WO1994001381A1

WO1994001381A1 - Gas generating agent for air bags

Info

Publication number: WO1994001381A1
Application number: PCT/JP1993/000634
Authority: WO
Inventors: Tadao Yoshida
Original assignee: Nippon Koki Co., Ltd.; Daicel Chemical Industries, Ltd.; Otsuka Kagaku Kabushiki Kaisha
Priority date: 1992-07-13
Filing date: 1993-05-13
Publication date: 1994-01-20
Also published as: EP0607446A1; EP0607446A4; DE69323410D1; KR100242401B1; EP0607446B1; DE69323410T2; CA2115557C

Abstract

A gas generating agent for air bags which consists of a nitrogen-containing organic compound and an oxohalogenate, has a high impact ignitability, a high combustion rate and a high gas generation rate, and can attain a comparatively low combustion temperature.

Description

Specification

Gas generating agent for air bag

Technical field

The present invention relates to a gas generating agent for an airbag.

Background technology

When a car or other vehicle collides at a high speed, a nylon mounted inside the handle or dash board to prevent the occupant from colliding with the handle or front glass of the vehicle and causing injury or death. The demand for a so-called airbag system, in which the safety bag inflates upon sensing a collision, is increasing dramatically as the demand for safety of automobiles and the like increases further.

In an airbag system, the gas generator is ignited and burned instantly after the collision is sensed by electrical or mechanical ignition, generating gas and inflating the bag. Thus, the gas generating agent is usually used in the form of a pellet or a disk. It is essential that such a gas generating agent has an appropriate burning rate. If the combustion speed is low, the bag does not inflate instantly and does not serve as an airbag. On the other hand, gas generating agents are made of powdered raw materials and have impact ignitability. Impact ignitability refers to the ignition sensitivity to impact.If it is too sharp, it can be used in manufacturing processes such as mixing operations and molding processes. The explosion risk of the air becomes large, which is not desirable for safety. Therefore, it is desirable that impact ignitability be as low as possible.

It is also required that the gas generating agent does not have a very high combustion temperature. This is because airbags usually release gas inside after inflation and then contract to absorb the impact of an occupant's crash and help the occupant escape, but when the combustion temperature is high, it is released. The higher the gas temperature, the greater the risk of occupant burns, reduced functionality due to perforations in the bag, and burning of the bag causing a vehicle fire.

Conventionally, as a gas generating agent for airbags, sodium azide is used as a gas generating base, and for example, an oxidizing agent (TioO,

_{M n O 2, F e 2} 0 3, metal oxides such as C u O,

N a N 0 J, KN 0 0, C u (N 0 3) nitrates such as -

_{KC 1 0 4, N a C} 1 0 4 perchloric salts, such as, KC 1 0 ₃ -

Chlorates such as NaC1O3), metal reducing agents (Zr.

M g, A 1, T i, etc.], a cooling agent [N a ₂ CO _3,

_{K 2 C 0 3, C a} C 0,, F e S 0 4 , etc.], p H adjusting agent [such as iron sulfate], mechanical performance enhancing agent [M o S 2,

It is known to include additives such as KBr, graphite, etc.].

Gas generators based on the above-mentioned azure sodium are the main sources Since the raw gas is only nitrogen gas, it is widely used as a gas generator for airbags because of its excellent performance of moderate combustion rate and relatively low combustion temperature, but sodium azide There are the following problems.

(1) There is a risk of fire due to decomposition or combustion.

Therefore, there is a risk that a fire may occur during the manufacturing process (for example, when mixing with an oxidizing agent or during granulation of a drug product).

(2) Decompose to generate Na. When Na reacts with water, it generates hydrogen and ignites, and further emits toxic fumes, making it extremely difficult to treat.

(3) Reacts with oxidizing agent, Nan0, its derivative

It emits toxic components such as (NaOH), so care must be taken during manufacturing.

(4) It is said that the gas generated by the combustion or decomposition of sodium azide has a high nitrogen concentration and a very low concentration of toxic components, so there is no practical problem. It is desired that the concentration be further reduced.

(5) Crude sodium azide used as a gas generating agent has a hygroscopic property, and if it absorbs moisture, its combustion performance is reduced. Therefore, it is necessary to take measures to prevent moisture absorption.

(6) Because it is a toxic and dangerous substance, There is capital investment.

In view of the problem of the azified sodium, impact ignitability equal to or lower than that of the gas generator based on the azide sodium, and a combustion rate and gas equivalent or higher than that There is a demand for a gas generator for air bags that has a relatively low combustion temperature, has a low emission temperature, is less dangerous and less toxic than a sodium azide-based gas generator, and is less expensive. .

On the other hand, various attempts have been made to use a nitrogen-containing compound as a base for a gas generating agent. For example, a metal reducing agent such as Zr or Mg and an oxidizing agent such as perchloric acid or chloric acid or the like may undergo an oxidation-reduction reaction, and the generated heat may be used to burn the gas generating base. Proposed. As gas generating bases, smokeless explosives, nitrocellulose, azodicarbonamide, aminoguanidine, thiourea and the like are mentioned (JP-B-49-19734, Tokiko Sho 4 9 1

No. 211171). However, the burning rate by the above method is not sufficient for practical use for airbags. In addition, since the mixture of the metal reducing agent and the oxidizing agent has a very high impact ignitability, handling There is also a problem that the above danger is large. In addition, very high combustion temperatures are expected.

Japanese Patent Application Laid-Open No. 50-1188979 discloses azological Airbags composed of nitrogen-containing organic compounds such as Bonamide and Trihydrazinotriazine and oxidizing agents such as potassium permanganate, manganese dioxide, barium dichromate, and parium peroxide. Disclose gas generators, but when oxidizing agents such as potassium permanganate and manganese dioxide are used, their impact ignitability and burning rate are unsatisfactory. If an oxidizing agent such as palladium or parium peroxide is used, toxic components are generated in the gas.

An object of the present invention is to provide a gas generating agent for airbags having an impact ignitability equal to or lower than that of a gas generating agent based on sodium azide.

Another object of the present invention is to provide a gas generating agent for an air bag having a combustion rate and a gas generation amount equal to or higher than that of a gas generating agent based on sodium azide. It is in.

Another object of the present invention is to provide a gas generating agent for an air bag which does not have the above-mentioned disadvantages (1) to (6) of an azide compound.

Another object of the present invention is to provide a gas generating agent for an airbag having a low combustion temperature and a lower risk and toxicity than sodium azide.

Disclosure of the invention In order to achieve the above object, the present inventors have conducted intensive studies focusing on nitrogen-containing compounds which are extremely low in toxicity and risk of fire due to decomposition or combustion, and as a result, the heat generated by the oxidation-reduction reaction has been reduced. This is not a secondary reaction of burning the nitrogen-containing compound by utilizing it, but the reaction of the nitrogen-containing compound directly with a specific oxidizing agent, that is, an oxohalogenate, by utilizing the reducibility of the nitrogen-containing compound. Impact ignitability equivalent to or lower than that of sodium fluoride-based gas generating agents, equivalent or higher combustion speed and gas generation amount, and low combustion temperature that is sufficiently satisfactory for practical use can be achieved. I found this.

That is, the present invention relates to a gas generating agent for an airbag comprising a nitrogen-containing organic compound and an oxohalogenate.

In the present invention, a nitrogen-containing compound is used as a gas generating base. The nitrogen-containing compound is not particularly limited as long as it is an organic compound having a nitrogen atom in the molecule, and examples thereof include an amino group-containing organic compound, a nitramine group-containing organic compound, and a ditorosamine group. Organic compounds and the like can be mentioned. Specific examples of the organic compound having an amino group are not particularly limited. Razides (eg, acetate hydrazide, 1, 2— Tylhydrazine, Lauric hydrazide, Salicylic hydrazide, Oxalic dihydrazide, Carbohydrazide, Adipic dihydrazide, Sebacin Acid dihydrazide, dodecangio hydrazide, isophthalic hydrazide, methylcanolenozate, semicarno, zid, honolem hydrazide, 1, 2 — Diformylhydrazine) and the like. There is no particular limitation on the compound containing a nitramine group, but examples thereof include dinitropentamethylentramine, trimethylentrylenetroamine (RDX), and tetramethylamine. Examples thereof include aliphatic compounds and alicyclic compounds having one or more nitramine groups as substituents, such as lamethylentranitroamine (HMX). The organic compound containing a nitrosoamine group is not particularly limited. For example, a nitrosoamine group is used as a substituent such as dinitrosopentamethylenetetrathamine (DPT). To a plurality of aliphatic compounds and alicyclic compounds. Among these nitrogen-containing compounds, azodicarbonamide has been widely used, for example, as a foaming agent for resins, and has a low risk of fire and low toxicity, and therefore has a low risk of handling. Therefore, it is particularly preferable. One nitrogen-containing compound may be used alone, or two or more nitrogen-containing compounds may be used in combination. A commercially available nitrogen-containing compound may be used as it is. Nitrogen The shape and particle size of the elementary compound are not limited, and may be appropriately selected and used.

The oxidizing agent used in the present invention is an oxohalogenate. Known oxohalogenates can be used. Of these, halides, perhalates and the like are preferred, and their alkali metal salts are particularly preferred. Examples of the alkali metal halide include chlorate and sodium chlorate, sodium chlorate, potassium bromate, sodium bromate and the like. Salts and the like can be mentioned. Examples of the alkali metal perhalates include potassium perchlorate, sodium perchlorate, potassium perbromate and sodium perbromate. Chlorate and perbromate can be mentioned. One oxohalogenate may be used alone, or two or more oxohalogenates may be used in combination. The compounding amount of the oxohalogenate may usually be a stoichiometric amount capable of completely oxidizing and burning the nitrogen-containing compound on the basis of the oxygen content, but the compounding ratio of the nitrogen-containing compound and the oxohalogenate may be adjusted. By making appropriate changes, it is possible to arbitrarily adjust the burning rate, the burning temperature, the composition of the combustion gas, and the like. 20 to 200 parts by weight of oxohalogenate, preferably 30 to 200 parts by weight. You may mix | blend about 200 weight part. The shape and dimensions of the oxohalogenate are not particularly limited, and may be appropriately selected and used.

The composition of the present invention may contain, in addition to the above two essential components, at least one selected from a combustion control catalyst, a detonation inhibitor, and an oxygen generator as long as the performance of the composition is not impaired. Good.

Combustion control catalysts are one of the basic performances while maintaining safety performance such as low impact ignitability and non-detonating properties, or while maintaining the basic performance as a gas generating agent such as the amount of generated gas. This is a catalyst for appropriately changing the combustion rate, which depends on the purpose of use. Examples of the combustion control catalyst include oxides, chlorides, carbonates, sulfates, cellulosic compounds, and organic polymer compounds of the fourth and sixth elements of the periodic table. Can be. Oxides of Period 4 element and the sixth period elements of the Periodic Table of the Elements, chloride, is a specific example of carbonate and sulfate salts, e.g., Z n O, Z n C 03, M n 0 2 , and F e C, C u O, P b 3 0 i P b 〇 _{2, P b O, P b} 2 0 3, S, T i 0 2, V 2 0 5,

_{_{C e 0 2, H o 2}} 0 3, C a 0 2, Y b 2 0 3,

A 1 2 (SO ₄ ) ₃ , Z n S 0 ₄ , M n S 0 ₄ ,

Such as F e S 0 ₄ can be mentioned. Cellulose based Specific examples of the compound include, for example, carboxymethyl cellulose and ethers thereof, and hydroxymethyl cellulose. Specific examples of the organic polymer compound include, for example, soluble starch, polyvinyl alcohol and partially genated products thereof. As the combustion control catalyst, one type may be used alone, or two or more types may be used in combination. The blending amount of the combustion control catalyst is not particularly limited and can be appropriately selected from a wide range. Usually, it is preferably about 0.1 to 50 parts by weight based on 100 parts by weight of the total amount of the nitrogen compound and the oxohalogenate. Should be about 0.2 to 10 parts by weight. The particle size of the combustion control catalyst is not particularly limited, and may be appropriately selected and used.

Detonation inhibitors are added to prevent gas generating agents from being involved in a fire during a manufacturing, handling, or transportation process, or from detonating when subjected to a strong impact. If the detonation of the gas generating agent is eliminated by the addition of the detonating deterrent, the safety in each process of manufacturing, handling, and transporting the gas generating agent can be further enhanced. Known explosive inhibitors can be used, for example, oxides such as bentonite, alumina, diatomaceous earth, Na, K, Ca, Mg, Zn, Cu, Al, etc. Metal carbonate, bicarbonate and the like. Distribution of detonation inhibitor The total amount is not particularly limited and can be appropriately selected from a wide range. However, it is usually 5 to 30 parts by weight with respect to 100 parts by weight of the total amount of the nitrogen-containing compound and oxohalic acid.

Oxygen generator, the 0 ₂ concentration of the combustion product gas of the present invention the composition is effective to further increase. And an oxygen generating agent, in particular can be used known ones without limitation, for example, and the like _{_{C u 0 2, K ¾ 0}} 4. The amount of the oxygen generator is not particularly limited and can be selected from a wide range.However, if it is usually about 100 to 100 parts by weight based on 100 parts by weight of the total amount of the nitrogen-containing compound and the oxohalogenate, Good.

Further, the composition of the present invention may contain a combustion temperature regulator or a combustion rate regulator as long as its performance is not impaired. Examples of the combustion temperature regulator include Na, K, and Ca. And carbonates of metals such as Mg and bicarbonate. Examples of the burn rate regulator include sulfates such as A1, Zn, Mn, and Fe. The compounding amount of the combustion temperature regulator and the combustion rate regulator is, specifically, about 10 parts by weight, preferably 5 parts by weight, per 100 parts by weight of the total amount of the nitrogen-containing compound and the oxohalogenate. The range may not exceed about parts by weight.

Furthermore, the composition of the present invention has a range in which its performance is not impaired. Various additives conventionally used in gas generating agents for airbags may be included.

The composition of the present invention is produced by mixing the above components, and the resulting mixture may be used as it is as a gas generating agent, or may be used in the form of a formulation. Formulation is performed according to a conventional method. For example, an appropriate amount of the composition of the present invention and a binder may be mixed and molded. A binder that is commonly used for such a purpose may be used. The formulation is not particularly limited, and examples thereof include pellets, discs, spheres, rods, hollow cylinders, sugary sugars, and tetrapods. It may be porous (for example, briquette). Alternatively, the respective components of the composition of the present invention may be individually formulated, and these may be used as a mixture.

The composition of the present invention has the following advantages.

(a) The composition of the present invention has a very low risk of decomposing or burning and causing a fire, and has a very low toxicity. Formulation is easy.

(b) The composition of the present invention has impact ignitability equal to or lower than that of a gas generating agent based on sodium azide, and is extremely high in safety. (c) The composition of the present invention has a combustion rate and a gas generation rate equal to or higher than that of a gas generating agent based on sodium azide.

(d) Since the composition of the present invention has a relatively low combustion temperature, similarly to a gas generating agent based on sodium azide, it may cause burns to the occupants or holes in the bag. There is no danger of burning the package, and the amount of toxic components in the generated gas is extremely small.

(e) Since the nitrogen-containing compound, which is the gas base of the composition of the present invention, has no hygroscopic property, it is not necessary to take any measures to prevent moisture absorption.

(f) The composition of the present invention can be produced at a very low cost.

(g) The composition of the present invention is easier to dispose of than conventional gas generating agents.

BEST MODE FOR CARRYING OUT THE INVENTION

The following examples are provided to further clarify the present invention. In the following examples, the formal names of the compounds represented by abbreviations or chemical formulas are as follows.

A DCA: azodicarbonamide

D P T: Gini small mouth sopentamethylenthramine

R D X: Trimethylene Trinitrin Amin

HMX: Tetramethylentry Tranitromin NQ: Nitroguanidine

Example 1 A nitrogen-containing compound, an oxohalogenate and, if necessary, a combustion control catalyst were mixed in the proportions (% by weight) shown in Table 1 below to obtain a composition of the present invention (Nos. 1 to 17). Was.

ADCA (30% ZnO): ADCA containing 30% by weight of ZnO

ZnO mixture The aforementioned compositions of the invention N o:.! ~ Molding 1 7 a hydraulic tablet molding machine at 6 0 kg Roh pressed at a pressure of cm ² to Perez bets (the diameter 5 mm, height 5. 0 mm) And subjected to a 7.5-liter bomb test. Table 2 shows the results.

[Bomb test]

The procedure of the bomb test will be described below with reference to Figs.

1. A predetermined amount of a sample (a gas generating agent (9), a pellet of the composition No. 1 to 15 of the present invention) is weighed in a reaction vessel (1). There are two types of reaction vessels, large and small, large with an inner diameter of 50 111 111 and a height of 50 111 111 (FIG. 2), and small with an inner diameter of 30 mm × 50 mm in height (FIG. 3).

2. Attach a nozzle (10) of specified diameter and an aluminum rupture plate (1 1) (0.2 mm thick) to the reaction vessel.

3. Install the igniter (12) in the reaction vessel. The igniter is a mixture of 0.3 or 1.0 g of boron and K N O,

(2: 8) was wrapped in Saran wrap, and a Nichrome wire (13) (diameter 0.3 mm x length 100 mm) wound around the coil was passed through it.

4. Attach the lid to the reaction vessel, and attach the reaction vessel to the gas collection pump (2).

5. Attach ignition leg (4) to bomb lid electrode (5) O

6. Attach the bomb lid (3) to the bomb (2).

7. Connect the measurement system circuit.

8. After the countdown, ignite and record the time and pressure curves inside the reaction vessel and the temperature inside the bomb.

Table 2 Amount used Ignition container C Pmax Wl / 2 Β Ρ max Β Tmax

Να ^Τ 90

(g) (g) Large and small Nozzle diameter (kgf / cnf) (ms e c) (kgf / cnf) (msec) (° C)

1 5 0.3 Small 6mm> 140 ― 7.5 ― 400

5 1.0 Large 4mm 140 39 4.7 34 1 50

2 0.3 Small 6 mm 46 4.2 0 0.7 1 0 72

2 1.0 Small 6mm 140 7.2 4. 4 8 280

5 1.0 Large 6mm 1 00 29 4.8 28 225

5 1.0 Large 4mm 1 49 27 4. 6 26 249

2 5 1.0 Large 4 mm Approx. 1 34 ― 3.4 ― 1 76

3 51.0 Large 4mm 65 66 3.5 5.66 1 76

5 51.0 Large 4mm 74 42 4.8 84 366

6 51.0 Large 4mm 82 56 2.4 38 1 28

7 5 1.0 Large 4mm 54 54 2.3 49 147

"

8 51.0 0 6mm 54 22 4.7 5 1 1 92

1 2 5 1.0 Large 4mm 50 1 5 1. 4 25

1.0 0 4mm 65 1 5 1.6 20 7 6

1 3 5

5 1.0 Small 6mm 79 4 1.8 3 1 06

1.45 11.0 Large 4mm 1 40 2 9 5.6 1 8 264

1 5 5 1.0 Large 4mm 90 5 7 4.2 50 243

1.65 11.0 Large 8mm 1 20 1 0 6.0 0 1 0

1 7 5 1.0 Large 9mm 70 1 2 6.0 0 1 5

In Table 2, CP _max is the maximum pressure in the chamber (kgcm ² ), and W〗 1 / / 2 is the maximum pressure of the chamber 1

2 (msec), BP _ma . Is the maximum pressure in the _bomb (kg Z cm ² ), _T9Q is the time required for the pressure in the _{bump to reach 90} % of the maximum value (msec), BT _ma „ Means the maximum temperature reached in the _bomb (K g / cn ^) Of these parameters, T _9Q is a numerical value that simulates the airbag deployment time, and cp _max is the value of the present invention. An index that indicates that the composition maintains good performance as a gas generant w _1/2 is a parameter that simulates the speed of combustion of the gas generant in the chamber BP _max is a parameter that indicates the gas generating capacity of a unit mass of gas generating agent BT _ma „is a parameter that simulates the temperature of gas in the air bag when the air bag is deployed.

Example 2

The composition of the present invention was obtained by mixing the nitrogen-containing compound, the oxohalogenate, and, if necessary, the combustion control catalyst in the mixing ratio (% by weight) shown in Table 3 below.

The composition of the present invention was subjected to the following impact ignition test. For comparison, the current of the gas generating agent was subjected to the impact ignitability test _{(N a N 3 - C u} 0 KC 1 0 4 - - F e J 0 4 and N a N _3). (Impact ignition test)

This test is a method to measure the “easiness of ignition by impact (impact ignition sensitivity)” of the gas generating composition. The experimental procedure will be described below with reference to FIGS.

1. [Fig. 4]

Weigh 5 g of powder sample (16) into stainless steel container (15) for test. The stainless steel container (15) is a stainless steel cylinder with a bottom (SUS304), 31 mm in inner diameter, 36 mm in outer diameter, 2.5 mm in thickness, and 55 mm in height.

2. [Fig. 5]

Place the required thickness of polyethylene card (17) on the sample. The total thickness of the polyethylene card (17) is called the gap length.

3. [Fig. 6]

Drill a hole with a diameter of 6.5 mm in two lmm-thick polyethylene cards (18), insert a primer (19) into them, and set them in a stainless steel container (15). A No. 0 electric detonator manufactured by Nippon Kayaku Co., Ltd. was used as the detonator.

4. [Fig. 7]

In the case of a gas generating agent containing a hygroscopic gas generating base (for example, sodium azide), use a paraffin (20) with a stainless steel container (15) to prevent moisture absorption. Lid on top I do.

5. Fix the stainless steel container in a vise inside the explosion dome, and turn on electricity to explode the primer.

6. At this time, observe whether the sample ignites.

7. (Fig. 8)

If the gap length is 1 mm but no ignition occurs, use a 20 g powder sample (16), insert a D-type detonator (19) into the sample, and use a stainless steel container (15). Attach the screw cap (21) to the test. Using this method, even very low impact ignitable substances can ignite and burn or explode.

Table 3 shows the limit gap length at the time of ignition (ignition up to the gap length) and the limit gap length at the time of non-ignition (ignition beyond the gap length).

In this test, the longer the limit gap length, the higher the sensitivity to impact ignition. In other words, the longer the limit gap length for ignition, the higher the ignition sensitivity to impact and the greater the danger. Table 3

Table 3 (continued)

C

From Table 3, it can be seen that the impact ignition properties of the composition of the present invention are equivalent to or less insensitive to the current product, and have the same or higher safety as the current product.

Example 3

The composition of the present invention was obtained by mixing azodicarbonamide (hereinafter referred to as “ADCA”) and oxohalogenate and, if necessary, a combustion control catalyst in the mixing ratio (% by weight) shown in Table 4 below to obtain the composition of the present invention. Was.

The present invention Perez preparative composition in a hydraulic tablet molding machine at a pressure of 6 0 kg / cm ^L (diameter 7. 6 mm, height 3 mm) was molded into said 7. 5 Li Tsu Torubonbu test Provided. The results are shown in Table 4.

For comparison, the current gas generant (NaN, —CuO) was subjected to a 7.5 liter bomb test. The results are shown in Table 4-9.

In this 7.5-liter pump test, two 0.1 mm thick aluminum rupture plates were used to attach to the reaction vessel lid. Table 4

C

Example 4

Azojikarubon'a mi de 4 5 parts by weight of chlorine Sanna Application Benefits um 5 5 parts by weight and M n 0 ₂ 2. 7 pellet of the present invention sets Narubutsu consisting of five parts by weight (diameter 1 2. 3 mm x thickness 3 mm ) 20 g was put into a gas generating chamber for an automobile airbag, and this was attached to a pump with a pressure sensor and a capacity of 28.61. The Perez bets B- ignited using 1 g of KN 0 ₃ to burn the composition. At that time, the maximum pressure in the tank was 4.3 kgf / cm ² gauge, and the pressure rise time in the tank due to combustion of the composition was 50 milliseconds.

For comparison, the composition suggested in JP-B-49-221171, namely 200 parts by weight of azodicarbonamide, 90 parts by weight of sodium chlorate and 110 parts by weight of A 20 g of a pellet (diameter: 12.3 mm × thickness: 3 mm) of a gas generating composition composed of the following gas was subjected to the same tank test as described above. As a result, only rapid burning of the igniting agent was observed, and no rapid burning of the gas composition was observed. The maximum ultimate pressure of the tank was only 0.3 kgfcm ² gauge. Example 5 and Example 6

200 parts by weight of azodicarbonamide (hereinafter referred to as “ADCA” in the table below) and 90 parts by weight of sodium chlorate (NaClO ₃ ) were mixed to obtain a composition of the present invention. For comparison, a gas generating agent suggested in Japanese Patent Publication No. 49-221171 was manufactured. That is, 200 parts by weight of azodicarbonamide, 90 parts by weight of sodium chlorate and 10 parts by weight of Zr powder were mixed to obtain a comparative composition.

Each of these was formed into a pellet (diameter 5 mm, height 5.0 mm) in the same manner as in Example 1 and subjected to a combustion test of a steel pipe with a nozzle and an impact ignition test. At that time, the presence of a flame was also observed. The results are shown in Tables 5 and 6.

[Steel tube with nozzle combustion test]

1. Put 5 g of gas generating agent into a flame-resistant steel container (a cylinder with an inner diameter of 50 mm and a height of 50 mm), set a nichrome wire, and close the lid. The lid has a 7 mm diameter hole.

2. Apply a voltage of 10 V through the nichrome wire through the slider to ignite the gas generant.

3. White smoke first comes out of the hole, then ignites. The duration (flame time) of the flame from ignition to the extinguishing of the flame shall be measured and recorded visually and by video. Table 5 Gas emission compounding amount Oxyhalo compounding amount Combustion control compounding amount Gap length (dragon) Combustion Fire base (wt¾) Genoic acid salt (wt) Reduced catalyst (wt%) Ignition time Non-ignition time Yes No Example 6 ADCA 200 Na C 10 ₃ 90 6 8 18 seconds C, NO, comparison ADCA 200 Na C 10 ₃ 90 Zr 10 12 16 14 seconds

D

-4 Table 6 Gas generation compounding amount Oxyhalo compounding amount Combustion control compounding amount Combustion

Raw base (wt¾) Genate (ft¾) Node catalyst (wt¾) Time Yes No

Example 7 ADCA 200 Na C 10 ₃ 90 15 seconds No disaster

Comparison ADCA 200 Na C 10 ₃ 90 Zr 10 7 seconds Partial disaster

Table 5 shows that the addition of a metal reducing agent such as Zr increases the danger of gas generating agents. In addition, the reaction (combustion) of the composition of the present invention is performed without flame and at low temperature.

The comparative composition containing Zr becomes flammable and the temperature of the reaction product (gas) increases. Therefore, it is not preferable to add a metal reducing agent such as Zr, Al, or Mg to the composition of the present invention.

From Table 6, it can be seen that the comparative composition containing Zr was flammable and the temperature of the reaction product (gas) was high.

Example 7

This composition was subjected to a strand burner test (for example, “The Combustion Characteristics of Azide Trim-based Gas Generating Agents”, pp. 98-99, Abstracts of Lectures, 1992 Annual Meeting of the Japan Industrial Explosives Association, Japan). The test was conducted to examine the flammability.

1. First, 55 parts by weight of azodicarbonamide, 55 parts by weight of sodium perchlorate and 5 parts by weight of zinc oxide were mixed to obtain the present invention composition.

2. This composition is pressed into a prism (8 mm x 5 mm x 50 mm) (pressure: 1.25 t // cm ² ), and a restrictor is placed on the side of the prism. Samples were prepared by applying silicon resin.

3. For this test, a chimney-type strand combustion test device was used. Using. At the time of measurement, two holes (0.6 mm in diameter) were opened in the sample at intervals of about 40 mm, and the sample was fixed in the instrument through a fuse (0.5 mm in diameter).

4. After setting the test temperature (20 ° C) in this state, ignite with a nichrome wire from the top to burn the sample, and determine the burning rate ( mmZ seconds).

5. This measurement was performed under a pressure of 10, 20, and 40 kgf / cm ² .

The burning rate was 28.3 mmZ seconds at l O kgf Z cm ² , 37.9 mmZ seconds at 20 kgf / cm ² , and 46. O mmZ seconds at 40 kgf Z cm ² .

Example 8

The burning rate (mmZ seconds) of the composition of the present invention obtained by mixing 30 parts by weight of azodicarbonamide and 70 parts by weight of sodium perchlorate was obtained in the same manner as in Example 8 above. As a result, it was found that no ignition occurred at l O kgf Z cm ² and 48.3 mm nos at 40 kgf Z cm ² . Example 9

Pellet of the composition of the present invention obtained by mixing 45 parts by weight of azodicarbonamide, 55 parts by weight of potassium perchlorate and 10 parts by weight of copper oxide (diameter 12.3 mm x thickness 3 mm) 40 g was put into a gas generating chamber for an automobile airbag, and this was attached to a 28.6 liter bomb with a pressure sensor and an internal volume. The pellet was ignited with 3 g of B-KNO to burn the composition of the present invention. As a result, the conventional gas generator (N a N3: KCIO ^: F e 0 4 = 6 0: 1 0: 3 0) 2 same as obtained with 8 0 g 8. 6 Li Tsu Torubonbu The time-in-pressure curve was obtained.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1 is a longitudinal sectional view of a gas collecting bomb used for a bomb test. FIG. 2 and FIG. 3 are enlarged views of the reaction vessel installed in the gas collecting bomb. 4 to 7 are drawings showing the procedure of the impact ignition test.

1… Reaction vessel

2… Gas collecting bomb

3… Bomb lid

4… leg lines

5… Electrode

6 ... thermoelectric ^ τ

7… Pressure sensor

8 ... venting

9 ... gas generating agent

1 0… Nozzle Aluminum bursting plate

2 Ignition agent

3 nikrom wire

4 Pressure sensor

5 Stainless steel container 6 Powder sample

7 Polyethylene card 8 Polyethylene card 9

0 paraffin

1 Screw lid

Claims

The scope of the claims

1. A gas generator for airbags consisting of a nitrogen-containing organic compound and an oxohalogenate.

2. The gas generating agent according to claim 1, wherein the oxohalogenate is a halogenate and Z or a perhalogenate c.

3. The gas generant according to claim 1, wherein the halogenate is an alkali metal halide.

4. The gas generating agent according to claim 1, wherein the perhalate is an alkali metal perhalate.

0 5. The claim 1, wherein the nitrogen-containing organic compound is at least one selected from an amino group-containing organic compound, a dithramine group-containing organic compound, and a ditrosoamine group-containing organic compound. Gas generating agent.

6. The gas generating agent according to claim 1, wherein the nitrogen-containing organic compound is azodicarbonamide.

7. The gas generating agent according to claim 1, comprising at least one selected from a combustion control catalyst, a detonation inhibitor, and an oxygen generating agent together with the nitrogen-containing organic compound and the oxohalogenate.

208. The combustion control catalyst according to claim 7, wherein the combustion control catalyst is at least one selected from oxides, chlorides and carbonates of the fourth and sixth elements of the periodic table. Departure from gas Crude drug.

9. The gas generating agent according to claim 7, wherein the combustion control catalyst is at least one selected from a cellulosic compound and an organic high molecular compound.