WO1997012849A1

WO1997012849A1 - Gas generator for air bag

Info

Publication number: WO1997012849A1
Application number: PCT/JP1996/002796
Authority: WO
Inventors: Tadao Yoshida; Yasuo Shimizu; Kazuo Hara; Shiro Chijiwa; Tsukasa Maekawa; Junichi Onishi; Shigeru Sumitomo; Takashi Kazumi
Original assignee: Otsuka Kagaku Kabushiki Kaisha; Nippon Koki Co., Ltd.
Priority date: 1995-09-29
Filing date: 1996-09-27
Publication date: 1997-04-10
Also published as: EP0801045A4; EP0801045A1

Abstract

A gas generator for air bags comprising (1) biscarbamoylhydrazine as a base of the generator, (2) a salt of oxoacid of halogen as an oxidizing agent, (3) a nitrate as another oxidizing agent, and (4) a combustion catalyst as the active ingredients. This generator has a proper combustion performance and a low combustion temperature, generates a gas lowered in the content of toxic components such as CO and NOx and that of emitted suspended particles, is excellent in heat stability, and is preferably far superior to azide and non-azide gas generators of prior art in safeness.

Description

Specification

Gas generating agent for paper bags

Technical field

The present invention relates to a gas generating agent for air packs.

INDUSTRIAL APPLICABILITY The gas generating agent for an air bag according to the present invention has an appropriate combustion performance, a low combustion temperature, a low concentration of toxic components such as CO and NOx in a gas generated by the combustion, and The concentration of released suspended particulate matter is low, the thermal stability is good, and the safety is significantly higher than conventional azide and non-azide gas generating agents. It has new characteristics.

Y M technology

The demand for airbag systems is increasing exponentially as the demands on vehicle safety increase. The airbag system inflates a nylon bag (air bag) installed inside a handle or dashboard when a car crashes at high speed. This prevents the occupant from colliding with any part of the vehicle and causing death or injury, and the expansion of the knock requires the inflation in the system. The gas generated by the combustion of the gas generating agent loaded in the tar (gas generating container) is used.

Various properties are required for a gas generating agent for a webbing. The following six requirements are particularly important. The first requirement is "showing a moderate burning rate in the inflator". In the air bag system, the impact on the vehicle is detected by a sensor, and it is determined whether or not the collision is a true collision. It ignites the gas generant inside and releases gas to inflate the airbag and protect the occupant's body, especially the head. Immediately, when a car collides, the occupant's head begins to move after a certain time, so the air bag needs to be deployed in accordance with the movement of the head. Therefore, it is inappropriate if the burning rate of the gas generating agent is too fast or too slow.

The second requirement is “low combustion temperature”. If the combustion temperature of the gas generating agent is high, the temperature of the gas released during the bag rises and damages the bag, and furthermore, the gas leaked outside due to the damage of the bag May cause burns to the occupants. In addition, during combustion, solids are usually produced as a by-product, and are removed by a finolator provided between the inflator and the bag. Not included in the released gas. If the combustion temperature is high, the solids evaporate and are released together with the gas into the bag, where they condense into suspended particulate matter, damaging the bag. In some cases, it can be done.

The third requirement is that “the concentration of toxic components such as C • and NOx in the gas generated by combustion should be low”. Airbag In the system, the bag releases some of the gas into the vehicle immediately after inflation and shrinks somewhat to reduce the impact of occupant collision with the inflated bag. High levels of components can cause occupant poisoning.

The fourth requirement is “good thermal stability”. Gas generants must have a long life, usually 10 years or more. It is imperative that the gas generants not decompose at temperatures to which vehicles are exposed, especially at high temperatures in summer.

The fifth requirement is that the raw materials, intermediates, and products be highly safe. In terms of safety, it is important that impact ignitability (ignition sensitivity to impact) is low. If the impact ignitability is high, there is a large risk of handling, and detonation is likely to occur during the manufacturing process such as mixing and molding, which may damage surrounding facilities and the environment, and even cause injury to humans. There is also a risk of incurring it.

The sixth requirement is “low toxicity”. High toxicity of gas generant raw materials, intermediates and products can cause manufacturing and disposal problems.

Conventionally, as an airbag gas generating agent, an azide-based gas generating agent using azurized sodium as a gas generating base has been widely used. Azide-based gas generating agents have the drawback of high force impact ignitability, which is an excellent gas generating agent that satisfies the above first to fourth requirements. Be careful with handling. In addition, sodium azide is toxic and requires protective equipment during handling. In addition, there is a drawback in that wastewater treatment for work using azide sodium requires special treatment equipment.

Under the current situation where emphasis is placed on environmental protection and the safety of workers and users, azide-based gas generating agents with the above-mentioned disadvantages are not preferred. Therefore, there is a strong demand for the development of a non-azide-based gas-generating base that can be used in place of azimuthized sodium.

As an alternative to the azide-based gas generating agent, for example, a non-azide-based gas generating agent containing a nitrogen-containing organic compound such as azodicarbonamide (ADCA) and an oxidizing agent is used. Known (JP-A-6-32698, JP-A-6-89)

JP-A-32690, JP-A-6-227840, etc.). The gas generating agent exhibits an appropriate burning rate comparable to that of a conventional azide-based gas generating agent, has a low impact ignition property, and has a remarkably low detonation property and toxicity. Further, it is desired to further reduce the combustion temperature and the concentration of active ingredients such as CO and N0X in the gas, which are sufficiently low to be practically usable. In addition, this non-azide gas generating agent is required to be further improved in terms of thermal stability.

Japanese Unexamined Patent Publication No. 7-300383 discloses excellent thermal stability. As non-azide gas generating agents, bis-carba'moinolehydrazine (hydrazolic canolebon amide) and oxono-oleate are used as active ingredients. Is disclosed. However, the gas generants are highly detonable and dangerous. In addition to the high combustion temperature, it also has the disadvantage that a large amount of chloride lime, which easily becomes suspended particulate matter, is produced as a by-product during the combustion.

German Published Patent Application No. 195 168 188 describes viscalbamoyl hydrazine and oxidizing agents such as oxohalogenates and nitrates and III, IV, V and VI A gas generating agent containing a heat reducing agent such as a sulfate hydrate, a nitrate hydrate, a carbonate, a carbonate hydrate, a hydroxide, a hydroxide hydrate, etc. of a periodic metal is described. ing. However, the gas generating agent does not have sufficient combustion performance, and often causes incomplete combustion.If incomplete combustion occurs, the air bag does not expand instantaneously. Serious defects.

Disclosure of the invention

One object of the present invention is to exhibit a combustion rate and combustion temperature equal to or higher than those of conventional azide-based and non-azide-based gas generating agents, and to reduce the concentration of toxic components such as CO and NOx in the gas. It is still another object of the present invention to provide a gas generating agent for airbags which is remarkably excellent in thermal stability. Another object of the present invention is to have remarkably low impact ignitability, detonation, and toxicity as compared with the above-mentioned non-azide gas generant, and to release suspended particulate matter. An object of the present invention is to provide a gas generating agent for an air pack having a low concentration of a substance.

Another object of the present invention is to provide a gas generating agent for an air bag which does not cause incomplete combustion.

Other features of the present invention will be apparent from the following description.

According to the present invention, (1) biscarbamoinolehydrazine, which is a gas generating base, (2) oxohalogenate, which is an acidifier, (3) A gas generating agent for an airbag, comprising a nitrate as an oxidizing agent and (4) a combustion catalyst as an active ingredient is provided.

In addition, according to the present invention, (1) biscanolevamoyl hydrazine, which is a gas generating base, (2) oxohalogenate or nitrate, which is an oxidizing agent, And (3) A gas generating agent for an air bag, which contains a combustion catalyst as an effective component, is provided.

The gas generating agent for an air bag of the present invention satisfies all of the above first to sixth requirements. That is, the gas generating agent for an air bag of the present invention does not cause incomplete combustion and has a combustion speed and a combustion temperature equal to or higher than those of the conventional azide and non-azide gas generating agents. Indicate CO, NOx, etc. in gas The concentration of toxic components is even lower, the impact ignitability, detonation and toxicity are remarkably low, the concentration of released suspended particulate matter is low, and the heat stability is remarkably excellent. is there.

Biscanoleno, which is the gas generating base of the gas generating agent for airbags of the present invention, is also known as piurea or hydrazolic amide. ) Is a compound that has been mainly used as a raw material for ADCA. In addition to the above, screw-power balbamoyl hydrazine is used to adjust the shape of the foamed cell when foaming a synthetic resin with high chemical resistance and heat resistance, such as vinyl chloride resin, using ADCA. It is only used as a cell nucleating agent.

Biskanolevamo inolehydrazine has a higher thermal stability than ADCA and a remarkably higher stability against alkali, so if the selection range of oxidizing agents and combustion catalysts is expanded, It has such advantages and contributes to remarkable improvement of the thermal stability of the gas generating agent of the present invention. Biscarno's hydrazine has very low toxicity and no danger of explosion, which contributes to the safety of the gas generating agent of the present invention.

In the present invention, commercially available biscarbamoyl hydrazine may be used as it is. In addition, the particle size is not particularly limited, and may be wide depending on various conditions such as, for example, the amount of the compound, the type and ratio of other components used in combination, and the capacity of the airbag. What is necessary is just to select from a range suitably.

In addition, viscous rubamoyl hydrazine has a scale-like or plate-like crystal shape and a weak bonding force between the particles, which may lead to insufficient moldability during formulation. . In the present invention, in order to minimize such a case, the binder described below is replaced with a non-azide gas generating agent (0.5 to 2.0 parts by weight). Or more)

(About 2.0 to 10 parts by weight, preferably about 3 to 6 parts by weight), or modify and modify bis-carbamic hydrazine without changing the amount of binder. No, or finely pulverized. Examples of the method for modifying bis-powered rubamoyl hydrazine include a method in which bis-powered rubamoyl hydrazine is subjected to a surface treatment with an inorganic surface treating agent, and a method in which bis-powered rubamoyl hydrazine is hydrophilically modified. And a method of coating the surface with a hydrophilic polymer compound or a crosslinked product thereof.

First, a method of surface-treating a bismuth rubamoyl hydrazine with an inorganic surface treating agent will be described. Known inorganic surface treatment agents can be used, and among them, water-soluble metal salts are preferable. Is a specific example of the water-soluble metal salts, for example, A 1 C] _{_{3, C o C l 2,}} Z r C l 4, S n C 1 2, S n C 1 T i C 1 3, T i C 1 F e Ch,

_{F e C 1 3, C u} C 1 2. N i C 1 2, M o C 1 ₅ like chloride Things, A], C o, Z r, S n, T i, F e, C u, N i, metal nitrates, such as _{M o, N a 4 S i} 0 4, K 2 S i 4 0 9 etc. silicate product _{of, Z r C 1 2 0,} N a a 1 0 2 , etc. can this and force include, among this is _{found, a l C l 3, N} a a 1 0 2,

_{F e C) z, F e} C l 3 etc. is rather preferred, N a A 1 0 ₂ or the like is arbitrarily favored especially. One type of surface treatment agent can be used alone, or two or more types can be used in combination. The amount of the surface treating agent used is not particularly limited, and the type of the surface treating agent, the type and amount of other components constituting the gas generating agent other than the modified bis-carbamoyl hydrazine, and the obtained gas generating agent The force can be appropriately selected from a wide range according to the desired performance, etc., and the weight of the total weight of the visco-metal hydrazine that is normally subjected to surface treatment It may be about 0.01 to 5% by weight, preferably about 0.1 to 2% by weight.

The surface treatment can be performed according to a known method.

For example, in the case of using a water-soluble metal salt as a surface treatment agent, biscarbamoyl hydrazine and a water-soluble metal salt were mixed in water to neutralize the mixture. After that, by separating and drying the screw-powered norebamoinolehydrazine, it is possible to obtain the modified biscalmeinolehydrazine. Here, the pH regulator used for neutralization is not particularly limited, and known acids and alkalis can be used. Specific examples of acids Examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, oxalic acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid. Specific examples of Al-Li are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and carbonic acid. Hydrogen potassium, ammonia, etc. can be mentioned. The drying is preferably performed at about 0 to 250 ° C, considering that the thermal decomposition temperature of bis-carbocene hydrazine hydrazine is about 2δ0 to 260 ° C. Is carried out at a temperature of about 50 to 50 ° C. Drying can also be performed under reduced pressure, which is usually performed under normal pressure. Before the surface treatment of the bismuth rubamoyl hydrazine, it can be finely pulverized or recrystallized.

Next, a method of surface-coating bis-forcebamoyl hydrazine with a hydrophilic polymer compound or a crosslinked product thereof will be described. In the case of coating with a hydrophilic polymer, the surface may be coated, for example, by adding the hydrophilic polymer to an aqueous solution or aqueous dispersion of biscarbamoyl hydrazine and mixing. . Since bis-hydranol hydrazine has low solubility in water, it is preferably used in the form of an aqueous dispersion in consideration of treatment efficiency and the like. During the mixing, the mixture may be heated if necessary.

Here, the hydrophilic polymer compound is not particularly limited. Any known ones can be used. For example, cellulose such as ruboxymethyl cellulose, modified canoleboxyl methylcellulose, hydroxymethyl cellulose, microcrystalline cellulose, etc. And polyvinyl alcohols such as fully-genated poly-vinyl alcohol and partially-genated poly-vinyl alcohol, and starches such as soluble starch. You. One of these hydrophilic polymer compounds can be used alone, or two or more can be used in combination.

The hydrophilic polymer compound can be added as it is or in the form of an aqueous solution. The amount of the hydrophilic polymer compound used is not particularly limited, and it can be selected from a wide range as appropriate, as well as the amount of viscanoleno to be treated normally. O About 0.1 to 5% by weight, preferably about 0.5 to 3% by weight o

In order to coat the surface with a crosslinked product of a hydrophilic polymer compound, for example, an aqueous solution or dispersion of biscarpa'moinolehydrazine is added to a hydrophilic polymer compound or an aqueous solution. The same compounds as described above can be used as the _c- hydrophilic polymer compound which may be added to the mixture and heated while adding a compound and a water-soluble polymerization initiator.

As the olefins, any of those conventionally known having a polymerizable double bond can be used. For example, acrylic acid, mesylate Examples include unsaturated carboxylic acids such as acrylic acid, maleic acid, and itaconic acid, and compounds having a vinyl group such as vinyl acetate and divinylbenzene. In addition, (meth) acrylic acid alkyl esters in which the alkyl portion is a linear or branched alkyl group having about 1 to 4 carbon atoms can also be used. Specific examples of the alkyl (meth) acrylate include, for example, (meth) ethyl acrylate and methyl (meth) acrylate. Can be done. Further, (meth) acrylic acid aryl esters such as phenyl (meth) acrylinoleate can also be used. One or more of the orifices can be used alone or in combination of two or more. The use amount of the olefins is not particularly limited and can be appropriately selected from a wide range. However, it is preferably about 0.1 to 3% by weight of the amount of the bismuth rubamoyl hydrazine that is usually processed. Or about 0.5 to 1% by weight.

The water-soluble polymerization initiator is not particularly limited, and any conventionally known water-soluble polymerization initiator can be used. For example, hydroxyperoxides such as cumene hydroxyperoxide and water-soluble polymerization initiators; Potassium peroxosulfate, ammonium peroxosulfate, hydrogen peroxide, azobisisobutyronitrile, azobiscyclohexanocanolevonil, azobis Valeric acid, 2, 2'-azobis (2-amidinopropane) · dihydrochloride, etc. Can be mentioned. As the water-soluble polymerization initiator, one type can be used alone, or two or more types can be used in combination. The amount of the water-soluble polymerization initiator used is not particularly limited, and can be appropriately selected from a wide range. The amount is about 0.01 to 5% by weight based on the amount of the ordinary olefins used. Preferably, it should be about 0.05 to 1 weight ^0/6 .

The temperature at the time of heating is not particularly limited. The force is usually about 50 to 90 ° C, preferably about 80 ° C. There is no particular limitation on the time required for mixing. Usually, it is about 30 minutes to 5 hours, preferably about 1 to 2 hours.

After the treatment, the modified bismuth rubamoyl hydrazine may be separated by a usual separation means such as filtration or centrifugation, and dried.

Furthermore, a method for finely pulverizing bis-carnoyl hydrazine is described. The pulverization can be produced, for example, by processing a powder of bis-forced hydrazine hydrohydrazine with a high-pressure pulverizer.

A high-pressure crusher, for example, blows high-pressure air into the device from at least two directions on the side of the device to generate an air current to pulverize the powder, and floats inside the device by air pressure. It is a method of collecting the fine powder that has risen, and specifically, for example, a counter jet minole (The Netherlands, Ano Piné Co., Ltd.) Manufactured by Kurimoto Tekkosho Co., Ltd.) and Crossjet Mill (manufactured by Kurimoto Iron Works).

In the present invention, in the pulverization by a high-pressure pulverizer, by appropriately selecting the air pressure, the pulverization time, and the like, it is possible to obtain a desired finely powdered viscous rubamoinolehydrazine. that force, air pressure is usually 3 ~ 8 kgf Z cm ² approximately, favored by rather is 5 ~ kgf Z cm ² or so, the grinding time is usually 5 0 0 0 -

About 200 000 rpm, preferably 100 000-

It is better to be about 150 000 rpm.

In the present invention, biscarbamoyl hydrazine which is finely pulverized as described above, usually has an average particle diameter of 20 zm or less and a BET specific surface area of 0.5 m ² Zg or more. However, it is preferable to use those having an average particle diameter of 10 m or less and a BET specific surface area of 5 m ² ng or more. The average particle size is significantly above 2 and the Z or BET specific surface area

If it is significantly less than 0.5 m ² Zg, as in the case of unground pulverized biscarbamoyl hydrazine, the moldability will not be sufficiently improved, and the pellet obtained by formulation will be insufficient. There is a possibility that the strength of the steel decreases. The average particle diameter in the present invention was measured using a laser diffraction type particle size distribution analyzer: Horiba, Ltd.]. The BET specific surface area in the present invention is a BET specific surface area measuring device [manufactured by Shimadzu Corporation] It was measured using.

The finely powdered bismuth rubamoyl hydrazine obtained in this way can be used as it is as a gas generating base, the moldability, the formability of the obtained gas generating agent, and the like. From the viewpoint of further improving combustion performance, it is more preferable to use granules. The particle size of the granules is usually about 0.05 to 1 mm, preferably about 0.1 to 0.5 mm. For granulation, a known method can be employed.For example, if necessary, an appropriate amount of water or hot water is added to finely powdered bis-forced rubamoyl hydrazine, followed by granulation and drying. Good. Known methods can be used for granulation, for example, various extrusion granulations such as a screw type, a roll type, a blade type, a self-molding type, and a ram type. The method of using a machine can be mentioned. Alternatively, a rolling granulation method, a spray-dry method, or the like may be employed.

As an oxidizing agent which is another active ingredient of the gas generating agent of the present invention, a nitrate or an oxohalogenate is used alone, or a nitrate and an oxohalogenate are used. Are used together.

Examples of the nitrate include alkali metal salts such as lithium nitrate, sodium nitrate, and potassium nitrate, magnesium nitrate, sodium nitrate, and sodium nitrate. Alkaline such as um Examples include earth metal salts and ammonium salts such as ammonium nitrate. Of these, alkali metal salts and alkaline earth metal salts are preferred, and potassium nitrate and sodium nitrate are particularly preferred.

Known oxohalogenates can be used, and examples thereof include perhalogenates and halogenates. Specific examples of perhalogenates include, for example, lithium perchlorate, potassium perchlorate, sodium perchlorate, lithium perbromate, Alkali metal salts such as potassium perbromate and sodium perbromate, magnesium perchlorate, barium perchlorate, calcium perchlorate, perbromine Alkaline earth metal salts such as magnesium acid salt, barium perbromate, and calcium perbromate; ammonia such as ammonium perchlorate and ammonium perbromate And the like. Specific examples of the halogenates include, for example, lithium chlorate, potassium chlorate, sodium chlorate, lithium bromate, and potassium bromate. Alkali metal salts such as sodium bromide, magnesium chlorate, barium chlorate, calcium chlorate, magnesium bromate, barium bromate , Alkaline earth metal salts such as calcium bromate, and ammonium salts such as ammonium chlorate and ammonium bromate. Ganoic acid and perhalogenic acid Metal salts are preferred, and potassium perchlorate and chlorinated lithium are particularly preferred.

Nitrate and oxohalogenate can be used as they are on the market, and their shapes, particle sizes, etc. are not particularly limited. It may be appropriately selected and used according to various conditions such as the ratio and the capacity of the airbag.

In both cases where nitrate or oxohalogenate is used alone or when nitrate and oxohalogenate are used in combination, the amount of these oxidizing agents is Normally, the stoichiometric amount may be sufficient to completely oxidize and burn the bis-powered rubamoyl hydrazine based on the oxygen amount.However, the mixing ratio of the gas generating base and the oxidizing agent may be appropriately changed. Thus, the combustion speed, the combustion temperature (gas temperature), the composition of the combustion gas, and the like can be arbitrarily adjusted, so that it is possible to appropriately select from a wide range. Nitrate, oxohalogenate, or nitrate and oxohalogenate is preferably used in an amount of about 100 to 400 parts by weight based on 100 parts by weight of hydrogen hydrazine. May be blended in an amount of about 100 to 240 parts by weight. When a nitrate and an oxohalogenate are used in combination, the mixing ratio thereof is not particularly limited and may be appropriately selected. If the mixing ratio of oxohalogenate is higher than the above-mentioned amount, the combustion temperature becomes high. This is not preferable because a large amount of halogenated metal, such as chlorinated lithium, is generated as a result of the possibility of detonation, which becomes suspended particulate matter.

In the gas generating agent for airbags of the present invention, the combustion catalyst, which is one of the active ingredients, mainly has an effect of lowering the combustion temperature and reducing the concentration of C0 and / or N0X in the gas. It is considered to have. As the combustion catalyst, an oxide of a metal having the fourth to sixth periods of the periodic table, an oxygen-containing metal compound capable of generating the metal oxide by heating, heteropoly acid, or the like is used.

Specific examples of the metal oxides of the fourth to sixth periods of the periodic table include copper oxide, nickel oxide, cobalt oxide, iron oxide, chromium oxide, manganese oxide, and oxide. Zinc, calcium oxide, titanium oxide, vanadium oxide, cerium oxide, holmium oxide, ytterbium oxide, molybdenum oxide-tungsten oxide, oxide Antimony, tin oxide, titanium oxide, and the like can be given. Among these, copper oxide, nickel oxide, cobalt oxide, molybdenum oxide, oxide oxide, iron oxide, tin oxide, zinc oxide, chromium oxide, and the like are preferred. , C u O, C o O , N i O, N i 20 3

_{_{M o 0 3, W 0 3}} , C r 2 0 a. T i O a, S n O, Z n O, F e 2 0 3 , etc. are more preferable arbitrariness. These metal oxides include: The hydrate is also included. Taking a hydrate of data down Goes te emission oxide as an example, W 0 ₃ 'H Ru ₂ 0 Hitoshidea. Is as a child are these metal oxides, preferred to rather than the BET specific surface area of 5 m ² "g or more on, rather than the preferred Ri good is 1 0 m ² Roh g or more, and still more preferred to rather than the 4 0 m ² Roh g have good to use more. Incidentally, in the above metals oxides, M o 0, W 0 _3, etc., preferred would leave that obtained simultaneously reduce the CO concentration and NOX concentration It has new characteristics.

The oxygen-containing metal compound capable of producing an oxide of a metal having the fourth to sixth periods of the periodic table by heating is not particularly limited, and any known compounds can be used. Taking oxygen - containing Mo Li Bude down compounds to generate a M o 0 ₃ Ri by the heating in Examples, mode re Bude phosphate edge Le Bok, mode re Buden dihydrogen Tsu VIII, the mode re Bude phosphate Kell such Metal salts, molybdenic acid, and molybdenum hydroxide. Also, oxygen Motota emissions Gusute emissions reduction Gobutsu that generates a W◦ ₃ Ri by the heating, for example, Ru metal salts thereof such as Der the motor down Holdings te phosphate. Examples of the metal salts of tangstenic acid include alkali metals such as lithium tangstenate, potassium tangstenate, and sodium tangstenate. Salts, alkaline earth metal salts such as magnesium tungstate, magnesium tungstate, copper tungstate, nickel tungstate Gels, Group VIII metal salts such as iron tungstate, tangs Copper tenate and the like can be mentioned.

Specific examples of heteropolyacids include, for example, linmolibdenic acid, linguistic acid, and metal salts thereof. The metal salt of heteropolyacid is not particularly limited. For example, a Group VIII metal salt such as Co salt, Ni salt, Fe salt, Mg salt, Sr salt, P salt b salt, Bi salt and the like can be mentioned, and among them, Group VIII metal salt is preferable, and Co salt is particularly preferable.

Among these combustion catalyst, C u O, C o O , N i O, N i 2 O a. M o O a, W 0 3, that generates an M o 0 ₃ Ri by the heating including oxygen Mo Li Bude down compounds, oxygen Motota down Gusute emissions compounds which form W 0 ₃ Ri by the heating, re Nmo Li Bude phosphate Copa 'Le DOO, C r 20 3, T i 0 2, S n O, _{Z n O, F e 2 0} 3 Hitoshiryoku rather specifically preferred, C o O, n i O , n i 2 O 3. M 0 O 3, WO 3, Group VIII metal salt of Mo Li Bude phosphate, Linmolibdenic acid phenol is more preferred.

One of the above-mentioned combustion catalysts can be used alone, or two or more can be used in combination.

The particle size of the combustion catalyst is not particularly limited, and may be appropriately selected from a wide range according to various conditions such as the amount of the catalyst, the ratio of the catalyst to other components, and the capacity of the airbag. When a combustion catalyst is blended with the gas generating agent of the present invention, the blending amount is 7/12849

21 There is no particular limitation, and it can be appropriately selected from a wide range according to various conditions such as the type and mixing ratio of other components used in combination and the capacity of the airbag.

The amount of the combustion catalyst varies depending on whether oxohalogenate and nitrate are used alone or in combination as oxidizing agents.

When oxohalogenate or nitrate is used alone as the oxidizing agent, the gas generating base and the oxidizing agent are used from the viewpoint of achieving further reduction of both CO and NOx. Usually about 5 to 150 parts by weight, preferably about 10 to 120 parts by weight, more preferably about 30 to 80 parts by weight, based on 100 parts by weight of the total amount of the agent It should be about the degree.

When oxohalogenate and nitrate are used in combination as oxidizing agents, the gas generating base is considered from the viewpoint of achieving a further reduction of both CO and NOx. 0.1 to 30 parts by weight, preferably 0.5 to 25 parts by weight, more preferably 3 to 1 part by weight based on 100 parts by weight of the total amount of It may be about 5 parts by weight.

When an oxygen-containing metal compound that generates a metal oxide by heating is used, the amount of the generated metal oxide may be set so as to fall within the range specified above.

The airbag gas generating agent of the present invention further includes It is preferable to add an agent. Combustion regulators generally lower the combustion temperature, adjust the combustion rate, and cause gas generators to become involved in fires or other impacts in the process of manufacturing, transporting, or storing gas generating agents. It is used to prevent the explosion forest from receiving fire.

Examples of the combustion regulator include the following (a) to (h).

(B) Simple metals such as B, Al, Mg, Ti, Zr, Mo, etc. (Mouth) Oxides of elements from the second to third periods of the periodic table, such as Al, Mg, Si, B, etc. , hydroxides, carbonates, bicarbonates (the rather then preferred, B ₂ 0 _3, hydroxide Anore Mi Niu arm, base down bets Nai DOO, Aluminum Na, diatomaceous earth, silicon dioxide, etc.)

(C) Alkali metal carbonates, bicarbonates, oxides such as Na and K

(Ii) Alkaline earth metal carbonates and bicarbonates such as Ca, Mg, Ba, and Sr

(E) Periodic table 4th to 6th periodic elements other than the above (mouth) to (c) (for example, Zn, Cu, Fe, Pb, Ti, V,

Ce, Ho, Ca, Yb, etc.) chlorides, carbonates, sulphates (f) carboxymethyl chillenololose, hydroxymethyl cellulose, their ethers, microcrystalline Cellulose compounds such as cellulose powder (G) Organic polymer compounds such as soluble starch, polyvinyl alcohol, and partial genated products

(H) Organic acids such as amino acids such as glycine, organic carboxylic acids such as acetic acid, and citric acid.

Among the above-mentioned combustion regulators, for example, it is preferable to use (i) to (ii) or (h), and to use a simple metal such as B, Al, Ti, Zr, or B _20. _3, a] ₂ 0 metal oxides such as _3, carbonate Li Ji © beam, carbonate magnesiate U beam, alkali metal and alkaline earth metal carbonates such as carbonates Kanoreshi © beam, hydroxide Aluminum two © Particularly preferred are metal hydroxides such as aluminum and amino acids such as glycine.

One type of combustion regulator can be used alone, or two or more types can be used in combination. Commercially available products may be used as the combustion control agents. The particle size 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 mixing ratio with other components, and the airbag capacity.

When a combustion regulator is blended with the gas generating agent of the present invention, the blending amount is not particularly limited, and the mixing ratio of biscarbamoyl hydrazine and the oxidizing agent, the type of the combustion regulator itself, and the other Can be appropriately selected from a wide range according to various conditions such as the type of component of the air bag and the capacity of the air bag. ^ Normal screw strength Luba 'Total amount of hydrazine and oxidant 100 Parts by weight The amount may be about 0.5 to 50 parts by weight, preferably about 1 to 30 parts by weight, and more preferably about 3 to 15 parts by weight. When boron is used as a combustion regulator, the amount of bismuth phenol and oxidized biscalpa molybdenum hydrazine is lower than the viewpoint of obtaining a lower combustion temperature and an appropriate combustion rate. The amount is preferably about 0.5 to 5 parts by weight, and more preferably about 1 to 3 parts by weight, based on 100 parts by weight of the total amount of the agent.

In the gas generating agent for an air bag of the present invention, a slag forming agent can be added. The slag forming agent is an additive that solidifies the residue generated after the combustion of the gas generating agent and makes it easier to remove by the filsator inside the airbag inflator. It is. Is a scan lag forming agent can be used known ones, for example, already silicon dioxide and Aluminum Na exemplified by the combustion modifiers, oxidation boric arsenide (especially this elevation gel B ₂ 0 etc. When the slag forming agent is added to the gas generating agent of the present invention, the amount thereof is not particularly limited. It may be appropriately selected from a wide range according to the composition of the gas generating agent, etc. For example, when silicon dioxide is used as the slag forming agent, the amount of the oxidizing agent is determined by the molar ratio of the oxidizing agent. An appropriate value is around 1/2 An oxide containing an alkaline earth metal and an alkaline earth metal compound which reacts to form an oxide, such as sulfur oxide Tronium, strontium nitrate, etc. can also be used as a slag-forming agent.

Further, various additives conventionally used for this purpose may be blended as long as the preferable properties of the gas generating agent of the present invention are not impaired.

Furthermore, in the present invention, at least one of known oxidizing agents other than nitrates and oxohalogenates can be used in combination as long as the preferable properties of the gas generating agent of the present invention are not impaired. Wear. The oxidizing agent is not particularly limited, and may be suitably selected from those conventionally used in the art, and those which can generate and / or supply oxygen at high temperature and are preferred. Examples include nitrites, metal peroxides, superoxides, ozone compounds and the like. Examples of the nitrite include alkali metal salts such as lithium nitrite, sodium nitrite, and lithium nitrite, magnesium nitrite, and barium nitrite. And alkaline earth metal salts such as calcium nitrite and the like. Examples of the metal peroxide include alkali metal salts such as lithium peroxide, sodium peroxide, and potassium peroxide, magnesium peroxide, and peroxide. Alkaline earth metal salts such as calcium and barium peroxide can be mentioned. Examples of the superoxide include alkali metal compounds such as sodium superoxide and potassium superoxide, and superoxide. Alkaline earth metal compounds such as calcium oxide, super-histonium oxide, and barium superoxide, rubidium superoxide, cesium superoxide and the like. Can be done. Is the o zone down compounds, for example, the formula M 0 ₃ (wherein M is N a, K, shows the I a group element such as a R b C s.) Compounds I table are exemplified up by . 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. These oxidizing agents may be used as they are commercially available, and their shape, particle size, etc. are not particularly limited.For example, the amount of the oxidizing agent, the type and the mixing ratio of each component used in combination, It may be appropriately selected and used according to various conditions such as the capacity of the air bag.

Preferred embodiments of the gas generating agent of the present invention described above may include a slag forming agent and other known additives.

In the present invention, in order to further improve the thermal stability, ease of formulation, etc. of the gas generating agent of the present invention, the gas generating base and / or components other than the gas generating base are reduced. Both types may be surface-treated with a coupling or chelating agent.

. The coupling agent is not particularly limited, and any known coupling agent can be used. For example, amide aminopropyl triethoxy Silane-based coupling agents such as lan, arginosine propylenoxy-produced methoxysilane, methyltrimethoxysilane, isopropynole Titanium-based couplings such as triisostealoinolecitaneate, etc.Alminium-based capacitors such as IJ, acetate alcohol miniatures, etc. Examples include a coupling agent. Known chelating agents can also be used. Examples thereof include ethylenediamine tetraacetic acid (EDTA) and its metal salts (EDTA.2Na salt, EDTA.2K salt, ETDA 2Li salt, EDTA / 2 ammonium salt, etc.), sodium getinoresitiocarbamate and the like. The surface treatment is carried out by mixing the component to be treated with a coupling agent and / or a chelating agent in an appropriate solvent or in the absence of a solvent according to a usual method.

The gas generating agent of the present invention is produced by mixing bis-carbamide molybdenum hydrazine, an oxidizing agent and, if necessary, other components according to a usual method.

The gas generating agent of the present invention can be formulated into an appropriate form. For example, an appropriate amount of a binder may be mixed with the gas generating agent of the present invention, followed by tableting or tablet drying. At this time, it is particularly preferable to add an appropriate amount of water or hot water for safety. Use a binder that is commonly used for such purposes. Just do it. The formulation is not particularly limited, and examples thereof include pellets, discs, spheres, spheres, rods, hollow cylinders, sugary sugars, tetrapods, and the like. It can be non-porous or perforated (for example, briquette-like). Further, the pellet-shaped or disk-shaped one may have one to several projections on one or both sides. The shape of the projection is not particularly limited, and examples thereof include a columnar shape, a conical shape, a polygonal pyramid shape, and a polygonal columnar shape. Further, the size of the preparation of the gas generating agent of the present invention is not particularly limited, and the particle size is selected in order to further lower the combustion temperature, which can be appropriately selected from a wide range, and to obtain a more appropriate combustion rate. It is preferable to formulate into a granule having a diameter of about 0.3 to 1.5 mm, preferably the above-mentioned particle diameter.

Alternatively, each of the components of the gas generating agent of the present invention may be formulated individually, and these may be mixed and used.

The gas generating agent of the present invention formulated as described above can be safely stored and transported by being filled in a synthetic resin or metal container such as polyethylene. can do.

The gas generating agent of the present invention is not limited to automobiles, and can be suitably used as a gas generating source of an air bag system mounted on various transportation devices.

_ The best form to harm the invention Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Test Examples. The manufacturers of the raw materials used below are as follows unless otherwise specified.

Biscanolenomoisolehydrazine (BCH): manufactured by Otsuka Chemical Co., Ltd.

Azoji Carbon Amide (ADC): Otsuka Chemical Co., Ltd.

Potassium nitrate: Otsuka Chemical Co., Ltd.

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

Silicon dioxide: Nippseil NPS, trade name, manufactured by Nihon Silica Industry Co., Ltd.

Soluble starch (starch): First-class reagent, manufactured by Wako Pure Chemical Industries, Ltd.

CuO: specific surface area 48 m ² Z g and average particle size about 7.4 m. JGC Chemicals, Inc.

Mo03: Japan Inorganic Chemical Industry Co., Ltd.

In the following, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Example 1

45 parts of bismuth hydramoyl hydrazine, 72.1 parts of perchloric acid lime, 10 parts of potassium nitrate, M 0 ₃ 10 parts and One part of each powder of silicon dioxide is mixed well, and a 20% aqueous solution of soluble starch is added to the mixture so that the starch content becomes 3.5 parts. Powder was produced. This wet powder is granulated by a granulator, and the obtained wet granules are dried and further pressed by a hydraulic tableting machine to form a pellet (diameter 6 mm) of a gas generating agent. , With a thickness of 3 mm and a weight of 0.15 g).

Example 2

The amount of perchloric acid value Li U beam was changed to 6 7.7 parts, except that use C u O l O unit in place of the且one M o 0 _3, the same procedure as in Example 1 A pellet of the gas generating agent of the present invention was produced.

Comparative Example 1

§ zone di Ca Rubo N'a mi de 4 5 parts, perchloric oxide Li c arm 5 6.3 parts of 1 0 parts nitrate Ca Li c arm, each powder of 1 part of silicon dioxide and M o 0 ₃ 6 parts Then, a 10% aqueous solution of soluble starch was added to the mixture so that the starch content became 1.5 parts, and further mixed to produce a wet powder. The wet powder is granulated by a granulator and dried, and then pressed by a tableting machine to form a pellet of a gas generating agent (diameter 6 mm, thickness 3 mm, weight 0%). . 15 g).

Test example 1 Example of a combustion chamber equipped with a gas exhaust hole with a diameter of 7 mm and filled with 0.8 g of Boron Z sodium phosphate as a transfer medium A 0.3 mm-thick aluminum cup filled with the gas generating agent pellets obtained in Examples 1 and 2 and Comparative Example 1 was loaded. This inflator is placed in a 60 liter tank and is operated by passing an electric current to burn the pellets of the 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-litre tank after combustion is sampled from a sampling hole into a 1-litre bag, and the C0 concentration and λ'0X concentration in the gas are detected. It was measured using a tube. Table 1 shows the results.

The English symbols in Table 1 have the following meanings.

C P max: the maximum pressure (kg i Z cm ^ a) in the combustion chamber

TP max: The maximum pressure (kgf Z cm ² ) within the 60-litre tank. This parameter indicates the gas generating capacity of the gas generating agent.

tTPMaX: Time required for the pressure in the 60 litre tank to reach its maximum (msec). A parameter that simulates the deployment speed when the airbag is deployed.

t TP 90: Time required for the pressure in the 60 liter tank to reach 90% of the maximum value (msec:). Airbag Parameter that simulates the deployment speed when

table 1

From Table 1, it can be seen that the gas generating agent of the present invention has the same combustion rate as the gas generating agent using azocarbonamide as the gas generating base, and the toxic components such as CO and NOX in the post-gas. It can also be seen that the concentration of Hb is as low as the same.

Comparative Example 2

Manufacture of a pellet of a gas generating agent in the same manner as in Example 2 except that azozinolamide is used instead of viscanoleva moisolehydrazine. did.

Test example 2

The pellet of the gas generating agent obtained in Example 2 was stored in a thermostat at 107 ° C. for 400 hours, and the residual weight ratio (%) was calculated. The extent of decomposition was investigated. Example 97/12849

33

The gas generating agent of No. 2 had a residual weight ratio of 99.5% or more, and it was confirmed that the bismuth rubamoinolehydrazine was not substantially decomposed.

On the other hand, also for the gas generating agent of Comparative Example 2, the residual weight ratio (%) was examined in the same manner as described above except that the storage time was set to 190 hours. The residual weight ratio was 75%. there were. Despite the storage time being less than half of the pellet of the gas generating agent of the present invention, the decomposition power of azodicarbon amide, and the fact that it has progressed considerably. I understand.

From the above results, it is clear that the gas generating agent of the present invention has much higher thermal stability than the gas generating agent using azodicarbonamide as a gas generating base. is there.

Test example 3

The combustion temperatures of the gas generating agents of Example 2 and Comparative Example 2 were measured using NASA's thermal equilibrium calculation program (B, J, McBride, 'CET89-Chemical Equilibrium with Transport Properties, 1989 Com ", COSMIC Program itLE W-15113 (1989). ), NASA, hereinafter, this program is referred to as “CET89”.) Based on the simulation calculation, the gas generating agent of Example 2 was about 210 1 The amount of the gas generating agent of Comparative Example 2 was about 2300Κ.

As described above, the gas generating agent of the present invention is preferably azodicarbon. It can be seen that the combustion temperature is about 200 K lower than the gas generating agent using amide as the gas generating base.

Example 3

A pellet of the gas generating agent of the present invention was produced in the same manner as in Example 1 except that the components were used in the amounts (parts) shown in Table 2 below.

Table 2

Test example 4

Using each of the pellets of the gas generating agent of the present invention obtained in Example 3, the same operation as in Test Example 1 was performed to determine the combustion performance of the gas generating agent, the C 0 concentration in the post-gas, and the N 0. The X concentration was determined.

Table 3 shows the results.

T / 96/02796

35

Three

From Table 3, it can be seen that the gas generating agent of the present invention has excellent combustion performance and a low C◦ concentration and NO X concentration in the post-gas.

Example 4 and Comparative Example 3

A pellet of the gas generating agent of the present invention was produced in the same manner as in Example 1 except that the components were used in the amounts (parts) shown in Table 4 below. In Table 4, the gas generating agents of Nos. 1 to 18 correspond to Example 4, and the gas generating agents of Nos. 19 to 20 correspond to Comparative Example 3 (German Patent Publication No. 1995). 1618-18).

Four

Test example 5

Using each pellet of the gas generating agent of the present invention obtained in Example 4 and Comparative Example 3, the same operation as in Test Example 1 was carried out, and the combustion performance of the gas generating agent and the C0 concentration in the gas were used. And N ◦ X concentration. Table 5 shows the results. Sample CPmax TPmax tTPmax tTP90 Ttemp.CO C〇 ₂ NO x

No.Amount (g) Kgf / cm ² msec ° C%% ppm

1 40 120 1.3 64 34 95 0.41 7.0 2500

2 40 104 1.0 115 57 78 0.34 6.8 2750

3 40 80 0.8 201 77 67 0.36 6.2 3500

4 40 88 1.2 76 36 87 0.37 8.0 1450

5 40 118 0.9 384 82 0.52 7.1〉 1200

6 40 46 0.7 24 16 56 0.68 7.7 1280

7 40 194 0.9 159 60 67 0.58 7.6 1500

8 40 158 0.6 1364 1 57 0.47 6.7 1700

9 40 1 丄 18 1 1 74 26 80 0.52 7.4 1050 in 35 122 1.2 21 13 77 0.37 7.3 950

11 40 194 1.4 19 10 60 0.47 7.5 370

12 40 106 0.9 35 49 0.82 6.5 980

13 40 162 0.4 22 1 35 1.02 5.8 1650

14 40 196 1.4 19 9 86 0.38 6.7 1050

15 40 120 1.3 23 14 63 0.37 8.5 950

16 40 204 1.8 27 8 72 0.27 9.0 1200

17 40 82 0.7 16 12 52 0.60 6.9 800

18 40 122 0.8 23 14 65 0.61 9.0 700

19 40 86 0.1 42 33 0.35 2.0 200

20 40 100 <0.1 25 0.16 1.2 120 The gas generating agent of Comparative Example 3 (No. 19 to 20) has remarkably low TP max power of 0.1 lkgi Z cm ² or less, and C 0 _{It is} clear that incomplete combustion has occurred from the power of 2%, '2.0% or 1.2%. Example 5 and Comparative Example 4 Each component was used in the amounts (parts) shown in Table 6 below. By operating in the same manner as in Example 1, the pellet of the gas generating agent of the present invention (Example 5) and the pellet of the gas generating agent described in Japanese Patent Application Laid-Open No. Hei 7-303383 (the Comparative Example 4) was produced. The following tests were performed on these gas generating agents. Table 6 shows the results.

1) Thermochemical calculation temperature ("Tc one")

The thermochemical calculation temperature (adiabatic flame temperature) of the gas generant was calculated based on the NASA thermal equilibrium calculation program (CET89) and used as a guide to know the combustion temperature.

2) D S C exothermic decomposition onset temperature (referred to as “T DSCJ”)

Exothermic decomposition onset temperature of D S C (differential scanning calorimetry)

(T DSC) was measured to determine the thermal stability of the gas generant. The thermal stability of the gas generating agent for air back is measured by maintaining the inflator loaded with the gas generating agent at 107 ° C for 400 hours and then operating the gas generator. The generation performance is evaluated based on the fact that it is the same as before heating. Force according to this method As already shown in Test Example 2, the canister was filled with a gas generating agent and kept at 107 ° C for 400 hours to reduce the amount of the gas generating agent. This is a method to evaluate weighing and thermal stability (heating loss test).

The present inventor has developed a correlation between the results of the weight loss test and the exothermic decomposition onset temperature (T DSC) of DSC (differential scanning calorimetry). And found that if the T DSC was 473 K or more, it passed the weight loss test on heating, and based on this finding, evaluated the thermal stability of the gas generating agent.

3) Strand burning rate test (referred to as “r”)

The gas generating agent was molded into a square rod-shaped strand of 7 mm in length and 3 O mm in length, and a restrictor was applied except for the upper end to prepare a sample body. This sample was burned in a pressure vessel with an internal volume of about 1 liter under nitrogen pressure (70 kg Zcm ² ), the time-pressure curve was recorded, and the linear burning rate (mmsec) was measured. It was calculated. The detonation tends to increase as the linear burning rate increases.

4) Detonation test

The detonation propagation of the gas generant was determined by a UN recommendation gap test. A sample (gas generating agent) is filled in a drawn steel pipe with an inner diameter of 40 mm and an outer diameter of 48 mm, and 160 g of pentelite (PETNZTNT = 550) at the lower end. A No. 6 detonator was attached, and a mild steel plate of 100 111 111 100 101 3 mm (thickness) was placed at the upper end as a proof plate. The No. 6 detonator was energized to detonate the detonator and the explosive. The fact that the sample propagated through the explosion forest was judged based on the fact that the steel pipe was broken. The non-detonation was judged based on the fact that the steel pipe did not become fragments and the unreacted sample remained. 6 Example 5 Comparative Example 4

B C H 1 6.8 3 7.0

Potassium nitrate 6 4.2

Silicon dioxide 14.0

Soluble starch 2.0

Boron 3.0

Perchloric acid power room 61.0

T c (K) 1 6 7 9 2 3 7 1

T DSC (K) 5 3 8 O Ό

O

r (mms) 20.4 (7. OMPa) Explosive forest Unexploded explosion Explosion Table 6 shows that the gas generating agent of the present invention has a low combustion temperature, good thermal stability, and no detonation. In addition, it is clear that it has the favorable property of sustaining combustion. On the other hand, the gas generating agent described in Japanese Patent Application Laid-Open No. 7-300383 has an appropriate burning rate and good thermal stability, but has a high burning temperature and explosive forest properties. I have a problem. Example 6 Pellets of the gas generating agent of the present invention were produced by using the components in the blending amounts (parts) shown in Table 7 below and operating in the same manner as in Example 1 to produce a pellet of the gas generating agent of the present invention. For the generator, calculate the thermochemical calculation temperature (Tc) of the gas generator based on the thermal equilibrium calculation program (CET89) of NASA in the same way as in Example 5, and calculate the DSC exothermic decomposition temperature (Tc). T DSC) measurement and strand A burning rate test (referred to as “r”) was performed. The results are shown in Table 7.

Table 7

Example 7

29 parts of hydrazodicanolone amide, 44 parts of potassium nitrate, 13 parts of silicon dioxide, 12 parts of potassium perchlorate, 5 parts of combustion catalyst shown in Table 8 and starch The exothermic decomposition onset temperature (T DSC) of DSC was measured and a strand test was performed on the gas generating agent consisting of three parts in the same manner as in Example 5. The results are shown in Table 8.

Table 8

Table 8 or et al., Combustion catalyst, Ri in particular by the added Caro M o 0 ₃ and C u 0, Ru this TogaAkira Rakadea the combustion speed increases.

Example 8

Gas generator consisting of hydrazodicarbonamide, potassium nitrate, potassium perchlorate, silicon dioxide, starch, and a combustion regulator with the composition (parts by weight) shown in Table 9 As for Example 5, the thermochemical calculation temperature (Tc) was calculated based on the thermal equilibrium calculation program of NASA (CET89) and a strand test was performed in the same manner as in Example 5. The results are shown in Table 9.

Table 9

From Table 9, it is clear that the addition of a combustion regulator, especially Zr, A1, Ti, etc., improves the combustion rate. Reference example 1

Disperse 70 g of biscanolenomoisolehydrazine in 630 ml of water, and add 1.668 g of sodium aluminate ( For hydra hydrazine as an ano mina 1 %) In 70 ml of water was added dropwise over 8 minutes with stirring. Further, sulfuric acid (a solution obtained by adding 15 parts of water to 1 part of concentrated sulfuric acid) was added dropwise with stirring, and the pH was adjusted to 60 over 60 minutes. After stirring for 30 minutes, sulfuric acid was added dropwise to readjust the pH. The solid (Bisubarumylhydrazine) is filtered off and washed with water.

Remove sodium sulfate generated by pH adjustment.

It was dried at 120 ° C for 1 hour and crushed (10 mesh) to produce a modified bismuth rubamoyl hydrazine. It is presumed that the modified bisphenol Luba and Moylhydrazine were adhered in a specific state to the surface of the aluminum hydroxide, Biskanolevamoylhydrazine generated by neutralization. Is done. The BET specific surface area of this modified bis-potassium hydramoylhydrazine is 3.38 m ² Z g, which is remarkably increased compared to that before the treatment (0.20 m ² Z g). Was.

Comparative Reference Example 1

70 g of biscanoleno's hydrazine hydrazine and 1.07 g of hydroxyaluminum (neutralizes 1.68 g of sodium aluminum phosphate) The theoretical amount of aluminum hydroxide produced by this is mixed.

Comparative Reference Example 2

70 g of biscarnoyl hydrazine and aluminum 0.7 2 g (theoretical amount of aluminum formed by heating 0.7 g of aluminum hydroxide to 200 ° C or more)

Test example 6

Modified bis-carpa 'molyhydrhydrazine of Reference Example 1, Bis-force molyhydrhydrazine of Comparative Reference Examples 1-2, and untreated bis-force molyhydrhydrazine Each 0.3 g of the gin was put into a mold (manufactured by Ishihi Seisakusho Co., Ltd.) with a diameter of 10 mm and a depth of 7 mm, and the punch was set. Lett was manufactured. These pellets are used as a hardness tester (trade name)

: ANDESSTESTERKHT-20N, manufactured by Fujiwara Seisakusho Co., Ltd.), and apply a load to the pellet. The load at the time when the pellet collapses is used to harden the pellet. It was decided. The hardness was measured several times and the average value was calculated. The results are shown in Table 10.

Table 10

In Table 10, "R" indicates the difference between the maximum value and the maximum value / J in the measurement. Table 10 By applying surface treatment to bismuth rubamoinolehydrazine, it is possible to mix biscarbamoinolehydrazine with a surface treatment agent without treatment or simply It is evident that the formability of the screw-powered Lubamoyl hydrazine is significantly improved as compared with the conventional case.

Example 9

45 parts of the modified bis-forced rubamoinolehydrazine of Reference Example 1, 72.1 parts of potassium perchlorate, 10 parts of potassium nitrate, 5 parts of molybdenum oxide and 5 parts of dioxide 1 part of silicon powder was mixed well, and then a 20% aqueous solution of soluble starch was added so that the starch content became 1.5 parts, and the mixture was further mixed. Was manufactured. This wet powder is granulated by a granulator, the obtained wet granules are dried, and further pressed by a hydraulic tableting machine, and a pellet of a gas generating agent for an air bag is formed. 6 mm in diameter, 3 mm in thickness, and 0.15 g in weight) were manufactured.

Example 10

Example 9 was repeated in the same manner as in Example 9 except that the amount of potassium perchlorate was changed to 67.7 parts and 10 parts of copper oxide was used instead of molybdenum oxide. A pellet of a gas generating agent for the invention airbag was manufactured.

For comparison, operate in the same manner as in Example 9 except that unmodified bis-canolebamoinolehydrazine was used. A pellet of gas generating agent (diameter 6 mm, thickness 3 mm, weight 0.15 g) was manufactured.

Test example 7

In the combustion chamber of an inflator equipped with a gas outlet of 7 mm in diameter and charged with 0.8 g of boron Z potassium nitrate as a transfer medium, Examples 9 to 0.3 mm thick plate filled with a pellet of gas generating agent and a pellet of gas generating agent manufactured using unmodified screw-powered rubamoinolehydrazine. A mini cup was loaded. This inflator is installed in a 60-litre tank, and is operated by passing an electric current to burn the pellet of gas generating agent, and the inflator is operated. Measurements of the pressure and temperature in the tank and in the 60-litre tank yielded comparable results for all of them. In addition, the gas in the 60 liter tank after combustion is sampled from the sampling hole into a 1 liter driver bag, and the C0 and N0X concentrations in the gas are detected. As a result, the same results were obtained for each of them.

Reference example 2

Visible Luba Moylhydrazine (manufactured by Otsuka Chemical Co., Ltd., BET specific surface area: 0.20 m ² / g, median diameter;

45.43 m, same hereafter) Disperse 100 g in 1 liter of water, and stir with stirring to this. 25 ml of a 10% aqueous solution of the above was added, and mixed at 50 ° C. for 2 hours under a vigorous force. The agitation was stopped, and the precipitated viscous Rubamoyl hydrazine was collected by filtration and dried at 80 ° C. for 1 hour to produce a modified biscalvamoyl hydrazine.

Reference example 3

Disperse 100 g of bisphenol hydrazine hydrazine in 1 liter of water, and stir with stirring to add 10% aqueous solution of carboxymethylcellose 2.5 g, tallinoleic acid 1 ml (about lg) and azobisvaleric acid 0.5 g were added, and mixed for 2 hours while heating to 80 ° C. The stirring was stopped, and the precipitated bismuth rubamoyl hydrazine was collected by filtration and dried at 80 ° C for 1 hour to produce a modified bismuth rubamoyl hydrazine.

Example 1 1

45 parts of modified bis-powered rubamoyl hydrazine of Reference Example 2, 72.1 parts of potassium perchlorate, 10 parts of potassium nitrate, 5 parts of molybdenum oxide and 5 parts of dioxide Mix well each powder of 1 part of silicon, add 20% aqueous solution of soluble starch so that the starch content becomes 1.5 parts, and further mix. Was manufactured. The wet powder is granulated by a press and then pressed by a hydraulic tableting machine to form a pellet of gas generator for airbag (diameter 6 mm, thickness 3 mm). , Weighing 0.15 g). Example 1 2

In the same manner as in Example 11 except that the modified screw power of Reference Example 2 was replaced with that of Reference Example 3 in place of the rubamoin hydrazine hydrazine, the pelletizing agent for the airbag gas generating agent was used. A tut was manufactured.

For comparison, a pellet of a gas generating agent for an air bag was manufactured in the same manner as in Example 11 except that untreated biscanolebacyl hydrazine was used.

Test example 8

Example 11 Pellets of three types of airbag gas generating agents obtained using 1 to 12 and untreated screw power Lubamoyl hydrazine were respectively applied to a hardness tester (product Name: HARDNESSTESTERKHT — 20 N, manufactured by Fujiwara Seisakusho Co., Ltd.), and apply a load to the pellet. The load when the pellet collapses Hardness. The hardness was measured several times and the average value was calculated. Table 11 shows the results.

Table 11

Test example 9 Example 11 A combustion chamber equipped with a gas outlet of 7 mm in diameter and filled with 0.8 g of boron / potassium nitrate as a transfer medium was installed in an infra-red combustion chamber. 0.3 mm-thick aluminum cutlet filled with 40 g of a pellet of a gas generating agent obtained using 〜12 and untreated screw-powered rubamoyl hydrazine. Was loaded. This inflator is installed in a 60-litre tank, and is operated by applying an electric current to burn a pellet of the gas generating agent. Measurements of the pressure and temperature in one tank and 60 liter tank yielded similar results for all of them. After burning

The gas in the 60 liter tank was sampled from a sampling hole into a 1 liter driver bag, and the c0 concentration and N0X concentration in the gas were measured using a detector tube. At the same time, similar results were obtained for all of them.

Reference example 4

Bi scan mosquito Runokumo Lee Sole arsenide de la di emissions (average particle size 5 2 m, BET specific surface area 0. ² m 2 Z g, Otsuka Chemical Co., Ltd.), mosquitoes c te over di E Tsu DOO Crushed with minole. The grinding conditions using a counterjet mill are air pressure 6.5 kgΪ / cm, rotation speed 1500 rpm, and feed rate 5 kgZ. Thus, the average particle size 2 ^ m, BET specific surface area

8.0 m ² / g powdered bismuth rubamoyl hydrazine ie.

Reference example 5

On a granulator (trade name: High Speed Mixer, manufactured by Fukae Kogyo Co., Ltd.) 100 g of the finely powdered bis-carbo-mono hydrazine obtained in Reference Example 4 Then, 20 顆粒 1 of water was gradually applied to generate granules. The granules were dried at 80 ° C. for 1 hour to produce granules of fine powdery bismuth rubamoinolehydrazine having an average particle diameter of 0.3 mm.

Example 13

45 parts of fine powdered bis-forced bamoyl hydrazine of Reference Example 4, 72.1 parts of potassium perchlorate, 10 parts of potassium nitrate, 5 parts of molybdenum oxide and One part of each powder of silicon dioxide is mixed well, and a 20% aqueous solution of a soluble starch is added thereto so that the starch content becomes 1.5 parts, and further mixed. A wet powder was produced. This wet powder is granulated by a granulator, and further pressed by a hydraulic compression molding machine, and a pellet of a gas generating agent for airbag (6 mm thick, 3 mm thick) , Weighing 0.15 g).

Example 14

In the same manner as in Example 13 except that the granules of Reference Example 5 were used instead of the fine powdered viscous lipa'moylhydrazine of Reference Example 4, a gas generating agent for an airpack was used. Manufactured pellets, For comparison, the same operation as in Example 13 was carried out except that unground pulverized bis-carbanol moist hydrazine was used in place of the finely powdered bis-rubber hydrazine hydrazine of Reference Example 4. To produce pellets of gas generating agents for air packs.

Test example 10

The pellets of the gas generating agents of Examples 13 to 14 and the pellets of the gas generating agent obtained by using the unmilled screw power Lubamoyl hydrazine were respectively used as hardness testers (products). Name: HARDNESSTESTERKHT — 20 N, manufactured by Fujiwara Seisakusho Co., Ltd.), apply a load to the pellet, and apply the load when the pellet collapses It was decided. The hardness was determined several times, and the average value was calculated. The results are shown in Table 12.

Table 1 2

Test example 1 1

Examples 13 to 1 were installed in the combustion chamber of an inflator equipped with a gas outlet of 7 mm in diameter and charged with 0.8 g of boron nitrate as a transfer medium. Pellet of gas generating agent and

>-1

δ 52 0.3 mm thick aluminum cup filled with 40 g of a gas generating agent pellet made from unmilled screw-powered Lubamoyl hydrazine did. This inflator is placed in a 60-litre tank, and is operated by passing an electric current to burn a pellet of a gas generating agent. Measurements of the pressure and temperature in the tank and in the 60-litre tank yielded comparable results for all of them. In addition, the gas in the 60 liter noretank after combustion is sampled from a sampling hole into a 1 liter driver bag, and the 0 C0 concentration and NOX concentration in the gas are detected using a detector tube. As a result, similar results were obtained for all of them.

2 0

Claims

The scope of the claims

(1) Bis-powered balbamoinolehydrazine as a gas generating base, (2) oxohalogenate as an oxidizing agent, (3) nitrate as an oxidizing agent, and (4) A gas generator for airbags containing a combustion catalyst as an active ingredient. Claim 1 further includes a combustion regulator

Three

The gas generating agent for airbags described.

(1) Biscarnomoyl hydrazine as a gas generating base, (2) oxohalogenate or nitrate as an oxidizing agent, and (3) Combustion catalyst as active ingredients. Gas generator for airbags.

4. The gas generating agent for airbags according to claim 3, further comprising a combustion regulator. Screw force Lubamoyl hydrazine force, force that has been surface-treated with an inorganic surface treating agent, force that has been surface-coated with a hydrophilic polymer compound or a crosslinked product thereof, or has been pulverized The gas generating agent for airbags according to claim 1 or 3, wherein A group consisting of a metal oxide of the fourth to sixth cycles of the periodic table, an oxygen-containing metal compound capable of producing the metal oxide by heating, and heteropolyacid; Claim 1 or Claim 3 which is at least one member selected from the group consisting of: Gas generating agent for webbing.

7. The airbag according to claim 1, wherein the blending amount of the combustion catalyst is 0.5 to 30 parts by weight with respect to 100 parts by weight of the total amount of the gas generating base and the oxidizing agent. Gas generating agent for rugs. 8. The airbag according to claim 3, wherein the blending amount of the combustion catalyst is 10 to 150 parts by weight based on 100 parts by weight of the total amount of the gas generating base and the oxidizing agent. Gas generating agent for rugs. 9. The combustion modifier is a simple metal selected from B, Al, Mg, Ti, Zr and Mo, and the second to third periodic elements of the periodic table (alkali metals and alkaline earth metals) Oxides, hydroxides, carbonates, bicarbonates, alkali metal carbonates, bicarbonates, oxides, alkaline earth metal carbonates, bicarbonates, other periods At least one selected from the group consisting of chlorides, carbonates, sulfates, cellulose compounds, organic polymer compounds, and organic carboxylic acids of the 4th to 6th periodic elements The gas generating agent for an air bag according to claim 2 or 4, which is a kind.

10. The airbag gas generating agent according to claim 1 or 3, which is formed into a granule having a particle size of 0.3 to 1.5 mm.