JPH0624888A - Gas generating agent - Google Patents
Gas generating agentInfo
- Publication number
- JPH0624888A JPH0624888A JP4206276A JP20627692A JPH0624888A JP H0624888 A JPH0624888 A JP H0624888A JP 4206276 A JP4206276 A JP 4206276A JP 20627692 A JP20627692 A JP 20627692A JP H0624888 A JPH0624888 A JP H0624888A
- Authority
- JP
- Japan
- Prior art keywords
- gas generating
- generating agent
- weight
- oxalic acid
- binder
- 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.)
- Granted
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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Air Bags (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、自動車、航空機等の人
体保護の用に供せられるエアーバッグシステムに於て、
作動ガスとなるガス発生剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an air bag system used for protecting a human body of an automobile, an aircraft, etc.
The present invention relates to a gas generating agent that becomes a working gas.
【0002】[0002]
【従来の技術】現在エアバッグの膨張に有用な気体発生
組成物には主にアジ化ソーダが使用されている。この組
成物はその燃焼特性に関しては特に問題なく、広く実用
に供されているのが現状である。しかし、アジ化ソーダ
は、本質的に色々の好ましくない特性を有している。例
えば、分解爆発に対する危険性が非常に大であり、アメ
リカではB級爆薬とされており、アジ化ソーダの火花感
度は、黒色火薬のそれに匹敵し、その取扱は細心の注意
を要する。実際にこの組成物の製造工程で世界的に事故
が多発しているのが現状である。BACKGROUND OF THE INVENTION Currently, sodium azide is mainly used in gas generating compositions useful for inflating airbags. This composition has no particular problem with respect to its combustion characteristics and is currently in wide practical use. However, sodium azide inherently has various undesirable properties. For example, the danger of decomposition and explosion is extremely high, and it is considered as a Class B explosive in the United States. The spark sensitivity of sodium azide is comparable to that of black explosive, and its handling requires careful attention. In fact, there are many accidents worldwide in the manufacturing process of this composition.
【0003】更に、アジ化ソーダが重金属と反応すると
衝撃感度の高い塩を生成する。特に銅との反応では非常
に衝撃感度の高いアジ化銅を生成する。銅金属またはそ
の合金は一般に部品材料として使用される頻度が高いの
で廃車時のエアーバッグの廃棄の問題とも絡み、今後社
会的な問題となる可能性が大きい。Furthermore, when sodium azide reacts with heavy metals, it produces salts with high impact sensitivity. In particular, the reaction with copper produces copper azide, which has very high impact sensitivity. Since copper metal or its alloy is generally frequently used as a material for parts, it is also likely to become a social problem in the future, because it is entangled with the problem of discarding airbags when the vehicle is scrapped.
【0004】更に、アジ化ソーダはその生理毒性にも問
題が多く、0.04grを飲んだ人が両腕に放散する狭
心症に似た激しい胸痛と、足のしびれを訴え床に倒れた
とか、アジ化ソーダにして0.05〜0.06gr飲ん
だ39才の男性が5分後突然失神卒倒して尿を失禁し、
10分後に吐き気と激しい頭痛を訴えた、と言った症例
も報告されている。Further, sodium azide has many physiological toxicity problems, and a person who drank 0.04 gr complained of severe chest pain resembling angina spread to both arms and numbness in the foot, and fell to the floor. A 39-year-old man who drank 0.05 to 0.06 gr of sodium azide suddenly fainted after 5 minutes and became incontinent.
There is also a case reported that he complained of nausea and severe headache 10 minutes later.
【0005】更に、アジ化ソーダは、酸と反応してアジ
化水素を発生する。これはシアンや硫化水素と共通点が
あり、チトクローム酸化酵素を抑制する。更に主な中毒
症状として、著しい血圧低下、ケイレン、頻脈、ついで
徐脈、心室細動が見られる、と言った多くの問題点を有
している。Further, sodium azide reacts with an acid to generate hydrogen azide. It has similarities with cyan and hydrogen sulfide and inhibits cytochrome oxidase. Further, it has many problems such as remarkable blood pressure drop, Keiren, tachycardia, then bradycardia, and ventricular fibrillation as main symptoms of poisoning.
【0006】[0006]
【発明が解決しようとする課題】本発明はアジ化ソーダ
を含まず製造取扱が容易で、且つ燃焼速度を容易に制御
出来、その燃焼安定性を保つことの出来るエアーバッグ
用のガス発生剤を提供するものである。DISCLOSURE OF THE INVENTION The present invention provides a gas generating agent for an air bag which does not contain sodium azide, is easy to manufacture and handle, and the burning rate can be easily controlled to maintain its combustion stability. It is provided.
【0007】[0007]
【課題を解決するための手段】本発明者等は前記した様
な問題点を解決すべく、鋭意研究を重ねた結果本発明に
至ったものである。即ち本発明はMeans for Solving the Problems The present inventors have achieved the present invention as a result of intensive studies to solve the above-mentioned problems. That is, the present invention
【0008】(1)蓚酸ジヒドラジドを含むガス発生
剤、(2)蓚酸ジヒドラジドと酸化剤と必要により結合
剤を含むガス発生剤、(3)蓚酸ジヒドラジドの含有量
が10重量%以上、酸化剤の含有量が90重量%以下、
結合剤の含有量が0〜5重量%である上記(2)のガス
発生剤、(1) A gas generating agent containing oxalic acid dihydrazide, (2) a gas generating agent containing oxalic acid dihydrazide and an oxidizing agent and optionally a binder, (3) a content of oxalic acid dihydrazide of 10% by weight or more, and an oxidizing agent. 90% by weight or less,
The gas generating agent according to (2) above, wherein the content of the binder is 0 to 5% by weight,
【0009】(4)酸化剤が、アルカリ金属もしくはア
ルカリ土類金属から選ばれるカチオンと水素を含まない
アニオンとを有する酸素酸塩である上記(2)または
(3)のガス発生剤、(5)酸素酸塩が硝酸塩、亜硝酸
塩、塩素酸塩及び過塩素酸塩からなる群より選ばれる酸
素酸塩である上記(4)のガス発生剤、に関する。(4) The gas generating agent according to the above (2) or (3), wherein the oxidizing agent is an oxyacid salt having a cation selected from alkali metals or alkaline earth metals and an anion containing no hydrogen. ) The gas generating agent according to (4) above, wherein the oxyacid salt is an oxyacid salt selected from the group consisting of nitrates, nitrites, chlorates and perchlorates.
【0010】ガス発生剤中の蓚酸ジヒドラジドの含有量
は100重量%でもよく、又、酸化剤等他の成分と併用
する場合は、蓚酸ジヒドラジドの含有量は10重量%以
上であることが好ましく、より好ましくは15〜90重
量%であり、特に好ましくは20〜85重量%である。The content of oxalic acid dihydrazide in the gas generating agent may be 100% by weight, and when used in combination with other components such as an oxidizing agent, the content of oxalic acid dihydrazide is preferably 10% by weight or more, It is more preferably 15 to 90% by weight, and particularly preferably 20 to 85% by weight.
【0011】酸化剤としては種々のものが使用できる
が、アルカリ金属またはアルカリ土類金属から選ばれる
カチオンと水素を含まないアニオンとを有する酸素酸塩
が好ましく、具体的には、硝酸リチウム、硝酸ナトリウ
ム、硝酸カリウム、硝酸マグネシウム、硝酸バリウム、
等の硝酸のアルカリ金属塩又はアルカリ土類金属塩、亜
硝酸リチウム、亜硝酸ナトリウム、亜硝酸カリウム、亜
硝酸マグネシウム、亜硝酸バリウム等の亜硝酸のアルカ
リ金属塩又はアルカリ土類金属塩、塩素酸ナトリウム、
塩素酸カリウム、塩素酸リチウム、塩素酸バリウム、塩
素酸マグネシウム、塩素酸カルシウム等の塩素酸のアル
カリ金属塩又はアルカリ土類金属塩、過塩素酸ナトリウ
ム、過塩素酸カリウム、過塩素酸リチウム、過塩素酸バ
リウム、過塩素酸マグネシウム、過塩素酸カルシウム等
の過塩素酸のアルカリ金属塩又はアルカリ土類金族塩が
挙げられる。Although various kinds of oxidants can be used, an oxyacid salt having a cation selected from alkali metals or alkaline earth metals and an anion containing no hydrogen is preferable, and specific examples thereof include lithium nitrate and nitric acid. Sodium, potassium nitrate, magnesium nitrate, barium nitrate,
Alkali metal salts or alkaline earth metal salts of nitric acid, such as lithium nitrite, sodium nitrite, potassium nitrite, magnesium nitrite, barium nitrite, etc. alkali metal salts or alkaline earth metal salts, sodium chlorate ,
Alkali metal salts or alkaline earth metal salts of chloric acid such as potassium chlorate, lithium chlorate, barium chlorate, magnesium chlorate, calcium chlorate, sodium perchlorate, potassium perchlorate, lithium perchlorate, perchlorate Examples thereof include alkali metal salts or alkaline earth metal salts of perchloric acid such as barium chlorate, magnesium perchlorate and calcium perchlorate.
【0012】酸化剤を用いる場合、ガス発生剤中の酸化
剤の含有量は90重量%以下であることが好ましく、よ
り好ましくは10〜85重量%であり、特に好ましくは
15〜80重量%である。When an oxidizing agent is used, the content of the oxidizing agent in the gas generating agent is preferably 90% by weight or less, more preferably 10 to 85% by weight, particularly preferably 15 to 80% by weight. is there.
【0013】ガス発生剤は結合剤を含有してもよく、結
合剤としては二硫化モリブデン等の適当な結合剤が使用
でき、ガス発生剤中の結合剤の含有量は0〜5重量%で
あることが好ましい。The gas generating agent may contain a binder, and a suitable binder such as molybdenum disulfide can be used as the binder, and the content of the binder in the gas generating agent is 0 to 5% by weight. Preferably there is.
【0014】本発明のガス発生剤は各成分を好ましくは
粉末状で混合することにより得られ、混合は必要により
水等の存在下に行うことが出来(ガス発生剤が蓚酸ジヒ
ドラジドのみからなる場合は、この化合物自体がガス発
生剤として使用され、この場合は粉末状であることが好
ましい)、ガス発生剤は、必要により顆粒状、ペレット
状、等の適当な形状に成形して使用することが出来る。
この際、成形するプレスの荷重を変化させることによ
り、容易にその燃焼速度を変えることができ、且つ、そ
の燃焼速度は安定している。The gas generating agent of the present invention can be obtained by mixing the respective components preferably in powder form, and the mixing can be carried out in the presence of water or the like, if necessary (when the gas generating agent consists of oxalic acid dihydrazide only). The compound itself is used as a gas generating agent, and in this case, it is preferable that the gas generating agent is in a powder form.) If necessary, the gas generating agent should be used after being formed into an appropriate shape such as granules or pellets. Can be done.
At this time, the combustion speed can be easily changed by changing the load of the press to be molded, and the combustion speed is stable.
【0015】本発明のガス発生剤は、自動車、航空機等
の高速移動体に配置された衝突時等に人体等をエアーバ
ッグ(ガスバッグ)を膨張させることによって保護する
ための安全装置において、エアーバッグを膨張させるた
めのガス発生剤として特に有用である。The gas generating agent of the present invention is used in a safety device for protecting a human body or the like by inflating an air bag (gas bag) at the time of a collision, etc., arranged in a high-speed moving body such as an automobile or an aircraft. It is particularly useful as a gas generant for inflating bags.
【0016】本発明のガス発生剤に含まれる蓚酸ジヒド
ラジドはその燃焼特性がエアーバッグ用に要求される燃
焼特性として極めて優れている。即ち、ガス発生剤のカ
サ比重に対して燃焼速度が直線的に変化するので、エア
ーバッグ用のガス発生剤としてその燃焼速度の制御が容
易であり、且つその燃焼速度が安定しており、又、長期
の経時安定性に優れている。The combustion characteristics of oxalic acid dihydrazide contained in the gas generating agent of the present invention are extremely excellent as the combustion characteristics required for an air bag. That is, since the combustion rate changes linearly with respect to the bulk specific gravity of the gas generating agent, it is easy to control the combustion rate as a gas generating agent for an air bag, and the combustion rate is stable. Excellent long-term stability over time.
【0017】更に、蓚酸ジヒドラジドはその取扱が極め
て容易である。特にアジ化ソーダではその吸湿性とアジ
化水素の毒性の面から完全な吸湿対策が不可欠である。
しかし、本発明の蓚酸ジヒドラジドを主剤とするガス発
生剤は、吸湿性が極めて少なく、この点での対策は殆ど
不要である。又毒性に関しても、蓚酸ジヒドラジド(C
AS番号996−98−5)は腹腔内投与−マウスのL
D50 が200mg/kgであるのに対し、アジ化ソー
ダ(CAS番号26628−22−8)の場合、経口投
与−マウスのLD50 が27mg/kgであり、極めて
安全性が高い。Furthermore, oxalic acid dihydrazide is extremely easy to handle. Especially in the case of sodium azide, complete hygroscopic measures are indispensable in terms of its hygroscopicity and toxicity of hydrogen azide.
However, the gas generating agent containing oxalic acid dihydrazide as the main component of the present invention has very little hygroscopicity, and measures in this respect are almost unnecessary. Regarding toxicity, oxalic acid dihydrazide (C
AS No. 996-98-5) is intraperitoneal administration-mouse L
While D 50 is 200 mg / kg, in the case of sodium azide (CAS No. 26628-22-8), the LD 50 of oral administration-mouse is 27 mg / kg, which is extremely safe.
【0018】蓚酸ジヒドラジド又はこれと他の成分との
混合物は、結合剤が存在しなくてもエアーバッグ用ガス
発生剤として充分な強度の凝集ペレットにプレスする事
が出来る。しかしながら、ガス発生剤中に少しの割合の
結合剤を加えることも出来る。二硫化モリブデンは、ガ
ス発生剤中にカリウム塩が存在する場合には特に好まし
い結合剤である。Oxalic acid dihydrazide or a mixture thereof with other components can be pressed into agglomerated pellets of sufficient strength as a gas generating agent for an air bag without the presence of a binder. However, it is also possible to add a small proportion of binder in the gas generant. Molybdenum disulfide is a particularly preferred binder when potassium salts are present in the gas generant.
【0019】実施例に示したように成形するプレスの荷
重を変化することにより容易にガス発生剤の燃焼速度を
変えることが出来、且つ、その燃焼速度が安定してお
り、更に本発明のガス発生剤はその経時熱安定性が優れ
ており、その信頼性は大であり、インフレータにおいて
使用する際に要求される特性によく適合している。As shown in the examples, the burning rate of the gas generating agent can be easily changed by changing the load of the press for molding, and the burning rate is stable. The generator has excellent thermal stability over time, its reliability is great, and it is well suited to the properties required for use in an inflator.
【0020】[0020]
【実施例】以下に実施例をあげて本発明を具体的に説明
する。 実施例1〜6 表1に示した割合で、蓚酸ジヒドラジド(SDH)と酸
化剤を粉末状でV型混合器を用いて均一に混合し、混合
物を直径10mm又は6mmの臼に入れ、600kg又
は300kgの荷重をかけてプレス成形した。得られた
ペレット1個あたりの重量を表1に示した。EXAMPLES The present invention will be specifically described with reference to the following examples. Examples 1 to 6 Oxalic acid dihydrazide (SDH) and an oxidizer were mixed in powder form at a ratio shown in Table 1 uniformly using a V-type mixer, and the mixture was put into a mortar having a diameter of 10 mm or 6 mm to obtain 600 kg or Press molding was performed by applying a load of 300 kg. The weight per pellet obtained is shown in Table 1.
【0021】 表1 実施例 SDHWT% 酸化剤 wt% 径mm 荷重kg 1個重量gr 1 36.5 KClO3 63.5 10 600 1.00 2 36.5 KClO3 63.5 10 600 0.50 3 36.5 KClO3 63.5 6 300 0.25 4 36.5 KClO3 63.5 6 600 0.25 5 40.5 KClO4 59.5 6 600 0.25 6 40.5 KClO4 59.5 6 600 0.15Table 1 Example SDHWT% Oxidizing agent wt% Diameter mm Load kg 1 piece Weight gr 1 36.5 KClO 3 63.5 10 600 1.00 2 36.5 KClO 3 63.5 10 600 0.50 3 36.5 KClO 3 63.5 6 300 0.25 4 36.5 KClO 3 63.5 6 600 0.25 5 40.5 KClO 4 59.5 6 600 0.25 6 40.5 KClO 4 59.5 6 600 0.15
【0022】得られたペレット8.0gr又は7.5g
rを1リットルのボンベに入れ、ジアゾジニトロフェノ
ール(DDNP)3mgの点火玉及びボロン/硝酸カ
リ;25/75混合比からなる伝火薬0.6grを含む
スクイブにて着火した。この時のボンベの圧力上昇と時
間の関係をプロットし、ボンベの圧力が上昇している時
間を燃焼時間とした。同じ実験を更に3回繰り返し、夫
々の実験で得られた燃焼時間を表2に示した。表2に示
した通り、非常に安定した燃焼時間を得た。8.0 g or 7.5 g of the obtained pellets
r was placed in a 1-liter cylinder and ignited with a squib containing 3 mg of a diazodinitrophenol (DDNP) ignition ball and 0.6 gr of a transfer charge of boron / potassium nitrate; 25/75 mixing ratio. The relationship between the pressure rise of the cylinder and the time at this time was plotted, and the time during which the pressure of the cylinder was rising was taken as the combustion time. The same experiment was repeated three more times, and the burning times obtained in each experiment are shown in Table 2. As shown in Table 2, a very stable burning time was obtained.
【0023】 表2 実施例 使用したペレット 燃焼時間 ms(ミリ秒) の重量gr 1回目 2回目 3回目 4回目 1 8.0 168 138 141 142 2 7.5 129 128 126 126 3 7.5 87 88 86 86 4 7.5 101 100 102 102 5 7.5 125 126 127 127 6 7.5 108 109 107 106Table 2 Examples Pellets used Examples Weight of burning time ms (milliseconds) gr 1st 2nd 3rd 4th 1 8 8.0 168 138 141 141 142 2 7.5 129 129 128 126 126 3 3 7.5 87 88 86 86 4 7.5 7.5 101 100 102 102 5 7.5 125 125 126 127 127 6 6 7.5 108 108 109 107 106
【0024】実施例7 実施例6のペレット7.5grを、高温環境後の機能保
証の面から、120℃に240時間保持後実施例1と同
様の操作で燃焼させた結果、その燃焼時間は108、1
09、106、105msであり、実施例6と同様非常
に安定した燃焼時間を得た。Example 7 The pellets of Example 6 (7.5 gr) were held at 120 ° C. for 240 hours and then burned in the same manner as in Example 1 as a result of burning, as a result of ensuring the function after high temperature environment. 108, 1
It was 09, 106, and 105 ms, and as in Example 6, a very stable combustion time was obtained.
【0025】[0025]
【発明の効果】本発明のガス発生剤は、その取扱が危険
な、且つ生理的にも有害なアジ化ソーダを使用せずに、
毒性が非常に低く、且つ取扱が容易な蓚酸ジヒドラジド
を含み、インフレータに要求される燃焼安定性を維持す
ることの出来るガス発生剤である。EFFECT OF THE INVENTION The gas generating agent of the present invention can be used without using sodium azide, which is dangerous to handle and physiologically harmful.
It is a gas generating agent that contains oxalic acid dihydrazide with extremely low toxicity and is easy to handle, and can maintain the combustion stability required for an inflator.
Claims (5)
合剤を含むガス発生剤。2. A gas generating agent containing oxalic acid dihydrazide, an oxidizing agent, and optionally a binder.
上、酸化剤の含有量が90重量%以下、結合剤の含有量
が0〜5重量%である請求項2のガス発生剤。3. The gas generating agent according to claim 2, wherein the content of oxalic acid dihydrazide is 10% by weight or more, the content of the oxidizing agent is 90% by weight or less, and the content of the binder is 0 to 5% by weight.
土類金属から選ばれるカチオンと水素を含まないアニオ
ンとを有する酸素酸塩である請求項2又は3のガス発生
剤。4. The gas generating agent according to claim 2, wherein the oxidizing agent is an oxyacid salt having a cation selected from alkali metals or alkaline earth metals and an anion containing no hydrogen.
び過塩素酸塩からなる群より選ばれる酸素酸塩である請
求項4のガス発生剤。5. The gas generating agent according to claim 4, wherein the oxyacid salt is an oxyacid salt selected from the group consisting of nitrates, nitrites, chlorates and perchlorates.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04206276A JP3132169B2 (en) | 1992-07-10 | 1992-07-10 | Gas generating agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04206276A JP3132169B2 (en) | 1992-07-10 | 1992-07-10 | Gas generating agent |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0624888A true JPH0624888A (en) | 1994-02-01 |
JP3132169B2 JP3132169B2 (en) | 2001-02-05 |
Family
ID=16520645
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP04206276A Expired - Fee Related JP3132169B2 (en) | 1992-07-10 | 1992-07-10 | Gas generating agent |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3132169B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4869073A (en) * | 1987-05-19 | 1989-09-26 | Kabushiki Kaisha Toshiba | Air conditioner with automatic selection and re-selection function for operating modes |
WO1997042142A1 (en) * | 1996-05-02 | 1997-11-13 | Trw Airbag Systems Gmbh & Co. Kg | Gas-generating, azide-free mixture |
US6332374B1 (en) | 1997-10-03 | 2001-12-25 | Bando Chemical Industries, Ltd. | Accelerator position sensor |
-
1992
- 1992-07-10 JP JP04206276A patent/JP3132169B2/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4869073A (en) * | 1987-05-19 | 1989-09-26 | Kabushiki Kaisha Toshiba | Air conditioner with automatic selection and re-selection function for operating modes |
WO1997042142A1 (en) * | 1996-05-02 | 1997-11-13 | Trw Airbag Systems Gmbh & Co. Kg | Gas-generating, azide-free mixture |
US6332374B1 (en) | 1997-10-03 | 2001-12-25 | Bando Chemical Industries, Ltd. | Accelerator position sensor |
Also Published As
Publication number | Publication date |
---|---|
JP3132169B2 (en) | 2001-02-05 |
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