EP1289910A1 - Rapid ignition powders for thermal temperature fuses used in airbag gas generators - Google Patents

Rapid ignition powders for thermal temperature fuses used in airbag gas generators

Info

Publication number
EP1289910A1
EP1289910A1 EP00945583A EP00945583A EP1289910A1 EP 1289910 A1 EP1289910 A1 EP 1289910A1 EP 00945583 A EP00945583 A EP 00945583A EP 00945583 A EP00945583 A EP 00945583A EP 1289910 A1 EP1289910 A1 EP 1289910A1
Authority
EP
European Patent Office
Prior art keywords
powder according
ignition powder
weight
stabilizer
parts
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.)
Granted
Application number
EP00945583A
Other languages
German (de)
French (fr)
Other versions
EP1289910B8 (en
EP1289910B1 (en
Inventor
Eduard Gast
Peter Semmler
Bernhard Schmid
Christian Recker
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.)
Nigu Chemie GmbH
Original Assignee
Nigu Chemie 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 Nigu Chemie GmbH filed Critical Nigu Chemie GmbH
Publication of EP1289910A1 publication Critical patent/EP1289910A1/en
Application granted granted Critical
Publication of EP1289910B1 publication Critical patent/EP1289910B1/en
Publication of EP1289910B8 publication Critical patent/EP1289910B8/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C9/00—Chemical contact igniters; Chemical lighters

Definitions

  • the present invention relates to pre-ignition powder for thermal fuses for the currentless ignition of the gas set of an airbag gas generator of motor vehicles.
  • the gas sets used in airbag gas generators of motor vehicles are generally very thermally stable.
  • controlled ignition so-called thermal fuses are used.
  • the thermal fuse ensures that the finished gas generator before and after installation, e.g. in the motor vehicle, is not first ignited at an uncontrolled high temperature and then there may be a leak or even fragmentation of the gas generator housing - especially in the case of an aluminum housing. Accordingly, the thermal fuse ensures that the conversion of the gas-generating mixture is triggered thermally far below this critical temperature. In such a case, it prevents the gas generator housing from being destroyed by its early implementation and controlled ignition of the gas set and avoids the associated dangers.
  • a possible embodiment for a thermal fuse includes a container which is filled with a pre-ignition powder (pyrotechnic mixture), for example in granular form (0.1 to 0.5 g), which ignites itself between 150 ° C. and 230 ° C. and so much heat releases that the ignition of the actual lighter and / or the gas set is guaranteed.
  • a pre-ignition powder for example in granular form (0.1 to 0.5 g)
  • pyrotechnic airbag gas generators are usually triggered by a current pulse by means of a sensor.
  • the ignition is amplified with an ignition charge which, with the hot gas and solid particles generated, almost synchronizes the actual gas charge - often in tablet form burning.
  • the burning gas set supplies the filling gas of the protective cushion.
  • the autoignition temperature of the gas sets currently in use is approximately 400 ° C. for the azide-containing gas sets and at least 300 ° C. for the azide-free gas sets.
  • nitrocellulose powders have been used as pre-ignition powder for thermal fuses. These have a self-ignition temperature (decomposition point) of 150-200 ° C.
  • the nitrocellulose powders do not meet the stability requirements that are currently required by the automotive industry. Thereafter, thermal fuses must withstand hot storage over 400 hours at 107 ° C (224 ° Fahrenheit; US Pat. No. 5,460,671, column 3) with a weight loss ⁇ 3% and maintaining full functionality.
  • nitrocellulose tends to decompose slowly even at low temperatures and thus does not guarantee the ability to function as pre-ignition powder over a longer period of time, as is necessary in motor vehicles.
  • thermal fuses which are said to be able to ignite the gas-generating mixtures usually used in gas generators in a thermally controlled manner far below the critical temperature and which do not have the disadvantages of nitrocellulose.
  • Compounds which are selected from the compound classes of oxalates, peroxodisulfates (persulfates), permanganates, nitrides, perborates, bismuthates, formates, nitrates, sulfamates, bromates or peroxides can be used as substances or as mixtures of substances for these thermal fuses.
  • oxidizable components for example explosives with low deflagration or decomposition points, preferably calcium bistetrazole-amine, 3-nitro-l, 2,4-triazol-5-one (NTO), 5-aminotetrazole nitrate, Nitroguanidine (NIGU), guanidine nitrate or bistrosrazolamine are used.
  • NTO 2,4-triazol-5-one
  • NIGU Nitroguanidine
  • guanidine nitrate or bistrosrazolamine are used.
  • the substances which have a lower Nerpufrungrios or decomposition point than the gas-generating mixture used, but decompose endothermic, require at least one fuel and possibly a reducing agent in order to be used as a thermal fuse.
  • the oxidizable components specified above are mentioned as examples of fuels.
  • Metal powder preferably titanium powder
  • oxidizing agents such as potassium nitrate or potassium perchlorate or mixtures of these oxidizing agents can be added.
  • US Pat. No. 5,460,671 describes ignition powders which consist of a mixture of a fuel and an oxidizing agent.
  • the oxidizing agents are selected from the group consisting of alkali metal or alkaline earth metal chlorates or mixtures thereof, in particular potassium or sodium chlorate.
  • the fuels are carbohydrates such as D-glucose, D-galactose, D-ribose, etc.
  • a pre-ignition powder is known from WO 99/41213, which comprises a mixture of at least one fuel, at least one oxidizing agent, at least one stabilizer and optionally auxiliary processing aids, auxiliary fuels and fillers.
  • the fuel is selected from the group consisting of thiourea and its derivatives, such as ⁇ , ⁇ '-diphenylthiourea. Chlorates, perchlorates and nitrates of sodium, potassium and strontium can be used as oxidizing agents.
  • the stabilizers include Cellulose derivatives, polystyrene and polystyrene copolymers, polyamides, polyacrylates.
  • the object of the present invention is to provide pre-ignition powders which have improved stability, which go beyond the stability requirements mentioned above and which meet the increasingly stringent requirements of the automotive industry.
  • the pre-ignition powders are intended to withstand hot storage for well over 400 hours at a temperature which is higher than the above requirements and with a weight loss well below 3%.
  • the gas generator overheats (at temperatures above 240 ° C)
  • the powders must be able to ignite the airbag gas set with a small amount (0.1 to 0.5 g) of pre-ignition powder (in the pre-ignition unit).
  • an early powder for thermal protection comprising:
  • processing aids selected from calcium and magnesium stearates, graphite and high-boiling paraffins (such as Naftolen P603 from Chemetall) and citric acid esters and acylcitric acid esters (such as triethyl citrate and acetyl triethlyl citrate), and if appropriate
  • auxiliary fuels selected from elemental aluminum, zirconium, titanium, magnesium, zinc and iron, and optionally
  • (F) fillers selected from the group of Al 2 O 3 , TiO 2 , ZrO, Fe 2 O 3 , Si 3 N 4 and boron nitride (BN).
  • the fuel (A) is present in the pre-ignition powders according to the invention for thermal fuses in an amount of 20 to 40 parts by weight, preferably 25-35 parts by weight and in particular 27-32 parts by weight.
  • the oxidizing agents (B), preferably potassium chlorate and potassium nitrate, are present in an amount of 40-80 parts by weight, preferably 50-75 parts by weight and in particular 60-75 parts by weight.
  • the stabilizers (C) cellulose acetobutyrate is particularly preferred.
  • the polyamides as stabilizers (C) include, according to the invention, amide derivatives such as dicyandiamide (cyanoguanidine).
  • the stabilizers are present in a proportion of 0.5-20 parts by weight, preferably 0.5-10 parts by weight and in particular 0.5-5 parts by weight.
  • Processing aids (D) may optionally be present in an amount of 0.5-5 parts by weight, preferably 0.5 to 3 parts by weight.
  • the stabilizer (C) cellulose acetobutyrate can preferably contain citric acid triethyl ester, in particular in a ratio of cellulose acetobutyrate to citric acid triethyl ester of about 3: 1, as processing aid (D) in the pre-ignition powders according to the invention.
  • auxiliary fuels (E) can optionally be used in an amount of 0.5-20 parts by weight, preferably 0.5-10 parts by weight and in particular 0.5-5 parts by weight available.
  • fillers (F) may optionally be present in a proportion of 0.5-12 parts by weight, preferably 0.5-10 parts by weight and in particular 0.5-5 parts by weight.
  • the pre-ignition powders according to the invention for thermal fuses are not only limited to the airbag area, but can also be used to trigger mechanical movements as well as in pressure and security elements.
  • the toxicities of the raw materials used for the thermal fuses according to the invention all correspond to Swiss poison classes 3, 4 and 5 (exception:
  • 2-thiobarbituric acid no classification known; LD 50 > 5000 mg / kg rat (oral)).
  • Fuses are made with other gas-generating mixtures or pyrotechnic sets, e.g. Boron / potassium nitrate well tolerated and can be mixed in as granules or tablets or housed in a container preferably made of aluminum (or steel). The purity and cone size of these raw materials as well as the various mixtures of oxidizing agents and fuels used
  • the type of stabilizer and the proportion of its mixture affects long-term stability and the release temperature.
  • 2-thiohydantoin (1) or 2-thiobarbituric acid (2) in combination with oxidizing agents and suitable stabilizers provides a system that both suddenly reacts strongly exothermically between 150-230 ° C and meets even more stringent stability criteria.
  • auxiliary fuels such as metal powders of aluminum, zirconium, titanium, magnesium, zinc, iron, etc.
  • the generation of hot particles can be positively influenced.
  • Another way of producing hot particles - which, however, is at the expense of the total energy of the thermal fuse mixtures - is by adding fillers such as Al O 3 , TiO 2 , ZrO, Fe 2 O 3 , Si 3 N, boron nitride, etc.
  • processing aids (D) such as graphite and stearates (especially calcium and magnesium stearate) or high-boiling paraffins (usually) increase the trigger temperature.
  • the ground, solid mixture components listed in Table I were premixed in the specified mixing ratios in a vertical mixer and by means of water and / or solvents (such as Cl-C4 alcohols, for example methanol, ethanol, iso- / n-propanol, n-butanol and acetone (Comparative example 3)) in an amount of 10-20% by weight and likewise added stabilizer processed to a heterogeneous mixture within one hour.
  • a ready-to-use granulate or a tableting granulate which only have to be sieved, can be produced; however, a highly viscous mixture can also be set, which is suitable for shaping by extrusion with subsequent cutting.
  • the preparation of the mixtures is completed by drying at 90 ° C. for one to two hours.
  • the thermal behavior was determined by means of differential scanning calorimetry (DSC method) of the various examples both before storage and after 400 hours at 107 ° C. (comparative examples) or after 400 hours at 110 ° C. (examples). Table I
  • the ignition (or decomposition) temperatures of the pre-ignition powder according to the invention are in the required range of 150-230 ° C.
  • the ignition powders according to the invention according to Examples 5 and 6 showed a change in the decomposition temperature between 0 and 6 ° C after 400 hours at 110 ° C.
  • the decomposition point was determined by means of differential scanning calorimetry (DSC method). The range in the decomposition temperature determination was ⁇ 5 ° C at the heating rate of 10 ° C / min.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Abstract

The invention relates to rapid ignition powders for thermal fuses that are capable of a thermally controlled ignition of gas-producing mixtures far below the critical temperature, said mixtures usually being used in gas generators. The inventive powders have a weight loss of far less than 3 % when kept for more than 400 hours at warm storage temperatures of 110 DEG C and still remain completely functional. The inventive rapid ignition powders contain at least one fuel selected from the group including 2-thiohydantoin and 2-thiobarbituric acid, at least one oxidant, at least one stabilizer and optionally processing agents, auxiliary fuels and fillers.

Description

FRUHZUNDPULVER FÜR THERMISCHE SICHERUNGEN FÜR EARLY POWDER FOR THERMAL FUSE FOR
AIRBAG-GASGENERATORENAIR BAG INFLATORS
Die vorliegende Erfindung betrifft Frühzündpulver für thermische Sicherungen zur stromlosen Anzündung des Gassatzes eines Airbag-Gasgenerators von Kraftfahrzeugen.The present invention relates to pre-ignition powder for thermal fuses for the currentless ignition of the gas set of an airbag gas generator of motor vehicles.
Die in Airbag-Gasgeneratoren von Kraftfahrzeugen verwendeten Gassätze sind in der Regel thermisch sehr stabil. Um den Gassatz bei hoher Umgebungstemperatur, z.B. im Falle eines Fahrzeugbrandes, kontrolliert anzuzünden, werden sogenannte thermische Sicherungen eingesetzt. Durch die thermische Sicherung wird sichergestellt, dass der fertige Gasgenerator vor und nach dem Einbau, z.B. im Kraftfahrzeug, nicht erst bei einer unkontrolliert hohen Temperatur gezündet wird und es dann eventuell zur Undichtigkeit oder gar zum Fragmentieren des Gasgeneratorgehäuses - speziell bei einem Aluminiumgehäuse - kommen kann. Demnach sorgt die thermische Sicherung dafür, dass die Umsetzung der gaserzeugenden Mischung weit unterhalb dieser kritischen Temperatur thermisch ausgelöst wird. Sie verhindert in einem solchen Fall durch ihre frühzeitige Umsetzung und kontrollierte Anzündung des Gassatzes die Zerstörung des Gasgeneratorgehäuses und vermeidet die damit verbundenen Gefahren.The gas sets used in airbag gas generators of motor vehicles are generally very thermally stable. To the gas set at high ambient temperature, e.g. in the event of a vehicle fire, controlled ignition, so-called thermal fuses are used. The thermal fuse ensures that the finished gas generator before and after installation, e.g. in the motor vehicle, is not first ignited at an uncontrolled high temperature and then there may be a leak or even fragmentation of the gas generator housing - especially in the case of an aluminum housing. Accordingly, the thermal fuse ensures that the conversion of the gas-generating mixture is triggered thermally far below this critical temperature. In such a case, it prevents the gas generator housing from being destroyed by its early implementation and controlled ignition of the gas set and avoids the associated dangers.
Eine mögliche Ausführungsform für eine thermische Sicherung beinhaltet einen Behälter, der mit einem beispielsweise in Granulatform vorliegenden Frühzündpulver (pyrotechnisches Gemisch) gefüllt ist (0,1 bis 0,5g), das sich zwischen 150°C und 230°C selbst entzündet und soviel Wärmemenge freisetzt, dass die Anzündung des eigentlichen Anzünders und/oder des Gassatzes gewährleistet ist.A possible embodiment for a thermal fuse includes a container which is filled with a pre-ignition powder (pyrotechnic mixture), for example in granular form (0.1 to 0.5 g), which ignites itself between 150 ° C. and 230 ° C. and so much heat releases that the ignition of the actual lighter and / or the gas set is guaranteed.
Üblicherweise werden pyrotechnische Airbag-Gasgeneratoren im Falle eines Fahrzeugcrash mittels Sensor durch einen Stromimpuls gezündet. Die Anzündung wird mit einer Anzündladung verstärkt, die mit den dabei erzeugten heißen Gas- und Feststoffpartikeln den eigentlichen Gassatz - oft in Tablettenform - nahezu synchron anbrennt. Der abbrennende Gassatz liefert das Füllgas des Schutzkissens. Die Selbstentzündungstemperatur der zur Zeit gebräuchlichen Gassätze liegt bei den azidhaltigen bei etwa 400°C und bei den azidfreien Gassätzen immerhin noch bei etwa 300°C.In the event of a vehicle crash, pyrotechnic airbag gas generators are usually triggered by a current pulse by means of a sensor. The ignition is amplified with an ignition charge which, with the hot gas and solid particles generated, almost synchronizes the actual gas charge - often in tablet form burning. The burning gas set supplies the filling gas of the protective cushion. The autoignition temperature of the gas sets currently in use is approximately 400 ° C. for the azide-containing gas sets and at least 300 ° C. for the azide-free gas sets.
Im Stand der Technik wurden bisher stabilisierte Nitrocellulosepulver als Frühzündpulver für thermische Sicherungen eingesetzt. Diese weisen eine Selbstentzündungstemperatur (Zersetzungspunkt) von 150-200°C auf. Die Nitrocellulosepulver genügen aber nicht den Stabilitätsanforderungen, die derzeit von der Automobilindustrie gefordert werden. Danach müssen thermische Sicherungen einer Warmlagerung über 400 Stunden bei 107°C (224°Fahrenheit; US-PS 5,460,671, Spalte 3) mit einem Gewichtsverlust < 3% und unter Erhalt der vollen Funktionsfähigkeit standhalten. Nitrocellulose neigt jedoch dazu, sich schon bei niedrigen Temperaturen langsam zu zersetzen und gewährleistet somit nicht die Funktionsfähigkeit als Frühzündpulver über einen längeren Zeitraum, wie dies bei Kraftfahrzeugen j edoch erforderlich ist.In the prior art, stabilized nitrocellulose powders have been used as pre-ignition powder for thermal fuses. These have a self-ignition temperature (decomposition point) of 150-200 ° C. The nitrocellulose powders, however, do not meet the stability requirements that are currently required by the automotive industry. Thereafter, thermal fuses must withstand hot storage over 400 hours at 107 ° C (224 ° Fahrenheit; US Pat. No. 5,460,671, column 3) with a weight loss <3% and maintaining full functionality. However, nitrocellulose tends to decompose slowly even at low temperatures and thus does not guarantee the ability to function as pre-ignition powder over a longer period of time, as is necessary in motor vehicles.
Aus der DE 197 30 873 sind thermische Sicherungen bekannt, die in der Lage sein sollen, die üblicherweise in Gasgeneratoren eingesetzten gaserzeugenden Mischungen weit unterhalb der kritischen Temperatur thermisch kontrolliert anzuzünden, und die nicht die Nachteile von Nitrocellulose aufweisen. Als Stoffe oder als Stoffgemische für diese thermischen Sicherungen können Verbindungen eingesetzt werden, die ausgewählt sind aus den Verbindungsklassen der Oxalate, Peroxodisulfate (Persulfate), Permanganate, Nitride, Perborate, Bismutate, Formiate, Nitrate, Sulfamate, Bromate oder Peroxide. Außerdem können gemäß der DE 197 30 873 oxidierbare Komponenten, beispielsweise Explosivstoffe mit niedrigen Verpuffungs- oder Zersetzungspunkten, vorzugsweise Calcium-bistetrazol-amin, 3-Nitro-l,2,4-triazol-5-on (NTO), 5-Aminotetrazolnitrat, Nitroguanidin (NIGU), Guanidinnitrat oder Bistetrazolamin eingesetzt werden. Die Stoffe, die zwar einen niedrigeren Nerpufrungspunkt oder Zersetzungspunkt als die verwendete gaserzeugende Mischung aufweisen, sich dabei aber endotherm zersetzen, benötigen mindestens einen Brennstoff und gegebenenfalls ein Reduktionsmittel, um als thermische Sicherung eingesetzt werden zu können. Als Beispiele für Brennstoffe sind die vorstehend angegebenen oxidierbaren Komponenten genannt. Als Reduktionsmittel kann beispielsweise Metallpulver, vorzugsweise Titanpulver eingesetzt werden. Zur Beeinflussung der Nerpuffungspunkte können unter anderem Oxidationsmittel wie Kaliumnitrat oder Kaliumperchlorat oder Mischungen dieser Oxidationsmittel zugegeben werden. Die US-PS 5,460,671 beschreibt Zündpulver, die aus einem Gemisch eines Brennstoffs und eines Oxidationsmittels bestehen. Die Oxidationsmittel sind ausgewählt aus der Gruppe bestehend aus Alkalimetall- oder Erdalkalimetallchloraten oder Gemischen davon, insbesondere Kalium- oder Natriumchlorat. Beispiele für die Brennstoffe sind Kohlenhydrate, wie D-Glucose, D-Galactose, D-Ribose, usw..From DE 197 30 873 thermal fuses are known which are said to be able to ignite the gas-generating mixtures usually used in gas generators in a thermally controlled manner far below the critical temperature and which do not have the disadvantages of nitrocellulose. Compounds which are selected from the compound classes of oxalates, peroxodisulfates (persulfates), permanganates, nitrides, perborates, bismuthates, formates, nitrates, sulfamates, bromates or peroxides can be used as substances or as mixtures of substances for these thermal fuses. According to DE 197 30 873, oxidizable components, for example explosives with low deflagration or decomposition points, preferably calcium bistetrazole-amine, 3-nitro-l, 2,4-triazol-5-one (NTO), 5-aminotetrazole nitrate, Nitroguanidine (NIGU), guanidine nitrate or bistrosrazolamine are used. The substances, which have a lower Nerpufrungpunkt or decomposition point than the gas-generating mixture used, but decompose endothermic, require at least one fuel and possibly a reducing agent in order to be used as a thermal fuse. The oxidizable components specified above are mentioned as examples of fuels. Metal powder, preferably titanium powder, can be used as the reducing agent, for example. To influence the nerpuffing points, oxidizing agents such as potassium nitrate or potassium perchlorate or mixtures of these oxidizing agents can be added. US Pat. No. 5,460,671 describes ignition powders which consist of a mixture of a fuel and an oxidizing agent. The oxidizing agents are selected from the group consisting of alkali metal or alkaline earth metal chlorates or mixtures thereof, in particular potassium or sodium chlorate. Examples of the fuels are carbohydrates such as D-glucose, D-galactose, D-ribose, etc.
Aus der WO 99/41213 ist ein Frühzündpulver bekannt, das ein Gemisch aus mindestens einem Brennstoff, mindestens einem Oxidationsmittel, mindestens einem Stabilisator und gegebenenfalls Nerarbeitungshilfsmitteln, Hilfsbrennstoffen und Füllstoffen umfasst. Der Brennstoff ist ausgewählt aus der Gruppe bestehend aus Thiohamstoff und seinen Derivaten, wie Ν,Ν'-Diphenylthioharnstoff. Als Oxidationsmittel können Chlorate, Perchlorate und Nitrate von Natrium, Kalium und Strontium eingesetzt werden. Beispiele für die Stabilisatoren sind u.a. Cellulosederivate, Polystyrol und Polystyrol-Copolymere, Polyamide, Polyacrylate. Diese Pulver genügen den vorstehend genannten Stabilitätsanforderungen der Automobilindustrie und halten demnach einer Warmlagerung über 400 Stunden bei 107°C mit einem Gewichtsverlust < 3% und unter Erhalt der vollen Funktionsfähigkeit stand.A pre-ignition powder is known from WO 99/41213, which comprises a mixture of at least one fuel, at least one oxidizing agent, at least one stabilizer and optionally auxiliary processing aids, auxiliary fuels and fillers. The fuel is selected from the group consisting of thiourea and its derivatives, such as Ν, Ν'-diphenylthiourea. Chlorates, perchlorates and nitrates of sodium, potassium and strontium can be used as oxidizing agents. Examples of the stabilizers include Cellulose derivatives, polystyrene and polystyrene copolymers, polyamides, polyacrylates. These powders meet the stability requirements of the automotive industry mentioned above and therefore withstand hot storage for 400 hours at 107 ° C with a weight loss of <3% and maintaining full functionality.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, Frühzündpulver bereitzustellen, die eine verbesserte Stabilität aufweisen, die über die vorstehend genannten Stabilitätsanforderungen hinausgeht und den immer strenger werdenden Anforderungen der Automobilindustrie gerecht wird. Insbesondere sollen die Frühzündpulver einer Warmlagerung weit über 400 Stunden bei einer gegenüber vorstehenden Anforderungen höheren Temperatur mit einem Gewichtsverlust weit unterhalb 3% standhalten. Ferner müssen die Pulver bei Überhitzung des Gasgenerators (bei Temperaturen oberhalb 240°C) mit einer geringen Menge (0,1 bis 0,5g) Frühzündpulver (in der Frühzündeinheit) den Gassatz des Airbags anzünden können.The object of the present invention is to provide pre-ignition powders which have improved stability, which go beyond the stability requirements mentioned above and which meet the increasingly stringent requirements of the automotive industry. In particular, the pre-ignition powders are intended to withstand hot storage for well over 400 hours at a temperature which is higher than the above requirements and with a weight loss well below 3%. Furthermore, if the gas generator overheats (at temperatures above 240 ° C), the powders must be able to ignite the airbag gas set with a small amount (0.1 to 0.5 g) of pre-ignition powder (in the pre-ignition unit).
Gelöst wurde diese erfindungsgemäße Aufgabe durch ein Fruhzundpulver für eine thermische Sicherung, umfassend:This object according to the invention was achieved by an early powder for thermal protection, comprising:
(A) mindestens einen Brennstoff ausgewählt aus der Gruppe bestehend aus 2- Thiohydantoin (1) und 2-Thiobarbitursäure (2),(A) at least one fuel selected from the group consisting of 2-thiohydantoin (1) and 2-thiobarbituric acid (2),
(B) mindestens ein Oxidationsmittel ausgewählt aus den Chloraten, Perchloraten und Nitraten von Natrium, Kalium und Strontium, d.h. NaNO3, KNO3, Sr(NO3)2, NaClO3, KClO3, Sr (ClO3)2, NaClO4, KClO4, Sr(ClO4)2, (B) at least one oxidizing agent selected from the chlorates, perchlorates and nitrates of sodium, potassium and strontium, ie NaNO 3 , KNO 3 , Sr (NO 3 ) 2 , NaClO 3 , KClO 3 , Sr (ClO 3 ) 2 , NaClO 4 , KClO 4 , Sr (ClO 4 ) 2 ,
(C) mindestens einen Stabilisator ausgewählt aus der Gruppe bestehend aus Cellulosederivaten, wie Celluloseether und Celluloseester, Polystyrol und Polystyrol-Copolymeren, Polyamiden, Polyacrylaten, Polycarbonaten, Polypropylenen, Polybutylenen, Polyoxymethylenen, Polyacetaten und Polyvinyl- Verbindungen, und gegebenenfalls(C) at least one stabilizer selected from the group consisting of cellulose derivatives, such as cellulose ethers and cellulose esters, polystyrene and polystyrene copolymers, polyamides, polyacrylates, polycarbonates, polypropylenes, polybutylenes, polyoxymethylenes, polyacetates and polyvinyl compounds, and optionally
(D) Verarbeitungshilfsmittel, ausgewählt aus Calcium- und Magnesiumstearaten, Graphit und hochsiedenden Paraffinen (wie Naftolen P603 der Fa. Chemetall) und Citronensäureester und Acylcitronensäureester (wie Triethylcitrat und Acetyltriethlylcitrat), und gegebenenfalls(D) processing aids selected from calcium and magnesium stearates, graphite and high-boiling paraffins (such as Naftolen P603 from Chemetall) and citric acid esters and acylcitric acid esters (such as triethyl citrate and acetyl triethlyl citrate), and if appropriate
(E) Hilfsbrennstoffe, ausgewählt aus elementarem Aluminium, Zirconium, Titan, Magnesium, Zink und Eisen, und gegebenenfalls(E) auxiliary fuels selected from elemental aluminum, zirconium, titanium, magnesium, zinc and iron, and optionally
(F) Füllstoffe, ausgewählt aus der Gruppe von Al2O3, TiO2, ZrO , Fe2O3, Si3N4 und Bornitrid (BN).(F) fillers selected from the group of Al 2 O 3 , TiO 2 , ZrO, Fe 2 O 3 , Si 3 N 4 and boron nitride (BN).
Der Brennstoff (A) liegt in den erfindungsgemäßen Frühzündpulvern für thermische Sicherungen in einer Menge von 20 bis 40 Gewichtsteilen, bevorzugt 25-35 Gewichtsteilen und insbesondere 27-32 Gewichtsteilen vor. Die Oxidationsmittel (B), vorzugsweise Kaliumchlorat und Kaliumnitrat, liegen in einer Menge von 40-80 Gewichtsteilen, vorzugsweise 50-75 Gewichtsteilen und insbesondere 60-75 Gewichtsteilen vor. Unter den Stabilisatoren (C) ist Celluloseacetobutyrat besonders bevorzugt. Zu den Polyamiden als Stabilisatoren (C) sind neben herkömmlichen Polyamiden erfindungsgemäß Amidderivate wie Dicyandiamid (Cyanoguanidin) zu zählen. Die Stabilisatoren liegen in einem Anteil von 0,5-20 Gewichtsteilen, bevorzugt 0,5-10 Gewichtsteilen und insbesondere 0,5-5 Gewichtsteilen vor. Verarbeitungshilfsmittel (D) können gegebenenfalls in einer Menge von 0,5-5 Gewichtsteilen, bevorzugt 0,5 bis 3 Gewichtsteilen enthalten sein. Der Stabilisator (C) Celluloseacetobutyrat kann in den erfindungsgemäßen Frühzündpulvern als Verarbeitungshilfsmittel (D) vorzugsweise Citronensäuretriethylester, insbesondere im Verhältnis Celluloseacetobutyrat zu Citronensäuretriethylester von etwa 3:1, enthalten. Ferner können gegebenenfalls Hilfsbrennstoffe (E) in einer Menge von 0,5-20 Gewichtsteilen, bevorzugt 0,5-10 Gewichtsteilen und insbesondere 0,5-5 Gewichtsteilen vorliegen. Des weiteren können gegebenenfalls Füllstoffe (F) in einem Anteil von 0,5-12 Gewichtsteilen, bevorzugt 0,5-10 Gewichtsteilen und insbesondere 0,5-5 Gewichtsteilen vorliegen.The fuel (A) is present in the pre-ignition powders according to the invention for thermal fuses in an amount of 20 to 40 parts by weight, preferably 25-35 parts by weight and in particular 27-32 parts by weight. The oxidizing agents (B), preferably potassium chlorate and potassium nitrate, are present in an amount of 40-80 parts by weight, preferably 50-75 parts by weight and in particular 60-75 parts by weight. Among the stabilizers (C), cellulose acetobutyrate is particularly preferred. In addition to conventional polyamides, the polyamides as stabilizers (C) include, according to the invention, amide derivatives such as dicyandiamide (cyanoguanidine). The stabilizers are present in a proportion of 0.5-20 parts by weight, preferably 0.5-10 parts by weight and in particular 0.5-5 parts by weight. Processing aids (D) may optionally be present in an amount of 0.5-5 parts by weight, preferably 0.5 to 3 parts by weight. The stabilizer (C) cellulose acetobutyrate can preferably contain citric acid triethyl ester, in particular in a ratio of cellulose acetobutyrate to citric acid triethyl ester of about 3: 1, as processing aid (D) in the pre-ignition powders according to the invention. Furthermore, auxiliary fuels (E) can optionally be used in an amount of 0.5-20 parts by weight, preferably 0.5-10 parts by weight and in particular 0.5-5 parts by weight available. Furthermore, fillers (F) may optionally be present in a proportion of 0.5-12 parts by weight, preferably 0.5-10 parts by weight and in particular 0.5-5 parts by weight.
Die erfindungsgemäßen Frühzündpulver für thermische Sicherungen sind nicht nur auf das Airbag-Gebiet beschränkt, sondern können auch zur Auslösung von mechanischen Bewegungen sowie in Druck- und Sicherheitselementen eingesetzt werden.The pre-ignition powders according to the invention for thermal fuses are not only limited to the airbag area, but can also be used to trigger mechanical movements as well as in pressure and security elements.
Die Toxizitäten der für die erfindungsgemäßen thermischen Sicherungen eingesetzten Rohstoffe entsprechen alle der Schweizer Giftklasse 3, 4 und 5 (Ausnahme:The toxicities of the raw materials used for the thermal fuses according to the invention all correspond to Swiss poison classes 3, 4 and 5 (exception:
2-Thiobarbitursäure; keine Klassifizierung bekannt; LD50 > 5000 mg/kg Ratte (oral)).2-thiobarbituric acid; no classification known; LD 50 > 5000 mg / kg rat (oral)).
Durch die Reaktionsprodukte dieser Mischungen ist durch die vorherigeDue to the reaction products of these mixtures is due to the previous one
Rohstoffbilanzierung und die geringe Einsatzmenge keine Gefährdung oder Schädigung beim Menschen/Kfz-Insassen zu befürchten. Die nicht benutzten Mischungen sind gut mit herkömmlichen Mitteln zu entsorgen bzw. recyceln. Die erfindungsgemäßen thermischenRaw material balance and the small amount used do not fear any danger or damage to people / vehicle occupants. The unused mixtures are easy to dispose of or recycle using conventional means. The thermal according to the invention
Sicherungen sind mit anderen gaserzeugenden Mischungen oder pyrotechnischen Sätzen, z.B. Bor/Kaliumnitrat gut verträglich und können als Granulat oder Tabletten zugemischt werden oder im vorzugsweise aus Aluminium (oder Stahl) bestehenden Behältnis untergebracht sein. Die Reinheit und die Konigröße dieser Rohstoffe sowie die verschiedenen eingesetzten Mischungen der Oxidationsmittel und Brennstoffe nehmenFuses are made with other gas-generating mixtures or pyrotechnic sets, e.g. Boron / potassium nitrate well tolerated and can be mixed in as granules or tablets or housed in a container preferably made of aluminum (or steel). The purity and cone size of these raw materials as well as the various mixtures of oxidizing agents and fuels used
Einfluss auf die Zersetzungstemperatur und -art.Influence on the decomposition temperature and type.
Insbesondere die Art des Stabilisators und dessen Mischungsanteil wirkt sich auf die Langzeitstabilität und Auslösungstemperatur aus.In particular, the type of stabilizer and the proportion of its mixture affects long-term stability and the release temperature.
In pyrotechnischen Mischungen z.B. Thiohamstoff mit Kaliumchlorat zu kombinieren, ist bekannt (DE 195 05 568). Diese Mischungen erfüllen aber nicht die von der Automobilindustrie geforderten Stabilitätskriterien einer Lagerfähigkeit von 400 Stunden bei 107°C (siehe Vergleichsbeispiel 1 in Tabelle I). Erst durch die Einbindung der Reaktionskomponenten in einen temperaturbeständigen Stabilisator kann diese Stabilität erreicht werden, ohne dass die Selbstentzündungstemperatur merklich angehoben wird (WO 99/41213). Es ist demnach bekannt, Thiohamstoff mit Kaliumchlorat als Oxidationsmittel und Dicyandiamid und Celluloseacetobutyrat als Stabilisatoren zu kombinieren. Diese Mischungen erfüllen die derzeit noch von der Automobilindustrie geforderten Stabilitätskriterien einer Lagerfähigkeit von 400 Stunden bei einer Temperatur von 107°C (siehe Vergleichsbeispiele 2, 3, 4 in Tabelle I). Erst durch die erfindungsgemäße Verwendung spezieller cyclischer Thioharnstoffderivate, die mindestens eine Carbonylgruppe im Ring aufweisen, als Brennstoffe, eingebunden in einen temperaturbeständigen Stabilisator, können jedoch zukünftige erhöhte Stabilitätsanforderungen erfüllt werden.It is known to combine, for example, thiourea with potassium chlorate in pyrotechnic mixtures (DE 195 05 568). However, these mixtures do not meet the stability criteria of 400 hours at 107 ° C. required by the automotive industry (see Comparative Example 1 in Table I). This stability can only be achieved by incorporating the reaction components in a temperature-resistant stabilizer without the self-ignition temperature being noticeably increased (WO 99/41213). It is therefore known to combine thiourea with potassium chlorate as an oxidizing agent and dicyandiamide and cellulose acetobutyrate as stabilizers. These mixtures meet the stability criteria currently required by the automotive industry of a shelf life of 400 hours at a temperature of 107 ° C. (see Comparative Examples 2, 3, 4 in Table I). However, future increased stability requirements can only be met through the use of special cyclic thiourea derivatives according to the invention, which have at least one carbonyl group in the ring, as fuels, incorporated in a temperature-resistant stabilizer.
2-Thiohydantoin (1) bzw. 2-Thiobarbitursäure (2) in Kombination mit Oxidationsmitteln und geeigneten Stabilisatoren liefert ein System, das sowohl zwischen 150-230°C schlagartig stark exotherm reagiert als auch noch strengere Stabilitätskriterien erfüllt.2-thiohydantoin (1) or 2-thiobarbituric acid (2) in combination with oxidizing agents and suitable stabilizers provides a system that both suddenly reacts strongly exothermically between 150-230 ° C and meets even more stringent stability criteria.
Mit der Zugabe der Hilfsbrennstoffe (E), wie Metallpulvern von Aluminium, Zirconium, Titan, Magnesium, Zink, Eisen, usw. kann die Erzeugung von Heißpartikeln positiv beeinflusst werden. Eine andere Möglichkeit, Heißpartikel zu erzeugen - die allerdings zu Lasten der Gesamtenergie der thermischen Sicherungsmischungen geht - erfolgt durch Zumischen von Füllstoffen wie Al O3, TiO2, ZrO , Fe2O3, Si3N , Bornitrid, usw. Mit dem Einsatz von Verarbeitungshilfsmitteln (D) wie Graphit und Stearaten (insbesondere Calcium- und Magnesiumstearat) oder hochsiedenden Paraffinen steigt die Auslösetemperatur (normalerweise) an.With the addition of auxiliary fuels (E), such as metal powders of aluminum, zirconium, titanium, magnesium, zinc, iron, etc., the generation of hot particles can be positively influenced. Another way of producing hot particles - which, however, is at the expense of the total energy of the thermal fuse mixtures - is by adding fillers such as Al O 3 , TiO 2 , ZrO, Fe 2 O 3 , Si 3 N, boron nitride, etc. With the use processing aids (D) such as graphite and stearates (especially calcium and magnesium stearate) or high-boiling paraffins (usually) increase the trigger temperature.
Die nachstehenden Beispiele veranschaulichen die Erfindung, schränken sie aber nicht auf diese ein.The following examples illustrate the invention, but do not limit it thereto.
Vergleichsbeispiele 1 bis 4 und Beispiele 5, 6:Comparative Examples 1 to 4 and Examples 5, 6:
Die in Tabelle I aufgeführten gemahlenen, festen Mischungskomponenten wurden in den angegebenen Mischverhältnissen in einem Vertikalmischer vorgemischt und mittels Wasser und/oder Lösungsmittel (wie Cl-C4-Alkohole, z.B. Methanol, Ethanol, iso-/n- Propanol, n-Butanol sowie Aceton (Vergleichsbeispiel 3)) in einer Menge von 10-20 Gew.-% und ebenfalls zugesetztem Stabilisator innerhalb einer Stunde zu einer heterogenen Mischung verarbeitet. Je nach Art und Menge des Stabilisators können so ein Fertiggranulat oder ein Tablettiergranulat, die lediglich abgesiebt werden müssen, hergestellt werden; es kann aber auch eine hochviskose Mischung eingestellt werden, die sich zur Formgebung durch Strangpressen mit anschließendem Schneiden eignet. Die Herstellung der Mischungen wird durch ein- bis zweistündiges Trocknen bei 90°C abgeschlossen.The ground, solid mixture components listed in Table I were premixed in the specified mixing ratios in a vertical mixer and by means of water and / or solvents (such as Cl-C4 alcohols, for example methanol, ethanol, iso- / n-propanol, n-butanol and acetone (Comparative example 3)) in an amount of 10-20% by weight and likewise added stabilizer processed to a heterogeneous mixture within one hour. Depending on the type and amount of stabilizer, a ready-to-use granulate or a tableting granulate, which only have to be sieved, can be produced; however, a highly viscous mixture can also be set, which is suitable for shaping by extrusion with subsequent cutting. The preparation of the mixtures is completed by drying at 90 ° C. for one to two hours.
Die Bestimmung des Wärmeverhaltens mittels Differential-Scanning-Kalorimetrie (DSC- Methode) der verschiedenen Beispiele erfolgte sowohl vor der Einlagerung wie auch nach 400 Stunden bei 107°C (Vergleichsbeispiele) bzw. nach 400 Stunden bei 110°C (Beispiele). Tabelle IThe thermal behavior was determined by means of differential scanning calorimetry (DSC method) of the various examples both before storage and after 400 hours at 107 ° C. (comparative examples) or after 400 hours at 110 ° C. (examples). Table I
*^ enthält als Verarbeitungshilfsmittel Citronensäuretriethylester (Verhältnis Celluloseacteobutyrat : Citronensäuretriethylester 3:1) Aus dem Vergleich von Vergleichsbeispiel 1 mit den Vergleichsbeispielen 2 bis 4 und den Beispielen 5 und 6 wird deutlich, dass erst durch Zusatz des Stabilisators die geforderte Stabilität erfüllt wird. Die Zusammensetzung nach Vergleichsbeispiel 1 zeigte bereits nach 216 Stunden einen Gewichtsverlust von >3%. Die Zusammensetzungen der Vergleichsbeispiele 2 bis 4 zeigten nach 400 Stunden bei 107°C einen Gewichtsverlust, der zwischen 1,3 und 2,4% liegt, und erfüllen damit das derzeit geforderte Stabilitätserfordernis. Die erfindungsgemäßen Zusammensetzungen der Beispiele 5 und 6 erfüllen darüber hinaus überraschenderweise noch strengere Stabilitätskriterien. Bei einer Warmlagerung bei 110°C, d.h. bei einer gegenüber vorstehenden Anforderungen um 3°C höheren Temperatur, weisen die erfindungsgemäßen Frühzündpulver einen beträchtlich geringeren Gewichtsverlust zwischen 0,15 und 0,30% auf, der sogar nach 620 Stunden noch deutlich unter dem Gewichtsverlust der Zusammensetzungen der Vergleichsbeispiele 2 bis 4 liegt.* ^ contains processing citric acid triethyl ester (ratio cellulose acetate butyrate: citric acid triethyl ester 3: 1) It is clear from the comparison of comparative example 1 with comparative examples 2 to 4 and examples 5 and 6 that the required stability is only achieved by adding the stabilizer. The composition according to Comparative Example 1 already showed a weight loss of> 3% after 216 hours. The compositions of Comparative Examples 2 to 4 showed a weight loss of between 1.3 and 2.4% after 400 hours at 107 ° C., and thus meet the stability requirement currently required. The compositions according to the invention of Examples 5 and 6 also surprisingly meet even stricter stability criteria. When stored at 110 ° C., that is to say at a temperature 3 ° C. higher than the above requirements, the pre-ignition powders according to the invention have a considerably lower weight loss of between 0.15 and 0.30%, which is still significantly less than the weight loss even after 620 hours of the compositions of Comparative Examples 2 to 4.
Ferner liegen die Zünd- (bzw. Zersetzungs-)Temperaturen der erfindungsgemäßen Frühzündpulver sowohl vor als auch nach der thermischen Belastung in dem geforderten Bereich von 150-230°C. Die erfindungsgemäßen Zündpulver gemäß den Beispielen 5 und 6 zeigten nach 400 Stunden bei 110°C eine Veränderung der Zersetzungstemperatur zwischen 0 und 6°C. Der Zersetzungspunkt wurde mittels Differential- Scanning- Kalorimetrie (DSC-Methode) bestimmt. Die Bandbreite in der Zersetzungstemperaturbestimmung betrug bei der verwendeten Aufheizrate von 10°C/min ± 5°C. Furthermore, the ignition (or decomposition) temperatures of the pre-ignition powder according to the invention, both before and after the thermal load, are in the required range of 150-230 ° C. The ignition powders according to the invention according to Examples 5 and 6 showed a change in the decomposition temperature between 0 and 6 ° C after 400 hours at 110 ° C. The decomposition point was determined by means of differential scanning calorimetry (DSC method). The range in the decomposition temperature determination was ± 5 ° C at the heating rate of 10 ° C / min.

Claims

Patentansprüche claims
1. Frühzündpulver für eine thermische Sicherung, umfassend:1. Early ignition powder for a thermal fuse, comprising:
(A) mindestens einen Brennstoff ausgewählt aus der Gruppe bestehend aus 2-Thiohydantoin und 2-Thiobarbitursäure,(A) at least one fuel selected from the group consisting of 2-thiohydantoin and 2-thiobarbituric acid,
(B) mindestens ein Oxidationsmittel ausgewählt aus NaNO , KNO3, Sr (NO3) , NaClO3, KClO3, Sr (ClO3)2, NaClO4, KClO4, Sr(ClO4)2,(B) at least one oxidizing agent selected from NaNO, KNO 3 , Sr (NO 3 ), NaClO 3 , KClO 3 , Sr (ClO 3 ) 2 , NaClO 4 , KClO 4 , Sr (ClO 4 ) 2 ,
(C) mindestens einen Stabilisator ausgewählt aus der Gruppe bestehend aus(C) at least one stabilizer selected from the group consisting of
Cellulosederivaten, wie Celluloseether und Celluloseester, Polystyrol und Polystyrol-Copolymeren, Polyamiden, Polyacrylaten, Polycarbonaten, Polypropylenen, Polybutylenen, Polyoxymethylenen, Polyacetaten und Polyvinyl- Verbindungen.Cellulose derivatives, such as cellulose ethers and cellulose esters, polystyrene and polystyrene copolymers, polyamides, polyacrylates, polycarbonates, polypropylenes, polybutylenes, polyoxymethylenes, polyacetates and polyvinyl compounds.
2. Frühzündpulver nach Anspruch 1, wobei das Oxidationsmittel (B) ausgewählt ist aus KClO3 und KNO3 und Gemischen davon.2. Early ignition powder according to claim 1, wherein the oxidizing agent (B) is selected from KClO 3 and KNO 3 and mixtures thereof.
3. Frühzündpulver nach Anspruch 1 oder 2, wobei der Stabilisator (C) ausgewählt ist aus Celluloseacetobutyrat und Dicyandiamid und Gemischen davon.3. Early ignition powder according to claim 1 or 2, wherein the stabilizer (C) is selected from cellulose acetobutyrate and dicyandiamide and mixtures thereof.
4. Frühzündpulver nach Anspruch 1, wobei der Brennstoff (A) 2-Thiohydantoin ist, das Oxidationsmittel (B) KNO3 und/oder KClO3 ist, und der Stabilisator (C) Dicyandiamid und/oder Celluloseacetobutyrat ist. 4. Early ignition powder according to claim 1, wherein the fuel (A) is 2-thiohydantoin, the oxidizing agent (B) is KNO 3 and / or KClO 3 , and the stabilizer (C) is dicyandiamide and / or cellulose acetate butyrate.
5. Frühzündpulver nach Anspruch 1, wobei der Brennstoff (A) 2-Thiobarbitursäure ist, das Oxidationsmittel (B) KNO3 und/oder KClO3 ist, und der Stabilisator (C) Dicyandiamid und/oder Celluloseacetobutyrat ist.5. Early ignition powder according to claim 1, wherein the fuel (A) is 2-thiobarbituric acid, the oxidizing agent (B) is KNO 3 and / or KClO 3 , and the stabilizer (C) is dicyandiamide and / or cellulose acetobutyrate.
6. Fruhzundpulver nach einem der Ansprüche 1-5 des weiteren umfassend:6. Early spring powder according to one of claims 1-5 further comprising:
(D) Verarbeitungshilfsmittel ausgewählt aus Calcium- und Magnesium- stearaten, Graphit, hochsiedenden Paraffinen und Citronensäureester und Acylcitronensäureester in einer Menge von 0,5-5 und bevorzugt 0,5-3 Gewichtsteilen.(D) Processing aids selected from calcium and magnesium stearates, graphite, high-boiling paraffins and citric acid esters and acylcitric acid esters in an amount of 0.5-5 and preferably 0.5-3 parts by weight.
7. Frül zündpulver nach einem der Ansprüche 1-6 des weiteren umfassend:7. Early ignition powder according to one of claims 1-6, further comprising:
(E) Hilfsbrennstoffe, ausgewählt aus elementarem Aluminium, Zirconium, Titan, Magnesium, Zink und Eisen in einer Menge von 0,5-20, bevorzugt(E) Auxiliary fuels selected from elemental aluminum, zirconium, titanium, magnesium, zinc and iron in an amount of 0.5-20, preferably
0,5-10 und insbesondere 0,5-5 Gewichtsteilen.0.5-10 and especially 0.5-5 parts by weight.
8. Frülizündpulver nach einem der Ansprüche 1-7, des weiteren umfassend:8. Pulp ignition powder according to any one of claims 1-7, further comprising:
(F) Füllstoffe, ausgewählt aus der Gruppe von Al2O3, TiO2, ZrO2, Fe O3, Si3N4 und Bornitrid in einer Menge von 0,5-12, bevorzugt 0,5-10 und insbesondere 0,5-5 Gewichtsteilen.(F) fillers selected from the group of Al 2 O 3 , TiO 2 , ZrO 2 , Fe O 3 , Si 3 N 4 and boron nitride in an amount of 0.5-12, preferably 0.5-10 and in particular 0 , 5-5 parts by weight.
9. Frühzündpulver nach einem der Ansprüche 1-8, wobei der Stabilisator (C) Cellu- loseacetobutyrat einschließt, wobei Celluloseacetobutyrat als Verarbeitungshilfsmittel9. Early ignition powder according to any one of claims 1-8, wherein the stabilizer (C) includes cellulose acetobutyrate, with cellulose acetobutyrate as a processing aid
(D) Citronensäuretriethylester, insbesondere im Verhältnis Celluloseacetobutyrat zu Citronensäuretriethylester von etwa 3:1, enthält.(D) contains citric acid triethyl ester, in particular in the ratio of cellulose acetobutyrate to citric acid triethyl ester of about 3: 1.
10. Frühzündpulver nach einem der Ansprüche 1-9, wobei der Brennstoff (A) in einer Menge von 20-40, bevorzugt 25-35 und insbesondere 27-32 Gewichtsteilen vorliegt. 10. Early ignition powder according to one of claims 1-9, wherein the fuel (A) is present in an amount of 20-40, preferably 25-35 and in particular 27-32 parts by weight.
11. Frühzündpulver nach einem der Ansprüche 1-10, wobei das Oxidationsmittel (B) in einer Menge von 40-80, vorzugsweise 50-75 und insbesondere 60-75 Gewichtsteilen vorliegt.11. Early ignition powder according to one of claims 1-10, wherein the oxidizing agent (B) is present in an amount of 40-80, preferably 50-75 and in particular 60-75 parts by weight.
12. Frühzündpulver nach einem der Ansprüche 1-11, wobei der Stabilisator (C) in einer Menge von 0,5-20, bevorzugt 0,5-10 und insbesondere 0,5-5 Gewichtsteilen vorliegt.12. Early ignition powder according to one of claims 1-11, wherein the stabilizer (C) is present in an amount of 0.5-20, preferably 0.5-10 and in particular 0.5-5 parts by weight.
13. Verwendung eines Frühzündpulvers nach einem der Ansprüche 1 bis 12 für thermische Sicherungen für Airbag-Gasgeneratoren. 13. Use of a pre-ignition powder according to one of claims 1 to 12 for thermal fuses for airbag gas generators.
EP00945583A 2000-05-26 2000-05-26 Autoignition powders for thermal fuses used in airbag gas generators Expired - Lifetime EP1289910B8 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/DE2000/001744 WO2001090032A1 (en) 2000-05-26 2000-05-26 Rapid ignition powders for thermal temperature fuses used in airbag gas generators

Publications (3)

Publication Number Publication Date
EP1289910A1 true EP1289910A1 (en) 2003-03-12
EP1289910B1 EP1289910B1 (en) 2004-03-31
EP1289910B8 EP1289910B8 (en) 2004-05-26

Family

ID=5647716

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00945583A Expired - Lifetime EP1289910B8 (en) 2000-05-26 2000-05-26 Autoignition powders for thermal fuses used in airbag gas generators

Country Status (6)

Country Link
EP (1) EP1289910B8 (en)
JP (1) JP2003534228A (en)
AT (1) ATE263130T1 (en)
AU (1) AU2000259631A1 (en)
DE (2) DE10084823D2 (en)
WO (1) WO2001090032A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108083959A (en) * 2017-12-20 2018-05-29 湖北航鹏化学动力科技有限责任公司 A kind of reliable ignition powder composition of ignition performance and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19805976C1 (en) * 1998-02-13 1999-04-29 Nigu Chemie Gmbh Pre-ignition powder for thermal safety device for car air-bags
DE19840993B4 (en) * 1998-09-08 2006-03-09 Trw Airbag Systems Gmbh & Co. Kg Use of a gas-generating mixture as ignition mixture in a gas generator

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0190032A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108083959A (en) * 2017-12-20 2018-05-29 湖北航鹏化学动力科技有限责任公司 A kind of reliable ignition powder composition of ignition performance and preparation method thereof

Also Published As

Publication number Publication date
EP1289910B8 (en) 2004-05-26
JP2003534228A (en) 2003-11-18
DE50005943D1 (en) 2004-05-06
WO2001090032A1 (en) 2001-11-29
EP1289910B1 (en) 2004-03-31
ATE263130T1 (en) 2004-04-15
AU2000259631A1 (en) 2001-12-03
DE10084823D2 (en) 2003-04-30

Similar Documents

Publication Publication Date Title
DE69423626T2 (en) GAS-GENERATING RESIDUE-FREE AZID-FREE COMPOSITION
EP0949225B1 (en) Non-azide gas generating composition
DE69424041T2 (en) IGNITION COMPOSITIONS FOR AIRBAG GAS GENERATORS
DE69103720T2 (en) Primer composition for gas inflator.
DE19805976C1 (en) Pre-ignition powder for thermal safety device for car air-bags
JP2002512167A (en) Pyrotechnic gas generant composition with high oxygen balance fuel
DE112006000826T5 (en) Gas generating compositions
DE19742203A1 (en) Particle-free gas-generating mixture
US5936195A (en) Gas generating composition with exploded aluminum powder
DE112006002030T5 (en) Ignition / booster composition
US20070181236A1 (en) Gas-generating pyrotechnical compositions and pyrotechnical compounds for automotive safety
EP0914305B2 (en) Temperature fuse
EP1162183B1 (en) Ignition mixture for use in gas generators
US6453816B2 (en) Temperature fuse with lower detonation point
DE20121826U1 (en) Self-igniting composition for gas developers
DE19643468A1 (en) Gas-generating, azide-free solid mixture
EP1289910B1 (en) Rapid ignition powders for thermal temperature fuses used in airbag gas generators
EP1171404B1 (en) Gas-generating substances
EP1064242B1 (en) Propellants for gas generator
DE112007001437T5 (en) Thermally initiated pyrotechnic compositions, use
DE202004009449U1 (en) Gas generating composition
US20060075681A1 (en) Pyrotechnic composition
DE102004057770B4 (en) Pyrotechnic composition for use as a preignition agent
CZ296114B6 (en) Rapid ignition powder for thermal fuses used in airbag gas generators
US10919818B1 (en) Auto-ignition 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

17P Request for examination filed

Effective date: 20021011

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: RECKER, CHRISTIAN

Inventor name: SCHMID, BERNHARD

Inventor name: SEMMLER, PETER

Inventor name: GAST, EDUARD

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040331

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20040331

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040331

Ref country code: GB

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040331

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040331

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040331

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

Ref country code: CH

Ref legal event code: EP

RTI2 Title (correction)

Free format text: AUTOIGNITION POWDERS FOR THERMAL FUSES USED IN AIRBAG GAS GENERATORS

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REF Corresponds to:

Ref document number: 50005943

Country of ref document: DE

Date of ref document: 20040506

Kind code of ref document: P

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

Ref country code: FR

Payment date: 20040510

Year of fee payment: 5

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

Ref country code: AT

Payment date: 20040512

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040531

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040531

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040531

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040531

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

Ref country code: DE

Payment date: 20040603

Year of fee payment: 5

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040630

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040630

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040712

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20040331

GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 20040331

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
BERE Be: lapsed

Owner name: NIGU CHEMIE G.M.B.H.

Effective date: 20040531

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

ET Fr: translation filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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: 20050104

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060131

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20060131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040831