EP1195367A1 - Gas generator composition - Google Patents
Gas generator composition Download PDFInfo
- Publication number
- EP1195367A1 EP1195367A1 EP00921099A EP00921099A EP1195367A1 EP 1195367 A1 EP1195367 A1 EP 1195367A1 EP 00921099 A EP00921099 A EP 00921099A EP 00921099 A EP00921099 A EP 00921099A EP 1195367 A1 EP1195367 A1 EP 1195367A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- basic
- gas generating
- nitrate
- bitetrazole
- salt
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
Definitions
- the present invention relates to a gas generating composition which is suitable for an air bag restraining system of automobiles or the like, its molded article and an inflator for an air bag using the same.
- US-A 4,909,549 discloses a composition comprising hydrogen-containing tetrazole and triazole compounds and an oxygen-containing oxidizing agent.
- US-A 4,370,181 discloses a gas generating composition comprising a hydrogen-free bitetrazole metal salt and an oxygen-free oxidizing agent.
- US-A 4,369,079 discloses a gas generating composition comprising a hydrogen-free bitetrazole metal salt and an alkali metal nitrate, an alkali metal nitrite, an alkaline earth metal nitrate, an alkaline earth metal nitrite or a mixture thereof.
- US-A 5, 542, 999 discloses a gas generating agent comprising a fuel such as GZT, TAGN, NG (nitroguanidine), NTO or the like, a basic copper nitrate, a catalyst for reducing toxic gases and a coolant.
- JP-A 10-72,273 discloses a gas generating composition comprising a bitetrazole metal salt, a bitetrazole ammonium salt or aminotetrazole and ammonium nitrate.
- the non-azide based gas generating composition is problematic in a combustion temperature, a burning rate, phase transfer, amounts of generated carbon monoxide and nitrogen oxides, a gas output and the like.
- the gas generating composition of US-A 4,369,079 has a high combustion temperature, and requires a large amount of a coolant in actual use.
- the composition of US-A 5,542,999 has a low burning rate, and might not be completely burned in a short time.
- a shape is changed due to phase transfer of ammonium nitrate in the range of the use temperature, which damages a molded article of the gas generating agent, and in result, stable combustion cannot be conducted.
- an object of the invention is to provide a gas generating composition which has a low combustion temperature, a high burning rate, small amounts of generated carbon monoxide and nitrogen oxides and an excellent combustion stability, its molded article and an inflator for an air bag using the same.
- the invention provides a gas generating composition
- a gas generating composition comprising (a) a bitetrazole compound as a fuel and (b) a basic metal nitrate as an oxidizing agent.
- the invention provides a gas generating composition
- a gas generating composition comprising (a) a bitetrazole compound as a fuel, (b) a basic metal nitrate as an oxidizing agent and (c) a binder and/or a slag-forming agent.
- the invention provides a molded article in the form of a single-perforated cylinder, a perforated (porous) cylinder or pellets, the molded article being obtained from the gas generating composition.
- the invention provides an inflator for an air bag using the gas generating composition and the molded article.
- the gas generating composition and its molded article of the invention are easy to handle because of a low toxicity and less hazard, and have a high burning rate and a low combustion temperature. Further, amounts of generated carbon monoxide and nitrogen oxides are reduced in the combustion.
- the bitetrazole compound being a fuel as component (a) which is used in the invention is preferable because the content of the nitrogen atom in a molecule is high, the toxicity is low and the burning rate is increased in combination with component (b).
- the bitetrazole compound at least one selected from metal salts of bitetrazole such as a potassium salt of bitetrazole, a sodium salt of bitetrazole, a magnesium salt of bitetrazole, a calcium salt of bitetrazole and a copper salt of bitetrazole, an ammonium salt of bitetrazole and a melamine salt of bitetrazole is proposed.
- metal salts of bitetrazole such as a potassium salt of bitetrazole, a sodium salt of bitetrazole, a magnesium salt of bitetrazole, a calcium salt of bitetrazole and a copper salt of bitetrazole, an ammonium salt of bitetrazole and a melamine salt of bitetrazole is proposed.
- an ammonium salt of bitetrazole is preferable because the content of the nitrogen atom is 81.4 % by weight, LD 50 (oral-rat) is 2,000 mg/kg and the combustion efficiency is good.
- the bitetrazole compound here includes 5-5' compounds and 1-5' compounds
- the basic metal nitrate being an oxidizing agent as component (b) which is used in the invention
- at least one selected from a basic copper nitrate, a basic cobalt nitrate, a basic zinc nitrate, a basic manganese nitrate, a basic iron nitrate, a basic molybdenum nitrate, a basic bismuth nitrate and a basic cerium nitrate is proposed.
- a basic copper nitrate is preferable.
- the basic copper nitrate is excellent in thermal stability, as compared with ammonium nitrate as an oxidizing agent, because no phase transfer occurs in the range of the use temperature and the melting point is high. Further, since the basic copper nitrate acts to decrease a combustion temperature of a gas generating agent, amounts of generated nitrogen oxides can be decreased.
- the gas generating composition of the invention is a two-component-type composition comprising components (a) and (b), the contents of the components are as follows.
- the content of component (a) is preferably 5 to 60 % by weight, more preferably 15 to 55 % by weight.
- the content of component (b) is preferably 40 to 95 % by weight, more preferably 45 to 85 % by weight.
- a preferable example of the two-component-type gas generating composition is a composition comprising 15 to 35 % by weight of ammonium bitetrazole as component (a) and 65 to 85 % by weight of a basic copper nitrate as component (b).
- the binder and/or the slag-forming agent as component (c) used in the invention at least one selected from carboxymethylcellulose (CMC), sodium carboxymethylcellulose (CMCNa), a potassium salt of carboxymethylcellulose, an ammonium salt of carboxymethylcellulose, cellulose acetate, cellulose acetatebutyrate (CAB), methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), ethylhydroxyethyl cellulose (EHEC), hydroxypropyl cellulose (HPC), carboxymethylethyl cellulose (CMEC), fine crystalline cellulose, polyacrylic amide, amine products of polyacrylic amide, polyacrylic hydrazide, a copolymer of an acrylic amide and a metal salt of acrylic acid, a copolymer of polyacrylic amide and polyacrylic ester, polyvinyl alcohol, acrylic rubber, guar gum, starch, silicone, molybdenum disulfide,
- a metal oxide being component (c) at least one selected from copper oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide and bismuth oxide is proposed.
- a metal hydroxide at least one selected from cobalt hydroxide and aluminum hydroxide is proposed.
- a metal carbonate and a basic metal carbonate at least one selected from calcium carbonate, cobalt carbonate, a basic zinc carbonate, a basic copper carbonate, a basic cobalt carbonate, a basic iron carbonate, a basic bismuth carbonate and a basic magnesium carbonate is proposed.
- a molybdate at least one selected from cobalt molybdate and ammonium molybdate is proposed.
- a sodium salt of carboxymethylcellulose and a potassium salt of carboxymethylcellulose are preferable.
- a sodium salt of carboxymethylcellulose is more preferable.
- the gas generating composition of the invention is a three-component-type composition comprising components (a) to (c), the contents of the components are as follows.
- the content of component (a) is preferably 5 to 60 % by weight, more preferably 15 to 55 % by weight.
- the content of component (b) is preferably 40 to 95 % by weight, more preferably 45 to 85 % by weight.
- the content of component (c) is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight in total of components (a) and (b).
- a preferable example of the three-component-type gas generating composition is a composition comprising 15 to 35 % by weight of an ammonium salt of bitetrazole as component (a), 65 to 85 % by weight of a basic copper nitrate as component (b) and 0.5 to 10 parts by weight, per 100 parts by weight in total of components (a) and (b), of a sodium salt of carboxymethylcellulose as component (c).
- the gas generating composition of the invention can be molded in a desired shape, and formed into a molded article in the shape of a single-perforated cylinder, a perforated (porous) cylinder or a pellet.
- These molded articles can be produced by a method in which the gas generating composition is added to and mixed with water or an organic solvent and the mixture is extrusion-molded (molded articles in the form of a single-perforated cylinder, a hollow tube having one through-hole in the longitudinal direction, a perforated (porous) cylinder and a hollow tube having plural through-holes in the longitudinal direction) or by a compression-molding method using a pelletizer (molded article in the form of a pellet) .
- the gas generating composition or the molded article obtained therefrom in the invention can be used in, for example, an inflator for an air bag of a driver side, an inflator for an air bag of a passenger side, an inflator for a side air bag, an inflator for an inflatable curtain, an inflator for a knee bolster, an inflator for an inflatable seat belt, an inflator for a tubular system and an inflator for a pretensioner in various vehicles.
- the inflator using the gas generating composition or the molded article obtained therefrom in the invention may be a pyrotechnic type in which a gas is supplied only from a gas generating agent or a hybrid type in which a gas is supplied from both of a pressurized gas such as argon or the like and a gas generating agent.
- a section having a function to generate a gas by burning a gas generating agent is "a gas generator".
- the gas generating composition or the molded article obtained therefrom in the invention can also be used as an igniting agent called an enhancer (or a booster) for transferring energy of a detonator or a squib to a gas generating agent.
- an enhancer or a booster
- BHTNH 3 indicates an ammonium salt of bitetrazole
- BHTK a potassium salt of bitetrazole
- BCN a basic copper nitrate
- CMCNa a sodium salt of carboxymethylcellulose respectively.
- Gas generating compositions each having a formulation shown in Table 1 were produced.
- a combustion temperature and a gas outlet (unit "mol/100 g" indicates the number of mols of a generated gas per 100 g of the composition) and amounts of generated CO and NO of these compositions according to theoretical calculations are shown in Table 1.
- Gas generating compositions each having a formulation shown in Table 2 were produced. These compositions were tested for a friction sensitivity and a drop hammer sensitivity according to the explosives performance test method of JIS K 4810-1979. The results are shown in Table 2.
- Gas generating composition Composition ratio (wt.%) Friction sensitivity (kgf) Drop hammer sensitivity (cm)
- Example 8 BHTNH 3 /BCN 28.75/71.25 >36.0 >100
- Example 9 BHTK/BCN 44.52/55.48 >36.0 70 - 80
- Example 10 BHTNH 3 /BCN/CMCNa 25.89/71.11/3 >36.0 >80
- Gas generating compositions each having a formulation shown in Table 3 were produced.
- a melting temperature, a temperature at which to start heat generation and a temperature at which to start TG weight loss were measured with a TAS-type differential thermal analyzer manufactured by Rigaku K.K.
- a rate of temperature rise in the measurement was 20°C/min
- a measurement atmosphere was a nitrogen gas
- an amount of a sample in the measurement was 1 to 2 mg.
- Table 3 The results are shown in Table 3.
- Gas generating compositions each having a formulation shown in Table 3 were produced. Each of these compositions was molded into a strand. A burning rate was measured in a nitrogen atmosphere at a pressure of 50, 70 or 90 kg/cm 2 . A burning rate at 70 kg/cm 2 and a pressure index of 50 to 90 kg/cm 2 are shown in Table 4. Gas generating composition Composition ratio (wt.%) Burning rate (mm/sec) Pressure index Example 13 BHTNH 3 /BCN 28.75/71.25 14.48 0.16 Example 14 BHTK/BCN 44.52/55.48 27.92 0.20 Example 15 BHTNH 3 /BCN/CMCNa 25.89/71.11/3 14.99 0.15
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Air Bags (AREA)
Abstract
A gas generating composition for an air bag having a low
toxicity, a high burning rate and a low combustion temperature
is provided.
A gas generating composition comprising (a) a
bitetrazole compound as a fuel, (b) a basic metal nitrate as
an oxidizing agent, (c) a binder and/or a slag-forming agent
and (d) a combustion controlling agent made of a metal oxide.
Description
The present invention relates to a gas generating
composition which is suitable for an air bag restraining system
of automobiles or the like, its molded article and an inflator
for an air bag using the same.
As a gas generating agent for an air bag as a
passenger-protecting device in automobiles, a composition
using sodium azide has been often used so far. However, a
toxicity [LD50 (oral-rat) = 27 mg/kg] to human bodies or hazard
in handling of sodium azide has been regarded as a serious
problem. Therefore, as safe non-azide based gas generating
compositions, gas generating compositions containing various
nitrogen-containing organic compounds have been developed to
replace the sodium-azide based composition.
For example, US-A 4,909,549 discloses a composition
comprising hydrogen-containing tetrazole and triazole
compounds and an oxygen-containing oxidizing agent. US-A
4,370,181 discloses a gas generating composition comprising a
hydrogen-free bitetrazole metal salt and an oxygen-free
oxidizing agent. US-A 4,369,079 discloses a gas generating
composition comprising a hydrogen-free bitetrazole metal salt
and an alkali metal nitrate, an alkali metal nitrite, an
alkaline earth metal nitrate, an alkaline earth metal nitrite
or a mixture thereof. US-A 5, 542, 999 discloses a gas generating
agent comprising a fuel such as GZT, TAGN, NG (nitroguanidine),
NTO or the like, a basic copper nitrate, a catalyst for reducing
toxic gases and a coolant. JP-A 10-72,273 discloses a gas
generating composition comprising a bitetrazole metal salt, a
bitetrazole ammonium salt or aminotetrazole and ammonium
nitrate.
However, the non-azide based gas generating composition
is problematic in a combustion temperature, a burning rate,
phase transfer, amounts of generated carbon monoxide and
nitrogen oxides, a gas output and the like. For example, the
gas generating composition of US-A 4,369,079 has a high
combustion temperature, and requires a large amount of a coolant
in actual use. The composition of US-A 5,542,999 has a low
burning rate, and might not be completely burned in a short time.
In the gas generating agent of JP-A 10-72, 273, a shape is changed
due to phase transfer of ammonium nitrate in the range of the
use temperature, which damages a molded article of the gas
generating agent, and in result, stable combustion cannot be
conducted.
Accordingly, an object of the invention is to provide a
gas generating composition which has a low combustion
temperature, a high burning rate, small amounts of generated
carbon monoxide and nitrogen oxides and an excellent combustion
stability, its molded article and an inflator for an air bag
using the same.
The invention provides a gas generating composition
comprising (a) a bitetrazole compound as a fuel and (b) a basic
metal nitrate as an oxidizing agent.
Further, the invention provides a gas generating
composition comprising (a) a bitetrazole compound as a fuel,
(b) a basic metal nitrate as an oxidizing agent and (c) a binder
and/or a slag-forming agent.
Still further, the invention provides a molded article
in the form of a single-perforated cylinder, a perforated
(porous) cylinder or pellets, the molded article being obtained
from the gas generating composition.
Furthermore, the invention provides an inflator for an
air bag using the gas generating composition and the molded
article.
The gas generating composition and its molded article of
the invention are easy to handle because of a low toxicity and
less hazard, and have a high burning rate and a low combustion
temperature. Further, amounts of generated carbon monoxide
and nitrogen oxides are reduced in the combustion.
The bitetrazole compound being a fuel as component (a)
which is used in the invention is preferable because the content
of the nitrogen atom in a molecule is high, the toxicity is low
and the burning rate is increased in combination with component
(b).
As the bitetrazole compound, at least one selected from
metal salts of bitetrazole such as a potassium salt of
bitetrazole, a sodium salt of bitetrazole, a magnesium salt of
bitetrazole, a calcium salt of bitetrazole and a copper salt
of bitetrazole, an ammonium salt of bitetrazole and a melamine
salt of bitetrazole is proposed. Of these, an ammonium salt
of bitetrazole is preferable because the content of the nitrogen
atom is 81.4 % by weight, LD50 (oral-rat) is 2,000 mg/kg and
the combustion efficiency is good. The bitetrazole compound
here includes 5-5' compounds and 1-5' compounds relating to two
tetrazole rings, and 5-5' compounds are preferable because of
the cost and the easy procurement.
As the basic metal nitrate being an oxidizing agent as
component (b) which is used in the invention, at least one
selected from a basic copper nitrate, a basic cobalt nitrate,
a basic zinc nitrate, a basic manganese nitrate, a basic iron
nitrate, a basic molybdenum nitrate, a basic bismuth nitrate
and a basic cerium nitrate is proposed. Of these, a basic copper
nitrate is preferable.
The basic copper nitrate is excellent in thermal
stability, as compared with ammonium nitrate as an oxidizing
agent, because no phase transfer occurs in the range of the use
temperature and the melting point is high. Further, since the
basic copper nitrate acts to decrease a combustion temperature
of a gas generating agent, amounts of generated nitrogen oxides
can be decreased.
When the gas generating composition of the invention is
a two-component-type composition comprising components (a) and
(b), the contents of the components are as follows.
The content of component (a) is preferably 5 to 60 % by
weight, more preferably 15 to 55 % by weight. The content of
component (b) is preferably 40 to 95 % by weight, more preferably
45 to 85 % by weight.
Further, a preferable example of the two-component-type
gas generating composition is a composition comprising 15 to
35 % by weight of ammonium bitetrazole as component (a) and 65
to 85 % by weight of a basic copper nitrate as component (b).
As the binder and/or the slag-forming agent as component
(c) used in the invention, at least one selected from
carboxymethylcellulose (CMC), sodium carboxymethylcellulose
(CMCNa), a potassium salt of carboxymethylcellulose, an
ammonium salt of carboxymethylcellulose, cellulose acetate,
cellulose acetatebutyrate (CAB), methyl cellulose (MC), ethyl
cellulose (EC), hydroxyethyl cellulose (HEC),
ethylhydroxyethyl cellulose (EHEC), hydroxypropyl cellulose
(HPC), carboxymethylethyl cellulose (CMEC), fine crystalline
cellulose, polyacrylic amide, amine products of polyacrylic
amide, polyacrylic hydrazide, a copolymer of an acrylic amide
and a metal salt of acrylic acid, a copolymer of polyacrylic
amide and polyacrylic ester, polyvinyl alcohol, acrylic rubber,
guar gum, starch, silicone, molybdenum disulfide, Japanese acid
clay, talc, bentonite, diatomaceous earth, kaolin, calcium
stearate, silica, alumina, sodium silicate, silicon nitride,
silicon carbide, hydrotalcite, mica, a metal oxide, a metal
hydroxide, a metal carbonate, a basic metal carbonate and a salt
of molybdic acid is proposed.
As a metal oxide being component (c), at least one selected
from copper oxide, iron oxide, zinc oxide, cobalt oxide,
manganese oxide, molybdenum oxide, nickel oxide and bismuth
oxide is proposed. As a metal hydroxide, at least one selected
from cobalt hydroxide and aluminum hydroxide is proposed. As
a metal carbonate and a basic metal carbonate, at least one
selected from calcium carbonate, cobalt carbonate, a basic zinc
carbonate, a basic copper carbonate, a basic cobalt carbonate,
a basic iron carbonate, a basic bismuth carbonate and a basic
magnesium carbonate is proposed. As a molybdate, at least one
selected from cobalt molybdate and ammonium molybdate is
proposed. These compounds as component (c) can act as the
slag-forming agent and/or the binder.
In case of increasing the ignitability of the gas
generating composition, a sodium salt of
carboxymethylcellulose and a potassium salt of
carboxymethylcellulose are preferable. Of these, a sodium
salt of carboxymethylcellulose is more preferable.
When the gas generating composition of the invention is
a three-component-type composition comprising components (a)
to (c), the contents of the components are as follows.
The content of component (a) is preferably 5 to 60 % by
weight, more preferably 15 to 55 % by weight. The content of
component (b) is preferably 40 to 95 % by weight, more preferably
45 to 85 % by weight. The content of component (c) is preferably
0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by
weight per 100 parts by weight in total of components (a) and
(b).
A preferable example of the three-component-type gas
generating composition is a composition comprising 15 to 35 %
by weight of an ammonium salt of bitetrazole as component (a),
65 to 85 % by weight of a basic copper nitrate as component (b)
and 0.5 to 10 parts by weight, per 100 parts by weight in total
of components (a) and (b), of a sodium salt of
carboxymethylcellulose as component (c).
The gas generating composition of the invention can be
molded in a desired shape, and formed into a molded article in
the shape of a single-perforated cylinder, a perforated
(porous) cylinder or a pellet. These molded articles can be
produced by a method in which the gas generating composition
is added to and mixed with water or an organic solvent and the
mixture is extrusion-molded (molded articles in the form of a
single-perforated cylinder, a hollow tube having one
through-hole in the longitudinal direction, a perforated
(porous) cylinder and a hollow tube having plural through-holes
in the longitudinal direction) or by a compression-molding
method using a pelletizer (molded article in the form of a
pellet) .
The gas generating composition or the molded article
obtained therefrom in the invention can be used in, for example,
an inflator for an air bag of a driver side, an inflator for
an air bag of a passenger side, an inflator for a side air bag,
an inflator for an inflatable curtain, an inflator for a knee
bolster, an inflator for an inflatable seat belt, an inflator
for a tubular system and an inflator for a pretensioner in
various vehicles.
Further, the inflator using the gas generating
composition or the molded article obtained therefrom in the
invention may be a pyrotechnic type in which a gas is supplied
only from a gas generating agent or a hybrid type in which a
gas is supplied from both of a pressurized gas such as argon
or the like and a gas generating agent. In the hybrid inflator,
a section having a function to generate a gas by burning a gas
generating agent is "a gas generator".
Moreover, the gas generating composition or the molded
article obtained therefrom in the invention can also be used
as an igniting agent called an enhancer (or a booster) for
transferring energy of a detonator or a squib to a gas generating
agent.
The invention is illustrated more specifically below by
referring to Examples. However, the invention is not limited
thereto. By the way, in Tables 1 to 4 below, BHTNH3 indicates
an ammonium salt of bitetrazole, BHTK a potassium salt of
bitetrazole, BCN a basic copper nitrate and CMCNa a sodium salt
of carboxymethylcellulose respectively.
Gas generating compositions each having a formulation
shown in Table 1 were produced. A combustion temperature and
a gas outlet (unit "mol/100 g" indicates the number of mols of
a generated gas per 100 g of the composition) and amounts of
generated CO and NO of these compositions according to
theoretical calculations are shown in Table 1.
It indicates that any combustion temperatures in
Examples 1 to 7 are quite lower than those in Comparative
Examples 1 and 2 and not more than 1,900 K. The amount of
generated NO is effectively decreased. Further, the amounts
of generated CO and NO are not permitted in practice unless
the amount of generated CO being 2 x 10-3 mol/100 g or less
and the amount of generated NO being 2 x 10-4 mol/100 g or less
are attained at the same time. It is found that Examples 1
to 7 satisfy these conditions.
Gas generating compositions each having a formulation
shown in Table 2 were produced. These compositions were tested
for a friction sensitivity and a drop hammer sensitivity
according to the explosives performance test method of JIS K
4810-1979. The results are shown in Table 2.
| Gas generating composition | Composition ratio (wt.%) | Friction sensitivity (kgf) | Drop hammer sensitivity (cm) | |
| Example 8 | BHTNH3/BCN | 28.75/71.25 | >36.0 | >100 |
| Example 9 | BHTK/BCN | 44.52/55.48 | >36.0 | 70 - 80 |
| Example 10 | BHTNH3/BCN/CMCNa | 25.89/71.11/3 | >36.0 | >80 |
Gas generating compositions each having a formulation
shown in Table 3 were produced. With respect to these
compositions, a melting temperature, a temperature at which
to start heat generation and a temperature at which to start
TG weight loss were measured with a TAS-type differential
thermal analyzer manufactured by Rigaku K.K. A rate of
temperature rise in the measurement was 20°C/min, a measurement
atmosphere was a nitrogen gas, and an amount of a sample in
the measurement was 1 to 2 mg. The results are shown in Table
3.
| Gas generating composition | Composition ratio (wt.%) | Melting temperature (°C) | Temperature at which to start decomposition with heat generation (°C) | Temperature at which to start TG weight loss (°C) | |
| Example 11 | BHTNH3/BCN | 28.75/71.25 | 208 | 230 | 216 |
| Example 12 | BHTK/BCN | 44.52/55.48 | 198 | 362 | 201 |
Gas generating compositions each having a formulation
shown in Table 3 were produced. Each of these compositions
was molded into a strand. A burning rate was measured in a
nitrogen atmosphere at a pressure of 50, 70 or 90 kg/cm2. A
burning rate at 70 kg/cm2 and a pressure index of 50 to 90 kg/cm2
are shown in Table 4.
| Gas generating composition | Composition ratio (wt.%) | Burning rate (mm/sec) | Pressure index | |
| Example 13 | BHTNH3/BCN | 28.75/71.25 | 14.48 | 0.16 |
| Example 14 | BHTK/BCN | 44.52/55.48 | 27.92 | 0.20 |
| Example 15 | BHTNH3/BCN/CMCNa | 25.89/71.11/3 | 14.99 | 0.15 |
As stated above, the respective values shown in Examples
8 to 15 reveal that the compositions in these Examples meet
the practical conditions as the gas generating composition for
the inflator gas.
Claims (9)
- A gas generating composition comprising (a) a bitetrazole compound as a fuel and (b) a basic metal nitrate as an oxidizing agent.
- A gas generating composition comprising (a) a bitetrazole compound as a fuel, (b) a basic metal nitrate as an oxidizing agent and (c) a binder and/or a slag-forming agent.
- The gas generating composition as claimed in Claim 1 or 2, wherein the fuel as component (a) is at least one selected from the group consisting of a potassium salt of bitetrazole, a sodium salt of bitetrazole, a magnesium salt of bitetrazole, a calcium salt of bitetrazole, a copper salt of bitetrazole, an ammonium salt of bitetrazole and a melamine salt of bitetrazole.
- The gas generating composition as claimed in Claim 1, 2 or 3, wherein the basic metal nitrate as component (b) is at least one selected from the group consisting of a basic copper nitrate, a basic cobalt nitrate, a basic zinc nitrate, a basic manganese nitrate, a basic iron nitrate, a basic molybdenum nitrate, a basic bismuth nitrate and a basic cerium nitrate.
- The gas generating composition as claimed in any one of Claims 1 to 4, comprising 15 to 35 % by weight of an ammonium salt of bitetrazole as component (a) and 65 to 85 % by weight of a basic copper nitrate as component (b).
- The gas generating composition as claimed in any one of Claims 2 to 5, wherein the binder and/or the slag-forming agent as component (c) is at least one selected from the group consisting of carboxymethylcellulose, a sodium salt of carboxymethylcellulose, a potassium salt of carboxymethylcellulose, an ammonium salt of carboxymethylcellulose, cellulose acetate, cellulose acetatebutyrate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethylhydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethylethyl cellulose, fine crystalline cellulose, polyacrylic amide, amine products of polyacrylic amide, polyacrylic hydrazide, a copolymer of an acrylic amide and a metal salt of acrylic acid, a copolymer of polyacrylic amide and polyacrylic ester, polyvinyl alcohol, acrylic rubber, guar gum, starch, silicone, molybdenum disulfide, Japanese acid clay, talc, bentonite, diatomaceous earth, kaolin, calcium stearate, silica, alumina, sodium silicate, silicon nitride, silicon carbide, hydrotalcite, mica, a metal oxide, a metal hydroxide, a metal carbonate, a basic metal carbonate and a salt of molybdic acid.
- A molded article in the shape of a single-perforated cylinder, a perforated (porous) cylinder or pellets, the molded article being obtained from the gas generating composition as claimed in any one of Claims 1 to 6.
- An inflator for an air bag using the gas generating composition as claimed in any one of Claims 1 to 7.
- An inflator for an air bag using the molded article as claimed in Claim 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11125012A JP2000319085A (en) | 1999-04-30 | 1999-04-30 | Gas generating composition |
| JP12501299 | 1999-04-30 | ||
| PCT/JP2000/002839 WO2000066518A1 (en) | 1999-04-30 | 2000-04-28 | Gas generator composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1195367A1 true EP1195367A1 (en) | 2002-04-10 |
| EP1195367A4 EP1195367A4 (en) | 2011-08-03 |
Family
ID=14899688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00921099A Withdrawn EP1195367A4 (en) | 1999-04-30 | 2000-04-28 | GAS GENERATING COMPOSITION |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1195367A4 (en) |
| JP (1) | JP2000319085A (en) |
| WO (1) | WO2000066518A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003048077A3 (en) * | 2001-11-30 | 2003-08-07 | Autoliv Asp Inc | Burn rate enhancement via a transition metal complex of diammonium bitetrazole |
| US7665764B2 (en) | 2004-01-15 | 2010-02-23 | Daicel Chemical Industries, Ltd. | Gas generator for air bag |
| EP1323696A3 (en) * | 2001-12-27 | 2012-05-16 | Trw Inc. | Cool burning gas generating material for a vehicle occupant protection apparatus |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4800469B2 (en) * | 1999-10-08 | 2011-10-26 | ダイセル化学工業株式会社 | Gas generant composition |
| JP2005231907A (en) * | 2000-03-10 | 2005-09-02 | Nippon Kayaku Co Ltd | Gas producing agent for use in air bag |
| EP1587775A2 (en) * | 2003-01-21 | 2005-10-26 | Autoliv Asp, Inc. | Gas generants |
| JP4494023B2 (en) * | 2004-01-15 | 2010-06-30 | ダイセル化学工業株式会社 | Gas generator for airbag |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4369079A (en) * | 1980-12-31 | 1983-01-18 | Thiokol Corporation | Solid non-azide nitrogen gas generant compositions |
| US4370181A (en) * | 1980-12-31 | 1983-01-25 | Thiokol Corporation | Pyrotechnic non-azide gas generants based on a non-hydrogen containing tetrazole compound |
| JP3468787B2 (en) * | 1992-11-27 | 2003-11-17 | 東洋化成工業株式会社 | Novel 5,5'-bi-1H-tetrazolamine salt |
| US5482579A (en) * | 1993-04-15 | 1996-01-09 | Nof Corporation | Gas generator compositions |
| US5682014A (en) * | 1993-08-02 | 1997-10-28 | Thiokol Corporation | Bitetrazoleamine gas generant compositions |
| DE4401213C1 (en) * | 1994-01-18 | 1995-03-02 | Fraunhofer Ges Forschung | Gas-generating mixture |
| KR100272955B1 (en) * | 1995-12-01 | 2000-11-15 | 구마모토 마사히로 | Gas generating agent and transfer charge for use in airbag gas generator, and gas generator comprising said gas generating agent and transfer charge |
| US5629494A (en) * | 1996-02-29 | 1997-05-13 | Morton International, Inc. | Hydrogen-less, non-azide gas generants |
| US5608183A (en) * | 1996-03-15 | 1997-03-04 | Morton International, Inc. | Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate |
| DE19643468A1 (en) * | 1996-10-22 | 1998-04-23 | Temic Bayern Chem Airbag Gmbh | Gas-generating, azide-free solid mixture |
| JPH10130086A (en) * | 1996-10-23 | 1998-05-19 | Nippon Kayaku Co Ltd | Gas generating agent for air bag |
| US5872329A (en) * | 1996-11-08 | 1999-02-16 | Automotive Systems Laboratory, Inc. | Nonazide gas generant compositions |
| JP4157176B2 (en) * | 1997-04-22 | 2008-09-24 | 東洋化成工業株式会社 | Novel 1,5'-bitetrazole compound, process for producing the same, and gas generating agent based on the 1,5'-bitetral compound |
| DE29821541U1 (en) * | 1998-12-02 | 1999-02-18 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azide-free, gas generating composition |
-
1999
- 1999-04-30 JP JP11125012A patent/JP2000319085A/en active Pending
-
2000
- 2000-04-28 WO PCT/JP2000/002839 patent/WO2000066518A1/en not_active Ceased
- 2000-04-28 EP EP00921099A patent/EP1195367A4/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003048077A3 (en) * | 2001-11-30 | 2003-08-07 | Autoliv Asp Inc | Burn rate enhancement via a transition metal complex of diammonium bitetrazole |
| US6712918B2 (en) | 2001-11-30 | 2004-03-30 | Autoliv Asp, Inc. | Burn rate enhancement via a transition metal complex of diammonium bitetrazole |
| EP1323696A3 (en) * | 2001-12-27 | 2012-05-16 | Trw Inc. | Cool burning gas generating material for a vehicle occupant protection apparatus |
| US7665764B2 (en) | 2004-01-15 | 2010-02-23 | Daicel Chemical Industries, Ltd. | Gas generator for air bag |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000066518A1 (en) | 2000-11-09 |
| EP1195367A4 (en) | 2011-08-03 |
| JP2000319085A (en) | 2000-11-21 |
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