JP2011111371A - Gas generator composition - Google Patents
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- JP2011111371A JP2011111371A JP2009269975A JP2009269975A JP2011111371A JP 2011111371 A JP2011111371 A JP 2011111371A JP 2009269975 A JP2009269975 A JP 2009269975A JP 2009269975 A JP2009269975 A JP 2009269975A JP 2011111371 A JP2011111371 A JP 2011111371A
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- ammonium nitrate
- nitrogen
- containing organic
- organic compound
- nitrate
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- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 239000007789 gas Substances 0.000 claims abstract description 51
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 50
- -1 nitrogen-containing organic compound Chemical class 0.000 claims abstract description 31
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 239000005749 Copper compound Substances 0.000 claims abstract description 11
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 11
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002357 guanidines Chemical class 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 2
- 238000002485 combustion reaction Methods 0.000 description 18
- 239000003381 stabilizer Substances 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- BAKYASSDAXQKKY-UHFFFAOYSA-N 4-Hydroxy-3-methylbenzaldehyde Chemical compound CC1=CC(C=O)=CC=C1O BAKYASSDAXQKKY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- KPTSBKIDIWXFLF-UHFFFAOYSA-N 1,1,2-triaminoguanidine Chemical compound NN=C(N)N(N)N KPTSBKIDIWXFLF-UHFFFAOYSA-N 0.000 description 1
- FQQQSNAVVZSYMB-UHFFFAOYSA-N 1,1-diaminoguanidine Chemical compound NN(N)C(N)=N FQQQSNAVVZSYMB-UHFFFAOYSA-N 0.000 description 1
- BVGPZRCQJJMXBI-UHFFFAOYSA-N 1,2-diaminoguanidine;nitric acid Chemical compound O[N+]([O-])=O.NN\C(N)=N/N BVGPZRCQJJMXBI-UHFFFAOYSA-N 0.000 description 1
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- MQHZNFQPUJDVKD-UHFFFAOYSA-N 1-amino-1-nitroguanidine Chemical compound NC(=N)N(N)[N+]([O-])=O MQHZNFQPUJDVKD-UHFFFAOYSA-N 0.000 description 1
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- FHNQNOARLHWMSH-UHFFFAOYSA-N 2-aminoguanidine;perchloric acid Chemical compound NN=C(N)N.OCl(=O)(=O)=O FHNQNOARLHWMSH-UHFFFAOYSA-N 0.000 description 1
- VPIXQGUBUKFLRF-UHFFFAOYSA-N 3-(2-chloro-5,6-dihydrobenzo[b][1]benzazepin-11-yl)-N-methyl-1-propanamine Chemical compound C1CC2=CC=C(Cl)C=C2N(CCCNC)C2=CC=CC=C21 VPIXQGUBUKFLRF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 241001455273 Tetrapoda Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- XPCFIDKRNBCWOS-UHFFFAOYSA-N carbonic acid 1,2-diaminoguanidine Chemical compound C(O)(O)=O.NNC(=N)NN XPCFIDKRNBCWOS-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 159000000006 cesium salts Chemical class 0.000 description 1
- VSQHTVCBHFZBOT-UHFFFAOYSA-M cesium;chlorate Chemical compound [Cs+].[O-]Cl(=O)=O VSQHTVCBHFZBOT-UHFFFAOYSA-M 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- KBJCHZXIAAWHMB-UHFFFAOYSA-N guanidine;perchloric acid Chemical compound NC(N)=N.OCl(=O)(=O)=O KBJCHZXIAAWHMB-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- UAGLZAPCOXRKPH-UHFFFAOYSA-N nitric acid;1,2,3-triaminoguanidine Chemical compound O[N+]([O-])=O.NNC(NN)=NN UAGLZAPCOXRKPH-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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
本発明は、自動車用等のエアバッグ向けインフレータ用のガス発生剤組成物に関する。 The present invention relates to a gas generant composition for an inflator for an air bag such as an automobile.
自動車などの乗り物に搭載されるエアバッグシステム用のガス発生剤組成物として、毒性面で問題のあるアジ化ナトリウムに代わる非アジド系ガス発生剤の開発がなされている。非アジド系ガス発生剤として、グアニジン誘導体やテトラゾール類等の含窒素有機化合物を燃料とし、硝酸アンモニウムを酸化剤とするガス発生剤組成物が提案されている。 As a gas generant composition for an air bag system mounted on a vehicle such as an automobile, a non-azide gas generant that replaces sodium azide, which is problematic in terms of toxicity, has been developed. As a non-azide gas generating agent, a gas generating composition using a nitrogen-containing organic compound such as a guanidine derivative or tetrazole as a fuel and ammonium nitrate as an oxidizing agent has been proposed.
一方、エアバッグには特に安全性の点から展開時間の安定性が求められている。展開時間はガス発生剤の燃焼速度に依存する。この燃焼速度は、一般に圧力の影響を受けやすく、燃焼速度と圧力との関係は次式（１）
ｒ＝ａＰn （１）
（式中、ｒは燃焼速度、Ｐは燃焼圧力、ａは定数、ｎは圧力指数を示す）
で表される。ａはガス発生剤組成物の種類、初期温度により異なる定数である。このように、ガス発生剤の燃焼速度は圧力に影響されるため、エアバッグ展開の状況次第では、展開時間が不安定となる。しかしながら、上記式（１）の圧力指数ｎが小さい場合には、ガス発生剤の燃焼速度の圧力依存性が低くなり、安定したエアバッグ展開時間を得ることが可能となる。
On the other hand, the airbag is required to have a stable deployment time particularly from the viewpoint of safety. The development time depends on the burning rate of the gas generant. This combustion rate is generally susceptible to pressure, and the relationship between the combustion rate and pressure is expressed by the following equation (1).
r = aP n (1)
(Wherein, r is the combustion rate, P is the combustion pressure, a is a constant, and n is the pressure index)
It is represented by a is a constant that varies depending on the type and initial temperature of the gas generant composition. As described above, since the combustion rate of the gas generating agent is influenced by the pressure, the deployment time becomes unstable depending on the situation of airbag deployment. However, when the pressure index n in the above formula (1) is small, the pressure dependency of the combustion rate of the gas generating agent is reduced, and a stable airbag deployment time can be obtained.
特開平１１−２９２６７８号公報には、グアニジン誘導体化合物、相安定化硝酸アンモニウム及び圧力指数調整剤又は爆ごう抑制剤として作用するケイ素化合物を含有し、前記式（１）から求められる、燃焼圧力Ｐが５０〜７０ｋｇ／ｃｍ2の範囲における圧力指数ｎが０．９５以下であるエアバッグ用ガス発生剤組成物が開示されている。しかし、実施例において、ｎの最小の値は０．４２９であるが、圧力指数調整剤を使用する必要があり、また、硝酸アンモニウムは相安定化したものを使用する必要がある。 JP-A-11-292678 contains a guanidine derivative compound, a phase-stabilized ammonium nitrate, and a silicon compound that acts as a pressure index regulator or detonation inhibitor, and has a combustion pressure P determined from the above formula (1). A gas generant composition for an air bag having a pressure index n in the range of 50 to 70 kg / cm 2 is 0.95 or less is disclosed. However, in the examples, the minimum value of n is 0.429, but it is necessary to use a pressure index regulator, and ammonium nitrate needs to be phase-stabilized.
特表２００２−５２２３３０号公報には、硝酸アンモニウムと、硝酸グアニジン、硝酸アミノグアニジン等の高酸化燃料と、硝酸セシウム等の相安定化成分と、銅又は銅化合物から選択される触媒とを含むガス発生組成物が開示されている。しかし、実施例で示されている圧力指数の最小の値は０．５６であり、また、相安定化成分を必要とする。 JP-T-2002-522330 discloses a gas generation comprising ammonium nitrate, highly oxidized fuel such as guanidine nitrate and aminoguanidine nitrate, a phase stabilizing component such as cesium nitrate, and a catalyst selected from copper or a copper compound. A composition is disclosed. However, the minimum value of the pressure index shown in the examples is 0.56 and requires a phase stabilizing component.
特許第４２４８２５４号公報には、含窒素有機化合物燃料と酸化剤を含有するガス発生剤組成物であって、該酸化剤の一部又は全部が、硝酸アンモニウムと塩基性硝酸銅とを混合し、１２０℃から１６０℃までの温度で加熱処理して得られる熱処理酸化剤であることを特徴とするガス発生剤組成物が開示されている。しかし、この文献には、圧力指数については全く触れられておらず、また、酸化剤は熱処理をする必要がある。 Japanese Patent No. 4248254 discloses a gas generating composition containing a nitrogen-containing organic compound fuel and an oxidant, wherein a part or all of the oxidant is a mixture of ammonium nitrate and basic copper nitrate. A gas generant composition characterized by being a heat-treating oxidant obtained by heat treatment at a temperature of from 160C to 160C is disclosed. However, this document does not mention the pressure index at all, and the oxidant needs to be heat-treated.
特開２００９−１３７８１９号公報には、硝酸アンモニウムを含む燃料とバインダを含有しており、前記バインダとして、前記硝酸アンモニウムの相安定化剤として作用する水溶性ポリマーのカリウム塩を含んでいるガス発生剤組成物が開示されている。しかし、この文献にも、圧力指数については全く触れられておらず、また、硝酸アンモニウムは相安定化剤を必要とする。 Japanese Patent Application Laid-Open No. 2009-137819 includes a fuel and a binder containing ammonium nitrate, and a gas generating composition containing a potassium salt of a water-soluble polymer that acts as a phase stabilizer for the ammonium nitrate as the binder. Things are disclosed. However, this document does not mention the pressure index at all, and ammonium nitrate requires a phase stabilizer.
本発明の目的は、圧力指数が非常に小さく、燃焼速度の圧力依存性が極めて低いガス発生剤組成物を提供することにある。
本発明の他の目的は、上記の特性を有しているとともに、調製の容易なガス発生剤組成物を提供することにある。
An object of the present invention is to provide a gas generant composition having a very low pressure index and extremely low pressure dependency of the combustion rate.
Another object of the present invention is to provide a gas generant composition having the above-mentioned characteristics and easy to prepare.
本発明者らは、上記目的を達成するため鋭意検討した結果、含窒素有機化合物を燃料、硝酸アンモニウムを酸化剤として含有するガス発生剤組成物において、含窒素有機化合物と硝酸アンモニウムとの比率を特定値以下にすると、圧力指数調整剤を添加するなど、原料成分に特別な処理を施さなくても、圧力指数の著しく低いガス発生剤組成物の得られることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have determined the ratio of the nitrogen-containing organic compound to ammonium nitrate in the gas generant composition containing the nitrogen-containing organic compound as a fuel and ammonium nitrate as an oxidizing agent. In the following, the present inventors have found that a gas generant composition having a remarkably low pressure index can be obtained without special treatment of raw material components such as addition of a pressure index adjusting agent.
すなわち、本発明は、含窒素有機化合物を燃料、硝酸アンモニウムを酸化剤として含有するガス発生剤組成物であって、含窒素有機化合物と硝酸アンモニウムの比率（前者／後者；重量比）が３５／６５以下であることを特徴とするガス発生剤組成物を提供する。 That is, the present invention is a gas generating composition containing a nitrogen-containing organic compound as a fuel and ammonium nitrate as an oxidizing agent, wherein the ratio of the nitrogen-containing organic compound and ammonium nitrate (the former / the latter; the weight ratio) is 35/65 or less. A gas generant composition is provided.
このガス発生剤組成物においては、硝酸アンモニウムが相安定化処理されていなくてもよく、また、圧力指数調整剤を含んでいなくてもよい。 In this gas generant composition, ammonium nitrate may not be phase-stabilized and may not contain a pressure index regulator.
このガス発生剤組成物においては、さらに、銅化合物が含窒素有機化合物と硝酸アンモニウムの総量１００重量部に対して０重量部より多く３０重量部以下の割合で配合されていてもよい。 In this gas generant composition, the copper compound may be further blended in a proportion of more than 0 parts by weight and 30 parts by weight or less with respect to 100 parts by weight of the total amount of the nitrogen-containing organic compound and ammonium nitrate.
前記銅化合物としては、塩基性硝酸銅が好ましい。また、前記含窒素有機化合物としては、グアニジン誘導体が好ましく、特に硝酸グアニジンが好ましい。 The copper compound is preferably basic copper nitrate. The nitrogen-containing organic compound is preferably a guanidine derivative, particularly preferably guanidine nitrate.
本発明によれば、含窒素有機化合物と硝酸アンモニウムとの比率が特定値以下であるため、圧力指数が従来のものと比較して非常に小さく、燃焼速度の圧力依存性が極めて低い。そのため、展開時間の安定性に優れたエアバッグを得ることができる。 According to the present invention, since the ratio between the nitrogen-containing organic compound and ammonium nitrate is not more than a specific value, the pressure index is very small compared to the conventional one, and the pressure dependence of the combustion rate is extremely low. Therefore, an airbag having excellent deployment time stability can be obtained.
本発明のガス発生剤組成物は、含窒素有機化合物を燃料、硝酸アンモニウムを酸化剤として含有している。 The gas generant composition of the present invention contains a nitrogen-containing organic compound as a fuel and ammonium nitrate as an oxidizing agent.
燃料として用いる含窒素有機化合物としては、例えば、グアニジン誘導体、テトラゾール類、トリアゾール類、ヒドラジン誘導体、トリアジン誘導体など、ガス発生剤の燃料として公知の含窒素有機化合物を使用できる。含窒素有機化合物は単独で又は２種以上を組み合わせて使用できる。上記含窒素有機化合物の中でも、特にグアニジン誘導体が好ましい。 As the nitrogen-containing organic compound used as a fuel, for example, a known nitrogen-containing organic compound can be used as a gas generating fuel, such as a guanidine derivative, a tetrazole, a triazole, a hydrazine derivative, or a triazine derivative. A nitrogen-containing organic compound can be used individually or in combination of 2 or more types. Of the nitrogen-containing organic compounds, guanidine derivatives are particularly preferable.
グアニジン誘導体としては、例えば、硝酸グアニジン、炭酸グアニジン、過塩素酸グアニジン、ニトログアニジン、アミノニトログアニジン、硝酸アミノグアニジン、炭酸アミノグアニジン、過塩素酸アミノグアニジン、硝酸ジアミノグアニジン、炭酸ジアミノグアニジン、過塩素酸ジアミノグアニジン、硝酸トリアミノグアニジン、過塩素酸トリアミノグアニジンなどが挙げられる。これらの中でも、特に硝酸グアニジンが好ましい。 Examples of guanidine derivatives include guanidine nitrate, guanidine carbonate, guanidine perchlorate, nitroguanidine, aminonitroguanidine, aminoguanidine nitrate, aminoguanidine carbonate, aminoguanidine perchlorate, diaminoguanidine nitrate, diaminoguanidine carbonate, and perchloric acid. Examples include diaminoguanidine, triaminoguanidine nitrate, and triaminoguanidine perchlorate. Among these, guanidine nitrate is particularly preferable.
前記含窒素有機化合物の使用量は、ガス発生剤組成物全体に対して、例えば５〜３５重量％、好ましくは７〜３３重量％、さらに好ましくは８〜３０重量％程度である。 The amount of the nitrogen-containing organic compound used is, for example, about 5 to 35% by weight, preferably about 7 to 33% by weight, and more preferably about 8 to 30% by weight with respect to the entire gas generant composition.
本発明のガス発生剤組成物においては、酸化剤として硝酸アンモニウムを用いる。硝酸アンモニウムはガス発生効率がよい酸化剤であるが、室温付近に多数の相転移温度があり、当該転移点を通過する際に大きな体積変化が生じ、組成物の性能不安定化を招きやすい。したがって、相転移点をシフトさせるとともに、体積変化を抑制するため、相安定化処理した硝酸アンモニウムを用いることが通常行われる。 In the gas generant composition of the present invention, ammonium nitrate is used as the oxidizing agent. Ammonium nitrate is an oxidizing agent with good gas generation efficiency, but has a large number of phase transition temperatures near room temperature, and a large volume change occurs when passing through the transition point, which easily leads to unstable performance of the composition. Therefore, in order to shift the phase transition point and suppress volume change, it is usually performed to use phase-stabilized ammonium nitrate.
しかし、本発明のガス発生剤組成物においては、硝酸アンモニウムに対して相安定化処理をしなくても、所望の効果を得られることが特徴である。ただし、相安定化処理をしても、所望の効果を得ることが可能である。 However, the gas generant composition of the present invention is characterized in that a desired effect can be obtained without subjecting ammonium nitrate to a phase stabilization treatment. However, the desired effect can be obtained even when the phase stabilization treatment is performed.
硝酸アンモニウムを相安定化処理する場合は、硝酸アンモニウム、相安定化剤を含む混合物を適当な物理的方法、例えば、硝酸アンモニウム、相安定化剤等の水溶液を加熱下（例えば、５０℃以上１２０℃未満、好ましくは８０℃以上１１０℃以下の温度下）で蒸発・乾燥させる等の処理により、相安定化された硝酸アンモニウムを得ることができる。 In the case of phase stabilization treatment of ammonium nitrate, a mixture containing ammonium nitrate and a phase stabilizer is subjected to an appropriate physical method, for example, heating an aqueous solution of ammonium nitrate, a phase stabilizer, etc. (for example, 50 ° C. or more and less than 120 ° C. The phase-stabilized ammonium nitrate can be obtained by treatment such as evaporation and drying at a temperature of preferably 80 ° C. or higher and 110 ° C. or lower.
相安定化剤としては、硝酸カリウム、過塩素酸カリウム、塩素酸カリウム、クロム酸カリウム、重クロム酸カリウム、過マンガン酸カリウム、硫酸カリウム、塩化カリウム、フッ化カリウム等のカリウム塩；硝酸セシウム、過塩素酸セシウム等のセシウム塩などが挙げられる。 Phase stabilizers include potassium nitrate, potassium perchlorate, potassium chlorate, potassium chromate, potassium dichromate, potassium permanganate, potassium sulfate, potassium chloride, potassium fluoride, and other potassium salts; cesium nitrate, Examples include cesium salts such as cesium chlorate.
硝酸アンモニウムと相安定化剤（例えば、カリウム塩及びセシウム塩から選択された相安定化剤）との混合比率は、燃焼時の残渣が実用上問題とならない範囲で適宜設定できるが、通常、硝酸アンモニウム／相安定化剤（重量比）＝７０／３０〜９８／２、好ましくは、硝酸アンモニウム／相安定化剤（重量比）＝８０／２０〜９７／３の範囲である。本発明では、上記のように、硝酸アンモニウムを相安定化処理しなくても所望の効果を得ることができるので、相安定化剤を用いたとしても、硝酸アンモニウム／相安定化剤（重量比）が９８／２より大きい値（例えば、前記比率が９９／１以上）でよい。 The mixing ratio of ammonium nitrate and a phase stabilizer (for example, a phase stabilizer selected from a potassium salt and a cesium salt) can be appropriately set within a range in which a residue during combustion does not cause a practical problem. Phase stabilizer (weight ratio) = 70/30 to 98/2, preferably ammonium nitrate / phase stabilizer (weight ratio) = 80/20 to 97/3. In the present invention, as described above, a desired effect can be obtained without subjecting ammonium nitrate to phase stabilization treatment. Therefore, even if a phase stabilizer is used, ammonium nitrate / phase stabilizer (weight ratio) is A value larger than 98/2 (for example, the ratio is 99/1 or more) may be used.
硝酸アンモニウムには、固化防止剤を配合してもよい。固化防止剤としては、例えば、酸化マグネシウム、粉末シリカ等が挙げられる。固化防止剤の配合割合は、硝酸アンモニウム全体に対して、例えば０．０５〜２．０重量％、好ましくは０．１〜１．０重量％程度である。 You may mix | blend an anti-caking agent with ammonium nitrate. Examples of the anti-caking agent include magnesium oxide and powdered silica. The blending ratio of the anti-caking agent is, for example, about 0.05 to 2.0% by weight, preferably about 0.1 to 1.0% by weight, based on the whole ammonium nitrate.
硝酸アンモニウムの使用量は、ガス発生剤組成物全体に対して、例えば４０〜９０重量％、好ましくは４５〜８５重量％、さらに好ましくは５０〜７５重量％程度である。 The amount of ammonium nitrate used is, for example, about 40 to 90% by weight, preferably 45 to 85% by weight, and more preferably about 50 to 75% by weight with respect to the entire gas generant composition.
本発明においては、燃料としての含窒素有機化合物と酸化剤としての硝酸アンモニウムの比率（前者／後者；重量比）が３５／６５以下であることが重要である。硝酸アンモニウムは、圧力指数が高く、圧力変化に対して燃焼速度が敏感に変化し、安定燃焼しにくい酸化剤であることが知られているが、燃料としての含窒素有機化合物と硝酸アンモニウムの比率をこの範囲に設定すると、驚くべきことに、前記圧力指数ｎが０．４５以下（例えば、０．３〜０．４５）という極めて小さい値となり、燃焼速度の圧力依存性（例えば、１〜９ＭＰａの圧力範囲）を大幅に低下させることができる。なお、含窒素有機化合物と硝酸アンモニウムの比率が３５／６５より大きくなると、圧力指数ｎが急激に増大し、例えば０．６５〜０．７５程度、若しくはそれ以上の値となる。 In the present invention, it is important that the ratio (the former / the latter; weight ratio) of the nitrogen-containing organic compound as the fuel and the ammonium nitrate as the oxidant is 35/65 or less. Ammonium nitrate is known to be a oxidizer that has a high pressure index, changes its combustion speed sensitively to pressure changes, and is difficult to stably burn. Surprisingly, the pressure index n becomes a very small value of 0.45 or less (for example, 0.3 to 0.45), and the pressure dependence of the combustion rate (for example, a pressure of 1 to 9 MPa) Range) can be greatly reduced. When the ratio between the nitrogen-containing organic compound and ammonium nitrate is greater than 35/65, the pressure index n increases rapidly, for example, about 0.65 to 0.75 or higher.
前記含窒素有機化合物と硝酸アンモニウムの比率（前者／後者；重量比）は、好ましくは３０／７０以下の範囲である。前記含窒素有機化合物と硝酸アンモニウムの比率（前者／後者；重量比）の下限は特に限定されないが、着火性を担保するため、実用的には２０／８０程度である。 The ratio of the nitrogen-containing organic compound and ammonium nitrate (the former / the latter; the weight ratio) is preferably in the range of 30/70 or less. The lower limit of the ratio of the nitrogen-containing organic compound and ammonium nitrate (the former / the latter; the weight ratio) is not particularly limited, but is practically about 20/80 in order to ensure ignitability.
本発明では、ガス発生剤組成物に、さらに燃焼促進剤として銅化合物を配合すると、着火性が大幅に改善される。銅化合物としては、例えば、塩基性硝酸銅、塩基性炭酸銅、酸化銅、水酸化銅、硫酸銅、硝酸銅などが挙げられる。これらの中でも、特に塩基性硝酸銅が好ましい。なお、本発明では、前記特許第４２４８２５４号公報に記載されているように、硝酸アンモニウムとこれらの銅化合物とを１２０℃〜１６０℃の範囲の温度で加熱処理しなくても、単に共存させるだけで（加熱したとしても１２０℃未満、例えば１１５℃以下）、十分で且つ安定な燃焼性が得られる。 In the present invention, when a copper compound is further added to the gas generating composition as a combustion accelerator, the ignitability is greatly improved. Examples of the copper compound include basic copper nitrate, basic copper carbonate, copper oxide, copper hydroxide, copper sulfate, and copper nitrate. Among these, basic copper nitrate is particularly preferable. In the present invention, as described in the above-mentioned Japanese Patent No. 4248254, the ammonium nitrate and these copper compounds are simply allowed to coexist without heat treatment at a temperature in the range of 120 ° C to 160 ° C. (Even when heated, less than 120 ° C., for example, 115 ° C. or less), sufficient and stable combustibility can be obtained.
銅化合物の配合量は、含窒素有機化合物と硝酸アンモニウムの総量１００重量部に対して、例えば０重量部より多く３０重量部以下、好ましくは１５〜３０重量部、さらに好ましくは１５〜２５重量部である。 The compounding amount of the copper compound is, for example, more than 0 parts by weight and 30 parts by weight or less, preferably 15 to 30 parts by weight, more preferably 15 to 25 parts by weight with respect to 100 parts by weight of the total amount of the nitrogen-containing organic compound and ammonium nitrate. is there.
本発明のガス発生剤組成物は、さらに、必要に応じて他の添加剤等を含んでいてもよい。なお、本発明のガス発生剤組成物は、含窒素有機化合物と硝酸アンモニウムとを特定の割合で用いるため、圧力指数調整剤（例えば、特開平１１−２９２６７８号公報に記載されている窒化ケイ素、シリコーン、炭化ケイ素、二酸化ケイ素、ケイ酸塩類及びケイ酸塩類の粘土鉱物から選ばれるケイ素化合物）を特に含有しなくても、極めて小さい圧力指数を得ることができる。しかし、上記圧力指数調整剤を含有していてもよく、その場合、ガス発生剤組成物中の上記圧力指数調整剤の含有量は、０．３重量％未満（例えば０．２重量％以下）であってもよい。 The gas generant composition of the present invention may further contain other additives as required. The gas generant composition of the present invention uses a nitrogen-containing organic compound and ammonium nitrate in a specific ratio, so that it is a pressure index adjuster (for example, silicon nitride, silicone described in JP-A-11-292678) , Silicon carbide selected from silicon carbide, silicon dioxide, silicates, and clay minerals of silicates), an extremely small pressure index can be obtained. However, the pressure index regulator may be contained. In that case, the content of the pressure index regulator in the gas generant composition is less than 0.3% by weight (for example, 0.2% by weight or less). It may be.
本発明のガス発生剤組成物は、所望の形状に成形することができる。成形方法としては、特に制限はなく、例えば、プレス成形、打錠成形、押出成形等を採用できる。成形されたガス発生剤の形状としては、特に制限はなく、例えば、ペレット状、中空円筒状、多孔円柱状などが挙げられる。成形されたガス発生剤はワングレイン型であってもよい。ただし、球状、金平糖状、テトラポッド状のように、燃焼中の表面積変化が極端に大きいものは圧力変動の原因となるため、好ましくない。 The gas generant composition of the present invention can be formed into a desired shape. There is no restriction | limiting in particular as a shaping | molding method, For example, press molding, tableting molding, extrusion molding, etc. are employable. There is no restriction | limiting in particular as a shape of the shape | molded gas generating agent, For example, a pellet form, a hollow cylinder shape, a porous column shape etc. are mentioned. The molded gas generating agent may be a one-grain type. However, it is not preferable that the surface area change during combustion is extremely large, such as spherical, confetti, or tetrapod, because it causes pressure fluctuation.
本発明のガス発生剤組成物やこれを成形して得られるガス発生剤は、例えば、自動車の運転席のエアバッグ用インフレータ、助手席のエアバッグ用インフレータ、サイドエアバッグ用インフレータ、インフレータブルカーテン用インフレータ、ニーボルスター用インフレータ、インフレータブルシートベルト用インフレータ、チューブラーシステム用インフレータ、プリテンショナー用ガス発生器等に利用できる。 Examples of the gas generant composition of the present invention and the gas generant obtained by molding the gas generator composition include, for example, an inflator for an airbag in a driver's seat of an automobile, an inflator for an airbag in a passenger seat, an inflator for a side airbag, and an inflatable curtain It can be used for inflators, inflators for knee bolsters, inflators for inflatable seat belts, inflators for tubular systems, gas generators for pretensioners, and the like.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
実施例１〜５、比較例１〜４
硝酸グアニジン（「ＧＮ」と略称する場合がある）、硝酸アンモニウム（「ＡＮ」と略称する場合がある）、及び塩基性硝酸銅（「ＢＣＮ」と略称する場合がある）を用い、表１に示す組成のガス発生剤組成物を、乾式で混合して得た。これらの組成物を、油圧シリンダを用いて１００ｋｇ/ｃｍ2の圧力下、高さ約１２．7ｍｍ、直径約１０ｍｍのストランドに圧搾成形した。次に、ストランドの表面を不燃性エポキシ系樹脂でコーティングした。所定圧力の窒素雰囲気下で、燃焼速度（ｍｍ／ｓ）を測定した。燃焼速度（ｍｍ／ｓ）と圧力（ＭＰａ）との下記関係式（１）
ｒ＝ａＰn （１）
（式中、ｒは燃焼速度、Ｐは燃焼圧力、ａは定数、ｎは圧力指数を示す）
に基づき、圧力指数ｎと定数ａの値を求めた。なお、燃焼速度の測定は燃焼圧力１ＭＰａ〜９ＭＰａの範囲内で行った。結果を表１に示す。
Examples 1-5, Comparative Examples 1-4
Table 1 uses guanidine nitrate (sometimes abbreviated as “GN”), ammonium nitrate (sometimes abbreviated as “AN”), and basic copper nitrate (sometimes abbreviated as “BCN”). A gas generant composition having a composition was obtained by dry mixing. These compositions were pressed into strands having a height of about 12.7 mm and a diameter of about 10 mm under a pressure of 100 kg / cm 2 using a hydraulic cylinder. Next, the surface of the strand was coated with a nonflammable epoxy resin. The burning rate (mm / s) was measured under a nitrogen atmosphere at a predetermined pressure. The following relational expression (1) between the burning rate (mm / s) and the pressure (MPa)
r = aP n (1)
(Wherein, r is the combustion rate, P is the combustion pressure, a is a constant, and n is the pressure index)
Based on the above, the values of the pressure index n and the constant a were determined. In addition, the measurement of the combustion rate was performed within the range of combustion pressure 1MPa-9MPa. The results are shown in Table 1.
表１に示されるように、硝酸グアニジン（ＧＮ）と硝酸アンモニウム（ＡＮ）の比率（前者／後者；重量比）が３５／６５より大きい場合には、圧力指数ｎは０．６５〜０．７５程度であるが、上記比率が３５／６５を境に、それ以下になると、圧力指数ｎが急激に減少して、０．３〜０．４５と極めて小さい値を示した。 As shown in Table 1, when the ratio of guanidine nitrate (GN) to ammonium nitrate (AN) (the former / the latter; weight ratio) is greater than 35/65, the pressure index n is about 0.65 to 0.75. However, when the ratio is less than or equal to 35/65, the pressure index n rapidly decreases and shows a very small value of 0.3 to 0.45.
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| CN201080052885XA CN102666439A (en) | 2009-11-27 | 2010-11-19 | Gas-generating agent composition |
| US13/508,939 US20120261040A1 (en) | 2009-11-27 | 2010-11-19 | Gas-generating agent composition |
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| JPH04248254A (en) | 1991-01-24 | 1992-09-03 | Shin Kobe Electric Mach Co Ltd | Hermetic type lead-acid battery and connecting method therefor |
| JPH11292678A (en) | 1998-04-15 | 1999-10-26 | Daicel Chem Ind Ltd | Gas generating agent composition for air bag |
| US6136113A (en) | 1998-08-07 | 2000-10-24 | Atlantic Research Corporation | Gas generating composition |
| CZ20033101A3 (en) * | 2001-04-20 | 2004-03-17 | Nippon Kayaku Kabushiki-Kaisha | Gas-generating mixture |
| CN100540513C (en) * | 2001-11-30 | 2009-09-16 | 大赛璐化学工业株式会社 | Aerator and gas-bag system |
| CN1544271A (en) * | 2003-11-13 | 2004-11-10 | 西安北方庆华电器（集团）有限责任公 | Gas generating powder used for gas generator of automobile safety airbag and preparation method thereof |
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| CN1927779B (en) * | 2006-02-22 | 2010-05-12 | 上海东方久乐汽车安全气囊有限公司 | Gas generation medicine for automobile safety air bag gas generator and preparation process thereof |
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Non-Patent Citations (1)
| Title |
|---|
| JPN6013052701; 火薬学会２００９年度春季研究発表会講演要旨集 Ｖｏｌ．５９, 20090521, ｐ．６１-６２ * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013060310A (en) * | 2011-09-12 | 2013-04-04 | Chori Co Ltd | Production method of nitrate converted into non-dangerous article |
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| WO2011065298A1 (en) | 2011-06-03 |
| JP5481723B2 (en) | 2014-04-23 |
| DE112010004588T5 (en) | 2012-11-22 |
| US20120261040A1 (en) | 2012-10-18 |
| CN102666439A (en) | 2012-09-12 |
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