WO1996023748A1 - Air bag gas generating agent - Google Patents

Abstract

An air bag gas generating agent which can markedly reduce the concentration of toxic components, particularly both CO and NOx, in the aftergas, while maintaining various favorable properties of non-azide gas generating agents. The agent is of non-azide type and contains a nitrogen-containing organic compound and an oxidizing agent as the active ingredients and at least one metal oxide selected among molybdenum oxide, tungsten oxide, and metal oxides having a BET specific surface area of not less than 5 m2/g as the combustion catalyst.

Description

 Specification

 TECHNICAL FIELD The present invention relates to a gas generating agent for airbags and an inflator for airbags.

 The gas generating agent for an air bag according to the present invention has a remarkably low concentration of toxic components such as 0 in a gas (hereinafter, referred to as “post-gas”) generated by the combustion, and the conventional air-generating agent. It has favorable characteristics that its safety is remarkably higher than that of a zide-based gas generant.

 Further, the use of the airbag inflator of the present invention can further reduce the C0 concentration in the post-gas.

 Background art

 The demand for airbag systems is growing exponentially as the demands on vehicle safety increase. When a car crashes at high speed, the airbag system inflates the nipple bag (air bag) installed inside the handlebar or dash board, etc., thereby increasing the occupant power. The purpose of the bag is to prevent accidental collisions with various parts of the vehicle and cause injury or death.When the bag expands, the gas generated by the gas generating agent loaded into the system burns or decomposes. Is used.

Gas generating agents for webbags mainly meet four requirements Things are desirable. The first requirement is that it have a moderate burning rate. If the combustion speed is too slow, the bag does not expand instantaneously and cannot protect the occupants. The second requirement is that impact ignitability (ignition sensitivity to impact) be low. If the impact ignitability is high, explosions and explosions are likely to occur during the manufacturing process such as mixing and molding, and there is a large risk of handling. The third requirement is that the gas temperature be low. The bag releases the gas after inflation to cause the occupant to escape from the vehicle, and contracts. However, if the gas temperature is high, the occupant may be burned. In addition, holes may be formed in the bag, resulting in reduced functionality, or the bag may burn and cause a fire. When the fourth requirement is "toxic component concentration is low this such as CO and NO x in the gas" Der Ru _t toxic component concentration is high, occupant Ru likely there ing to gas poisoning during outgassing. In addition, in the gas generated by the combustion of organic compounds, the concentrations of C 0 and N 0 X are generally opposite.

It is said that it is very difficult to reduce both concentrations at the same time, as one concentration goes down and the other goes up.

Azide-based gas generators that use sodium azide as a gas-generating base are now widely used, exhibit an appropriate combustion rate and gas temperature, and most of the gas is harmless. Although it is a nitrogen gas, it has the disadvantage of high impact ignition performance. Gas generating group Sodium azide, which is an oxidizing agent, decomposes to cause a fire or emits toxic fumes, and further reacts with an oxidizing agent to form sodium oxyhydroxide and sodium hydroxide. To produce toxic components such as um, strict attention must always be paid to handling and equipment for ensuring safety is essential. Also, sodium azide degrades combustion performance due to moisture absorption, so it is necessary to take measures to prevent moisture absorption. In addition, since sodium azide is toxic, sodium azide may leak from vehicles equipped with airbags that have fallen into rivers or the sea, causing serious environmental pollution.

On the other hand, Japanese Patent Application Laid-Open Nos. Hei 6-32689, Hei 6-32690 and Hei 6-27884 disclose nitrogen-containing materials proposed by the present inventors. A non-azide gas generating agent containing an organic compound and an oxidizing agent as active ingredients is disclosed. The gas generating agent exhibits a moderate amount of gas generated, a burning rate and a gas temperature comparable to those of the conventional azide gas generating agent, has relatively low impact ignition properties, and has a significant explosion risk and toxicity. It has the advantage of being low in azide-based gas generants and is inexpensive. In addition, the non-azide gas generating agent has a sufficiently low concentration of toxic components such as CO and NOx in the gas generated by combustion, which can be practically used, but further reduces the concentration. Is desired. According to Japanese Patent Application Laid-Open No. 5-238687, metal oxides having a specific surface area of 5 m ² Z g or more (particularly, atomic numbers 21 (S c) to 30 (Z n) It has been proposed to use (oxide of) as a gas generating agent. However, the invention described in this publication relates to a gas generating agent using azide sodium as a gas generating base, and the metal oxide mainly improves the combustion rate and the ignitability. It is only added for the purpose of. In addition this publication, metallic oxides effects are specifically disclosed is only F e ₂ 0 _3.

 Disclosure of the invention

 The present inventor has made intensive studies to solve the above-mentioned conventional problems. As a result, when a specific metal oxide and / or a metal oxide having specific physical properties are added as a combustion catalyst to the non-azide gas generating agent, the non-azide gas generating agent is preferred. It has been found that the concentration of toxic components, especially both CO and NO x, in post-gas can be significantly reduced while maintaining the various properties. Also, by placing an oxidizing agent in at least one part of the gas ejection path in the airbag inflator, the concentration of toxic components can be reduced and the layer can be reduced. I found this. The present invention has been completed based on these findings.

According to the present invention, a nitrogen-containing organic compound and an oxidizing agent are effectively used. A non-azide gas generating agent used as a component, selected from molybdenum oxide, tungsten oxide, and metal oxides with a BET specific surface area of 5 m ² / g or more as a combustion catalyst The present invention provides a gas generating agent for a wafer characterized by containing at least one kind of metal oxide.

 Further, according to the present invention, it is an inflator for an air bag, wherein a combustion chamber is filled with a gas generating agent for an air bag, and is generated by combustion of the gas generating agent. An airbag inflator is provided, characterized in that an external oxidant is placed on at least one part of the path for blowing gas into the airbag.

 The gas generating agent for an airbag of the present invention contains a nitrogen-containing organic compound as a gas generating base, an oxidizing agent and a specific combustion catalyst as effective components.

 As the nitrogen-containing organic compound, an organic compound containing at least one nitrogen atom in the molecule is used. Specifically, for example, an amino group-containing organic compound, a nitramine group-containing organic compound, a nitrosoamine group-containing organic compound, and the like can be given.

Specific examples of the amino group-containing organic compound include, for example, azodicanolone amide, azodicarboxylic acid and a salt thereof (alkali metal, alkaline earth metal, etc.), urea, and hexamethyl Rentetramin, bicarbonate aminoguanidine, triamine aminoguanidine, biuret, cyanoguanidine, nitrogannidine, dicyanginia Mids, hydrazides and the like can be mentioned. Here, known hydrazides can be used, for example, acetate hydrazide, 1,2-diacetinole hydrazide, and lauric hydrazide. Azide, salicylic acid hydrazide, oxalic acid hydrazide, oxalic acid dihydrazide, carbohydrazide, adipic acid hydrazide, sepa 'Silonic acid hydrazide, dodecangio hydrazide, isophthalic acid hydrazide, methyl phenol hydrate, semican phenol, holm hydrazide, 1, 2 — dihonole mizore hydrazine and the like.

 Specific examples of the nitramine group-containing organic compound include, for example, ', dinitropentenemethyltriamine, trimethylenetrinitroamine ( Aliphatic compounds and alicyclic compounds having one or more nitramine groups as substituents such as RDX), tetramethylentetranitramine (HMX) and the like. Can be listed.

 Further, specific examples of the organic compound containing a ditorosamine group include, for example, dinitrosopentamethylentramine

Aliphatic compounds and alicyclic compounds having one or more nitrosamine groups as substituents such as (DPT) It can be.

 Among these, an amino group-containing organic compound is preferred. Azodicarbonamide is particularly preferred. One of such nitrogen-containing organic compounds may be used alone, or two or more thereof may be used in combination. A commercially available nitrogen-containing organic compound may be used as it is. The particle size of the nitrogen-containing organic compound is not particularly limited, and may be appropriately selected from a wide range according to various conditions such as, for example, the compounding amount, the compounding ratio with other components, and the capacity of the airbag.

 The oxidizing agent is not particularly limited, and may be appropriately selected from those conventionally used in this field, but those which can generate and Z or supply oxygen at a high temperature are preferable. Oxohalogenates, nitrates, nitrites, metal peroxides. Superoxides, ozone compounds and the like.

Known oxohalogenates can be used, and examples thereof include perhalates and halogenates. Specific examples of perhalogenates include, for example, lithium perchlorate, potassium perchlorate, sodium perchlorate, lithium perbromate, and potassium perbromate. Alkali metal salts such as sodium, sodium perbromate, magnesium perchlorate, barium perchlorate, calcium perchlorate, magnesium perbromate, barium perbromate , Such as calcium perbromate Examples thereof include alkaline earth metal salts, ammonium salts such as ammonium perchlorate and ammonium perbromate. Specific examples of halogenates include, for example, lithium chlorate, potassium chlorate, sodium chlorate, lithium bromate, and potassium bromate. Alkali metal salts such as sodium bromide, sodium bromate, magnesium chlorate, barium chlorate, calcium chlorate, magnesium bromate, barium bromate arm, alkaline earth metal salts such as bromate calcivirus © beam, chlorine San'a Nmoniu厶, among bromine Sana Nmoni © beam etc. _c these § Nmoniu beam salts and the like of, c b gate Alkali metal salts of acid and perhalogenic acid are preferred.

 Examples of the nitrate include alkali metal salts such as lithium nitrate, sodium nitrate, and potassium nitrate, magnesium nitrate, potassium nitrate, and sodium nitrate. Examples thereof include alkaline earth metal salts such as lonium, ammonium salts such as ammonium nitrate, and the like. Among them, alkali metal salts are preferred.

 Examples of the nitrite include alkali metal salts such as lithium nitrite, sodium nitrite, and potassium nitrite, magnesium nitrite, and barium nitrite. And alkaline earth metal salts such as calcium nitrite and the like.

Examples of the metal peroxide include lithium peroxide and peroxide. Alkali metal salts such as sodium oxide and potassium peroxide, alkaline earth metal salts such as magnesium peroxide, calcium peroxide and barium peroxide And so on.

 Examples of the superoxide include alkali metal compounds such as sodium superoxide and superoxide, calcium superoxide, strontium superoxide, and barium superoxide. Alkaline earth metal compounds such as calcium, rubidium superoxide, cesium superoxide and the like can be mentioned.

Is the o zone down compounds, for example (the formula Μ N a, K, R b , the periodic table I a group element such as C s shown to.) In formula Micromax 0 ₃ you express in Compounds.

 In the present invention, metal sulfides such as molybdenum disulfide, bismuth-containing compounds, lead-containing compounds and the like can also be used as the oxidizing agent.

 Among these oxidizing agents, oxohalogenates, nitrates, nitrites and the like are preferable, and oxohalogenates, nitrates and the like are particularly preferable.

 Such oxidizing agents can be used alone or in combination of two or more. The shape and particle size of the oxidizing agent are not particularly limited, and may be appropriately selected and used according to various conditions such as, for example, the amount of the oxidizing agent, the mixing ratio with each component, and the capacity of the airbag.

The amount of the oxidizing agent is usually nitrogen-containing based on the amount of oxygen. The stoichiometric amount may be sufficient to completely oxidize and burn the organic compound, but by appropriately changing the mixing ratio of the nitrogen-containing organic compound and the oxidizing agent, the burning rate, the burning temperature (gas temperature), Since the composition of the combustion gas can be arbitrarily adjusted, it can be selected from a wide range as appropriate.

The oxidizing agent may be added in an amount of about 100 to 400 parts by weight, preferably about 100 to 240 parts by weight, based on 100 parts by weight.

In the gas generating agent of the present invention, in addition to the above two components, a small amount selected from a molybdenum oxide, a tungsten oxide, and a metal oxide having a BET specific surface area of 5 m ² / g or more. Both contain one kind of metal oxide as an essential component. By adding these metal oxides, the concentration of toxic components such as CO and NOx in the after-gas is significantly reduced. The reason why such an excellent effect is achieved is not yet fully understood.'According to research conducted by the present inventors, for example, azodicarbonamide was used as a gas generating base. In non-azide gas generators using oxohalogenate as the oxidizing agent, the thermal decomposition temperature of azodicanolevonamide and the thermal decomposition temperature of oxohalogenate are reduced. When the above metal oxides are added to this combustion reaction system, the thermal decomposition temperature of oxohalogenates decreases and the azodicarbonamide It is presumed that this is due to the fact that the temperature approaches the thermal decomposition temperature, and a smooth reaction close to the stoichiometric amount by both occurs. Known molybdenum oxides can be used, for example, molybdenum oxide (VI) and other molybdenum oxides (VI) produced by heating. Oxygen molybdenum compounds, molybdenic acid, metal salts of molybdic acid and the like can be mentioned. Is a said oxygen-Motomo Li Bude down compounds, for example, hydroxide mode re Buden and M 0 2 0 5, MO 3 0 8, M 0 8 0 2 3,

M o ₉ 0 and can be that or this include a _{2 s} mode Li Bude down oxide such as such, is a metal salt of the model Li Bude phosphate, for example Mo Li Bude phosphate cobalt, model Li Bude Group VIII metal salts such as nickel acid. Of these, molybdenum oxide (VI) and metal salts of molybdenic acid are preferred, and molybdenum oxide (VI) is particularly preferred.

Also, known tungsten oxides can be used, for example, oxidized tungsten (VI) and other materials that generate oxidized tungsten (VI) by heating. Examples thereof include an oxygen tungstate compound, tungstic acid, and a metal salt of tungstic acid. And said oxygen-Motota down Gusute emission compounds, for _{example, W 0 2, W 0 3} , W 0 3 · H 2 0 , etc. data down the Gusute phosphorylation, etc. Ru can and this exemplified. In addition, examples of the metal salt of evening gustanoic acid include, for example, potassium sungstenate, potassium tungstate, sodium sodium tungstate, and the like. Tungstenic acid magnesium, tangs Examples thereof include cobalt tartrate, nickel tungstate, iron tungstate and the like. Among these, tangsten oxide (VI) and metal salts of tangstenic acid are preferred, and tangsten oxide (VI) and iron tangstenate are particularly preferred. I like it.

As a metal oxide having a BET specific surface area of 5 m ² Zg or more, the specific surface area conforms to the above-mentioned specification, and the above-mentioned molybdenum oxide and tungsten oxide There is no particular limitation as long as it is a metal oxide other than, for example, copper oxide, nickel oxide, cobalt oxide, iron oxide, chromium oxide, magnesium oxide, aluminum oxide, Oxides of elements of the 3rd to 4th period of the periodic table, such as zinc oxide and manganese oxide, can be mentioned, among which copper oxide, nickel oxide, cobalt oxide, etc. The Group VI 11 and Group Ib elements are preferred, and copper oxide is particularly preferred. One metal oxide having a BET specific surface area of 5 m ² Zg or more can be used alone or in combination of two or more. In addition, BET specific surface area of Ru der usually S n ^ Z g or more force, 1 0 m ² / g or more of what is rather preferred, 4 0 m ² / g or more also of the preferred Ri good of arbitrariness.

A metal oxide having a large specific surface area can be produced according to a known method. Taking copper oxide as an example, basic copper nitrate fine particles of basic copper nitrate are obtained by adding warm water of 60 ° C or more to basic copper nitrate. Pulverized and then calcined at about 300 to 500 ° C (Japanese Patent Application Laid-Open No. Hei 11-313), by neutralizing an aqueous solution of copper nitrate by adding an alkaline agent. The copper nitrate particles formed by the above method are filtered, dried, and baked at a temperature of about 200 to 50,000 (Japanese Patent Application Laid-Open No. 2-144542). We can list methods for using it as a raw material. It can also be obtained by subjecting a metal hydroxide or carbonate to a low-temperature plasma treatment (Japanese Patent Application Laid-Open No. 2-26810).

 Of these three types of combustion catalysts, molybdenum oxide and tungsten oxide substantially convert nitrogen-containing organic compounds even if they coexist for a long time with nitrogen-containing organic compounds such as azodicarbonamide. It has a favorable property of not decomposing. In addition, in the gas generated by the combustion of nitrogen-containing organic compounds, the CO concentration and the NOx concentration are generally opposite, and if one of the concentrations decreases, the other increases. It is very difficult to reduce the CO2 simultaneously.Especially, molybdenum oxide and tungsten oxide both significantly reduce the concentration of CO and NOx in the post-gas. It also has the favorable property that it can be reduced.

The particle size of molybdenum oxide, tungsten oxide, and metal oxides having a BET specific surface area of 5 mVg or more is not particularly limited. For example, the compounding amount, the mixing ratio with other components, air It may be appropriately selected from a wide range according to various conditions such as the structure, shape and capacity of the bag. The amount of these metal oxides is not particularly limited, and can be appropriately selected from a wide range in accordance with the various conditions described above, and is usually based on 100 parts by weight of the nitrogen-containing organic compound. The amount may be about 0.1 to 50 parts by weight. From the viewpoint of stabilizing the amount of generated gas and the combustion performance, the preferred amount is about 0.5 to 30 parts by weight with respect to 100 parts by weight of the nitrogen-containing organic compound. In addition, an oxygen-containing molybdenum compound that generates molybdenum oxide (VI) by heating and an oxygen-containing tungsten compound that generates oxide tungsten (VI) by heating When used, the amounts of oxidized molybdenum (VI) and oxidized tungsten (VI) may be adjusted so as to fall within the ranges specified above.

 The gas generating agent for an airbag of the present invention contains a combustion regulator, a detonation inhibitor, a combustion rate regulating catalyst, and the like in addition to the above three essential components as long as its performance is not impaired. Is also good.

Combustion regulators are generally used to lower the combustion temperature and, consequently, the gas temperature. Specific examples thereof include hydroxides such as AI and alkalis such as Na and K. metal carbonates, bicarbonates or _{oxides, C a, M g, B} a. ani the S r like Al force Li earth metal carbonates or bicarbonates etc. I can do it. Among them, hydroxides and carbonates are preferred, and hydroxides are particularly preferred. The compounding amount of the combustion regulator is not particularly limited and can be appropriately selected from a wide range, and usually does not exceed 50 parts by weight with respect to 100 parts by weight of the total amount of the nitrogen-containing organic compound and the oxidizing agent. It is preferred that the amount be not more than 20 parts by weight.

 Explosive forest inhibitors are used in manufacturing, transportation, and storage processes to prevent gas generating agents from being entrained in flames or subjected to strong impacts to cause explosive forests. Addition of detonation inhibitors can further enhance the safety in manufacturing, transportation, storage and other processes. Known explosives can be used, for example, metal oxides such as bentonite, alumina, diatomaceous earth, silicon dioxide, Na, K, Ca, Mg.Z. Metal carbonates, bicarbonates, etc. of metals such as n, Cu and AI can be mentioned. Note that carbonates and bicarbonates of alkali metals and alkaline earth metals also have a function as a combustion regulator as described above. The amount of the explosive forest inhibitor is not particularly limited and can be appropriately selected from a wide range.Generally, if the total amount of the nitrogen-containing organic compound and the oxidizing agent is about 100 to 100 parts by weight, it is about 5 to 30 parts by weight. Good.

Combustion rate regulating catalysts are mainly used to regulate the burning rate. Examples of the combustion rate control catalyst include (ii) lb Period of element such as zinc carbonate, iron chloride, lead oxide, titanium oxide, vanadium oxide, cerium oxide, holmium oxide, cadmium oxide, ytterbium oxide, etc. Oxides, chlorides, carbonates and sulfates of the 4th to 6th periodic elements in the table (however, molybdenum oxides, tungsten oxides, alkali metal carbonates and alkaline earths) (Excluding metal carbonates), (mouth) Cellulose-based materials such as carboxymethinoresorerose, hydroxymethinoresorerose, their ethers, and microcrystalline cellulose powder Compounds, and (c) organic polymers such as soluble starch, polyvinyl alcohol, and their partially genated compounds can be mentioned. The particle size of the combustion rate controlling catalyst is not particularly limited, and may be appropriately selected and used. The combustion rate controlling catalyst is used alone or in combination of two or more. The amount of the catalyst for controlling the burning rate is not particularly limited and can be appropriately selected from a wide range. Force, ', usually 0.1 to 5 with respect to 100 parts by weight of the total amount of the nitrogen-containing organic compound and the oxidizing agent. The amount may be about 0 parts by weight, preferably about 0.2 to 10 parts by weight.

 Furthermore, in the present invention, various additives conventionally used for this purpose may be blended within a range that does not impair the preferable characteristics of the gas generating agent for an air back.

Among the components of the gas generating agent for airbags of the present invention described above, decomposition of nitrogen-containing organic compounds such as azodicarbonamide is included. There are compounds that induce Specifically, for example, compounds that contain or decompose an alkaline component such as calcium peroxide, which is a kind of oxidizing agent, to release an alkaline component, and a combustion catalyst. Copper oxide, chromium oxide, manganese oxide, etc. Therefore, when these decomposition-inducing compounds are used as components of a gas generating agent for airbags, it is preferable to apply a surface treatment to the gas-generating base and / or the decomposition-inducing compound. For the surface treatment, a coupling agent, a chelating agent or the like can be preferably used.

 Known coupling agents can be used, for example, silane-based coupling agents, titanium-based coupling agents, and aluminum-based coupling agents. Can be mentioned.

Specific examples of silane coupling agents include, for example, aminaminopropyltriethoxysilane, N—3— (aminopenetinole) K-β- (Amino ethynole) K-β- (Amino ethynole) Mino-propinolone-method registrar Ν, Ν-フ ノ フ フ フ ユ ユ ユ ユAmino-silan-based coupling agents such as rietoxy-silan, agar-doxi-xipro-built-lime xylan, β — (3, 4 — Epoxy cyclohexyl) ethyl trimethyoxylan, alpha Epoxy silane coupling agents such as glycidoxy propyl methyl tyl jet xylan, vinylinoletrichlorosilane, vinylinoletrime Vinyl lan-based coupling agents such as xylan, vinyl triethoxy silane, vinyl tris (^ one-meth quin ethoxy) silane, etc. Melcaptosilan-based coupling agents such as alpha-molecapto-probe remeasurement silane Acrylinolecin-based coupling agents, such as rimethoxysilane, methinolate trimet Kishiran, Methinoret Trieti Kishiran, Acro-open Propinolate Trimet Kisishiran, Trifnorrelo Metyl Trimet Kisila Expression

RS i (OR ') 3 (wherein R is a straight-chain or branched-chain alkyl having about 1 to 4 carbon atoms which may be substituted by one or more halogen atoms. And R 'represents a linear or branched alkyl group having about 1 to 4 carbon atoms.) A silane coupling agent represented by the formula: Can be done.

Specific examples of the titanate-based coupling agents include, for example, isopropilitol tristearoinolecitrate, isopropilitol Lithodisilisobenzene Sulfonyl titanate, isoploprobiolrisn-decylbenzensul -1 honyl titanate, isopro built-in tris (phosphate host) Titanite, tetraiso propyl vis (geoctinole phosphate) It) Titanate. Tetra-aged octyl bis (ditridecyl phosphite) titanate, tetra (2,2—dialoleoxymethyltinole) Bis (di-tridecyl phosphate) bis-net, bis (polyoctane pyrophosphate) sodium phosphate, bis-ne (bis) (Cucinole pyrophosphate) Echilen titanate, Isopropyl trioctanoinone titanate

10 ル イ イ, ソ ピ ピ ピ ジ ソ イ ソ イ イ イ イ イ ス テ ス テ イ イ イ イ イ イ イ 、 、 Isopropyl nitric acid nitrate titanate. Isopropyl nitrate (（-aminoethylaminoethyl) titanate, diisopropyl Examples include cuminorefrinolequine acetate titanate, diisostearoylinoleethylene titanate, and the like.

 Specific examples of aluminum-based coupling agents include, for example, aluminum monoacetyl acetate net bis.

20 (ethyl acetate), aluminum tris

(Acetyl acetate), acetoalkoxy aluminum diisoprolate, and the like. One of these coupling agents can be used alone, or two or more can be used in combination.

 In performing the surface treatment using the coupling agent, a known method such as a wet method or a dry method can be employed.

Processing by the wet method generally involves mixing the component to be treated with a solution or dispersion of a coupling agent, separating the treated component from the mixture, and drying the mixture. More done. The coupling agent may be an organic solvent such as water, aqueous acetic acid, methanol, ethanol, cellosonoreb, anolequinoleamine, or alkylamine, or a mixture thereof. It is soluble or dispersible in solvents. At this time, the concentration of the coupling agent is not particularly limited, and can be appropriately selected from a wide range, for example, about 0.1 to 5% by weight, preferably about 0.5 to 5% by weight. It may be about 2% by weight. Known methods such as filtration, centrifugation, and decantation can be used to separate the treated components. When the components treated by drying are agglomerated, pulverization may be performed according to a known method. Further, the solution or dispersion of the component to be treated and the solution or dispersion of the coupling agent may be mixed, and the treated component may be separated from the mixture and dried. No. As the solvent for dissolving or dispersing the component to be treated, the same solvents as described above can be used. The wet method can be performed with heating or heating, if necessary. Temperature at that time The standard of the degree is about 30 to 100.

In the dry method, a coupling agent or a solution or a dispersion thereof is added to a powder of a component to be treated, with stirring and / or Z or preheating, if necessary, and then mixed (preferably, Mixing under heating). For agitation and mixing, use a conventional blender, preferably a henenomixer or souvenir. A mixer with strong shear, such as a mixer, is used. Solutions and dispersions of mosquito-up Li in g agent Note _c the same wet method even for the you can use, preheating and heating, the decomposition or deterioration of the component to be treated is caused this should not be a temperature or in It may be performed in a temperature range.

 Further, when the respective components of the gas generating composition are mixed, a surface treatment can be performed by simultaneously adding a silane coupling agent or a solution or a dispersion thereof.

 In any of the above methods, the amount of the coupling agent used can be appropriately selected from a wide range according to the type of the coupling agent, the temporal stability of the component to be treated, and the like. The amount is preferably about 0.01 to 10 parts by weight, and more preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the component to be treated. When a solution or dispersion of a coupling agent is used, the amount of the solution or dispersion may be adjusted so as to achieve the above-mentioned mixing ratio.

-As a chelating agent, soluble in water and / or organic solvent Metals that do not exhibit an alkaline property when dissolved or dispersed and that induce the decomposition of the gas generating base (for example, Cu, Co, Cr, C a)) or any known compounds that can form a chelate with an ion thereof can be used without particular limitation. Examples thereof include chelating reagents, colorimetric reagents, and metal indicators. Can be mentioned.

Specific examples of chelating reagents include, for example, ethylenediaminetetraacetic acid (EDTA) and its metal salts (EDTA.2Na salt, EDTA.2K salt, EDTA.2Li) Salt, EDTA.2 ammonium salt, etc., trans — 1, 2 — diaminocyclohexane — N, N, Ν ', Ν' — 4 acetic acid 'monohydrate ( C y DTA), —, N — bis (2 — hydroxy shechyl) glycine (DHGE), 1, 3 — diamin 2 — hydroxypropane N, N, N ' , N '— 4 acetic acid (DPTA-OH), diethylamine, N, N, N', N '', Ν, '-5 acetic acid (DTPA), ethylamine N, N'-diacetic acid (EDDA), ethylenediamine-N, N'-dipropionic acid.dihydrochloride (EDDP) .ethylenediamine-N, N'-bis ( Methylene phosphonic acid) · 1/2 dihydrate (EDDPO), N— ( 2 — Hydroxyshetyl) Ethylenediamine N, N, N'-13 Acetic acid (EDTA-OH), Ethylenediamine N, Κ, ¹ ,, N'-Tetrakis (methylenphosphonate) (EDTPO), 0, 0 '— Bis (2—amino ethynole) Ethylene glycol N, N, Ν'一, Ν'-Acetate, Ν, Ν-bis (2-hydroxybenzylamine) ethylenediamine Ν, Ν-2 acetic acid (HBED), 1, 6-hexamethyl Les emission di § Mi down one N, N, N ', N 1 - 4 acid (HDTA;), N - ( 2 - arsenate mud key Shechinore) I Mi Bruno 2 acetate (HIDA), I Mi Bruno 2 acetic acid (IDA), 1, 2 — diamino brono. N, N, N ', N' monoacetic acid (methinole EDTA), tri-triacetic acid (NTA), tri-tripropionic acid (NTP :), tri-triethyl Lithium (methylenphosphonate) · 3Na salt (NTPO), triethylenetetramine, Ν, Ν ', Ν''', Ν '''', Ν ',' — 6 Acetic acid (Τ Τ Η Α).

 Specific examples of the colorimetric reagent and the metal indicator include, for example,

3 — [Ν, Ν—bis (canolepox methyl) amino chinole] — 1, 2 — dihydroxyanthraquinone, 3, 3 '— dimethoxy Benzidine 100, Ν, Ν ', Ν' acetic acid 4Na salt, dimethinoresitiocarnoxamic acid Na salt (DDTC), 2,7_bis (2 — Phanole sonophenylazo) 1 1, 8 — dihydroxy 3, 6 — naphthalene 'disnolephonate, 2, 9 — dimethyltin 1, 4, 7 — di Fenino 1, 1 0 — Linoles of phenantone 2, 9 — Dimethylone 4, 7 — Diphenylene 1, 1, 10 — Linoles of phenolic acid 2 Na salt, 4, 7 — diphenone 1, 10 — fenant mouthline, 5 — menolecapte 3 — feninole 1, 3, 4, 4 — AZIA ZONO 1-2-thione salt, Ν-benzo 1-phenyl hydrazine (BPA), N-benzo 1 N — (2 — Methyl phenol) Hydroxyamine

(BTA), N—Cynnamo Inlet N—Feninole Hydroxylamin (CPA), 5 ', 5''— Jibromipirogalore Phthalane (BPR), 2 — Hydroquinone 1 — (1-Hydroxy 2 — Naphthinazo) _ 6 — Nitro 4 1 Naphthale N-Sulfonate 'Na salt (BT), 3, 3'-bis [N, N-bis (carboxymethyl) aminomethinole] phenolic resin (canolecin) (C a 1 cein)), 8— [N, N—bis (canolepoxmethyl) aminomethyl] 1-4-methylenolan-beryferon (canoleisei) (Ca) cein Blue)), 2, 8—Dihydroxy 1— (8—Hydroxy 3, 6—Dishonorejo 1-naphthyla Ezo) I 3, 6 — Naftare Disulfuric acid '4Na salt, 2-hydroquinone (2-hydroquinone-5-methylphenylazo) -141 naphthaleneノ 2 レ レ 2 2 レ-ノ レ レ レ ノ 1,8-Dihydroxy 3,6 -Naphthalenesnolefonic acid, 2,5 -Dichloro 3,6 -Dihydro Ρ-benzoquinone, 2, 7-screw (4-chloro-1 2 _ phoshonofenilazo) 1, 8-dihydroxy 3, 6-naphthalenes-norephonic acid, 2, 6-dichloro- 1 4 '-hydroxy 1-3', 3 ', 1-dimethino-le 3-snore-hofone 5 ', 5', dicanolevonic acid '3Na salt, 4,4'-diantipyrenolemethan monohydrate, 1-hide mouth —Hydroxy phenylenobenzo) benzene, 2,7—bis (4-methylinole2—sulfophenylazo) —1,8—Dihydroxy3, 6 — Naphthalenes norephonic acid, 2, 2 — Biviridine, 1, 2 — Bis (2 — Fluorinole) ethanedioxiosim · monohydrate, 2, 2 — Benzoxazolin, 3, 3 ' — Screw [N — (Kanoreboximemin) Aminomethyl] Timonolesulfonephthalein (GTB), 2 — Hydroxy 1 1 — (2 — Hydrokin 1 4 — Snorrefo 1-naphthylazo) 1 3, 6-naphthalene snolefonic acid • 3 Na salt, 5-chloro 2-hydroxy 3-(2, 4 -Hydroxysifeninoreazo) Benzenesnorephonic acid, 3,3'-bis [N, N-bis (canolepoximetyl) aminomethyl] Timoles Lein Νa salt, pnolepuric acid 'ammonium salt, 3, 3'-[N, N — bis (Canole box) Aminomethyl] 1p — xylenopresole phone phthalein, 2, 9 — dimethizole 1, 10 — phe Nanslorin, 2 _ (2 — anoresonofuenoinoreazo) — 1, 8 — dihydroxy-1, 3, 6 — naphthalenes olenoic acid '2 Na salt, 2—nitrotropinolenolesanoic acid, 5—nitro-1,1,0—phenanthroline, 2—ditorosone 5— [N—n — Pro-Pinole N — (3—Snore Hop-Prop) Amino] phenol, 2—Nitroso 5— [N—Echino—N— (3—Snore (Pinole) amino] phenol, 2-Hydroxy 1-1 (2-Hydrox 1-4-Snore 1-Naphthyrazo) 1-3 — Naphthoic acid, 2 (5—Bromo 1—Pyridine) 1—5— [N—n—Propir-1 N— (3—Sulphopropir) amino] anilinin Ka salt , 1, 3 — diamine 4 — (5 — bromine 2 — pyri-norazo) benzene, 1, 8 — dihydroxy 2 — (2 — pyrrole 1,3,6—Naphthalene disulfonate · 2Na salt, 2- (5—Bromo-1—Pyridinoreazo) -1 5— [N-n 1-Propyl-1N — (3—Snorre-hop-Pinole) amino] phenonole'2Na salt dihydrate, 2 — (5—Cro- mouth 1-2—Pyridine Sole azo) 1 5—Jetinorea mino phenol, 2—

(3, 5 — dibromo 1 2 — pyri-norazo) 1 5 — dicilumina-no-no-nore, 2-(5 — 2-tro 2-pyridyl Azo) 1 5 — [N — n — propylinole N — (3 — sulfopropinole) amino] phenolic '2Na salt dihydrate, 2-(3, 5 — Jib mouth 2 — pyridylazo) 1 5 — dimethylaminobenzoic acid, 5 — dimethylamino 2 — (2 — thiazolinoureazo) benzoic acid, 4 — (3 , 5 — Jib mouth mode 2 — pyridinoreazo) 1 N — ethinore 1 N — (3 — sulfoplopyr) aniline monohydrate, 4 methyl — 5 — ( 1 2 — (2 — thiazole i noreazo) Benzoic acid, 1 (2 — pyridylazo) 1-2-naphthol, 4 1-(2 — pyridylua) Zo) Resorcinol, 3, 3'-bis [N, N-bis (canolepoxmethyl) amino] -o-cresole Rain, 5, 6 — Dipheninole 1 3 — (2 — Pyridinole) 1 1, 2, 4 — Triazine. 3 — (2 — Pyridinole) 1 5, 6 — Bis (4-norrenophane) 1 1,2,41 Triazine · 2Νa salt, 1,10 — phenanthone phosphorus monohydrate, 3, 3 '— Bis [Ν, Ν — bis (carboxymethyl) aminomethyl] phenolic phthalein, 5, 10, 0, 15, 20, 0 — tetrax ( Ν — Methyl pyridinium 1 4 — inole) 一 1 1H, 23Η-Posolefilin and its tetrax (ρ—tonolenesulfonate), 5, 1 0, 1 5, 20 — Tetrahedral one 21 Η, 23 ポ — Ponole filin, 5, 10, 0, 15, 20 — Tetrafenino 21 H, 23 H — Borfurintetrasnorrefonic acid · 2sulfuric acid tetrahydrate, 5,10,15,20 —Tetra Kiss {4 1 [Ν-(trimethyl) ammonio: feninole]-21 Η, 23 Η-Ponole iriin and its tetrakis (ρ-trunosnorehone) Acid salt), syn — phenol 2-pyridinolex toxim, pirogallol sulhoff lan, pilocatechol, snollehoff urain, N, N '— bis salicyliden 1 2.3 — diaminobenzofuran, salicylaldehyde — 2 — succinyl, 3, 3' — bis {[N — methylー N — (Kanoreboshi methyl)] Aminomechinore) 1 0 — Kle Zonolesnorehoff Evening rain '1 Na salt, 4, 4' — Zika norebox 1 2 2'-Bikinoline • 2Na salt, 4,4'-bis (3,4-dihydroxyphenylazo)-2,2'-Stilbene disnolephonate '2 ammonium salt, 4,4'-diamino-1,2'-disulfostilbene —N, N, N' N '—tetraacetic acid' 2Na salt, 1 , 1, 1 — Trifluoro 1-4-Menolecapto 1-4 (2-Chenyl)-1-3-Butene 1-2-On, 4-1 (2-Anolesone 4-Nito) L-Fenilazo) amino: Fenilazo} benzensnolefonic acid · 1Na salt, 1,8-dihydroxy-1,2,7-bis (5-chloroー 2 — Hydroxy 1 3 — Sunorejo Feninoleazo) 1 3, 6 — Naphtharanges Rufonic acid4Na salt, 1,8—dihydroxy-1,2,7-bis (2—ssolefofenilazo) —3,6—Naphthalene disulphonic acid 4Na salt, 41-methyl-2- (2-thiazolinoleazo) phenol, 5—dimethylamino-2

(2 — thiazoliazo) 1, 1 (2 _ thiazoliazo) 1 2 — naphthol, 4 1 (2 — thiazolinazo) Zonore Shino Nore, 3 '-2tro 4' 1 (2, 4, 6-Trinitrophenylamino) Benzo 1 18-Klauun 6, N, N ', N' ', N' '' Tetramethylpurpuric acid 'Ammonia salt, 4' mono (2,4-dinitro-1-6-trifluoromethyltin) Nole) Aminobenzene 1 5 — Clane 5, 8 — Menolecaptoquinolin 'hydrochloride, 1, 2 — Dihydroxy 3, 5 — Benze 2,3'-bis [N, N-bis (canoleboximetyl) aminomethyl] thymolphthalein, 2,4 ' , 6 — Tris (2 — Piri Ginole) 1 1, 3, 5 — triazine,

N — (4-methoxyphenyl) 1-1,4-phenylenediamine 'hydrochloride, 2 — [3— (2,4—Dimethyldiamine) Canolebox) _ 2 — Hydroxy — 1-naphthylazo2phenol, 3, 3 '— Bis [N, N — Bis (Rubikoshi Mechinore) Aminome [Chinole] 1 o — Cresole Leaf phthalein, 2 — [1 — (2 — Hydroxy 5 — 1- 3—Pininole-5—Formazano: Benzoic acid '1Na salt, 1, 2—dimenol power Ptosuccinic acid, N— (dithiocanolepoxy) ) Sarcosine '2 ammonium salt, tetrafenolinolevoate Νa salt, 3-Menolecaptopropionic acid, phenylanolesonic acid, tetraflune Anyone hoshonium chloride etc. can be mentioned.

 Of these, chelating reagents are preferred, and EDTA • 2Na salt is particularly preferred.

 One of the above chelating agents can be used alone, or two or more can be used in combination.

The surface treatment with the chelating agent can be performed according to a known method. Specifically, for example, a chelating agent may be dissolved or dispersed in an appropriate solvent, and then mixed with a compound to be subjected to surface treatment. As a solvent in which ice is mainly used as a solvent, some chelating agents are poorly water-soluble. Therefore, when such a chelating agent is used, it is suitable. Relevant organic solvents, for example, methanol, ethanol, isopropanol, n-aminoleanol, methinolaysobutylketone, chlorophenol, carbon tetrachloride , Benzene, Nitoguchi Benzene, Triethanolamine, etc. may be selected as appropriate. Is the amount of chelating agent used in a wide range depending on the type of chelating agent, the type of compound to be subjected to surface treatment, and the like? The chelating agent strength is about 100 to 200 parts by weight, preferably about 50 to 100 parts by weight, based on 100 parts by weight of the compound to be subjected to the surface treatment. The concentration and mixing amount may be adjusted so as to be about 150 parts by weight. The mixing time can also be selected as appropriate.Generally, it should be about 0.5 to 4 hours. ₍ If necessary, the surface treatment is performed under heating, for example, at a temperature of about 50 to 80 ° C. You may.

The gas generating agent for an air bag of the present invention is produced by mixing three essential components and, if necessary, other components. Further, the gas generating agent for an airbag of the present invention can be formulated into a suitable shape. For example, an appropriate amount of a binder may be added to and mixed with the gas generating composition of the present invention, followed by tableting or tableting and drying. At that time, it is particularly preferable for safety to add an appropriate amount of a solvent such as water. As the binder, a binder commonly used for such a purpose may be used. The formulation is not particularly limited, and examples thereof include pellets, disks, spheres, rods, hollow cylinders, sugary sugars, tetrapods, and the like. It may be non-porous, but may be porous (for example, briquette-like). Further, a pellet-shaped or disk-shaped one may have one to several projections on one or both sides. The shape of the protrusion is not particularly limited, and is, for example, a columnar shape, a conical shape, a polygonal pyramid, a polygonal prism. Can be mentioned. Further, the size of the formulation of the gas generating agent for airbags of the present invention is not particularly limited, and the force, which can be appropriately selected from a wide range, the combustion temperature is further reduced, and the combustion temperature is further reduced. moderate or earthenware pots have obtains a burn rate standpoint et al, particle size 0. 3 ~ 1. 5 mm approximately correct for the favored and size _c or the components of the present invention airbags gas generating agent Each of them may be formulated alone, and these may be used as a mixture.

 The preparation of the gas generating agent of the present invention can be safely stored and transported by filling a container made of synthetic resin such as polyethylene or a metal.

 Next, the airbag inflator of the present invention will be described. An airbag inflator according to the present invention is characterized in that an external oxidizing agent is mounted on at least a part of a path for injecting a rear gas into the airbag. It is. Therefore, it is not particularly limited as an inflator, and a known structure can be widely used.

 In the present invention, as the external oxidizing agent, a known oxidizing agent of the same type as or different from the oxidizing agent contained in the airbag gas generating agent of the present invention can be used.

In the present invention, the part of the inflator on which the external oxidant is placed is particularly provided if it is a rear gas ejection path other than the combustion chamber. There is no limitation, and examples thereof include a clamp, a wire mesh filter, a ceramic filter, and the like. The location where the external oxidant is placed need not be at one location, but may be more than one location.

 The present invention utilizes the fact that the gas generated by the combustion of the gas generating agent is at a high temperature to thermally decompose an external oxidizing agent to generate oxygen and oxidize CO and the like in the gas. By doing so, it is intended to achieve a further reduction in the -C 0 concentration. Therefore, it is desirable that the temperature of the gas that comes into contact with the external oxidant is somewhat high. Specifically, the gas that comes out of the combustion chamber in the inflator first comes into contact with the gas. It is preferable to put an external oxidizer on the lamp.

 The external oxidizing agent can be placed, for example, on an aqueous solution or aqueous dispersion of the oxidizing agent or an organic solvent solution or dispersion, using a coolant, a wire mesh filter, or a ceramic mixer. This is performed by dipping and drying inflator parts such as isolators. More specifically, the oxidizing agent aqueous solution or aqueous dispersion or the organic solvent solution or the dispersion is heated to, for example, about 70 to 100 ° C. After immersing the inflator component and cooling it as it is to deposit an oxidizing agent on the surface of the inflator component, the component may be taken out and dried.

Also, the placement of the external oxidant may cause the This may be done by spraying a solution or dispersion of the agent and drying.

 Furthermore, an oxidizing agent formulated in pellet or disk form can be loaded into at least one part of the gas ejection path.

 The airbag gas generant filled in the combustion chamber of the airbag inflator of the present invention is not particularly limited, but a non-azide gas generant is preferred. And the gas generating agent of the present invention is particularly preferred. When the gas generating agent is charged into the combustion chamber, at least one selected from an oxidizing agent, a gas-releasing inorganic compound, and an inert inorganic compound can be charged together with the gas generating agent. Hereinafter, these three components are referred to as “combustion chamber oxidation promoters” for convenience.

 As the oxidizing agent of the oxidation accelerator for the combustion chamber, any of the oxidizing agents described above can be used. Among them, nitrates such as nitric acid lime and oxohalogenates such as sodium chlorate are preferred. As the gas-releasing inorganic compound, known compounds that release gas by thermal decomposition can be widely used, and examples thereof include sodium bicarbonate. As the inert inorganic compound, known compounds that do not cause thermal decomposition can be widely used, and examples thereof include silicon dioxide.

Among the specific examples of the above-mentioned oxidation promoter for combustion chamber, nitric acid The oxidizing agent such as lithium and sodium chlorate and the inert inorganic compound such as silicon dioxide are the same as the components which are included in the gas generating agent for airbag of the present invention. Even if the total amount of the gas generating agent used as a component of the gas generating agent and the amount used as the oxidation promoter for the combustion chamber is included in the gas generating agent of the present invention from the beginning, the appropriate burning rate can be obtained. Cannot be obtained, and a reduction in C 0 concentration cannot be achieved.

 The shape of the oxidation promoter for the combustion chamber is not particularly limited, and may be used in the form of powder or various types such as pellets, disks, deposits, and granules. It may be used after being formed into a shape.

 When filling the combustion chamber with the oxidation promoter for the combustion chamber together with the gas generating agent of the present invention, a partition may be provided between the two by a thin aluminum sheet or aluminum foil.

 The airbag gas generating agent, airbag, and airbag airbag of the present invention are not limited to automobiles, but are suitably used as gas sources for airbag systems mounted on various transportation equipment. it can.

According to the present invention, a non-azide airbag gas generating agent using a nitrogen-containing organic compound as a gas generating base is equivalent to an azide gas generating agent by including a specific combustion catalyst. Or higher combustion rate, gas generation rate and gas It retains the above-mentioned favorable properties of non-azide gas generators such as temperature, lower impact ignitability than azide gas generators, and high safety, low toxicity and low cost. In addition, a gas generator for non-azide-based debugging, in which the concentration of toxic components such as C 0 in the after-gas is further reduced, is provided. Further, an inflator for an air bag, which can further reduce the C 0 concentration in the after-gas, is provided. In addition, a method to solve the disadvantage of non-azide gas generating agents that nitrogen-containing organic compounds such as azodicarbonamide decompose during long-term storage after formulation, and specifically, A method of surface treatment with a coupling or chelating agent is provided.

 BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a drawing schematically showing an apparatus used for a combustion test of a gas generating agent in the following examples.

 FIG. 2 is a schematic sectional view showing an example of the inflator of the present invention.

 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Reference Examples.

 Manufacturers of the general raw materials used below are as follows unless otherwise noted.

Azodicarbonamide: Otsuka Chemical Co., Ltd. Potassium nitrate: Otsuka Chemical Co., Ltd.

 Potassium perchlorate: manufactured by Nihon Carrit Co., Ltd.

 Silicon dioxide: trade name Toksil N, manufactured by Tokuyama Soda Co., Ltd. Soluble starch: manufactured by Wako first grade, manufactured by Wako Pure Chemical Co., Ltd. In the following, they are simply referred to as "part" and "%". Means “parts by weight” and “% by weight”, respectively.

Example 1

45 parts of azodicarbonamide, 55 parts of potassium perchlorate, copper oxide (specific surface area: 48 m ² Zg, average particle size: about 7.4 m, manufactured by Nikki Chemical Co., Ltd.) ) 10 parts of silicon dioxide and 1.1 parts of each powder were mixed well and the starch content was reduced.

A 10% aqueous solution of soluble starch was added to 1.5 parts and mixed further to produce a wet powder. The wet powder is granulated by a granulator, the obtained wet granules are dried, and further pressed by a hydraulic tableting machine, and a gas generating agent pellet (diameter 6 mm) is pressed. And a thickness of 3 mm and a weight of 0.15 g). The above gas generating agent pellets were installed in the combustion chamber overnight, equipped with a gas outlet of 6 mm in diameter and charged with 0.8 g of boron boron nitrate as a transfer medium. The tube was filled with 30 g. This inflator is set in a 60-liter solenoid tank, activated by passing electric current, and then the gas in the tank is removed through a sampling hole through a sampling hole. Collected in tornado bugs. Of this gas When the C0 concentration was measured using a detector tube, it was 0.8% and was 7%.

Comparative Example 1

The same procedure as in Example 1 was carried out except that copper oxide for a general gas generating agent having a specific surface area of 0.77 m ² Z g and an average particle diameter of about 4.5 ^ m was used. Pellets were manufactured.

 Using the pellet of this gas generating agent, the same operation as in Example 1 was carried out, and as a result, (: 0% was 1.5%.

 From the above results, it is clear that Cu0 having a large specific surface area has a remarkable effect on reducing the C0 concentration in the gas. Example 2

Powders of 45 parts of azodicarbonamide, 55 parts of potassium perchlorate, 10 parts of a combustion catalyst having the composition shown in Table 1 below, 1.1 parts of silicon dioxide and 0.55 parts of soluble starch are often used. The powder was mixed, 0.2 g of this powder was packed in a mold having a diameter of 6 mm, and pressed with a hand-operated hydraulic press machine at a pressure of 40 kgcm ² , and the pellet of the gas generating agent of the present invention was used. mm, weight

0.2 g) was produced. table 1

The catalysts of No. l to No. 3 are all manufactured by JGC Corporation.

 The obtained gas generating agent was subjected to a combustion test using the combustion test apparatus shown in Fig. 1.

 (1) Put the pellet of gas generating agent on the chrome wire and assemble the equipment as shown in the figure.

 (2) Replacing the inside of the Tedlar bag and the test tube with a rim (300 ml for 10 minutes).

 (3) The helium gas in the Tedlar bag is extruded and released into the test tube, and the cock of the hook (not shown) is closed.

 (4) Pull out the residual gas remaining in the teddy bag with a gas syringe (not shown).

 (5) Close the glass tube of the test tube and adjust the three-way cock so that the generated gas after combustion is discharged into the teddy bag9.

(6) Stop supplying helium gas and reduce bag clicks. Open.

 (7) Connect an ignition bus (not shown) to the nickel wire, and ignite the pellets of the gas generating agent with a slider (not shown) and burn them.

 (8) Analyze the gas discharged into the Tedlar bag using a gas inlet mat graph.

 (9) Measure the gas volume in the teddy bag with a gas syringe.

 Table 2 shows the results.

Comparative Example 2

As in Example 2, except that copper oxide for a general gas generating agent having a specific surface area of 0.77 m ² Zg and an average particle diameter of about 4.5 was used alone as the combustion catalyst To produce a pellet of gas generating agent.

The obtained pellets were subjected to the same combustion test as in Example 2, and only the C0 concentration was measured. Table 2 shows the results.

Table 2

表 2 から、 本発明の燃焼触媒及びそれと他の酸化剤の 組合せが、 C 0濃度の低減化に顕著な効果を有する こ と が判る

Table 2 shows that the combustion catalyst of the present invention and a combination of the combustion catalyst and another oxidizing agent have a remarkable effect in reducing the C0 concentration.

Example 3

 Using the No. 2 combustion catalyst of Example 2, the content of potassium perchlorate was increased by 5, 10, or 15%, and the content of soluble starch was increased to 0.55 parts. Except for the above, the same procedure as in Example 1 was carried out to produce a pellet of the gas generating agent of the present invention.

Table 3 shows the results of subjecting the obtained pellets to the same combustion test as in Example 2. Table 3

表 3 か ら、 過塩素酸カ リ ウ ムの量を微量増加させる こ と に よ り、 更に C 0濃度が低減化する こ とが判 る。

Table 3 shows that a slight increase in the amount of potassium perchlorate further reduces the C0 concentration.

Example 4

 Radiation force Norebon amide 45 parts, potassium perchlorate

56.3 parts, 10 parts of potassium nitrate, 1 part of silicon dioxide, and the powders of molybdenum oxide having the compounding amount (parts) shown in Table 4 were mixed well, and the mixture was added to the dumping. A 10% aqueous solution of a soluble starch was added to the mixture so that the content of the starch became 1.5 parts, and the mixture was further mixed to produce a wet powder. Thereafter, the same operation as in Example 1 was carried out to produce pellets (diameter 6 mm, thickness 3 mm, weight 0.15 g) of nine kinds of gas generating agents. Table 4

比較例 3

Comparative Example 3

§ zone di force Norebo N'a mi de 4 5 parts, perchloric oxide Li c arm 5 5 parts, the specific surface area 0. 7 7 m ² Z g and an average particle diameter of about 4. For typical gas generating agent 5 m The powders of 10 parts of copper oxide and 1 part of silicon dioxide are mixed well, and a 10% aqueous solution of soluble starch is added to the mixture so that the starch content is 1.0 part. The mixture was further mixed to produce a wet powder. Thereafter, the same operation as in Example 1 was performed to produce a gas generating agent pellet (N0.1).

Pelletizing the gas generating agent in the same manner as above, except that the blending amount of the perchloric acid rim was changed to 65 parts and the amount of copper oxide was changed to 20 parts. (No. 2) The pellets of the gas generating agent obtained above were subjected to the following 60 liter no-reaction test.

 [60 liter no-tank test]

 Example 4 and Comparative Example were installed in a combustion chamber of an inflator equipped with a gas outlet of 7 mm in diameter and charged with 0.8 g of boron boron nitrate as a transfer medium. The pellets of 11 kinds of gas generating agents obtained in 3 were filled respectively. This inflator is installed in a 60-litre tank, and is operated by applying an electric current to burn a pellet of a gas generating agent. The pressure and temperature in the tank and in the 60 liter tank were measured. In addition, the gas in the 60 liter tank after combustion is sampled from the sampling hole into a 1 liter notched rubber bag, and the CO concentration and NOx concentration in the gas are detected using a detector tube. Measured. Table 5 shows the results.

 The English symbols in Table 5 have the following meanings.

CP max: Maximum pressure (kgf Z cm ² ) in the combustion chamber (chamber) of the inflator.

 T P max: Maximum pressure in 60 liter tank

(kgf Z cm ² ). This is a parameter that indicates the gas generating capacity of the gas generating agent.

t TP max: Time (msec) required for the pressure in the 60-litre tank to reach its maximum. The air bag is deployed Parameter to simulate the gas temperature in the bag at the time of loading t TP 90: Required until the pressure in the 60-litre tank reaches 90% of the maximum value Time (msec). A parameter that simulates the gas temperature in the air bag when the bag is deployed.

Table 5 Sample No. Filling amount CPmax TPraax tTPraax tTP90 Ttemp. CO Ox

β kgfZcm ² msec% ni

1 35 92 0.7 35 20 41 1.20 1200

2 35 100 1.1 29 20 67 0.96 1500

3 30 84 0.5 580 1 39 0.96 1300

4 30 122 0.5 27 17 49 0.82 1100 Al 5 30 102 0.6 140 42 0.90 1300

 6 20 80 0.3 34 0.45 750 Example 6 30 190 1.0 42 22 61 0.42 1100

 7 30 62 0.7 250 170 30 0.65 1600

8 40 94 1.2 80 1 75 0.49 2300

9 30 44 0.7 140 47 0.67 2150 Ratio 1 30 90 1.4 57 1.35 800 Example 2 30 74 1.24 96 0.32 1800

From Table 5, it can be seen that (1) the airbag gas generating agent of the present invention can generate an appropriate amount of gas and has good combustion performance; and (2) the airbag of the present invention. Copper oxide by containing molybdenum oxide (VI) C 0 concentration and equivalent or higher than Comparative Example 3 used

That both the NOX concentration and the NOx concentration can generate gas at the same time; and (3) In particular, the compositional power of Example 4, No. 6, and the remarkable reduction of the C0 and N0X concentrations It is clear that this can be achieved.

 In addition, the pellets of the nine gas generating agents obtained in Example 4 were stored in a thermostat at 107 ° C for 400 hours, respectively, to calculate the residual weight ratio (%). After all, both

99.5% or more. This value, you are shown the this substantial degradation of § zone dicarbonate Na Mi de is not Tsu caused this _c - how, Bae les of the two gas generating agent obtained in Comparative Example 3 The same procedure was followed as above except that the test pieces were used and the storage time was set at 190 hours. The residual weight ratio (%) was calculated to be 72% (No. 1 ), 68% (No. 2), which clearly indicates that the decomposition of azodicarbonamide is remarkably progressing.

Example 5

45 parts of azodicarbonamide, 65 parts of potassium perchlorate, 1 part of silicon dioxide, and tungsten oxide (No. 1) in the amount (parts) shown in Table 6 The powders are mixed well, and a 10% aqueous solution of soluble starch is added to the mixture so that the starch content becomes 1.5 parts, and further mixed to produce a wet powder. Built. Thereafter, the same operation as in Example 1 was carried out to produce a pellet of a gas generating agent (diameter 6 mm, thickness 3 mm, weight 0.15 g).

 The amount of potassium perchlorate was changed to 56.3 parts, using the tungsten oxide Nos. 2 to 8 shown in Table 6 and newly adding 10% by weight of potassium nitrate A gas generating agent pellet (diameter: 6 mm, thickness: 3 mm, weight: 0.15 g) was manufactured in the same manner as above, except for adding the parts.

 Table 6

実施例 5 で得 られたガス発生剤のペ レ ツ ト を使用 して 6 0 リ ッ ト ノレタ ン ク 試験を実施 し、 イ ン フ レ一 夕一内及 び 6 0 リ ッ ト ノレタ ン ク 内の圧力、 温度、 後ガス 中の C 0 濃度及び N 0 X 濃度を測定 した。 結果を表 7 に示す。 尚 ペ レ ツ ト 充填量は全て 4 0 gであ る。

ま た実施例 5 で得 られた 8 種のガス発生剤のペ レ ツ ト を、 それぞれ 1 0 7 °Cの恒温機中にて 4 0 0 時間保存 し て重量残存率 （％ ) を算出 した と こ ろ、 いずれ も

Using the pellets of the gas generant obtained in Example 5, a 60-liter no-reservation test was conducted, and within 60-liter and 60-liter noretank The pressure, temperature, C 0 concentration and N 0 X concentration in the post-gas were measured. Table 7 shows the results. The pellet filling amount was all 40 g.

Further, the pellets of the eight gas generating agents obtained in Example 5 were stored in a thermostat at 107 ° C. for 400 hours, respectively, and the weight residual ratio (%) was calculated. By the way,

99.5% or more. This value, _c decomposition of completion Zojikanorebo Na mi de is shows a this does not substantially Tsu cause this Example 6

 (1) Pellet of the gas generating agent of Comparative Example 1: 30 g

 (2) Combustion chamber oxidation promoter (sodium chlorate): 10 g

 (3) Explosive powder (potassium boron nitrate): 0.8 g

 A pellet of a gas generating agent was placed in the combustion chamber of an inflator equipped with a gas ejection hole with a hole diameter of 6 mm.

Place 15 m aluminum foil and add sodium chlorate Was put in.

 The inflator was set in a 60 liter tank, and the gas generating agent was burned by passing an electric current to measure the combustion chamber pressure and the tank pressure. After the operation, the gas in the tank was sampled from the sampling hole into a one-liter liter driver. When the sampled gas was analyzed using a detector tube, the CO concentration was 0.95%. Also, the maximum combustion chamber pressure is

1 0 9 kgf Z cm ² , Maximum tank pressure 0.7 kgf Z cm ²

 Comparing with the value of Comparative Example 1 (C 0 concentration: 1.5%), it can be seen that the C 0 concentration was further reduced.

Example 7

In Example 6, the same operation was performed except that potassium nitrate was used instead of sodium chlorate as the oxidation promoter for the combustion chamber. It was 1.0%. The maximum combustion chamber pressure was 8.2 kgf Z cm ² , and the maximum tank pressure was 0.8 kgf Z cm ² .

Examples 8 and 9

Combustion tests were performed using the pellets of Comparative Example 1 and potassium nitrate as the oxidation promoter for the combustion chamber in the amounts (parts) shown in Table 8. Equipped with a 7 mm gas exhaust hole The combustion chamber of the obtained inflator was filled with a nitric acid rim, and a 15-zm-thick aluminum foil was placed on top of it, and a gas generating agent pellet was placed on top of it. .

 This inflator was set in a 60 liter tank and operated in the same manner as in Example 6. The results are shown in Table 8 below.

Comparative Example 4

 The operation was performed in the same manner as in Examples 8 to 9 except that nitric acid lime was not used as the oxidation promoter for the combustion chamber. Table 8 shows the results.

 Table 8

表 8 か ら、 燃焼室用酸化促進剤の添加に よ り、 燃焼室 圧力が下が り、 更に後ガス 中の C 0濃度が低下する こ と が判る。

Table 8 shows that the addition of the oxidation promoter for the combustion chamber lowers the pressure in the combustion chamber and further lowers the C0 concentration in the post-gas.

Example 10

FIG. 2 is a schematic sectional view showing an example of the inflator of the present invention. The inflation is basically performed in the combustion chamber (1). Gas generating agent (2), squib (3), explosive (4), gas vent (5), coolant (6), wire mesh filter

 (7) and ceramic finolators (8), and have a known structure except that the coolant (6) is loaded with an external oxidant (not shown). It is a thing.

 The squib (3) consists of a lead wire (9), a platinum electrode (not shown), and a sensitizer (10).

 The mechanism of gas generation is as follows. First, lead wire

 When electricity flows through (9), the platinum electrode is heated and the heat ignites the sensitizer (10) electrically, which in turn ignites the transfer charge (4). The ignited charge (4) burns the gas generating agent (2) to generate gas. The high-temperature gas immediately after generation is led to the coolant (6) through the gas gushing L (5), where it is cooled. At the same time, C 0 in the gas is oxidized by the oxygen generated by the thermal decomposition of the external oxidant loaded in the coolant (6) to carbon dioxide, reducing the CO concentration. It is transformed. After passing through the coolant (6), the gas passes through the wire mesh filter (7), the ceramic filter (1), and the wire mesh filter (7). By passing through, solid impurities are removed, and the solid impurities are discharged from the discharge holes 9 into an air bag (not shown).

The external oxidant is not charged into the coolant (6). The lamp (6) is immersed in an aqueous solution of sodium chlorate heated to 100 ° C, and the aqueous solution is cooled as it is to cool the sodium chlorate. After precipitation on the surface of the lamp (6), the coolant to which sodium chlorate had adhered was taken out from the aqueous solution and heated and dried. . At this time, a copper wire mesh having a mass of 10 g was used as the coolant (6), and the amount of sodium chlorate adhering to the coolant (6) was 2 It was 2 g.

Example 1 1

 Pellet of gas generating agent of Comparative Example 1 30 g, squib

(Daicel Chemical Industry Co., Ltd.) and 0.8 g of explosive (potassium boron nitrate) were charged into the inflatable overnight of the present invention shown in FIG. In this inflation system of the present invention, sodium chlorate as an external oxidizing agent was placed on a coolant, and the loading amount was as shown in Table 9 below. It is as shown below.

This inflator is set in a 60 liter solenoid and activated by passing current through it and the internal pressure of the inflator and 60 liters are set. The tank internal pressure was measured. In addition, the gas in the tank after operation was sampled from the sampling hole into a 1-litre bag. The C0 concentration in the gas collected in the 1 liter note dropper was measured using a detector tube. Table 9 shows the results. Table 9

比較例 1 の C 0濃度 （ 1. 5 % ) と比較する と、 ク ー ラ ン ト へ外部酸化剤 と して塩素酸ナ ト リ ゥ ムを載置する こ と に よ り、 C O濃度の よ り 一層の低減化が達成さ れる こ とが明 らかであ る。

When compared with the C 0 concentration (1.5%) of Comparative Example 1, the CO concentration was reduced by placing sodium chlorate as an external oxidant on the coolant. It is clear that further reductions can be achieved.

Example 1 2

 The same operation as in Example 11 was repeated except that sodium chlorate (loading amount: 10 g) was used instead of sodium chlorate as the external oxidizing agent. At the time of the no-lean tank test, the CO concentration in the post-gas was 0.8%. Example 13

 In Example 11, the filling of the pellet of the gas generating agent was changed to 35 g, and sodium nitrate (mounting) was used instead of sodium chlorate as the external oxidizing agent. Except for using the amount of 20 g), the same operation was performed to conduct a 60 liter tank test. The concentration of CO in the post-gas was 0.5% d. Reference example 1

Copper oxide with a specific surface area of 50 m ² Z g (manufactured by JGC Corporation) A 100% solution of 7-aminopropyltriethoxysilane (trade name: A-110, manufactured by Nihon Nikka Co., Ltd.) in 100% 10 parts were added, and mixed with a Super Mixer (manufactured by Kawada Seisakusho) at 40, 600 rpm for 5 minutes, dried, and surface-treated copper oxide was produced.

Reference example 2

 ―-シ 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 え 代 えA surface-treated copper oxide was manufactured in the same manner as in Reference Example 1 except that the product manufactured by Co., Ltd. was used.

Reference example 3

The specific surface area of 5 0 m ² of copper oxide (day揮化Studies made Co., Ltd.) 1 0 0 part, Lee Seo professional pill door Li Yi-Soviet steer B A Ruchi data ne over door (trade name: flops of Na-click bet KR — 10 parts of a 3% hexane solution of TTS (manufactured by Ajinomoto Co., Inc.) was added and mixed and dried in the same manner as in Reference Example 1 to produce surface-treated copper oxide.

Reference example 4

100 parts of copper oxide having a specific surface area of 50 m ² / g (manufactured by JGC Chemicals Co., Ltd.) 10 parts of a 2% hexane solution of NACACT AL-M (manufactured by Ajinomoto Co., Inc.) was added. The same procedure was followed for mixing and drying to produce surface-treated copper oxide.

Reference example 5

 100 parts of copper oxide with a specific surface area of 5 On ^ Zg (manufactured by JGC Chemicals, Inc.) was added to acetate acetic acid aluminum diisoprolate (trade name: aluminum oxide) A, 0.5 part of a 0.5% toluene solution of Kawaken Fine Chemicals Co., Ltd.) was added, and the mixture was mixed and dried in the same manner as in Reference Example 1 to perform surface treatment. Copper oxide was manufactured.

Examples 14 to 18

Powders of 45 parts of azodicarbonamide, 55 parts of potassium perchlorate, 10 parts of surface-treated copper oxide and 1.0 part of silicon dioxide obtained in Reference Examples 1 to 5 were used. Then, a 5% aqueous solution of soluble starch was added to the mixture so that the starch content was 1.5 parts, and the mixture was further mixed to produce a wet powder. After adjusting the particle size and water content of this product, it is pressed with a hydraulic tableting machine at a pressure of about 120 kg / cm ² to form a pellet (diameter 9.7 mm x thickness 4 mm). mm) gas generator for airbags.

Comparative Example 5

A pellet-shaped gas generating agent was manufactured in the same manner as in the above example except that copper oxide without surface treatment was used. Was.

 The airbag gas generating agents obtained in Examples 14 to 18 and Comparative Example 5 were stored in a thermostat at 107 ° C for 400 hours, and the weight loss was examined. The (%) of rubonamide was calculated. The results are shown in Table 10 below.

 Table 10

表 1 0 か ら、 酸化銅をカ ッ プ リ ン グ剤に よ っ て表面処 理する こ と に よ り、 ァ ゾジカルボ ンア ミ ドの安定性が著 し く 向上する こ と が明 らかであ る。 ま た実施例 1 4 〜

From Table 10, it is evident that the surface treatment of copper oxide with a coupling agent significantly improves the stability of azodicarbonamide. It is. Examples 14 to

Each of the 18 gas generating agents is a non-azide gas generating agent that has a moderate combustion rate and gas generation amount, low combustion temperature, impact ignition, high safety, low toxicity, and low cost. It had good properties.

 Reference example 6

Mix equal amounts of a 10% aqueous solution of calcium peroxide and a 10% aqueous solution of methyltrimethoxysilane, and heat to about 80 ° C. After stirring for 2 hours under reduced pressure, the solid matter was collected by filtration, washed with water, and dried to produce a surface-treated calcium peroxide.

Example 19

 A pellet of a gas generating agent was produced in the same manner as in Example 14 except that the surface-treated calcium peroxide produced in Reference Example 6 was used instead of the surface-treated copper oxide.

 This airbag gas generating agent was stored in a thermostat at 107 ° C for 400 hours in the same manner as above, and the residual ratio of azodicarbonamide based on weight loss was determined. The residual ratio of urenobon amide was 99.5%, which clearly indicates that the surface treatment achieved a remarkable decomposition prevention effect.

Comparative Example 7

 A pellet of a gas generating agent was produced in the same manner as in Example 19 except that calcium peroxide not subjected to a surface treatment was used. With regard to this pellet, azodicarbonamide was decomposed at the time when the aqueous solution of soluble starch was added, without performing a storage test at 107 ° (:, 400 hours).

Based on the above results, by subjecting calcium peroxide to surface treatment with a capping agent, azo as a gas generating base was obtained. _ _Q

 58 It is clear that the stability of dicarbonamide is significantly improved.

Reference Example 7

EDTA 'to 2 N a 1 0% aqueous solution of l OO ml of salt, was added a specific surface area 5 0 m ² of copper oxide (day揮化Science Ltd. (Ltd.)) 1 O g, was mixed under stirring for 1 hour, oxide The copper was collected by filtration and dried to produce a surface-treated copper oxide.

Reference Example 8

 80 g of copper oxide (manufactured by Nikki Chemical Co., Ltd.) having a specific surface area of SO m ZZ g was added to 50 ml of a 10% aqueous solution of sodium diginate calcium carbamic acid (DDTC). After adding and mixing with stirring for 2 hours, the copper oxide was collected by filtration and dried to produce a surface-treated copper oxide.

Reference Example 9

Except that in place of the copper oxide Ru with an oxidizing click b arm (C r 20 ₃₎ or an oxide Ma emission gun (M n ₂ 0 _3), and operation in the same manner as in Reference Example 7 was facilities surface treatment oxide Chrome and manganese oxide were manufactured respectively.

Example 20 to 24

The surface treatments obtained in azodicarbonamide (ADCA), potassium perchlorate, potassium nitrate, and Reference Examples 7 to 9 at the blending amounts (parts) shown in Table 1I below Metal oxide and dioxide Each powder of silicon was mixed well, and a 5% aqueous solution of soluble starch was added thereto so that the starch content became 1.5 parts, and further mixed to produce a wet powder. In Example 20, the surface-treated copper oxide obtained in Reference Example 8 was used, and in Example 21 and Example 22, the surface-treated copper oxide obtained in Reference Example 7 was used. After adjusting the particle size and water content of the obtained wet powder, it is pressed with a hydraulic punching machine at a pressure of about 120 kgf / cm ² , and the pellet (diameter) of the gas generating agent for air bag is used. 9.7 mm x 4 mm thick) was manufactured.

Comparative Example 8

 A pellet of a gas generating agent was produced in the same manner as in Example 20 except that copper oxide without surface treatment was used.

The gas generating agents obtained in Examples 20 to 24 and Comparative Example 8 were stored in a thermostat at 107 for 400 hours, the weight loss was examined, and the residual ratio of azodicarbonamide (%) Was calculated. The results are also shown in Table 11.

table 1

表 1 1 か ら、 金属酸化物をキ レー ト 剤に よ っ て表面処 理する こ と によ り、 ァ ゾジカ ルボ ンア ミ ドの安定性が著 し く 向上する こ と が明 らかであ る。 ま た実施例 2 0 〜 2 4 のガス発生剤は、 いずれ も適度な燃焼速度やガス発 生量、 低い燃焼温度ゃ衝擊着火性、 高安全性、 低毒性、 安価 さ と い つ た非ア ジ ド系ガス発生剤の好ま しい特性を 保持 した も のであ る。

Table 11 shows that the surface treatment of metal oxides with chelating agents significantly improves the stability of azodicarbonamide. is there. In addition, all of the gas generating agents of Examples 20 to 24 have non-aqueous properties such as appropriate combustion speed and gas generation amount, low combustion temperature, impact ignitability, high safety, low toxicity, and low cost. It retains the favorable characteristics of a gide-based gas generant.

Claims

The scope of the claims A non-azide gas generating agent containing a nitrogen-containing organic compound and an oxidizing agent as active ingredients. It has a molybdenum oxide, tungsten oxide and BET specific surface area of 5 as a combustion catalyst. gas generating agents for airbags characterized that you containing one metal oxides least for a selected from m ² Z g or more metal oxides.  2. The nitrogen-containing organic compound according to claim 1, wherein the nitrogen-containing organic compound is at least one selected from an amino group-containing organic compound, a ditriamine group-containing organic compound, and a nitrosoamine group-containing organic compound. Gas generator for airbags.  The gas generating agent for an airbag according to claim 1, wherein the nitrogen-containing organic compound is azodicarbonamide.  2. The gas generating agent according to claim 1, wherein the oxidizing agent is at least one selected from oxohalogenates, nitrates and nitrites.  3. The gas generating agent for airbag according to claim 1, wherein the oxidizing agent comprises an oxohalogenate and a nitrate. 2. The nitrogen-containing organic compound and / or a compound which induces the decomposition of the nitrogen-containing organic compound is surface-treated with a force-removing agent and Z or a chelating agent. The gas generating agent for airbag described in the item. An airbag inflator that fills a combustion chamber with a gas generating agent for an air bag and discharges gas generated by combustion of the gas generating agent into an air pad. An air pack inflator characterized in that an external oxidizing agent is placed on at least one part of the path for injecting air into the air bag.  8. The airbag inflator according to claim 7, wherein the gas generating agent for an air bag is a non-azide gas generating agent.  The airbag inflator according to claim 7, wherein the combustion chamber is filled with an oxidation promoter for the combustion chamber together with the gas generating agent for the airbag.  0. The airbag inflator according to claim 7, wherein the external oxidant is placed on the coolant and the filter.