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WO2003011798A1 - Binder for gas-generating agent and gas-generating agent composition containing the same - Google Patents

Binder for gas-generating agent and gas-generating agent composition containing the same Download PDF

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Publication number
WO2003011798A1
WO2003011798A1 PCT/JP2002/007775 JP0207775W WO03011798A1 WO 2003011798 A1 WO2003011798 A1 WO 2003011798A1 JP 0207775 W JP0207775 W JP 0207775W WO 03011798 A1 WO03011798 A1 WO 03011798A1
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Prior art keywords
binder
gas generating
cationic
gas
anionic
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PCT/JP2002/007775
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French (fr)
Japanese (ja)
Inventor
Tameo Kawakami
Ryoi Kodama
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Nippon Kayaku Kabushiki-Kaisha
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Publication of WO2003011798A1 publication Critical patent/WO2003011798A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin

Definitions

  • the present invention relates to a binder for a gas generating agent, a gas generating composition and a gas generating method using the same, and is particularly suitable for a small and lightweight gas generator.
  • gas generating agents for airbags as occupant protection devices in automobiles gas generating agents containing various nitrogen-containing organic compounds, which are safer non-azide fuels, have been developed in place of sodium azide.
  • U.S. Pat. No. 5,545,272 discloses a gas generant composition of ammonium nitrate and nitroguanidine phase stabilized with 7-20% by weight of a potassium salt
  • Japanese Patent Application Laid-Open No. 7_33047 discloses a gas generating agent comprising a composition of nitroguanidine, phase-stabilized ammonium nitrate and a rubbery binder. Acrylate-terminated polybutadiene, polypudadienepolycarbonic acid, epoxy-modified polybutadiene, a curing agent and an oxidizing agent, and a gas generating composition disclosed in JP-A-6-927770.
  • the binder comprises the reaction product of a hydroxyl-containing polyglycidyl azide and at least one polyisocyanate, particularly comprising an organic binder, an active plasticizer and an oxidizing filler. At least 8 fivefold Japanese Patent Application Laid-Open No.
  • H10-72273 discloses a gas generant composition in which the amount of ammonium nitrate is% by weight; ammonium nitrate and metal salts of tetrazole, aminotetrazole, bitetrazole, bitetrazole, A gas generating agent comprising one or more reducing agents such as bitetrazole ammonium salt, nitroguanidine, guanidine nitrate and dicyandiamide and a combustion regulator such as copper oxide and manganese dioxide is disclosed.
  • the present inventors have conducted intensive studies on the components of the gas generating composition, that is, the combination of the fuel component, the oxidizing agent component, and the additive, in order to solve the above-mentioned problems.
  • the inventors have found that the above problems can be solved by using a mixture with a molecular compound as a binder, and have completed the present invention. Disclosure of the invention
  • a binder for a gas generator comprising a mixture of a cationic polymer compound and an anionic polymer compound.
  • the binder for a gas generating agent of the present invention contains a cationic polymer compound and an anionic high-molecular compound.
  • the cationic polymer compound used in the present invention is used in a gas generating composition. It is a component having an indigenous action, and may also exhibit an action as a fuel.
  • the cationic polymer compound is not particularly limited as long as it is ionized in the presence of water or the like and shows cationicity, and the colloid equivalent value (cationicity) shows a positive value. Examples include high molecular compounds having a group, but solid compounds are preferable within the operating temperature range of the gas generating agent (140T to 120 ° C). Oxygen balance, flammability, thermal stability, etc. of the high molecular compound From the viewpoint, it is preferable to use at least one selected from cationic polyacrylamide, cationic polyvinyl alcohol and cationic methyl cellulose.
  • cationic polymer compound among the above (1) to (3), cationic polyacrylamide having a colloid equivalent value (degree of cation) of (1) of 0 to 105.0 meq Z grams is particularly preferable. .
  • the anionic polymer compound used in the present invention is a component having a binder function in the gas generating composition, and may be a compound having a function as a fuel.
  • the anionic polymer-conjugated product is not particularly limited as long as it is ionized in the presence of water or the like, exhibits anionic properties, and has a negative colloid equivalent value (degree of anion). Examples include a polymer compound having a carboxylic acid residue ⁇ ⁇ a sulfonic acid residue, but a solid compound is preferable in the operating temperature range of the gas generating agent (140 ° C. (: up to 120 ° C.). It is preferable to use at least one selected from sodium polyacrylate, anionic polyacrylamide, anionic polyvinyl alcohol, and anionic methylcellulose from the viewpoints of oxygen balance, flammability, thermal stability and the like.
  • M represents a cation such as ammonium, sodium, or potassium
  • m and n represent the degree of polymerization
  • m + n 1.
  • the colloid equivalent value (degree of anion) of (2) is 0 to 15.0 milliequivalents.
  • Acrylamide is particularly preferred.
  • the binder of the present invention is a mixture of the above-mentioned cationic polymer compound and an anionic polymer compound. At this time, a neutralization reaction of charges between the cationic / anionic polymers is performed. As a result, a large polymer of the ion complex is formed, and as a result, a strong binding force is exhibited. For this reason, the binder of the present invention has a higher elasticity than a binder using only a cationic polymer compound or an anionic polymer compound or a binder using a nonionic polymer compound. Yes, it does not get stuck on the wall of the squeezer, making it easy to process the gas generating agent, and it can obtain extremely good thermal stability.
  • the binder for a gas generating agent of the present invention mixes the cationic polymer conjugate and the anionic polymer compound to neutralize the charge.
  • the charge equivalent of the compound and the charge equivalent of the anionic polymer compound are mixed to be equal, but either one may be present in excess.
  • the elasticity and sticking property of the binder of the present invention to a vessel wall and the like depend on the colloid equivalent value of a mixed system in which a cationic polymer compound and an anionic polymer compound are mixed, and are ⁇ 1.5 milliequivalent.
  • Z gram or less is preferable, and a value of zero to near zero is particularly preferable, so that the whole gas generating agent can be more strongly bonded and extremely good thermal stability can be obtained.
  • a cationic polymer compound and an anionic polymer compound are mixed in a weight ratio of 0.05: 1 to 1: 0.05.
  • a specific example is a binder obtained by mixing 0.05 to 1 part by weight of cationic polyacrylamide and 0.05 to 1 part by weight of anionic polyacrylamide.
  • the gas generating composition of the present invention contains the binder described above.
  • the amount of the binder used is not particularly limited, but is preferably 0.5 to 10% by weight in the gas generating composition.
  • the gas generating composition of the present invention can contain a plurality of binders.
  • a fuel component, an oxidizing agent, a slag forming agent, and a combustion controlling agent which are usually used can be used in addition to the binder described above. Etc. can be used.
  • a nitrogen-containing organic compound is preferable, and guanidine derivatives, tetrazole derivatives, bitetrazol derivatives, triazole derivatives, hydrazine derivatives, triazine derivatives, azodicarbonamide derivatives, disocyanamide derivatives, and nitrogen-containing compounds are preferable.
  • guanidine derivatives, tetrazole derivatives, bitetrazol derivatives, triazole derivatives, hydrazine derivatives, triazine derivatives, azodicarbonamide derivatives, disocyanamide derivatives, and nitrogen-containing compounds are preferable.
  • One type or a mixture of two or more types selected from the group consisting of transition metal complexes is exemplified.
  • nitroguanidine guanidine nitrate, 5-aminotetrazole, bitetrazole diammonium salt, 5-oxo-11,2,41-triazole, cyanoguanidine, triaminoguanidine nitrate, trihydrazinotriazine, and pyruret.
  • Azodicarbonamide, piurea, lipohydrazide, lipohydrazide transition metal complex nitrate, oxalic acid dihydrazide, hydrazine metal complex nitrate, sodium dicyanamide, bis (dicyandiamide) copper (I) nitrate, 5-aminotetrazole Copper complexes and the like can be mentioned.
  • oxidizing agents can be used as the oxidizing agent that can be used in the gas generating composition according to the present invention, and include nitrates, nitrites, and cations selected from ammonium, alkali metals, alkaline earth metals, and transition metals. At least one or two or more oxidizing agents selected from the group consisting of perchlorates, chlorates, hydroxides and oxides are preferred. Specific examples thereof include ammonium nitrate (ammonium nitrate), sodium nitrate, potassium nitrate, Examples include magnesium nitrate, strontium nitrate, basic copper nitrate, and ammonium perchlorate.
  • transition metal complexes such as diammine copper (II) nitrate and hexammine cobalt (III) can also be used.
  • ammonium nitrate phase-stabilized ammonium nitrate (PSAN), which is stabilized by adding 5 to 20% by weight of nitrite, is preferable.
  • PSAN stabilized with transition metal amine nitrate especially diammine copper (II) nitrate, diammine zinc (II) nitrate, diammine nickel (II) nitrate, and PSAN stabilized with other substances can be used. .
  • the function of the slag forming agent that can be used in the gas generating composition according to the present invention is, particularly, an alkali metal or an alkali metal generated by decomposition of an oxidizing component in the gas generating composition. This is a function to change from a liquid state to a solid state and stop it in the combustion chamber in order to avoid the release of alkaline earth metal oxides as mist outside the inflation environment.Slag formation optimized by differences in metal components You can choose the agent.
  • the slag forming agent include naturally occurring clay mainly composed of aluminogate such as acid clay, silica, bentonite, and force-oligin; synthetic artificial force such as synthetic force, synthetic force orinite, and synthetic smectite.
  • Slag forming agents selected from at least one of the following: clay, a hydrated magnesium silicate mineral such as talc; alumina, aluminum hydroxide, and silicon nitride.
  • acid clay, Alumina, silicon nitride or silica is preferred.
  • combustion control agent that can be used in the present invention may be any as long as it can control the combustion of the gas generating agent.
  • any binder can be used as long as it does not significantly affect the combustion behavior of the composition.
  • a binder include hydroxyethyl cellulose, hydroxypropyl methylcellulose, methyl cellulose, cellulose acetate, cellulose propionate, cellulose acetate butyrate, nitrocellulose, microcrystalline cellulose, polyvinyl alcohol, guar gum, and starch.
  • the gas generating composition of the present invention can obtain the desired gas generating performance by using the binder, the fuel component, the oxidizing agent, the slag forming agent, the combustion regulator, the binder other than the binder of the present invention, and the like. What is necessary is just to mix it.
  • the gas generating composition of the present invention can be formed into a molded article having a desired shape so that the gas generating composition (inflation overnight) can be filled.
  • the shape of the molded body is not particularly limited.
  • a gas generating composition comprising a fuel component, an oxidizing agent, a slag forming agent, a combustion controlling agent, a binder other than the binder of the present invention, and the like may be used.
  • a binder is added to a content of 0.5 to 10% by weight, and water or an organic solvent (for example, methanol, ethanol, etc.) is further added according to each component, uniformly mixed, kneaded, and extruded.
  • a pellet-shaped molded body obtained by using a tableting machine or the like.
  • the binder of the present invention is very suitable for extrusion molding, it is preferable that the gas generant composition of the present invention using the binder is molded by extrusion.
  • the gas generating composition of the present invention can be applied to a micro gas generating agent for airbag inflation in a driver's seat, airbag inflation in a passenger seat, side inflation in a passenger seat, and a seat belt pretensioner. Applicable to overnight lid inflation. Since the gas generating composition of the present invention has a high gas generation efficiency and a small amount of generated residue, the number of filters passing through the residue can be reduced, and the inflation rate can be reduced.
  • the above-mentioned gas generating composition is burned as fuel in a gas generator, and the air bag is inflated using the gas generated by the burning.
  • the above-described gas generating composition is burned as fuel in a gas generator, and the seatbelt is rolled up by using the gas generated by the combustion so that the seatbelt is not extended.
  • a gas generating composition was prepared according to the composition and composition ratio (weight ratio) in Table 1 (Example 1).
  • CPAM has a colloid equivalent value (cationic degree) of +2.5 meq.
  • Z-gram cationic polyacrylamide and A-PAM has a colloid equivalent value (anionic degree) of -2.5 meq.
  • HPMC stands for hydroxypropylmethylcellulose
  • MC stands for methylcellulose
  • NQ stands for nitroguanidine
  • BHT 2 NH3 stands for bitetrazolodiammonium salt
  • GN stands for guanidine nitrate
  • ATZ stands for 5-aminotetrazole
  • PSAN stands for phase Stabilized ammonium nitrate
  • SrN indicates strontium nitrate
  • bcN indicates basic copper nitrate
  • KN indicates potassium nitrate
  • AP ammonium perchlorate
  • SiN indicates silicon nitride
  • AC acid clay.
  • the gas generant composition of the present invention using the binder of the present invention is excellent in heat stability and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)

Abstract

A binder for gas-generating agents which comprises at least one cationic polymer selected from the group consisting of cationic polyacrylamide, cationic polyvinyl alcohol, and cationic methyl cellulose and at least one anionic polymer selected from the group consisting of sodium polyacrylate, anionic polyacrylamide, anionic polyvinyl alcohol, and anionic methyl cellulose. The binder has high binding power and excellent thermal stability.

Description

明 細 書 ガス発生剤用バインダ一、 及びそれを用いたガス発生剤組成物 技術分野  Description Binder for gas generating agent, and gas generating composition using the same
本発明は、 ガス発生剤用バインダー、 ガス発生剤組成物およびそれを用いたガ ス発生方法に関し、 特に小型 ·軽量のガス発生器に好適なものである。 背景技術  The present invention relates to a binder for a gas generating agent, a gas generating composition and a gas generating method using the same, and is particularly suitable for a small and lightweight gas generator. Background art
自動車における乗員保護装置としてのエアバッグ用のガス発生剤として、 アジ 化ナトリゥムに替わるより安全な非アジド系燃料である各種の含窒素有機化合物 を含むガス発生剤が開発されている。  As gas generating agents for airbags as occupant protection devices in automobiles, gas generating agents containing various nitrogen-containing organic compounds, which are safer non-azide fuels, have been developed in place of sodium azide.
例えば、 米国特許 5， 5 4 5 , 2 7 2号には、 7〜 2 0重量％のカリウム塩で 相安定化された硝酸アンモニゥムとニトログァニジンとのガス発生剤組成物が開 示され； W 0 9 6 / 2 7 5 7 4には、 ニトログァニジン、 相安定化硝酸アンモニ ゥムとゴム状バインダーとの組成物のガス発生剤が開示され；特開平 7 _ 3 3 0 4 7 7号公報には、 ァクリレート末端ポリブダジェン、 ポリプダジエンポリカル ボン酸、 エポキシ変性ポリブダジェン、 硬化剤及び酸化剤のガス発生剤組成物が 開示され；特開平 6— 9 2 7 7 0号公報には、 アジド基を発生する有機結合剤、 活性可塑剤及び酸化充填剤を特に含んでなる、 結合剤がヒドロキシル基を含むポ リグリシジルアジドと少なくとも 1種のポリィソシァネ一トとの反応生成物から なり、 酸化充填剤の少なくとも 8 5重量％が硝酸アンモニゥムからなるガス発生 剤組成物が開示され；特開平 1 0— 7 2 2 7 3号公報には、 硝酸アンモニゥムと テトラゾ一ル、 アミノテトラゾ一ル、 ビテトラゾール、 ビテトラゾール金属塩、 ビテトラゾールアンモニゥム塩、 ニトログァニジン、 硝酸グァニジン、 ジシアン ジアミドなどの 1種以上の還元剤及び酸化銅、 二酸化マンガン等の燃焼調整剤か らなるガス発生剤が開示されている。  For example, U.S. Pat. No. 5,545,272 discloses a gas generant composition of ammonium nitrate and nitroguanidine phase stabilized with 7-20% by weight of a potassium salt; Japanese Patent Application Laid-Open No. 7_33047 discloses a gas generating agent comprising a composition of nitroguanidine, phase-stabilized ammonium nitrate and a rubbery binder. Acrylate-terminated polybutadiene, polypudadienepolycarbonic acid, epoxy-modified polybutadiene, a curing agent and an oxidizing agent, and a gas generating composition disclosed in JP-A-6-927770. Wherein the binder comprises the reaction product of a hydroxyl-containing polyglycidyl azide and at least one polyisocyanate, particularly comprising an organic binder, an active plasticizer and an oxidizing filler. At least 8 fivefold Japanese Patent Application Laid-Open No. H10-72273 discloses a gas generant composition in which the amount of ammonium nitrate is% by weight; ammonium nitrate and metal salts of tetrazole, aminotetrazole, bitetrazole, bitetrazole, A gas generating agent comprising one or more reducing agents such as bitetrazole ammonium salt, nitroguanidine, guanidine nitrate and dicyandiamide and a combustion regulator such as copper oxide and manganese dioxide is disclosed.
しかしながら、 これらのガス発生剤においては、 例えば、 相安定化硝酸アンモ 二ゥムを配合薬剤とした場合、 ガス発生剤形状の熱安定性が、 不安定で、 熱の影 響を受けて、 膨張したり、 割れたりすることをふせぐために、 強い結合力のある 熱安定性に優れたバインダ一の系が求められていた。 However, in these gas generating agents, for example, when a phase-stabilized ammonium nitrate is used as a compounding agent, the heat stability of the gas generating agent is unstable, and In order to prevent them from expanding or cracking under the influence, a binder system with strong bonding power and excellent thermal stability was required.
本発明者等は、 上記の課題を解決すべく、 ガス発生剤組成物の成分、 即ち燃料 成分、 酸化剤成分、 及び添加物の組合せを鋭意検討した結果、 カチオン性高分子 化合物とァニオン性高分子化合物との混合物をバインダ一として用いることによ り上記の課題を解決できることを見出し、 本発明の完成に至ったものである。 発明の開示  The present inventors have conducted intensive studies on the components of the gas generating composition, that is, the combination of the fuel component, the oxidizing agent component, and the additive, in order to solve the above-mentioned problems. The inventors have found that the above problems can be solved by using a mixture with a molecular compound as a binder, and have completed the present invention. Disclosure of the invention
即ち、 本発明は、  That is, the present invention
(1) カチォン性高分子化合物とァニォン性高分子化合物との混合物からなるガ ス発生剤用バインダ一。  (1) A binder for a gas generator comprising a mixture of a cationic polymer compound and an anionic polymer compound.
(2) カチオン性ポリアクリルアミド、 カチオン性ポリピニルアルコール及び力 チオン性メチルセルロースからなる群より選ばれる 1種以上からなるカチ オン性高分子化合物と、 ポリアクリル酸ナトリウム、 ァニオン性ポリアク リルアミド、 ァニオン性ポリビエルアルコール及びァニオン性メチルセル ロースからなる群より選ばれる 1種以上からなるァニオン性高分子化合物 と、 を含有するガス発生剤用バインダー。  (2) Cationic polymer compound of at least one selected from the group consisting of cationic polyacrylamide, cationic polypinyl alcohol and cationic methylcellulose, sodium polyacrylate, anionic polyacrylamide, anionic A binder for a gas generating agent, comprising: an anionic polymer compound comprising at least one selected from the group consisting of polyvier alcohol and anionic methyl cellulose.
(3) (1) 又は （2) に記載のガス発生剤用バインダーを用いたガス発生剤組 成物。  (3) A gas generant composition using the gas generant binder according to (1) or (2).
(4) (1) 又は （2) に記載のガス発生剤用バインダーを 0. 5〜10. 0重 量％含有するガス発生剤組成物。  (4) A gas generating composition containing the binder for a gas generating agent according to (1) or (2) in an amount of 0.5 to 10.0% by weight.
(5) (3) 又は （4) に記載のガス発生剤組成物を燃焼させて得られる発生ガ スを用いてエアバッグを膨張させる方法。  (5) A method of inflating an airbag using generated gas obtained by burning the gas generating composition according to (3) or (4).
、 に関する。 発明を実施するための最良の形態  , Concerning. BEST MODE FOR CARRYING OUT THE INVENTION
本発明のガス発生剤用バインダ一は、 カチオン性高分子化合物とァニオン性高 分子ィ匕合物とを含有するするものである。  The binder for a gas generating agent of the present invention contains a cationic polymer compound and an anionic high-molecular compound.
本発明に用いられるカチオン性高分子化合物は、 ガス発生剤組成物においてバ インダ一の作用を有する成分であり、燃料として作用を示すものであってもよい。 カチオン性高分子化合物としては、 水等の存在下、 イオン化して、 カチオン性 を示して、 コロイド当量値 （カチオン度） はプラスの値を示すものであれば特に 限定はなく、 4級ァミン残基を有する高分子化合物などが挙げられるが、 ガス発 生剤の使用温度範囲 （一 40T〜 120°C) で固体状のものが好ましく、 高分子 化合物の酸素バランス、 燃焼性、 熱安定性などの観点からカチオン性ポリアクリ ルアミド、 カチオン性ポリビニルアルコール及びカチオン性メチルセルロースよ り選ばれる 1種以上を用いるのがよい。 The cationic polymer compound used in the present invention is used in a gas generating composition. It is a component having an indigenous action, and may also exhibit an action as a fuel. The cationic polymer compound is not particularly limited as long as it is ionized in the presence of water or the like and shows cationicity, and the colloid equivalent value (cationicity) shows a positive value. Examples include high molecular compounds having a group, but solid compounds are preferable within the operating temperature range of the gas generating agent (140T to 120 ° C). Oxygen balance, flammability, thermal stability, etc. of the high molecular compound From the viewpoint, it is preferable to use at least one selected from cationic polyacrylamide, cationic polyvinyl alcohol and cationic methyl cellulose.
このようなカチオン性高分子化合物の具体例を次に示す。  Specific examples of such a cationic polymer compound are shown below.
(1) カチオン性ポリアクリルアミド  (1) Cationic polyacrylamide
(CH 2CHCONH2) m (CH2CHC OO C2H4N (CH3) 3CL) n (CH 2 CHCONH 2 ) m (CH 2 CHC OO C 2 H 4 N (CH 3 ) 3 CL) n
(2) カチオン性ポリビニルアルコール (2) Cationic polyvinyl alcohol
(CH 2CHOH) m (CH2CHO C O CH3) n (CH 2 CHOH) m (CH 2 CHO CO CH 3 ) n
(3) カチオン性メチルセルロース  (3) Cationic methyl cellulose
(カチオン性メチルセルロースの例としてカチオン化セルロースの化学構造式 を示す）  (The chemical structural formula of cationized cellulose is shown as an example of cationic methyl cellulose.)
OH CH3 OH CH 3
0 - (CH CH2O) 2-CH CHCH N+-C12H25 Cellulose—〇一Cellulose CH3 0-(CH CH2O) 2-CH CHCH N + -C12H25 Cellulose—〇One Cellulose CH3
[上記の一般式中、 m、 nは重合度を示し、 m+n=lである] [In the above general formula, m and n indicate the degree of polymerization, and m + n = l]
カチオン性高分子化合物としては、 上記の （1) 〜 （3) の中でも （1) のコ ロイド当量値 （カチオン度） が 0〜十 5. 0ミリ当量 Zグラムのカチオン性ポリ アクリルアミドが特に好ましい。  As the cationic polymer compound, among the above (1) to (3), cationic polyacrylamide having a colloid equivalent value (degree of cation) of (1) of 0 to 105.0 meq Z grams is particularly preferable. .
本発明に用いられるァニオン性高分子化合物は、 ガス発生剤組成物においてパ インダ一の作用を有する成分であり、燃料として作用を示すものであってもよい。 ァニオン性高分子ィ匕合物としては、 水等の存在下、 イオン化して、 ァニオン性 を示して、 コロイド当量値 （ァニオン度） はマイナスの値を示すものであれば特 に限定はなく、 カルボン酸残基ゃスルホン酸残基を有する高分子化合物などが挙 げられるが、 ガス発生剤の使用温度範囲 （一 40° (：〜 120°C) で固体状のもの が好ましく、 高分子化合物の酸素バランス、 燃焼性、 熱安定性などの観点からポ リアクリル酸ナトリウム、 ァニオン性ポリアクリルアミド、 ァニオン性ポリビニ ルアルコール及びァニォン性メチルセルロースより選ばれる 1種以上を用いるの がよい。 The anionic polymer compound used in the present invention is a component having a binder function in the gas generating composition, and may be a compound having a function as a fuel. The anionic polymer-conjugated product is not particularly limited as long as it is ionized in the presence of water or the like, exhibits anionic properties, and has a negative colloid equivalent value (degree of anion). Examples include a polymer compound having a carboxylic acid residue 残 基 a sulfonic acid residue, but a solid compound is preferable in the operating temperature range of the gas generating agent (140 ° C. (: up to 120 ° C.). It is preferable to use at least one selected from sodium polyacrylate, anionic polyacrylamide, anionic polyvinyl alcohol, and anionic methylcellulose from the viewpoints of oxygen balance, flammability, thermal stability and the like.
このようなァニオン性高分子ィヒ合物の具体例を次に示す。  Specific examples of such an anionic polymer compound are shown below.
(1) ポリアクリル酸金属塩  (1) Metal polyacrylate
(CH 2CHCOOM) m (CH 2 CHCOOM) m
(2) ァニォン性ポリアクリルァミド  (2) Anionic polyacrylamide
(CH 2CHCONH2) m (CH2CHCOOM) n (CH 2CHCONH2) m (CH2CHCOOM) n
(3) ァニオン性ポリビニルアルコール  (3) Anionic polyvinyl alcohol
(CH 2CHOH) m (CH2CHOCOCH3) n (CH 2CHOH) m (CH 2 CHOCOCH 3 ) n
(4) ァニオン性メチルセル口一ス  (4) Anionic methylcell
(ァニオン性メチルセルロースの例としてカルポキシメチルセルロースナトリ ゥムの化学構造式を示す）  (The chemical structural formula of carboxymethylcellulose sodium is shown as an example of anionic methylcellulose.)
CH2OCH2CO2" Na+ CH2OCH2CO2 "Na +
-Cellulose— O— Cellulose- 0--Cellulose— O— Cellulose- 0-
II
CH2OCH2CO2 - Na+ CH2OCH2CO2-Na +
[上記の一般式中、 Mはアンモニゥム、 ナトリウム、 カリウム等の陽イオンを示 し、 m、 nは重合度を示し、 m+n=lである] [In the above general formula, M represents a cation such as ammonium, sodium, or potassium, m and n represent the degree of polymerization, and m + n = 1.]
ァニオン性高分子化合物としては、 上記の （1) 〜 （4) の中でも （2) のコ ロイド当量値 （ァニオン度） が 0〜一 5. 0ミリ当量 Zグラムのァニオン性ポリ アクリルアミドが特に好ましい。 As the anionic polymer compound, among the above (1) to (4), the colloid equivalent value (degree of anion) of (2) is 0 to 15.0 milliequivalents. Acrylamide is particularly preferred.
本発明のバインダ一は、 上記のカチオン性高分子化合物とァニオン性高分子化 合物と混合してなるものであるが、 この時、 カチオン性/ァニオン性高分子同士 の電荷の中和反応が起こり、 イオンコンプレックスの大きい高分子を形成して、 その結果、 強力な結合力を示すようになる。 このため、 本発明のバインダーは、 カチオン性高分子化合物のみを或いはァニオン性高分子化合物のみを用いたバイ ンダ一や、非イオン性高分子化合物を用いたバインダ一に比して、弾力性があり、 力つ器壁に引っ付くことがなく、 ガス発生剤の加工がし易くなるばかりか、 極め て良好な熱安定性を得ることができる。  The binder of the present invention is a mixture of the above-mentioned cationic polymer compound and an anionic polymer compound. At this time, a neutralization reaction of charges between the cationic / anionic polymers is performed. As a result, a large polymer of the ion complex is formed, and as a result, a strong binding force is exhibited. For this reason, the binder of the present invention has a higher elasticity than a binder using only a cationic polymer compound or an anionic polymer compound or a binder using a nonionic polymer compound. Yes, it does not get stuck on the wall of the squeezer, making it easy to process the gas generating agent, and it can obtain extremely good thermal stability.
本発明のガス発生剤用バインダーは、 前述の通り、 カチオン性高分子ィ匕合物と ァニオン性高分子化合物とを混合し荷電中和するものであるため、 その混合割合 は、 カチオン性高分子化合物の荷電当量とァニオン性高分子化合物の荷電当量と が等しくなるように混合するのが理想的ではあるが、 いずれかが過剰に存在して もよい。  As described above, the binder for a gas generating agent of the present invention mixes the cationic polymer conjugate and the anionic polymer compound to neutralize the charge. Ideally, the charge equivalent of the compound and the charge equivalent of the anionic polymer compound are mixed to be equal, but either one may be present in excess.
本発明のバインダ一の弾力性や器壁などへの引っ付き性は、 カチオン性高分子 化合物とァニオン性高分子化合物とを混合した、 混合系のコロイド当量値に依存 し、 ± 1 . 5ミリ当量 Zグラム以下が好ましく、 ゼロないしゼロ近くの値が特に 好ましく、 ガス発生剤全体をより強く結合させることができ、 またきわめて良好 な熱安定を得ることができる。  The elasticity and sticking property of the binder of the present invention to a vessel wall and the like depend on the colloid equivalent value of a mixed system in which a cationic polymer compound and an anionic polymer compound are mixed, and are ± 1.5 milliequivalent. Z gram or less is preferable, and a value of zero to near zero is particularly preferable, so that the whole gas generating agent can be more strongly bonded and extremely good thermal stability can be obtained.
このようなバインダーを得るためには、 例えば、 カチオン性高分子化合物とァ 二オン性高分子化合物とを、 重量比で、 0 . 0 5 ： 1〜1 ： 0 . 0 5の範囲で混 合すればよく、 具体的な例としては、 カチオン性ポリアクリルアミド 0 . 0 5〜 1重量部とァニオン性ポリアクリルアミド 0 . 0 5〜1重量部とを混合したバイ ンダ一が挙げられる。  In order to obtain such a binder, for example, a cationic polymer compound and an anionic polymer compound are mixed in a weight ratio of 0.05: 1 to 1: 0.05. A specific example is a binder obtained by mixing 0.05 to 1 part by weight of cationic polyacrylamide and 0.05 to 1 part by weight of anionic polyacrylamide.
引き続き、 本発明のガス発生剤組成物について説明する。  Subsequently, the gas generating composition of the present invention will be described.
本発明のガス発生剤組成物は、 前述のバインダーを含有するものである。 バイ ンダ一の使用量は特に限定はないが、 好ましくは、 ガス発生剤組成物中 0 . 5〜 1 0重量％となるようにするのがよい。 また、 本発明のガス発生剤組成物は、 バ ィンダーを複数種含有することができる。 また、 本発明のガス発生剤は、 前述のバインダーのほかに、 通常使用する燃料 成分、 酸化剤、 スラグ形成剤、 燃焼調節剤を用いることができ、 更に本発明のバ ィンダ一以外のバインダ一などを用いることができる。 The gas generating composition of the present invention contains the binder described above. The amount of the binder used is not particularly limited, but is preferably 0.5 to 10% by weight in the gas generating composition. In addition, the gas generating composition of the present invention can contain a plurality of binders. As the gas generating agent of the present invention, a fuel component, an oxidizing agent, a slag forming agent, and a combustion controlling agent which are usually used can be used in addition to the binder described above. Etc. can be used.
本発明で用いることができる燃料成分としては、含窒素有機化合物が好ましく、 グァニジン誘導体、 テトラゾール誘導体、 ビテトラゾ一ル誘導体、 トリァゾール 誘導体、 ヒドラジン誘導体、 トリアジン誘導体、 ァゾジカルボンアミド誘導体、 ジシァナミド誘導体、 含窒素遷移金属錯体から成る群から選ばれる 1種又は 2種 以上の混合物などが挙げられる。 これらの具体例としては、 ニトログァニジン、 硝酸グァニジン、 5—アミノテトラゾール、 ビテトラゾールジアンモニゥム塩、 5—ォキソ一 1 , 2， 4一トリァゾール、 シァノグァニジン、 トリアミノグァ二 ジン硝酸塩、 トリヒドラジノトリアジン、 ピウレツト、 ァゾジカルボンアミド、 ピウレア、 力ルポヒドラジド、 力ルポヒドラジド遷移金属錯体硝酸塩、 蓚酸ジヒ ドラジド、 ヒドラジン金属錯体硝酸塩、 ナトリウムジシアナミド、 ビス （ジシァ ンジアミド） 銅 （I ) 硝酸塩、 5—アミノテトラゾ一ルの銅錯体等を挙げること ができる。  As the fuel component that can be used in the present invention, a nitrogen-containing organic compound is preferable, and guanidine derivatives, tetrazole derivatives, bitetrazol derivatives, triazole derivatives, hydrazine derivatives, triazine derivatives, azodicarbonamide derivatives, disocyanamide derivatives, and nitrogen-containing compounds are preferable. One type or a mixture of two or more types selected from the group consisting of transition metal complexes is exemplified. Specific examples of these include nitroguanidine, guanidine nitrate, 5-aminotetrazole, bitetrazole diammonium salt, 5-oxo-11,2,41-triazole, cyanoguanidine, triaminoguanidine nitrate, trihydrazinotriazine, and pyruret. Azodicarbonamide, piurea, lipohydrazide, lipohydrazide transition metal complex nitrate, oxalic acid dihydrazide, hydrazine metal complex nitrate, sodium dicyanamide, bis (dicyandiamide) copper (I) nitrate, 5-aminotetrazole Copper complexes and the like can be mentioned.
本発明に係わるガス発生剤組成物に用いることができる酸化剤としては種々の ものが使用できるが、 アンモニゥム、 アルカリ金属、 アルカリ土類金属又は遷移 金属から選ばれたカチオンを含む硝酸塩、 亜硝酸塩、 過塩素酸塩、 塩素酸塩、 水 酸化物及び酸化物からなる群より選ばれる少なくとも 1種又は 2種以上の酸化剤 が好ましく、 その具体例として、 硝酸アンモニゥム （硝安） 、 硝酸ナトリウム、 硝酸カリウム、 硝酸マグネシウム、 硝酸ストロンチウム、 塩基性硝酸銅、 過塩素 酸アンモニゥム等が挙げられる。 また、 ジアンミン銅 （I I ) 硝酸塩、 へキサァ ンミンコバルト （I I I ) 等の遷移金属錯体も使用できる。 硝安は、 硝石を 5— 2 0重量％添加して安定化した相安定化硝安 （P S AN) が好ましい。  Various oxidizing agents can be used as the oxidizing agent that can be used in the gas generating composition according to the present invention, and include nitrates, nitrites, and cations selected from ammonium, alkali metals, alkaline earth metals, and transition metals. At least one or two or more oxidizing agents selected from the group consisting of perchlorates, chlorates, hydroxides and oxides are preferred. Specific examples thereof include ammonium nitrate (ammonium nitrate), sodium nitrate, potassium nitrate, Examples include magnesium nitrate, strontium nitrate, basic copper nitrate, and ammonium perchlorate. In addition, transition metal complexes such as diammine copper (II) nitrate and hexammine cobalt (III) can also be used. As for ammonium nitrate, phase-stabilized ammonium nitrate (PSAN), which is stabilized by adding 5 to 20% by weight of nitrite, is preferable.
また、 遷移金属アミン硝酸塩、 特にジアンミン銅 （I I ) 硝酸塩、 ジアンミン 亜鉛 ( I I ) 硝酸塩、 ジアンミンニッケル （I I ) 硝酸塩等で安定化した P S A Nや、 その他の、 物質で、 安定化した P S ANも使用できる。  Also, PSAN stabilized with transition metal amine nitrate, especially diammine copper (II) nitrate, diammine zinc (II) nitrate, diammine nickel (II) nitrate, and PSAN stabilized with other substances can be used. .
本発明に係わるガス発生剤組成物に用いることができるスラグ形成剤の機能は、 ガス発生剤組成物中の特に酸化剤成分の分解によって生成するアルカリ金属又は アルカリ土類金属の酸化物をミストとしてインフレ一夕外へ放出することを避け るため液状から固体状に変えて燃焼室内に止める機能であり、 金属成分の違いに よつて最適化されたスラグ形成剤を選ぶことができる。 The function of the slag forming agent that can be used in the gas generating composition according to the present invention is, particularly, an alkali metal or an alkali metal generated by decomposition of an oxidizing component in the gas generating composition. This is a function to change from a liquid state to a solid state and stop it in the combustion chamber in order to avoid the release of alkaline earth metal oxides as mist outside the inflation environment.Slag formation optimized by differences in metal components You can choose the agent.
スラグ形成剤の具体例としては、 酸性白土、 シリカ、 ベントナイト系、 力オリ ン系等のアルミノゲイ酸塩を主成分とする天然に産する粘土；合成マイ力、 合成 力オリナイト、 合成スメクタイト等の人工的粘土；含水マグネシウムケィ酸塩鉱 物の 1種であるタルク等；アルミナ、 水酸化アルミニウム、 窒化珪素等の少なく とも 1種から選ばれたスラグ形成剤が挙げられ、 これらの中では酸性白土、 アル ミナ、 窒化珪素又はシリカが好ましい。  Specific examples of the slag forming agent include naturally occurring clay mainly composed of aluminogate such as acid clay, silica, bentonite, and force-oligin; synthetic artificial force such as synthetic force, synthetic force orinite, and synthetic smectite. Slag forming agents selected from at least one of the following: clay, a hydrated magnesium silicate mineral such as talc; alumina, aluminum hydroxide, and silicon nitride. Among these, acid clay, Alumina, silicon nitride or silica is preferred.
また、 本発明において用いうる燃焼調節剤としては、 ガス発生剤の燃焼を調節 できるものであればよいが、 具体的には、 酸化鉄、 酸化ニッケル、 酸化銅、 酸化 亜鉛、 酸化マンガン、 酸化クロム、 酸化コバルト、 酸化モリブデン、 酸化バナジ ゥム、 酸化タングステン等の遷移金属酸化物や、 活性炭、 グラフアイト、 力一ポ ンブラック等の炭素類等を例示することができる。  In addition, the combustion control agent that can be used in the present invention may be any as long as it can control the combustion of the gas generating agent. Specifically, iron oxide, nickel oxide, copper oxide, zinc oxide, manganese oxide, chromium oxide And transition metal oxides such as cobalt oxide, molybdenum oxide, vanadium oxide, and tungsten oxide; and carbons such as activated carbon, graphite, and black carbon.
本発明のガス発生剤組成物において用いることができる、 本発明のバインダー 以外のバインダ一としては、 組成物の燃焼挙動に大幅な悪影響を与えないもので あれば何れでも使用可能である。 このようなバインダーの具体例としては、 ヒド ロキシェチルセルロース、 ヒドロキシプロピルメチルセルロース、 メチルセル口 ース、 酢酸セルロース、 プロピオン酸セルロース、 酢酸酪酸セルロース、 ニトロ セルロース、 微結晶性セルロース、 ポリビニルアルコール、 グァガム、 澱粉等の 多糖誘導体、ポリアクリルアミド、ポリビニールピロリドン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、 合成ヒドロタルサイト等の無機バインダーが挙げられる。 そして、 本発明のガス発生剤組成物は、 本発明のバインダー、 燃料成分、 酸化 剤、 スラグ形成剤、 燃焼調節剤、 本発明のバインダー以外のバインダーなどを、 目的とするガス発生性能が得られるように配合すればよい。  As the binder other than the binder of the present invention that can be used in the gas generating composition of the present invention, any binder can be used as long as it does not significantly affect the combustion behavior of the composition. Specific examples of such a binder include hydroxyethyl cellulose, hydroxypropyl methylcellulose, methyl cellulose, cellulose acetate, cellulose propionate, cellulose acetate butyrate, nitrocellulose, microcrystalline cellulose, polyvinyl alcohol, guar gum, and starch. And organic binders such as polyacrylamide and polyvinylpyrrolidone, and inorganic binders such as molybdenum disulfide, acid clay, talc, bentonite, diatomaceous earth, kaolin, silica, alumina, and synthetic hydrotalcite. Then, the gas generating composition of the present invention can obtain the desired gas generating performance by using the binder, the fuel component, the oxidizing agent, the slag forming agent, the combustion regulator, the binder other than the binder of the present invention, and the like. What is necessary is just to mix it.
本発明のガス発生剤組成物では、 その成分としてバインダー、 含窒素有機化合 物、 酸化剤を含む場合、 それぞれの組成 （重量比） の範囲は、 バインダー：含窒 素有機化合物：酸化剤 = 1 : 2〜 1 0 8 : 6〜 1 6 5であることが好ましい。 ま た、 更にその成分にスラグ形成剤を含む場合、 それぞれの組成 （重量比） の範囲 は、 バインダー：含窒素有機化合物：酸化剤：スラグ形成剤 = 1 ： 2〜 1 0 8 ： 6〜： L 6 5 : 0 . 1〜 1 2であることが好ましい。 When the gas generating composition of the present invention contains a binder, a nitrogen-containing organic compound, and an oxidizing agent as its components, the range of each composition (weight ratio) is as follows: binder: nitrogen-containing organic compound: oxidizing agent = 1 : 2 to 108: 6 to 165. Ma When the component further contains a slag forming agent, the range of each composition (weight ratio) is as follows: binder: nitrogen-containing organic compound: oxidizing agent: slag forming agent = 1: 2 to 108: 6 to: L It is preferably 65: 0.1 to 12.
本発明のガス発生剤組成物は、 ガス発生器 （インフレ一夕） に充填可能な形態 にするため、 所望の形状の成型体にすることができる。 この成型体の形状は特に 限定されるものではなく、 例えば、 燃料成分、 酸化剤、 スラグ形成剤、 燃焼調節 剤、 本発明のバインダー以外のバインダーなどからなるガス発生剤組成物に、 本 発明のバインダーを含有率で 0 . 5〜1 0重量％になるように添加し、 さらに各 成分に応じて水又は有機溶媒 （例えばメタノール、 エタノール等） を添加し均一 に混合した後、 混練し押出成型し裁断して得られる円柱状の成型体、 打錠機等を 用いて得られるペレツト状の成型体にすることができる。  The gas generating composition of the present invention can be formed into a molded article having a desired shape so that the gas generating composition (inflation overnight) can be filled. The shape of the molded body is not particularly limited. For example, a gas generating composition comprising a fuel component, an oxidizing agent, a slag forming agent, a combustion controlling agent, a binder other than the binder of the present invention, and the like may be used. A binder is added to a content of 0.5 to 10% by weight, and water or an organic solvent (for example, methanol, ethanol, etc.) is further added according to each component, uniformly mixed, kneaded, and extruded. And a pellet-shaped molded body obtained by using a tableting machine or the like.
特に、 本発明のバインダーは押出成型に極めて好適であるため、 これを用いた 本発明のガス発生剤組成物は押出成型により成型するのが好ましい。  In particular, since the binder of the present invention is very suitable for extrusion molding, it is preferable that the gas generant composition of the present invention using the binder is molded by extrusion.
本発明のガス発生剤組成物は、 運転席のエアバッグインフレ一夕、 助手席のェ ァバッグインフレ一夕及びサイドインフレ一夕及びシートベルトプリテンショナ —用マイクロガス発生剤に適用でき、 さらにハイプリッドインフレ一夕にも適用 できる。 本発明のガス発生剤組成物は、 ガス発生効率が高く、 残渣の生成量が少 ないので、 残渣を通過するフィルターを減らすことができ、 インフレ一夕を小型 化することができる。  INDUSTRIAL APPLICABILITY The gas generating composition of the present invention can be applied to a micro gas generating agent for airbag inflation in a driver's seat, airbag inflation in a passenger seat, side inflation in a passenger seat, and a seat belt pretensioner. Applicable to overnight lid inflation. Since the gas generating composition of the present invention has a high gas generation efficiency and a small amount of generated residue, the number of filters passing through the residue can be reduced, and the inflation rate can be reduced.
本発明の方法は、 上述したガス発生剤組成物をガス発生器において燃料として 燃焼させ、 この燃焼により発生したガスを用いてエアバッグを膨張させるもので ある。  According to the method of the present invention, the above-mentioned gas generating composition is burned as fuel in a gas generator, and the air bag is inflated using the gas generated by the burning.
またシートベルトプリテンショナ一において上述したガス発生剤組成物をガス 発生器において燃料として燃焼させ、 この燃焼により発生したガスを用いてシー トベルトを巻き込むことによってシートベルトを伸びないようにする。 実施例  Further, in the seatbelt pretensioner, the above-described gas generating composition is burned as fuel in a gas generator, and the seatbelt is rolled up by using the gas generated by the combustion so that the seatbelt is not extended. Example
以下実施例により本発明を詳細に説明するが、 本発明はこれらの実施例に限定 されるものではない。 表 1の組成 ·組成比 （重量比） に従ってガス発生剤組成物を調製し （実施例 1Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. A gas generating composition was prepared according to the composition and composition ratio (weight ratio) in Table 1 (Example 1).
〜 5及び比較例 1〜 5 ) 、 耐熱試験（ 107 C, 400時間）及び熱衝撃試験 （一 40°C〜100°C, 200回） 後の重量減少 (マイナス％) を測定した。 耐熱試 験はタバイエスペック社製高温 (耐熱性)試験装置、 熱衝撃試験はタバイエスぺッ ク社製熱衝撃 （耐温度特性） 試験装置により測定した。 その結果を表 1に示す。 -5 and Comparative Examples 1-5), the heat loss test (107 C, 400 hours) and the weight loss (minus%) after the thermal shock test (one 40 ° C to 100 ° C, 200 times) were measured. The heat resistance test was performed using a high-temperature (heat resistance) test device manufactured by Tabai Espec Corporation, and the thermal shock test was performed using a thermal shock (temperature resistance) test device manufactured by Tabai Espec Corporation. The results are shown in Table 1.
組成 組成比 耐熱試験熱衝撃試験 実施例 1 C-PAM/A-PAM/HPMC/ 0.5/0.5/1.7/ -0.02¾ -0.01% Composition Composition ratio Heat resistance test Thermal shock test Example 1 C-PAM / A-PAM / HPMC / 0.5 / 0.5 / 1.7 / -0.02¾ -0.01%
GN/PSAN/SrN/bcN 46.5/9.6/32.3/8.9  GN / PSAN / SrN / bcN 46.5 / 9.6 / 32.3 / 8.9
比較例 1 HPMC/GN/PSAN/SrN/ 2.7/46.5/9.6/32.3/ -0.07% -0.28% bcN 8.9 Comparative Example 1 HPMC / GN / PSAN / SrN / 2.7 / 46.5 / 9.6 / 32.3 / -0.07% -0.28% bcN 8.9
実施例 2 C-PAM/A-PAM/HPMC/ I.0/1.0/3.4/ 0.00% 0.00% Example 2 C-PAM / A-PAM / HPMC / I.0 / 1.0 / 3.4 / 0.00% 0.00%
BHT2NH3/PSAN/SrN 13.8/78.1/2.7  BHT2NH3 / PSAN / SrN 13.8 / 78.1 / 2.7
比較例 2 HPMC/BHT2NH3/ 10.0/12.2/ -0.02% -0.02% Comparative Example 2 HPMC / BHT2NH3 / 10.0 / 12.2 / -0.02% -0.02%
PSAN/SrN 75.1/2.7  PSAN / SrN 75.1 / 2.7
実施例 3 C-PAM/A-PAM/GUARGUM/ 0.5/0.5/3.0/ -0.06¾ 0.00% Example 3 C-PAM / A-PAM / GUARGUM / 0.5 / 0.5 / 3.0 / -0.06¾ 0.00%
NQ/GN/SrN/KN/SiN 26.8/17.4/42.9/5.4/3.5  NQ / GN / SrN / KN / SiN 26.8 / 17.4 / 42.9 / 5.4 / 3.5
比較例 3 GUARGUM/NQ/GN/ 4.0/26.8/17.4/ -0.34% -0.04% Comparative Example 3 GUARGUM / NQ / GN / 4.0 / 26.8 / 17.4 / -0.34% -0.04%
SrN/KN/SiN 42.9/5.4/3.5  SrN / KN / SiN 42.9 / 5.4 / 3.5
実施例 4 C-PAM/A-PAM/MC/GN/ 0.5/0.5/2.0/43.9/ -0.04¾ 0.00% Example 4 C-PAM / A-PAM / MC / GN / 0.5 / 0.5 / 2.0 / 43.9 / -0.04¾ 0.00%
SrN/bcN/AC 27.2/23.9/2  SrN / bcN / AC 27.2 / 23.9 / 2
比較例 4 MC/GN/SrN/bcN 3.0/43.9/27.2/23.9 —0.20% 0.00% Comparative Example 4 MC / GN / SrN / bcN 3.0 / 43.9 / 27.2 / 23.9 —0.20% 0.00%
/AC /2  / AC / 2
実施例 5 C-PAM/A-PAM/MC/GN/ 0.5/0.5/3.0/40.6/ -0.02% -0.02% Example 5 C-PAM / A-PAM / MC / GN / 0.5 / 0.5 / 3.0 / 40.6 / -0.02% -0.02%
ATZ/SrN/AP II.8/13.8/29.8  ATZ / SrN / AP II.8 / 13.8 / 29.8
比較例 5 MC/GN/ATZ/ 4.0/40.6/11.8/ -0.11% -0.09% Comparative Example 5 MC / GN / ATZ / 4.0 / 40.6 / 11.8 / -0.11% -0.09%
SrN/AP 13.8/ 29.8 表 1によれば、 本発明のガス発生剤組成物のように、 重量減少が少ないほど、 熱安定であることを示している。 SrN / AP 13.8 / 29.8 According to Table 1, like the gas generating composition of the present invention, the smaller the weight loss, the more heat stable.
なお、 表 1中、 C-P AMはコロイド当量値 （カチオン度） が +2. 5ミリ当量 Zグラムのカチオン性ポリアクリルアミド、 A- PAMはコロイド当量値（ァニォ ン度） がー 2. 5ミリ当量/グラムのァニオン性ポリアクリルアミド、 HPMC はヒドロキシプロピルメチルセルロース、 MCはメチルセルロースを表し、 NQ はニトログァニジン、 BHT 2 NH 3はビテトラゾ一ルジアンモニゥム塩、 GN は硝酸グァニジン、 ATZは 5—アミノテトラゾ一ル、 PSANは相安定化硝酸 アンモニゥム、 S rNは硝酸ストロンチウム、 b cNは塩基性硝酸銅、 KNは硝 酸カリウム、 A Pは過塩素酸アンモニゥム、 S i Nは窒化珪素、 ACは酸性白土 を示す。 産業上の利用可能性  In Table 1, CPAM has a colloid equivalent value (cationic degree) of +2.5 meq. Z-gram cationic polyacrylamide, and A-PAM has a colloid equivalent value (anionic degree) of -2.5 meq. Per gram of anionic polyacrylamide, HPMC stands for hydroxypropylmethylcellulose, MC stands for methylcellulose, NQ stands for nitroguanidine, BHT 2 NH3 stands for bitetrazolodiammonium salt, GN stands for guanidine nitrate, ATZ stands for 5-aminotetrazole, PSAN stands for phase Stabilized ammonium nitrate, SrN indicates strontium nitrate, bcN indicates basic copper nitrate, KN indicates potassium nitrate, AP indicates ammonium perchlorate, SiN indicates silicon nitride, and AC indicates acid clay. Industrial applicability
以上のように、 本発明のバインダーを用いた本発明のガス発生剤組成物は、 熱安 定性などに優れるものである。 As described above, the gas generant composition of the present invention using the binder of the present invention is excellent in heat stability and the like.

Claims

請 求 の 範 囲 The scope of the claims
1 . カチオン性高分子化合物とァニオン性高分子化合物との混合物からなるガス 発生剤用パインダ一。  1. A binder for a gas generant comprising a mixture of a cationic polymer compound and an anionic polymer compound.
2 . カチオン性ポリアクリルアミド、 カチオン性ポリビエルアルコール及びカチ オン性メチルセルロースからなる群より選ばれる 1種以上からなるカチオン性高 分子化合物と、 ポリアクリル酸ナトリウム、 ァニオン性ポリアクリルアミド、 ァ 二オン性ポリビニルアルコール及びァニオン性メチルセルロースからなる群より 選ばれる 1種以上からなるァニオン性高分子化合物と、 を含有するガス発生剤用 バインダ一。  2. Cationic high molecular weight compound consisting of at least one selected from the group consisting of cationic polyacrylamide, cationic polybiol alcohol and cationic methylcellulose, sodium polyacrylate, anionic polyacrylamide, and cationic polyvinyl A binder for a gas generating agent, comprising: an anionic polymer compound comprising at least one selected from the group consisting of an alcohol and an anionic methyl cellulose;
3 . 請求の範囲 1又は請求の範囲 2に記載のガス発生剤用バインダーを用いたガ ス発生剤組成物。  3. A gas generating composition using the binder for a gas generating agent according to claim 1 or 2.
4. 請求の範囲 1又は請求の範囲 2に記載のガス発生剤用バインダーを 0 . 5〜 1 0 . 0重量％含有するガス発生剤組成物。  4. A gas generating composition comprising the binder for a gas generating agent according to claim 1 or 0.5 to 1.0% by weight.
5 .請求の範囲 3又は請求の範囲 4に記載のガス発生剤組成物を燃焼させて得ら れる発生ガスを用いてエアバッグを膨張させる方法。  5. A method for inflating an airbag using a generated gas obtained by burning the gas generating composition according to claim 3 or 4.
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WO2012128302A1 (en) * 2011-03-23 2012-09-27 株式会社ダイセル Gas-generating agent composition
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WO2000018705A1 (en) * 1998-09-28 2000-04-06 Daicel Chemical Industries, Ltd. Gas generator composition

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7811397B2 (en) 2004-09-27 2010-10-12 Daicel Chemical Industries, Ltd. Gas generating agent
WO2012128302A1 (en) * 2011-03-23 2012-09-27 株式会社ダイセル Gas-generating agent composition
JP2012211064A (en) * 2011-03-23 2012-11-01 Daicel Corp Gas-generating agent composition
US9487454B2 (en) 2011-03-23 2016-11-08 Diacel Corporation Gas generating composition
WO2012133072A1 (en) * 2011-03-31 2012-10-04 株式会社ダイセル Gas-forming agent composition
JP2012211035A (en) * 2011-03-31 2012-11-01 Daicel Corp Gas-generating agent composition
CN103443055A (en) * 2011-03-31 2013-12-11 株式会社大赛璐 Gas-forming agent composition
CN103443055B (en) * 2011-03-31 2015-11-25 株式会社大赛璐 Gas generant composition
US9458065B2 (en) 2011-03-31 2016-10-04 Daicel Corporation Gas generating composition

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