EP1036781A1 - Composition servant a generer un gaz pour sac gonflable avec une quantite limitee de residus - Google Patents

Composition servant a generer un gaz pour sac gonflable avec une quantite limitee de residus Download PDF

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Publication number
EP1036781A1
EP1036781A1 EP98907271A EP98907271A EP1036781A1 EP 1036781 A1 EP1036781 A1 EP 1036781A1 EP 98907271 A EP98907271 A EP 98907271A EP 98907271 A EP98907271 A EP 98907271A EP 1036781 A1 EP1036781 A1 EP 1036781A1
Authority
EP
European Patent Office
Prior art keywords
gas generating
potassium
generating composition
weight
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98907271A
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German (de)
English (en)
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EP1036781A4 (fr
Inventor
Xingxi Zhou
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.)
Daicel Corp
Original Assignee
Daicel Chemical Industries Ltd
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Filing date
Publication date
Application filed by Daicel Chemical Industries Ltd filed Critical Daicel Chemical Industries Ltd
Publication of EP1036781A1 publication Critical patent/EP1036781A1/fr
Publication of EP1036781A4 publication Critical patent/EP1036781A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06DMEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06DMEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

  • the present invention concerns a gas generating composition for use in an air bag. More specifically, it relates to a gas generating composition with less residues for use in an air bag which forms an operation gas in an air bag system mounted in traffic facilities such as automobiles and used for protecting passengers.
  • gas generating base agents used generally for air bag systems include inorganic azide compounds, particularly, sodium azide.
  • Compositions comprising such inorganic azide compounds have no particular problems in view of burning characteristics and are generally put to practical use at present.
  • sodium azide essentially has various undesired properties. For example, it is an extremely toxic substance and, further, sodium azide readily reacts with a heavy metal such as copper or lead to form a highly sensitive compound tending to cause abrupt ignition or explosion. Accordingly, a special handling is required for production, storage and disposal of such compositions.
  • JP-A 3-208878 discloses a composition comprising, as essential ingredients, tetrazole, triazole or a metal salt thereof and an oxygen-containing oxidizer such as an alkali metal nitrate.
  • an oxygen-containing oxidizer such as an alkali metal nitrate.
  • a gas generating agent comprising a phase stabilized ammonium nitrate (PSAN) and nitrogen-containing compound such as triaminoguanidine nitrate is disclosed in the specification of WO95/04710. Further, a gas generating agent comprising a mixture of ammonium nitrate phase-stabilized with 7 to 20% by weight of a potassium salt and nitroguanidine is disclosed in US-A 5,545,272 and WO96/27574. Such compositions enable to increase the gas generating efficiency upon burning to a high level. However, heat of combustion is rather great and theoretical combustion temperature exceeds 2500K, and CO and NO x gases at high concentrations are generated.
  • PSAN phase stabilized ammonium nitrate
  • nitrogen-containing compound such as triaminoguanidine nitrate
  • Nitrogen-containing compounds have a drawback that the heat of combustion is greater and the combustion temperature is higher compared with those of azide compounds in general combustion, when using an oxidizer in a stoichiometrical amount, that is, in an amount sufficient to form oxygen required for burning of carbon, hydrogen and other elements in the compound.
  • an oxidizer in a stoichiometrical amount, that is, in an amount sufficient to form oxygen required for burning of carbon, hydrogen and other elements in the compound.
  • a metal compound for example, metal oxide
  • solid and liquid particles formed discharged from a gas generator may hit directly against a bag to possibly break the bag.
  • the present invention provides a gas generating composition which generates less residues and a great amount of gases by combustion for inflating an air bag suitable to various purposes including the use as a shock absorbing safety bag for traffic facilities such as automobiles, wherein the composition comprises an oxidizer comprising a mixture comprising a phase stabilized ammonium nitrate (PSAN) and nitroguanidine as essential ingredients and the content of nitroguanidine in the composition is 35% by weight or less.
  • PSAN phase stabilized ammonium nitrate
  • the amount of residues generated is decreased compared with gas generating compositions disclosed so far and the use of the gas generating composition according to the present invention can remarkably decrease the number and the amount of additional parts for removing residues, to make way to the downsize of a gas generator itself.
  • the gas generating composition according to the present invention suppresses the formation of solid residues as much as possible thereby enabling to remarkably decrease the number and the amount of additional parts compared with conventional gas generators, by utilizing the features that ammonium nitrate is entirely converted into non corrosive gases without forming solid residues upon combustion and generating no corrosive gases such as chlorine and hydrogen chloride.
  • the combustion temperature can be lowered by about 150 to 300K and the heat of combustion can also be reduced to some extent compared with the existent compositions, by defining the content of nitroguanidine to 35% by weight or less, preferably, 5 to 33% by weight in the composition. Lowering of the combustion temperature is advantageous for decreasing toxic CO and NO x gases. Further, low combustion temperature and less heat of combustion are also advantageous for reducing additional parts in a gas generator.
  • Table 1 shows the result of theoretical calculation for the combustion temperature and the heat of combustion with respect to the composition of the present invention in which nitroguanidine is blended by 35% by weight or less and an conventional composition.
  • PSANKP10 indicates a phase stabilized ammonium nitrate comprising 90% by weight of ammonium nitrate and 10% by weight of potassium perchlorate and NQ indicates nitroguanidine.
  • Pure ammonium nitrate causes phase transition with about 3% volumic change when passing a temperature of 32°C.
  • Great volumic change of a molding product may possibly cause occurrence of abnormal combustion or burning which is not desirable for a gas generating agent. Accordingly, a phase stabilized ammonium nitrate is used in the present invention.
  • phase stabilized ammonium nitrate used in the present invention, a mixture of 98 to 70% by weight of ammonium nitrate and 2 to 30% by weight of a phase stabilizer is preferred. It has been known generally to stabilize the phase of ammonium nitrate, for example, by introducing potassium cations into crystal lattices of ammonium nitrate. In the present invention, it is preferred to use at least one compound selected from the group consisting of organic or inorganic potassium salts being soluble in hot water. Phase transition of ammonium nitrate can be prevented by blending a phase stabilizer in an amount of 2% by weight or more in the phase stabilized ammonium nitrate. However, since an excessive blending amount of the phase stabilizer is disadvantageous for the purpose of decreasing solid residues, the blending amount of the phase stabilizer in the phase stabilized ammonium nitrate is preferably about from 2 to 30% by weight.
  • the organic or inorganic potassium salts being soluble in hot water used as the phase stabilizer in the present invention can include at least one compound selected from the group consisting of potassium nitrate, potassium perchlorate, potassium sulfate, potassium chloride, potassium chlorate, potassium chromate, potassium bichromate, potassium permanganate and potassium oxalate.
  • the gas generating composition according to the present invention comprises an oxidizer comprising a mixture comprising the phase stabilized ammonium nitrate, and the oxidizer according to the present invention is preferably blended with an oxygen-containing oxidizer, a metal oxide or a mixture thereof in addition to the phase stabilized ammonium nitrate.
  • the oxygen-containing oxidizer used in the present invention can include, for example, at least one compound selected from the group consisting of alkali metal salts, alkaline earth metal salts and ammonium salts of nitric acid, perchloric acid and chloric acid and, specifically, they include potassium perchlorate, ammonium perchlorate, potassium chlorate, potassium nitrate, sodium nitrate and strontium nitrate.
  • the metal oxide used in the present invention can include oxides or composite oxides of metals selected from the group consisting of copper, cobalt, iron, manganese, nickel, chromium, zinc, molybdenum and bismuth.
  • the blending amount of the phase stabilized ammonium nitrate in the composition of the present invention is preferably from 60 to 85% by weight. Further, the blending amount of the oxygen-containing oxidizer, metal oxide or a mixture thereof in the composition according to the present invention is preferably from 0 to 25% by weight.
  • a combustion rate accelerating catalyst is preferably blended for accelerating the combustion rate.
  • the combustion rate accelerating catalyst used in the present invention can include at least one compound selected from the group consisting of powdery copper, copper compounds, iron compounds, nickel compounds and chromium compounds.
  • the copper compound used in the present invention can include, for example, copper oxide and copper chromite
  • the iron compound can include, for example, iron oxide, ferrocene and a derivative thereof
  • the nickel compound can include, for example, nickel oxide and tire chromium compound can include, for example, chromium oxide, ammonium bichromate and potassium bichromate.
  • the blending amount of the combustion rate accelerating catalyst in the composition according to the present invention is preferably 10% by weight or less.
  • the combustion rate of the composition can be selected properly within a wide range by blending the oxygen-containing oxidizer, the metal oxide or the combustion rate accelerating catalyst as described above. Further, the shape, the grain size and the like of the oxidizer or the catalyst can be selected properly.
  • the gas generating composition according to the present invention can comprise an organic or inorganic binder by 20% by weight or less for forming and maintaining a molding product.
  • a powdery mixture can be molded into a molding product by the addition of such organic or inorganic binder.
  • organic or inorganic binder can include organic binders such as sodium salt of carboxymethyl cellulose, cellulose acetate, starch, polyvinyl alcohol and sodium polyacrylate, and inorganic binders such as sodium silicate, bentonite, glass fiber and silicon rubber.
  • the amount of the binder used is preferably 20% by weight or less since use of an excessive amount deteriorates the performance of the gas generating agent. Further, it has been well-known that combustion behavior of the gas generating agent essentially undergoes the effect of a geometrical structure of a molding product in combustion, and the gas generating composition of the present invention may be molded into an optimal geometrical structure depending on the composition selected, with no particular restriction.
  • a solution prepared by dissolving a mixture of 90% of ammonium nitrate (AN) and 10% of potassium perchlorate (KClO 4 ) under stirring into a sufficient amount of distilled water was put in a heat drier at about 85°C (preferably under reduced pressure) to evaporate water. After evaporation of most of water, formed solids were distributed thinly on a stainless steel tray and dried thoroughly at about 85°C. Drying products were collected and ground in a mortar so as to pass a 300 ⁇ m sieve. It was confirmed if the phase stabilized ammonium (PSAN) was formed or not and whether it was homogeneous or not by detecting thermally varying peaks and the content of ammonium nitrate of products by TG-DTA.
  • PSAN phase stabilized ammonium
  • the strand was coated with a non-combustible epoxy type resin.
  • the combustion rate was measured under a nitrogen pressure of 70 kg/cm 2 , the strand showed a combustion rate of 7.6 mm/s.
  • the composition showed a theoretical combustion temperature of 2158K and a theoretical residue (amount of metal compound formed per 100 g of composition) of 3.8 g.
  • the composition showed a theoretical combustion temperature of 2151K and the theoretical amount of residues was 4.1 g.
  • the composition showed a theoretical combustion temperature of 2435K and the theoretical amount of residue was 4.8 g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Air Bags (AREA)
EP98907271A 1997-03-21 1998-03-17 Composition servant a generer un gaz pour sac gonflable avec une quantite limitee de residus Withdrawn EP1036781A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP6768797 1997-03-21
JP06768797A JP3641343B2 (ja) 1997-03-21 1997-03-21 低残渣エアバッグ用ガス発生剤組成物
PCT/JP1998/001125 WO1998042641A1 (fr) 1997-03-21 1998-03-17 Composition servant a generer un gaz pour sac gonflable avec une quantite limitee de residus

Publications (2)

Publication Number Publication Date
EP1036781A1 true EP1036781A1 (fr) 2000-09-20
EP1036781A4 EP1036781A4 (fr) 2000-09-20

Family

ID=13352159

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98907271A Withdrawn EP1036781A4 (fr) 1997-03-21 1998-03-17 Composition servant a generer un gaz pour sac gonflable avec une quantite limitee de residus

Country Status (6)

Country Link
EP (1) EP1036781A4 (fr)
JP (1) JP3641343B2 (fr)
KR (1) KR20000076253A (fr)
CN (1) CN1250429A (fr)
TW (1) TW495496B (fr)
WO (1) WO1998042641A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0915813A1 (fr) * 1996-07-29 1999-05-19 Automotive Systems Laboratory Inc. Gaz propulseurs thermostables non-azide pour coussins gonflables de securite pour automobiles
EP2399884A2 (fr) * 2000-10-10 2011-12-28 Nippon Kayaku Kabushiki Kaisha Composition d'agent de génération de gaz, et générateur de gaz fonctionnant avec cette composition
CN113087582A (zh) * 2021-03-31 2021-07-09 陕西庆华汽车安全系统有限公司 一种含有硝基胍的安全气囊用产气药的生产方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6872265B2 (en) * 2003-01-30 2005-03-29 Autoliv Asp, Inc. Phase-stabilized ammonium nitrate
JP5031255B2 (ja) * 2006-03-02 2012-09-19 株式会社ダイセル ガス発生剤組成物
JP2009137820A (ja) 2007-12-11 2009-06-25 Daicel Chem Ind Ltd インフレータ用ゲル状伝火薬
CN102584504A (zh) * 2012-01-16 2012-07-18 南京理工大学 一种改善点火能力的无烟型礼花弹用开苞药及其制备方法
CN106478323A (zh) * 2016-10-21 2017-03-08 重庆大学 一种高性能电控固体推进剂及其制备方法
CN111517899B (zh) * 2020-06-28 2021-10-01 上海集瀛汽车安全技术有限公司 一种高燃速型微型气体发生器用气体发生剂及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE884170C (de) * 1946-11-08 1953-07-23 Ici Ltd Gaserzeugende Ladung
EP0519485A1 (fr) * 1991-06-21 1992-12-23 Dynamit Nobel Aktiengesellschaft Propellent pour générateurs de gaz
DE9416112U1 (de) * 1993-10-06 1994-12-15 Contec - Chemieanlagen GmbH, 84544 Aschau Gasgeneratortreibstoff
DE4411654A1 (de) * 1993-10-20 1995-04-27 Temic Bayern Chem Airbag Gmbh Gaserzeugendes Gemisch
WO1996025375A1 (fr) * 1995-02-16 1996-08-22 Royal Ordnance Plc Systemes automatiques de retenue d'un occupant de vehicule, actionnes par des compositions produisant du gaz
WO1996027574A1 (fr) * 1995-03-03 1996-09-12 Primex Technologies, Inc. Composition gazogene thermostable

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2692257B1 (fr) * 1992-06-12 1995-05-05 Divbag Snc Composition pyrotechnique génératrice de gaz chauds non toxiques et son utilisation dans un dispositif de protection des occupants d'un véhicule automobile.
FR2713632B1 (fr) * 1993-12-07 1996-01-12 Poudres & Explosifs Ste Nale Compositions pyrotechniques génératrices de gaz propres et non toxiques, contenant un liant élastomère thermoplastique.
US5545272A (en) * 1995-03-03 1996-08-13 Olin Corporation Thermally stable gas generating composition
US6306232B1 (en) * 1996-07-29 2001-10-23 Automotive Systems Laboratory, Inc. Thermally stable nonazide automotive airbag propellants

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE884170C (de) * 1946-11-08 1953-07-23 Ici Ltd Gaserzeugende Ladung
EP0519485A1 (fr) * 1991-06-21 1992-12-23 Dynamit Nobel Aktiengesellschaft Propellent pour générateurs de gaz
DE9416112U1 (de) * 1993-10-06 1994-12-15 Contec - Chemieanlagen GmbH, 84544 Aschau Gasgeneratortreibstoff
DE4411654A1 (de) * 1993-10-20 1995-04-27 Temic Bayern Chem Airbag Gmbh Gaserzeugendes Gemisch
WO1996025375A1 (fr) * 1995-02-16 1996-08-22 Royal Ordnance Plc Systemes automatiques de retenue d'un occupant de vehicule, actionnes par des compositions produisant du gaz
WO1996027574A1 (fr) * 1995-03-03 1996-09-12 Primex Technologies, Inc. Composition gazogene thermostable

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9842641A1 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0915813A1 (fr) * 1996-07-29 1999-05-19 Automotive Systems Laboratory Inc. Gaz propulseurs thermostables non-azide pour coussins gonflables de securite pour automobiles
EP0915813A4 (fr) * 1996-07-29 2003-04-02 Automotive Systems Lab Gaz propulseurs thermostables non-azide pour coussins gonflables de securite pour automobiles
EP2399884A2 (fr) * 2000-10-10 2011-12-28 Nippon Kayaku Kabushiki Kaisha Composition d'agent de génération de gaz, et générateur de gaz fonctionnant avec cette composition
EP2399884A3 (fr) * 2000-10-10 2012-01-18 Nippon Kayaku Kabushiki Kaisha Composition d'agent de génération de gaz, et générateur de gaz fonctionnant avec cette composition
CN113087582A (zh) * 2021-03-31 2021-07-09 陕西庆华汽车安全系统有限公司 一种含有硝基胍的安全气囊用产气药的生产方法

Also Published As

Publication number Publication date
KR20000076253A (ko) 2000-12-26
WO1998042641A1 (fr) 1998-10-01
EP1036781A4 (fr) 2000-09-20
TW495496B (en) 2002-07-21
JPH10259085A (ja) 1998-09-29
CN1250429A (zh) 2000-04-12
JP3641343B2 (ja) 2005-04-20

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