treibstoff nach Vergleichsbeispiel 1 541 266 Gasgenerator mit 136 g Treibstoff nach Ausführungsbeispiel 3 374 33 The following gas emissions were included in the decision of gas generators with typical performance for the passenger side (approx. 2.3 bar in a 146 can): CO concentration [ppm] NH 3 concentration [ppm] Gas generator with 150 g of fuel according to Comparative Example 1 541 266 Gas generator with 136 g of fuel according to embodiment 3 374 33

Durch die gleichzeitige Vewendung von Fe2O3 und CuO als Oxidatorkomponente kann somit die Emission toxischer Gase weiter reduziert werden.The simultaneous use of Fe 2 O 3 and CuO as an oxidizer component can thus further reduce the emission of toxic gases.

Claims (10)

  1. An azide-free gas-generating composition, in particular for use in safety devices for motor vehicles, comprising a fuel in a proportion of 20 to 60 % by weight and consisting of one or more components, and an oxidizer mixture in a proportion of 40 to 80 % by weight and consisting of at least three components, each in relation to the total composition, characterized in that the fuel consists of a guanidine compound in a proportion of at least 95 % by weight and a further fuel component in a proportion of 0 to less than 5 % by weight, each in relation to the fuel, and that the oxidizer mixture consists of one or more transition metal oxides in a proportion of 20 to 80 % by weight, basic copper nitrate in a proportion of 0 to 50 % by weight, metal chlorate, metal perchlorate, ammonium perchlorate or mixtures thereof in a proportion of 1 to 15 % by weight and alkali nitrate, alkaline earth nitrate or mixtures thereof in a proportion of 1 to 15 % by weight, each in relation to the oxidizer mixture.
  2. The composition according to claim 1, characterized in that the guanidine compound is selected from the group consisting of guanidine carbonate, guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, nitroguanidine or mixtures thereof.
  3. The composition according to any of claims 1 to 2, characterized in that the further fuel component is an organic compound which has an oxygen balance of more than -90%.
  4. The composition according to any of claims 1 to 3, characterized in that the further fuel component is selected from the group consisting of cyanuric acid, urea, oxamide, urazol, alloxane, alloxantine and parabanic acid or mixtures thereof.
  5. The composition according to any of claims 1 to 4, characterized in that the transition metal oxide is selected from the group consisting of Cr2O3, MnO2, Fe2O3, Fe3O4, CuO, Cu2O or mixtures thereof
  6. The composition according to any of claims 1 to 5, additionally characterized by processing aids in a proportion of up to 5 % by weight, in relation to the total composition, the processing aids being selected from the group consisting of the trickling aids, pressure aids and/or lubricants.
  7. The composition according to claim 1, consisting of 30 to 60 % by weight guanidine nitrate, 0 to 3.15 % by weight cyanuric acid, 15 to 30 % by weight CuO, 15 to 30 % by weight basic copper nitrate, 1 to 5 % by weight ammonium perchlorate and 1 to 5 % by weight alkali- and/or alkaline earth metal nitrate, each in relation to the total composition.
  8. The composition according to any of the preceding claims, characterized in that the oxidizer mixture simultaneously contains CuO and Fe2O3.
  9. The composition according to claim 8, characterized in that the Fe2O3 is present in a proportion of at least 4 % by weight, in relation to the total composition.
  10. The composition according to claim 7, characterized in that the CuO is partly replaced by Fe2O3.
EP99123906A 1998-12-02 1999-12-01 Non-azide gas generating composition Expired - Lifetime EP1006096B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE29821541U 1998-12-02
DE29821541U DE29821541U1 (en) 1998-12-02 1998-12-02 Azide-free, gas generating composition

Publications (2)

Publication Number Publication Date
EP1006096A1 EP1006096A1 (en) 2000-06-07
EP1006096B1 true EP1006096B1 (en) 2002-09-25

Family

ID=8066128

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99123906A Expired - Lifetime EP1006096B1 (en) 1998-12-02 1999-12-01 Non-azide gas generating composition

Country Status (3)

Country Link
US (1) US20050189052A1 (en)
EP (1) EP1006096B1 (en)
DE (2) DE29821541U1 (en)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE29806504U1 (en) * 1998-04-08 1998-08-06 TRW Airbag Systems GmbH & Co. KG, 84544 Aschau Azide-free, gas generating composition
US5985060A (en) * 1998-07-25 1999-11-16 Breed Automotive Technology, Inc. Gas generant compositions containing guanidines
DE29821544U1 (en) * 1998-12-02 1999-02-18 TRW Airbag Systems GmbH & Co. KG, 84544 Aschau Azide-free, gas generating composition
JP2000319085A (en) * 1999-04-30 2000-11-21 Daicel Chem Ind Ltd Gas generating agent composition
DE10064285C1 (en) * 2000-12-22 2002-10-17 Nigu Chemie Gmbh Gas generator fuel composition and its use
JP4672975B2 (en) * 2002-10-31 2011-04-20 ダイセル化学工業株式会社 Gas generant composition
US7618506B2 (en) 2002-10-31 2009-11-17 Daicel Chemical Industries, Ltd. Gas generating composition
FR2857359B1 (en) * 2003-07-10 2006-12-01 Snpe Materiaux Energetiques GAS GENERATING PYROTECHNIC COMPOSITION FOR MOTOR VEHICLE SAFETY AND BURNING AT COMBUSTION TEMPERATURES LESS THAN 2200 K
JP4767487B2 (en) * 2003-10-20 2011-09-07 ダイセル化学工業株式会社 Gas generant composition
FR2866022B1 (en) * 2004-02-10 2006-07-28 Snpe Materiaux Energetiques GAS GENERATING PYROTECHNIC COMPOSITION FOR MOTOR VEHICLE SAFETY
WO2007012348A1 (en) * 2005-07-26 2007-02-01 Dalphi Metal España, S.A. Gas generating composition for automotive use manufactured by pellet formation
FR2949778B1 (en) * 2009-09-10 2013-05-10 Snpe Materiaux Energetiques PYROTECHNIC COMPOUNDS GENERATORS OF GAS
FR2964656B1 (en) * 2010-09-15 2012-10-12 Snpe Materiaux Energetiques PYROTECHNIC COMPOUNDS GENERATORS OF GAS
JP5785768B2 (en) * 2011-03-23 2015-09-30 株式会社ダイセル Gas generant composition
JP5663369B2 (en) * 2011-03-31 2015-02-04 株式会社ダイセル Gas generant composition
FR2975097B1 (en) 2011-05-09 2015-11-20 Sme PYROTECHNIC COMPOUNDS GENERATORS OF GAS
DE102012004468A1 (en) 2012-03-08 2013-09-12 Trw Airbag Systems Gmbh Gas generating composition and its use in pedestrian protection devices
DE102012005759A1 (en) 2012-03-23 2013-09-26 Trw Airbag Systems Gmbh GAS-CREATING COMPOSITION

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4366010A (en) * 1978-09-21 1982-12-28 Sedat Georges A Smoke-producing pyrotechnic composition and its application
FR2531071B1 (en) * 1982-07-28 1984-12-21 France Etat
DE4412871C2 (en) * 1993-04-15 1997-08-14 Nof Corp Gas generator compositions
HUT76867A (en) * 1993-10-06 1997-12-29 Nigu Chemie Gmbh Gas developing agent
US5431103A (en) * 1993-12-10 1995-07-11 Morton International, Inc. Gas generant compositions
US5518054A (en) * 1993-12-10 1996-05-21 Morton International, Inc. Processing aids for gas generants
US5538567A (en) * 1994-03-18 1996-07-23 Olin Corporation Gas generating propellant
DE4423088A1 (en) 1994-07-01 1996-01-04 Temic Bayern Chem Airbag Gmbh Gas-generating, acid-free mixture of substances
DE4442037C1 (en) 1994-11-25 1995-12-21 Fraunhofer Ges Forschung Non-toxic gas-generating mixt. with low combustion temp.
DE19505568A1 (en) 1995-02-18 1996-08-22 Dynamit Nobel Ag Gas generating mixtures
US5780768A (en) * 1995-03-10 1998-07-14 Talley Defense Systems, Inc. Gas generating compositions
EP0801045A4 (en) * 1995-09-29 2000-11-02 Otsuka Kagaku Kk Gas generator for air bag
US5670740A (en) * 1995-10-06 1997-09-23 Morton International, Inc. Heterogeneous gas generant charges
US5817972A (en) 1995-11-13 1998-10-06 Trw Inc. Iron oxide as a coolant and residue former in an organic propellant
US5756929A (en) * 1996-02-14 1998-05-26 Automotive Systems Laboratory Inc. Nonazide gas generating compositions
US5661261A (en) * 1996-02-23 1997-08-26 Breed Automotive Technology, Inc. Gas generating composition
US5844164A (en) * 1996-02-23 1998-12-01 Breed Automotive Technologies, Inc. Gas generating device with specific composition
US5629494A (en) * 1996-02-29 1997-05-13 Morton International, Inc. Hydrogen-less, non-azide gas generants
US5608183A (en) * 1996-03-15 1997-03-04 Morton International, Inc. Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate
US5959242A (en) * 1996-05-14 1999-09-28 Talley Defense Systems, Inc. Autoignition composition
JPH09328387A (en) * 1996-06-03 1997-12-22 Daicel Chem Ind Ltd Gas producing agent composition
WO1998003449A1 (en) 1996-07-20 1998-01-29 Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik Pyrotechnic mixture as propellant or a gas charge with carbon monoxide-reduced vapors
DE19643468A1 (en) 1996-10-22 1998-04-23 Temic Bayern Chem Airbag Gmbh Gas-generating, azide-free solid mixture
US5962808A (en) * 1997-03-05 1999-10-05 Automotive Systems Laboratory, Inc. Gas generant complex oxidizers
US5841065A (en) * 1997-04-15 1998-11-24 Autoliv Asp, Inc. Gas generants containing zeolites
US5861571A (en) * 1997-04-18 1999-01-19 Atlantic Research Corporation Gas-generative composition consisting essentially of ammonium perchlorate plus a chlorine scavenger and an organic fuel
DE19742203A1 (en) 1997-09-24 1999-03-25 Trw Airbag Sys Gmbh Particle-free gas-generating mixture
DE29722912U1 (en) * 1997-12-29 1998-02-19 TRW Airbag Systems GmbH & Co. KG, 84544 Aschau Azide free gas generating composition
DE29806504U1 (en) * 1998-04-08 1998-08-06 TRW Airbag Systems GmbH & Co. KG, 84544 Aschau Azide-free, gas generating composition
US6096147A (en) * 1998-07-30 2000-08-01 Autoliv Asp, Inc. Ignition enhanced gas generant and method

Also Published As

Publication number Publication date
EP1006096A1 (en) 2000-06-07
DE29821541U1 (en) 1999-02-18
US20050189052A1 (en) 2005-09-01
DE59902827D1 (en) 2002-10-31

Similar Documents

Publication Publication Date Title
EP1006096B1 (en) Non-azide gas generating composition
EP0949225B1 (en) Non-azide gas generating composition
EP0691317B1 (en) Non-azide gas generant formulations
EP0905108B1 (en) Particle-free gas generating mixture
EP0519485A1 (en) Propellant for gas generators
DE112005000805T5 (en) Gas generation system
DE19548917A1 (en) Ceramic fibre-contg. gas generating compsn.
EP1345872B1 (en) Gas generator fuel composition
DE102005042812B4 (en) Gas forming composition
DE4411654C2 (en) Gas generating mixture
EP1069096B1 (en) Non-azide gas generating composition
DE19840993B4 (en) Use of a gas-generating mixture as ignition mixture in a gas generator
EP1162183B1 (en) Ignition mixture for use in gas generators
EP1275629B1 (en) Nitrocellulose-free gas-generating composition
WO1998017607A1 (en) Azide-free, gas-generating solid mixture
DE4218531C1 (en)
DE3935869C1 (en)
DE102020104119A1 (en) GAS GENERATING COMPOSITION AND ITS USE IN A GAS GENERATOR
DE10230402B4 (en) Process for the preparation of a gas generating composition
DE60106076T2 (en) GAS PRODUCTION WITH METAL COMPLEXES OF GUANYLHARN NITRATE
EP1051373B1 (en) Acid-free, gas-generating composition
EP1064242A1 (en) Propellants for gas generator
DE60012933T2 (en) COMPOSITE, GAS-PRODUCING MATERIAL FOR GAS-OPERATED VEHICLE SAFETY DEVICES
DE19617538C1 (en) Gas-generating, acid-free mixture of substances
DE102012005759A1 (en) GAS-CREATING COMPOSITION

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: 20001205

AKX Designation fees paid

Free format text: AT BE CH CY LI

RBV Designated contracting states (corrected)

Designated state(s): DE FR NL SE

REG Reference to a national code

Ref country code: DE

Ref legal event code: 8566

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

17Q First examination report despatched

Effective date: 20020322

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

REF Corresponds to:

Ref document number: 59902827

Country of ref document: DE

Date of ref document: 20021031

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: 20030626

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20041111

Year of fee payment: 6

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 NON-PAYMENT OF DUE FEES

Effective date: 20060701

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20060701

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20061204

Year of fee payment: 8

EUG Se: european patent has lapsed
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: 20071202

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 18

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20181226

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20181231

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59902827

Country of ref document: DE