JP2000154086A - Gas generating agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a gas generating agent composition giving clean combustion gas. SOLUTION: The gas generating agent composition contains one or more complexes selected from the group of complexes of transition metals such as copper and nickel having hydroxylamine as ligands and complexes of alkaline earth metals such as magnesium and calcium having hydroxylamine as ligands. Since the metallic complexes contain no or few carbon atoms, carbon monoxide is not contained at all in combustion gas or the quantity of carbon monoxide in combustion gas is considerably reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas generating composition serving as a working gas in an airbag system or a pretensioner system for protecting a human body mounted on an automobile, an aircraft or the like. The present invention also relates to an inflator system and a pretensioner system using the gas generating composition.

[0002]

2. Description of the Related Art As a fuel for a gas generating agent, a compound which replaces highly toxic sodium azide has been studied. For example, Japanese Patent Application Laid-Open No. 5-254
977 discloses a gas generating agent containing triaminoguanidine nitrate; JP-A-6-239683 discloses a gas generating agent containing carbohydrazide;
JP-A-7-61885 discloses a gas generant comprising cellulose acetate, potassium perchlorate and a nitrogen-containing nonmetallic compound; US Pat.
A gas generant containing a cellulosic binder such as 30% nitrocellulose and an energy substance is disclosed; Japanese Patent Publication No. Hei 9-503194 discloses a gas generant containing triaminoguanidine nitrate and ammonium nitrate phase-stabilized. Disclosed; WO 98/06486 discloses a gas generating agent containing an ammine complex or a hydrazine complex.

However, the above-mentioned non-sodium azide gas generating agents have some problems, respectively, and further improvement is required. For example, triaminoguanidine nitrate and hydrazine complex are very sensitive and dangerous, so that it is difficult to produce a gas generating agent. Gas generating agents containing carbohydrazide, triaminoguanidine nitrate and nitrocellulose have poor heat resistance and have problems in long-term use, and gas generating agents containing cellulose acetate, potassium perchlorate and nitrogen-containing nonmetallic compounds are: The combustion temperature is very high and gas cooling is difficult.

[0004] Originally, non-sodium azide gas generants were primarily intended to remedy the inherently undesirable disadvantages of sodium azide. However, the standardization of airbags as safety equipment for automobiles is progressing, and now, inflators for airbags are required to be much smaller and cheaper than those that have been mass-produced and used so far. . Therefore, in order to improve the inherent disadvantages of the sodium azide-based gas generating agent and to meet the demand for downsizing and cost reduction of the gas generator, the gas generating agent must be toxic and heat-resistant. Appropriate balance must be maintained in each item such as properties, gas generation efficiency, combustion temperature, filterability of combustion residue, amount of combustion residue, burning speed, safety, density, gas composition after combustion, etc.

Accordingly, the present invention solves the problems of the sodium azide-based gas generating agent, and in particular, in order to satisfy the demand for downsizing and cost reduction of the gas generator, a gas generating device having the above-mentioned characteristics in a well-balanced manner. It is intended to provide an agent composition. It is another object of the present invention to provide an inflator system and a pretensioner system for an airbag using the gas generating composition.

[0006]

The present invention provides a gas generating composition comprising at least one selected from a transition metal complex containing hydroxylamine as a ligand and an alkaline earth metal complex. provide. Further, the present invention provides an inflator system and a pretensioner system for an airbag, which use the gas generating composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The transition metal complex and the alkaline earth metal complex containing hydroxylamine as a ligand used in the gas generant composition of the present invention can be used as a fuel or an oxidant depending on the amount of oxygen atoms contained therein. Although it acts as an agent, it contains no or little carbon in the molecule, so that the gas generated during combustion contains no or little carbon monoxide.

As the transition metal complex or alkaline earth metal complex containing hydroxylamine as a ligand, the following general formula (I): M _a L _b L ′ _c X _d (I) [where M is a transition L represents a hydroxylamine as a ligand, L ′ represents a ligand other than hydroxylamine, and X represents an anion. a represents the number of metal atoms and represents 1-4, preferably 1-2, b represents the number of ligands and represents 1-8, preferably 1-6, and c represents the number of ligands other than hydroxylamine. 1 to 8, preferably 1 to 6
And d is the number of anions, 1 to 6, preferably 1 to 4
Is shown. And at least one selected from those represented by the following formula:

In the general formula (I), the transition metal represented by M includes zinc, copper, nickel, cobalt, iron, manganese, chromium, vanadium, titanium, palladium, platinum,
Zirconium, molybdenum, bismuth, tungsten and the like can be mentioned, and as the alkaline earth metal, magnesium, calcium, strontium and the like can be mentioned.

In the general formula (I), the ligands other than hydroxylamine represented by L 'include H ₂ O, O ₂ , CO,
NO, ethylenediaminetetraacetic acid (EDTA), carbohydrazide (CDH), ethylenediamine, ammonia,
Hydrazine and the like can be mentioned, but in the present invention, it is preferable that L ′ is not contained (c = 0 in the general formula (I)).

The anion represented by X in the general formula (I) includes NO ₃ ⁻ , NO ₂ ⁻ , NO ⁻ , ClO ₄ ⁻ , ClO ₃ ⁻ ,
Cl ⁻ , Br ⁻ , SCN ⁻ , SO ₄ ²⁻ , OH ⁻ , CO ₃ ²⁻ , P
^{_{O 4 3-, C 2 O 4}} 2-, BO 4 5-, MnO 4 -, MoO 4 2-, can be cited deprotonated hydroxylamine. These anions may be present either in direct coordination with the metal or in the absence of coordination.

The following compounds can be used as the complex represented by the general formula (I). Here, L-H indicates deprotonated hydroxylamine as an anion.

For example, M.N.Hughes and K.Shrimanker, I
norg. Chim. Acta. 18. 69 (1976)
L₆Cl_Two, NiL₆Br_Two, NiL₆(ClO_Four)_Two, NiL_Four
Cl_Two, NiL_FourBr_Two, NiL_Four(NO_Three)_Two, NiL_Four(Cl
O_Four)_Two, NiL_ThreeCl_Two, NiL_ThreeBr_Two, NiL_TwoCl_Two,
NiL_TwoBr_Two, NiLCl_Two, NiL (NO_Three)_Two, NiL_Four
(L-H)_Two, Ni_TwoL₆(LH) Cl_Three, CdL_TwoCl_Two, C
dL_TwoBr_Two, ZnL_TwoCl_Two, Zn_TwoL_Three(LH) Cl_Three,
Zn_TwoL_Three(LH) Br_Three, CoL_TwoCl_Two, CoL₆C
l_Three, MnL_TwoCl_Two, Ni_TwoL₆(LH) Br_Three, ZnL_Two
Br_Two, NiL₆(SCN)_Two, NiL_Four(SCN)_Two, CoL_Two
SO_FourMetal complexes such as E.M.Ivashkovich, N.I.Lazorchak
O.D.Gumanitskaya and M.Yu Shpontak, Zh.Neorg.Khi
m., 21, 2125 (1976)._TwoCl_Two, C
oL_FourCl_Two, CoL_FiveCl_Three, NiL₆Cl_Two, NiL_FourC
l_Two, CuL_FourCl_Two, CuL_Four(NO_Three)_Two, ZnL_TwoCl_Two,
CoL _TwoCl_Two, CoL (SO_Four), CoL₆Cl_Three, NiL₆
(SO_Four), NiL₆I_Two, NiL_TwoCl_Two, CoL_ThreeCl_Threeetc
Metal complex; Ya.V.Salyn, V.I.Nefedov, M.A.Sarukhano
vand Yu.Ya.Kharitonov, Koord.Khim., 1, 945 (1975)
PtL described in_TwoCl_Two, PtL_TwoI_Two, PtL
_Two(NH_Three)_TwoCl_Two, PtL_FourCl_Two, PtL_Four(OH)_Two, Co
L₆Cl_Three, NiL_FourCl_Two, NiL_FourI_Two, ZnL_TwoCl_Two,
CdL_TwoCl_Two, MnL_TwoCl_Two, BaL_TwoCl_Two, CaL_Two
Cl_Two, PtL_FourCl_Four, CdL_TwoBr_Two, CoL_TwoCl_Two,
NiL_TwoCl_Two, NiL_TwoBr_Two, [PtL_Four] [PtCl_Four],
PtL_FourBr_Two, PtL_TwoBr_Two, PtL_TwoBr_Four, PtL_Four
Br_FourAnd the like.

The gas generating composition of the present invention may further contain, as a fuel, another nitrogen-containing compound generally used as a fuel for a gas generating agent. Examples of the nitrogen-containing compound include tetrazole derivatives such as 5-aminotetrazole, bitetrazole derivatives such as bitetrazole diammonium salt, triazole derivatives such as 4-aminotriazole, dicyandiamide, nitroguanidine,
One or more selected from guanidine derivatives such as guanidine nitrate, triazine derivatives such as trihydrazinotriazine, oxamide, ammonium oxalate, azodicarbonamide, hydrazodicarbonamide and the like can be mentioned.

[0015] The content of the fuel in the gas generating composition is preferably from 8 to 70% by weight, particularly preferably from 10 to 60% by weight.

The gas generating composition of the present invention may further contain an oxidizing agent. Examples of the oxidizing agent include one or more selected from oxyacid salts, metal oxides, metal double oxides, metal hydroxides, and metal peroxides.

Examples of the oxyacid salt include ammonium, alkali metal, alkaline earth metal, alkaline earth metal complex, transition metal and nitrate, nitrite, chlorate or perchlorate of the transition metal complex. .

Examples of such oxyacid salts include ammonium nitrate, such as ammonium nitrate, sodium nitrate, potassium nitrate, magnesium nitrate and strontium nitrate.
Alkali metal salt or alkaline earth metal salt; ammonium nitrite such as ammonium nitrite, sodium nitrite, potassium nitrite, magnesium nitrite, strontium nitrite, etc., alkali metal salt or alkaline earth metal salt; ammonium chlorate, chlorine Ammonium salt, alkali metal salt or alkaline earth metal salt of chloric acid such as sodium citrate, potassium chlorate, magnesium chlorate, barium chlorate; ammonium perchlorate, sodium perchlorate, potassium perchlorate, perchloric acid Magnesium, ammonium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, ammonium perchlorate, etc., ammonium salt, alkali metal salt or alkaline earth metal salt of perchloric acid; Mg (N ₂ H ₄ ) ₂ (NO ₃ ) ₂ , Mg (N ₂ H ₄ ) ₂ (ClO ₄ ) ₂
Nitrate, perchlorate of alkaline earth metal complex such as Cu; Cu
(NO ₃ ) ₂ .3Cu (OH) ₂ , Co ₂ (OH) ₃ (NO ₃ ), Co _{2
(OH) 3 (NO 3)} , Mn (OH) 2 (NO 3) transition metal nitrates, such _{as; Co (NH 3) 3 (} NO 3) 3, Co (NH 3) 6 (NO 3) 3,
Cu (NH ₃ ) ₂ (NO ₃ ) ₂ , Co (NH ₃ ) ₃ (NO ₂ ) ₃ , Co
Examples thereof include nitrates, nitrites, perchlorates and the like of transition metal complexes such as (NH ₃ ) ₆ (ClO ₄ ) ₃ .

Examples of the metal oxide, metal double oxide and metal hydroxide include copper, cobalt, iron, manganese, nickel,
Oxides, double oxides or hydroxides of zinc, molybdenum and bismuth can be mentioned. Such metal oxides and metal double oxides include CuO, Cu ₂ O, Co ₂ O
_{3, CoO, Co 3 O 4} , Fe 2 O 3, FeO, Fe 3 O 4,
MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , NiO, ZnO, Mo
O ₃ , MoO ₃ .H ₂ O, CoMoO ₄ , Bi ₂ MoO _6, Bi ₂ O _{3, and the} like can be given.

As the metal hydroxide, Fe (OH) ₃ , C
o (OH) ₃ , Co (OH) ₂ , Ni (OH) ₂ , Cu (OH) ₂ ,
Zn (OH) ₂ , CoO (OH) ₂ , FeO (OH) ₂ , MnO
(OH) ₂ , MnO (OH) _{3 and the} like.

Examples of the metal peroxide include magnesium, calcium, and strontium peroxides. Such metal peroxides include MgO ₂ , C
aO ₂ , SrO _{2 and the} like can be mentioned.

The content of the oxidizing agent in the gas generating composition is preferably from 25 to 90% by weight, particularly preferably from 30 to 85% by weight.

The gas generating composition of the present invention may further contain a slag forming agent. Examples of the slag forming agent include acid clay, talc, bentonite, diatomaceous earth, kaolin, silica, alumina, glass fiber,
One or more selected from alumina fibers, ceramic fibers, sodium silicate, aluminum silicate, silicon nitride, silicon carbide, hydrotalcite, and mixtures thereof can be used.

The content of the slag forming agent in the gas generating composition is preferably from 1 to 15% by weight, particularly preferably from 3 to 12% by weight.

The gas generating composition of the present invention may further contain a binder. As the binder, sodium salt of carboxymethyl cellulose,
Organic binders such as starch, guar gum, polyvinyl alcohol, microcrystalline cellulose, polyacrylamide, polyacrylic acid, calcium stearate, molybdenum disulfide, acid clay, talc, bentonite, diatomaceous earth, kaolin, silica, alumina, sodium silicate, etc. Or more selected from inorganic binders and the like.

The content of the binder in the gas generating composition is preferably 0.5 to 20% by weight, particularly preferably 3 to 15% by weight.

The gas generating composition of the present invention can be produced by a dry method in which a fuel, an oxidizing agent and the like are mixed in powder form, or a wet method in which the fuel and the oxidizing agent are mixed in the presence of water, an organic solvent and the like.

Further, the gas generating composition of the present invention can be molded into a desired shape. For example, compression molding into a pellet using a tableting machine, compression molding into a disk using a disk molding machine, crushing of pellets or a disk, or granulation using a granulator, drawing machine (Extrusion molding machine) to be extruded to make a drawn medicine (non-porous, single-hole, porous).

These molding methods can be appropriately selected according to the properties to be imparted to the molded article of the gas generating composition. For example, when the extrusion molding method is applied, it is easier to mold a thin web than the compression molding method, so that a molded article can be obtained even with a composition having a slow burning rate. Furthermore, the extrusion molding method is suitable for mass production because molding can be performed in a relatively short time. Further, in the case of a composition having a high burning rate, the size of the molded product can be increased, so that the production efficiency can be further increased. In addition, when the extrusion molding method is applied, since a molded article having a complicated shape such as non-porous, single-pored, or porous can be manufactured, various combustion characteristics can be imparted.

The gas generating composition of the present invention is useful as a gas generating agent for an inflator system of an airbag system provided for protecting a human body mounted on an automobile, an aircraft, or the like. The inflator system includes a pyro type in which gas is supplied only from a solid gas generating agent and a hybrid type including both a compressed gas such as argon and a solid gas generating agent, but any type may be used.

Also, the inflator system of the present invention
The above-described gas generating composition can also be used as a transfer agent called an enhancer (or booster) for transmitting the energy of the primer or the squib to the gas generating agent. When used as an enhancer, those molded into an appropriate shape such as powder, granules, pellets, non-porous rolled, single-hole drawn, and porous drawn as described above can be used.

Further, the gas generating composition of the present invention can be used as a gas generating agent for a pretensioner system provided for protecting a human body mounted on an automobile, an aircraft or the like. The pretensioner is an emergency retraction device attached to a winding device that winds up a seatbelt, and the pretensioner system uses combustion gas of a gas generating composition as power for the pretensioner.

The gas generating composition of the present invention can be used in any device that requires gas generating ability, and is used not only for the inflator system and pretensioner system of the air bag system described above but also for propellants. be able to.

[0034]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples.

Examples 1 to 16 Gas generating compositions having the compositions shown in Table 1 were produced. The theoretical gas generation amounts of these gas generating agents were determined. In Table 1, L represents hydroxylamine as a ligand, and LH represents deprotonated hydroxylamine as an anion.

[0036]

[Table 1]

Example 17 10 g of the gas generating composition shown in Example 5 was burned under normal pressure and observed. The combustion test was conducted on a gas generating composition of 10 g.
Was put in a mortar, and the nichrome wire was energized to ignite. Table 2 shows the results.

[0038]

[Table 2]

The gas generant composition completely burned, and formed a combustion residue having high slag property and easy to filter.

[0040]

Since the transition metal complex or the alkaline earth metal complex containing hydroxylamine as a ligand used in the present invention contains no or little carbon, the gas generant composition containing this complex cannot be used for combustion. After gas can be very clean. Also, the amount of generated gas is large. Therefore, by using the gas generating composition of the present invention, the safety of the gas generator can be improved, and the size and cost of the gas generator can be reduced.

Claims (13)

[Claims] 1. A compound selected from a transition metal complex containing a hydroxylamine as a ligand and an alkaline earth metal complex.
A gas generating composition comprising at least one species. 2. The transition metal is at least one selected from zinc, copper, nickel, cobalt, iron, manganese, chromium, vanadium, titanium, palladium, platinum, zirconium, molybdenum, bismuth and tungsten.
The gas generating composition according to any one of the preceding claims. 3. The gas generating composition according to claim 1, wherein the alkaline earth metal is at least one selected from magnesium, calcium and strontium. 4. The method according to claim 1, wherein the anion of the metal complex is NO ₃ ⁻ , N
O ₂ ⁻ , NO ⁻ , ClO ₄ ⁻ , ClO ₃ ⁻ , Cl ⁻ , Br ⁻ , S
CN ⁻ , SO ₄ ²⁻ , OH ⁻ , CO ₃ ²⁻ , PO ₄ ³⁻ , C
^{_{2 O 4 2-, BO 4 5-}} , MnO 4 -, MoO 4 2- and the gas generating composition of any one of claims 1 to 3 is at least one selected from the deprotonated hydroxylamine . 5. A fuel comprising one or more nitrogen-containing compounds selected from tetrazole derivatives, bitetrazole derivatives, triazole derivatives, guanidine derivatives, triazine derivatives, oxamides, ammonium oxalate, azodicarbonamide, and hydrazodicarbonamide. The gas generating composition according to any one of claims 1 to 4, further comprising: 6. The method according to claim 1, further comprising, as an oxidizing agent, at least one selected from oxyacid salts, metal oxides, metal double oxides, metal hydroxides and metal peroxides. Item 8. The gas generating composition according to Item 1. 7. The oxyacid salt is ammonium, an alkali metal, an alkaline earth metal, an alkaline earth metal complex, a transition metal and a nitrate, nitrite, chlorate or perchlorate of a transition metal complex. 7. The gas generating composition according to 6. 8. The method according to claim 1, wherein the metal oxide, the metal double oxide, and the metal hydroxide are copper, cobalt, iron, manganese, nickel, zinc,
7. The gas generating composition according to claim 6, which is an oxide, a double oxide or a hydroxide of molybdenum and bismuth. 9. The method according to claim 1, further comprising a binder.
9. The gas generant composition according to any one of items 8 to 8. 10. The gas generating composition according to claim 1, further comprising a slag forming agent. 11. An inflator system for an airbag, wherein the gas generating composition according to any one of claims 1 to 10 is used. 12. An inflator system for an airbag, wherein the gas generating composition according to any one of claims 1 to 10 is used as an enhancer. 13. A pretensioner system using the gas generating composition according to claim 1. Description: