EP1805123A2 - Melange de matieres utilise comme melange d'allumage a initiation thermique - Google Patents

Melange de matieres utilise comme melange d'allumage a initiation thermique

Info

Publication number
EP1805123A2
EP1805123A2 EP05798076A EP05798076A EP1805123A2 EP 1805123 A2 EP1805123 A2 EP 1805123A2 EP 05798076 A EP05798076 A EP 05798076A EP 05798076 A EP05798076 A EP 05798076A EP 1805123 A2 EP1805123 A2 EP 1805123A2
Authority
EP
European Patent Office
Prior art keywords
mixture
carboxylic acid
acid
group
weight
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.)
Withdrawn
Application number
EP05798076A
Other languages
German (de)
English (en)
Inventor
Lothar Anacker
Karl Bayer
Matthias Grimm
Josef Kraft
Joachim Niederwieser
Gerrit Scheiderer
Waldemar Weuter
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.)
Petri DN GmbH Inflator Systems
Original Assignee
Petri DN GmbH Inflator Systems
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 Petri DN GmbH Inflator Systems filed Critical Petri DN GmbH Inflator Systems
Publication of EP1805123A2 publication Critical patent/EP1805123A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/02—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate
    • C06B31/08—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate with a metal oxygen-halogen salt, e.g. inorganic chlorate, inorganic perchlorate
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C9/00—Chemical contact igniters; Chemical lighters
    • 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 a mixture for the production of gases, in particular propellants for occupant protection devices in motor vehicles, according to the preamble of claim 1 and the use of the mixture according to claims 14 and 16.
  • Passive safety devices for motor vehicles such as airbag systems, contain in a combustion chamber of a gas generator, a gas-generating mixture in the form of tablets, pellets, moldings or granules, which generates an electric activation of a propellant gas, which in turn inflates an airbag, thereby enabling protection of the vehicle occupants becomes.
  • the gas-generating mixtures used in the gas generators of motor vehicle safety systems are characterized by a very high stability.
  • the high stability also combines a self-release, which is at high temperature.
  • the gas generators are not designed for an accelerated or vigorous reaction of the gas-generating mixtures.
  • the generator housings are additionally weakened by the high temperature effect in the material strength and can not withstand the resulting pressures when triggered above certain temperature limits. A not less endangerment of the vehicle occupants could be the result.
  • thermally initiatable igniter compositions are used to avoid this hazard, which are capable of generating the gas mixtures typically used in gas generators below the critical temperature in a temperature range function between 145-210 0 C controlled to light. These thus enable a controlled conversion of the gas-producing Mixture in the gas generator eg in the case of a vehicle fire.
  • a thermally initiated ignition mixture ensures the safe implementation of the gas-generating mixtures in the passive safety system by early controlled triggering and at the same time contributes to hazard minimization.
  • thermally initiatable igniter mixtures Various mixtures of substances are known as thermally initiatable igniter mixtures.
  • an igniting mixture comprising an oxidizing agent from the group of alkali metal and alkaline earth chlorates, such as potassium chlorate or sodium chlorate, and a fuel such as low-melting, easily decomposable organic fuels from the group of hydrocarbons such as monosaccharides, preferably glucose, Galactose, ascorbic acid.
  • an oxidizing agent from the group of alkali metal and alkaline earth chlorates, such as potassium chlorate or sodium chlorate
  • a fuel such as low-melting, easily decomposable organic fuels from the group of hydrocarbons such as monosaccharides, preferably glucose, Galactose, ascorbic acid.
  • a gas-generating mixture as ignition mixture of at least one non-hygroscopic organic compound having a melting point less than or equal to 150 0 C, such as dicarboxylic acids having at most 5 carbon atoms, urea compounds or triazole compounds as fuel, and at least one oxidizing agent from Group of alkali and / or alkaline earth metal nitrates, chlorates or perchlorates known.
  • thermal igniting mixtures which contain an oxidizing agent from the class of the oxalates, persulfates, nitrates, peroxides, explosives such as nitroguanidine or 5-aminotetrazole nitrate and optionally as reducing agent a metal powder.
  • explosives such as nitroguanidine or 5-aminotetrazole nitrate and optionally as reducing agent a metal powder.
  • the use of explosives in igniting mixtures is, however, in view of the necessary safety measures for their use in passenger vehicles of great disadvantage. Accordingly, the thermal igniting mixtures known from the prior art generally have components which have a high formation rate of toxicologically relevant gases and are classified as explosives, which is not advantageous for the general safety of vehicle occupants.
  • the invention is therefore based on the problem to provide a thermally-initiatable substance mixture for use in gas generators of motor vehicle safety systems, which has a high thermal and chemical stability, is free of compounds classified as explosives, easy to process and ecologically compatible.
  • a) contains at least one inorganic oxidizing agent from the group of chlorates and at least one second inorganic oxidizing agent from the group of nitrates, and additionally b) contains at least one fuel selected from the class of dicarboxylic acids, tricarboxylic acids, amino acids,
  • Carboxylic acid amides, the carboxylic acid hydrazides, the carboxylic acid diamides, the carboxylic acid dihydrazides and / or derivatives thereof is selected.
  • the mixture of substances according to the invention is based on a pyrotechnic mixture whose components are not classified as explosives and are therefore ecologically compatible. This results in higher safety characteristics and thus a simpler manufacturing process, which translates into lower production costs.
  • the mixture according to the invention offers the possibility of targeted adjustment of the thermal initiation point through the selection or modification the fuel component or component quantities used in the mixture.
  • the pyrotechnic mixture also makes it possible to adjust different oxygen balances by the targeted selection of the oxidizing agents and their weight ratios in the formulation. As a result, it is additionally possible to achieve a further minimization of the harmful gas components such as carbon monoxide or nitrogen oxides in the passive safety systems.
  • the substance mixture advantageously comprises 30 to 85% by weight, preferably 40 to 65% by weight, of at least one inorganic oxidizing agent from the group of the chlorates and at least one inorganic oxidizing agent from the group of the nitrates and 10 to 55% by weight, preferably 20 to 40% by weight, a fuel selected from the class of dicarboxylic acids, tricarboxylic acids, amino acids, carboxylic acid amides, carboxylic acid hydrazides, carboxylic acid diamides, carboxylic dihydrazides and / or derivatives thereof.
  • the inorganic oxidizing agents used are preferably compounds from the group of alkali metal and / or alkaline earth metal chlorates and alkali metal and / or alkaline earth metal nitrates, in particular potassium chlorate KCIO 3 and potassium nitrate KNO 3 .
  • Preferably used fuels are glycine, ⁇ -alanine, L-glutamine, L-glutamic acid, oxalic acid, oxalic acid diamide, oxalic acid dihydrazide, malonic acid, malonamide, malonyl dihydrazide, succinic acid, succinic acid, glutaric acid, adipic acid, adipamide, tartaric acid, barbituric acid, citric acid and azodicarboxylic acid diamide.
  • the preferred fuels have in the presence of KCIO 3 and KNO 3 a sufficiently low ignition temperature between 145 0 C and 21O 0 C, so that the mixture can also be used in gas generators made of materials with lower strength, such as aluminum.
  • the substance mixture contains up to 8% by weight of a metal oxide or transition metal nitrate as catalysts.
  • the metal oxides belong in particular to the group of cobalt oxides, copper oxides, iron oxides and / or silver oxide.
  • copper oxide is used.
  • transition metal nitrates copper nitrate and silver nitrate are preferably used.
  • the mixture according to the invention is also up to 5% by weight with conventional processing aids such as flow aids, lubricants and / or compression auxiliaries, in particular Aerosil, alumina, boron nitride and / or graphite added.
  • processing aids such as flow aids, lubricants and / or compression auxiliaries, in particular Aerosil, alumina, boron nitride and / or graphite added.
  • the substance mixture up to 5% by weight of one or more additives, in particular metal powder, boron and silicon, admixed.
  • the functional temperatures of the gas-generating substance mixture are adjustable in certain areas. This is preferably carried out in a temperature range of 145 ° C to 210 ° C.
  • the triggering temperature is preferably between 155 ° C to 195 ° C.
  • the mixture according to the invention has a high thermal and long-term stability.
  • the mixture according to the invention is for easier use in the form of pellets, tablets and / or as granules with a particle size between 0.2 to 5 mm, which are prepared by known methods.
  • the production processes are based on shaping the mixture powders by pressing into tablets, kneading, extruding, or extruding into shaped articles, and granulating by breaking and sieving of shaped articles and tablets or granulation by means of tumbling or extrusion.
  • the mixtures to be processed may be dry, moistened or solvent-containing.
  • the addition of a binder is also possible.
  • the mixture of substances can be used in various ways.
  • the solid mixture can optionally be housed in a separate location in the gas generator or in the ignition chain itself.
  • the substance mixture can also be used in other areas in pressure and safety elements.
  • the applications intend to use them alone or in conjunction with other gas generants or booster charges in various gas generators, pressure elements, ignition elements, micro gas generators, fire trigger mechanisms and thermal protection devices.
  • Figure 1 is a table in which the ratio of mass loss and load duration at 110 0 C during a stability test (so-called Holland test) is shown;
  • FIG. 2 shows a diagram with the ratio of SDTA (Single Differential Thermal Analysis) signal position and load duration after loading at 110 0 C depending on the type and amount of the mixture used.
  • SDTA Single Differential Thermal Analysis
  • the determined deflagration points of the mixture are at 173 ° C without thermal stress, at 175 ° C after 100 h storage at 11O 0 C according to Hollandtest, at 171 0 C after 330 h at 11O 0 C and 17O 0 C after 600 h at 11O 0 C.
  • the use of the TIA mixture leads, as can be seen from Table 1, to significantly lower formation rates of carbon monoxide and nitrogen monoxide in the reaction reaction. The emission of harmful gas is thus reduced in comparison to the previously known igniter mixtures.
  • the unit for indicating the friction sensitivity is Newton, with a higher value meaning less friction sensitivity.
  • the mixtures 1 to 3 and the mixtures 4 and 5 are examples of the decrease in the friction sensitivity of the pyrotechnic mixture according to the invention caused by a reduction in the Kaliumchloratanteils and at the same time corresponding increase in the nitrate content.
  • a low friction sensitivity allows better processing and higher long-term stability of the processed into tablets or granules mixtures due to a higher strength of the material to be pressed.
  • Table 3 shows possible influences on the initiation point by using catalysts in mixtures based on the deflagration point and the SDTA signal layer. It becomes clear that both the amount of catalyst used and the type of catalyst influence the initiation point or deflagration point. Thus, with 3.23 wt% copper (II) oxide, blend 4 has the lowest deflagration point of 174 ° C, whereas using the same amount of cobalt oxide increases the deflagration point to 194 ° C.
  • Table 4 shows the influence of the fuel components on the properties of the thermal ignition mixture.
  • the triggering temperature and ignition strength can be set by the targeted selection of fuels and their mixing ratio.
  • the triggering temperature determined by deflagration point and SDTA signal position is lowest for mixture No. 4 with adipic acid and oxalic dihydrazide.
  • the addition or substitution of other fuel components can affect the functional temperature. This is shown by Examples 1 to 6, where an increase in the triggering temperature by the replacement of adipic acid by barbituric acid or adipamide from about 160 0 C to about 17O 0 C and 180 ° C causes.
  • An analogous effect can be achieved by the substitution of potassium nitrate by strontium nitrate, as can be seen from Examples 7 and 8.
  • a similar trend can be observed in the ignition strength, as determined by the SDTA signal size, where the signal magnitude is a measure of the energy released during the ignition process 50
  • the ignition intensity required in each case can be set in order to ensure safe burning of the gas-generating mixture to be ignited.
  • FIG. 1 shows the result of a Holland test of a substance mixture according to exemplary embodiment 1 (identified as TIA-1) at a temperature of 110 ° C. over a period of time from 0 to 600 h.
  • column A denotes the mass loss of TIA-1 in% by weight with a loading mass of 2 g granules
  • column B the mass loss of TIA-1 in% by weight with a loading mass of 4 g granules
  • column C the mass loss of TIA-1 in % By weight with a loading mass of 4 g tablets.
  • the weight loss of the mixture according to the invention after 100 hours was between 0.108% by weight and 0.132% by weight and after 600 hours between 0.454% by weight and 0.487% by weight.
  • the composition according to the invention has a higher long-term stability compared to conventionally used mixtures.
  • the occurring fluctuations in the mass losses are due in particular to the mass of the substance mixture used. As the loading mass increases, the mass loss increases. Thus, the mass loss at a loading mass of 4 g granules after 600 h 4.4% above that at a loading mass of 2 g of granules. On the other hand, the processing form of the mixture as granules or tablet has no particular effects on the mass loss.
  • FIG. 2 shows the SDTA - Signal position of a igniter according to Embodiment 1 (identified as TIA-1) after stress at 110 0 C according to Holland test for a loading mass of 2 g of granules, 4 g of granules and 4 g tablets.
  • the diagram also illustrates here that the properties of the igniter mixtures do not change significantly even after loading and are therefore not subject to any aging process like conventional igniter mixtures.
  • the ignition temperatures do not increase significantly even after a load time of 600 h.
  • the igniting temperatures of the mixtures in the unloaded state at 171, 5 0 C and after a load at 110 0 C for 600 h between 172.3 for a loading mass of 4 g tablets, 174 ° C for a loading mass of 4 g granules and 174 , 5 ° C for a load of 2 g of granules.
  • a dependency on the Processing form can not be determined and the influence of the mass of the mixtures used is negligible.
  • the invention is not limited in its execution to the above-mentioned preferred embodiments. Rather, a number of variants are conceivable that make use of the mixture according to the invention and its use even in fundamentally different versions.

Abstract

L'invention concerne un mélange de matières permettant de produire des gaz, notamment des gaz propulseurs pour des dispositifs de protection de passagers de véhicules automobiles. Le mélange de matières contient un mélange d'allumage à initiation thermique contenant au moins un agent oxydant inorganique du groupe des chlorates et au moins un deuxième agent oxydant inorganique du groupe des nitrates. L'invention est caractérisée en ce que le mélange d'allumage contient au moins un combustible qui est sélectionné dans la classe des acides dicarboxyliques, acides tricarboxyliques, acides aminés, amides d'acide carboxylique, hydrazides d'acide carboxylique, diamides d'acide carboxylique, dihydrazides d'acide carboxyliques et/ou leur dérivés. L'invention concerne également l'utilisation du mélange de matières comme mélange d'allumage à initiation thermique dans un générateur de gaz pour la production de gaz propulseurs pour des dispositifs de protection de passagers d'un véhicule automobile.
EP05798076A 2004-10-08 2005-09-29 Melange de matieres utilise comme melange d'allumage a initiation thermique Withdrawn EP1805123A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102004049432 2004-10-08
DE102004062168A DE102004062168A1 (de) 2004-10-08 2004-12-17 Stoffgemisch als thermisch initiierbare Anzündmischung
PCT/DE2005/001750 WO2006039892A2 (fr) 2004-10-08 2005-09-29 Melange de matieres utilise comme melange d'allumage a initiation thermique

Publications (1)

Publication Number Publication Date
EP1805123A2 true EP1805123A2 (fr) 2007-07-11

Family

ID=36088952

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05798076A Withdrawn EP1805123A2 (fr) 2004-10-08 2005-09-29 Melange de matieres utilise comme melange d'allumage a initiation thermique

Country Status (5)

Country Link
US (1) US20070246923A1 (fr)
EP (1) EP1805123A2 (fr)
JP (1) JP2008515754A (fr)
DE (1) DE102004062168A1 (fr)
WO (1) WO2006039892A2 (fr)

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
US8097103B2 (en) * 2009-06-18 2012-01-17 Autoliv Asp, Inc. Copper complexes with oxalyldihydrazide moieties
FR2950624B1 (fr) * 2009-09-25 2013-05-10 Snpe Materiaux Energetiques Compose pyrotechnique generateur de gaz
DE102010049765A1 (de) * 2010-10-29 2012-05-03 Trw Airbag Systems Gmbh Verfahren zur Herstellung von Festtreibstofftabletten, Gasgenerator und Modul mit Gasgenerator

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GB1601392A (en) * 1978-04-12 1981-10-28 Pyrodex Corp Gas generating compositions
US5542688A (en) * 1992-10-27 1996-08-06 Atlantic Research Corporation Two-part igniter for gas generating compositions
JPH0812480A (ja) * 1994-06-29 1996-01-16 Otsuka Chem Co Ltd エアバッグ用ガス発生剤
DE19617538C1 (de) * 1996-05-02 1997-10-30 Temic Bayern Chem Airbag Gmbh Gaserzeugendes, azidfreies Stoffgemisch
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DE19805976C1 (de) * 1998-02-13 1999-04-29 Nigu Chemie Gmbh Frühzündpulver für thermische Sicherungen für Airbag-Gasgeneratoren
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DE19840993B4 (de) * 1998-09-08 2006-03-09 Trw Airbag Systems Gmbh & Co. Kg Verwendung eines gaserzeugenden Gemisches als Anzündmischung in einem Gasgenerator
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Title
See references of WO2006039892A2 *

Also Published As

Publication number Publication date
US20070246923A1 (en) 2007-10-25
JP2008515754A (ja) 2008-05-15
DE102004062168A1 (de) 2006-04-13
WO2006039892A2 (fr) 2006-04-20
WO2006039892A3 (fr) 2006-08-31

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