EP1289910B1 - Poudres a allumage precoce pour dispositifs de securite thermiques de generateurs de gaz d'airbags - Google Patents

Poudres a allumage precoce pour dispositifs de securite thermiques de generateurs de gaz d'airbags Download PDF

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Publication number
EP1289910B1
EP1289910B1 EP00945583A EP00945583A EP1289910B1 EP 1289910 B1 EP1289910 B1 EP 1289910B1 EP 00945583 A EP00945583 A EP 00945583A EP 00945583 A EP00945583 A EP 00945583A EP 1289910 B1 EP1289910 B1 EP 1289910B1
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EP
European Patent Office
Prior art keywords
composition according
amount
autoignition composition
parts per
per weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00945583A
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German (de)
English (en)
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EP1289910B8 (fr
EP1289910A1 (fr
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
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Nigu Chemie GmbH
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Publication of EP1289910B1 publication Critical patent/EP1289910B1/fr
Publication of EP1289910B8 publication Critical patent/EP1289910B8/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 the form of granules (0.1 to 0.5 g), which ignites between 150 ° C. and 230 ° C. and contains 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 the form of granules (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 currently demanded 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 well below the critical temperature and which do not have the disadvantages of nitrocellulose.
  • Compounds which are selected from the 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-1,2,4-triazol-5-one (NTO), 5-aminotetrazole nitrate, Nitroguanidine (NIGU), guanidine nitrate or bistrazolamine can be used.
  • the oxidizable components given above are mentioned as examples of fuels.
  • Metal powder preferably titanium powder, can be used as the reducing agent, for example.
  • 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.
  • 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 processing aids, auxiliary fuels and fillers.
  • the fuel is selected from the group consisting of thiourea and its derivatives, such as N, N'-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 warm 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).
  • 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, in addition to conventional polyamides, 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) can optionally be contained 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 safeguards 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)).
  • the reaction products of these mixtures mean that there is no danger or damage to humans / vehicle occupants due to the previous raw material balance and the small amount used.
  • the unused mixtures are easy to dispose of or recycle using conventional means.
  • the thermal fuses according to the invention are well compatible with other gas-generating mixtures or pyrotechnic compositions, for example boron / potassium nitrate, and can be mixed in as granules or tablets or can be accommodated in a container preferably made of aluminum (or steel).
  • the purity and the grain size of these raw materials as well as the various mixtures of oxidizing agents and fuels used influence the decomposition temperature and type.
  • 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 reacts suddenly and strongly between 150-230 ° C and meets even stricter 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 to add fillers such as Al 2 O 3 , TiO 2 , ZrO 2 , Fe 2 O 3 , Si 3 N 4 , boron nitride, etc.
  • processing aids (D) such as graphite and stearates (especially calcium and magnesium stearate) or high-boiling paraffins, the release temperature increases (normally).
  • 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 C1-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).
  • the pre-ignition powders according to the invention have a considerably lower weight loss of between 0.15 and 0.30%, which even after 620 hours is still significantly less than the weight loss of the compositions of Comparative Examples 2 to 4.
  • the ignition (or decomposition) temperatures of the pre-ignition powders according to the invention are in the required range of 150-230 ° C. both before and after the thermal load.
  • 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)

Claims (13)

  1. Poudre à allumage précoce pour un dispositif de sécurité thermique, comprenant :
    (A) au moins un carburant sélectionné au sein du groupe constitué de 2-thiohydantoïne et d'acide 2-thiobarbiturique, en quantité de 20 à 40 parties pondérales ;
    (B) au moins un agent d'oxydation, sélectionné parmi le NaNO3, le KNO3, le Sr(NO3)2, le NaClO3, le KClO3, le Sr(ClO3)2, le NaClO4, le KClO4, le Sr(ClO4)2, en quantité de 40 à 80 parties pondérales ;
    (C) au moins un stabilisateur sélectionné au sein du groupe constitué des dérivés de cellulose (notamment éthers de cellulose et esters de cellulose), du polystyrol et des copolymères de polystyrol, des polyamides, des polyacrylates, des polycarbonates, des polypropylènes, des polybutylènes, des polyoxyméthylènes, des polyacétates et des composés de polyvinyle, en quantité de 0,5 à 20 parties pondérales.
  2. Poudre à allumage précoce selon la revendication 1, dans laquelle l'agent d'oxydation (B) est sélectionné parmi le KClO3, le KNO3 et leurs mélanges.
  3. Poudre à allumage précoce selon la revendication 1, dans laquelle le stabilisateur (C) est sélectionné parmi l'acétobutyrate de cellulose, le dicyandiamide et leurs mélanges.
  4. Poudre à allumage précoce selon la revendication 1, dans laquelle le carburant (A) est la 2-thiohydantoïne, l'agent d'oxydation (B) est le KNO3 et/ou le KClO3, et le stabilisateur (C) est le dicyandiamide et/ou l'acétobutyrate de cellulose.
  5. Poudre à allumage précoce selon la revendication 1, dans laquelle le carburant (A) est la l'acide 2-thiobarbiturique, l'agent d'oxydation (B) est le KNO3 et/ou le KClO3, et le stabilisateur (C) est le dicyandiamide et/ou l'acétobutyrate de cellulose.
  6. Poudre à allumage précoce selon l'une des revendications 1 à 5, comprenant en outre :
    (D) des adjuvants de traitement sélectionnés parmi les stéarates de calcium et de magnésium, graphite, les paraffines à point d'ébullition élevé, les esters d'acide citrique et les esters d'acide acylcitrique, en quantité de 0,5 à 5, et de préférence de 0,5 à 3, parties pondérales.
  7. Poudre à allumage précoce selon l'une des revendications 1 à 6, comprenant en outre :
    (E) des carburants auxiliaires sélectionnés parmi l'aluminium, le zirconium, le titane, le magnésium, le zinc et le fer, à l'état élémentaire, en quantité de 0,5 à 20, de préférence de 0,5 à 10, et plus particulièrement de 0,5 à 5, parties pondérales.
  8. Poudre à allumage précoce selon l'une des revendications 1 à 7, comprenant en outre :
    (F) des matières de remplissage sélectionnées au sein du groupe constitué de l'Al2O3, du TiO2, du ZrO2, du Fe2O3, du Si3N4 et du nitrure de bore, en quantité de 0,5 à 12, de préférence de 0,5 à 10, et plus particulièrement de 0,5 à 5, parties pondérales.
  9. Poudre à allumage précoce selon l'une des revendications 1 à 8, dans laquelle le stabilisateur (C) comprend l'acétobutyrate de cellulose, lequel contient comme agent de traitement (D) le triéthylester d'acide citrique, en particulier selon un rapport d'environ 3 : 1 entre l'acétobutyrate de cellulose et le triéthylester d'acide citrique.
  10. Poudre à allumage précoce selon l'une des revendications 1 à 9, dans laquelle le carburant (A) est contenu en quantité de 25 à 35, et plus particulièrement de 27 à 32, parties pondérales.
  11. Poudre à allumage précoce selon l'une des revendications 1 à 10, dans laquelle l'agent d'oxydation (B) est contenu en quantité de 50 à 75, et plus particulièrement de 60 à 75, parties pondérales.
  12. Poudre à allumage précoce selon l'une des revendications 1 à 11, dans laquelle le stabilisateur (C) est contenu en quantité de 0,5 à 10, et plus particulièrement de 0,5 à 5, parties pondérales.
  13. Poudre à allumage précoce selon l'une des revendications 1 à 12, pour dispositifs de sécurité thermiques pour générateurs de gaz d'airbags.
EP00945583A 2000-05-26 2000-05-26 Poudres a allumage precoce pour dispositifs de securite thermiques de generateurs de gaz d'airbags Expired - Lifetime EP1289910B8 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/DE2000/001744 WO2001090032A1 (fr) 2000-05-26 2000-05-26 Poudres a allumage precoce pour dispositifs de securite thermiques de generateurs de gaz d'airbags

Publications (3)

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

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EP00945583A Expired - Lifetime EP1289910B8 (fr) 2000-05-26 2000-05-26 Poudres a allumage precoce pour dispositifs de securite thermiques de generateurs de gaz d'airbags

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EP (1) EP1289910B8 (fr)
JP (1) JP2003534228A (fr)
AT (1) ATE263130T1 (fr)
AU (1) AU2000259631A1 (fr)
DE (2) DE50005943D1 (fr)
WO (1) WO2001090032A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108083959A (zh) * 2017-12-20 2018-05-29 湖北航鹏化学动力科技有限责任公司 一种点火性能可靠的点火药剂组合物及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19805976C1 (de) * 1998-02-13 1999-04-29 Nigu Chemie Gmbh Frühzündpulver für thermische Sicherungen für Airbag-Gasgeneratoren
DE19840993B4 (de) * 1998-09-08 2006-03-09 Trw Airbag Systems Gmbh & Co. Kg Verwendung eines gaserzeugenden Gemisches als Anzündmischung in einem Gasgenerator

Also Published As

Publication number Publication date
WO2001090032A1 (fr) 2001-11-29
AU2000259631A1 (en) 2001-12-03
EP1289910B8 (fr) 2004-05-26
EP1289910A1 (fr) 2003-03-12
JP2003534228A (ja) 2003-11-18
ATE263130T1 (de) 2004-04-15
DE50005943D1 (de) 2004-05-06
DE10084823D2 (de) 2003-04-30

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