EP1195367A1 - Composition generatrice de gaz - Google Patents
Composition generatrice de gaz Download PDFInfo
- Publication number
- EP1195367A1 EP1195367A1 EP00921099A EP00921099A EP1195367A1 EP 1195367 A1 EP1195367 A1 EP 1195367A1 EP 00921099 A EP00921099 A EP 00921099A EP 00921099 A EP00921099 A EP 00921099A EP 1195367 A1 EP1195367 A1 EP 1195367A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- basic
- gas generating
- nitrate
- bitetrazole
- salt
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
Definitions
- the present invention relates to a gas generating composition which is suitable for an air bag restraining system of automobiles or the like, its molded article and an inflator for an air bag using the same.
- US-A 4,909,549 discloses a composition comprising hydrogen-containing tetrazole and triazole compounds and an oxygen-containing oxidizing agent.
- US-A 4,370,181 discloses a gas generating composition comprising a hydrogen-free bitetrazole metal salt and an oxygen-free oxidizing agent.
- US-A 4,369,079 discloses a gas generating composition comprising a hydrogen-free bitetrazole metal salt and an alkali metal nitrate, an alkali metal nitrite, an alkaline earth metal nitrate, an alkaline earth metal nitrite or a mixture thereof.
- US-A 5, 542, 999 discloses a gas generating agent comprising a fuel such as GZT, TAGN, NG (nitroguanidine), NTO or the like, a basic copper nitrate, a catalyst for reducing toxic gases and a coolant.
- JP-A 10-72,273 discloses a gas generating composition comprising a bitetrazole metal salt, a bitetrazole ammonium salt or aminotetrazole and ammonium nitrate.
- the non-azide based gas generating composition is problematic in a combustion temperature, a burning rate, phase transfer, amounts of generated carbon monoxide and nitrogen oxides, a gas output and the like.
- the gas generating composition of US-A 4,369,079 has a high combustion temperature, and requires a large amount of a coolant in actual use.
- the composition of US-A 5,542,999 has a low burning rate, and might not be completely burned in a short time.
- a shape is changed due to phase transfer of ammonium nitrate in the range of the use temperature, which damages a molded article of the gas generating agent, and in result, stable combustion cannot be conducted.
- an object of the invention is to provide a gas generating composition which has a low combustion temperature, a high burning rate, small amounts of generated carbon monoxide and nitrogen oxides and an excellent combustion stability, its molded article and an inflator for an air bag using the same.
- the invention provides a gas generating composition
- a gas generating composition comprising (a) a bitetrazole compound as a fuel and (b) a basic metal nitrate as an oxidizing agent.
- the invention provides a gas generating composition
- a gas generating composition comprising (a) a bitetrazole compound as a fuel, (b) a basic metal nitrate as an oxidizing agent and (c) a binder and/or a slag-forming agent.
- the invention provides a molded article in the form of a single-perforated cylinder, a perforated (porous) cylinder or pellets, the molded article being obtained from the gas generating composition.
- the invention provides an inflator for an air bag using the gas generating composition and the molded article.
- the gas generating composition and its molded article of the invention are easy to handle because of a low toxicity and less hazard, and have a high burning rate and a low combustion temperature. Further, amounts of generated carbon monoxide and nitrogen oxides are reduced in the combustion.
- the bitetrazole compound being a fuel as component (a) which is used in the invention is preferable because the content of the nitrogen atom in a molecule is high, the toxicity is low and the burning rate is increased in combination with component (b).
- the bitetrazole compound at least one selected from metal salts of bitetrazole such as a potassium salt of bitetrazole, a sodium salt of bitetrazole, a magnesium salt of bitetrazole, a calcium salt of bitetrazole and a copper salt of bitetrazole, an ammonium salt of bitetrazole and a melamine salt of bitetrazole is proposed.
- metal salts of bitetrazole such as a potassium salt of bitetrazole, a sodium salt of bitetrazole, a magnesium salt of bitetrazole, a calcium salt of bitetrazole and a copper salt of bitetrazole, an ammonium salt of bitetrazole and a melamine salt of bitetrazole is proposed.
- an ammonium salt of bitetrazole is preferable because the content of the nitrogen atom is 81.4 % by weight, LD 50 (oral-rat) is 2,000 mg/kg and the combustion efficiency is good.
- the bitetrazole compound here includes 5-5' compounds and 1-5' compounds
- the basic metal nitrate being an oxidizing agent as component (b) which is used in the invention
- at least one selected from a basic copper nitrate, a basic cobalt nitrate, a basic zinc nitrate, a basic manganese nitrate, a basic iron nitrate, a basic molybdenum nitrate, a basic bismuth nitrate and a basic cerium nitrate is proposed.
- a basic copper nitrate is preferable.
- the basic copper nitrate is excellent in thermal stability, as compared with ammonium nitrate as an oxidizing agent, because no phase transfer occurs in the range of the use temperature and the melting point is high. Further, since the basic copper nitrate acts to decrease a combustion temperature of a gas generating agent, amounts of generated nitrogen oxides can be decreased.
- the gas generating composition of the invention is a two-component-type composition comprising components (a) and (b), the contents of the components are as follows.
- the content of component (a) is preferably 5 to 60 % by weight, more preferably 15 to 55 % by weight.
- the content of component (b) is preferably 40 to 95 % by weight, more preferably 45 to 85 % by weight.
- a preferable example of the two-component-type gas generating composition is a composition comprising 15 to 35 % by weight of ammonium bitetrazole as component (a) and 65 to 85 % by weight of a basic copper nitrate as component (b).
- the binder and/or the slag-forming agent as component (c) used in the invention at least one selected from carboxymethylcellulose (CMC), sodium carboxymethylcellulose (CMCNa), a potassium salt of carboxymethylcellulose, an ammonium salt of carboxymethylcellulose, cellulose acetate, cellulose acetatebutyrate (CAB), methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), ethylhydroxyethyl cellulose (EHEC), hydroxypropyl cellulose (HPC), carboxymethylethyl cellulose (CMEC), fine crystalline cellulose, polyacrylic amide, amine products of polyacrylic amide, polyacrylic hydrazide, a copolymer of an acrylic amide and a metal salt of acrylic acid, a copolymer of polyacrylic amide and polyacrylic ester, polyvinyl alcohol, acrylic rubber, guar gum, starch, silicone, molybdenum disulfide,
- a metal oxide being component (c) at least one selected from copper oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide and bismuth oxide is proposed.
- a metal hydroxide at least one selected from cobalt hydroxide and aluminum hydroxide is proposed.
- a metal carbonate and a basic metal carbonate at least one selected from calcium carbonate, cobalt carbonate, a basic zinc carbonate, a basic copper carbonate, a basic cobalt carbonate, a basic iron carbonate, a basic bismuth carbonate and a basic magnesium carbonate is proposed.
- a molybdate at least one selected from cobalt molybdate and ammonium molybdate is proposed.
- a sodium salt of carboxymethylcellulose and a potassium salt of carboxymethylcellulose are preferable.
- a sodium salt of carboxymethylcellulose is more preferable.
- the gas generating composition of the invention is a three-component-type composition comprising components (a) to (c), the contents of the components are as follows.
- the content of component (a) is preferably 5 to 60 % by weight, more preferably 15 to 55 % by weight.
- the content of component (b) is preferably 40 to 95 % by weight, more preferably 45 to 85 % by weight.
- the content of component (c) is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight in total of components (a) and (b).
- a preferable example of the three-component-type gas generating composition is a composition comprising 15 to 35 % by weight of an ammonium salt of bitetrazole as component (a), 65 to 85 % by weight of a basic copper nitrate as component (b) and 0.5 to 10 parts by weight, per 100 parts by weight in total of components (a) and (b), of a sodium salt of carboxymethylcellulose as component (c).
- the gas generating composition of the invention can be molded in a desired shape, and formed into a molded article in the shape of a single-perforated cylinder, a perforated (porous) cylinder or a pellet.
- These molded articles can be produced by a method in which the gas generating composition is added to and mixed with water or an organic solvent and the mixture is extrusion-molded (molded articles in the form of a single-perforated cylinder, a hollow tube having one through-hole in the longitudinal direction, a perforated (porous) cylinder and a hollow tube having plural through-holes in the longitudinal direction) or by a compression-molding method using a pelletizer (molded article in the form of a pellet) .
- the gas generating composition or the molded article obtained therefrom in the invention can be used in, for example, an inflator for an air bag of a driver side, an inflator for an air bag of a passenger side, an inflator for a side air bag, an inflator for an inflatable curtain, an inflator for a knee bolster, an inflator for an inflatable seat belt, an inflator for a tubular system and an inflator for a pretensioner in various vehicles.
- the inflator using the gas generating composition or the molded article obtained therefrom in the invention may be a pyrotechnic type in which a gas is supplied only from a gas generating agent or a hybrid type in which a gas is supplied from both of a pressurized gas such as argon or the like and a gas generating agent.
- a section having a function to generate a gas by burning a gas generating agent is "a gas generator".
- the gas generating composition or the molded article obtained therefrom in the invention can also be used as an igniting agent called an enhancer (or a booster) for transferring energy of a detonator or a squib to a gas generating agent.
- an enhancer or a booster
- BHTNH 3 indicates an ammonium salt of bitetrazole
- BHTK a potassium salt of bitetrazole
- BCN a basic copper nitrate
- CMCNa a sodium salt of carboxymethylcellulose respectively.
- Gas generating compositions each having a formulation shown in Table 1 were produced.
- a combustion temperature and a gas outlet (unit "mol/100 g" indicates the number of mols of a generated gas per 100 g of the composition) and amounts of generated CO and NO of these compositions according to theoretical calculations are shown in Table 1.
- Gas generating compositions each having a formulation shown in Table 2 were produced. These compositions were tested for a friction sensitivity and a drop hammer sensitivity according to the explosives performance test method of JIS K 4810-1979. The results are shown in Table 2.
- Gas generating composition Composition ratio (wt.%) Friction sensitivity (kgf) Drop hammer sensitivity (cm)
- Example 8 BHTNH 3 /BCN 28.75/71.25 >36.0 >100
- Example 9 BHTK/BCN 44.52/55.48 >36.0 70 - 80
- Example 10 BHTNH 3 /BCN/CMCNa 25.89/71.11/3 >36.0 >80
- Gas generating compositions each having a formulation shown in Table 3 were produced.
- a melting temperature, a temperature at which to start heat generation and a temperature at which to start TG weight loss were measured with a TAS-type differential thermal analyzer manufactured by Rigaku K.K.
- a rate of temperature rise in the measurement was 20°C/min
- a measurement atmosphere was a nitrogen gas
- an amount of a sample in the measurement was 1 to 2 mg.
- Table 3 The results are shown in Table 3.
- Gas generating compositions each having a formulation shown in Table 3 were produced. Each of these compositions was molded into a strand. A burning rate was measured in a nitrogen atmosphere at a pressure of 50, 70 or 90 kg/cm 2 . A burning rate at 70 kg/cm 2 and a pressure index of 50 to 90 kg/cm 2 are shown in Table 4. Gas generating composition Composition ratio (wt.%) Burning rate (mm/sec) Pressure index Example 13 BHTNH 3 /BCN 28.75/71.25 14.48 0.16 Example 14 BHTK/BCN 44.52/55.48 27.92 0.20 Example 15 BHTNH 3 /BCN/CMCNa 25.89/71.11/3 14.99 0.15
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Air Bags (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11125012A JP2000319085A (ja) | 1999-04-30 | 1999-04-30 | ガス発生剤組成物 |
JP12501299 | 1999-04-30 | ||
PCT/JP2000/002839 WO2000066518A1 (fr) | 1999-04-30 | 2000-04-28 | Composition generatrice de gaz |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1195367A1 true EP1195367A1 (fr) | 2002-04-10 |
EP1195367A4 EP1195367A4 (fr) | 2011-08-03 |
Family
ID=14899688
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00921099A Withdrawn EP1195367A4 (fr) | 1999-04-30 | 2000-04-28 | Composition generatrice de gaz |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1195367A4 (fr) |
JP (1) | JP2000319085A (fr) |
WO (1) | WO2000066518A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003048077A2 (fr) * | 2001-11-30 | 2003-06-12 | Autoliv Asp, Inc. | Amelioration de la vitesse de combustion par l'intermediaire d'un complexe de metal de transition de bitetrazole de diammonium |
EP1323696A2 (fr) * | 2001-12-27 | 2003-07-02 | Trw Inc. | Composition combustible à basse température pour la génération de gaz pour dispositif de protection de l'occupant d'un véhicule |
US7665764B2 (en) | 2004-01-15 | 2010-02-23 | Daicel Chemical Industries, Ltd. | Gas generator for air bag |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4800469B2 (ja) * | 1999-10-08 | 2011-10-26 | ダイセル化学工業株式会社 | ガス発生剤組成物 |
JP2005231907A (ja) * | 2000-03-10 | 2005-09-02 | Nippon Kayaku Co Ltd | エアバック用ガス発生剤 |
WO2004067477A2 (fr) * | 2003-01-21 | 2004-08-12 | Autoliv Asp, Inc. | Generateurs de gaz |
JP4494023B2 (ja) * | 2004-01-15 | 2010-06-30 | ダイセル化学工業株式会社 | エアバッグ用ガス発生器 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4369079A (en) * | 1980-12-31 | 1983-01-18 | Thiokol Corporation | Solid non-azide nitrogen gas generant compositions |
US5482579A (en) * | 1993-04-15 | 1996-01-09 | Nof Corporation | Gas generator compositions |
US5542998A (en) * | 1994-01-18 | 1996-08-06 | Fraunhofer Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Gas-generating mixture |
US5608183A (en) * | 1996-03-15 | 1997-03-04 | Morton International, Inc. | Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate |
EP0792857A1 (fr) * | 1996-02-29 | 1997-09-03 | Morton International, Inc. | Générateurs de gaz exempts d'hydrogène et d'azoture |
WO1998017607A1 (fr) * | 1996-10-22 | 1998-04-30 | Trw Airbag Systems Gmbh & Co. Kg | Melange de substances solides generateur de gaz et exempt d'acide |
WO1998022208A2 (fr) * | 1996-11-08 | 1998-05-28 | Automotive Systems Laboratory, Inc. | Compositions d'agent generant un gaz non azide |
EP0864553A1 (fr) * | 1995-12-01 | 1998-09-16 | Kabushiki Kaisha Kobeseikosho | Agent generateur de gas et charge de transfert pour air-bag et generateur de gas les utilisant |
DE29821541U1 (de) * | 1998-12-02 | 1999-02-18 | Trw Airbag Sys Gmbh & Co Kg | Azidfreie, gaserzeugende Zusammensetzung |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4370181A (en) * | 1980-12-31 | 1983-01-25 | Thiokol Corporation | Pyrotechnic non-azide gas generants based on a non-hydrogen containing tetrazole compound |
JP3468787B2 (ja) * | 1992-11-27 | 2003-11-17 | 東洋化成工業株式会社 | 新規な5,5′−ビ−1h−テトラゾールアミン塩 |
US5682014A (en) * | 1993-08-02 | 1997-10-28 | Thiokol Corporation | Bitetrazoleamine gas generant compositions |
JPH10130086A (ja) * | 1996-10-23 | 1998-05-19 | Nippon Kayaku Co Ltd | エアバッグ用ガス発生剤 |
JP4157176B2 (ja) * | 1997-04-22 | 2008-09-24 | 東洋化成工業株式会社 | 新規な1,5′−ビテトラゾール系化合物とその製造法及び該1,5′−ビテトラール系化合物を主剤とするガス発生剤 |
-
1999
- 1999-04-30 JP JP11125012A patent/JP2000319085A/ja active Pending
-
2000
- 2000-04-28 EP EP00921099A patent/EP1195367A4/fr not_active Withdrawn
- 2000-04-28 WO PCT/JP2000/002839 patent/WO2000066518A1/fr active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4369079A (en) * | 1980-12-31 | 1983-01-18 | Thiokol Corporation | Solid non-azide nitrogen gas generant compositions |
US5482579A (en) * | 1993-04-15 | 1996-01-09 | Nof Corporation | Gas generator compositions |
US5542998A (en) * | 1994-01-18 | 1996-08-06 | Fraunhofer Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Gas-generating mixture |
EP0864553A1 (fr) * | 1995-12-01 | 1998-09-16 | Kabushiki Kaisha Kobeseikosho | Agent generateur de gas et charge de transfert pour air-bag et generateur de gas les utilisant |
EP0792857A1 (fr) * | 1996-02-29 | 1997-09-03 | Morton International, Inc. | Générateurs de gaz exempts d'hydrogène et d'azoture |
US5608183A (en) * | 1996-03-15 | 1997-03-04 | Morton International, Inc. | Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate |
WO1998017607A1 (fr) * | 1996-10-22 | 1998-04-30 | Trw Airbag Systems Gmbh & Co. Kg | Melange de substances solides generateur de gaz et exempt d'acide |
WO1998022208A2 (fr) * | 1996-11-08 | 1998-05-28 | Automotive Systems Laboratory, Inc. | Compositions d'agent generant un gaz non azide |
DE29821541U1 (de) * | 1998-12-02 | 1999-02-18 | Trw Airbag Sys Gmbh & Co Kg | Azidfreie, gaserzeugende Zusammensetzung |
Non-Patent Citations (1)
Title |
---|
See also references of WO0066518A1 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003048077A2 (fr) * | 2001-11-30 | 2003-06-12 | Autoliv Asp, Inc. | Amelioration de la vitesse de combustion par l'intermediaire d'un complexe de metal de transition de bitetrazole de diammonium |
WO2003048077A3 (fr) * | 2001-11-30 | 2003-08-07 | Autoliv Asp Inc | Amelioration de la vitesse de combustion par l'intermediaire d'un complexe de metal de transition de bitetrazole de diammonium |
US6712918B2 (en) | 2001-11-30 | 2004-03-30 | Autoliv Asp, Inc. | Burn rate enhancement via a transition metal complex of diammonium bitetrazole |
EP1323696A2 (fr) * | 2001-12-27 | 2003-07-02 | Trw Inc. | Composition combustible à basse température pour la génération de gaz pour dispositif de protection de l'occupant d'un véhicule |
EP1323696A3 (fr) * | 2001-12-27 | 2012-05-16 | Trw Inc. | Composition combustible à basse température pour la génération de gaz pour dispositif de protection de l'occupant d'un véhicule |
US7665764B2 (en) | 2004-01-15 | 2010-02-23 | Daicel Chemical Industries, Ltd. | Gas generator for air bag |
Also Published As
Publication number | Publication date |
---|---|
JP2000319085A (ja) | 2000-11-21 |
EP1195367A4 (fr) | 2011-08-03 |
WO2000066518A1 (fr) | 2000-11-09 |
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Legal Events
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RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: DAICEL CHEMICAL INDUSTRIES, LTD. |
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A4 | Supplementary search report drawn up and despatched |
Effective date: 20110705 |
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RIC1 | Information provided on ipc code assigned before grant |
Ipc: B60R 21/26 20110101ALI20110629BHEP Ipc: C06D 5/00 20060101AFI20110629BHEP |
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