WO2000029355A1 - Composition generatrice de gaz - Google Patents

Composition generatrice de gaz Download PDF

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Publication number
WO2000029355A1
WO2000029355A1 PCT/JP1999/006338 JP9906338W WO0029355A1 WO 2000029355 A1 WO2000029355 A1 WO 2000029355A1 JP 9906338 W JP9906338 W JP 9906338W WO 0029355 A1 WO0029355 A1 WO 0029355A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas generating
generating composition
metal
composition according
gas
Prior art date
Application number
PCT/JP1999/006338
Other languages
English (en)
Japanese (ja)
Inventor
Yo Yamato
Original Assignee
Daicel Chemical Industries, Ltd.
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 Daicel Chemical Industries, Ltd. filed Critical Daicel Chemical Industries, Ltd.
Publication of WO2000029355A1 publication Critical patent/WO2000029355A1/fr

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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

Definitions

  • the present invention relates to a gas generating composition which becomes a working gas in an airbag system for protecting a human body mounted on an automobile, an aircraft, or the like, ie, a pretensioner system.
  • the present invention also relates to an inflation system and a pretensioner system using the gas generating composition.
  • Japanese Patent Application Laid-Open No. 5-254977 discloses a gas generating agent containing triaminoguanidine nitrate
  • Japanese Patent Application Laid-Open No. Hei 6-239,683 discloses lipohydrazide.
  • JP-A-7-61885 discloses a gas generant containing cellulose acetate, potassium perchlorate and a nitrogen-containing nonmetallic compound
  • USP 5,125 , 684 disclose a gas generating agent containing 15 to 30% of a cellulosic binder such as nitrocellulose and an energy substance
  • WO 98 Z 0 648 discloses a gas generating agent containing an ammine complex and a hydrazine complex.
  • each of the above non-sodium azide gas generating agents has some problems, and further improvement is required.
  • triaminoguanidine nitrate-hydrazine complex is very sensitive and dangerous, and it is difficult to produce a gas generant.
  • Carbohydrazide, triaminoguanidine nitrate and nitrocellulose Gas generating agents containing cellulose acetate, potassium perchlorate, and non-metallic compounds containing nitrogen have a very high combustion temperature, making it difficult to cool the gas. It is.
  • the present invention solves the problems of the sodium azide-based gas generating agent, and in particular, in order to satisfy the demand for downsizing and cost reduction of the gas generator, a gas generating agent composition having the above-mentioned characteristics in a well-balanced manner.
  • the purpose is to provide things.
  • the present invention provides a gas generating composition comprising at least one selected from a transition metal complex containing hydroxylamine as a ligand and an alkaline earth metal complex.
  • the present invention also provides an airbag inflation system and a pretensioner system using the gas generating composition.
  • Transition metal complex containing hydroxylamine as a ligand used in the present invention Since the potassium earth metal complex contains no or very little carbon, gas generant compositions containing this complex can be very clean after combustion. In addition, the amount of generated gas is large. Therefore, by using the gas generating composition of the present invention, the safety of the gas generator can be improved, and the size and cost of the gas generator can be reduced.
  • the transition metal complex and the alkaline earth metal complex containing hydroxylamine as a ligand used in the gas generant composition of the present invention act as a fuel or an oxidizing agent depending on the amount of oxygen atoms contained. Although it does, it contains no or very little carbon in its molecules, so the gas generated during combustion contains no or little carbon monoxide.
  • transition metal complex or the alkaline earth metal complex containing hydroxylamine as a ligand, the following general formula (I): MaLbL'cXd (I)
  • M represents a transition metal or an alkaline earth metal
  • L represents hydroxylamine as a ligand
  • L ′ represents a ligand other than hydroxylamine
  • X represents anion.
  • a is the number of metal atoms, 1 to 4, preferably 1 to 2;
  • b is the number of ligands, 1 to 8, preferably 1 to 6;
  • c is the number of ligands other than hydroxylamine 1-8 a few, preferably an 1-6,
  • d is Anion number, 1-6, preferably. 1 to 4 3 ⁇ 4 shows 9 "0
  • the transition metals represented by M include zinc, copper, nickel, cobalt, iron, manganese, chromium, vanadium, titanium, palladium, platinum, zirconium, molybdenum, bismuth, and tungsten.
  • alkaline earth metals include magnesium, calcium, strontium and the like.
  • the anion represented by X includes ⁇ , N ⁇ 2 —, NO—, CI ⁇ 4 —, C 1 ⁇ , C 1, Br—, SCN—, S 0 4 2 —, OH @ -, C_ ⁇ 3 2 _, P_ ⁇ one, C 2 0 4 2 -, B0 4 5 -, Mn_ ⁇ 4 -, Mo 0 4 2, can be cited deprotonated hydroxylamine or the like. These anions may be present either in direct coordination with the metal or in the absence of coordination.
  • L-H indicates deprotonated hydroxylamine as anion.
  • the gas generating composition of the present invention may further contain, as a fuel, another nitrogen-containing compound generally used as a fuel for a gas generating agent.
  • the nitrogen-containing compound include tetrazole derivatives such as 5-aminotetrazole, bitetrazole derivatives such as bitetrazole diammonium salt, triazole derivatives such as 4-aminotriazole, guanidine such as dicyandiamide, nitroguanidine, and guanidine nitrate.
  • triazine derivatives such as trihydrazino triazine, oxamide, ammonium oxalate, azodicarbonamide, hydrazodicarbonamide and the like.
  • the content of the fuel in the gas generant composition is preferably from 8 to 70% by weight, particularly preferably from 10 to 60% by weight.
  • the gas generating composition of the present invention may further contain an oxidizing agent.
  • the oxidizing agent include one or more selected from oxyacid salts, metal oxides, metal double oxides, metal hydroxides, and metal peroxides.
  • oxyacid salts include ammonium, alkali metals, alkaline earth metals, alkaline earth metal complexes, transition metals and nitrates, nitrites, chlorates or perchlorates of transition metal complexes.
  • oxyacid salts include ammonium nitrate, sodium nitrate, potassium nitrate, magnesium nitrate, ammonium nitrate salts such as strontium nitrate, alkali metal salts or alkaline earth metal salts; ammonium nitrite, sodium nitrite. , Potassium nitrite, magnesium nitrite, strontium nitrite, etc.
  • ammonium salt, alkali metal salt or alkaline earth metal salt ammonium chlorate, sodium chlorate, potassium chlorate, magnesium chlorate, barium chlorate Ammonium chloride, alkali metal salt or alkaline earth metal salt of ammonium chloride; ammonium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, ammonium perchlorate, sodium perchlorate, etc.
  • Potassium perchlorate, Magneto perchlorate Ammonium salt, alkali metal salt or alkaline earth metal salt of perchloric acid such as shim or barium perchlorate; Mg (N 2 H 4 ) 2 (N 0 3 ) 2, Mg (N 2 H 4 ) 2 (C 1 ⁇ 4) 2 and the like alkaline earth metal complexes of the nitrate, the perchlorate; Cu (N0 3) 2 ⁇ 3 Cu ( ⁇ _H) 2, Co 2 (0 H ) 3 ( N_ ⁇ 3), C theta Nitrate of transition metal such as 2 ( ⁇ ) 3 ( ⁇ 3 ), Mn (OH) 2 (N ⁇ 3 ); C ⁇ ( ⁇ 3 ) 3 ( ⁇ 3) 3 , C ⁇ ( ⁇ 3 ) 6 ( ⁇ 0 3 ) 3 , transition of Cu ( ⁇ 3 ) 2 ( ⁇ 3 ) 2 , Co (NH 3 ) 3 (N ( 2 ) 3 , Co (NH 3 ) 6 (C 1 ⁇ 4
  • metal oxide, metal double oxide and metal hydroxide examples include oxides, double oxides and hydroxides of copper, cobalt, iron, manganese, nickel, zinc, molybdenum and bismuth.
  • metal oxides and metal double oxides CuO, Cu 2 0, Co 2 0 3, CoO, Co 3 0 F e 2 ⁇ 3, FeO, Fe 3 0 4 , Mn0 2, Mn 2 ⁇ 3 , Mn 3 ⁇ 4, N I_ ⁇ , ZnO, Mo_ ⁇ 3, may be mentioned ⁇ 0 3 ⁇ ⁇ 2 0, C oMo0 4, B i 2 Mo0 6 or B i 2 ⁇ 3 or the like.
  • Metal hydroxides include Fe (OH) 3 , Co (OH) 3 , Co ( ⁇ H) 2 , Ni (OH) 2 , Cu (OH) 2 , Zn (OH) 2 , CoO (OH) 2 , F eO (OH) 2 , MnO ( ⁇ H) 2 , Mn 0 (OH) 3 and the like.
  • metal peroxide examples include magnesium, calcium, and strontium peroxides. Such metal peroxides, mention may be made of M G_ ⁇ 2, C A_ ⁇ 2, S R_ ⁇ 2.
  • the content of the oxidizing agent in the gas generating composition is preferably 25 to 90% by weight, and particularly preferably 30 to 85% by weight.
  • the gas generating composition of the present invention may further contain a slag forming agent.
  • a slag forming agent examples include acid clay, talc, bentonite, diatomaceous earth, copper, silica, alumina, glass fiber, alumina fiber, ceramics fiber, sodium silicate, aluminum silicate, silicon nitride, and silicon carbide. And at least one selected from silicon, hydrotalcite, and mixtures thereof.
  • the content of the slag forming agent in the gas generating composition is preferably 1 to 15% by weight, particularly preferably 3 to 12% by weight.
  • the gas generating composition of the present invention may further contain a binder.
  • the binder include organic salts such as sodium salt of carboxymethyl cellulose, starch, guar gum, polyvinyl alcohol, microcrystalline cellulose, polyacrylamide, polyacrylic acid, calcium stearate, molybdenum disulfide, acid clay, talc, bentonite, One or more selected from inorganic binders such as diatomaceous earth, kaolin, silica, alumina, sodium silicate and the like can be mentioned.
  • the content of the binder in the gas generant composition is preferably 0.5 to 20% by weight, particularly preferably 3 to 15% by weight.
  • the gas generating composition of the present invention may be prepared by a dry method in which a fuel, an oxidizing agent, and the like are mixed in powder form, or It can be produced by a wet method of mixing in the presence of water or an organic solvent.
  • the gas generating composition of the present invention can be molded into a desired shape.
  • compression molding into pellets using a tableting machine compression molding into a disk using a disk molding machine, grinding of a pellet disk or granulation using a granule mill, It can be extruded using a drawing machine (extrusion molding machine) to make a drawn medicine (non-porous, single-hole, porous).
  • molding methods can be appropriately selected according to the properties to be imparted to the molded article of the gas generating composition.
  • the extrusion molding method when the extrusion molding method is applied, it is easier to mold a thin web than the compression molding method, so that a molded product can be obtained even with a composition having a slow burning rate.
  • the extrusion method is suitable for mass production because molding can be performed in a relatively short time. In the case of a composition having a high burning rate, the size of the molded product can be increased, so that the production efficiency can be further increased.
  • a molded article having a complicated shape such as non-porous, single-hole, or porous can be manufactured, so that various combustion characteristics can be imparted.
  • the gas generating composition of the present invention is useful as a gas generating agent for an infra-free system of an airbag system provided for protecting a human body mounted on an automobile, an aircraft or the like.
  • inflation systems There are two types of inflation systems: a pie-mouth type, in which gas is supplied only from a solid gas generating agent, and a hybrid type, which includes both a compressed gas such as argon and a solid gas generating agent. Is also good.
  • the inflation system of the present invention may use the above-described gas generant composition as a heat transfer agent called an enhancer agent (or booster) for transmitting the energy of the primer / squib to the gas generant. it can.
  • an enhancer agent or booster
  • powders, granules, pellets, non-porous rolls, single-hole rolls, multi-roll rolls, etc. as described above. it can.
  • the gas generating composition of the present invention can be used as a gas generating agent for a pretensioner system provided for protecting a human body mounted on an automobile, an aircraft, or the like.
  • the pretensioner is an emergency retraction device attached to a winding device that winds a sheet belt, and the pretensioner system uses combustion gas of a gas generating composition as power for the pretensioner. It is.
  • the gas generating composition of the present invention can be used in any device that requires gas generating ability.
  • it can also be used for propellants and the like. Can be used.
  • a gas generating composition having the composition shown in Table 1 was produced. The theoretical amount of generated gas for these gas generating agents was determined.
  • L represents hydroxylamine as a ligand
  • L-H represents deprotonated hydroxylamine as anion.
  • Example 5 10 g of the gas generating composition shown in Example 5 was burned under normal pressure and observed. The combustion test was performed by placing 10 g of the gas generating composition in a mortar and igniting by passing a current through a nichrome wire. Table 2 shows the results.
  • the gas generant composition burned completely and formed a combustion residue with high slag properties and easy filtration. Generating power S-square (wt%) ⁇ mol / i OUgfl
  • Composition (wt%) Combustion time (sec) Combustion state and combustion residue

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Automotive Seat Belt Assembly (AREA)

Abstract

L'invention concerne une composition génératrice de gaz qui génère un gaz de combustion propre. Ladite composition contient au moins un élément choisi parmi des complexes de métaux de transition, tels que le cuivre et le nickel, et des métaux terreux alcalins, tels que le magnésium et le calcium, contenant chacun une hydroxylamine en tant que ligand. Etant donné que le nombre d'atomes de carbone contenus dans chaque complexe est nul ou faible, la composition génère un gaz de combustion ne contenant pas de monoxyde de carbone ou en contenant une quantité considérablement réduite.
PCT/JP1999/006338 1998-11-13 1999-11-12 Composition generatrice de gaz WO2000029355A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10323191A JP2000154086A (ja) 1998-11-13 1998-11-13 ガス発生剤組成物
JP10/323191 1998-11-13

Publications (1)

Publication Number Publication Date
WO2000029355A1 true WO2000029355A1 (fr) 2000-05-25

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JP (1) JP2000154086A (fr)
WO (1) WO2000029355A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104744185A (zh) * 2013-12-30 2015-07-01 比亚迪股份有限公司 一种气体发生剂组合物及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0536916A1 (fr) * 1991-10-09 1993-04-14 Morton International, Inc. Compositions génératrices de gaz exempt d'azoture
US5472535A (en) * 1995-04-06 1995-12-05 Morton International, Inc. Gas generant compositions containing stabilizer
US5592812A (en) * 1994-01-19 1997-01-14 Thiokol Corporation Metal complexes for use as gas generants
JPH09104687A (ja) * 1995-10-06 1997-04-22 Daicel Chem Ind Ltd トリス（カルボヒドラジド−ｏ，ｎ）マグネシウム（ｉｉ）硝酸塩錯体とその製造方法及びガス発生剤組成物
JPH09110574A (ja) * 1995-10-12 1997-04-28 Nippon Kayaku Co Ltd ガス発生剤及びその製造方法
JPH10251267A (ja) * 1997-03-13 1998-09-22 Daicel Chem Ind Ltd ジニトラトアクア（カルボヒドラジド−ｏ，ｎ）ストロンチウム（ｉｉ）又はその脱配位水錯体及びそれらの製造方法並びにガス発生剤組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0536916A1 (fr) * 1991-10-09 1993-04-14 Morton International, Inc. Compositions génératrices de gaz exempt d'azoture
US5592812A (en) * 1994-01-19 1997-01-14 Thiokol Corporation Metal complexes for use as gas generants
US5472535A (en) * 1995-04-06 1995-12-05 Morton International, Inc. Gas generant compositions containing stabilizer
JPH09104687A (ja) * 1995-10-06 1997-04-22 Daicel Chem Ind Ltd トリス（カルボヒドラジド−ｏ，ｎ）マグネシウム（ｉｉ）硝酸塩錯体とその製造方法及びガス発生剤組成物
JPH09110574A (ja) * 1995-10-12 1997-04-28 Nippon Kayaku Co Ltd ガス発生剤及びその製造方法
JPH10251267A (ja) * 1997-03-13 1998-09-22 Daicel Chem Ind Ltd ジニトラトアクア（カルボヒドラジド−ｏ，ｎ）ストロンチウム（ｉｉ）又はその脱配位水錯体及びそれらの製造方法並びにガス発生剤組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104744185A (zh) * 2013-12-30 2015-07-01 比亚迪股份有限公司 一种气体发生剂组合物及其制备方法
CN104744185B (zh) * 2013-12-30 2017-11-17 比亚迪股份有限公司 一种气体发生剂组合物及其制备方法

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Publication number Publication date
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