WO2000029355A1 - Gas generator composition - Google Patents
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- 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
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- gas generating
- generating composition
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- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Air Bags (AREA)
- Automotive Seat Belt Assembly (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
Abstract
Description
明細書 ガス発生剤組成物 発明の属する技術分野 Description Gas generating composition Technical field to which the invention pertains
本発明は、 自動車、 航空機等に搭載される人体保護のためのエアバッグシステ ムゃプリテンショナ一システムにおいて作動ガスとなるガス発生剤組成物に関す る。 また本発明は、 前記ガス発生剤組成物を用いるインフレ一夕システム及びプ リテンショナ一システムに関する。 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.
従来の技術 Conventional technology
ガス発生剤の燃料として、 毒性の高いアジ化ナトリウムに替わる化合物が検討 されている。 例えば、 特開平 5— 2 5 4 9 7 7号公報には、 トリアミノグァニジ ン硝酸塩を含むガス発生剤が開示され；特開平 6— 2 3 9 6 8 3号公報には、 力 ルポヒドラジドを含むガス発生剤が開示され；特開平 7— 6 1 8 8 5号公報には 酢酸セルロースと過塩素酸カリウム及び窒素含有非金属化合物を含むガス発生剤 が開示され； U S P 5 , 1 2 5， 6 8 4には、 1 5〜 3 0 %のニトロセルロース 等のセルロース系バインダーとエネルギー物質を含有するガス発生剤が開示され ；特表平 9— 5 0 3 1 9 4号公報には、 トリアミノグァ二ジン硝酸塩と相安定化 した硝酸アンモニゥムを含むガス発生剤が開示され； WO 9 8 Z 0 6 4 8 6には アンミン錯体ゃヒドラジン錯体を含むガス発生剤が開示されている。 Compounds to replace the highly toxic sodium azide are being studied as fuels for gas generating agents. For example, 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; Japanese Patent Application Laid-Open No. 9-503191 discloses that Disclosed is a gas generating agent containing ammonium nitrate phase-stabilized with triaminoguanidine nitrate; WO 98 Z 0 648 discloses a gas generating agent containing an ammine complex and a hydrazine complex.
しかし、 前記の非アジ化ナトリウム系ガス発生剤は、 それぞれ何らかの問題点 を持っており、 さらに改善が求められている。 例えば、 トリアミノグァ二ジン硝 酸塩ゃヒドラジン錯体は非常に感度が高く危険なため、 ガス発生剤の製造が困難 である。 カルボヒドラジド、 トリアミノグァ二ジン硝酸塩やニトロセルロースを 含むガス発生剤は、 耐熱性が悪く、 長期にわたる使用において問題があり、 酢酸 セルロースと過塩素酸カリウム及び窒素含有非金属化合物を含むガス発生剤は、 燃焼温度が非常に高くガスの冷却が困難である。 However, each of the above non-sodium azide gas generating agents has some problems, and further improvement is required. For example, 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.
元来、 非アジ化ナトリウム系ガス発生剤は、 アジ化ナトリウムの本質的に好ま しくない欠点を改善することが第一目的であった。 しかし自動車の安全装備とし てエアバッグの標準化が進行し、 現在ではさらに、 エアバッグ用インフレ一夕は これまでに量産され使用されてきたものに比べて、 かなりの小型化及び低価格化 が求められている。 従って、 アジ化ナトリウム系ガス発生剤の本質的に好ましく ない問題点の改善と共に、 ガス発生器の小型化及び低価格化という要求を合わせ て実現するためには、 ガス発生剤は、 毒性、 耐熱性、 ガス発生効率、 燃焼温度、 燃焼残渣の濾過性、 燃焼残渣量、 燃焼速度、 安全性、 密度、 燃焼後ガス組成等の 各項目において、 適切なバランスを保持していなくてはならない。 Originally, the primary objective of non-sodium azide-based gas generants was to remedy the inherently undesirable disadvantages of sodium azide. However, the standardization of airbags as safety equipment for automobiles has been progressing, and furthermore, inflation for airbags needs to be much smaller and cheaper than those that have been mass-produced and used so far. Have been. Therefore, in order to improve the inherent disadvantages of sodium azide-based gas generators and to meet the demand for smaller and lower cost gas generators, gas generators must be toxic and heat resistant. Appropriate balance must be maintained in each of the parameters such as water quality, gas generation efficiency, combustion temperature, filterability of combustion residue, amount of combustion residue, burning speed, safety, density, and post-combustion gas composition.
発明の開示 Disclosure of the invention
そこで本発明は、 アジ化ナトリウム系ガス発生剤の問題点を解決し、 特にガス 発生器の小型化及び低価格化という要求を満たすため、 前記した各特性をバラン スよく具備したガス発生剤組成物を提供することを目的とする。 Accordingly, 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.
また、 本発明は、 前記ガス発生剤組成物を用いるエアバッグ用インフレ一夕シ ステム及びプリテンショナ一システムを提供することを他の目的とする。 It is another object of the present invention to provide an inflation system for airbags and a pretensioner system using the gas generating composition.
本発明は、 ヒドロキシルアミンを配位子として含む遷移金属錯体及びアルカリ 土類金属錯体から選ばれる 1種以上を含有することを特徴とするガス発生剤組成 物を提供する。 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.
また本発明は、 前記ガス発生剤組成物を用いることを特徴とするエアバッグ用 ィンフレー夕システム及びプリテンショナ一システムを提供する。 The present invention also provides an airbag inflation system and a pretensioner system using the gas generating composition.
本発明で用いるヒドロキシルアミンを配位子として含む遷移金属錯体又はアル カリ土類金属錯体は、 炭素を全く又はわずかしか含まないので、 この錯体を含む ガス発生剤組成物は、 燃焼後ガスを非常に清浄にできる。 また、 発生ガス量も多 レ 。 よって、 本発明のガス発生剤組成物を用いることにより、 ガス発生器の安全 性を高めることができるほか、 ガス発生器の小型化及び低価格化が達成できる。 発明の実施の形態 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. Embodiment of the Invention
本発明のガス発生剤組成物で用いるヒドロキシルアミンを配位子として含む遷 移金属錯体及びアルカリ土類金属錯体は、 含有される酸素原子の量に応じて、 燃 料又は酸化剤としての作用をなすものであるが、 分子中に炭素を全く又はわずか しか含まないため、 燃焼時に発生するガス中に一酸化炭素が全く含まれないか又 はわずかしか含まれない。 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.
ヒドロキシルアミンを配位子として含む遷移金属錯体又はアルカリ土類金属錯 体としては、 次の一般式 （I) ： M a L b L 'c X d (I) As the transition metal complex or the alkaline earth metal complex containing hydroxylamine as a ligand, the following general formula (I): MaLbL'cXd (I)
式中、 Mは遷移金属又はアルカリ土類金属を示し、 Lは配位子としてのヒドロキ シルァミンを示し、 L ' はヒドロキシルァミン以外の配位子を示し、 Xはァニォ ンを示す。 aは金属原子数で、 1〜4、 好ましくは 1〜2を示し、 bは配位子数 で、 1〜8、 好ましくは 1〜6を示し、 cはヒドロキシルァミン以外の配位子の 数で 1〜8、 好ましくは 1〜6を示し、 dはァニオン数で、 1〜6、 好ましくは 1〜 4 ¾示 9"0 In the formula, M represents a transition metal or an alkaline earth metal, L represents hydroxylamine as a ligand, L ′ represents a ligand other than hydroxylamine, and 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 ¾ shows 9 "0
で表されるものから選ばれる 1種以上を挙げることができる。 One or more selected from those represented by
—般式 （I) 中、 Mで示される遷移金属としては、 亜鉛、 銅、 ニッケル、 コバ ルト、 鉄、 マンガン、 クロム、 バナジウム、 チタン、 パラジウム、 白金、 ジルコ 二ゥム、 モリブデン、 ビスマス、 タングステン等を挙げることができ、 アルカリ 土類金属としては、 マグネシウム、 カルシウム、 ストロンチウム等を挙げること ができる。 一般式 （I) 中、 L' で示されるヒドロキシルァミン以外の配位子としては、 H2〇、 02、 CO, NO、 エチレンジァミン四酢酸 （EDTA)、 カルボヒドラ ジド （CDH)、 エチレンジァミン、 アンモニア、 ヒドラジン等を挙げることが できるが、 本発明においては L' を含まないこと （一般式 （I) 中の c = 0) が 好ましい。 —In the general formula (I), the transition metals represented by M include zinc, copper, nickel, cobalt, iron, manganese, chromium, vanadium, titanium, palladium, platinum, zirconium, molybdenum, bismuth, and tungsten. And alkaline earth metals include magnesium, calcium, strontium and the like. The formula (I), ligands other than hydroxyl § Min represented by L ', H 2 〇, 0 2, CO, NO, Echirenjiamin tetraacetic acid (EDTA), Karubohidora disilazide (CDH), Echirenjiamin ammonia And hydrazine, but in the present invention, it is preferable that L ′ is not contained (c = 0 in the general formula (I)).
一般式 （I) 中 Xで示されるァニオンとしては、 ΝΟΓ、 N〇2—、 NO—、 C I 〇4—、 C 1 ΟΓ、 C 1 、 B r―、 S CN―、 S 04 2—、 OH―、 C〇3 2_、 P〇 一、 C204 2—、 B04 5—、 Mn〇4—、 Mo 04 2 、 脱プロトン化したヒドロキシルアミ ン等を挙げることができる。 これらのァニオンは、 直接金属に配位して存在する 場合と、 配位せずに存在する場合のいずれでもよい。 In the general formula (I), the anion represented by X includes ΝΟΓ, N〇 2 —, NO—, CI 〇 4 —, C 1 ΟΓ, C 1, Br—, SCN—, S 0 4 2 —, OH @ -, C_〇 3 2 _, P_〇 one, C 2 0 4 2 -, B0 4 5 -, Mn_〇 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.
一般式 （I) で表される錯体としては、 下記に挙げるものを用いることができ る。 なお、 L—Hはァニオンとしての脱プロトン化したヒドロキシルアミンを示 すものである。 The following compounds can be used as the complex represented by the general formula (I). L-H indicates deprotonated hydroxylamine as anion.
例えば、 MN.Hughes and K.Shrimanker, Inorg. Chim. Acta. 18.69(1976)に記載さ れている N i LsC l 2、 N i LeB r 2, N i L6(C 104)2、 N i L4C 12, N i L4B r 2 N i L4(N03)2、 N i L4(C l〇4)2、 N i L3C l 2、 N i L3B r 2、 N i L2C 12, N i L2B r 2, N i LC l N i L(N〇3)2、 N i L4(L - H)2、 N i 2L6(L— H)C 13、 C d L 2C 1 2, C d L2B r 2, Z n L2C 1 2, Z n2L3(L— H)C 13、 Z n 2 L 3(L— H)B r 3、 C o L2C 12, C o LeC 13, Mn L2C 12, N i 2L6(L - H)B r 3、 Z n L2B r 2、 N i L6(S CN)2、 N i L 4(S C N)2、 C o L 2 S〇4等の金属錯体 ； E.M.Ivashkovich, N.I.Lazorchak O.D.Gumanitskaya and M.Yu Shpontak, Zh.Neorg. Khim., 21, 2125(1976)に記載され ている MnL2C l 2、 C o L4C l 2、 C oLsC l N i L6C l 2、 N i L^CFor example, N i LsCl 2 , N i LeBr 2, N i L 6 (C 10 4 ) 2 , N N described in MN.Hughes and K.Shrimanker, Inorg.Chim.Acta. 18.69 (1976) i L 4 C 1 2 , N i L 4 B r 2 N i L 4 (N 0 3 ) 2 , N i L 4 (C l〇 4 ) 2 , N i L 3 C l 2 , N i L 3 B r 2 , N i L 2 C 12, N i L 2 B r 2, N i LC l N i L (N〇 3 ) 2 , N i L 4 (L-H) 2 , N i 2 L 6 (L—H) C 1 3, C d L 2 C 1 2, C d L2B r 2, Z n L2C 1 2, Z n 2 L 3 (L- H) C 1 3, Z n 2 L 3 (L- H) B r 3, C o L2C 12, C o LeC 13, Mn L 2 C 12, n i 2 L 6 (L - H) B r 3, Z n L 2 B r 2, n i L 6 (S CN) 2, N i L 4 (SCN) 2 , C o L 2 S_〇 4 such metal complex;.. EMIvashkovich, NILazorchak ODGumanitskaya and M.Yu Shpontak, Zh.Neorg Khim, MnL listed in 21, 2125 (1976) 2 C l 2, C o L 4 C l 2, C oLsC l N i L 6 C l 2, N i L ^ C
12、 Cuし C l 2、 C u L.i(N03)2, Z n L2C 12, C o L2C 12, C o L(S 〇4)、 C o L 6C 13, N i L6(S〇4)、 N i L 6 I 2 , N i L2C 12, C o LaC 13等の金属錯体； Ya.V.Salyn, V.I.Nefedov, M.A.Sarukhanov and Yu.Ya.Kharitonov, Koord. Khim., 1, 945(1975)に記載されている P t L2C 12、 P t L2 I 2、 P t L2 (NH3)2C 12, P t L C 12, P t L4(OH)2、 CoLsC l N iし C l 2、 N i L4 I 2, Z n L2C 12 C d L2C 12 Mn L2C 12, B a L2C 12, C a L2C 12, P t L4C 14, C d L2B r 2, C o L2C 12, N i L2C 12, N i L 2B r 2, [P t L4][P t C 14] P t L4B r 2, P t L2B r 2, P tし B r" P t L,B r4等の金属錯体を挙げることができる。 1 2, Cu and C l 2, C u Li ( N0 3) 2, Z n L2C 12, C o L2C 1 2, C o L (S 〇 4), C o L 6 C 13, N i L 6 ( S_〇 4), N i L 6 I 2, N i L 2 C 1 2, C o LaC 1 3 such metal complexes; Ya.V. Salyn, VINefedov, MASarukhanov and Yu.Ya.Kharitonov, Koord. Khim., 1, 945 P t L 2 C 1 2 as described in (1975), P t L 2 I 2, P t L 2 (NH 3 ) 2 C 12, P t LC 12, P t L4 (OH) 2 , CoLsC l N i C l 2 , N i L 4 I 2, Zn L2C 1 2 C d L2C 1 2 Mn L2C 12, B a L2C 12, C a L2C 12, Pt L 4 C 14, C d L2B r 2, C o L2C 12, N i L2C 12, Ni L 2 B r 2, [P t L 4 ] [P t C 1 4] can be mentioned P t L 4 B r 2, P t L2B r 2, P t and B r "P t L, metal complexes such as B r 4.
本発明のガス発生剤組成物は、 さらに燃料として、 一般にガス発生剤の燃料と して用いられている他の含窒素化合物を配合することができる。 この含窒素化合 物としては、 5—アミノテトラゾール等のテトラゾール誘導体、 ビテトラゾ一ル ジアンモニゥム塩等のビテトラゾ一ル誘導体、 4—ァミノトリァゾ一ル等のトリ ァゾール誘導体、 ジシアンジアミド、 ニトログァニジン、 硝酸グァニジン等のグ ァニジン誘導体、 トリヒドラジノ トリアジン等のトリァジン誘導体、ォキサミド、 シユウ酸アンモニゥム、 ァゾジカルボンアミド、 ヒドラゾジカルボンアミド等か ら選ばれる 1種以上を挙げることができる。 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. Examples of 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. And at least one selected from derivatives, triazine derivatives such as trihydrazino triazine, oxamide, ammonium oxalate, azodicarbonamide, hydrazodicarbonamide and the like.
ガス発生剤組成物中における燃料の含有量は、 好ましくは 8〜 70重量％であ り、 特に好ましくは 10〜60重量％である。 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.
本発明のガス発生剤組成物には、 さらに酸化剤を配合することができる。 酸化 剤としては、 酸素酸塩、 金属酸化物、 金属複酸化物、 金属水酸化物及び金属過酸 化物から選ばれる 1種以上を挙げることができる。 The gas generating composition of the present invention may further contain an oxidizing agent. Examples of the oxidizing agent include one or more selected from oxyacid salts, metal oxides, metal double oxides, metal hydroxides, and metal peroxides.
酸素酸塩としては、 アンモニゥム、 アルカリ金属、 アルカリ土類金属、 アル力 リ土類金属錯体、 遷移金属及び遷移金属錯体の硝酸塩、 亜硝酸塩、 塩素酸塩又は 過塩素酸塩を挙げることができる。 このような酸素酸塩としては、 硝酸アンモニゥム、 硝酸ナトリウム、 硝酸カリ ゥム、 硝酸マグネシウム、 硝酸ストロンチウム等の硝酸のアンモニゥム塩、 アル カリ金属塩又はアルカリ土類金属塩；亜硝酸アンモニゥム、 亜硝酸ナトリウム、 亜硝酸カリウム、 亜硝酸マグネシウム、 亜硝酸ストロンチウム等の亜硝酸のアン モニゥム塩、 アルカリ金属塩又はアルカリ土類金属塩；塩素酸アンモニゥム、 塩 素酸ナトリウム、 塩素酸カリウム、 塩素酸マグネシウム、 塩素酸バリウム等の塩 素酸のアンモニゥム塩、 アルカリ金属塩又はアルカリ土類金属塩；過塩素酸アン モニゥム、 過塩素酸ナトリウム、 過塩素酸カリウム、 過塩素酸マグネシウム、 過 塩素酸アンモニゥム、 過塩素酸ナトリウム、 過塩素酸カリウム、 過塩素酸マグネ シゥム、 過塩素酸バリウム等の過塩素酸のアンモニゥム塩、 アルカリ金属塩又は アルカリ土類金属塩； Mg(N2H4)2(N03)2、 Mg(N2H4)2(C 1〇4)2等のアル カリ土類金属錯体の硝酸塩、 過塩素酸塩； Cu(N03)2 · 3 Cu(〇H)2、 Co 2(0 H)3(N〇3)、 C θ 2(ΟΗ)3(Ν〇3)、 Mn(OH)2(N〇3)等の遷移金属の硝酸塩； C ο(ΝΗ3)3(Ν〇3)3、 C ο(ΝΗ3)6(Ν03)3、 C u (ΝΗ3)2(Ν〇3)2、 C o(NH3) 3(N〇2)3、 C o(NH3)6(C 1〇4)3等の遷移金属錯体の硝酸塩、 亜硝酸塩、 過塩 素酸塩等を挙げることができる。 Examples of 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. Examples of such 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 〇 4) 2 and the like alkaline earth metal complexes of the nitrate, the perchlorate; Cu (N0 3) 2 · 3 Cu ( 〇_H) 2, Co 2 (0 H ) 3 ( N_〇 3), C theta Nitrate of transition metal such as 2 (ΟΗ) 3 (Ν〇 3 ), Mn (OH) 2 (N〇 3 ); C ο (ΝΗ 3 ) 3 (Ν〇3) 3 , C ο (ΝΗ 3 ) 6 (遷移 0 3 ) 3 , transition of Cu (ΝΗ 3 ) 2 (Ν〇 3 ) 2 , Co (NH 3 ) 3 (N ( 2 ) 3 , Co (NH 3 ) 6 (C 1〇 4 ) 3 Nitrate, nitrite, perchlorate and the like of a metal complex can be exemplified.
金属酸化物、 金属複酸化物及び金属水酸化物としては、 銅、 コバルト、 鉄、 マ ンガン、 ニッケル、 亜鉛、 モリブデン及びビスマスの酸化物、 複酸化物又は水酸 化物を挙げることができる。 このような金属酸化物及び金属複酸化物としては、 CuO、 Cu20、 Co 203、 CoO、 Co30 F e2〇3、 FeO、 Fe 304、 Mn02、 Mn2〇3、 Mn3〇4、 N i〇、 ZnO、 Mo〇3、 Μο03 · Η20、 C oMo04、 B i 2Mo06又は B i 2〇3等を挙げることができる。 Examples of the metal oxide, metal double oxide and metal hydroxide include oxides, double oxides and hydroxides of copper, cobalt, iron, manganese, nickel, zinc, molybdenum and bismuth. Examples of such metal oxides and metal double oxides, CuO, Cu 2 0, Co 2 0 3, CoO, Co 3 0 F e 2 〇 3, FeO, Fe 3 0 4 , Mn0 2, Mn 2 〇 3 , Mn 3 〇 4, N I_〇, ZnO, Mo_〇 3, may be mentioned Μο0 3 · Η 2 0, C oMo0 4, B i 2 Mo0 6 or B i 2 〇 3 or the like.
金属水酸化物としては、 F e(OH)3、 Co(OH)3、 Co(〇H)2、 N i (OH)2、 Cu(OH)2、 Zn(OH)2、 CoO(OH)2、 F eO(OH)2、 MnO(〇H)2、 Mn 0(O H)3等を挙げることができる。 Metal hydroxides include Fe (OH) 3 , Co (OH) 3 , Co (〇H) 2 , Ni (OH) 2 , Cu (OH) 2 , Zn (OH) 2 , CoO (OH) 2 , F eO (OH) 2 , MnO (〇H) 2 , Mn 0 (OH) 3 and the like.
金属過酸化物としては、 マグネシウム、 カルシウム、 ストロンチウムの過酸化 物を挙げることができる。 このような金属過酸化物としては、 M g〇2、 C a〇2、 S r〇 2等を挙げることができる。 Examples of the metal peroxide include magnesium, calcium, and strontium peroxides. Such metal peroxides, mention may be made of M G_〇 2, C A_〇 2, S R_〇 2.
ガス発生剤組成物中における酸化剤の含有量は、 好ましくは 2 5〜9 0重量％ であり、 特に好ましくは 3 0〜8 5重量％である。 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.
本発明のガス発生剤組成物には、さらにスラグ形成剤を配合することができる。 このスラグ形成剤としては、 酸性白土、 タルク、 ベントナイト、 ケイソゥ土、 力 ォリン、 シリカ、 アルミナ、 ガラスファイバ一、 アルミナファイバ一、 セラミツ クスファイバー、 ケィ酸ナトリウム、 ケィ酸アルミニウム、 窒化ケィ素、 炭化ケ ィ素、 ヒドロタルサイト及びこれらの混合物等から選ばれる 1種以上を挙げるこ とができる。 The gas generating composition of the present invention may further contain a slag forming agent. Examples of the slag forming agent 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.
ガス発生剤組成物中におけるスラグ形成剤の含有量は、 好ましくは 1〜 1 5重 量％であり、 特に好ましくは 3〜 1 2重量％である。 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.
本発明のガス発生剤組成物には、 さらにバインダーを配合することができる。 このバインダーとしては、 カルボキシルメチルセルロースのナトリウム塩、 デン プン、 グァガム、 ポリビニルアルコール、 微結晶性セルロース、 ポリアクリルァ ミド、 ポリアクリル酸、 ステアリン酸カルシウム等の有機バインダー、 二硫化モ リブデン、 酸性白土、 タルク、 ベントナイト、 ケイソゥ土、 カオリン、 シリカ、 アルミナ、 ケィ酸ナトリゥム等の無機バインダ一等から選ばれる 1種以上を挙げ ることができる。 The gas generating composition of the present invention may further contain a binder. Examples of 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.
ガス発生剤組成物中におけるバインダーの含有量は、 好ましくは 0 . 5〜2 0 重量％であり、 特に好ましくは 3〜 1 5重量％である。 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.
本発明のガス発生剤組成物は、 燃料、 酸化剤等を粉末状で混合する乾式法又は 水や有機溶剤等の存在下で混合する湿式法により製造することができる。 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.
また、 本発明のガス発生剤組成物は、 所望の形状に成型することもできる。 例 えば、 打錠機を用いて圧縮成型してペレットにしたり、 ディスク成型機を用いて 圧縮成型してディスクにしたり、 ペレツトゃディスクを粉砕するか又はグラニュ レ一夕を用いて顆粒にしたり、 圧伸機 （押出成型機） を用いて押出成型して圧伸 薬 （無孔、 単孔、 多孔） にしたりすることができる。 Further, the gas generating composition of the present invention can be molded into a desired shape. For example, 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).
これらの成型方法は、 ガス発生剤組成物の成型品に対して付与しょうとする性 質等に応じて適宜選択することができる。 例えば、 押出成型法を適用した場合、 ウェブが薄いものを成型することが圧縮成型法よりも容易であるので、 燃焼速度 の遅い組成でも成型品を得ることができる。 さらに、 押出成型法は成型が比較的 短時間ですむため大量生産に向いている。 また、 燃焼速度が速い組成の場合は成 型品のサイズを大きくできるために、 より製造効率を上げることができる。 その ほか、 押出成型法を適用した場合には、 無孔、 単孔、 多孔等の複雑な形状の成型 品を製造できるため、 種々の燃焼特性を付与することができる。 These molding methods can be appropriately selected according to the properties to be imparted to the molded article of the gas generating composition. For example, 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. In addition, 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. In addition, when the extrusion molding method is applied, 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.
本発明のガス発生剤組成物は、 自動車、 航空機等に搭載される人体保護のため に供せられるエアバッグシステムのィンフレー夕システム用のガス発生剤として 有用である。 インフレ一夕システムにはガスの供給が固体ガス発生剤からだけで あるパイ口タイプと、 アルゴン等の圧縮ガスと固体ガス発生剤の両者を含むハイ ブリッドタイプがあるが、 いずれのタイプであってもよい。 INDUSTRIAL APPLICABILITY 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. 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.
また、 本発明のインフレ一夕システムは、 雷管ゃスクイブのエネルギーをガス 発生剤に伝えるためのェンハンサ剤 （又はブースター） 等と呼ばれる伝火剤とし て、 上記したガス発生剤組成物を用いることもできる。 ェンハンサ剤として用い る場合も、 上記したような粉体、 顆粒、 ペレツ卜、 無孔圧伸薬、 単孔圧伸薬、 多 孔圧伸薬等の適当な形状に成型したものを用いることができる。 さらに、 本発明のガス発生剤組成物は、 自動車、 航空機等に搭載される人体保 護のために供せられるプリテンショナ一システム用のガス発生剤としても用いる ことができる。 プリテンショナ一とは、 シートベル卜の巻き取りを行う巻き取り 装置に取り付けられた緊急引き込み装置であり、 プリテンショナ一システムは、 プリテンショナ一の動力としてガス発生剤組成物の燃焼ガスを利用するものであ る。 In addition, 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. When used as an enhancer, it is also possible to use powders, granules, pellets, non-porous rolls, single-hole rolls, multi-roll rolls, etc. as described above. it can. Furthermore, 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.
本発明のガス発生剤組成物は、 ガス発生能を必要とするいかなる装置にも用い ることができ、 上記したェアバッグシステムのィンフレー夕システムゃプリテン ショナ一システムのほか、 発射薬等にも用いることができる。 The gas generating composition of the present invention can be used in any device that requires gas generating ability. In addition to the air bag system of the air bag system and the pretensioner system described above, it can also be used for propellants and the like. Can be used.
実施例 Example
以下、 実施例及び比較例をあげて本発明を具体的に説明するが、 本発明はこれ らの実施例のみに限定されるものではない。 Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples.
実施例 1〜： L 6 Example 1: L 6
表 1に示す組成のガス発生剤組成物を製造した。 これらのガス発生剤の理論発 生ガス量を求めた。 表 1中、 Lは配位子としてのヒドロキシルァミンを、 L一 H はァニオンとしての脱プロトン化したヒドロキシルァミンを示している。 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. In Table 1, L represents hydroxylamine as a ligand, and L-H represents deprotonated hydroxylamine as anion.
実施例 1 7 Example 17
実施例 5に示したガス発生剤組成物 1 0 gを常圧下で燃焼し、 観察した。 燃焼 試験は、 ガス発生剤組成物 1 0 gを乳鉢に入れ、 ニクロム線に通電して着火させ ることにより行った。 結果を表 2示す。 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.
ガス発生剤組成物は完全に燃焼し、 スラグ性が高く、 濾過しやすい燃焼残渣を 形成した。 発生力'ス S 羝 成 (wt%) ^mol/ i OUgfl 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
7 Φ 7 Φ
Cu(L)4(N03)2 (100) 3ク 施例 2 Cu(L)4(N03)2/CMC-Na (85.5/14.5) Cu (L) 4 (N0 3 ) 2 (100) 3 Example 2 Cu (L) 4 (N0 3 ) 2 / CMC-Na (85.5 / 14.5)
Cu (し )4(N03)2/硝酸ゲァ二' ン/ GMC-Na (72.7/19.3/8) Cu (teeth) 4 (N0 3) 2 / nitrate gate § two 'down / GMC-Na (72.7 / 19.3 / 8)
実 例 4 Gu(L)4(N03)2/5-アミノ亍トラゾール /CMG-Na (81.6/10.4/8) Real Example 4 Gu (L) 4 (N0 3) 2 / 5- amino亍Torazoru / CMG-Na (81.6 / 10.4 / 8)
笑施例 5 Cu(L)4(N03)2/ニト αク'ァニシ 'ン/デンフ 'ン (74.4/17.6/8) 3 5 Lol Example 5 Cu (L) 4 (N0 3 ) 2 / Nit α '
Cu(L)4(N03)2/Co(NH3)6( Ν03)3 (18.5/81.5) 3フ 夭 Bfc J / Ni(LXN03)2/硝酸ク'ァニシ 'ン (44/56) Cu (L) 4 (N0 3 ) 2 / Co (NH 3 ) 6 (Ν0 3 ) 3 (18.5 / 81.5) 3F Premature Bfc J / Ni (LXN0 3 ) 2 / Nitric acid nitric acid (44/56 )
Νί(Ι_ΧΝ03)2/ニトロゲァニ 'ノン/デンプン (59/33/8) 3 0 夭/ Ni(L)4(L-H)2 (100) 4.2 実施例 1 0 Ni(L)4(L-H)2/S N03)2 (66.7/33.3) 3.0 実施例" Ni(L)4(L-H)2/CuO (51.6/48.4) 2.2 実施例 1 2 Ni(L)4(L-H)2/Cu(OH)2 (50/50) 2.7 実施例 1 3 Ni(L)4(L-H)2/NH4N03 (51.5/48.5) 4.0 実施例 1 4 Ni(L)4(L-H)2/Ni(LXN03)2 (63.9/36.1 ) 3.3 実施例 1 5 Ni(L)6(CI04)2 (100) 3.2 実施例 1 6 Ni(L)6(CI04)2 /硝酸ゲァ:：シ'ン (59.8/40.2) 3.7 Νί (Ι_ΧΝ0 3 ) 2 / Nitrogenani 'non / starch (59/33/8) 3 0 premature / Ni (L) 4 (LH) 2 (100) 4.2 Example 10 Ni (L) 4 (LH) 2 / S N0 3 ) 2 (66.7 / 33.3) 3.0 Example "Ni (L) 4 (LH) 2 / CuO (51.6 / 48.4) 2.2 Example 1 2 Ni (L) 4 (LH) 2 / Cu (OH) 2 (50/50) 2.7 Example 13 Ni (L) 4 (LH) 2 / NH 4 N0 3 (51.5 / 48.5) 4.0 Example 14 Ni (L) 4 (LH) 2 / Ni (LXN0 3 ) 2 (63.9 / 36.1) 3.3 example 1 5 Ni (L) 6 ( CI0 4) 2 (100) 3.2 example 1 6 Ni (L) 6 ( CI0 4) 2 / nitrate gate § :: Shi 'emissions (59.8 / 40.2) 3.7
表 2 Table 2
組 成 （wt%) 燃焼時間 (秒） 燃焼状態及び燃焼残渣の様子Composition (wt%) Combustion time (sec) Combustion state and combustion residue
Cu(L)4(N03)2/ 黄緑色の炎が見られた。組成物は 実施例 1 7ニトロゲァこシ 'ン / ンフ *ン 6 完全に燃焼した。赤色及び黒色の Cu (L) 4 (N0 3 ) 2 / yellow-green flame was observed. The composition was completely burned as in Example 17 7 Nitrogen / Nin * 6. Red and black
(74.4/17.6/8) 残渣が生成した。 (74.4 / 17.6 / 8) A residue was formed.
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10323191A JP2000154086A (en) | 1998-11-13 | 1998-11-13 | Gas generating composition |
| JP10/323191 | 1998-11-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2000029355A1 true WO2000029355A1 (en) | 2000-05-25 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1999/006338 Ceased WO2000029355A1 (en) | 1998-11-13 | 1999-11-12 | Gas generator composition |
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| Country | Link |
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| JP (1) | JP2000154086A (en) |
| WO (1) | WO2000029355A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744185A (en) * | 2013-12-30 | 2015-07-01 | 比亚迪股份有限公司 | Gas generating agent composition and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0536916A1 (en) * | 1991-10-09 | 1993-04-14 | Morton International, Inc. | Non-azide gas generant formulations |
| 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 (en) * | 1995-10-06 | 1997-04-22 | Daicel Chem Ind Ltd | Tris(carbohydradizo-o,n)magnesium (ii) nitrate complex, its production and gas producer composition |
| JPH09110574A (en) * | 1995-10-12 | 1997-04-28 | Nippon Kayaku Co Ltd | Gas generator and its production |
| JPH10251267A (en) * | 1997-03-13 | 1998-09-22 | Daicel Chem Ind Ltd | Dinitratoaqua(cabohydrazido-o,n) strontium (ii) or its coordinated water-removed complex and their production and gas-generating agent composition |
-
1998
- 1998-11-13 JP JP10323191A patent/JP2000154086A/en active Pending
-
1999
- 1999-11-12 WO PCT/JP1999/006338 patent/WO2000029355A1/en not_active Ceased
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0536916A1 (en) * | 1991-10-09 | 1993-04-14 | Morton International, Inc. | Non-azide gas generant formulations |
| 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 (en) * | 1995-10-06 | 1997-04-22 | Daicel Chem Ind Ltd | Tris(carbohydradizo-o,n)magnesium (ii) nitrate complex, its production and gas producer composition |
| JPH09110574A (en) * | 1995-10-12 | 1997-04-28 | Nippon Kayaku Co Ltd | Gas generator and its production |
| JPH10251267A (en) * | 1997-03-13 | 1998-09-22 | Daicel Chem Ind Ltd | Dinitratoaqua(cabohydrazido-o,n) strontium (ii) or its coordinated water-removed complex and their production and gas-generating agent composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744185A (en) * | 2013-12-30 | 2015-07-01 | 比亚迪股份有限公司 | Gas generating agent composition and preparation method thereof |
| CN104744185B (en) * | 2013-12-30 | 2017-11-17 | 比亚迪股份有限公司 | A kind of gas generant composition and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP2000154086A (en) | 2000-06-06 |
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