WO2003011798A1 - Liant pour agent generateur de gaz et composition d'agent generateur de gaz contenant ce liant - Google Patents

Liant pour agent generateur de gaz et composition d'agent generateur de gaz contenant ce liant 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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WO
WIPO (PCT)
Prior art keywords
binder
gas generating
cationic
gas
anionic
Prior art date
Application number
PCT/JP2002/007775
Other languages
English (en)
Japanese (ja)
Inventor
Tameo Kawakami
Ryoi Kodama
Original Assignee
Nippon Kayaku Kabushiki-Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Kabushiki-Kaisha filed Critical Nippon Kayaku Kabushiki-Kaisha
Publication of WO2003011798A1 publication Critical patent/WO2003011798A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
    • 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

L'invention concerne un liant pour des agents générateurs de gaz qui contient au moins un polymère cationique choisi dans le groupe polyacrymalide cationique, alcool polyvinylique cationique, et cellulose méthylique cationique et au moins un polymère anionique choisi dans le groupe polyacrylate de sodium, polyacrymalide anionique, alcool polyvinylique anionique, et cellulose méthylique anionique. Ce liant possède une propriété de liaison élevée et une excellente stabilité thermique.
PCT/JP2002/007775 2001-08-01 2002-07-31 Liant pour agent generateur de gaz et composition d'agent generateur de gaz contenant ce liant WO2003011798A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-233062 2001-08-01
JP2001233062 2001-08-01

Publications (1)

Publication Number Publication Date
WO2003011798A1 true WO2003011798A1 (fr) 2003-02-13

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Cited By (3)

* 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 (fr) * 2011-03-23 2012-09-27 株式会社ダイセル Composition d'agent générateur de gaz
WO2012133072A1 (fr) * 2011-03-31 2012-10-04 株式会社ダイセル Composition d'agent gazogène

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10131086A (ja) * 1996-10-30 1998-05-19 Arakawa Chem Ind Co Ltd 製紙用添加剤および紙の製造方法
EP0913375A1 (fr) * 1997-03-24 1999-05-06 DAICEL CHEMICAL INDUSTRIES, Ltd. Composition servant a generer un gaz et son moulage
WO2000018705A1 (fr) * 1998-09-28 2000-04-06 Daicel Chemical Industries, Ltd. Composition de generateur de gaz

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10131086A (ja) * 1996-10-30 1998-05-19 Arakawa Chem Ind Co Ltd 製紙用添加剤および紙の製造方法
EP0913375A1 (fr) * 1997-03-24 1999-05-06 DAICEL CHEMICAL INDUSTRIES, Ltd. Composition servant a generer un gaz et son moulage
WO2000018705A1 (fr) * 1998-09-28 2000-04-06 Daicel Chemical Industries, Ltd. Composition de generateur de gaz

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 (fr) * 2011-03-23 2012-09-27 株式会社ダイセル Composition d'agent générateur de gaz
JP2012211064A (ja) * 2011-03-23 2012-11-01 Daicel Corp ガス発生剤組成物
US9487454B2 (en) 2011-03-23 2016-11-08 Diacel Corporation Gas generating composition
WO2012133072A1 (fr) * 2011-03-31 2012-10-04 株式会社ダイセル Composition d'agent gazogène
JP2012211035A (ja) * 2011-03-31 2012-11-01 Daicel Corp ガス発生剤組成物
CN103443055A (zh) * 2011-03-31 2013-12-11 株式会社大赛璐 气体发生剂组合物
CN103443055B (zh) * 2011-03-31 2015-11-25 株式会社大赛璐 气体发生剂组合物
US9458065B2 (en) 2011-03-31 2016-10-04 Daicel Corporation Gas generating composition

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