DE2063586A1 - Gas-forming mass - Google Patents

Description

Asahi Easei Kogyo Kabushiki Kaisha 25-1, 1-chome, Dojimahamadori, Kitaku, Osaka, Japan

regarding gas-forming mass

Priority: December 26, 1969, No. 104298/69, Japan August 25, 1970, No. 73846/70, Japan

Due to the ever increasing number of traffic accidents, inflatable containers have recently been rapidly developed, used as a safety device to protect passengers in head-on collisions or rear-end collisions can be. These containers are intended to unfold from the folded form at the moment of the collision of the car and inflated to catch a human body moved by inertia and against it to protect the so-called secondary collision that causes the Impact of the human body against internal parts of a car 'forms. In this case, the gas source is used

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ORiGiNAL INSPECTED

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Inflating the container of liquefied gas, such as freon, Carbon dioxide and the like or a compressed gas such as nitrogen, air and the like is used. The liquefied Gas or the compressed gas is stored in a high pressure bomb used as a gas generating device, and if necessary, a sealing plate of the breaks The bomb and the gas, are introduced into the interior of the container and inflates it.

At present, however, this gas generating device is not put into practical use because of the following disadvantages: When the gas generating device is used to fill a container, it is that generated when the container is inflated Sound pressure level so high that the passengers' hearing is often damaged. Because the volume of gas in a container changes with temperature, the internal pressure of the container changes and, as a result, the pressure fluctuates Effectiveness of containers for shelting passengers due to the effect of the ambient temperature. aside from that there are difficulties in storage stability of the high pressure gas generating apparatus and on the large space requirements of a large-scale work- | tendency gas generating device that; in an automobile j should be carried. 'ι

On the other hand, attempts have been made to use explosives or flammable ' Masses to use. But if such masses

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or mixtures in a safety device are used, it is required that they operate the device safely, quickly and without generating a high level of noise inflate the inflammation pressure. In this regard, however, none of the known compositions are completely satisfactory.

It is therefore an object of the invention to use one to make suitable gas-forming mass accessible in a safety device, which causes a relatively rapid combustion reaction and a high one during combustion Generated amount of heat and a relatively large amount of gas without making a booming explosion sound. Another object of the invention is to provide a gas-generating composition which has low friction and impact sensitivity, so that it can be safely handled, can be transported and installed in a vehicle.

The invention provides a gas-forming mixture that is used to protect passengers in moving vehicles. This mixture according to the invention contains 10 to 80 percent by weight of a combustible component, which causes a rapid oxidation and reduction reaction, and 20 to 90 percent by weight of a gas-forming component, which can be one of the following products: smokeless powder, nitrocellulose,

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high molecular weight organic materials or compounds and easily decomposable organic substances.

By using the gas-forming composition according to the invention it is possible to get a container quickly and adequately with the highest level of security and at such a low one

Inflate sound pressure level at the moment of ignition, that no harmful effect is exerted on the passengers.

If one is traveling at a speed of 50 kin / h If the automobile hits an obstacle head-on, a passenger will pass through the vehicle within about 30 to 40 milliseconds Inertia thrown forward from his seat. Therefore, the gas-forming mass required to inflate the said Serving the container, have the ability to use the container, which -generally has a volume of less than 300 1, inflate with gas within about ^ 30 milliseconds.

The limit of the sound pressure level at the moment inflating the said container does not affect the passengers harms, is about 160 decibels.

The combustible constituents used according to the invention, the rapid combustion, that is to say an oxidation-reduction reaction cause include a mixture of at least one metallic reducing agent, '* "in particular Zircon, magnesium, boron, aluminum ", silicon, ferrosilicon,

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and at least one oxidizing agent, in particular potassium perchlorate, Potassium chlorate, potassium bromate, potassium nitrate, Ammonium perchlorate, barium nitrate, barium peroxide, lead tetroxide, lead peroxide, lead monoxide and lead chromate. The mixture may contain additive materials such as a binder and the like.

When used as a gas generating agent smokeless powder or nitrocellulose is used, 20 to 90 percent by weight (based on the weight of the mass) of the gas generating Means mixed with 10 to 80 percent by weight of the above combustible ingredient. Will the achieved mass or mixture ignited, it initiates a rapid combustion reaction, the one for rapid inflation of the container generates a sufficient amount of gas.

If the proportion of the combustible component exceeds 80% by weight, the amount of gas generated becomes insufficient, and if the proportion of smokeless powder or nitrocellulose exceeds 90 percent by weight, so will the burning rate is reduced. The practical one

The value of the composition according to the invention is therefore drastically reduced,

If the specified proportions are not adhered to. .

To high molecular weight organic materials, 'the: as a gas-forming agent' in the & ε £ indungsgemäßen suitable mixtures

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include one or more thermoplastic resins such as polyvinyl chloride, polyethylene, polystyrene, polyether, Polyvinyl acetate and the like, thermoplastic elastomers such as styrene-butadiene block copolymers and the like, thermosetting resins such as polyacetals, epoxy resins and the like and thermally curable rubbers, such as polyurethanes, polysulfides, polybutadiene, polybutadiene-acrylic acid copolymers and the same. Easily decomposable organic substances include one or more of the compounds Azodicarbpnamide, azoisobutyronitrile, aminoguanidines Hexamethylenetetramine, dicyandiamide and thiourea. These compounds are predominantly nitrogen compounds. By Use of these substances will produce a suitable gas evolution obtained during combustion. These materials can be used alone or in the form of mixtures will.

When a high-molecular organic material or an easily decomposable organic compound is used as a gas-generating Agent is used, the mixing ratio of the gas-generating agent to the combustible component has the value given above. However, mixtures are preferred the 20 to 50 weight percent of the combustible ingredient

and 50 to 8θί weight percent of the high molecular weight organic Material or the easily decomposable organic compound. If the proportion of combustible Ί

If the ingredient exceeds 80 percent by weight, an insufficient amount of gas is generated and exceeds that Proportion of the high molecular weight organic substance or the easily decomposable organic compound 90 percent by weight, so the rate of combustion is reduced.

The rate of gas formation and the amount of gas generated Gas from the gas-forming constituent of the composition according to the invention can optionally be in the direction of high speed can be varied by the mixing ratio of oxidizing agent, reducing agent and gas-generating agent is changed. When making the mass, these three ingredients are usually mixed together at the same time. However, it is also possible to prepare two different types of mixtures beforehand, consisting of one flammable component (a mixture of oxidizing agent and reducing agent) and a gas-generating agent (smokeless Powder, nitrocellulose, high molecular weight organic substance or easily decomposable organic substance) or from a flammable component (mixture of oxidizing agent and reducing agent) and a mixture of a gas-forming one Medium (smokeless powder, nitrocellulose, high molecular organic material or easily decomposable organic matter) and an oxidizing agent, and these two types are optional if necessary

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to mix. For more convenient handling and mixing, it is advantageous in this pail if the specified Mixtures can be shaped into grains with the help of a suitable binder. Furthermore, a flammable agent or a the combustion promoting agent, if necessary, with the specified Mixtures are mixed.

The gas-forming mass according to the invention is obtained by mixing the gas-forming agent with a component, the causes a combustion reaction in which no substantial amounts of gas are formed. By combining the gas heated to a high temperature, which is produced in the rapid combustion reaction of a metallic reducing agent occurs with an oxidizing agent and additionally through the reaction of smokeless powder, nitrocellulose, a high molecular weight .organic substance and an easily decomposable one organic substance generated gas, a container can quickly

be inflated.

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The gas-forming mass according to the invention is placed in a vessel filled and placed in a container. After a Another embodiment can be used to form cartridges or molded explosives can be deformed to any shape on which an electric ignition device and which are placed in a container. When the mass is ignited, it is swiftly Expansion of the reaction product, caused by the high

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The heat of formation of the rapid exothermic reaction is converted into gaseous form and this is achieved by combustion of the gas mixture A container is instantly inflated by means of generated gas. Due to the contraction of the gas due to the subsequent drop in temperature, the container pulls gradually together. If a passenger hits this container, so will the rebound force that the container acts on exerted on the passenger is reduced in this way, and the shock exerted on the passenger is also reduced. The use of the gas-forming composition according to the invention therefore has the advantage that "superior properties for Shock absorption and a low rebound force can be achieved. Since the gas-forming mass according to the invention by mixing a metallic reducing agent and an oxidizing agent with smokeless powder, nitrocellulose, high molecular organic matter or an easily decomposable one organic substance is produced, it does not lead to the formation of a loud explosion noise and the The sound pressure level at the moment of ignition is so low that it does not harm passengers.

Since _1, as mentioned, the gas formation reaction proceeds rapidly without the occurrence of a loud explosion noise in the gas forming mass, it is. possible, the ¹ inflation of a container

quickly with such a low sound pressure level

durchzufurirei) that the hearing of passengers is not 'damaged . becomes, if a container with the help of this gas-forming mass

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inflated. should.

Since the gas-forming mass according to the invention is a high-pressure bomb Eliminating the need, as applied to liquefied petroleum gas or compressed gas, can result in decreased effectiveness due to gas leakage during storage be avoided. Since the mass is also provided with a wrapper and a folded one in different places Can be arranged container, does not have to necessary installation space for the gas generating device are provided and the installation in a vehicle therefore very easy.

In addition, since the gas formed as the reaction product of the mass is a high temperature gas, the gas pressure becomes in the container not influenced by the ambient temperature. Therefore, the shock absorbing properties of the Container at a constant value without being affected by the outside temperature. . ·. ■ ·

The invention is illustrated in more detail by the following examples. In it all mean parts ^; and percentages

i I

Parts by weight and percent by weight *

example 1

■ - 'i'. ^j

In this example a mass of the following composition was used: ·>'. _]

■ ■ - 11 -

Zircon lead oxide (Plumbo-plumbi-oxide) Pb, 0, Chlorinated rubber

20 parts

79 parts. 1 part

To produce this mass, chlorinated rubber was first dissolved in toluene to produce a binder. That scored Binder was then added to the zirconium and lead oxide. These ingredients were mixed and the mass then granulated.

A gas-forming mass obtained by mixing 4 g of this granular product with 11 g of smokeless powder was filled in a tube made of polyvinyl chloride. After connecting to an igniter, the filled polyvinyl chloride tube mounted in a rubber bag that had an internal volume of 70.1.

After the ignition of the gas-forming composition by applying an electric current to the electric igniter, the rubber bag expanded within 2O ^- from milliseconds up to a sufficiently high volume. The sound pressure level at the moment of ignition was 125 decibels.

Example 2 In this example the following material was used:

Zircon

30 parts

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Lead tetroxide (Pb ₃ O ₄ ) 69 parts

Styrene-butadiene block copolymer 1 part

(Asahi Ka's trademark Toughprene is Kogyo Co. Ltd.)

The styrene-butadiene block copolymer was first made in toluene dissolved to make a binder. That. The binder obtained was then added to the zirconium and lead oxide. The mixture was kneaded and granulated. One by mixing 5 g of the granular mass with 10 g Gas generating composition containing nitrocellulose filled in a polyvinyl chloride pipe. After connecting to an igniter, the filled polyvinyl chloride tube mounted in a rubber bag with an internal volume of 70 l.

The gas-forming mass was then ignited by applying an electric current to the electric igniter and the rubber bag expanded to a sufficiently large volume within 30 milliseconds. The sound pressure level at the time of ignition was 113 decibels.

Example 3

In this example a mass of the following composition was used used:

Boron 20 parts

Barium peroxide 79 parts

Chlorinated rubber 1 part

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Using this composition, in In the manner described in Example 1, a granular mass was produced.

Three containers made of polyethylene were each loaded with one load of 5 g of a gas-forming mass provided by mixing 7 g of said granular agent with 9 g of smokeless powder. . The containers were provided with electric ignition devices, and then in a nylon fabric container, the surface of which was rubber-coated, with a Capacity of 70 1 attached. The gas-forming mass was then by applying an electric current to the electric igniter ignited and the container inflated to a sufficient within 29 milliseconds high volume. The sound pressure at the moment of ignition was 120 decibels.

Example 4

In this example a mass of the following composition was used used:

BoV 10 parts

Silicon. '5 parts

Lead tetroxide, 84 parts

St ^ rol-butadiene block copolymer 1 part

f (Toughprene trademark of. Asahi

■ Ka sei Kogyo Co. Ltd.)

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Using this mass, a granular agent was prepared in the manner described in Example 1. A gas generating mass obtained by mixing 8 g of the granular agent with 8 g of smokeless powder was obtained filled in a tube made of * polyvinyl chloride. The filled tube was fitted with an electric igniter and mounted in a nylon fabric container with a rubber-coated surface having an internal volume of 70 1 had. .

The gas-forming mass was then ignited by applying an electric current to the electric ignition device and the container was expanded to a sufficiently large volume in 28 milliseconds. Of the Sound pressure level at the moment of ignition was 120 Decibel.

Example 5

In this example a mass of the following composition was used:

Zircon 20 parts

Lead tetroxyd 79 parts

Chlorinated rubber 1 part

In the manner described in Example 1, using this mass produced a granular agent. One by mixing 10.5 grams of this granular agent

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gas-forming mass obtained with 4.5 g of nitrocellulose was filled in a polyvinyl chloride pipe. The tube was connected to an electric igniter and placed in a container made of rubber-coated nylon fabric which had an internal volume of 70 liters. the Gas-forming mass was then ignited by applying an electric current to the electric igniter and the container expanded to a sufficiently high volume within 18 milliseconds. The sound pressure level at the moment of ignition was 118 decibels.

Example 6

In this example the following two components were used:

Component A:

Ammonium perchlorate '90 parts

Polybutadiene 10 parts

Methylarylidenylphosphine oxide 0.35 parts

Epoxy resin 0.5 parts

Polyvinyl chloride powder 30 parts

Component B:

Boron 5 parts

Lead tetroxide. '' - 95 parts

Styrene-butadiene block copolymer 0.5 part

(Trademark Toughpreneder Asahi Kasei Kogyo Co. Ltd.)

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Components A and B were mixed separately and shaped into granular masses. After that, the two became grainy Completely mixed agent in a weight ratio A: B of 2: 1, a gas-forming mass being achieved 80 g of this gas-forming mass were put into a JPoIyäthylengefäß filled. The jar was connected to an electric igniter and placed in a nylon container mounted, which had an internal volume of 250 l. The gas-forming mass was then applied by applying an electric Ignited current to the electrical ignition device and the .Duration to expand and unfold the container and the Sound pressure level measured at the time of ignition. The container unfolded and expanded within 23 Milliseconds and the resulting sound pressure level was 138 decibels.

Example 7

In this example a mass of the following composition was used used:"

Barium peroxide 90 parts

Zircon 10 parts

⁽ Azodicarbonamide x 200 parts

Styrene-butadiene block copolymer 1 part

(Toughpreneder Asahi Kasei Kogyo Co. Ltd.) -. _v

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This mass was mixed thoroughly and then granulated. 80 g of this granular product was placed in a polyethylene jar filled. The filled vessel was connected to an electrical ignition device and placed in a nylon container with an internal volume of 250 1 attached. The gas generating mass was then applied by applying an electric Ignited current to the electric igniter and the duration of the deployment and expansion of the container and the sound pressure level measured. This duration was 25 milliseconds and it became a sound pressure level of 140 decibels noted.

Example 8

The following two components were used in this example:

Component A:

Lead tetroxyd 180 parts

Boron 5 parts

Styrene-butadiene block copolymer 0.5 part

(Asahi's trademark Toughprene

! 'Kasei Kogyo Co. 109830/0216 Ltd.) Parts - 19th Component B: Parts Polybutadiene - 14 Parts itoethylarylidenylphosphine oxide 0.5 Epoxy resin 1.5

The specified component A was mixed and made into one. ' deformed granular product. Then the component B was mixed, hardened and cut into small grains. the both granular products were thoroughly mixed together in a B: A weight ratio of 2: "1, with one gas-forming mass was achieved. 80 g of this gas-forming mass were poured into a container made of polyethylene. An electrical igniter was connected to the jar and then the jar was placed in a nylon container with a Internal volume of 250 1 assembled. Then the gas-forming mass was created by applying an electric current to the electric Ignition device ignited and the duration of deployment and the expansion of the container and the sound pressure level are measured. The measured duration was 22 milliseconds and the sound pressure level was 135 decibels.

Example 9
The mass used had the following composition:

Boron (B) 5 parts

Lead tetroxide (Pb ₃ O ₄ ) 95 parts styrene-butadiene block copolymer 1 part '(trademark Toughprene by Asahi

Kasei Kogyo Co. Ltd.)

The styrene-butadiene block copolymer was previously

. ■ ■ * t ■

position of a binder dissolved in toluene. That scored

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Binder was added to boron and lead oxide and after mixing the mass into a granular product granulated.

Smokeless "powder was made with this granular product too a gas-forming mass completely mixed, with a weight ratio of smokeless powder to granular product of 2: 1 was adhered to. A polyethylene vessel was filled with 80 g of the gas-forming mass obtained. The filled vessel, to which an electrical ignition device was connected, was placed in a container made of nylon fabric installed with a volume of 250 1. The gas-forming mass was then applied by applying an electric current the electrical ignition device ignited and the duration of the unfolding and expansion of the container and the sound pressure level measured at the moment of ignition. A value of 21 milliseconds and obtained for the sound pressure level 138 decibels.

Example 10 The mass used consisted of:

Zircon (Zr) 21 parts

· ■ Lead tetroxide (Pb ₅ O ₄ ), 79 parts

Styrene-butadiene block copolymer 1 part

(Toughprene trademark of Asahi Kasei Kogyo Co. Ltd.).

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The styrene-butadiene block copolymer was first made in toluene dissolved to make a binder. The binder obtained was added to zirconium and lead oxide and after mixing the mass obtained is granulated into a granular product.

Smokeless powder was mixed with the granular product thus obtained in a weight ratio of smokeless powder mixed to a granular product of 2: 1 to achieve a gas-forming mass. 80 g of the gas-forming obtained Mass were placed in a polyethylene jar. The filled vessel to which an electrical ignition device is connected was installed in a container made of nylon fabric with a volume of 250 liters. The gas-forming mass was then ignited by applying an electric current to the electric igniter and allowed to deploy and the time required for the container to expand and the sound pressure level measured at the moment of ignition. The duration was determined to be 25 milliseconds, the sound pressure level to 134 decdbels.

Example 11

This example has the following two components used:

Component A:

Boron (B) -5 parts

Lead tetroxide (Pb ₃ O ₄ ). ' 95 pieces

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Styrene-butadiene block copolymer '1 part

(Trademark Toughprene of Asahi Kasei Kogyo Go. Ltd.)

Component B:

Polybutadiene - 1.5 parts

Methylarylidenylphosphine oxide. 0.5 parts

Epoxy resin '■ 1.5 parts

Copper chromate (CuO.CrO,) 5 parts

Aluminum (Al). . -10 parts

Ammonium perchlorate ■ 83 parts

The component A mentioned was described in Example 9 ″ Mixed way and granulated into a granular product. Component B was then mixed, cured and crushed into "small grains. The small ones obtained Grains were mixed with the aforementioned granular product in a weight ratio of component A to component B of T: completely mixed, a gas-forming mass was achieved. 70 g of the gas-forming mass obtained was placed in a polyethylene vessel filled. The filled vessel, to which an electric igniter was attached, was in a Container made of nylon fabric with a volume of 250 l attached. The gas-forming mass was then applied by applying a electric current ignited to the electric igniter and the duration of the expansion of the container and the Sound pressure level measured at the moment of ignition. Pure

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a value of 23 milliseconds was measured for this duration and a value of 140 decibels for the sound pressure level was measured.

Example 12 The following composition was chosen:

. Component A: ₍

Zircon (Zr). 21 parts

Lead tetroxide (Pb ₅ O ₄ ) 79 parts

Styrene-butadiene block copolymer 1 part

(Trademark Toughprene of Asahi Kasei Kogyo Go ^. Ltd.)

Component B:

Polybutadiene - 15 parts

Methylarylidenylphosphine oxide 0.5 parts

Epoxy resin. 1.5 parts

Copper chromate (CuO.CrO,) 5 parts

Aluminum (Al) 10 parts

Ammanium perchlorate 83 parts

The specified component A was in the same way as in j Example 10 mixed and granulated into a granular product. Then component B was mixed, cured and chopped into small grains. The small grains obtained were mixed with the aforementioned granular product ^ in a mixture, Weight ratio component A: component B of 1: 3

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mixed thoroughly to produce a gas-forming mass. 70 g of the gas-forming mass obtained were poured into a polyethylene vessel . The filled vessel, to which an electric igniter was attached, was installed in a nylon fabric container having a fit of 250 liters. The gas-generating mass was then ignited by applying an electric current to the electric igniter and the time required for the container to expand and the sound pressure level at the moment of ignition were measured. A value of 28 milliseconds was measured for the expansion and a value of 135 decibels for the sound pressure level.

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Claims (12)

Claims Gas-forming mass, characterized by the content of (A) 10 to 80 weight percent of a combustible ingredient consisting essentially of at least one metallic reducing agent and at least one inorganic oxidizing agent, and (B) 20 to 90 percent by weight of a gas generating agent. 2. Gas-forming mass according to claim 1, characterized in that that they use smokeless powder, nitrocellulose, a flammable high molecular weight, as a gas-forming agent polymeric organic material or an easily decomposable organic compound. 3. Gas-forming composition according to claim 1 or 2, characterized in that it is a metallic one Reducing agent ^ contains zirconium, magnesium, boron, aluminum, silicon or ferrosilicon. 4. Gas-forming composition according to claim 1 to 3, characterized in that it is an inorganic one Oxidizing agents potassium perchlorate, potassium chlorate, potassium bromate, Potassium nitrate, ammonium perchlorate, barium nitrate, barium peroxide, lead tetroxide, lead peroxide, lead monoxide or contains lead chromate. - 25 -1-09830 / 0216 5. Gas-forming mass according to claim 2 to 4, characterized labeled as flammable . high molecular weight polymer material polyvinyl chloride, Polyethylene, polystyrene, polyacetals, polyvinyl acetate, styrene-butadiene copolymer rubber, polyether, epoxy resins, Polyurethanes, polysulfides, polybutadiene or polybutadiene-acrylic acid copolymers contains. 6. Gas-forming mass according to claim 2 to 5, characterized characterized as being easily decomposable organic compound azodicarbonamide, azoisobutyrodinitrile, aminoguanidine, hexamethylenetetramine, Contains dicyandiamide or thiourea. 7. A method for producing a gas-forming mass according to claim 1 to 6, characterized in that . Ze refuses to use a solution of a binder with the metallic reducing agent and the inorganic Oxidizing agents mixed, the resulting mixture formed into a granular product and this granular Product with a gas generating agent or with a * previously prepared and granulated mixture of a gas-generating agent and an oxidizing agent and optionally mixed with a reducing agent. - a, 8. The method according to claim 1, characterized in that there is a binder solution as a - 26 -109830/02 1 6 Solution of one part by weight of styrene-butadiene block copolymer used in toluene, this solution with 5 parts by weight of boron and 95 parts by weight of lead tetroxide mixed and the granular product obtained from this mixture with. smokeless powder in a weight ratio of granular product mixed to smokeless powder of 1: 2. 9. The method according to claim 7, characterized that the binder solution is a 'solution of one part by weight of styrene-butadiene block copolymer in toluene, as a metallic reducing agent 21 parts by weight of zirconium and as an oxidizing agent 79 Parts by weight of lead tetroxide used and that made from it granular product with smokeless powder in a mixing ratio of granular product to smokeless Powder mixed at 1: 2. 10. The method according to claim ^ 7, characterized in that that one from the solution of the binder, the metallic reducing agent and the inorganic Granular product (A) produced by oxidizing agents mixed with a product (B) obtained by mixing . of 15 parts by weight of polybutadiene, 0.5 parts by weight of methylaryldinylphosphine oxide iMethylarylidenylphosphine oxide, 1.5 parts by weight epoxy resin, 5 parts by weight copper chromate, 10 parts by weight . - 27 1Ö9830 / 0218 Aluminum and 83 parts by weight of ammonium chlorate, hardening the mixture obtained and crushing the hardened mixture was obtained into small grains and a mixing ratio (A) to (B) of 1: 3 is maintained. 11. The method according to claim 10, characterized in that that the granular product (A) by mixing a solution of one part by weight Styrene-butadiene block copolymer in toluene with 5 parts by weight of boron and 95 parts by weight of lead tetroxide and forming it into grains. 12. The method according to claim 10, characterized in that the granular product (A) by mixing a solution of one part by weight Styrene-butadiene block copolymer in toluene with 21 parts by weight of zirconium and 79 parts by weight Manufactures lead hydroxide and shaping the resulting mixture into grains. 109830/0216