EP1816113A1 - Gas generating composition - Google Patents

Gas generating composition Download PDF

Info

Publication number
EP1816113A1
EP1816113A1 EP07000356A EP07000356A EP1816113A1 EP 1816113 A1 EP1816113 A1 EP 1816113A1 EP 07000356 A EP07000356 A EP 07000356A EP 07000356 A EP07000356 A EP 07000356A EP 1816113 A1 EP1816113 A1 EP 1816113A1
Authority
EP
European Patent Office
Prior art keywords
gas generating
rare earth
generating composition
nitrate
mist
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP07000356A
Other languages
German (de)
French (fr)
Other versions
EP1816113B1 (en
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/en
Application granted granted Critical
Publication of EP1816113B1 publication Critical patent/EP1816113B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
    • 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.
  • the present invention provides a gas generating composition including a light rare earth compound.
  • 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 preferably a compound of a rare earth element selected from scandium, yttrium, lanthanum, cerium, praseodymium, and neodymium.
  • the preferred light rare earth compound is selected from oxides, hydroxides, halogenides (halides), nitrates, sulfates, acetates, phosphates, and carbonates of rare earth elements.
  • the light rare earth compound preferably 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.
  • Other components can be selected from fuels, oxidizing agents, binders, and 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 act to convert the generated mist into a slag residue inside the gas generator.
  • the light rare earth compound is a compound of a rare earth element selected from scandium, yttrium, lanthanum, cerium, praseodymium and neodymium.
  • the compound can be selected from oxides, hydroxides, halogenides, nitrates, sulfates, acetates, phosphates, and carbonates of rare earth elements.
  • oxides and hydroxides of lanthanum, cerium, praseodymium, and neodymium are preferred.
  • the light rare earth compound preferably has a mean particle size within a range of 0.5 to 500 ⁇ m, more preferably within a range of 0.5 to 100 ⁇ m, and even 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 preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, and even more preferably 0.5 to 10 mass%.
  • At least one selected from among tetrazole compounds, guanidine compounds, triazine compounds, and nitroamine compounds can be 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.
  • oxidizing agent at least one selected from among basic metal nitrates, nitrates, ammonium nitrate, perchlorates, and chlorates can be 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.
  • binder examples include 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.
  • ⁇ has a lump-like shape and is not fractured when pressed with a finger.
  • ⁇ has a lump-like shape, but is fractured when pressed with a finger.
  • ⁇ has a powder shape.
  • 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.
  • La(OH) 3 manufactured by Taiyo Koko Co., Ltd., lanthanum hydroxide - 100.
  • Nd (OH) 3 manufactured by Taiyo Koko Co., Ltd., neodymium hydroxide - 98.
  • Cu electrolytic copper powder, manufactured by Nikko Materials Co., Ltd., #6.
  • Glass powder phosphate glass [P 2 O 5 (54 to 56 mass%), Al 2 O 3 (9 to 11 mass%), Na 2 O (19 to 21 mass%), K 2 O (14 to 16 mass%), softening point about 400°C.
  • 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)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Abstract

The present invention provides a gas generating composition comprising a light rare earth compound.

Description

    BACKGROUND OF INVENTION Field of Invention
  • The present invention relates to a gas generating composition suitable for airbag restraint systems of automobiles or the like.
    • Description of Related Art
  • 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.
  • However, because 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.
    • SUMMARY OF THE INVENTION
  • The present invention provides a gas generating composition including a light rare earth compound.
    • DETAILED DESCRIPTION OF INVENTION
  • 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 preferably a compound of a rare earth element selected from scandium, yttrium, lanthanum, cerium, praseodymium, and neodymium. The preferred light rare earth compound is selected from oxides, hydroxides, halogenides (halides), nitrates, sulfates, acetates, phosphates, and carbonates of rare earth elements. The light rare earth compound preferably has a mean particle size within a range of 0.5 to 500 µm.
  • 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.
    • Embodiments of Invention
  • The gas generating composition in accordance with the present invention includes a light rare earth compound. Other components can be selected from fuels, oxidizing agents, binders, and 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 act to convert the generated mist into a slag residue inside the gas generator.
  • The light rare earth compound is a compound of a rare earth element selected from scandium, yttrium, lanthanum, cerium, praseodymium and neodymium. The compound can be selected from oxides, hydroxides, halogenides, nitrates, sulfates, acetates, phosphates, and carbonates of rare earth elements.
  • Among them, oxides and hydroxides of lanthanum, cerium, praseodymium, and neodymium are preferred.
  • The light rare earth compound preferably has a mean particle size within a range of 0.5 to 500 µm, more preferably within a range of 0.5 to 100 µm, and even more preferably within a range of 0.7 to 20 µm.
  • 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 (D50) 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 preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, and even more preferably 0.5 to 10 mass%.
  • At least one selected from among tetrazole compounds, guanidine compounds, triazine compounds, and nitroamine compounds can be 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.
  • As the oxidizing agent, at least one selected from among basic metal nitrates, nitrates, ammonium nitrate, perchlorates, and chlorates can be used.
  • As 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.
  • For the basic metal nitrate to increase the burning rate, the mean particle size thereof is preferably 30 µm or less, more preferably 10 µm 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 (D50) of the number of particles is found and the mean value obtained in two cycles of measurements is taken as a mean particle size.
  • Examples of the nitrate 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. On the other hand, 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.
  • Examples of the binder include 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.
  • Examples of 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.
  • No specific limitation is placed on the contents of components other than the rare earth compound. For example, they 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). In a molded article having a single-perforated cylindrical shape or a porous cylindrical shape, 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.
  • Furthermore, the 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.
  • When a gas generating agent burns during the actuation of the airbag gas generator, a mist (solid components, such as a metal component, included in the gas generating agent that are generated by combustion of the gas generating agent) is generated. If the generated amount of mist is large, the filter is heavily damaged and the mist that passed through the filter flows into the air bag. When this problem is solved by increasing the filter thickness (or increasing the bulk density thereof), the weight of the entire gas generator is increased and the demand for weight reduction cannot be met.
  • In 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.
    • Examples
  • The present invention will be described below in greater detail based on Examples, but the present invention is not limited thereto.
    • Examples and Comparative Examples
  • 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.
    • (Composition of generated gas)
  • 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 NH3 (ppm; mass standard) was analyzed with a detection tube.
    • (Evaluation of slag state)
  • 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. Upon completion of combustion, the combustion residue (slag) was sampled and the state thereof was evaluated according to the following criteria.
    ○ : has a lump-like shape and is not fractured when pressed with a finger.
    Δ : has a lump-like shape, but is fractured when pressed with a finger.
    × : has a powder shape.
    • (Measurement of slag amount)
  • 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.
    • (Detailed description of components shown in Tables 1, 2)
  • La(OH)3: manufactured by Taiyo Koko Co., Ltd., lanthanum hydroxide - 100.
    Nd (OH) 3: manufactured by Taiyo Koko Co., Ltd., neodymium hydroxide - 98.
    La(NO3)3[La(NO3)3·6H2O]: Kohnan Muki Ltd., lanthanum nitrate hexahydrate.
    Cu: electrolytic copper powder, manufactured by Nikko Materials Co., Ltd., #6.
    Glass powder: phosphate glass [P2O5 (54 to 56 mass%), Al2O3 (9 to 11 mass%), Na2O (19 to 21 mass%), K2O (14 to 16 mass%), softening point about 400°C.
    • GN:
    guanidine nitrate.
    BCN:
    basic copper nitrate.
    CeO2 :
    particle size 0.6 µm.
    Nd2O3
    particle size 6 µm.
    La2O3:
    particle size 6 µm.
    Pr6O11:
    particle size 15 µm.
    La(OH)3:
    particle size 1.2 µm.
    Nd(OH)3:
    particle size 1 µm
    Table 1
    Gas generating composition (mass%) Composition of generated gas (ppm) Slag state (g)
    GN BCN CMCNa Al(OH)3 Light rare earth compound- additive NO CO NH3
    Example 1 41.20 49.80 5.00 - La(OH)3 (4.00) 200 350 5 ○
    2 39.00 48.00 5.00 - La(OH)3 (8.00) 210 300 6 ○
    3 37.00 46.00 5.00 - La(OH)3 (12.00) 150 270 11 ○
    4 42.50 50.50 5.00 - La(OH)3 (2.00) 80 370 7 ○
    5 43.80 49.20 5.00 - La(NO3) (2.00) 50 450 6 ○
    6 44.00 47.00 5.00 - La(NO3)3 (4.00) 80 410 5 ○
    7 44.50 42.50 5.00 - La(NO3)3 (8.00) 55 420 5 ○
    8 42.80 48.20 5.00 - La(OH)3 (2.00)/ La(NO3)3 (2.00) 50 400 7 ○
    9 41.20 46.80 5.00 - La(OH)3 (500)/ La (NO3)3 (2.00) 60 390 4 ○
    10 41.50 44.50 5.00 - La(OH)3 (5.00)/ La(NO3)3 (4.00) 60 380 6 ○
    11 31.50 41.50 5.00 4.00 La(OH)3 (3.00) 75 300 5 Δ
    12 36.00 45.00 5.00 4.00 La(OH)3 (10.00) 125 180 7 Δ
    13 31.00 41.00 5.00 - La(OH)3 (8.00)/ Cu (15.00) 150 210 9 ○
    14 34.50 43.50 5.00 - La(OH)3 (12.00)/ Cu (5.00) 110 300 13 ○
    15 41.20 49.80 5.00 - Nd(OH)3 (4.00) 85 400 13 ○
    16 39.00 48.00 5.00 - Nd(OH)3 (8.00) 65 360 11 ○
    17 37.00 46.00 5.00 - Nd(OH)3 (12.00) 150 240 8 ○
    Comparative Example 1 40.71 49.29 5.00 5.00 - 55 340 6 ×
    2 40.71 49.29 5.00 4.00 Glass powder (1.00) 60 370 11 ×
    Table 2
    Gas generating composition (mass%) Composition of generated gas (ppm) Slag amount (g)
    GN BCN CMCNa Al(OH)3 Light rare earth compound - additive NO CO NH3
    Embodiment 18 37.00 46.00 5.00 - La(OH)3 (12.00) 4 73 33 8.55
    Embodiment 19 34.50 43.50 5.00 - La(OH)3 (12.00)/ Cu (5.00) 3 60 29 10.33
    Comparative Example 3 43.22 46.78 3.00 6.00 Glass powder (1.00) 7 60 9 2.92
  • As is clear from Tables 1 and 2, with the gas generating composition of the Examples, generation of NO and the like was suppressed, and a solid-lump-like slag was formed. Because the mist thus remained in the form of solid slag, the problems associated with the filter being damaged by the mist and the mist passing through the filter can be resolved. A contribution is also made to the decrease in the weight of gas generator because the thickness or bulk density of the filter can be reduced.
  • With the gas generating composition of the Comparative Examples, 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.
  • The invention thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.

Claims (4)

  1. A gas generating composition comprising a light rare earth compound.
  2. The gas generating composition according to claim 1, wherein the light rare earth compound is a compound of a rare earth element selected from the group consisting of scandium, yttrium, lanthanum, cerium, praseodymium, and neodymium.
  3. The gas generating composition according to claim 1 or 2, wherein the light rare earth compound is selected from the group consisting of oxides, hydroxides, halogenides, nitrates, sulfates, acetates, phosphates, and carbonates of rare earth elements.
  4. The gas generating composition according to any one of claims 1 to 3, wherein a mean particle size of the light rare earth compound is within a range of 0.5 to 500 µm.
EP07000356.1A 2006-01-26 2007-01-09 Gas generating composition Not-in-force EP1816113B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2006017386A JP4847143B2 (en) 2006-01-26 2006-01-26 Gas generant composition

Publications (2)

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

Family

ID=38055398

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07000356.1A Not-in-force EP1816113B1 (en) 2006-01-26 2007-01-09 Gas generating composition

Country Status (3)

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104876780A (en) * 2015-04-13 2015-09-02 喻自达 Pyrotechnic explosive composition prepared by using environment-friendly bamboo charcoals
EP2698360A3 (en) * 2012-08-17 2017-08-16 Diehl Defence GmbH & Co. KG Material with an additive for a spectral decoy flare which burns the material

Citations (5)

* 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
EP0952131A1 (en) * 1996-12-28 1999-10-27 Nippon Kayaku Kabushiki Kaisha Gas-generating agent for air bag
WO2000064839A2 (en) * 1999-04-13 2000-11-02 Atlantic Research Corporation Propellant compositions with salts and complexes of lanthanide and rare earth elements
WO2001034516A2 (en) * 1999-11-12 2001-05-17 General Dynamics Ots (Aerospace), Inc. Gas generation system
US6328906B1 (en) * 1997-12-18 2001-12-11 Atlantic Research Corporation Chemical delivery systems for fire suppression

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5725699A (en) * 1994-01-19 1998-03-10 Thiokol Corporation Metal complexes for use as gas generants
BR9711958A (en) * 1996-07-25 2000-10-24 Thiokol Corp Metal complexes for use as gas generators
EP0922015A1 (en) * 1996-08-30 1999-06-16 Talley Defence Systems, Incorporated Gas generating compositions
US6093269A (en) * 1997-12-18 2000-07-25 Atlantic Research Corporation Pyrotechnic gas generant composition including high oxygen balance fuel
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

Patent Citations (5)

* 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
EP0952131A1 (en) * 1996-12-28 1999-10-27 Nippon Kayaku Kabushiki Kaisha Gas-generating agent for air bag
US6328906B1 (en) * 1997-12-18 2001-12-11 Atlantic Research Corporation Chemical delivery systems for fire suppression
WO2000064839A2 (en) * 1999-04-13 2000-11-02 Atlantic Research Corporation Propellant compositions with salts and complexes of lanthanide and rare earth elements
WO2001034516A2 (en) * 1999-11-12 2001-05-17 General Dynamics Ots (Aerospace), Inc. Gas generation system

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2698360A3 (en) * 2012-08-17 2017-08-16 Diehl Defence GmbH & Co. KG Material with an additive for a spectral decoy flare which burns the material
CN104876780A (en) * 2015-04-13 2015-09-02 喻自达 Pyrotechnic explosive composition prepared by using environment-friendly bamboo charcoals

Also Published As

Publication number Publication date
EP1816113B1 (en) 2017-08-09
WO2007086329A1 (en) 2007-08-02
JP4847143B2 (en) 2011-12-28
JP2007197252A (en) 2007-08-09

Similar Documents

Publication Publication Date Title
EP1538137B1 (en) Gas generant composition
US6964716B2 (en) Gas generating composition
EP2690081B1 (en) Gas-generating agent composition
KR20020071028A (en) Gas-generating agent composition comprising triazine derivative
EP2444383A1 (en) Gas generant composition
JP4767487B2 (en) Gas generant composition
US20050127324A1 (en) Gas generating composition
JP4672974B2 (en) Gas generant composition
US8034133B2 (en) Gas generating composition
JP5422096B2 (en) Gas generant composition
EP1816113B1 (en) Gas generating composition
US8137771B2 (en) Gas generating composition
US7887650B2 (en) Gas generating composition
JP4610266B2 (en) Gas generant composition
US7833365B2 (en) Rare earth compound containing gas generating composition
US20060191614A1 (en) Gas generating composition
EP2910538A1 (en) Gas-generating-agent composition
JP5031255B2 (en) Gas generant composition
JP4794813B2 (en) Gas generant composition
US20050155681A1 (en) Gas generating composition
US20050098247A1 (en) Gas generating composition
JP4627662B2 (en) Gas generant composition
US8002918B2 (en) Gas generating composition
US20080092998A1 (en) Gas generating composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20070905

17Q First examination report despatched

Effective date: 20071119

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: DAICEL CHEMICAL INDUSTRIES, LTD.

AKX Designation fees paid

Designated state(s): DE FR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170315

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602007051893

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602007051893

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20180511

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180131

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20180928

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20220119

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602007051893

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230801