EP1006096B1 - Composition génératrice de gaz exempt d'azoture - Google Patents

Composition génératrice de gaz exempt d'azoture Download PDF

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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
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German (de)
English (en)
Other versions
EP1006096A1 (fr
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/fr
Application granted granted Critical
Publication of EP1006096B1 publication Critical patent/EP1006096B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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)

Claims (10)

  1. Composition exempte d'azide engendrant du gaz, en particulier pour être utilisée dans des dispositifs de sécurité pour véhicules automobiles, comportant un combustible dans une proportion de 20 à 60 % en poids, constitué d'un ou de plusieurs composants et un mélange oxydant dans une proportion de 40 à 80 % en poids, constitué d'au moins trois composants, respectivement par rapport à la composition totale, caractérisée en ce que le combustible est constitué d'un composé guanidine dans une proportion d'au moins 95 % en poids et d'un autre composant de combustible dans une proportion de 0 à moins de 5 % en poids, respectivement par rapport au combustible, et en ce que le mélange oxydant est constitué d'un ou de plusieurs oxydes métalliques transitoires dans une proportion de 20 à 80 % en poids, de nitrate de cuivre basique dans une proportion de 0 à 50 % en poids, de chlorate de métal, de perchlorate de métal, de perchlorate d'ammonium ou de leurs mélanges dans une proportion de 1 à 15 % en poids, et de nitrate alcalin, de nitrate alcalinoterreux ou de leurs mélanges dans une proportion de 1 à 15 % en poids, respectivement par rapport au mélange oxydant.
  2. Composition selon la revendication 1, caractérisée en ce que le composé guanidine est choisi parmi le groupe constitué de carbonate de guanidine, de nitrate de guanidine, de perchlorate de guanidine, de nitrate d'aminoguanidine, de nitrate de diaminoguanidine, de nitrate de triaminoguanidine, de nitroguanidine ou de leurs mélanges.
  3. Composition selon l'une des revendications 1 à 2, caractérisée en ce que l'autre composant de combustible est un composé organique qui présente un bilan d'oxygène de plus de -90 %.
  4. Composition selon l'une des revendications 1 à 3, caractérisée en ce que l'autre composant de combustible est choisi parmi le groupe constitué d'acide cyanurique, d'urée, d'oxamide, d'urazol, d'alloxane, d'alloxantine et d'acide parabanique ou de leurs mélanges.
  5. Composition selon l'une des revendications 1 à 4, caractérisée en ce que l'oxyde de métal transitoire est choisi parmi le groupe constitué de Cr2O3, MnO2, Fe2O3, Fe3O4, CuO, Cu2O ou de leurs mélanges.
  6. Composition selon l'une des revendications 1 à 5, caractérisée en outre par des produits auxiliaires dans une proportion allant jusqu'à 5 % en poids par rapport à la composition totale, les produits auxiliaires étant choisis parmi le groupe constitué de produits auxiliaires de ruissellement, de produits auxiliaires de pressage et/ou de lubrifiants.
  7. Composition selon la revendication 1, constituée de 30 à 60 % en poids de nitrate de guadinine, de 0 à 3,15 % en poids d'acide cyanurique, de 15 à 30 % en poids de CuO, de 15 à 30 % en poids de nitrate de cuivre basique, de 1 à 5 % en poids de perchlorate d'ammonium et de 1 à 5 % en poids de nitrate alcalin et/ou de nitrate alcalinoterreux, respectivement par rapport à la composition totale.
  8. Composition selon l'une des revendications précédentes, caractérisée en ce que le mélange oxydant contient en même temps du CuO et du Fe2O3
  9. Composition selon la revendication 8, caractérisée en ce que le Fe2O3 est contenu dans une proportion d'au moins 4 % en poids par rapport à la composition totale.
  10. Composition selon la revendication 7, caractérisée en ce que le CuO est en partie remplacé par du Fe2O3.
EP99123906A 1998-12-02 1999-12-01 Composition génératrice de gaz exempt d'azoture Expired - Lifetime EP1006096B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE29821541U 1998-12-02
DE29821541U DE29821541U1 (de) 1998-12-02 1998-12-02 Azidfreie, gaserzeugende Zusammensetzung

Publications (2)

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

Family

ID=8066128

Family Applications (1)

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EP99123906A Expired - Lifetime EP1006096B1 (fr) 1998-12-02 1999-12-01 Composition génératrice de gaz exempt d'azoture

Country Status (3)

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

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DE29806504U1 (de) * 1998-04-08 1998-08-06 TRW Airbag Systems GmbH & Co. KG, 84544 Aschau Azidfreie, gaserzeugende Zusammensetzung
US5985060A (en) * 1998-07-25 1999-11-16 Breed Automotive Technology, Inc. Gas generant compositions containing guanidines
DE29821544U1 (de) * 1998-12-02 1999-02-18 TRW Airbag Systems GmbH & Co. KG, 84544 Aschau Azidfreie, gaserzeugende Zusammensetzung
JP2000319085A (ja) * 1999-04-30 2000-11-21 Daicel Chem Ind Ltd ガス発生剤組成物
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JP4672975B2 (ja) * 2002-10-31 2011-04-20 ダイセル化学工業株式会社 ガス発生剤組成物
FR2857359B1 (fr) * 2003-07-10 2006-12-01 Snpe Materiaux Energetiques Composition pyrotechnique generatrice de gaz destinee a la securite automobile et brulant a des temperatures de combustion inferieures a 2200 k
JP4767487B2 (ja) * 2003-10-20 2011-09-07 ダイセル化学工業株式会社 ガス発生剤組成物
FR2866022B1 (fr) * 2004-02-10 2006-07-28 Snpe Materiaux Energetiques Composition pyrotechnique generatrice de gaz destinee a la securite automobile
WO2007012348A1 (fr) * 2005-07-26 2007-02-01 Dalphi Metal España, S.A. Composition generatrice de gaz destinee a une utilisation automobile fabriquee par formation de granules
FR2949778B1 (fr) * 2009-09-10 2013-05-10 Snpe Materiaux Energetiques Composes pyrotechniques generateurs de gaz
FR2964656B1 (fr) * 2010-09-15 2012-10-12 Snpe Materiaux Energetiques Composes pyrotechniques generateurs de gaz
JP5785768B2 (ja) * 2011-03-23 2015-09-30 株式会社ダイセル ガス発生剤組成物
JP5663369B2 (ja) * 2011-03-31 2015-02-04 株式会社ダイセル ガス発生剤組成物
FR2975097B1 (fr) 2011-05-09 2015-11-20 Sme Composes pyrotechniques generateurs de gaz
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Also Published As

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

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