JP2015086095A - Gas generating agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas generating agent composition capable of reducing a burning temperature while maintaining a burning speed and capable of being used for a gas generating device for vehicle air bag or the like.SOLUTION: There is provided a gas generating agent containing a nitrogen-containing organic compound (A-1), a polyol compound (A-2) as a fuel component (A) and basic metal nitrate as an oxidant component (B), and the content of the polyol compound (A-2) is 5 to 50 mass% based on the fuel content (A). There is provided a gas generating agent where the nitrogen-containing organic compound is at least one kind selected from guanidine, triazole, tetrazole, bitriazole, bitetrazole and a salt thereof, the polyol compound is at least one kind selected from pentaerythritol, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and polyvinyl alcohol.

Description

  The present invention relates to a gas generant composition useful for an automobile airbag and a molded article of the gas generant composition.

  In the measures for improving the safety of automobiles, in recent years, airbags and seat belt pretensioners are widely used as vehicle occupant safety devices using explosives. The principle is that the sensor generates an electrical signal when a collision is detected, burns the gas generant filled in the gas generator to generate gas, deploys the airbag with the gas pressure, Work to soften the impact. The same applies to the seat belt pretensioner. When the sensor detects a vehicle collision, it generates an electric signal, burns the gas generating agent filled in the gas generator, generates gas, and the gas pressure generates the seat belt. The occupant is protected by operating the winding mechanism and increasing the restraint force of the seat belt. The performance required for the gas generator includes generating a gas that does not contain harmful substances, generating a necessary and sufficient gas within a desired time, and the like.

In recent years, gas generating agents in which nitrogen-containing organic compounds are used as fuel instead of metal azide compounds and combined with inorganic oxidizing agents have been proposed. These have the advantage that the amount of gas generation is large and the danger in the production process is low. However, most of these gas generating agents using nitrogen-containing organic compounds as fuel have high combustion heat of 2500 J / g or more, and the generated gas is high temperature and high pressure. Requires material. Although the thing which consists of a metal wire is used widely as a coolant, it becomes the biggest cause of the mass increase of a gas generator, and the weight reduction of a coolant is calculated | required from a viewpoint of weight reduction.
As a method for reducing the size of the coolant, it is conceivable to reduce the combustion heat of the gas generating agent. Patent Document 1 or 2 describes that in a gas generating composition using a nitrogen-containing organic compound and an inorganic oxidizing agent, the heat of combustion is reduced by adding allantoin, cyanuric acid, melamine, or the like. Yes.

Special table 2013-500204 JP2008-1105030

  The present invention provides a gas generant composition that can be used in a gas generator for a vehicle airbag device and the like, and a molded article of the gas generant composition, which can reduce the combustion temperature while maintaining the combustion speed. That is.

The present invention has found that by using two types of fuel components, a nitrogen-containing organic compound and a polyol compound, as the fuel component, the combustion temperature can be lowered while maintaining the combustion rate. The gist of the present invention is as follows.
[1] A nitrogen-containing organic compound (A-1) and a polyol compound (A-2) as a fuel component (A), and a basic metal nitrate as an oxidant component (B), and the polyol compound (A-2) ) Content of 5 to 50% by mass with respect to the total amount of the fuel component (A).
[2] The [1], wherein the polyol compound is at least one selected from the group consisting of pentaerythritol, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and polyvinyl alcohol. The gas generant composition described in 1.
[3] The above [1] or [2], wherein the nitrogen-containing organic compound is at least one selected from the group consisting of guanidine, triazole, tetrazole, vitriazole, bitetrazole and derivatives thereof. The gas generant composition described in 1.
[4] The gas generating composition according to any one of [1] to [3], further including a metal nitrate as the oxidant component (B).
[5] The content of the nitrogen-containing organic compound (A-1) is 10 to 60% by mass, the content of the polyol compound (A-2) is 1 to 30% by mass, and the basic metal nitrate is contained. The gas generating composition according to any one of [1] to [4], wherein the amount is 35 to 75% by mass.
[6] The gas generating composition according to any one of [1] to [5], further including a binder agent.
[7] The gas generating composition according to any one of [1] to [6], further including a slag forming agent.
[8] A gas generant composition molded product obtained by extrusion molding the gas generant composition according to any one of [1] to [7].
[9] A pellet-shaped gas generant composition molded body obtained by compression molding the gas generant composition according to any one of [1] to [7].
[10] An inflator for an airbag using the gas generant molded article according to [8] or [9].

  The gas generant composition of the present invention uses a mixed fuel component of a nitrogen-containing organic compound and a polyol compound, together with a basic metal nitrate, thereby reducing the combustion heat of the gas generant and maintaining the combustion rate. The improvement of property can be realized. In particular, while the heat of combustion can be controlled by the amount of polyol compound added, the rate of change in the combustion rate due to the amount of polyol compound added is small, which is suitable for selective control of the amount of combustion heat. Furthermore, by using the gas generating agent of the present invention in a gas generator, the amount of coolant in the gas generator can be reduced, and a lightweight gas generator can be provided.

  The present invention is described in detail below. The present invention is a gas generant composition containing a nitrogen-containing organic compound (A-1) and a polyol compound (A-2) as a fuel component (A) and a basic metal nitrate as an oxidant component (B). The content of the polyol compound (A-2) is 5 to 50% by weight based on the total amount of the fuel component (A). The gas generating agent of the present invention is suitable for use in a gas generator for a vehicle occupant safety device.

  As the fuel component (A) of the gas generant composition of the present invention, a nitrogen-containing organic compound (A-1) is used. The nitrogen-containing organic compound (A-1) is not particularly limited, and a nitrogen-containing organic compound usually used in a gas generant composition for a gas generator for a vehicle occupant safety device can be suitably used. Examples of preferable use include guanidine or a derivative thereof, triazole or a derivative thereof, tetrazole or a derivative thereof, vitriazole or a derivative thereof, bitetrazole or a derivative thereof, azodicarbonamide or a derivative thereof, hydrazine or a derivative thereof, and a hydrazide derivative. More specifically, 5-oxo-1,2,4-triazole, tetrazole, 5-aminotetrazole, aminotetrazole nitrate, nitroaminotetrazole, bitetrazole (5,5′-bi-1H-tetrazole) ), 5,5′-bi-1H-tetrazole diammonium salt, azobistetrazole, 5,5′-azobistetrazole diguanidinium salt, guanidine, nitroguanidine, cyanoguanidine, triaminoguanidine nitrate, guanidinium nitrate , Aminoguanidine nitrate, biuret, azodicarbonamide, carbohydrazide, carbohydrazide nitrate complex, oxalic acid hydrazide, hydrazine nitrate complex, ammine complex and the like are preferably exemplified. Among these nitrogen-containing organic compounds, tetrazole derivatives, bitetrazole derivatives and guanidine derivatives are preferred because they are inexpensive, reactive and relatively easy to handle, and nitroguanidine, guanidine nitrate, bitetrazole, azobistetrazole and More preferred is 5-aminotetrazole. Among these, guanidine nitrate contains oxygen in the molecule, so the amount of the oxidant component can be reduced, it has good thermal stability, and further, low cost and high gas yield during combustion are expected. There is a merit that it can be performed, and it is particularly preferable. In addition, these nitrogen-containing organic compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The nitrogen-containing organic compound (A-1) is preferably in the form of powder or granules because it is easy to handle, and its 50% particle size is preferably 5 to 80 μm, more preferably 10 to 50 μm. . When the 50% particle size of the nitrogen-containing organic compound is too large, the strength of the molded product of the gas generant composition is lowered. On the other hand, when the particle size is too small, a large cost is required for pulverization. In the present invention, the 50% particle size means a 50% particle size based on the number of measured particles, and can be measured by, for example, a laser diffraction / scattering method.

  10-60 mass% is preferable and, as for the content rate (mixing ratio) of the nitrogen-containing organic compound (A-1) which occupies in the gas generating composition of this invention, 10-50 mass% is still more preferable. When the content (mixing ratio) of the nitrogen-containing organic compound is less than 15% by mass, the number of generated gas moles per 100 g of the gas generant composition tends to decrease, and the generation of nitrogen oxides tends to increase due to excess oxygen. On the other hand, when the content rate (mixing ratio) of the nitrogen-containing organic compound exceeds 60% by mass, it becomes difficult to suppress the heat of combustion in the combustion of the gas generating agent. Moreover, since there is a shortage of the oxidant component, a lot of toxic carbon monoxide tends to be generated. In addition, since the true specific gravity of the gas generant composition decreases due to an increase in the amount of organic matter, there arises a problem that the filling amount per volume of the gas generator decreases.

  In the present invention, the polyol compound (A-2) is used as the fuel component (A). The said polyol compound (A-2) is a compound which has a 2 or more hydroxy group in a molecule | numerator. In the present invention, it is preferable to use a polyol compound having 3 or more hydroxy groups in the molecule and a melting point of 100 ° C. or higher. Preferable polyol compounds (A-2) include pentaerythritol, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and polyvinyl alcohol. It can be used by 1 type, or 2 or more types of mixtures selected from these groups. Particularly preferred is pentaerythritol.

The content of the polyol compound (A-2) in the gas generant composition of the present invention is preferably set in the range of 1 to 30% by mass, and more preferably 3 to 25% by mass.
Moreover, this invention uses the two-component fuel component of a nitrogen-containing organic compound (A-1) and a polyol compound (A-2) as a fuel component (A), and this polyol compound (A-2) The fuel (A) whose content in the fuel component (A) is 5 to 50% by weight is used.

  The content of the fuel component (A) including the nitrogen-containing organic compound (A-1) and the polyol compound (A-2) in the gas generant composition of the present invention is set in the range of 16 to 65% by mass. Is preferred. More preferably, it is 20-65 mass%. When the fuel component (A) is less than 16% by mass, the number of moles of gas generated per 100 g of the gas generant composition tends to decrease, and the generation of nitrogen oxides tends to increase due to excess oxygen. On the other hand, when the fuel component (A) exceeds 65% by mass, it becomes difficult to suppress the combustion heat in the combustion of the gas generating agent. Moreover, since there is a shortage of the oxidant component, a lot of toxic carbon monoxide tends to be generated. In addition, since the true specific gravity of the gas generant composition decreases due to an increase in the amount of organic matter, there arises a problem that the filling amount per volume of the gas generator decreases.

  In the present invention, a basic metal nitrate is used as the oxidizing agent (B). Specific examples of the basic metal nitrate include basic copper nitrate, basic cobalt nitrate, basic zinc nitrate, basic magnesium nitrate, and basic iron nitrate. Among these, basic copper nitrate having a low combustion temperature and good thermal stability is particularly preferable.

  The blending ratio of the basic metal nitrate as the oxidizing agent (B) in the gas generating agent varies depending on the types and amounts of the nitrogen-containing organic compound (A-1) and the polyol compound (A-2) used. Usually, the range of 35 to 75% by mass is preferable with respect to the gas generant composition, and particularly in the range of 40 to 75% by mass in order to reduce the concentration of carbon monoxide and nitrogen oxides in the generated gas. Is more preferable.

  The basic metal nitrate is preferably in the form of powder or granules because it is easy to handle, and its 50% particle size is preferably 1 to 80 μm, more preferably 1 to 50 μm. When the 50% particle size of the basic metal nitrate is too large, the strength of the molded product of the gas generant composition is lowered. On the other hand, when the particle size is too small, a large cost is required for pulverization.

  The gas generant composition of the present invention may further contain a metal nitrate as a co-oxidant. Preferred co-oxidants are alkali metal nitrates and alkaline earth metal nitrates, and sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and the like can be used. In addition, these metal nitrates may be used individually by 1 type, and may be used in combination of 2 or more type. Particularly preferred is strontium nitrate, and it is preferable to use a mixed oxidizing agent of basic copper nitrate and strontium nitrate. When a co-oxidant is used, the mixing ratio (w / w) of basic metal nitrate and metal nitrate is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5. .

The gas generant composition of the present invention is based on the assumption that the content of the polyol compound (A-2) is 5 to 50% by weight based on the total amount of the fuel component (A). It is preferable that the content of 1) is 10 to 60% by mass, the content of the polyol compound (A-2) is 1 to 30% by mass, and the content of the basic metal nitrate is 35 to 75% by mass. . More preferably, the content of the nitrogen-containing organic compound (A-1) is 10 to 50% by mass, the content of the polyol compound (A-2) is 3 to 20% by mass, and the basic metal nitrate is Content is 40-75 mass%.
A particularly preferred embodiment of the gas generant composition according to the present invention is a composition containing 10 to 50% by mass of guanidine nitrate, 1 to 20% by mass of pentaerythritol, and 40 to 75% by mass of basic copper nitrate. It is.

  The gas generant composition of the present invention may further contain any additive. As this additive, the additive which can generally be used for the gas generant composition for gas generators for vehicle occupant safety devices can be used. For example, a binder agent for imparting moldability and shape retention to maintain suitable combustion characteristics, a slag forming agent for enabling easy filtration of combustion residues, other lubricants, and a combustion modifier Etc. can be used. When these additives are used, the content varies depending on the use, but in any use, if the content of the additive is excessive, performance such as combustibility is deteriorated. 0.1-15 mass% is preferable and, as for content of the additive which occupies, 0.1-10 mass% is still more preferable.

  The binder agent is an additive that imparts moldability and shape retention in order to maintain suitable combustion characteristics, and maintains the shape of the gas generant molded body even in a harsh environment where the inflator is used. The combustion performance can be maintained by sagging. The binder agent can be used without any particular limitation as long as it does not have a significant adverse effect on the combustion behavior of the gas generant composition, such as metal salts of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, cellulose propionate, Cellulose acetate butyrate, nitrocellulose, microcrystalline cellulose, guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polysaccharide derivatives such as starch, organic binders such as stearate, molybdenum disulfide, synthetic hydrotalcite, acid clay, talc Preferable examples include inorganic binders such as bentonite, diatomaceous earth, kaolin, silica, and alumina. Among these, cellulosic binders, acid clay and the like are particularly preferable. 1-10 mass% is preferable and, as for content of the binder agent in the gas generating composition of this invention, 1-5 mass% is still more preferable. When the content of the binder agent is high, the fracture strength of the molded product can be increased, but the number of carbon elements and hydrogen elements in the composition increases, and carbon monoxide gas which is an incomplete combustion product of carbon elements. Therefore, it is preferable to use the gas generator composition in the minimum amount that can maintain the shape of the gas generant composition. In particular, when the content of the binder agent exceeds 10% by mass, it is necessary to increase the relative abundance of the oxidant component, the relative abundance of the fuel component in the gas generant composition decreases, and the gas generator May be difficult to put into practical use.

  The slag forming agent is an additive that makes it possible to easily filter the combustion residue generated after combustion of the gas generant composition, and is added for the purpose of preventing it from being released out of the inflator. Specific examples of the slag forming agent include natural minerals such as silicon nitride, silicon carbide, silicon dioxide, silicate, aluminum oxide, titanium oxide, acid clay, and clay. When using a slag formation agent in this invention, 0.5-10 mass% is preferable and, as for content in a gas generant composition, 1-5 mass% is still more preferable. When the content of the slag forming agent is high, the combustibility is lowered, and further the number of moles of the generated gas is lowered, so that the passenger protection performance may not be sufficiently exhibited.

  The above-mentioned lubricant is added for the purpose of improving the mixing property and fluidity of the raw material components during the preparation of the gas generant composition. Specific examples of the lubricant include graphite, magnesium stearate, zinc stearate, calcium stearate, sodium stearate, boron nitride, highly dispersed silica (silicon dioxide), talc and the like. Among these, highly dispersed silica (silicon dioxide) has a function of uniformly dispersing and mixing while suppressing sticking and agglomeration during raw material mixing, and has the effect of maintaining the particle size characteristics and action of each component. It is particularly useful. When the lubricant is used in the present invention, the content of the lubricant in the gas generant composition is preferably 0.1 to 5% by mass, and more preferably 0.1 to 2% by mass. When the content of the lubricant is high, there is a risk that the combustibility decreases, the number of moles of the generated gas decreases, and further the concentration of carbon monoxide in the generated gas increases.

  The combustion modifier is an additive for adjusting the combustion of the gas generant composition. Specific examples thereof include iron oxide, nickel oxide, copper oxide, zinc oxide, manganese oxide, chromium oxide, cobalt oxide, and oxidation. Metal oxides such as molybdenum, vanadium oxide, and tungsten oxide, metal hydroxides such as copper hydroxide, cobalt hydroxide, zinc hydroxide, and aluminum hydroxide, carbons such as activated carbon powder, graphite, and carbon black . When a combustion regulator is used in the present invention, the content of the combustion regulator in the gas generant composition is preferably 10% by mass or less, and more preferably 5% by mass or less.

  The gas generant composition of the present invention is preferably used as a molded product having an appropriate shape. Hereinafter, the molded body of the gas generating agent composition is also referred to as a gas generating agent. The gas generating agent of the present invention can be formed into various shapes according to the combustion performance and the combustion characteristics of the gas generator. The shape of the gas generating agent of the present invention is not particularly limited, and examples thereof include a pellet shape, a disk shape, a spherical shape, a rod shape, a columnar shape, a cylindrical shape, a gold flat sugar shape, and a tetrapot shape. The molded body may be non-porous, or may be single-hole or porous (for example, single-hole cylindrical shape or porous cylindrical shape). Further, the pellet-shaped or disk-shaped molded body may be provided with one or a plurality of protrusions on one side or both sides. The shape of the protrusion is not particularly limited, and examples thereof include a columnar shape, a cylindrical shape, a conical shape, and a polygonal pyramid shape.

Examples of the method for molding the gas generating agent of the present invention include a pressure molding method and an extrusion molding method.
The manufacturing method by the pressure molding method of the molded object of the gas generating agent of this invention is illustrated. When molding a gas generant composition into tablets, pellets, or disks by pressure molding, the fuel component, oxidant component, and various additives are added to a dry mixer such as a V-type mixer or rocking mixer. And mix. At the time of mixing, the spheres are dispersed and interposed in the mixture of the components, so that the powder of the components is subjected to force by the spheres in detail, so that each component is uniformly dispersed in the composition. Use of a mixer that rotates and swings like a rocking mixer is desirable because a gas generating composition in which each component is more uniformly dispersed can be obtained. A solution containing a binder agent (binder solution) is added to the obtained gas generant composition (powder), and the gas generant composition is granulated using a wet granulator such as a stirring granulator. . Although the addition amount of the binder solution cannot be generally described, it can be added in an amount of 1 to 10% by mass with respect to the mixed powder. Then, it heat-processes at 80-100 degreeC, and obtains a granule. If the moisture content of the granule after heat treatment exceeds 1%, the fluidity is lowered, and there is a risk that the subsequent pressure molding cannot be performed stably. Preferably, it is 0.5% by mass or less. Next, the granules are pressed into a desired shape by a rotary tableting machine. During the pressure molding, a commonly used lubricant such as magnesium stearate can be added in the range of 0.1 to 5% by mass. The pressure-molded molded body can be used as a gas generating agent after heat treatment at 100 to 110 ° C. for 5 to 20 hours. The water content in the gas generating agent after the heat treatment is 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.3% by mass or less.

  On the other hand, when the molded product of the gas generant composition of the present invention is produced by an extrusion molding method, a fuel component, an oxidant component, and various additives are mixed in a mixer, and the obtained mixed powder is externally divided. Add 10-20% by mass of water or an organic solvent and knead thoroughly to obtain a viscous moistening agent. Thereafter, the wet agent is passed through a die that can be extruded into a desired shape, and the extruded product is appropriately cut. The extruded molded body is a columnar body, and a more preferable form is a long cylindrical shaped body.

  In addition, in the said heat processing, the molded object of a gas generant composition with little change with time can be obtained by performing heat processing for about 10 to 20 hours at the temperature of 50-150 degreeC. In the production method by extrusion molding, a molded body containing 10 to 20% by mass of water is heat-treated, and therefore it is necessary to heat-treat at a low temperature for a long time. In particular, this heat treatment is extremely effective in order to meet a severe heat aging test of 107 ° C. × 400 hours. Note that if the heat treatment time is less than 10 hours, the heat treatment is insufficient. On the other hand, the heat treatment time exceeding 20 hours is meaningless, so it is preferable to select the heat treatment time in the range of 10 to 20 hours. Also, if the heat treatment temperature is less than 50 ° C., the effect of improving the quality of the molded product is small, and if it exceeds 80 ° C., the moisture evaporation rate is too fast, resulting in bubbles in the molded product, insufficient strength of the molded product, Causes abnormal combustion during combustion. Therefore, the primary heat treatment is performed at 50 to 70 ° C., and the moisture content in the gas generating agent is set to 7% or less, preferably 5% or less, and then the secondary heat treatment is performed at 80 to 150 ° C. in the gas generating agent. It is desirable that the water content is 1 mass% or less, preferably 0.5 mass% or less.

  The gas generating agent of the present invention is used by being loaded into a gas generator. A suitable gas generator is an inflator used for airbag deployment. Therefore, the present application also includes an inflator for an airbag using the gas generating agent. The inflator for an air bag according to the present invention is not particularly limited as long as it is an inflator having a structure mounted on a vehicle. However, since the gas generating agent of the present invention has a low calorific value, the air bag inflator can be reduced in the amount of gas coolant. That is, the air bag inflator can be reduced in weight and / or reduced in size by reducing the amount of the filter material as the coolant.

Example 1
39.9 parts by mass of guanidine nitrate, 55.7 parts by mass of basic copper nitrate and 4.4 parts by mass of pentaerythritol are mixed, further sprayed with deionized water, and then heat treated at 90 ° C. for 10 hours to produce granules. did. Thereafter, 0.2 part by mass of magnesium stearate is added, and after forming into a cylinder having a diameter of 3.0 mm and a thickness of 1.50 mm, heat treatment is performed at 110 ° C. for 10 hours to form the gas generating composition of the present invention. A body (gas generating agent) was obtained.

Example 2
A mixture of 13.2 parts by mass of guanidine nitrate, 73.6 parts by mass of basic copper nitrate, and 13.2 parts by mass of pentaerythritol is further sprayed, followed by heat treatment at 90 ° C. for 10 hours to produce granules. did. Thereafter, 0.2 part by mass of magnesium stearate is added, and after forming into a cylinder having a diameter of 3.0 mm and a thickness of 1.50 mm, heat treatment is performed at 110 ° C. for 10 hours to form the gas generating composition of the present invention. A body (gas generating agent) was obtained.

Comparative Example 1
53.4 parts by mass of guanidine nitrate and 46.6 parts by mass of basic copper nitrate were mixed, further sprayed with deionized water, and then heat treated at 90 ° C. for 10 hours to produce granules. Thereafter, 0.2 parts by mass of magnesium stearate was added and formed into a cylindrical body having a diameter of 3.0 mm and a thickness of 1.50 mm, and then heat-treated at 110 ° C. for 10 hours, so that the gas generating composition of Comparative Example 1 A molded body (gas generating agent) was obtained.

Comparative Example 2
45.6 parts by mass of guanidine nitrate, 49.3 parts by mass of basic copper nitrate, and 5.1 parts by mass of cyanuric acid are mixed, sprayed with deionized water, and then heat treated at 90 ° C. for 10 hours to produce granules. did. Thereafter, 0.2 part by mass of magnesium stearate was added and formed into a cylindrical body having a diameter of 3.0 mm and a thickness of 1.50 mm, and then heat-treated at 110 ° C. for 10 hours, so that the gas generating composition of Comparative Example 2 A molded body (gas generating agent) was obtained.

Comparative Example 3
Mix 21.1 parts by mass of guanidine nitrate, 57.7 parts by mass of basic copper nitrate and 21.1 parts by mass of cyanuric acid, spray with deionized water, and then heat-treat at 90 ° C. for 10 hours to produce granules. did. Thereafter, 0.2 part by mass of magnesium stearate was added and formed into a cylindrical body having a diameter of 3.0 mm and a thickness of 1.50 mm, and then heat-treated at 110 ° C. for 10 hours to produce the gas generating composition of Comparative Example 3. A molded body (gas generating agent) was obtained.

Test Example 1: Combustion Heat Measurement In order to measure the heat of combustion of the gas generating agent of the present invention and the gas generating agent of the comparative example, a molded body (gas generating agent) of each gas generating agent composition using a calorimeter. 0 g was burned in a closed vessel and the heat of combustion was measured. The test results are summarized in Table 1.

Test Example 2: Combustion test in a closed container In order to evaluate the combustion characteristics of the gas generant of the present invention and the gas generant of the comparative example, 2.0 g of each gas generant composition (gas generant) was combusted with a capacity of 18 cc. The gas generating agent was burned by filling in a closed container for use, and the maximum pressure reached and the time to reach the maximum pressure were measured to calculate the pressure increase rate. The ignition tool and 0.4 g of boron nitrate were used as a charge transfer agent, and the mixture was ignited and burned. Using a pressure sensor, the change in pressure in the tank due to the generated gas during combustion was measured. The test results are summarized in Table 1.

Test Example 3: Observation of self-sustainable combustibility The self-sustainable combustibility of the gas generating agent of the present invention and the gas generating agent of the comparative example was evaluated. After preparing granules with the gas generant compositions of Examples 1 and 2 and Comparative Examples 1 to 3, 0.2 parts by mass of magnesium stearate was added, and a cylinder having a diameter of 9.6 mm and a thickness of 5.0 mm Molded into. Then, it heat-processed at 110 degreeC for 10 hours, and obtained the molded object (gas generant) of each gas generant composition. The molded body was ignited with a flame, the combustion time was measured with a stopwatch, and evaluated according to the following criteria.
○: Burns out in less than 10 seconds.
Δ: Burns out in 10 seconds or more and less than 15 seconds.
X: It burns out in 15 seconds or more.

ＧＮ：硝酸グアニジン
ＢＣＮ：塩基性硝酸銅
ＰＥ：ペンタエリスリトール
α：第二燃焼成分（ＰＥまたはシアヌル酸） [Table 1]

GN: guanidine nitrate BCN: basic copper nitrate PE: pentaerythritol α: second combustion component (PE or cyanuric acid)

  When Examples 1 and 2 were compared with Comparative Example 1, it was confirmed that the amount of combustion heat decreased by adding 9.9 to 50% by mass of pentaerythritol as a fuel component. Further, as the amount of pentaerythritol added increased, the amount of combustion heat further decreased.

On the other hand, when Examples 1 and 2 are compared with Comparative Examples 2 and 3, Example 1 using pentaerythritol as the second fuel component despite the fact that the weight ratio of guanidine nitrate and the second combustion component is the same. No. 2 was found to have a high pressure rise rate. In addition, when pentaerythritol is used as the second fuel component, it should be noted that the rate of change in the pressure increase rate according to the amount of addition is small. Furthermore, in the self-sustained combustion, the compositions of Examples 1 and 2 were combusted faster than Comparative Examples 2 and 3, and the use of pentaerythritol as the second fuel component makes it possible to maintain the combustibility. ing. From the above results, it was confirmed that the gas generant composition of the present invention has sufficient combustibility with low combustion heat.

Claims (10)

Nitrogen-containing organic compound (A-1) and polyol compound (A-2) as fuel component (A), basic metal nitrate as oxidant component (B), and inclusion of polyol compound (A-2) A gas generating composition characterized in that the amount is 5 to 50% by mass relative to the total amount of the fuel component (A). The gas according to claim 1, wherein the polyol compound is at least one selected from the group consisting of pentaerythritol, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and polyvinyl alcohol. Generator composition. The gas generating agent according to claim 1 or 2, wherein the nitrogen-containing organic compound is at least one selected from the group consisting of guanidine, triazole, tetrazole, vitriazole, bitetrazole, and derivatives thereof. Composition. The gas generant composition according to any one of claims 1 to 3, further comprising a metal nitrate as the oxidant component (B). The content of the nitrogen-containing organic compound (A-1) is 10 to 60% by mass, the content of the polyol compound (A-2) is 1 to 30% by mass, and the content of the basic metal nitrate is 35. It is -75 mass%, The gas generating composition as described in any one of Claims 1-4 characterized by the above-mentioned. Furthermore, the binder is included, The gas generating composition as described in any one of Claims 1-5 characterized by the above-mentioned. Furthermore, the slag formation agent is included, The gas generant composition as described in any one of Claims 1-6 characterized by the above-mentioned. A gas generant composition molding obtained by extruding the gas generant composition according to any one of claims 1 to 7. A pellet-shaped gas generant composition molded body obtained by compression molding the gas generant composition according to any one of claims 1 to 7. An inflator for an airbag using the gas generant molded article according to claim 8 or 9.