EP1816113B1 - Gaserzeugende Zusammensetzung - Google Patents

Gaserzeugende Zusammensetzung Download PDF

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Publication number
EP1816113B1
EP1816113B1 EP07000356.1A EP07000356A EP1816113B1 EP 1816113 B1 EP1816113 B1 EP 1816113B1 EP 07000356 A EP07000356 A EP 07000356A EP 1816113 B1 EP1816113 B1 EP 1816113B1
Authority
EP
European Patent Office
Prior art keywords
cellulose
gas generating
rare earth
compounds
light rare
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
EP07000356.1A
Other languages
English (en)
French (fr)
Other versions
EP1816113A1 (de
Inventor
Kenji Kitayama
Shogo Tomiyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daicel Corp
Original Assignee
Daicel Chemical Industries Ltd
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 Daicel Chemical Industries Ltd filed Critical Daicel Chemical Industries Ltd
Publication of EP1816113A1 publication Critical patent/EP1816113A1/de
Application granted granted Critical
Publication of EP1816113B1 publication Critical patent/EP1816113B1/de
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/02—Compositions characterised by non-explosive or non-thermic constituents for neutralising poisonous gases from explosives produced during blasting

Definitions

  • the present invention relates to a gas generating composition suitable for airbag restraint systems of automobiles or the like.
  • Gas generating agents typically generate a large amount of fine combustion residue and mist (solid components (for example, metal components) in the gas generating agent that are generated by combustion of the gas generating agent) after the combustion. Combustion residue that has been just generated bears heat. If the combustion residue is released into an air bag, the air bag is damaged and there is a risk of inflicting burns to a vehicle occupant. Further, if the airbag is damaged, the mist is released into the vehicle cabin. In order to avoid such danger, a fine-mesh metal filter is disposed inside an inflator.
  • the filter has the highest weight ratio among the inflator components, although the filter purifies the gas, the use thereof causes the increase in weight and size of the inflator.
  • Decreasing the combustion temperature of the gas generating agent can be considered as a method for reducing the size and weight of the filter.
  • JP-A No. 2003-525106 and JP-A No. 2005-126262 describes adding the components for decreasing the combustion temperature.
  • US-A-5035757 discloses a pyrotechnic, combustion filterable slag-particles forming gas generating mixture useful for inflating an automobile or aircraft safety crash bag, said pyrotechnic mixture comprising at least one material of each of the following functional groups of materials: (a) a fuel selected from the group of azole compounds consisting of triazole aminotetrazole, tetrazole, bitetrazole and metal salts of these compounds; (b) an oxygen containing oxidizer compound selected from the group consisting of alkali metal, alkaline earth metal, lanthanide and ammonium nitrates and perchlorates or from the group consisting of alkali metal and alkaline earth metal chlorates and peroxides; (c) a high temperature slag forming material selected from the group consisting of alkaline earth metal oxides, hydroxides, cabonates, and oxalates; (d) a low-temperature slag forming material which is sufficient in amount during combustion to
  • the present invention provides a gas generating composition
  • a gas generating composition comprising a light rare earth compound, a fuel, an oxidizing agent and a binder
  • the light rare earth compound is selected from the group consisting of oxides, hydroxides, halogenides, nitrates, sulfates, acetates, phosphates, and carbonates of lanthanum, wherein the mean particle size of the light rare earth compound is within a range of 0.5 to 500 ⁇ m, wherein the content of the light rare earth compound in the gas generating composition is 0.1 to 20 mass%
  • the fuel is at least one selected from among tetrazole compounds, guanidine compounds, triazine compounds, and nitroamine compounds
  • the oxidizing agent is at least one selected from among basic metal nitrates, nitrates, ammonium nitrate, perchlorates, and chlorates
  • the binder includes at least one selected from among carboxymethyl cellulose, carboxymethyl cellulose sodium salt,
  • the present invention provides a gas generating composition that purifies the gas by using a rare earth compound that is not described in JP-A No. 2003-525106 and JP-A No. 2005-126262 and generates hardly any mist during combustion.
  • the light rare earth compound is a compound of lanthanum.
  • the light rare earth compound is selected from oxides, hydroxides, halogenides (halides), nitrates, sulfates, acetates, phosphates, and carbonates of lanthanum.
  • the light rare earth compound has a mean particle size within a range of 0.5 to 500 ⁇ m.
  • the gas generating composition in accordance with the present invention generates but a small amount of carbon monoxide or nitrogen oxide during combustion and generates hardly any mist during combustion.
  • the gas generating composition in accordance with the present invention includes a light rare earth compound, a fuel, an oxidizing agent and a binder.
  • Other components can be selected from additives that are used in the known gas generating compositions.
  • the light rare earth compound acts to decrease the generated amount of toxic nitrogen oxide and carbon monoxide after the combustion and also acts to convert the generated mist into a slag residue inside the gas generator.
  • the light rare earth compound is a compound of lanthanum.
  • the compound is selected from oxides, hydroxides, halogenides, nitrates, sulfates, acetates, phosphates, and carbonates of lanthanum.
  • oxides and hydroxides of lanthanum are preferred.
  • the light rare earth compound has a mean particle size within a range of 0.5 to 500 ⁇ m, preferably within a range of 0.5 to 100 ⁇ m, and more preferably within a range of 0.7 to 20 ⁇ m.
  • the mean particle size is measured by a particle size distribution method based on laser light scattering.
  • the measurement sample is prepared by dispersing a basic metal nitrate in water and irradiating for three minutes with ultrasonic waves. Then, a 50% accumulated value (D 50 ) of the number of particles is found and the mean value obtained in two cycles of measurements is taken as a mean particle size.
  • the content of the rare earth compound in the gas generating composition is 0.1 to 20 mass%, preferably 0.5 to 15 mass%, and more preferably 0.5 to 10 mass%.
  • At least one selected from among tetrazole compounds, guanidine compounds, triazine compounds, and nitroamine compounds is used as the fuel.
  • the preferred tetrazole compounds include 5-aminotetrazole and bitetrazole ammonium salt.
  • the preferred guanidine compounds are guanidine nitrate, aminoguanidine nitrate, nitroguanidine, and triaminoguanidine nitrate.
  • the preferred triazine compounds are melamine, cyanuric acid, ammeline, ammelide, and ammeland.
  • the preferred nitroamine compound is cyclo-1,3,5-trimethylene-2,4,6-trinitramine.
  • the oxidizing agent at least one selected from among basic metal nitrates, nitrates, ammonium nitrate, perchlorates, and chlorates is used.
  • basic metal nitrate at least one selected from among basic copper nitrate, basic cobalt nitrate, basic zinc nitrate, basic manganese nitrate, basic iron nitrate, basic molybdenum nitrate, basic bismuth nitrate, and basic cerium nitrate can be used.
  • the mean particle size thereof is preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the mean particle size is measured by a particle size distribution method based on laser light scattering. The measurement sample is prepared by dispersing a basic metal nitrate in water and irradiating for three minutes with ultrasonic waves. Then, a 50% accumulated value (D 50 ) of the number of particles is found and the mean value obtained in two cycles of measurements is taken as a mean particle size.
  • nitrate examples include alkali metal nitrates such as potassium nitrate and sodium nitrate and alkaline earth metal nitrates such as strontium nitrate.
  • Perchlorates and chlorates are compounds also producing both the oxidizing action and the combustion enhancing action.
  • the oxidizing action means the action that efficiently advances combustion by generating oxygen during combustion and decreases the generation amount of toxic gases such as ammonia and carbon monoxide.
  • the combustion enhancing action means the action that improves the ignition ability of the gas generating composition or increases the burning rate.
  • At least one selected from among ammonium perchlorate, potassium perchlorate, sodium perchlorate, potassium chlorate, and sodium chlorate can be used as the perchlorates and chlorates.
  • the binder includes at least one selected from among carboxymethyl cellulose, carboxymethyl cellulose sodium salt, carboxymethyl cellulose potassium salt, carboxymethyl cellulose ammonium salt, cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethylhydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethylethyl cellulose, microcrystalline cellulose, polyacrylamide, polyacrylamide amino compound, polyacryl hydrazide, acrylamide - acrylic acid metal salt copolymers, polyacrylamide - polyacrylic acid ester compound copolymers, polyvinyl alcohol, acrylic rubber, guar gum, starch, and silicone.
  • the additive include at least one selected from among copper (for example, electrolytic copper powder), metal oxides such as copper oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide, bismuth oxide, silica, and alumina, metal carbonates and basic metal carbonates such as cobalt carbonate, calcium carbonate, basic zinc carbonate, and basic copper carbonate, complex compounds of metal oxides or hydroxides such as Japanese acid clay, kaolin, talc, bentonite, deatomaceous earth, and hydrotalcite, aluminum hydroxide, magnesium hydroxide, metallic acid salts such as sodium silicate, mica molybdenic acid salt, cobalt molybdate, and ammonium molybdate, molybdenum disulfide, calcium stearate, silicon nitride, and silicon carbide.
  • copper for example, electrolytic copper powder
  • metal oxides such as copper oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide
  • components other than the rare earth compound can be selected within the range identical to that of an additive selected from among organic compounds as fuels, oxygen-containing oxidizing agents, binders, metal oxide, and metal carbonates as described in JP-A No. 2005-126262 .
  • the gas generating composition in accordance with the present invention can be molded to any desired shape such as a single-perforated cylindrical shape, a porous cylindrical shape, or a pellet.
  • Such a molded article can be manufactured by adding water or an organic solvent to the gas generating composition, mixing them and extruding (in the case of a molded article having a single-perforated cylindrical shape or a porous cylindrical shape) or by compression-molding (by using a palletizer (in the case of molded article in the form of a pellet).
  • the hole can be either of a through hole which pierces in the longitudinal direction or a recess which does not pierce.
  • the gas generating composition in accordance with the present invention or a molded article obtained therefrom can be applied, for example, to an airbag inflator of a driver side, an airbag inflator for a passenger side next to a driver, a side airbag inflator, an inflatable curtain inflator, a knee bolster inflator, an inflatable seat belt inflator, a tubular system inflator, and a pretensioner gas generator of various vehicles.
  • the inflator using the gas generating composition in accordance with the present invention or a molded article obtained therefrom may be of a pyrotechinc type in which gas is supplied only from the gas generating agent, or of a hybrid type, gas is supplied from both the gas generating agent and a compressed gas such as argon.
  • gas generating composition in accordance with the present invention or a molded article obtained therefrom can be also used as an ignition agent called an enhancer agent (or booster) for transmitting the energy of a detonator or squib to the gas generating agent.
  • an enhancer agent or booster
  • mist solid components, such as a metal component, included in the gas generating agent that are generated by combustion of the gas generating agent
  • the filter is heavily damaged and the mist that passed through the filter flows into the air bag.
  • the gas generating composition in accordance with the present invention due to the action of the light rare earth compound that is a component thereof, mist generation is made difficult and the generated mist can be caused to remain inside the gas generator as a slag (residue) (the slag is a mist that was retained and solidified inside the gas generator, without passing through the filter). If the generation of mist is thus inhibited and the mist is caused to remain as the slag, the filter is prevented from being damaged by the mist, and the mist does not flow through the filter into the airbag. Therefore, the filter thickness or bulk density can be decreases. As a result, the air bag gas generator employing the gas generating composition in accordance with the present invention can be reduced in weight.
  • a total of 5000 g of the components shown in Table 1 and 737 g of water were charged into a mixer and mixed.
  • the mixture was extruded with an extruder, cut, and dried to obtain a gas generating composition in the form of a single-perforated pellet having an outer diameter of 3.8 mm, an inner diameter of 1.1 mm, and a length of 4.1 mm.
  • a total of 2 g of the gas generating composition (powdered) including the components shown in Table 1 was used and molded to obtain a strand.
  • the strand was attached to a tightly closed cylinder having an inner capacity of one liter, and the atmosphere inside the cylinder was replaced with nitrogen. Then, the inside of the cylinder was pressurized up to 6860 kPa with nitrogen, and the strand was ignited by passing an electric current via a nichrome wire to cause the complete combustion. In about twenty seconds after the electric current was passed, the combustion gas was sampled into a gas sampling bag, and the concentrations of NO, CO, and NH 3 (ppm; mass standard) was analyzed with a detection tube.
  • a total of 2 g of the gas generating composition (powdered) including the components shown in Table 1 was used and molded to obtain a strand.
  • the strand was attached to tightly closed cylinder having an inner capacity of one liter, and the atmosphere inside the cylinder was replaced with nitrogen. Then, the inside of the cylinder was pressurized up to 6860 kPa with nitrogen, and the strand was ignited by passing an electric current via a nichrome wire to cause complete combustion.
  • the combustion residue (slag) was sampled and the state thereof was evaluated according to the following criteria.
  • the slag remaining inside the tightly sealed cylinder after the test for evaluating the slag state was sampled and sieved via a sieve having a mesh size of 3.3 mm.
  • the mass of the slag remaining on the sieve was measured.
  • a large amount of the slag remaining on the sieve means that the amount of mist that came into contact with the filter and passed therethrough is small.
  • the slag remains in the powdered form. Therefore, the amount of mist that came into contact with the filter and passed therethrough was larger than that in the case of the Examples, provided that the same amount of mist was generated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Claims (1)

  1. Gaserzeugende Zusammensetzung umfassend eine Verbindung eines leichten Seltenerdmetalls, einen Treibstoff, ein Oxidationsmittel und ein Bindemittel,
    worin die Verbindung des leichten Seltenerdmetalls gewählt wird aus der Gruppe bestehend aus Oxiden, Hydroxiden, Halogeniden, Nitraten, Sulfaten, Acetaten, Phosphaten und Carbonaten von Lanthan,
    worin die mittlere Teilchengröße der Verbindung des leichten Seltenerdmetalls im Bereich von 0,5 bis 500 µm liegt,
    worin der Gehalt der Verbindung des leichten Seltenerdmetalls in der gaserzeugenden Zusammensetzung 0,1 bis 20 Masse-% beträgt,
    worin der Treibstoff mindestens einer ist, gewählt aus Tetrazol-Verbindungen, Guanidin-Verbindungen, Triazin-Verbindungen und Nitroamin-Verbindungen,
    worin das Oxidationsmittel mindestens eines ist, gewählt aus basischen Metallnitraten, Nitraten, Ammoniumnitrat, Perchloraten und Chloraten, und
    worin das Bindemittel mindestens eines umfasst, gewählt aus Carboxymethylcellulose, Natriumsalz von Carboxymethylcellulose, Kaliumsalz von Carboxymethylcellulose, Ammoniumsalz von Carboxymethylcellulose, Celluloseacetat, Celluloseacetat-Butyrat, Methylcellulose, Ethylcellulose, Hydroxyethylcellulose, Ethylhydroxyethylcellulose, Hydroxypropylcellulose, Carboxymethylethylcellulose, mikrokristalline Cellulose, Polyacrylamid, Polyacrylamid-Aminoverbindung, Polyacrylhydrazid, Acrylamid-Acrysäuremetallsalz-Copolymere, Polyacrylamid-Polyacrylsäureesterverbindungs-Copolymere, Polyvinylalkohol, Acrylkautschuk, Guar-Gummi, Stärke und Silikon.
EP07000356.1A 2006-01-26 2007-01-09 Gaserzeugende Zusammensetzung Expired - Fee Related EP1816113B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2006017386A JP4847143B2 (ja) 2006-01-26 2006-01-26 ガス発生剤組成物

Publications (2)

Publication Number Publication Date
EP1816113A1 EP1816113A1 (de) 2007-08-08
EP1816113B1 true EP1816113B1 (de) 2017-08-09

Family

ID=38055398

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07000356.1A Expired - Fee Related EP1816113B1 (de) 2006-01-26 2007-01-09 Gaserzeugende Zusammensetzung

Country Status (3)

Country Link
EP (1) EP1816113B1 (de)
JP (1) JP4847143B2 (de)
WO (1) WO2007086329A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012016452B4 (de) * 2012-08-17 2014-07-24 Diehl Bgt Defence Gmbh & Co. Kg Wirkmasse für ein beim Abbrand der Wirkmasse spektral strahlendes Scheinziel mit einem Zusatzstoff
CN104876780A (zh) * 2015-04-13 2015-09-02 喻自达 一种采用环保竹炭配制烟火爆响药剂

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5035757A (en) * 1990-10-25 1991-07-30 Automotive Systems Laboratory, Inc. Azide-free gas generant composition with easily filterable combustion products
US5725699A (en) * 1994-01-19 1998-03-10 Thiokol Corporation Metal complexes for use as gas generants
KR100767838B1 (ko) * 1996-07-25 2007-10-17 앨리언트 테크시스템즈 인코포레이티드 가스 발생제로 사용하기 위한 금속 착체
CA2264734A1 (en) * 1996-08-30 1998-03-05 Talley Defense Systems, Inc. Gas generating compositions
WO1998029361A1 (fr) * 1996-12-28 1998-07-09 Nippon Kayaku Kabushiki-Kaisha Agent gazogene pour airbag
US6093269A (en) * 1997-12-18 2000-07-25 Atlantic Research Corporation Pyrotechnic gas generant composition including high oxygen balance fuel
US6435552B1 (en) * 1997-12-18 2002-08-20 Atlantic Research Corporation Method for the gas-inflation articles
CA2333942A1 (en) * 1998-06-10 2000-01-06 Robert S. Scheffee Pyrotechnic gas generant composition including high oxygen balance fuel
US6017404A (en) * 1998-12-23 2000-01-25 Atlantic Research Corporation Nonazide ammonium nitrate based gas generant compositions that burn at ambient pressure
US6277221B1 (en) * 1999-04-13 2001-08-21 Atlantic Research Corporation Propellant compositions with salts and complexes of lanthanide and rare earth elements
ATE501101T1 (de) * 1999-11-12 2011-03-15 Zodiac Automotive Us Inc Gaserzeugende zusammensetzung

Non-Patent Citations (1)

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Title
None *

Also Published As

Publication number Publication date
JP4847143B2 (ja) 2011-12-28
WO2007086329A1 (ja) 2007-08-02
JP2007197252A (ja) 2007-08-09
EP1816113A1 (de) 2007-08-08

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