JP2002507542A - Propellants for gas generants - Google Patents

Abstract

The present invention relates to solid propellants for gas generators (gas-generating mixtures), wherein said propellants are mainly intended for use in propelling charges for gas generators used in airbags or seat-belt pre-tensioning devices. The solid propellants for gas generators further include an essentially chemically-inert slag trap which has a high fusion point and a good dispersion, wherein said slag trap acts as an inner filter and globally prevents the formation of powder particles as well as their exit from the housing of the gas generator. A portion of the slag trap having a good dispersion may be used as a carrier substance for catalyst metals.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a gas generating agent (Gasgenerator treibstoffe) (gas generating mixture (gaserzeu)
gende Mischungen)), wherein the propellant is a gas generant used in an airbag or seatbelt pretensioning device based on a nitrogen-rich fuel having a carbon content as low as possible. Propellant filler (Gas
Primarily intended for use in generatortreibsatze). Solid propellants for gas generants further include, in highly dispersed form, an essentially chemically inert slag trap (Schlackenfanger) with a high melting point, wherein the slag trap is Acts as an internal filter, substantially preventing the formation of powder (dust type) particles as well as their discharge from the gas generant housing.

The present invention therefore relates to a method for trapping liquid and solid combustion products and dust-type slag particles, respectively, during formation directly in a propellant filler for gas generants. Therefore, it is possible to use a filter package with a simple structure in the housing of the gas generant.

[0003] The present invention further relates to platinum metal (Ru, Os, Rh, Ir, Pd, Pt) or a metal alloy of platinum metal or copper on a slag trap as a carrier in a solid propellant for a gas generant. The use of catalysts based on In particular, it relates to its use in solid propellant fillers for gas generants used in airbags.

[0004] Airbags are essentially a gas generant housing filled with a propellant filler for the gas generant, generally in tablet form, and an initial propellant for exploding the propellant filler for the gas generant. Includes priming (ignition tube) and gas bag. Suitable explosives are disclosed, for example, in US 4,931,111. The gas bag, which is initially folded into a small bag, is filled with the gas produced by the burning of the propellant filler for the gas generant after the first explosion, and its filling in about 10-50 ms. Reach the quantity. The discharge of thermal sparks, molten material and solids from the gas generant into the gas bag must be sufficiently prevented as it can result in collapse of the gas bag or injury to the occupant. This is achieved by combining and filtering the slag formed by burning the propellant filler for the gas generant.

Propellant fillers for gas generants used in airbags based on sodium azide are well known. However, the use of highly toxic sodium azide requires dense operations and expensive processes for the preparation of propellant fillers for gas generants. Further, the worldwide growing number of non-combustible propellants for gas generants in vehicles used creates disposal and safety issues.

[0006] Therefore, efforts have recently been made to find a suitable alternative to sodium azide.

[0007] DE-A-44 35 790 discloses a propellant for a gas generant based on a guanidine compound on a suitable carrier, which essentially consists of an improved combustion behavior and an improved slag Shows the completed construction. DE-A-44 35 790 describes the use of an essentially chemically inert slag trap in a highly dispersed form with a high melting point, or a catalyst in a propellant filler for gas generants It doesn't give any hints about the use of.

[0008] EP-B-0 482 852 and the prior art referred to in this document disclose azide-free propellant fillers for gas generants, in particular for use in airbags. It is. The gas generating mixture disclosed in EP-B-0 482 852 comprises: a) a fuel selected from aminotetrazole, tetrazole, bitetrazole and their metal salts and triazole compounds and their metal salts; b) alkali metals, alkaline earths Nitrates and perchlorates of class III metals, lanthanoids and ammonium, and chlorates and peroxides of alkali and alkaline earth metals; and c) oxides, hydroxides, carbonates, oxalic acids of alkaline earth metals High temperature slag forming materials selected from salts, peroxides, nitrates, chlorates and perchlorates and alkaline earth metal salts of tetrazole, bitetrazole and triazole, and d)
Silicon dioxide, boron oxide, vanadium pentoxide, naturally occurring clay and talc, alkali metal silicates, borates, carbonates, nitrates, perchlorates and chlorates and alkalis of tetrazole, bitetrazole and triazole A low temperature slag forming material selected from metal salts; or e) a high temperature slag selected from transition metal oxides, hydroxides, carbonates, oxalates, peroxides, nitrates, chlorates and perchlorates. And f) a low temperature slag forming material that is silicon dioxide, wherein the amount of d) or f) is sufficient to achieve the formation of a coherent mass or slag, however, Not large enough to build a liquid with viscosity. It is clear that a single material can be used in more than one category.

[0009] An essential advantage of propellant fillers for such gas generants is the advantageous formation of slag which can be easily filtered from the gaseous combustion products formed. A further advantage is a high gas yield.

However, disadvantages of this type of propellant filler for gas generants are as follows: With regard to providing a propellant filler for gas generants with the most advantageous slag formation, the combustion behavior ( A compromise had to be made regarding the properties relating to (burn rate), the gas formation, the preparation of the pellets and, in particular, the quality of the gas, ie other processing factors relating to the portion of the toxic gaseous combustion products. Further, the number of suitable fuels is relatively limited.

[0011] EP-B-0 482 852 does not give any hint as to how these problems can be solved by modifying the composition of the propellant filler for the gas generant.

In US Pat. No. 4,948,439, the same inventor found that when using azide substitutes such as tetrazole compounds (eg, aminotetrazole and its metal salts) and mixtures thereof in a propellant filler for gas generants. Mentions the problem of the formation of toxic gaseous combustion products.

[0013] However, the teaching of US Pat. No. 4,948,439 teaches the toxic gaseous combustion products generated during combustion of propellant fillers for gas generants containing tetrazole or triazole compounds, their metal salts or mixtures as fuel. Does not provide any suggestions as to how some of these could be reduced. Conversely, a process for inflating an airbag is described, whereby a primary gas mixture is first obtained by ignition of a propellant filler for a gas generant containing at least one tetrazole or triazole compound as fuel. The primary gas mixture is subsequently passed to the surrounding air (Umgebungslu
ft) and to some extent by mixing, so that the content of toxic gaseous combustion products from the primary gas mixture is reduced to a toxicologically acceptable amount.

However, mixing with ambient air results in a more complex total airbag system (size, construction, etc.). The problem is the speed (10-50ms) at which the airbag must be inflated if more ambient air has to be drawn in.

DE-C-44 01 213 discloses a gas generating mixture comprising a fuel, an oxidizing agent, a “catalyst” and a cooling agent, wherein the oxidizing agent is Cu (NO ₃ ) ₂ .3Cu (OH ₂ ) wherein the catalyst is a metal oxide or a mixture of metal oxides or a mixed metal oxide.

[0016] Furthermore, DE-C-44 01 214 discloses a gas generating mixture having a similar composition, wherein the catalyst comprises a metal or metal alloy, preferably a pyrophoric (pyrop)
horen) metal or ignitable metal alloy. The carrier is a silicate, preferably a single silicate or a framework silicate (Gerustsilikat). Ag is particularly useful as a metal. Among the known fuels, triaminoguanidine nitrate is used.
(TAGN), nitroguanidine (NIGU, NQ), 3-nitro-1,2,3-triazol-5-one,
And especially diguanidine-5,5'-azotetrazolate (GZT).

The most important advantages of the gas generating mixtures described in the two German patents mentioned above are, according to the teachings in these patents, a reduction in the combustion temperature and an increase in the combustion rate.

The gas-evolving mixtures described in DE-C-44 01 213 and DE-C-44 01 214 are free of low- and high-melting slag formers and have any slag trap according to the invention. do not do. Conversely, slag formers are said to be unnecessary.

Contrary to this recommendation, the inventor has found that the use of slag formers that melt at low and high temperatures, in particular the use of slag traps according to the invention, results in a significant reduction of toxic gaseous combustion products. Was. A portion of the hot melt slag trap can be used as a support for platinum metal or for a metal alloy consisting of platinum metal, and thus can function as part of a catalyst.

In both of the above mentioned German patents, the term “catalyst” is used in an expanded sense and is the active part of the reaction, which “catalyst” can be reacted, direct the reaction and / or
Or it acts to accelerate the reaction.

Therefore, it is not a catalyst in the strict sense of the word, since the catalyst is not a component that reacts in the reaction. The catalyst in the strict sense of the word is not consumed during the reaction, ie is not reacted.

[0022] The definition of a catalyst further includes that the catalyst is only added at very low concentrations in the reaction mixture. However, in both German patents, the portion of the "catalyst" in the gas-evolving mixture is up to 30% by weight and is therefore also an essential part of the gas-evolving mixture with regard to its proportion in the mixture.

Thus, in summary, in DE-C-44 01 213 and DE-C-44 01 214 it is true that the term “catalyst” is used, but the meaning of this term is two It does not correspond to the general definition of a catalyst as set forth in the patents themselves.

The technical problem underlying the present invention compared to the prior art is to provide an improved propellant for gas generants, especially for airbags, whose combustion behavior is It can be adjusted as desired and particularly minimizes the formation of toxic gases and powders (dust type) of components that can escape from the gas generant housing and enter the lungs.

A propellant filler for a gas generant prepared from a propellant for a gas generant comprises:
It is intended to be thermally stable, easily ignitable, burn quickly even at low temperatures, and be sufficiently stored to ensure high gas yields. In addition, the propellant for the gas generant reduces the size and number of components of the gas generant housing, simplifies the gas generant housing and consequently reduces its weight in comparison to known generators. It is intended to be able to reduce it.

According to the present invention, these objects are achieved by a propellant for a gas generant, which comprises: (A) guanidine nitrate (GUNI; GuNO ₃ ), dicyanamide, ammonium dicyanamide, Sodium dicyanamide (Na-DCA), copper dicyanamide, tin dicyanamide, calcium dicyanamide (Ca-DCA), guanidine dicyanamide (GDCA), aminoguanidine hydrogencarbonate (AGB), aminoguanidine nitrate (AGN), triaminoguanidine nitrate (TAGN)
, Nitroguanidine (NIGU), dicyandiamide (DCD), azodicarbonamide (ADCA
) And at least one member selected from the group comprising tetrazole (HTZ), 5-aminotetrazole (ATZ), 5-nitro-1,2,4-triazol-3-one (NTO), salts and mixtures thereof A fuel; (B) at least one alkali metal or alkaline earth metal nitrate or ammonium nitrate, ammonium chlorate or ammonium perchlorate; (C) at least one essentially chemically inert slag trap; It has a high melting point and is selected from the group comprising Al ₂ O ₃ , TiO ₂ and ZrO ₂ and mixtures thereof in a highly dispersed form, and optionally, (D) an alkali metal And at least one slag former selected from carbonates and oxides of alkaline earth metals, silicates, aluminates and aluminum silicates, iron (III) oxide and silicon nitride (Si ₃ N ₄ ). The foam may, during combustion, result in the formation of nitrogen (N ₂ ) and silicon dioxide (SiO ₂ ) for further reaction. Optionally, (E) at least one soluble in water at room temperature. And a binder.

The preferred fuel, component (A), is nitroguanidine (NIGU), 5-aminotetrazole (ATZ), dicyandiamide (DCD), dicyanamide, their salts, especially sodium dicyanamide and calcium dicyanamide and nitric acid. Guanidine, and mixtures thereof. They are substantially non-toxic, non-hygroscopic, poorly water soluble, thermally stable, burn even at low temperatures, and have low impact and friction sensitivity. The gas yield during combustion is high, where most of the nitrogen gas is evolved.

Alkali metal salts (Li, Na, K) and alkaline earth metal salts (Mg, Ca, Sr, Ba)
-Is an example of a suitable salt of aminotetrazole.

As the oxidizing agent, component (B), alkali metal or alkaline earth metal nitrates (eg, lithium nitrate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate or barium nitrate), ammonium nitrate Chlorates or perchlorates of alkali metals or alkaline earth metals (e.g., lithium chlorate, sodium chlorate, potassium chlorate, magnesium chlorate,
(Calcium chlorate, strontium chlorate or barium chlorate and lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, calcium perchlorate, strontium perchlorate or barium perchlorate) and perchlorine Ammonates and mixtures thereof can be used. Potassium nitrate and strontium nitrate are preferred. Strontium nitrate is non-hygroscopic and non-toxic, allowing for high gas yields during combustion. Potassium nitrate also has a low combustion temperature.

Examples of component (C), which is an essentially chemically inert slag trap with a high melting point, are Al ₂ O ₃ , TiO ₂ and ZrO ₂ in highly dispersed form or mixtures thereof. . 100
+/- 15 m ² / g of BET surface Al ₂ O ₃ having (by DIN 66131) (mp about 2,050 ℃), 50 +/- 15
TiO ₂ with a BET surface of m ² / g (melting point about 1,850 ° C.) and ZrO ₂ with a BET surface of 40 +/− 10 m ² / g (melting point about 2,700 ° C.) are particularly preferred. These highly dispersed oxides include, for example, Degussa AG's Aluminumoxid C, Titanoxid P25, and VP Zirkonoxi
It is marketed under the trade name d.

These exothermic oxides are obtained by gas-phase reactions (flamehydrolysis) by reacting the respective metal chlorides with H ₂ and O ₂ in corresponding molar ratios. These oxides usually have no pores or well-defined agglomerates, as in the case of preparation by wet processes.

The term “slag trap” according to the present invention, ie component (C), refers to an essentially chemically inert metal oxide in a highly dispersed form with a high melting point, That is,
These oxides have a considerably larger surface compared to the oxides in conventional form.

For example, Al ₂ O ₃ commonly used as α-oxide has a BET surface of only 5-10 m ² / g, and commonly used dye-TiO ₂ is 5-10 m ² / g has a BET surface of only and customary to ZrO ₂ is, although having a BET surface of only 3-8m ² / g (for refractory products), propellant charge for a gas generating agent according to the invention The metal oxide used in the agent,
It has a BET surface of from about 40 to about 100 m ² / g, particularly preferably from about 50 to about 100 m ² / g, and especially about 100 m ² / g.

Further, the slag traps according to the present invention are characterized by their high melting point of about 1,850 to about 2,700 ° C. As a result of these high melting points, the slag trap does not melt during the reaction and therefore functions as a solid.

Furthermore, the slag trap according to the invention is essentially a chemically inert compound, ie the slag trap according to the invention is chemically reactive during the combustion reaction of the propellant filler for the gas generant. And does not participate to a small extent on the surface of metal oxides used as slag traps. Highly dissolved grid (hocha
Large internal surfaces of, for example, Al ₂ O ₃ , TiO ₂ or ZrO ₂ (in a highly dispersed form) cause cooling of the combustion products due to their inertness and combustion on the other hand In particular, entrapment of the liquid and / or solid slag portions and particles, respectively, occurring during. Thus, the propellant filler in tablet form for the gas generant remains during and after combustion, and the possibly formed fragments and pieces can be easily filtered. That means that little dust can be formed from the propellant filler for the gas generant and consequently from the housing of the burning gas generant. Thus, the slag trap acts as an internal filter in the propellant filler for the gas generant itself, thus substantially preventing the formation and discharge of dust-type slag portions from the gas generant housing. Thus, a substantial simplification of the filter of the gas generant housing is obtained, in which an additional (mechanical) fine filter in the gas generant housing is not partly necessary. This also results in an advantageous saving in the weight of the gas generant in the airbag.

At the same time, the formation of dust-type particles that can be evacuated from the airbag gas generant and enter the lungs is minimized by the formation of slag. Dust-type particles that can enter the lung have a diameter of about 6 μm or less.

If necessary, component (D) which is a slag former, for example, alkali metal and alkaline earth metal carbonates (eg, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate) And barium carbonate), alkali metal or alkaline earth metal oxides (e.g., sodium oxide, potassium oxide, magnesium oxide, calcium oxide, strontium oxide and barium oxide), silicates (e.g., Hectrit) ), Aluminates (e.g., beta sodium aluminate (Na ₂ O ₁₁ Al ₂ O ₃ ) or tricalcium aluminate (Ca ₃ A
l ₂ O ₆ )) or aluminum silicate (eg bentonite or zeolite) or iron (III) oxide or mixtures thereof may be used.

[0038] The function of component (D) is to form a slag that can be easily filtered during combustion of the propellant for the gas generant.

Further, the slag former, component (D), can function as a coolant. Silicates, aluminates and aluminum silicates react with alkali and alkaline earth metal oxides formed during combustion.

The present invention further relates to a carrier in a solid propellant for the gas generant of the present invention,
Use of catalysts based on platinum metal (Ru, Os, Rh, Ir, Pd, Pt) or metal alloys of platinum metal on highly dispersed slag traps, especially for gas generating agents for airbags For use in solid propellant fillers.

Component (C), which is part of the slag trap, can function as a support for platinum metal or a metal alloy of platinum metal or copper in a catalytically effective layer thickness.

Platinum metals include ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (I
r), palladium (Pd) and platinum (Pt). The catalyst used in the present invention is preferably based on Rh, Pd or Pt, especially Pt.

Examples of metal alloys of platinum metal are all the above-mentioned catalytically effective metal alloys of platinum metal, preferably Pt / Pd and Pt / Rh alloys.

The metal or metal alloy of platinum metal is present on the support in a catalytically effective layer thickness, preferably a single layer.

The catalyst is contained only in catalytic amounts in the propellant filler for the gas generant. component
The weight fraction for (C) is 0.1-5% by weight of component (C), preferably 0.2-1.2% by weight.

Preferred catalysts are those having Al ₂ O ₃ as a highly dispersed support and Pt, Pd or Cu as metal, especially Pt.

Suitable catalysts can be obtained from Degussa AG, for example, on gamma-Al ₂ O ₃
1% Pt or 1% Pd + Pt on gamma-Al ₂ O ₃ .

The catalyst is useful for directing reactions in which toxic gaseous combustion products such as carbon monoxide (CO), nitrogen oxides (NO _x ) and ammonia (NH ₃ ) are formed little. .

The catalysts described above are particularly useful for use in propellant fillers for gas generants in airbags.

In addition to the advantages resulting from the use of highly dispersed metal oxides (ie, reduction of solid dust type particles, ie, coarse and fine dust), the portion of the originally low toxic gas is even more reduced Is done.

The catalyst can be recycled by known processes from open, ie, used, airbags as well as from unopened, ie, from used vehicles, airbags. This results in a reduction of waste that can pollute the environment and allows for the reuse of catalytic metals. The catalytic metal and metal alloy, respectively, are not oxidized during combustion.

[0052] The catalyst should not be added as an additional part of the propellant filler for the gas generant, but the catalyst may be a component present in the propellant filler for the gas generant (component (C )
Part).

Component (A) is present in an amount of about 20-60%, preferably about 28-52%, especially about 45-51% by weight; component (B) is present in an amount of about 38 to about 63% by weight. %, Preferably about 38 to about 55% by weight, especially about 39 to 45% by weight; component (C) is present in an amount of about 5 to 22% by weight, preferably about
Finally, component (D), when present, is present in an amount of about 2 to 12% by weight, preferably about 4 to 10% by weight, in particular in an amount of about 8 to 20% by weight, in particular about 9 to 11% by weight. Present in the amount. All given weight percentages refer to the total composition of the propellant filler for the gas generant.

If desired, the propellant for the gas generant may further comprise a binder which is soluble in water at room temperature as component (E). Preferred binders are cellulose compounds or polymers of one or more polymerizable olefinically unsaturated monomers. Examples of cellulose compounds are carboxymethylcellulose, methylcellulose ethers, especially cellulose ethers such as methylhydroxyethylcellulose.
A methyl hydroxyethyl cellulose that can be used satisfactorily is CULMINAL® MHEC 30000 PR supplied by Aqualon. Suitable polymers with a binding action are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and polyvinyl butyral, for example Wacker Chemi, Burghausen, Germany
Pioloform® B supplied by Company e.

In addition, metal salts of stearic acid that are insoluble in water at room temperature, such as aluminum stearate, magnesium stearate, calcium stearate or zinc stearate, can be used as binder (component (E)).

Further, graphite is suitable as a binder.

[0057] Component (E) is present in an amount of 0-2% by weight, preferably 0.3-0.8% by weight.

[0058] The binder, component (E), comprises a granular substance or a tablet from a propellant for a gas generant (
In the production of pellets), it acts as a desensitizer and as a processing aid. It further serves to reduce the hydrophilic nature of the propellant fillers for gas generants and to stabilize them.

Working Examples: Preparation of propellants for gas generants (Examples 1 to 57 of Table I) and propellant fillers for gas generant was carried out as described below: The coarsely premixed raw materials (components (A), (B), (C) and, if necessary (D) and (E)) are each milled and pre-densified using a ball mill. Done.

The granulation of the propellant mixture for the gas generant was performed in a vertical mixer, where about 20% water was added at an elevated temperature of about 40 ° C. during the operation. After a short aeration, the resulting mixed mass was milled at room temperature with a mill having a 1 mm sieve. The granules thus obtained were dried in a drying oven at 80 ° C. for about 2 hours. Granules (particle- (size) distribution 0-1 mm) ready for use with propellants for gas generants were compressed into tablets (pellets) using a rotary pelletizer. These pellets for the propellant filler for the gas generant were dried again at 80 ° C. in a drying oven.

The tablets and pellets used in the gas generant and prepared from the propellant for the gas generant are each prepared by processes known in the art, for example a rotary pelletizing (compression) machine or a tablet machine. It can be prepared by hot pressing, extrusion in. The size of each of the pellets and tablets depends in each case on the desired burning time.

The propellants for the gas generants according to the invention consist of non-toxic and inexpensive components that can be easily prepared and their processing is not problematic. The more expensive component, ie, the catalytic metal, can be recycled by known procedures. Excellent storage stability is obtained due to the thermal stability of the components. The mixture is easily ignitable. They burn fast and ensure high gas yields with very low proportions of CO, NO _x , NH ₃ whose proportions are below the acceptable upper limit. The mixtures according to the invention are therefore particularly suitable as gas generants in various airbag systems, as fire extinguisher or propellant.

The following Examples 1 to 57 are illustrative and do not limit the present invention. Examples 15, 18 and 21 are comparative examples in which conventional ZrO ₂ , TiO ₂ and Al ₂ O ₃ were used.

Table I : The superscripts in the table have the following meanings: 1 Titandioxid P25, supplied from Degussa AG 2 Zirkonoxid VP, supplied from Degussa AG 3 Aluminumoxid C, supplied from Degussa AG 4 Titandioxid Kronos 3025, Kronos Titan -Supplied by -GmbH 5 Supplied by Zirkonoxid, Merck 6Aluminumoxid NO 615-30 II 24, Supplied by Nabaltec 7 Oxidation catalyst 1% Pt on Gamma-Aluminiumoxid, Supplied from Degussa AG Supplied by Degussa AG 9 Iron oxide, Bayoxide E8710, Supplied by Bayer AG 10 Supplied by Bentone EW, Rheox, Inc. 11 Supplied by CULMINAL MHEC 30000 PR, Aqualon

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4]

[0069]

[Table 5]

[0070]

[Table 6]

[0071]

[Table 7]

[0072]

[Table 8]

[0073]

[Table 9]

[0074]

[Table 10]

The combustion test was performed in a gas generant practice housing for a 60 liter driver airbag with an initial size, igniter and stainless steel filter package.

The weight of the propellant filler for the gas generant was between 50 and 55 g, depending on the gas yield of the individual composition of the propellant for the gas generant.

Depending on the burning properties, the pellets had a diameter of 4-6 mm and a height of 1.5 and 2.1 mm, respectively.

Gas yields and temperatures are in a range that favors propellants for gas generants for airbags.

In the tables, the terms “coarse dust” and “fine dust” refer to dust in the can after combustion.

The values measured for CO, NO _x and NH ₃ shown in the table are for 60 liter cans (K
anne). The values obtained are good considering that a non-optimized test gas generant was used.

A comparison of Examples 14 and 15, 17 and 18, and 20, and 21, illustrates the effect obtained by using a highly dispersed oxide as compared to commonly used oxides. The reduction in Partikelausstossen (coarse and fine dust) for the nitroguanidine / strontium nitrate system is comparable to that of conventional oxides of the same chemical structure but with a lower specific surface area. About 20-40%, depending on the particular highly dispersed slag trap (C) used according to the invention. Furthermore, the use of the specific slag trap (C) used according to the invention and its properties, a reduction of toxic gas by about 10-25% due to improved combustion is evident.

Furthermore, with regard to the formation of toxic gases, further advantageous effects of the highly dispersed slag trap (C) with the catalyst on the surface are, for example, the gas generation according to Examples 2-8 and 10 A comparison of propellants for agents can be found.

The CO and NO _x portions are, according to Examples 8 and 10 (with catalyst), less than those of Example 2 (without catalyst, but apart from those having the same composition) It is.

Particularly preferred compositions are those of Examples 14, 17 and 20.

The thermodynamic data for the various compositions is based on the oxygen balance (Sauerstoffbilanzubershuss
), For which the minimum possible amount of toxic gas during combustion was predicted.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission Date] April 27, 2000 (2000.4.27)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR , BY, CA, CH, CN, CU, CZ, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG , KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW

Claims (18)

[Claims] (A) Guanidine nitrate (GUNI; GuNO ₃ ), dicyanamide, ammonium dicyanamide, sodium dicyanamide (Na-DCA), copper dicyanamide, tin dicyanamide, calcium dicyanamide (Ca-DCA), guanidine dicyanamide (GDCA),
Aminoguanidine hydrogen carbonate (AGB), aminoguanidine nitrate (AGN), triaminoguanidine nitrate (TAGN), nitroguanidine (NIGU), dicyandiamide (DCD), azodicarbonamide (ADCA) and tetrazole (HTZ), 5-aminotetrazole ( ATZ),
At least one fuel selected from the group consisting of 5-nitro-1,2,4-triazol-3-one (NTO), salts and mixtures thereof; (B) at least one alkali metal nitrate or alkaline earth Metal nitrates or ammonium nitrate, ammonium chlorate or ammonium perchlorate, (C) a group comprising Al ₂ O ₃ , TiO ₂ and ZrO _{2 in} a highly dispersed form with a high melting point and mixtures thereof A propellant for a gas generant, comprising at least one essentially chemically inert slag trap selected from: 2. Component (A) is present in an amount of about 20-60% by weight, preferably about 28-52% by weight, especially about 45-51% by weight, and component (B) is present in an amount of about 38-about 63% by weight. % By weight, preferably from about 38 to about 55% by weight, especially from about 39 to 45% by weight, component (C) being from about 5 to 22% by weight, preferably from about 8 to 20% by weight, especially about 9 to 9% by weight. The propellant for a gas generant according to claim 1, which is present in an amount of 1111% by weight. 3. The composition of claim 1, wherein component (A) is selected from the group consisting of nitroguanidine, 5-aminotetrazole, dicyandiamide, dicyanamide, sodium dicyanamide and calcium dicyanamide and guanidine nitrate, and mixtures thereof. A propellant for the gas generant according to 1 or 2. 4. The propellant for a gas generant according to claim 1, wherein component (B) is selected from the group consisting of sodium nitrate, potassium nitrate and strontium nitrate. 5. The composition of claim 1, wherein component (C) is selected from the group consisting of highly dispersed Al ₂ O ₃ , highly dispersed TiO ₂ and highly dispersed ZrO ₂ . A propellant for a gas generant according to any one of the preceding claims. 6. A highly dispersed Al ₂ O ₃ having a specific surface area of 100 +/− 15 m ² / g, a component (C) having a specific surface area of 50 +/− 15 m ² / g. Dispersed TiO ₂ and 40 +/- 1
0 m ² / g is selected from the group consisting of ZrO _2, which are highly dispersed with a specific surface area of the propellant for gas generators according to請Motomeko 5. 7. The gas evolution according to claim 5, wherein part of component (C) is a support for platinum metal or a metal alloy of platinum metal or copper in a catalytically effective layer thickness. Propellant for the agent. 8. The platinum metal may be ruthenium (Ru), osmium (Os), rhodium (R
h), iridium (Ir), palladium (Pd) and platinum (Pt).
A propellant for a gas generant according to claim 1. 9. The propellant for a gas generant according to claim 7, wherein the metal alloy of platinum metal is selected from Pt / Pd and Pt / Rh alloys. 10. The gas generant according to claim 7, wherein the weight fraction of the catalyst with respect to component (C) is from 0.1 to 5% by weight, preferably from 0.2 to 1.2% by weight. Propellant for. 11. Component (A) is nitroguanidine, component (B) is strontium nitrate, and component (C) is highly dispersed Al ₂ O ₃ , TiO ₂ or ZrO _2. A propellant for a gas generant according to any one of 1 to 10. 12. Component (A) is present in an amount of 45-51% by weight, component (B) is present in an amount of 39-45% by weight, and component (C) is present in an amount of 9-45% by weight based on the total composition. The propellant for a gas generant according to claim 11, which is present in an amount of 1111% by weight. 13. Further, as component (D), carbonates of alkali metals and alkaline earth metals, oxides of alkali metals and alkaline earth metals, silicates, aluminates, aluminum silicates, silicon nitrides (Si ₃ N ₄₎ is selected from iron (III) oxide containing at least one slag former, propellant for gas generators according to any one of claims 1 to 11. 14. The propellant for a gas generant according to claim 13, wherein component (D) is present in an amount of about 2 to 12% by weight, preferably about 4 to 10% by weight. 15. A propellant for a gas generant according to claim 1, further comprising as component (E) at least one binder which is soluble in water at room temperature. medicine. 16. The binder is selected from the group consisting of a cellulose compound, a polymer of one or more polymerizable olefinically unsaturated monomers, a metal salt of stearic acid that is insoluble in water at room temperature, and graphite. Item 16. A propellant for a gas generant according to Item 15. 17. The propellant for a gas generant according to claim 15, wherein the binder is present in an amount of 0 to 2% by weight, preferably 0.3 to 0.8% by weight. 18. Use of a propellant for a gas generant according to any one of claims 1 to 17, as a gas generant in an airbag, as a fire extinguisher or as a propellant.