EP1275629A2 - Nitrocellulose-free gas-generating composition - Google Patents

Nitrocellulose-free gas-generating composition Download PDF

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Publication number
EP1275629A2
EP1275629A2 EP02014052A EP02014052A EP1275629A2 EP 1275629 A2 EP1275629 A2 EP 1275629A2 EP 02014052 A EP02014052 A EP 02014052A EP 02014052 A EP02014052 A EP 02014052A EP 1275629 A2 EP1275629 A2 EP 1275629A2
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Prior art keywords
composition according
weight
composition
moderator
gas
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German (de)
French (fr)
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EP1275629B1 (en
EP1275629A3 (en
Inventor
Siegfried Dr. Zeuner
Roland Dr. Schropp
Achim Dr. Hofmann
Karl-Heinz Rödig
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ZF Airbag Germany GmbH
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TRW Airbag Systems GmbH
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • 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 nitrocellulose-free gas-generating A composition for use in vehicle occupant restraint systems essentially from a nitrogenous organic fuel in one Proportion of 55 to 70 wt .-%, an inorganic oxidizer in a proportion of 30 to 45 wt .-% and, optionally, up to 10 wt .-% of a Abbrandmoderators and up to 5 wt .-% of conventional auxiliaries and additives consists.
  • nitrocellulose fuels are their poor aging resistance.
  • these fuels put down because of their extremely negative Oxygen balance during combustion large amounts of incompletely oxidized Reaction products, in particular carbon monoxide, free.
  • US 5,538,567 A discloses a gas generating composition about 55 to 75 weight percent guanidine nitrate, about 25 to 45 weight percent of an oxidizer, in particular potassium perchlorate, about 0.5 to 5 wt .-% of a flow improver such as graphite or carbon black and up to 5% by weight of a binder such as calcium resinate.
  • the average particle size of the guanidine nitrate is between about 75 and 350 ⁇ m, and the average particle size of the oxidizer is between about 50 and 200 microns.
  • US-A-5 854 442 discloses a gas generating composition about 30 to 45 wt% potassium perchlorate, between about 55 and 70 wt% Guanidine nitrate and 1 to 3 wt .-% cellulose acetate butyrate as a binder.
  • the Particle size of the oxidizer should be between 15 and 20 microns.
  • compositions described above are suitable for their use chemical and physical properties only for use in driver or Passenger inflators.
  • the invention provides the opposite one nitrocellulose-free gas generating composition with higher Burning rate and improved ignition, which therefore also in a belt tensioner gas generator can be used, in relation to the Driver and passenger gas generators shorter reaction and operating times requires.
  • a nitrocellulose-free gas-generating composition consisting essentially of a nitrogen-containing organic Fuel in a proportion of 55 to 70 wt .-%, an inorganic oxidizer in a proportion of 30 to 45 wt .-%, up to 10 wt .-% of one or more Abbrandmoderatoren and up to 5 wt .-% of conventional auxiliaries and additives each based on the total weight of the composition, wherein the Pressure exponent of the composition is less than 0.35 and the Abbrandgeschwindingkeit at 200 bar at least 40 millimeters per second (mm / s) is.
  • Such a composition is especially for use in a Belt tensioner gas generator suitable.
  • the oxygen balance of the composition is preferably between -5 and +5%.
  • the oxygen balance is understood to mean the percentage by weight of oxygen which is released when the compound or mixture is completely converted to CO 2 , H 2 O, Al 2 O 3 , B 2 O 3 , etc. (oxygen overbalancing). If the available oxygen is insufficient for this purpose, the shortfall required for the complete conversion is indicated with a negative sign (oxygen sub-balancing). Due to the advantageous oxygen balance of the gas-generating composition according to the invention, the quantity of noxious gas produced during combustion, in particular the proportion of carbon monoxide, is low.
  • the organic fuel is preferably a guanidine compound, particularly preferably guanidine nitrate, in admixture with at least one other Nitrogen-containing compound consisting of nitroguanidine, nitrotriazolone (NTO), Hexogen (RDX), octogen (HMX), ethylenediamine dinitrate (EDDN), Triaminoguanidine nitrate (TAGN), azobisformamidine dinitrate and dinitroammelin existing group.
  • the fuel is from 75 to 90 wt .-% Guanidine nitrate and 10 to 25 wt .-% of the further compound, respectively on the total weight of the fuel, composed.
  • the further compound nitroguanidine is especially preferred.
  • the other nitrogenous Connection increases the burning rate in the entire pressure range.
  • addition of more than 25% of the further compound causes a too strong increase in the burning temperature, so that damage to the Gas generator is to be feared.
  • the proportion of further connection are kept as low as possible.
  • the inorganic oxidizer is preferably a perchlorate, especially an alkali metal perchlorate and / or ammonium perchlorate, and more preferably potassium perchlorate.
  • oxygen-containing compounds of transition metals preferably of iron, copper, manganese, titanium, vanadium, molybdenum and chromium, including combinations thereof, can be used as burn-on moderators.
  • the burn-off moderator is preferably selected from the group consisting of CuO, Cu 2 O, CuCr 2 O 4 , Fe 2 O 3 , 3Cu (OH) 2 x Cu (NO 3 ) 2 and mixtures thereof. Very particularly preferred is the Abbrandmoderator CuO.
  • the mean particle size of the Abbrandmoderators is preferably less than 5 microns and more preferably less than 1 micron, with a preferred specific surface of at least 2 m 2 / g, more preferably at least 5 m 2 / g.
  • the addition of such fine-grained Abbrandmoderatoren improves the ignition willingness of the gas-generating compositions of the invention, so that ignition delays of at most 6 milliseconds (ms) and more preferably at most 5 ms can be achieved.
  • the mean particle size of the fuel and the oxidizer is preferably less than 15 microns and more preferably less than 10 microns. This contributes to the gas-generating composition according to the invention a sufficiently high burning rate for use in belt tensioner gas generators having.
  • compositions of the invention can Burning rates of at least 40 mm / s under operating conditions, that is usually a pressure of 200 bar, can be achieved. Especially the burning rate at 200 bar is preferably at least 45 mm / s.
  • a is a fuel-specific Constant
  • p the pressure
  • n the pressure exponent
  • the printing exponent of the compositions according to the invention is smaller as 0.35 and preferably less than or equal to 0.3. Higher pressure exponents cause at low pressures and a worse ignition.
  • the setting of the burning rate of the invention Compositions are preferably made by selecting the appropriate one Fuel composition, in particular the nature and proportion of others nitrogen-containing compound, the nature and proportion of each Abbrandmoderators and the average particle size of the fuel, the Oxidator and, optionally, the Abbrand moderator.
  • a suitable Combining these parameters can optimally match the composition Use be adapted in belt tensioner gas generators.
  • auxiliaries and additives include processing aids, such as Lubricants, pressing and pouring aids.
  • processing aids such as Lubricants, pressing and pouring aids.
  • these compounds can especially calcium stearate, silica, graphite or carbon black.
  • the processing aids are preferably used in a proportion of up to 2 wt .-%, based on the total composition used.
  • a particularly preferred composition according to the invention consists of 48 to 52 parts by weight of guanidine nitrate, 13 to 17 parts by weight of nitroguanidine, 33 to 37 parts by weight of potassium perchlorate, 2.0 to 5.0 parts by weight of copper oxide (CuO) and in each case up to 1 wt .-% calcium stearate and graphite.
  • CuO copper oxide
  • Guanidine nitrate with a mean particle size of 5 microns, nitroguanidine with an average particle size of 11 microns, potassium perchlorate with a mean particle size of 7 microns, copper oxide (CuO) with an average particle size of 0.5 microns and a specific surface area of 8 m 2 / g and calcium stearate and graphite were mixed in the parts by weight given in the following Table 1, ground together in a ball mill and pressed into tablets of 6 x 2.5 mm.
  • Example # 3 a firing delay of 11 ms was determined; Examples Nos. 4 and 5 showed an ignition delay of 6 and 5 ms, respectively.
  • the composition according to Example 5 was also subjected to an aging test subjected to over 400 hours at 107 ° C. After this test was a Weight loss of 0.07% was detected, that is, the composition showed a satisfying the requirements for vehicle occupant restraint systems Aging resistance. A comparison experiment with a standard fuel on the basis of nitrocellulose under the same conditions gave one Weight loss of 14%. This indicates complete decomposition and thus a complete malfunction of the fuel out.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Automotive Seat Belt Assembly (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

A nitrocellulose-free gas-generating composition for use in vehicle passenger safety systems (especially seat belt tensioners) has a pressure exponent below 0.35 and a combustion rate at 200 bar of ≥ 40mm/second and comprises by wt. (A) a nitrogen-containing organic fuel (55-70%); (B) an inorganic oxidizer (30-45%); (C) a combustion moderator (up to10%); and (D) conventional additives (up to 5%).

Description

Die Erfindung betrifft eine nitrozellulosefreie gaserzeugende Zusammensetzung zur Verwendung in Fahrzeuginsassenrückhaltesystemen, die im wesentlichen aus einem stickstoffhaltigen organischen Brennstoff in einem Anteil von 55 bis 70 Gew.-%, einem anorganischen Oxidator in einem Anteil von 30 bis 45 Gew.-% sowie, gegebenenfalls, bis zu 10 Gew.-% eines Abbrandmoderators und bis zu 5 Gew.-% üblichen Hilfs- und Zusatzstoffen besteht.The invention relates to a nitrocellulose-free gas-generating A composition for use in vehicle occupant restraint systems essentially from a nitrogenous organic fuel in one Proportion of 55 to 70 wt .-%, an inorganic oxidizer in a proportion of 30 to 45 wt .-% and, optionally, up to 10 wt .-% of a Abbrandmoderators and up to 5 wt .-% of conventional auxiliaries and additives consists.

Treibstoffe auf der Grundlage von Nitrozellulose zeigen eine hohe Abbrandgeschwindigkeit. Aus diesem Grund werden diese Treibstoffe überwiegend in Gasgeneratoren für Gurtstraffer verwendet. Nachteilig an Nitrozellulose-Treibstoffen ist jedoch deren schlechte Alterungsbeständigkeit. Außerdem setzen diese Treibstoffe aufgrund ihrer extrem negativen Sauerstoffbilanz beim Abbrand große Mengen an unvollständig oxidierten Reaktionsprodukten, insbesondere Kohlenmonoxid, frei.Propellants based on nitrocellulose show a high Burning rate. Because of this, these fuels become mainly used in gas generators for belt tensioners. Disadvantageous However, nitrocellulose fuels is their poor aging resistance. In addition, these fuels put down because of their extremely negative Oxygen balance during combustion large amounts of incompletely oxidized Reaction products, in particular carbon monoxide, free.

Die US-5,538,567 A offenbart eine gaserzeugende Zusammensetzung aus etwa 55 bis 75 Gew.-% Guanidinnitrat, etwa 25 bis 45 Gew.-% eines Oxidators, insbesondere Kaliumperchlorat, etwa 0,5 bis 5 Gew.-% eines Fließverbesserers wie Graphit oder Ruß und bis zu 5 Gew.-% eines Binders wie Calciumresinat. Die mittlere Teilchengröße des Guanidinnitrats beträgt zwischen etwa 75 und 350 µm, und die mittlere Teilchegröße des Oxidators liegt zwischen etwa 50 und 200 µm.US 5,538,567 A discloses a gas generating composition about 55 to 75 weight percent guanidine nitrate, about 25 to 45 weight percent of an oxidizer, in particular potassium perchlorate, about 0.5 to 5 wt .-% of a flow improver such as graphite or carbon black and up to 5% by weight of a binder such as calcium resinate. The average particle size of the guanidine nitrate is between about 75 and 350 μm, and the average particle size of the oxidizer is between about 50 and 200 microns.

Die US-A-5 854 442 beschreibt eine gaserzeugende Zusammensetzung aus etwa 30 bis 45 Gew.-% Kaliumperchlorat, zwischen etwa 55 und 70 Gew.-% Guanidinnitrat sowie 1 bis 3 Gew.-% Celluloseacetatbutyrat als Binder. Die Teilchengröße des Oxidators soll zwischen 15 und 20 µm liegen.US-A-5 854 442 discloses a gas generating composition about 30 to 45 wt% potassium perchlorate, between about 55 and 70 wt% Guanidine nitrate and 1 to 3 wt .-% cellulose acetate butyrate as a binder. The Particle size of the oxidizer should be between 15 and 20 microns.

Die oben beschriebenen Zusammensetzungen eignen sich aufgrund ihrer chemischen und physikalischen Eigenschaften nur zur Verwendung in Fahreroder Beifahrergasgeneratoren. Die Erfindung schafft dem gegenüber eine nitrozellulosefreie gaserzeugende Zusammensetzung mit höherer Abbrandgeschwindigkeit und verbesserter Anzündwilligkeit, die somit auch in einem Gurtstraffer-Gasgenerator eingesetzt werden kann, der gegenüber den Fahrer- und Beifahrergasgeneratoren kürzere Reaktions- und Funktionszeiten erfordert.The compositions described above are suitable for their use chemical and physical properties only for use in driver or Passenger inflators. The invention provides the opposite one nitrocellulose-free gas generating composition with higher Burning rate and improved ignition, which therefore also in a belt tensioner gas generator can be used, in relation to the Driver and passenger gas generators shorter reaction and operating times requires.

Hierzu wird eine nitrozellulosefreie gaserzeugende Zusammensetzung bereitgestellt, die im wesentlichen aus einem stickstoffhaltigen organischen Brennstoff in einem Anteil von 55 bis 70 Gew.-%, einem anorganischen Oxidator in einem Anteil von 30 bis 45 Gew.-%, bis zu 10 Gew.-% eines oder mehrerer Abbrandmoderatoren und bis zu 5 Gew.-% an üblichen Hilfs- und Zusatzstoffen besteht, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, wobei der Druckexponent der Zusammensetzung kleiner als 0,35 ist und die Abbrandgeschwindingkeit bei 200 bar mindestens 40 Millimeter pro Sekunde (mm/s) beträgt.For this purpose, a nitrocellulose-free gas-generating composition provided, consisting essentially of a nitrogen-containing organic Fuel in a proportion of 55 to 70 wt .-%, an inorganic oxidizer in a proportion of 30 to 45 wt .-%, up to 10 wt .-% of one or more Abbrandmoderatoren and up to 5 wt .-% of conventional auxiliaries and additives each based on the total weight of the composition, wherein the Pressure exponent of the composition is less than 0.35 and the Abbrandgeschwindingkeit at 200 bar at least 40 millimeters per second (mm / s) is.

Eine derartige Zusammensetzung ist insbesondere zur Verwendung in einem Gurtstraffer-Gasgenerator geeignet.Such a composition is especially for use in a Belt tensioner gas generator suitable.

Die Sauerstoffbilanz der Zusammensetzung beträgt vorzugsweise zwischen -5 und +5 %. Unter der Sauerstoffbilanz ist dabei diejenige Sauerstoffmenge in Gewichtsprozent zu verstehen, die bei vollständiger Umsetzung einer Verbindung oder eines Gemischs zu CO2, H2O, Al2O3, B2O3, etc. frei wird (Sauerstoffüberbilanzierung). Reicht der vorhandene Sauerstoff hierzu nicht aus, so wird die zum vollständigen Umsatz notwendige Fehlmenge mit negativem Vorzeichen angegeben (Sauerstoffunterbilanzierung). Aufgrund der vorteilhaften Sauerstoffbilanz der erfindungsgemäßen gaserzeugenden Zusammensetzung ist die beim Abbrand entstehende Schadgasmenge, insbesondere der Kohlenmonoxidanteil, gering.The oxygen balance of the composition is preferably between -5 and +5%. The oxygen balance is understood to mean the percentage by weight of oxygen which is released when the compound or mixture is completely converted to CO 2 , H 2 O, Al 2 O 3 , B 2 O 3 , etc. (oxygen overbalancing). If the available oxygen is insufficient for this purpose, the shortfall required for the complete conversion is indicated with a negative sign (oxygen sub-balancing). Due to the advantageous oxygen balance of the gas-generating composition according to the invention, the quantity of noxious gas produced during combustion, in particular the proportion of carbon monoxide, is low.

Der organische Brennstoff ist vorzugsweise eine Guanidinverbindung, besonders bevorzugt Guanidinnitrat, im Gemisch mit mindestens einer weiteren stickstoffhaltigen Verbindung aus der aus Nitroguanidin, Nitrotriazolon (NTO), Hexogen (RDX), Octogen (HMX), Ethylendiamindinitrat (EDDN), Triaminoguanidinnitrat (TAGN), Azobisformamidindinitrat und Dinitroammelin bestehenden Gruppe. Bevorzugt ist der Brennstoff aus 75 bis 90 Gew.-% Guanidinnitrat und 10 bis 25 Gew.-% der weiteren Verbindung, jeweils bezogen auf das Gesamtgewicht des Brennstoffs, zusammengesetzt. Besonders bevorzugt ist die weitere Verbindung Nitroguanidin. Die weitere stickstoffhaltige Verbindung erhöht die Abbrandgeschwindigkeit im gesamten Druckbereich. Ein Zusatz von mehr als 25 % der weiteren Verbindung bewirkt allerdings eine zu starke Erhöhung der Abbrandtemperatur, so daß eine Beschädigung des Gasgenerators zu befürchten ist. Auch aus Kostengründen sollte der Anteil der weiteren Verbindung so gering wie möglich gehalten werden.The organic fuel is preferably a guanidine compound, particularly preferably guanidine nitrate, in admixture with at least one other Nitrogen-containing compound consisting of nitroguanidine, nitrotriazolone (NTO), Hexogen (RDX), octogen (HMX), ethylenediamine dinitrate (EDDN), Triaminoguanidine nitrate (TAGN), azobisformamidine dinitrate and dinitroammelin existing group. Preferably, the fuel is from 75 to 90 wt .-% Guanidine nitrate and 10 to 25 wt .-% of the further compound, respectively on the total weight of the fuel, composed. Especially preferred is the further compound nitroguanidine. The other nitrogenous Connection increases the burning rate in the entire pressure range. One However, addition of more than 25% of the further compound causes a too strong increase in the burning temperature, so that damage to the Gas generator is to be feared. Also for cost reasons, the proportion of further connection are kept as low as possible.

Der anorganische Oxidator ist bevorzugt ein Perchlorat, insbesondere ein Alkalimetallperchlorat und/oder Ammoniumperchlorat, und besonders bevorzugt Kaliumperchlorat. Als Abbrandmoderatoren können insbesondere sauerstoffhaltige Verbindungen von Übergangsmetallen, bevorzugt von Eisen, Kupfer, Mangan, Titan, Vanadium, Molybdän und Chrom, einschließlich Kombinationen davon, eingesetzt werden. Bevorzugt ist der Abbrandmoderator aus der aus CuO, Cu2O, CuCr2O4, Fe2O3, 3Cu(OH)2 x Cu(NO3)2 und deren Gemischen bestehenden Gruppe ausgewählt. Ganz besonders bevorzugt ist der Abbrandmoderator CuO. The inorganic oxidizer is preferably a perchlorate, especially an alkali metal perchlorate and / or ammonium perchlorate, and more preferably potassium perchlorate. In particular, oxygen-containing compounds of transition metals, preferably of iron, copper, manganese, titanium, vanadium, molybdenum and chromium, including combinations thereof, can be used as burn-on moderators. The burn-off moderator is preferably selected from the group consisting of CuO, Cu 2 O, CuCr 2 O 4 , Fe 2 O 3 , 3Cu (OH) 2 x Cu (NO 3 ) 2 and mixtures thereof. Very particularly preferred is the Abbrandmoderator CuO.

Eine Verwendung der vorbeschriebenen Abbrandmoderatoren in einem Anteil von zwischen 2 und 5 Gew.-% hat sich als vorteilhaft herausgestellt. Höhere Anteile senken die Gasausbeute des Treibstoffs, was nicht in allen Fällen wünschenswert ist.A use of the above-described Abbrandmoderatoren in one share of between 2 and 5 wt .-% has been found to be advantageous. higher Shares lower the gas yield of the fuel, which is not always the case is desirable.

Die mittlere Teilchengröße des Abbrandmoderators ist vorzugsweise kleiner als 5 µm und besonders bevorzugt kleiner als 1 µm, bei einer bevorzugten spezifischen Oberfläche von mindestens 2 m2/g, besonders bevorzugt mindestens 5 m2/g. Der Zusatz von derartigen feinkörnigen Abbrandmoderatoren verbessert die Anzündwilligkeit der erfindungsgemäßen gaserzeugenden Zusammensetzungen, so daß Anzündverzögerungen von höchstens 6 Millisekunden (ms) und besonders bevorzugt höchstens 5 ms erreicht werden können.The mean particle size of the Abbrandmoderators is preferably less than 5 microns and more preferably less than 1 micron, with a preferred specific surface of at least 2 m 2 / g, more preferably at least 5 m 2 / g. The addition of such fine-grained Abbrandmoderatoren improves the ignition willingness of the gas-generating compositions of the invention, so that ignition delays of at most 6 milliseconds (ms) and more preferably at most 5 ms can be achieved.

Die mittlere Teilchengröße des Brennstoffs und des Oxidators ist vorzugsweise kleiner als 15 µm und besonders bevorzugt kleiner als 10 µm. Dies trägt dazu bei, daß die erfindungsgemäße gaserzeugende Zusammensetzung eine ausreichend hohe Abbrandgeschwindigkeit zur Verwendung in Gurtstraffer-Gasgeneratoren aufweist.The mean particle size of the fuel and the oxidizer is preferably less than 15 microns and more preferably less than 10 microns. This contributes to the gas-generating composition according to the invention a sufficiently high burning rate for use in belt tensioner gas generators having.

Mit den erfindungsgemäßen Zusammensetzungen können Abbrandgeschwindigkeiten von mindestens 40 mm/s unter Betriebsbedingungen, das heißt üblicherweise einem Druck von 200 bar, erreicht werden. Besonders bevorzugt beträgt die Abbrandgeschwindigkeit bei 200 bar mindestens 45 mm/s.With the compositions of the invention can Burning rates of at least 40 mm / s under operating conditions, that is usually a pressure of 200 bar, can be achieved. Especially the burning rate at 200 bar is preferably at least 45 mm / s.

Die Abbrandgeschwindigkeit ist druckabhängig und läßt sich gemäß der folgenden Gleichung berechnen: r = a · pn The burning rate is pressure dependent and can be calculated according to the following equation: r = a · p n

Darin bedeutet r die Abbrandgeschwindigkeit, a eine treibstoffspezifische Konstante, p den Druck und n den Druckexponenten. Sind r und n bei einem bestimmten Druck p bekannt, läßt sich die Konstante a ermitteln. Where r is the burning rate, a is a fuel-specific Constant, p the pressure and n the pressure exponent. Are r and n at one known pressure p, the constant a can be determined.

Der Druckexponent der erfindungsgemäßen Zusammensetzungen ist kleiner als 0,35 und vorzugsweise kleiner oder gleich 0,3. Höhere Druckexponenten bewirken bei niedrigen Drücken auch eine schlechtere Anzündwilligkeit.The printing exponent of the compositions according to the invention is smaller as 0.35 and preferably less than or equal to 0.3. Higher pressure exponents cause at low pressures and a worse ignition.

Die Einstellung der Abbrandgeschwindigkeit der erfindungsgemäßen Zusammensetzungen erfolgt vorzugsweise durch Auswahl der geeigneten Brennstoffzusammensetzung, insbesondere der Art und des Anteils der weiteren stickstoffhaltigen Verbindung, der Art und des Anteils des jeweiligen Abbrandmoderators sowie der mittleren Teilchengröße des Brennstoffs, des Oxidators und, gegebenenfalls, des Abbrandmoderators. Durch eine geeignete Kombination dieser Parameter kann die Zusammensetzung optimal an die Verwendung in Gurtstraffer-Gasgeneratoren angepaßt werden.The setting of the burning rate of the invention Compositions are preferably made by selecting the appropriate one Fuel composition, in particular the nature and proportion of others nitrogen-containing compound, the nature and proportion of each Abbrandmoderators and the average particle size of the fuel, the Oxidator and, optionally, the Abbrand moderator. By a suitable Combining these parameters can optimally match the composition Use be adapted in belt tensioner gas generators.

Die üblichen Hilfs- und Zusatzstoffe umfassen Verarbeitungshilfen, wie Gleitmittel, Preß- und Rieselhilfen. Als Beispiele für diese Verbindungen können insbesondere Calciumstearat, Siliciumdioxid, Graphit oder Ruß genannt werden. Die Verarbeitungshilfen werden vorzugsweise in einem Anteil von bis zu 2 Gew.-%, bezogen auf die Gesamtzusammensetzung, eingesetzt.The usual auxiliaries and additives include processing aids, such as Lubricants, pressing and pouring aids. As examples of these compounds can especially calcium stearate, silica, graphite or carbon black. The processing aids are preferably used in a proportion of up to 2 wt .-%, based on the total composition used.

Eine besonders bevorzugte erfindungsgemäße Zusammensetzung besteht aus 48 bis 52 Gewichtsteilen Guanidinnitrat, 13 bis 17 Gewichtsteilen Nitroguanidin, 33 bis 37 Gewichtsteilen Kaliumperchlorat, 2,0 bis 5,0 Gewichtsteilen Kupferoxid (CuO) und jeweils bis zu 1 Gew.-% Calciumstearat und Graphit.A particularly preferred composition according to the invention consists of 48 to 52 parts by weight of guanidine nitrate, 13 to 17 parts by weight of nitroguanidine, 33 to 37 parts by weight of potassium perchlorate, 2.0 to 5.0 parts by weight of copper oxide (CuO) and in each case up to 1 wt .-% calcium stearate and graphite.

Weitere Merkmale und Vorteile der Erfindung ergeben sich aus der nachfolgenden Beschreibung von besonders bevorzugten Ausführungsbeispielen, die jedoch nicht einschränkend zu verstehen sind.Other features and advantages of the invention will become apparent from the following description of particularly preferred embodiments, but they are not meant to be limiting.

Beispiele 1 bis 5Examples 1 to 5

Guanidinnitrat mit einer mittleren Teilchengröße von 5 µm, Nitroguanidin mit einer mittleren Teilchengröße von 11 µm, Kaliumperchlorat mit einer mittleren Teilchengröße von 7 µm, Kupferoxid (CuO) mit einer mittleren Teilchengröße von 0,5 µm und einer spezifischen Oberfläche von 8 m2/g sowie Calciumstearat und Graphit wurden in den in der nachfolgenden Tabelle 1 angegebenen Gewichtsteilen gemischt, zusammen in einer Kugelmühle aufgemahlen und zu Tabletten von 6 x 2,5 mm verpreßt. Beispiel Nr. 1 (Vergleichsbeispiel) 2 (Vergleichsbeispiel) 3 (Vergleichsbeispiel) 4 5 Guanidinnitrat 65 57,5 50,0 50,0 50,0 Nitroguanidin 0 7,5 15,0 15,0 15,0 KClO4 35 35,0 35,0 35,0 35,0 CuO 0 0 0 2,5 5,0 Calciumstearat 0,5 0,5 0,5 0,5 0,5 Graphit 0,4 0,4 0,4 0,4 0,4 O2-Bilanz -3,3 % -3,6 % -4,0 % -3,5 % -3,0 % Guanidine nitrate with a mean particle size of 5 microns, nitroguanidine with an average particle size of 11 microns, potassium perchlorate with a mean particle size of 7 microns, copper oxide (CuO) with an average particle size of 0.5 microns and a specific surface area of 8 m 2 / g and calcium stearate and graphite were mixed in the parts by weight given in the following Table 1, ground together in a ball mill and pressed into tablets of 6 x 2.5 mm. Example no. 1 (comparative example) 2 (comparative example) 3 (comparative example) 4 5 guanidine nitrate 65 57.5 50.0 50.0 50.0 nitroguanidine 0 7.5 15.0 15.0 15.0 KClO 4 35 35.0 35.0 35.0 35.0 CuO 0 0 0 2.5 5.0 calcium stearate 0.5 0.5 0.5 0.5 0.5 graphite 0.4 0.4 0.4 0.4 0.4 O 2 balance -3.3% -3.6% -4.0% -3.5% -3.0%

Die Abbrandgeschwindigkeit der Zusammensetzungen gemäß den Beispielen 1 bis 5 wurde durch Beschuß von je 10 Gramm Treibstoff in einer geschlossenen 100 cm3 Bombe bestimmt. Die Versuchsergebnisse sowie weitere Eigenschaften der Zusammensetzungen sind in Tabelle 2 dargestellt. Beispiel Nr. Abbrandgeschwindigkeit r bei 200 bar [mm/s] theoretische Abbrandtemperatur [K] Gasausbeute (%) Druckexponent n 1 30,8 2377 81,31 0,374 2 32,5 2419 81,32 0,387 3 34,7 2462 81,32 0,380 4 42,9 2441 79,84 0,289 5 46,2 2438 78,44 0,242 The burning rate of the compositions according to Examples 1 to 5 was determined by bombardment of 10 grams of fuel in a closed 100 cm 3 bomb. The experimental results and other properties of the compositions are shown in Table 2. Example no. Burning rate r at 200 bar [mm / s] theoretical burning temperature [K] Gas yield (%) Pressure exponent n 1 30.8 2377 81.31 0.374 2 32.5 2419 81.32 0.387 3 34.7 2462 81.32 0,380 4 42.9 2441 79.84 0,289 5 46.2 2438 78.44 0,242

Für das Beispiel Nr. 3 wurde eine Anzündverzögerung von 11 ms ermittelt; die Beispiele Nr. 4 und 5 zeigten eine Anzündverzögerung von 6 bzw. 5 ms.For Example # 3, a firing delay of 11 ms was determined; Examples Nos. 4 and 5 showed an ignition delay of 6 and 5 ms, respectively.

Die Zusammensetzung gemäß Beispiel 5 wurde außerdem einem Alterungstest über 400 Stunden bei 107 °C unterzogen. Nach diesem Test wurde ein Gewichtsverlust von 0,07 % festgestellt, das heißt die Zusammensetzung zeigte eine den Anforderungen an Fahrzeuginsassenrückhaltesysteme genügende Alterungsbeständigkeit. Ein Vergleichsversuch mit einem üblichen Treibstoff auf der Grundlage von Nitrozellulose unter den gleichen Bedingungen ergab einen Gewichtsverlust von 14 %. Dies deutet auf eine vollständige Zersetzung und damit einen vollständigen Funktionsausfall des Treibstoffs hin.The composition according to Example 5 was also subjected to an aging test subjected to over 400 hours at 107 ° C. After this test was a Weight loss of 0.07% was detected, that is, the composition showed a satisfying the requirements for vehicle occupant restraint systems Aging resistance. A comparison experiment with a standard fuel on the basis of nitrocellulose under the same conditions gave one Weight loss of 14%. This indicates complete decomposition and thus a complete malfunction of the fuel out.

Die oben dargestellten Abbrandversuche zeigen die Eignung der erfindungsgemäßen Zusammensetzungen zur Verwendung in Gurtstraffer-Gasgeneratoren. Die für die Abbrandgeschwindigkeit und auch die Anzündverzögerung erzielten Werte entsprechen bei Einsatz gleicher Treibstoffmengen denen von herkömmlichen Nitrozellulosetreibstoffen.The abrading tests shown above show the suitability of the Compositions according to the invention for use in belt tensioner gas generators. The for the burn rate and also the Ignition delay values correspond when using the same Fuel levels of conventional nitrocellulose fuels.

Claims (25)

Nitrozellulosefreie, gaserzeugende Zusammensetzung zur Verwendung in Fahrzeuginsassenrückhaltesystemen, insbesondere einem Gurtstraffer-Gasgenerator, im wesentlichen bestehend aus
   wenigstens einem stickstoffhaltigen organischen Brennstoff in einem Anteil von 55 bis 70 Gew.-%,
   einem anorganischen Oxidator in einem Anteil von 30 bis 45 Gew.-%,
   einem oder mehreren Abbrandmoderatoren in einem Anteil von bis zu 10 Gew.-% und
   bis zu 5 Gew.-% üblichen Hilfs- und Zusatzstoffen, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung,
   wobei die Zusammensetzung einen Druckexponenten von kleiner als 0,35 und eine Abbrandgeschwindigkeit bei 200 bar von mindestens 40 mm/s aufweist.A nitrocellulose-free gas generating composition for use in vehicle occupant restraint systems, in particular a belt tensioner inflator, consisting essentially of
at least one nitrogen-containing organic fuel in a proportion of 55 to 70% by weight,
an inorganic oxidizer in a proportion of 30 to 45% by weight,
one or more Abbrandmoderatoren in an amount of up to 10 wt .-% and
up to 5% by weight of customary auxiliaries and additives, in each case based on the total weight of the composition,
the composition having a pressure exponent of less than 0.35 and a burnup rate of 200 bar of at least 40 mm / s. Gaserzeugende Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die Sauerstoffbilanz der Zusammensetzung zwischen -5 und + 5 % liegt.A gas generant composition according to claim 1, characterized in that the oxygen balance of the composition is between -5 and + 5%. Zusammensetzung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der stickstoffhaltige organische Brennstoff Guanidinnitrat im Gemisch mit wenigstens einer weiteren aus der aus Nitroguanidin, Nitrotriazolon, Hexogen, Octogen, Ethylendiamindinitrat, Triaminoguanidinnitrat, Azobisformamidindinitrat und Dinitroammelin bestehenden Gruppe ausgewählten Verbindung ist.A composition according to claim 1 or 2, characterized in that the nitrogen-containing organic fuel is guanidine nitrate in admixture with at least one other compound selected from the group consisting of nitroguanidine, nitrotriazolone, hexogen, octogen, ethylenediamine dinitrate, triaminoguanidine nitrate, azobisformamidine dinitrate and dinitroammine. Zusammensetzung nach Anspruch 3, dadurch gekennzeichnet, daß der Brennstoff aus 75 bis 90 Gew.- % Guanidinnitrat und 10 bis 25 Gew.- % Nitroguanidin, jeweils bezogen auf das Brennstoffgewicht, besteht. Composition according to Claim 3, characterized in that the fuel consists of 75 to 90% by weight of guanidine nitrate and 10 to 25% by weight of nitroguanidine, in each case based on the weight of the fuel. Zusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Oxidator ein Perchlorat ist.Composition according to any one of Claims 1 to 4, characterized in that the oxidizer is a perchlorate. Zusammensetzung nach Anspruch 5, dadurch gekennzeichnet, daß der Oxidator Kaliumperchlorat ist.Composition according to Claim 5, characterized in that the oxidizer is potassium perchlorate. Zusammensetzung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Abbrandmoderator eine sauerstoffhaltige Verbindung von Fe, Cu, Mn, Ti, V, Mo, Cr oder Kombinationen davon ist.Composition according to any one of Claims 1 to 6, characterized in that the erosion moderator is an oxygen-containing compound of Fe, Cu, Mn, Ti, V, Mo, Cr or combinations thereof. Zusammensetzung nach Anspruch 7, dadurch gekennzeichent, daß der Abbrandmoderator aus der aus CuO, Cu2O, CuCr2O4, Fe2O3, und 3Cu(OH)2 x Cu(NO3)2 bestehenden Gruppe ausgewählt ist.A composition according to claim 7, characterized in that the burn-off moderator is selected from the group consisting of CuO, Cu 2 O, CuCr 2 O 4 , Fe 2 O 3, and 3Cu (OH) 2 x Cu (NO 3 ) 2 . Zusammensetzung nach Anspruch 7, dadurch gekennzeichnet, daß der Abbrandmoderator CuO ist.Composition according to Claim 7, characterized in that the erosion moderator is CuO. Zusammensetzung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß der Abbrandmoderator in einem Anteil von zwischen 2 und 5 Gew.- % enthalten ist.Composition according to any one of Claims 1 to 9, characterized in that the erosion moderator is present in a proportion of between 2 and 5% by weight. Zusammensetzung nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die mittlere Teilchengröße des Brennstoffs und des Oxidators kleiner als 15 µm ist.Composition according to any one of Claims 1 to 10, characterized in that the mean particle size of the fuel and of the oxidizer is less than 15 μm. Zusammensetzung nach Anspruch 11, dadurch gekennzeichnet, daß die mittlere Teilchengröße des Brennstoffs und des Oxidators kleiner als 10 µm ist.Composition according to Claim 11, characterized in that the average particle size of the fuel and of the oxidizer is less than 10 μm. Zusammensetzung nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die mittlere Teilchengröße des Abbrandmoderators kleiner als 5 µm ist.Composition according to any one of Claims 1 to 12, characterized in that the mean particle size of the erosion moderator is less than 5 μm. Zusammensetzung nach Anspruch 13, dadurch gekennzeichnet, daß die mittlere Teilchengröße des Abbrandmoderators kleiner als 1 µm ist. Composition according to Claim 13, characterized in that the mean particle size of the erosion moderator is less than 1 μm. Zusammensetzung nach Anspruch 13 oder 14, dadurch gekennzeichnet, daß die spezifische Oberfläche des Abbrandmoderators mindestens 2 m2/g beträgt.Composition according to Claim 13 or 14, characterized in that the specific surface of the erosion moderator is at least 2 m 2 / g. Zusammensetzung nach Anspruch 15, dadurch gekennzeichnet, daß die spezifische Oberfläche mindestens 5 m2/g beträgt.Composition according to Claim 15, characterized in that the specific surface area is at least 5 m 2 / g. Zusammensetzung nach einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, daß die Abbrandgeschwindigkeit der Zusammensetzung mindestens 45 mm/s beträgt.Composition according to any one of Claims 1 to 16, characterized in that the burning rate of the composition is at least 45 mm / s. Zusammensetzung nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, daß der Druckexponent kleiner oder gleich 0,3 ist.Composition according to any one of Claims 1 to 17, characterized in that the pressure exponent is less than or equal to 0.3. Zusammensetzung nach einem der Ansprüche 1 bis 18, dadurch gekennzeichnet, daß die Zusammensetzung eine Anzündverzögerung von höchstens 6 ms aufweist.Composition according to any one of Claims 1 to 18, characterized in that the composition has an ignition delay of at most 6 ms. Zusammensetzung nach Anspruch 19, dadurch gekennzeichnet, daß die Anzündverzögerung höchstens 5 ms beträgt.Composition according to Claim 19, characterized in that the ignition delay is at most 5 ms. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die üblichen Hilfs- und Zusatzstoffe in einem Anteil von bis zu 2 Gew.- % enthalten sind.Composition according to one of the preceding claims, characterized in that the customary auxiliaries and additives are contained in a proportion of up to 2% by weight. Zusammensetzung nach einem der Ansprüche 1 bis 21, dadurch gekennzeichnet, daß die üblichen Hilfs- und Zusatzstoffe aus der aus Calciumstearat, Siliciumdioxid, Graphit und Ruß bestehenden Gruppe ausgewählt sind.Composition according to any one of Claims 1 to 21, characterized in that the usual auxiliaries and additives are chosen from the group consisting of calcium stearate, silica, graphite and carbon black. Zusammensetzung nach einem der vorhergehenden Ansprüche, bestehend aus 48 bis 52 Gewichtsteilen Guanidinnitrat, 13 bis 17 Gewichtsteilen Nitroguanidin, 33 bis 37 Gewichtsteilen Kaliumperchlorat, 2,0 bis 5,0 Gewichtsteilen CuO und bis zu zwei Gewichtsteilen wenigstens einer der Verbindungen Calciumstearat, Siliciumdioxid, Graphit und Ruß. Composition according to one of the preceding claims, consisting From 48 to 52 parts by weight of guanidine nitrate, 13 to 17 parts by weight Nitroguanidine, 33 to 37 parts by weight potassium perchlorate, 2.0 to 5.0 Parts by weight of CuO and up to two parts by weight at least one of Compounds calcium stearate, silica, graphite and carbon black. Gurtstraffer mit einem Gasgenerator und einem Gurtstrafferantrieb, wobei der Gasgenerator eine bei Verbrennung ein Gas oder Gasgemisch erzeugende Zusammensetzung gemäß einem der Ansprüche 1 bis 23 enthält und der Gurtstrafferantrieb durch das Gas oder Gasgemisch betätigbar ist.Belt tensioner with a gas generator and a belt tensioner drive, wherein the gas generator when burning a gas or gas mixture generating A composition according to any one of claims 1 to 23 and the Belt tensioner drive can be actuated by the gas or gas mixture. Verwendung einer gaserzeugenden Zusammensetzung gemäß einem der Ansprüche 1 bis 23 in einem Gurtstraffer eines Fahrzeuginsassen-Rückhaltesystems.Use of a gas generating composition according to any one of Claims 1 to 23 in a belt tensioner of a vehicle occupant restraint system.
EP02014052A 2001-07-10 2002-06-28 Nitrocellulose-free gas-generating composition Expired - Lifetime EP1275629B1 (en)

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