WO2023167222A1 - Gas-generating agent composition - Google Patents
Gas-generating agent composition Download PDFInfo
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- WO2023167222A1 WO2023167222A1 PCT/JP2023/007486 JP2023007486W WO2023167222A1 WO 2023167222 A1 WO2023167222 A1 WO 2023167222A1 JP 2023007486 W JP2023007486 W JP 2023007486W WO 2023167222 A1 WO2023167222 A1 WO 2023167222A1
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- gas generant
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- gas
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
- B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
- B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
- B60R21/26—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow
- B60R21/264—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow using instantaneous generation of gas, e.g. pyrotechnic
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
Definitions
- the present disclosure relates to gas generant compositions.
- Patent Document 1 Attempts have been made to ensure product reliability in inflators using gas generant compositions, which are used in vehicle safety devices such as airbag devices mounted on vehicles. For example, attempts have been made to lower the combustion temperature of the gas generant composition, improve the ignitability, and reduce the pressure index (Patent Document 1).
- the invention described in Patent Document 1 solves the problem by setting the ratio of melamine cyanurate and nitroguanidine within a specific range.
- an object of the present disclosure is to provide a gas generant composition having a high combustion temperature, a small pressure index, good ignitability, and an appropriate combustion rate.
- the present inventors added melamine cyanurate in addition to guanidine nitrate and basic copper nitrate to make a three-component system with a combustion temperature of 1680 K or higher. It was found that the above problems could be solved when In particular, when melamine cyanurate is added to a gas generant composition containing guanidine nitrate as a fuel and basic copper nitrate as an oxidant, the pressure index of the gas generant composition is lowered and combustion It has been found that the speed can be adjusted to the desired value. In addition, when the combustion temperature is 1680K or higher, ignitability is improved. In this specification, good ignitability is synonymous with short ignition time.
- a gas generant composition containing the following components (a) to (c), wherein the combustion temperature calculated based on the composition consisting of the following (a) to (c) is 1680 K or higher.
- a gas generant composition (a) guanidine nitrate (b) basic copper nitrate (c) melamine cyanurate [2] The content of (a) guanidine nitrate is 30% by weight or more and 60% by weight or less, The content of the (b) basic copper nitrate is 40% by weight or more and 65% by weight or less, The gas generant composition according to [1], wherein the content of (c) melamine cyanurate is 0.5% by weight or more and 12% by weight or less.
- the weight ratio (((a)+(b))/(c)) of the total amount of the component (a) and the component (b) to the component (c) is in the range of 8 or more and 150 or less.
- a gas generant composition that has a high combustion temperature, a small pressure index, good ignitability, and an appropriate combustion rate.
- the component (a) is guanidine nitrate. Since guanidine nitrate contains oxygen in its molecule, it is possible to reduce the amount of oxidizing agent to be compounded, and it has good thermal stability. Furthermore, it is expected to be low in cost and high in gasification rate during combustion. There are merits.
- the lower limit of the content of guanidine nitrate in the gas generant composition according to the embodiment of the present disclosure is usually 30% by weight or more and 60% by weight or less, and in a preferred aspect, 32% by weight or more and 55% by weight. It is below. If the content of guanidine nitrate (blending ratio) is less than 30% by weight, the number of moles of gas generated per 100 g of the gas generating composition tends to decrease, and the excess oxygen tends to increase the generation of nitrogen oxides. On the other hand, if the content of guanidine nitrate (blending ratio) exceeds 60% by weight, the amount of the oxidizing agent component becomes insufficient, so that a large amount of carbon monoxide tends to be generated.
- tetrazole compounds including 5-aminotetrazole, bitetrazole ammonium salts
- guanidine compounds including dicyandiamide
- perchlorates trihydrazinotriazines, and triazine compounds including nitrated compounds of melamine.
- the (b) component according to embodiments of the present disclosure is basic copper nitrate.
- the content of basic copper nitrate is usually in the range of 40% by weight or more and 65% by weight or less in a preferred embodiment of the gas generant composition. In order to reduce the concentration, in another preferred aspect, it is more preferable to set the content in the range of 43% by weight or more and 60% by weight or less.
- the gas generant composition of the present disclosure may contain other oxidizing agents as long as they do not impair the effects of the gas generant composition of the present disclosure.
- one or more selected from basic cobalt nitrate, basic zinc nitrate and basic manganese nitrate can be used.
- Other oxidizing agents include ammonium nitrate, metal perchlorate, ammonium perchlorate, metal nitrite, metal chlorate, and the like.
- (c) Melamine Cyanurate Component (c) according to the embodiment of the present disclosure is melamine cyanurate.
- the pressure index of the gas generant composition can be reduced. By reducing the pressure index, it is possible to prevent fluctuations in combustion temperature due to changes in pressure.
- the content of melamine cyanurate as component (c) in the gas generant composition according to the embodiment of the present disclosure is usually 0.5% by weight or more and 12% by weight or less, preferably 1% by weight or more, It is 11% by weight or less, and more preferably 1% by weight or more and 6.5% by weight or less.
- the total amount of component (a) and component (b) and the weight ratio of component (c) (((a) + (b))/(c)) range From the viewpoint of reducing the index, it is usually 8 or more, can be 11.6 or more, preferably 14.5 or more, more preferably 20 or more, and further preferably 21 or more. .
- the upper limit of this ratio may be 150 or less, 125 or less, or 100 or less. That is, usually 8 or more and 150 or less, 11.6 or more and 125 or less in another embodiment, 14.5 or more and 125 or less in still another embodiment, and 20 or more and 100 or less in still another embodiment.
- this ratio is as large as possible. This ratio can be adjusted by adjusting the contents of guanidine nitrate, basic copper nitrate, and melamine cyanurate within the range where the combustion temperature is 1680K or higher.
- component (c) In order to reduce the pressure index of the gas generant composition, it is necessary to add component (c) to the gas generant composition in addition to components (a) and (b).
- the weight ratio (((a)+(b))/(c)) of component (a) and component (b) to the total amount of component (c) is preferably as large as possible. That is, it is preferable that the weight ratio of component (c) to the total amount of components (a) and (c) is small.
- combustion temperature of gas generant composition The combustion temperatures of the gas generant compositions in this disclosure are calculated using a program known as "NEWPEP".
- the "NEWPEP” was published in 1960, 1979 and 1990, entitled “Theoretical Computation of Equilibrium Composition, Thermodynamic Properties and Performance Characteristics of Propellant Systems.” System)”, based on the PEP program described in the Naval Weapons Center Report. This program is in the public domain and readily available to those skilled in the art.
- the combustion temperature of the gas generant composition is determined by the types and composition ratios of the components contained in the gas generant composition.
- the combustion temperature of the gas generant composition is calculated based on the composition consisting of guanidine nitrate, basic copper nitrate and melamine cyanurate, and the combustion temperature is 1680K or higher. Therefore, even if the gas generant composition in the present disclosure contains other optional ingredients, the combustion temperature is calculated based on the composition consisting of guanidine nitrate, basic copper nitrate and melamine cyanurate.
- the composition of guanidine nitrate, basic copper nitrate and melamine cyanurate may be appropriately changed in order to set the combustion temperature of the gas generating composition to 1680K.
- the combustion temperature of the gas generant composition of the present disclosure may be 1680 K or higher, may be 1700 K or higher, may be 1750 K or higher, may be 1800 K or higher, or may be 1850 K or higher.
- the upper limit may be, for example, 2000K or less, may be 1950K or less, or may be 1900K or less. These lower and upper limits of the combustion temperature can be combined as appropriate. For example, when the lower limit is set to 1680K or more, the upper limit can be set to 200K or less or 1950 or less, or the lower limit can be changed to another numerical value to set the upper limit to 200K or less or 1950 or less.
- the gas generant composition of the present disclosure uses a high combustion temperature. is.
- the gas generation efficiency of the gas generating agent composition is also calculated from the NEWPEP program in the same manner as the combustion temperature.
- the gas generating efficiency of the gas generating agent composition of the present disclosure is not particularly limited, but may be, for example, 2.5 mol/100 g or more and 3.5 mol/100 g or less, 2.7 mol/100 g or more, 3. 2 mol/100 g or less can be mentioned.
- the oxygen balance calculated based on the composition consisting of guanidine nitrate, basic copper nitrate and melamine cyanurate is preferably -2.5 or more and -0.1 or less. . This oxygen balance is calculated from the composition ratio of guanidine nitrate, basic copper nitrate and melamine cyanurate contained in the gas generating composition.
- the pressure index and burning coefficient of the gas generant composition are calculated from burning rates measured under pressures of 5 MPa, 7 MPa, and 9 MPa, based on the above equations.
- the pressure index of the gas generant composition of the present disclosure is desirably as small as possible in order to prevent fluctuations in ignition speed due to changes in pressure, for example, preferably 0.35 or less, preferably 0.31 or less. It is more preferably 0.23 or less, and particularly preferably less than 0.2.
- the lower limit of the pressure index of the gas generating composition can be, for example, 0.01 or more, and may be 0.05 or more.
- the upper and lower limits of these pressure indices can be combined as appropriate.
- the lower limit can be 0.01 or more or 0.05 or more, or the upper limit can be changed to another numerical value and the lower limit is 0.01 or more or 0.05 or more.
- the gas generant composition of the present disclosure contains melamine cyanurate. can be made smaller.
- the gas generant composition of the present disclosure contains various known additives for the purpose of adjusting the combustion rate of the gas generant composition and cleaning the combustion gas, etc., within the range that can solve the problems of the present disclosure. can do.
- Known additives include metal oxides such as cupric oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide, bismuth oxide, silica, and alumina; aluminum hydroxide, magnesium hydroxide, Metal hydroxides such as cobalt hydroxide and iron hydroxide; cobalt carbonate, calcium carbonate; composite compounds of metal oxides or hydroxides such as acid clay, kaolin, talc, bentonite, and diatomaceous earth; sodium silicate, molybdenum mica metal salts such as acid salts, cobalt molybdate, and ammonium molybdate; molybdenum disulfide, calcium stearate, silicon nitride, silicon carbide, metaboric acid
- the content of optional components other than components (a) to (c) may be, for example, 5% by weight or less, or 3% by weight or less. It may be less than or equal to 0% by weight.
- the gas generant composition of the present disclosure is an aspect in which the content of optional components other than components (a) to (c) is 0% by weight, that is, an aspect composed only of components (a) to (c). may
- the gas generant composition according to the embodiments of the present disclosure can be molded into a desired shape, and can be formed into a single-hole cylindrical shape, a multi-hole cylindrical shape, or a pellet-like shaped body. These molded bodies are produced by adding and mixing water or an organic solvent to the gas generant composition, followed by extrusion molding (single-hole cylindrical or porous cylindrical moldings) or compression molding using a tableting machine or the like. (Pellet shaped compact). Since the gas generant composition according to the embodiment of the present disclosure has a high burning rate, there is no need to reduce the size of the compact, and the manufacturing process does not become complicated.
- the gas generant composition according to the embodiment of the present disclosure or a molded article obtained therefrom can be used, for example, for driver airbag inflators, passenger airbag inflators, side airbag inflators, and inflatable curtains of various vehicles. It can be applied to inflators, knee bolster inflators, inflatable seat belt inflators, tubular system inflators, and pretensioner inflators. Among these, the gas generant composition according to the embodiment of the present disclosure or the molded article obtained therefrom can be preferably applied to side airbag inflators that require early deployment.
- the inflator containing the gas generating agent composition or the molded article obtained therefrom includes a pyrotype in which gas is supplied only from the gas generating agent, and a compressed gas such as argon and a gas generating agent. Any of the hybrid types may be used.
- the gas generant composition according to the embodiment of the present disclosure or a molded article obtained therefrom can also be used as an ignition agent called an enhancer (or booster) or the like for transmitting the energy of a detonator or a squib to the gas generant.
- an enhancer or booster
- Each configuration and combination thereof in each embodiment is an example, and addition, omission, replacement, and other changes of configuration are possible as appropriate without departing from the scope of the present invention. This disclosure is not limited by the embodiments, but only by the scope of the claims.
- a gas generant composition having a high combustion temperature, a small pressure index and a desired combustion rate.
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Abstract
Provided is a gas-generating agent composition including the following components (a) to (c), wherein the combustion temperature calculated on the basis of a composition comprising the following components (a) to (c) is 1680K or higher: (a) guanidine nitrate; (b) basic copper nitrate; and (c) melamine cyanurate.
Description
本開示はガス発生剤組成物に関する。
The present disclosure relates to gas generant compositions.
車両に搭載されるエアバッグ装置等の車両安全装置に使用される、ガス発生剤組成物を使用するインフレータにおいて、製品の信頼性を確保する試みがなされている。例えば、ガス発生剤組成物の燃焼温度を下げ、着火性を向上させるとともに、圧力指数を小さくする試みが行われている（特許文献１）。
特許文献１に記載の発明は、メラミンシアヌレートとニトログアニジンの比率を特定範囲に設定することを解決手段として課題を解決している。 Attempts have been made to ensure product reliability in inflators using gas generant compositions, which are used in vehicle safety devices such as airbag devices mounted on vehicles. For example, attempts have been made to lower the combustion temperature of the gas generant composition, improve the ignitability, and reduce the pressure index (Patent Document 1).
The invention described in Patent Document 1 solves the problem by setting the ratio of melamine cyanurate and nitroguanidine within a specific range.
特許文献１に記載の発明は、メラミンシアヌレートとニトログアニジンの比率を特定範囲に設定することを解決手段として課題を解決している。 Attempts have been made to ensure product reliability in inflators using gas generant compositions, which are used in vehicle safety devices such as airbag devices mounted on vehicles. For example, attempts have been made to lower the combustion temperature of the gas generant composition, improve the ignitability, and reduce the pressure index (Patent Document 1).
The invention described in Patent Document 1 solves the problem by setting the ratio of melamine cyanurate and nitroguanidine within a specific range.
ガス発生剤組成物の特性の一つに燃焼温度がある。従来、ガス発生剤組成物の燃焼温度が高い場合、ガス発生時のガスの温度を下げ、エアバッグを保護するための措置を講じる必要があると考えられていた。そのため、ガス発生剤組成物の燃焼温度をできるだけ低くしたいという要求があった。一方、ガス発生剤組成物の燃焼温度を低くすると、ガス発生剤組成物の着火性が悪くなるという問題があった。
また、ガス発生剤組成物の特性である圧力指数についても、圧力の変化に伴う燃焼速度の変動を防ぐために、できるだけその値を小さくしたいという要求がある。
さらに、ガス発生剤組成物には、用途に応じた適切な燃焼速度が求められる。
これらのことから、本開示は、高い燃焼温度を有し、圧力指数が小さく、着火性が良く、適切な燃焼速度を有するガス発生剤組成物の提供を課題とする。 One of the properties of the gas generant composition is the combustion temperature. Conventionally, when the combustion temperature of the gas generant composition is high, it has been considered necessary to take measures to lower the temperature of the gas at the time of gas generation and protect the airbag. Therefore, there has been a demand to lower the combustion temperature of the gas generant composition as much as possible. On the other hand, when the combustion temperature of the gas generant composition is lowered, there is a problem that the ignitability of the gas generant composition is deteriorated.
In addition, there is also a demand for the pressure index, which is a characteristic of the gas generant composition, to be as small as possible in order to prevent fluctuations in the combustion rate due to changes in pressure.
Furthermore, the gas generant composition is required to have an appropriate burning rate according to the application.
Accordingly, an object of the present disclosure is to provide a gas generant composition having a high combustion temperature, a small pressure index, good ignitability, and an appropriate combustion rate.
また、ガス発生剤組成物の特性である圧力指数についても、圧力の変化に伴う燃焼速度の変動を防ぐために、できるだけその値を小さくしたいという要求がある。
さらに、ガス発生剤組成物には、用途に応じた適切な燃焼速度が求められる。
これらのことから、本開示は、高い燃焼温度を有し、圧力指数が小さく、着火性が良く、適切な燃焼速度を有するガス発生剤組成物の提供を課題とする。 One of the properties of the gas generant composition is the combustion temperature. Conventionally, when the combustion temperature of the gas generant composition is high, it has been considered necessary to take measures to lower the temperature of the gas at the time of gas generation and protect the airbag. Therefore, there has been a demand to lower the combustion temperature of the gas generant composition as much as possible. On the other hand, when the combustion temperature of the gas generant composition is lowered, there is a problem that the ignitability of the gas generant composition is deteriorated.
In addition, there is also a demand for the pressure index, which is a characteristic of the gas generant composition, to be as small as possible in order to prevent fluctuations in the combustion rate due to changes in pressure.
Furthermore, the gas generant composition is required to have an appropriate burning rate according to the application.
Accordingly, an object of the present disclosure is to provide a gas generant composition having a high combustion temperature, a small pressure index, good ignitability, and an appropriate combustion rate.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、硝酸グアニジンと塩基硝酸銅に加え、メラミンシアヌレートを添加し、これらの３成分系としたときの燃焼温度を１６８０Ｋ以上としたときに、上記課題を解決できることを見出した。
特に、燃料として硝酸グアニジンを含み、酸化剤として塩基性硝酸銅を含むガス発生剤組成物において、メラミンシアヌレートを添加した場合には、ガス発生剤組成物の圧力指数を低下させられるとともに、燃焼速度を所望の値に調整できること分かった。
また、燃焼温度が１６８０Ｋ以上であることで、着火性が良好となる。なお、本明細書において、着火性が良好であることは着火時間が短いことと同義である。 As a result of intensive studies to solve the above problems, the present inventors added melamine cyanurate in addition to guanidine nitrate and basic copper nitrate to make a three-component system with a combustion temperature of 1680 K or higher. It was found that the above problems could be solved when
In particular, when melamine cyanurate is added to a gas generant composition containing guanidine nitrate as a fuel and basic copper nitrate as an oxidant, the pressure index of the gas generant composition is lowered and combustion It has been found that the speed can be adjusted to the desired value.
In addition, when the combustion temperature is 1680K or higher, ignitability is improved. In this specification, good ignitability is synonymous with short ignition time.
特に、燃料として硝酸グアニジンを含み、酸化剤として塩基性硝酸銅を含むガス発生剤組成物において、メラミンシアヌレートを添加した場合には、ガス発生剤組成物の圧力指数を低下させられるとともに、燃焼速度を所望の値に調整できること分かった。
また、燃焼温度が１６８０Ｋ以上であることで、着火性が良好となる。なお、本明細書において、着火性が良好であることは着火時間が短いことと同義である。 As a result of intensive studies to solve the above problems, the present inventors added melamine cyanurate in addition to guanidine nitrate and basic copper nitrate to make a three-component system with a combustion temperature of 1680 K or higher. It was found that the above problems could be solved when
In particular, when melamine cyanurate is added to a gas generant composition containing guanidine nitrate as a fuel and basic copper nitrate as an oxidant, the pressure index of the gas generant composition is lowered and combustion It has been found that the speed can be adjusted to the desired value.
In addition, when the combustion temperature is 1680K or higher, ignitability is improved. In this specification, good ignitability is synonymous with short ignition time.
本開示は以下の内容に関する。
［１］ 以下の（ａ）～（ｃ）の成分を含むガス発生剤組成物であって、以下の（ａ）～（ｃ）からなる組成に基づき算出される燃焼温度が１６８０Ｋ以上である、ガス発生剤組成物。
（ａ）硝酸グアニジン
（ｂ）塩基性硝酸銅
（ｃ）メラミンシアヌレート
［２］ 前記（ａ）硝酸グアニジンの含有量が３０重量％以上、６０重量％以下であり、
前記（ｂ）塩基性硝酸銅の含有量が４０重量％以上、６５重量％以下であり、
前記（ｃ）メラミンシアヌレートの含有量が０．５重量％以上１２重量％以下である、［１］に記載のガス発生剤組成物。
［３］ 前記（ａ）硝酸グアニジンの含有量が３２重量％以上、５５重量％以下である、［２］に記載のガス発生剤組成物。
［４］ 前記（ｂ）塩基性硝酸銅の含有量が４３重量％以上、６０重量％以下である、［２］に記載のガス発生剤組成物。
［５］ 前記（ｃ）メラミンシアヌレートの含有量が１重量％以上、１１重量％以下である、［２］に記載のガス発生剤組成物。
［６］ 前記（ａ）～（ｃ）からなる組成に基づき算出される燃焼温度が１７００Ｋ以上である、［１］～［５］のいずれかに記載のガス発生剤組成物。
［７］ 前記（ａ）～（ｃ）からなる組成に基づき算出される燃焼温度が２０００Ｋ以下である、［１］～［６］のいずれかに記載のガス発生剤組成物。
［８］ 圧力指数が０．３５以下である、［１］～［７］のいずれかに記載のガス発生剤組成物。
［９］ 圧力指数が０．２３以下である、［８］に記載のガス発生剤組成物。
［１０］ 圧力指数が０．０１以上である、［８］に記載のガス発生剤組成物。
［１１］ 前記成分（ａ）及び前記成分（ｂ）の合計量と、前記成分（ｃ）の重量比（（（ａ）＋（ｂ））／（ｃ））の範囲が、８以上１５０以下である、［１］～［１０］のいずれかに記載のガス発生剤組成物。
［１２］ 前記成分（ａ）及び成分（ｂ）の合計量と、成分（ｃ）の重量比（（（ａ）＋（ｂ））／（ｃ））の範囲が、１１．６以上１２５以下である、［１１］に記載のガス発生剤組成物。
［１３］ ［１］～［１２］のいずれかに記載のガス発生剤組成物を含む、インフレータ。 This disclosure relates to:
[1] A gas generant composition containing the following components (a) to (c), wherein the combustion temperature calculated based on the composition consisting of the following (a) to (c) is 1680 K or higher. A gas generant composition.
(a) guanidine nitrate (b) basic copper nitrate (c) melamine cyanurate [2] The content of (a) guanidine nitrate is 30% by weight or more and 60% by weight or less,
The content of the (b) basic copper nitrate is 40% by weight or more and 65% by weight or less,
The gas generant composition according to [1], wherein the content of (c) melamine cyanurate is 0.5% by weight or more and 12% by weight or less.
[3] The gas generant composition according to [2], wherein the content of (a) guanidine nitrate is 32% by weight or more and 55% by weight or less.
[4] The gas generant composition according to [2], wherein the content of (b) basic copper nitrate is 43% by weight or more and 60% by weight or less.
[5] The gas generant composition according to [2], wherein the content of (c) melamine cyanurate is 1% by weight or more and 11% by weight or less.
[6] The gas generant composition according to any one of [1] to [5], wherein the combustion temperature calculated based on the composition consisting of (a) to (c) is 1700K or higher.
[7] The gas generant composition according to any one of [1] to [6], wherein the combustion temperature calculated based on the composition consisting of (a) to (c) is 2000K or less.
[8] The gas generant composition according to any one of [1] to [7], which has a pressure index of 0.35 or less.
[9] The gas generant composition according to [8], which has a pressure index of 0.23 or less.
[10] The gas generant composition according to [8], which has a pressure index of 0.01 or more.
[11] The weight ratio (((a)+(b))/(c)) of the total amount of the component (a) and the component (b) to the component (c) is in the range of 8 or more and 150 or less. The gas generant composition according to any one of [1] to [10], wherein
[12] The weight ratio of the total amount of components (a) and (b) to the component (c) (((a)+(b))/(c)) ranges from 11.6 to 125. The gas generant composition according to [11], wherein
[13] An inflator comprising the gas generant composition according to any one of [1] to [12].
［１］ 以下の（ａ）～（ｃ）の成分を含むガス発生剤組成物であって、以下の（ａ）～（ｃ）からなる組成に基づき算出される燃焼温度が１６８０Ｋ以上である、ガス発生剤組成物。
（ａ）硝酸グアニジン
（ｂ）塩基性硝酸銅
（ｃ）メラミンシアヌレート
［２］ 前記（ａ）硝酸グアニジンの含有量が３０重量％以上、６０重量％以下であり、
前記（ｂ）塩基性硝酸銅の含有量が４０重量％以上、６５重量％以下であり、
前記（ｃ）メラミンシアヌレートの含有量が０．５重量％以上１２重量％以下である、［１］に記載のガス発生剤組成物。
［３］ 前記（ａ）硝酸グアニジンの含有量が３２重量％以上、５５重量％以下である、［２］に記載のガス発生剤組成物。
［４］ 前記（ｂ）塩基性硝酸銅の含有量が４３重量％以上、６０重量％以下である、［２］に記載のガス発生剤組成物。
［５］ 前記（ｃ）メラミンシアヌレートの含有量が１重量％以上、１１重量％以下である、［２］に記載のガス発生剤組成物。
［６］ 前記（ａ）～（ｃ）からなる組成に基づき算出される燃焼温度が１７００Ｋ以上である、［１］～［５］のいずれかに記載のガス発生剤組成物。
［７］ 前記（ａ）～（ｃ）からなる組成に基づき算出される燃焼温度が２０００Ｋ以下である、［１］～［６］のいずれかに記載のガス発生剤組成物。
［８］ 圧力指数が０．３５以下である、［１］～［７］のいずれかに記載のガス発生剤組成物。
［９］ 圧力指数が０．２３以下である、［８］に記載のガス発生剤組成物。
［１０］ 圧力指数が０．０１以上である、［８］に記載のガス発生剤組成物。
［１１］ 前記成分（ａ）及び前記成分（ｂ）の合計量と、前記成分（ｃ）の重量比（（（ａ）＋（ｂ））／（ｃ））の範囲が、８以上１５０以下である、［１］～［１０］のいずれかに記載のガス発生剤組成物。
［１２］ 前記成分（ａ）及び成分（ｂ）の合計量と、成分（ｃ）の重量比（（（ａ）＋（ｂ））／（ｃ））の範囲が、１１．６以上１２５以下である、［１１］に記載のガス発生剤組成物。
［１３］ ［１］～［１２］のいずれかに記載のガス発生剤組成物を含む、インフレータ。 This disclosure relates to:
[1] A gas generant composition containing the following components (a) to (c), wherein the combustion temperature calculated based on the composition consisting of the following (a) to (c) is 1680 K or higher. A gas generant composition.
(a) guanidine nitrate (b) basic copper nitrate (c) melamine cyanurate [2] The content of (a) guanidine nitrate is 30% by weight or more and 60% by weight or less,
The content of the (b) basic copper nitrate is 40% by weight or more and 65% by weight or less,
The gas generant composition according to [1], wherein the content of (c) melamine cyanurate is 0.5% by weight or more and 12% by weight or less.
[3] The gas generant composition according to [2], wherein the content of (a) guanidine nitrate is 32% by weight or more and 55% by weight or less.
[4] The gas generant composition according to [2], wherein the content of (b) basic copper nitrate is 43% by weight or more and 60% by weight or less.
[5] The gas generant composition according to [2], wherein the content of (c) melamine cyanurate is 1% by weight or more and 11% by weight or less.
[6] The gas generant composition according to any one of [1] to [5], wherein the combustion temperature calculated based on the composition consisting of (a) to (c) is 1700K or higher.
[7] The gas generant composition according to any one of [1] to [6], wherein the combustion temperature calculated based on the composition consisting of (a) to (c) is 2000K or less.
[8] The gas generant composition according to any one of [1] to [7], which has a pressure index of 0.35 or less.
[9] The gas generant composition according to [8], which has a pressure index of 0.23 or less.
[10] The gas generant composition according to [8], which has a pressure index of 0.01 or more.
[11] The weight ratio (((a)+(b))/(c)) of the total amount of the component (a) and the component (b) to the component (c) is in the range of 8 or more and 150 or less. The gas generant composition according to any one of [1] to [10], wherein
[12] The weight ratio of the total amount of components (a) and (b) to the component (c) (((a)+(b))/(c)) ranges from 11.6 to 125. The gas generant composition according to [11], wherein
[13] An inflator comprising the gas generant composition according to any one of [1] to [12].
本開示の実施形態によれば、高い燃焼温度を有し、圧力指数が小さく、着火性が良く、適切な燃焼速度を有するガス発生剤組成物を提供できる。
According to the embodiments of the present disclosure, it is possible to provide a gas generant composition that has a high combustion temperature, a small pressure index, good ignitability, and an appropriate combustion rate.
以下、本開示を具体的な実施形態に基づき説明する。なお、本明細書において、数値範囲の下限値及び上限値を分けて記載する場合、当該数値範囲は、それらのうち任意の下限値と任意の上限値とを組み合わせたものとすることができる。
The present disclosure will be described below based on specific embodiments. In this specification, when the lower limit and upper limit of a numerical range are described separately, the numerical range may be a combination of any lower limit and any upper limit.
（ａ）硝酸グアニジン
本開示の実施形態にかかる（ａ）成分は、硝酸グアニジンである。硝酸グアニジンは、分子中に酸素を含有するため、酸化剤成分の配合量を低減でき、また良好な熱安定性を有し、更には低コスト、燃焼時の高いガス化率が期待できる等のメリットがある。 (a) Guanidine Nitrate The component (a) according to embodiments of the present disclosure is guanidine nitrate. Since guanidine nitrate contains oxygen in its molecule, it is possible to reduce the amount of oxidizing agent to be compounded, and it has good thermal stability. Furthermore, it is expected to be low in cost and high in gasification rate during combustion. There are merits.
本開示の実施形態にかかる（ａ）成分は、硝酸グアニジンである。硝酸グアニジンは、分子中に酸素を含有するため、酸化剤成分の配合量を低減でき、また良好な熱安定性を有し、更には低コスト、燃焼時の高いガス化率が期待できる等のメリットがある。 (a) Guanidine Nitrate The component (a) according to embodiments of the present disclosure is guanidine nitrate. Since guanidine nitrate contains oxygen in its molecule, it is possible to reduce the amount of oxidizing agent to be compounded, and it has good thermal stability. Furthermore, it is expected to be low in cost and high in gasification rate during combustion. There are merits.
本開示の実施形態にかかるガス発生剤組成物中に占める硝酸グアニジンの含有量の下限としては、通常３０重量％以上、６０重量％以下であり、好ましい一態様では３２重量％以上、５５重量％以下である。硝酸グアニジンの含有率（配合割合）が３０重量％未満では、ガス発生剤組成物１００ｇ当たりの発生ガスモル数が減少し、酸素過剰で窒素酸化物の発生が増加する傾向にある。一方、硝酸グアニジンの含有率（配合割合）が６０重量％を超えると酸化剤成分が不足するために一酸化炭素が多く発生する傾向にある。
さらに本開示の課題を解決できる範囲で公知の他の燃料を含有することもできる。
公知の他の燃料としては、５－アミノテトラゾール、ビテトラゾールアンモニウム塩を含むテトラゾール類化合物；ジシアンジアミドを含むグアニジン類化合物；メラミン、トリメチロールメラミン、アルキル化メチロールメラミン、アンメリン、アンメランド、メラミンの硝酸塩、メラミンの過塩素酸塩、トリヒドラジノトリアジン、メラミンのニトロ化化合物を含むトリアジン類化合物から選ばれる１種以上を挙げることができる。 The lower limit of the content of guanidine nitrate in the gas generant composition according to the embodiment of the present disclosure is usually 30% by weight or more and 60% by weight or less, and in a preferred aspect, 32% by weight or more and 55% by weight. It is below. If the content of guanidine nitrate (blending ratio) is less than 30% by weight, the number of moles of gas generated per 100 g of the gas generating composition tends to decrease, and the excess oxygen tends to increase the generation of nitrogen oxides. On the other hand, if the content of guanidine nitrate (blending ratio) exceeds 60% by weight, the amount of the oxidizing agent component becomes insufficient, so that a large amount of carbon monoxide tends to be generated.
Furthermore, other known fuels can be contained as long as the problems of the present disclosure can be solved.
Other known fuels include tetrazole compounds, including 5-aminotetrazole, bitetrazole ammonium salts; guanidine compounds, including dicyandiamide; perchlorates, trihydrazinotriazines, and triazine compounds including nitrated compounds of melamine.
さらに本開示の課題を解決できる範囲で公知の他の燃料を含有することもできる。
公知の他の燃料としては、５－アミノテトラゾール、ビテトラゾールアンモニウム塩を含むテトラゾール類化合物；ジシアンジアミドを含むグアニジン類化合物；メラミン、トリメチロールメラミン、アルキル化メチロールメラミン、アンメリン、アンメランド、メラミンの硝酸塩、メラミンの過塩素酸塩、トリヒドラジノトリアジン、メラミンのニトロ化化合物を含むトリアジン類化合物から選ばれる１種以上を挙げることができる。 The lower limit of the content of guanidine nitrate in the gas generant composition according to the embodiment of the present disclosure is usually 30% by weight or more and 60% by weight or less, and in a preferred aspect, 32% by weight or more and 55% by weight. It is below. If the content of guanidine nitrate (blending ratio) is less than 30% by weight, the number of moles of gas generated per 100 g of the gas generating composition tends to decrease, and the excess oxygen tends to increase the generation of nitrogen oxides. On the other hand, if the content of guanidine nitrate (blending ratio) exceeds 60% by weight, the amount of the oxidizing agent component becomes insufficient, so that a large amount of carbon monoxide tends to be generated.
Furthermore, other known fuels can be contained as long as the problems of the present disclosure can be solved.
Other known fuels include tetrazole compounds, including 5-aminotetrazole, bitetrazole ammonium salts; guanidine compounds, including dicyandiamide; perchlorates, trihydrazinotriazines, and triazine compounds including nitrated compounds of melamine.
（ｂ）塩基性硝酸銅
本開示の実施形態にかかる（ｂ）成分は塩基性硝酸銅である。塩基性硝酸銅を用いることで、ガス発生剤組成物の燃焼温度を所望の範囲に調整できる。具体的には、ガス発生剤組成物の燃焼温度を高くし過ぎないようにできる。
塩基性硝酸銅の含有量は、通常はガス発生剤組成物に対して、好ましい一態様では４０重量％以上、６５重量％以下の範囲であり、特に発生ガス中の一酸化炭素と窒素酸化物濃度を低減させるために、別の好ましい一態様では４３重量％以上、６０重量％以下の範囲に設定することがより好ましい。
本開示のガス発生剤組成物は、本開示のガス発生剤組成物の効果を損なわない限り、他の酸化剤を含有してもよい。例えば、塩基性硝酸コバルト、塩基性硝酸亜鉛及び塩基性硝酸マンガンから選ばれる１種以上を挙げることができる。他の酸化剤としては、硝酸アンモニウム、金属過塩素酸塩、過塩素酸アンモニウム、金属亜硝酸塩、金属塩素酸塩等を挙げることができる。 (b) Basic copper nitrate The (b) component according to embodiments of the present disclosure is basic copper nitrate. By using basic copper nitrate, the combustion temperature of the gas generating composition can be adjusted within a desired range. Specifically, the combustion temperature of the gas generant composition can be prevented from being too high.
The content of basic copper nitrate is usually in the range of 40% by weight or more and 65% by weight or less in a preferred embodiment of the gas generant composition. In order to reduce the concentration, in another preferred aspect, it is more preferable to set the content in the range of 43% by weight or more and 60% by weight or less.
The gas generant composition of the present disclosure may contain other oxidizing agents as long as they do not impair the effects of the gas generant composition of the present disclosure. For example, one or more selected from basic cobalt nitrate, basic zinc nitrate and basic manganese nitrate can be used. Other oxidizing agents include ammonium nitrate, metal perchlorate, ammonium perchlorate, metal nitrite, metal chlorate, and the like.
本開示の実施形態にかかる（ｂ）成分は塩基性硝酸銅である。塩基性硝酸銅を用いることで、ガス発生剤組成物の燃焼温度を所望の範囲に調整できる。具体的には、ガス発生剤組成物の燃焼温度を高くし過ぎないようにできる。
塩基性硝酸銅の含有量は、通常はガス発生剤組成物に対して、好ましい一態様では４０重量％以上、６５重量％以下の範囲であり、特に発生ガス中の一酸化炭素と窒素酸化物濃度を低減させるために、別の好ましい一態様では４３重量％以上、６０重量％以下の範囲に設定することがより好ましい。
本開示のガス発生剤組成物は、本開示のガス発生剤組成物の効果を損なわない限り、他の酸化剤を含有してもよい。例えば、塩基性硝酸コバルト、塩基性硝酸亜鉛及び塩基性硝酸マンガンから選ばれる１種以上を挙げることができる。他の酸化剤としては、硝酸アンモニウム、金属過塩素酸塩、過塩素酸アンモニウム、金属亜硝酸塩、金属塩素酸塩等を挙げることができる。 (b) Basic copper nitrate The (b) component according to embodiments of the present disclosure is basic copper nitrate. By using basic copper nitrate, the combustion temperature of the gas generating composition can be adjusted within a desired range. Specifically, the combustion temperature of the gas generant composition can be prevented from being too high.
The content of basic copper nitrate is usually in the range of 40% by weight or more and 65% by weight or less in a preferred embodiment of the gas generant composition. In order to reduce the concentration, in another preferred aspect, it is more preferable to set the content in the range of 43% by weight or more and 60% by weight or less.
The gas generant composition of the present disclosure may contain other oxidizing agents as long as they do not impair the effects of the gas generant composition of the present disclosure. For example, one or more selected from basic cobalt nitrate, basic zinc nitrate and basic manganese nitrate can be used. Other oxidizing agents include ammonium nitrate, metal perchlorate, ammonium perchlorate, metal nitrite, metal chlorate, and the like.
（ｃ）メラミンシアヌレート
本開示の実施形態にかかる（ｃ）成分はメラミンシアヌレートである。（ａ）硝酸グアニジンと（ｂ）塩基性硝酸銅とを含むガス発生剤組成物において、メラミンシアヌレートを含有する場合、ガス発生剤組成物の圧力指数を小さくすることができる。圧力指数を小さくすることで、圧力の変化に伴う燃焼温度の変動を防ぐことができる。
本開示の実施形態にかかるガス発生剤組成物中における（ｃ）成分のメラミンシアヌレートの含有量としては、通常０．５重量％以上、１２重量％以下、好ましい一態様では１重量％以上、１１重量％以下であり、さらに好ましい一態様として１重量％以上、６．５重量％以下である。 (c) Melamine Cyanurate Component (c) according to the embodiment of the present disclosure is melamine cyanurate. When the gas generant composition containing (a) guanidine nitrate and (b) basic copper nitrate contains melamine cyanurate, the pressure index of the gas generant composition can be reduced. By reducing the pressure index, it is possible to prevent fluctuations in combustion temperature due to changes in pressure.
The content of melamine cyanurate as component (c) in the gas generant composition according to the embodiment of the present disclosure is usually 0.5% by weight or more and 12% by weight or less, preferably 1% by weight or more, It is 11% by weight or less, and more preferably 1% by weight or more and 6.5% by weight or less.
本開示の実施形態にかかる（ｃ）成分はメラミンシアヌレートである。（ａ）硝酸グアニジンと（ｂ）塩基性硝酸銅とを含むガス発生剤組成物において、メラミンシアヌレートを含有する場合、ガス発生剤組成物の圧力指数を小さくすることができる。圧力指数を小さくすることで、圧力の変化に伴う燃焼温度の変動を防ぐことができる。
本開示の実施形態にかかるガス発生剤組成物中における（ｃ）成分のメラミンシアヌレートの含有量としては、通常０．５重量％以上、１２重量％以下、好ましい一態様では１重量％以上、１１重量％以下であり、さらに好ましい一態様として１重量％以上、６．５重量％以下である。 (c) Melamine Cyanurate Component (c) according to the embodiment of the present disclosure is melamine cyanurate. When the gas generant composition containing (a) guanidine nitrate and (b) basic copper nitrate contains melamine cyanurate, the pressure index of the gas generant composition can be reduced. By reducing the pressure index, it is possible to prevent fluctuations in combustion temperature due to changes in pressure.
The content of melamine cyanurate as component (c) in the gas generant composition according to the embodiment of the present disclosure is usually 0.5% by weight or more and 12% by weight or less, preferably 1% by weight or more, It is 11% by weight or less, and more preferably 1% by weight or more and 6.5% by weight or less.
本開示のガス発生剤組成物における、成分（ａ）及び成分（ｂ）合計量と、成分（ｃ）の重量比（（（ａ）＋（ｂ））／（ｃ））の範囲は、圧力指数を小さくする観点から、通常８以上であり、１１．６以上を挙げることができ、１４．５以上であることが好ましく、２０以上であることがより好ましく、２１以上であることがさらに好ましい。一方、この比の上限は１５０以下であってよく、１２５以下であってよく、１００以下であってもよい。すなわち、通常８以上、１５０以下、別の態様では１１．６以上、１２５以下、さらに別の態様では１４．５以上、１２５以下、さらに別の態様では２０以上、１００以下を挙げることができる。圧力指数を小さくする観点では、この比はできるだけ大きい方が好ましい。
この比を調整するには、燃焼温度が１６８０Ｋ以上となる範囲で、硝酸グアニジン、塩基性硝酸銅、メラミンシアヌレートの含有量を調整すればよい。
ガス発生剤組成物の圧力指数を小さくするためには、ガス発生剤組成物として成分（ａ）及び成分（ｂ）に加え、成分（ｃ）を添加することが必要である。一方で、成分（ａ）及び成分（ｂ）合計量と、成分（ｃ）の重量比（（（ａ）＋（ｂ））／（ｃ））は、できるだけ大きいほど好ましい。つまり、成分（ａ）と成分（ｃ）の合計量に対する成分（ｃ）の重量割合は小さい方が好ましい。 In the gas generant composition of the present disclosure, the total amount of component (a) and component (b) and the weight ratio of component (c) (((a) + (b))/(c)) range From the viewpoint of reducing the index, it is usually 8 or more, can be 11.6 or more, preferably 14.5 or more, more preferably 20 or more, and further preferably 21 or more. . On the other hand, the upper limit of this ratio may be 150 or less, 125 or less, or 100 or less. That is, usually 8 or more and 150 or less, 11.6 or more and 125 or less in another embodiment, 14.5 or more and 125 or less in still another embodiment, and 20 or more and 100 or less in still another embodiment. From the viewpoint of reducing the pressure index, it is preferable that this ratio is as large as possible.
This ratio can be adjusted by adjusting the contents of guanidine nitrate, basic copper nitrate, and melamine cyanurate within the range where the combustion temperature is 1680K or higher.
In order to reduce the pressure index of the gas generant composition, it is necessary to add component (c) to the gas generant composition in addition to components (a) and (b). On the other hand, the weight ratio (((a)+(b))/(c)) of component (a) and component (b) to the total amount of component (c) is preferably as large as possible. That is, it is preferable that the weight ratio of component (c) to the total amount of components (a) and (c) is small.
この比を調整するには、燃焼温度が１６８０Ｋ以上となる範囲で、硝酸グアニジン、塩基性硝酸銅、メラミンシアヌレートの含有量を調整すればよい。
ガス発生剤組成物の圧力指数を小さくするためには、ガス発生剤組成物として成分（ａ）及び成分（ｂ）に加え、成分（ｃ）を添加することが必要である。一方で、成分（ａ）及び成分（ｂ）合計量と、成分（ｃ）の重量比（（（ａ）＋（ｂ））／（ｃ））は、できるだけ大きいほど好ましい。つまり、成分（ａ）と成分（ｃ）の合計量に対する成分（ｃ）の重量割合は小さい方が好ましい。 In the gas generant composition of the present disclosure, the total amount of component (a) and component (b) and the weight ratio of component (c) (((a) + (b))/(c)) range From the viewpoint of reducing the index, it is usually 8 or more, can be 11.6 or more, preferably 14.5 or more, more preferably 20 or more, and further preferably 21 or more. . On the other hand, the upper limit of this ratio may be 150 or less, 125 or less, or 100 or less. That is, usually 8 or more and 150 or less, 11.6 or more and 125 or less in another embodiment, 14.5 or more and 125 or less in still another embodiment, and 20 or more and 100 or less in still another embodiment. From the viewpoint of reducing the pressure index, it is preferable that this ratio is as large as possible.
This ratio can be adjusted by adjusting the contents of guanidine nitrate, basic copper nitrate, and melamine cyanurate within the range where the combustion temperature is 1680K or higher.
In order to reduce the pressure index of the gas generant composition, it is necessary to add component (c) to the gas generant composition in addition to components (a) and (b). On the other hand, the weight ratio (((a)+(b))/(c)) of component (a) and component (b) to the total amount of component (c) is preferably as large as possible. That is, it is preferable that the weight ratio of component (c) to the total amount of components (a) and (c) is small.
（ガス発生剤組成物の燃焼温度）
本開示におけるガス発生剤組成物の燃焼温度は“ＮＥＷＰＥＰ”として知られるプログラムを用いて計算されるものである。“ＮＥＷＰＥＰ”は１９６０年、１９７９年および１９９０年に発行された“平衡組成の理論的計算（Theoretical Computation of Equilibrium Composition、熱力学的性質（Thermodynamic Properties）および推進薬系の性能特性（Performance Characteristics of Propellant System））”と題する海軍武器センター報告（Naval Weapons Center Report）に記載のPEPプログラムに基づいている。このプログラムは公有財産であり、当業者は容易に利用できる。
このガス発生剤組成物の燃焼温度は、ガス発生剤組成物に含まれる構成要素の種類と組成比により決まるものである。本開示において、ガス発生剤組成物の燃焼温度は、硝酸グアニジン、塩基性硝酸銅およびメラミンシアヌレートからなる組成に基づき算出されるものであり、その燃焼温度を１６８０Ｋ以上とするものである。したがって、本開示におけるガス発生剤組成物にその他の任意成分が含まれている場合でも、燃焼温度は硝酸グアニジン、塩基性硝酸銅およびメラミンシアヌレートからなる組成に基づき算出する。ガス発生剤組成物の燃焼温度を１６８０Ｋとするには、硝酸グアニジン、塩基性硝酸銅およびメラミンシアヌレートの組成を適宜変更すればよい。
本開示のガス発生剤組成物の燃焼温度は、１６８０Ｋ以上であり、１７００Ｋ以上であってもよく、１７５０Ｋ以上であってもよく、１８００Ｋ以上であってもよく、１８５０Ｋ以上であってもよい。上限値は、例えば、２０００Ｋ以下を挙げることができ、１９５０Ｋ以下であってもよく、１９００Ｋ以下であってもよい。これらの燃焼温度の下限と上限は適宜組み合わせることができる。例えば下限を１６８０Ｋ以上とした場合に上限を２００Ｋ以下または１９５０以下とすることができるし、下限を他の数値に変え、上限を２００Ｋ以下または１９５０以下とすることもできる。上記でも説明したとおり、従来技術では、ガス発生剤組成物の燃焼温度を低くしようとするのが技術常識であったのに対し、本開示のガス発生剤組成物は燃焼温度を高く使用するものである。 (Combustion temperature of gas generant composition)
The combustion temperatures of the gas generant compositions in this disclosure are calculated using a program known as "NEWPEP". The "NEWPEP" was published in 1960, 1979 and 1990, entitled "Theoretical Computation of Equilibrium Composition, Thermodynamic Properties and Performance Characteristics of Propellant Systems." System)”, based on the PEP program described in the Naval Weapons Center Report. This program is in the public domain and readily available to those skilled in the art.
The combustion temperature of the gas generant composition is determined by the types and composition ratios of the components contained in the gas generant composition. In the present disclosure, the combustion temperature of the gas generant composition is calculated based on the composition consisting of guanidine nitrate, basic copper nitrate and melamine cyanurate, and the combustion temperature is 1680K or higher. Therefore, even if the gas generant composition in the present disclosure contains other optional ingredients, the combustion temperature is calculated based on the composition consisting of guanidine nitrate, basic copper nitrate and melamine cyanurate. The composition of guanidine nitrate, basic copper nitrate and melamine cyanurate may be appropriately changed in order to set the combustion temperature of the gas generating composition to 1680K.
The combustion temperature of the gas generant composition of the present disclosure may be 1680 K or higher, may be 1700 K or higher, may be 1750 K or higher, may be 1800 K or higher, or may be 1850 K or higher. The upper limit may be, for example, 2000K or less, may be 1950K or less, or may be 1900K or less. These lower and upper limits of the combustion temperature can be combined as appropriate. For example, when the lower limit is set to 1680K or more, the upper limit can be set to 200K or less or 1950 or less, or the lower limit can be changed to another numerical value to set the upper limit to 200K or less or 1950 or less. As explained above, in the prior art, it was common general knowledge to try to lower the combustion temperature of the gas generant composition, whereas the gas generant composition of the present disclosure uses a high combustion temperature. is.
本開示におけるガス発生剤組成物の燃焼温度は“ＮＥＷＰＥＰ”として知られるプログラムを用いて計算されるものである。“ＮＥＷＰＥＰ”は１９６０年、１９７９年および１９９０年に発行された“平衡組成の理論的計算（Theoretical Computation of Equilibrium Composition、熱力学的性質（Thermodynamic Properties）および推進薬系の性能特性（Performance Characteristics of Propellant System））”と題する海軍武器センター報告（Naval Weapons Center Report）に記載のPEPプログラムに基づいている。このプログラムは公有財産であり、当業者は容易に利用できる。
このガス発生剤組成物の燃焼温度は、ガス発生剤組成物に含まれる構成要素の種類と組成比により決まるものである。本開示において、ガス発生剤組成物の燃焼温度は、硝酸グアニジン、塩基性硝酸銅およびメラミンシアヌレートからなる組成に基づき算出されるものであり、その燃焼温度を１６８０Ｋ以上とするものである。したがって、本開示におけるガス発生剤組成物にその他の任意成分が含まれている場合でも、燃焼温度は硝酸グアニジン、塩基性硝酸銅およびメラミンシアヌレートからなる組成に基づき算出する。ガス発生剤組成物の燃焼温度を１６８０Ｋとするには、硝酸グアニジン、塩基性硝酸銅およびメラミンシアヌレートの組成を適宜変更すればよい。
本開示のガス発生剤組成物の燃焼温度は、１６８０Ｋ以上であり、１７００Ｋ以上であってもよく、１７５０Ｋ以上であってもよく、１８００Ｋ以上であってもよく、１８５０Ｋ以上であってもよい。上限値は、例えば、２０００Ｋ以下を挙げることができ、１９５０Ｋ以下であってもよく、１９００Ｋ以下であってもよい。これらの燃焼温度の下限と上限は適宜組み合わせることができる。例えば下限を１６８０Ｋ以上とした場合に上限を２００Ｋ以下または１９５０以下とすることができるし、下限を他の数値に変え、上限を２００Ｋ以下または１９５０以下とすることもできる。上記でも説明したとおり、従来技術では、ガス発生剤組成物の燃焼温度を低くしようとするのが技術常識であったのに対し、本開示のガス発生剤組成物は燃焼温度を高く使用するものである。 (Combustion temperature of gas generant composition)
The combustion temperatures of the gas generant compositions in this disclosure are calculated using a program known as "NEWPEP". The "NEWPEP" was published in 1960, 1979 and 1990, entitled "Theoretical Computation of Equilibrium Composition, Thermodynamic Properties and Performance Characteristics of Propellant Systems." System)”, based on the PEP program described in the Naval Weapons Center Report. This program is in the public domain and readily available to those skilled in the art.
The combustion temperature of the gas generant composition is determined by the types and composition ratios of the components contained in the gas generant composition. In the present disclosure, the combustion temperature of the gas generant composition is calculated based on the composition consisting of guanidine nitrate, basic copper nitrate and melamine cyanurate, and the combustion temperature is 1680K or higher. Therefore, even if the gas generant composition in the present disclosure contains other optional ingredients, the combustion temperature is calculated based on the composition consisting of guanidine nitrate, basic copper nitrate and melamine cyanurate. The composition of guanidine nitrate, basic copper nitrate and melamine cyanurate may be appropriately changed in order to set the combustion temperature of the gas generating composition to 1680K.
The combustion temperature of the gas generant composition of the present disclosure may be 1680 K or higher, may be 1700 K or higher, may be 1750 K or higher, may be 1800 K or higher, or may be 1850 K or higher. The upper limit may be, for example, 2000K or less, may be 1950K or less, or may be 1900K or less. These lower and upper limits of the combustion temperature can be combined as appropriate. For example, when the lower limit is set to 1680K or more, the upper limit can be set to 200K or less or 1950 or less, or the lower limit can be changed to another numerical value to set the upper limit to 200K or less or 1950 or less. As explained above, in the prior art, it was common general knowledge to try to lower the combustion temperature of the gas generant composition, whereas the gas generant composition of the present disclosure uses a high combustion temperature. is.
また、ガス発生剤組成物のガス発生効率についても、燃焼温度と同様にＮＥＷＰＥＰのプログラムから計算されるものである。本開示のガス発生剤組成物のガス発生効率については特に制限はないが、例えば、２．５ｍｏｌ／１００ｇ以上、３．５ｍｏｌ／１００ｇ以下を挙げることができ、２．７ｍｏｌ／１００ｇ以上、３．２ｍｏｌ／１００ｇ以下を挙げることができる。
また、本開示のガス発生剤組成物において、硝酸グアニジン、塩基性硝酸銅およびメラミンシアヌレートからなる組成に基づき算出される酸素バランスは－２．５以上、－０．１以下であることが好ましい。この酸素バランスは、ガス発生剤組成物に含有される硝酸グアニジン、塩基性硝酸銅およびメラミンシアヌレートからなる組成比から算出されるものである。 The gas generation efficiency of the gas generating agent composition is also calculated from the NEWPEP program in the same manner as the combustion temperature. The gas generating efficiency of the gas generating agent composition of the present disclosure is not particularly limited, but may be, for example, 2.5 mol/100 g or more and 3.5 mol/100 g or less, 2.7 mol/100 g or more, 3. 2 mol/100 g or less can be mentioned.
Further, in the gas generant composition of the present disclosure, the oxygen balance calculated based on the composition consisting of guanidine nitrate, basic copper nitrate and melamine cyanurate is preferably -2.5 or more and -0.1 or less. . This oxygen balance is calculated from the composition ratio of guanidine nitrate, basic copper nitrate and melamine cyanurate contained in the gas generating composition.
また、本開示のガス発生剤組成物において、硝酸グアニジン、塩基性硝酸銅およびメラミンシアヌレートからなる組成に基づき算出される酸素バランスは－２．５以上、－０．１以下であることが好ましい。この酸素バランスは、ガス発生剤組成物に含有される硝酸グアニジン、塩基性硝酸銅およびメラミンシアヌレートからなる組成比から算出されるものである。 The gas generation efficiency of the gas generating agent composition is also calculated from the NEWPEP program in the same manner as the combustion temperature. The gas generating efficiency of the gas generating agent composition of the present disclosure is not particularly limited, but may be, for example, 2.5 mol/100 g or more and 3.5 mol/100 g or less, 2.7 mol/100 g or more, 3. 2 mol/100 g or less can be mentioned.
Further, in the gas generant composition of the present disclosure, the oxygen balance calculated based on the composition consisting of guanidine nitrate, basic copper nitrate and melamine cyanurate is preferably -2.5 or more and -0.1 or less. . This oxygen balance is calculated from the composition ratio of guanidine nitrate, basic copper nitrate and melamine cyanurate contained in the gas generating composition.
（圧力指数）
ガス発生剤組成物の燃焼速度は、インフレータ内の圧力変動により、圧力指数ｎのべき乗の幅で変動することが知られている。
ｒｂ＝αＰn（式中、ｒｂ：燃焼速度、α：燃焼係数、Ｐ：圧力、ｎ：圧力指数）
本開示において、ガス発生剤組成物の圧力指数及び燃焼係数は、上記の式に基づき、５ＭＰａ、７ＭＰａ、および９ＭＰａの圧力下で測定された燃焼速度から算出されるものである。
本開示のガス発生剤組成物の圧力指数は、圧力の変化に伴う着火速度の変動を防ぐためにできるだけ小さいことが望ましく、例えば０．３５以下であることが好ましく、０．３１以下であることがより好ましく、０．２３以下であることがさらに好ましく、０．２未満であることが特に好ましい。一方、ガス発生剤組成物の圧力指数の下限値は、例えば０．０１以上を挙げることができ、０．０５以上であってもよい。これらの圧力指数の上限と下限は適宜組み合わせることができる。例えば上限を０．３５以下とした場合に下限を０．０１以上または０．０５以上とすることができるし、上限を他の数値に変え、下限を０．０１以上または０．０５以上とすることもできる。
本開示におけるガス発生剤組成物では、硝酸グアニジン及び塩基性硝酸銅を含有することに加え、メラミンシアヌレートを含有することで、メラミンシアヌレートを含有しないガス発生剤組成物に比べて、圧力指数を小さくすることができる。 (pressure index)
It is known that the combustion rate of the gas generating composition fluctuates within the power of the pressure index n due to pressure fluctuations in the inflator.
rb=αP n (where, rb: combustion rate, α: combustion coefficient, P: pressure, n: pressure index)
In the present disclosure, the pressure index and burning coefficient of the gas generant composition are calculated from burning rates measured under pressures of 5 MPa, 7 MPa, and 9 MPa, based on the above equations.
The pressure index of the gas generant composition of the present disclosure is desirably as small as possible in order to prevent fluctuations in ignition speed due to changes in pressure, for example, preferably 0.35 or less, preferably 0.31 or less. It is more preferably 0.23 or less, and particularly preferably less than 0.2. On the other hand, the lower limit of the pressure index of the gas generating composition can be, for example, 0.01 or more, and may be 0.05 or more. The upper and lower limits of these pressure indices can be combined as appropriate. For example, when the upper limit is 0.35 or less, the lower limit can be 0.01 or more or 0.05 or more, or the upper limit can be changed to another numerical value and the lower limit is 0.01 or more or 0.05 or more. can also
In addition to containing guanidine nitrate and basic copper nitrate, the gas generant composition of the present disclosure contains melamine cyanurate. can be made smaller.
ガス発生剤組成物の燃焼速度は、インフレータ内の圧力変動により、圧力指数ｎのべき乗の幅で変動することが知られている。
ｒｂ＝αＰn（式中、ｒｂ：燃焼速度、α：燃焼係数、Ｐ：圧力、ｎ：圧力指数）
本開示において、ガス発生剤組成物の圧力指数及び燃焼係数は、上記の式に基づき、５ＭＰａ、７ＭＰａ、および９ＭＰａの圧力下で測定された燃焼速度から算出されるものである。
本開示のガス発生剤組成物の圧力指数は、圧力の変化に伴う着火速度の変動を防ぐためにできるだけ小さいことが望ましく、例えば０．３５以下であることが好ましく、０．３１以下であることがより好ましく、０．２３以下であることがさらに好ましく、０．２未満であることが特に好ましい。一方、ガス発生剤組成物の圧力指数の下限値は、例えば０．０１以上を挙げることができ、０．０５以上であってもよい。これらの圧力指数の上限と下限は適宜組み合わせることができる。例えば上限を０．３５以下とした場合に下限を０．０１以上または０．０５以上とすることができるし、上限を他の数値に変え、下限を０．０１以上または０．０５以上とすることもできる。
本開示におけるガス発生剤組成物では、硝酸グアニジン及び塩基性硝酸銅を含有することに加え、メラミンシアヌレートを含有することで、メラミンシアヌレートを含有しないガス発生剤組成物に比べて、圧力指数を小さくすることができる。 (pressure index)
It is known that the combustion rate of the gas generating composition fluctuates within the power of the pressure index n due to pressure fluctuations in the inflator.
rb=αP n (where, rb: combustion rate, α: combustion coefficient, P: pressure, n: pressure index)
In the present disclosure, the pressure index and burning coefficient of the gas generant composition are calculated from burning rates measured under pressures of 5 MPa, 7 MPa, and 9 MPa, based on the above equations.
The pressure index of the gas generant composition of the present disclosure is desirably as small as possible in order to prevent fluctuations in ignition speed due to changes in pressure, for example, preferably 0.35 or less, preferably 0.31 or less. It is more preferably 0.23 or less, and particularly preferably less than 0.2. On the other hand, the lower limit of the pressure index of the gas generating composition can be, for example, 0.01 or more, and may be 0.05 or more. The upper and lower limits of these pressure indices can be combined as appropriate. For example, when the upper limit is 0.35 or less, the lower limit can be 0.01 or more or 0.05 or more, or the upper limit can be changed to another numerical value and the lower limit is 0.01 or more or 0.05 or more. can also
In addition to containing guanidine nitrate and basic copper nitrate, the gas generant composition of the present disclosure contains melamine cyanurate. can be made smaller.
（その他の任意成分）
本開示のガス発生剤組成物は、本開示の課題を解決できる範囲で、ガス発生剤組成物の燃焼速度を調整し、燃焼ガスを清浄にする目的等のために公知の各種添加剤を含有することができる。公知の添加剤としては、酸化第二銅、酸化鉄、酸化亜鉛、酸化コバルト、酸化マンガン、酸化モリブデン、酸化ニッケル、酸化ビスマス、シリカ、アルミナ等の金属酸化物；水酸化アルミニウム、水酸化マグネシウム、水酸化コバルト、水酸化鉄等の金属水酸化物；炭酸コバルト、炭酸カルシウム；酸性白土、カオリン、タルク、ベントナイト、ケイソウ土等の金属酸化物又は水酸化物の複合化合物；ケイ酸ナトリウム、マイカモリブデン酸塩、モリブデン酸コバルト、モリブデン酸アンモニウム等の金属酸塩；二硫化モリブデン、ステアリン酸カルシウム、窒化ケイ素、炭化ケイ素、メタホウ酸、ホウ酸、無水ホウ酸等を挙げることができる。
本開示のガス発生剤組成物において、成分（ａ）～（ｃ）以外の任意成分の含有量は、例えば、５重量％以下であってもよく、３重量％以下であってもよく、１重量％以下であってもよく、０重量％であってもよい。本開示のガス発生剤組成物は、成分（ａ）～（ｃ）以外の任意成分の含有量が０重量％である態様、すなわち成分（ａ）～（ｃ）のみから構成される態様であってもよい。 (Other optional ingredients)
The gas generant composition of the present disclosure contains various known additives for the purpose of adjusting the combustion rate of the gas generant composition and cleaning the combustion gas, etc., within the range that can solve the problems of the present disclosure. can do. Known additives include metal oxides such as cupric oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide, bismuth oxide, silica, and alumina; aluminum hydroxide, magnesium hydroxide, Metal hydroxides such as cobalt hydroxide and iron hydroxide; cobalt carbonate, calcium carbonate; composite compounds of metal oxides or hydroxides such as acid clay, kaolin, talc, bentonite, and diatomaceous earth; sodium silicate, molybdenum mica metal salts such as acid salts, cobalt molybdate, and ammonium molybdate; molybdenum disulfide, calcium stearate, silicon nitride, silicon carbide, metaboric acid, boric acid, boric anhydride, and the like.
In the gas generant composition of the present disclosure, the content of optional components other than components (a) to (c) may be, for example, 5% by weight or less, or 3% by weight or less. It may be less than or equal to 0% by weight. The gas generant composition of the present disclosure is an aspect in which the content of optional components other than components (a) to (c) is 0% by weight, that is, an aspect composed only of components (a) to (c). may
本開示のガス発生剤組成物は、本開示の課題を解決できる範囲で、ガス発生剤組成物の燃焼速度を調整し、燃焼ガスを清浄にする目的等のために公知の各種添加剤を含有することができる。公知の添加剤としては、酸化第二銅、酸化鉄、酸化亜鉛、酸化コバルト、酸化マンガン、酸化モリブデン、酸化ニッケル、酸化ビスマス、シリカ、アルミナ等の金属酸化物；水酸化アルミニウム、水酸化マグネシウム、水酸化コバルト、水酸化鉄等の金属水酸化物；炭酸コバルト、炭酸カルシウム；酸性白土、カオリン、タルク、ベントナイト、ケイソウ土等の金属酸化物又は水酸化物の複合化合物；ケイ酸ナトリウム、マイカモリブデン酸塩、モリブデン酸コバルト、モリブデン酸アンモニウム等の金属酸塩；二硫化モリブデン、ステアリン酸カルシウム、窒化ケイ素、炭化ケイ素、メタホウ酸、ホウ酸、無水ホウ酸等を挙げることができる。
本開示のガス発生剤組成物において、成分（ａ）～（ｃ）以外の任意成分の含有量は、例えば、５重量％以下であってもよく、３重量％以下であってもよく、１重量％以下であってもよく、０重量％であってもよい。本開示のガス発生剤組成物は、成分（ａ）～（ｃ）以外の任意成分の含有量が０重量％である態様、すなわち成分（ａ）～（ｃ）のみから構成される態様であってもよい。 (Other optional ingredients)
The gas generant composition of the present disclosure contains various known additives for the purpose of adjusting the combustion rate of the gas generant composition and cleaning the combustion gas, etc., within the range that can solve the problems of the present disclosure. can do. Known additives include metal oxides such as cupric oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide, bismuth oxide, silica, and alumina; aluminum hydroxide, magnesium hydroxide, Metal hydroxides such as cobalt hydroxide and iron hydroxide; cobalt carbonate, calcium carbonate; composite compounds of metal oxides or hydroxides such as acid clay, kaolin, talc, bentonite, and diatomaceous earth; sodium silicate, molybdenum mica metal salts such as acid salts, cobalt molybdate, and ammonium molybdate; molybdenum disulfide, calcium stearate, silicon nitride, silicon carbide, metaboric acid, boric acid, boric anhydride, and the like.
In the gas generant composition of the present disclosure, the content of optional components other than components (a) to (c) may be, for example, 5% by weight or less, or 3% by weight or less. It may be less than or equal to 0% by weight. The gas generant composition of the present disclosure is an aspect in which the content of optional components other than components (a) to (c) is 0% by weight, that is, an aspect composed only of components (a) to (c). may
本開示の実施形態にかかるガス発生剤組成物は所望の形状に成形することができ、単孔円柱状、多孔円柱状又はペレット状の成形体にすることができる。これらの成形体は、ガス発生剤組成物に水又は有機溶媒を添加混合し、押出成型する方法（単孔円柱状、多孔円柱状の成形体）又は打錠機等を用いて圧縮成型する方法（ペレット状の成形体）により製造することができる。
本開示の実施形態にかかるガス発生剤組成物は高い燃焼速度を有しているので、成形体を小さくする必要がなく、製造工程が煩雑にならない。 The gas generant composition according to the embodiments of the present disclosure can be molded into a desired shape, and can be formed into a single-hole cylindrical shape, a multi-hole cylindrical shape, or a pellet-like shaped body. These molded bodies are produced by adding and mixing water or an organic solvent to the gas generant composition, followed by extrusion molding (single-hole cylindrical or porous cylindrical moldings) or compression molding using a tableting machine or the like. (Pellet shaped compact).
Since the gas generant composition according to the embodiment of the present disclosure has a high burning rate, there is no need to reduce the size of the compact, and the manufacturing process does not become complicated.
本開示の実施形態にかかるガス発生剤組成物は高い燃焼速度を有しているので、成形体を小さくする必要がなく、製造工程が煩雑にならない。 The gas generant composition according to the embodiments of the present disclosure can be molded into a desired shape, and can be formed into a single-hole cylindrical shape, a multi-hole cylindrical shape, or a pellet-like shaped body. These molded bodies are produced by adding and mixing water or an organic solvent to the gas generant composition, followed by extrusion molding (single-hole cylindrical or porous cylindrical moldings) or compression molding using a tableting machine or the like. (Pellet shaped compact).
Since the gas generant composition according to the embodiment of the present disclosure has a high burning rate, there is no need to reduce the size of the compact, and the manufacturing process does not become complicated.
本開示の実施形態にかかるガス発生剤組成物又はそれから得られる成形体は、例えば、各種乗り物の運転席のエアバッグ用インフレータ、助手席のエアバッグ用インフレータ、サイドエアバック用インフレータ、インフレータブルカーテン用インフレータ、ニーボルスター用インフレータ、インフレータブルシートベルト用インフレータ、チューブラーシステム用インフレータ、プリテンショナー用インフレータに適用できる。本開示の実施形態にかかるガス発生剤組成物又はそれから得られる成形体は、これらの中でも、早期展開が必要とされるサイドエアバッグ用インフレータに好ましく適用できる。
The gas generant composition according to the embodiment of the present disclosure or a molded article obtained therefrom can be used, for example, for driver airbag inflators, passenger airbag inflators, side airbag inflators, and inflatable curtains of various vehicles. It can be applied to inflators, knee bolster inflators, inflatable seat belt inflators, tubular system inflators, and pretensioner inflators. Among these, the gas generant composition according to the embodiment of the present disclosure or the molded article obtained therefrom can be preferably applied to side airbag inflators that require early deployment.
また本開示の実施形態にかかるガス発生剤組成物又はそれから得られる成形体を含むインフレータは、ガスの供給が、ガス発生剤からだけのパイロタイプと、アルゴン等の圧縮ガスとガス発生剤の両方であるハイブリッドタイプのいずれでもよい。
In addition, the inflator containing the gas generating agent composition or the molded article obtained therefrom according to the embodiment of the present disclosure includes a pyrotype in which gas is supplied only from the gas generating agent, and a compressed gas such as argon and a gas generating agent. Any of the hybrid types may be used.
本開示の実施形態にかかるガス発生剤組成物又はそれから得られる成形体は、***やスクイブのエネルギーをガス発生剤に伝えるためのエンハンサ剤（又はブースター）等と呼ばれる着火剤として用いることもできる。
各実施形態における各構成及びそれらの組み合わせ等は、一例であって、本発明の主旨から逸脱しない範囲内で、適宜、構成の付加、省略、置換、及びその他の変更が可能である。本開示は、実施形態によって限定されることはなく、クレームの範囲によってのみ限定される。 The gas generant composition according to the embodiment of the present disclosure or a molded article obtained therefrom can also be used as an ignition agent called an enhancer (or booster) or the like for transmitting the energy of a detonator or a squib to the gas generant.
Each configuration and combination thereof in each embodiment is an example, and addition, omission, replacement, and other changes of configuration are possible as appropriate without departing from the scope of the present invention. This disclosure is not limited by the embodiments, but only by the scope of the claims.
各実施形態における各構成及びそれらの組み合わせ等は、一例であって、本発明の主旨から逸脱しない範囲内で、適宜、構成の付加、省略、置換、及びその他の変更が可能である。本開示は、実施形態によって限定されることはなく、クレームの範囲によってのみ限定される。 The gas generant composition according to the embodiment of the present disclosure or a molded article obtained therefrom can also be used as an ignition agent called an enhancer (or booster) or the like for transmitting the energy of a detonator or a squib to the gas generant.
Each configuration and combination thereof in each embodiment is an example, and addition, omission, replacement, and other changes of configuration are possible as appropriate without departing from the scope of the present invention. This disclosure is not limited by the embodiments, but only by the scope of the claims.
以下、実施例を参照して本開示を具体的に説明する。ただし、本開示は以下の実施例の態様に制限されない。
＜ガス発生剤組成物の調製＞
表１に示す組成を有する、成形前のガス発生剤組成物を調製した。
＊燃焼温度、ガス発生効率はＮＥＷＰＥＰに基づき算出された数値である。
＊＊酸素バランスは組成から導かれる計算値である。 The present disclosure will be specifically described below with reference to examples. However, the present disclosure is not limited to the aspects of the following examples.
<Preparation of gas generant composition>
A pre-molding gas generant composition having the composition shown in Table 1 was prepared.
*Combustion temperature and gas generation efficiency are values calculated based on NEWPEP.
**Oxygen balance is a calculated value derived from composition.
＜ガス発生剤組成物の調製＞
表１に示す組成を有する、成形前のガス発生剤組成物を調製した。
＊燃焼温度、ガス発生効率はＮＥＷＰＥＰに基づき算出された数値である。
＊＊酸素バランスは組成から導かれる計算値である。 The present disclosure will be specifically described below with reference to examples. However, the present disclosure is not limited to the aspects of the following examples.
<Preparation of gas generant composition>
A pre-molding gas generant composition having the composition shown in Table 1 was prepared.
*Combustion temperature and gas generation efficiency are values calculated based on NEWPEP.
**Oxygen balance is a calculated value derived from composition.
＜円柱状ストランドへの成形＞
表１に記載の実施例及び比較例の各ガス発生剤組成で秤量後、混合した原料を圧縮成型し、成形体を得た。
得られた成形体をめのう乳鉢で粉砕し、５００μｍの目開きの金網を通過させた粉体を所定の金型の臼側に充填した。
次に、杵側端面より油圧ポンプで圧力１４．７ＭＰａにて５秒間圧縮保持させた後、取り出し、外径９．６±０．１ｍｍ、長さ１２．７±１．０ｍｍの円柱状ストランドに成形し、成形後のガス発生剤組成物を得た。 <Forming into a cylindrical strand>
After weighing the compositions of the gas generating agents of Examples and Comparative Examples shown in Table 1, the mixed raw materials were compression-molded to obtain molded bodies.
The resulting compact was pulverized in an agate mortar, and the powder passed through a wire mesh with an opening of 500 μm was filled in the mortar side of a predetermined mold.
Next, after compressing and holding for 5 seconds at a pressure of 14.7 MPa from the end face of the punch with a hydraulic pump, it was taken out and made into a cylindrical strand having an outer diameter of 9.6 ± 0.1 mm and a length of 12.7 ± 1.0 mm. It was molded to obtain a molded gas generant composition.
表１に記載の実施例及び比較例の各ガス発生剤組成で秤量後、混合した原料を圧縮成型し、成形体を得た。
得られた成形体をめのう乳鉢で粉砕し、５００μｍの目開きの金網を通過させた粉体を所定の金型の臼側に充填した。
次に、杵側端面より油圧ポンプで圧力１４．７ＭＰａにて５秒間圧縮保持させた後、取り出し、外径９．６±０．１ｍｍ、長さ１２．７±１．０ｍｍの円柱状ストランドに成形し、成形後のガス発生剤組成物を得た。 <Forming into a cylindrical strand>
After weighing the compositions of the gas generating agents of Examples and Comparative Examples shown in Table 1, the mixed raw materials were compression-molded to obtain molded bodies.
The resulting compact was pulverized in an agate mortar, and the powder passed through a wire mesh with an opening of 500 μm was filled in the mortar side of a predetermined mold.
Next, after compressing and holding for 5 seconds at a pressure of 14.7 MPa from the end face of the punch with a hydraulic pump, it was taken out and made into a cylindrical strand having an outer diameter of 9.6 ± 0.1 mm and a length of 12.7 ± 1.0 mm. It was molded to obtain a molded gas generant composition.
＜燃焼速度及び圧力指数の測定方法＞
サンプルとなる円柱状ストランドを内容積１ＬのＳＵＳ製密閉ボンブ内に設置して、ボンブ内を完全に窒素置換しながら、５ＭＰａ、７ＭＰａまたは９ＭＰａにまで加圧安定させた。その後、ストランド端面に接触させたニクロム線に所定の電流を流し、その溶断エネルギーにより着火、燃焼させた。ボンブ内の経時圧力挙動は、記録計のチャートにて確認し、燃焼開始から圧力上昇ピークまでの経過時間をチャートの目盛りから確認し、燃焼前のストランド長さをこの経過時間で除して算出した数値を燃焼速度とした。実施例及び比較例の７ＭＰａの加圧時の試験結果を表１に示す。また、それぞれの圧力下で得られた燃焼速度の数値を用いて圧力指数を求めた。結果を表１に示す。 <Measuring method of burning velocity and pressure index>
A cylindrical strand as a sample was placed in a sealed SUS bomb having an internal volume of 1 L, and was pressurized and stabilized to 5 MPa, 7 MPa or 9 MPa while completely replacing the inside of the bomb with nitrogen. After that, a predetermined current was passed through the nichrome wire brought into contact with the strand end face, and the fusion energy was used to ignite and burn the wire. The time-dependent pressure behavior in the bomb is checked on the chart of the recorder, the elapsed time from the start of combustion to the pressure rise peak is checked from the scale of the chart, and the strand length before combustion is divided by this elapsed time. The calculated numerical value was taken as the burning speed. Table 1 shows the test results of Examples and Comparative Examples when a pressure of 7 MPa was applied. Also, the pressure index was determined using the numerical value of the burning rate obtained under each pressure. Table 1 shows the results.
サンプルとなる円柱状ストランドを内容積１ＬのＳＵＳ製密閉ボンブ内に設置して、ボンブ内を完全に窒素置換しながら、５ＭＰａ、７ＭＰａまたは９ＭＰａにまで加圧安定させた。その後、ストランド端面に接触させたニクロム線に所定の電流を流し、その溶断エネルギーにより着火、燃焼させた。ボンブ内の経時圧力挙動は、記録計のチャートにて確認し、燃焼開始から圧力上昇ピークまでの経過時間をチャートの目盛りから確認し、燃焼前のストランド長さをこの経過時間で除して算出した数値を燃焼速度とした。実施例及び比較例の７ＭＰａの加圧時の試験結果を表１に示す。また、それぞれの圧力下で得られた燃焼速度の数値を用いて圧力指数を求めた。結果を表１に示す。 <Measuring method of burning velocity and pressure index>
A cylindrical strand as a sample was placed in a sealed SUS bomb having an internal volume of 1 L, and was pressurized and stabilized to 5 MPa, 7 MPa or 9 MPa while completely replacing the inside of the bomb with nitrogen. After that, a predetermined current was passed through the nichrome wire brought into contact with the strand end face, and the fusion energy was used to ignite and burn the wire. The time-dependent pressure behavior in the bomb is checked on the chart of the recorder, the elapsed time from the start of combustion to the pressure rise peak is checked from the scale of the chart, and the strand length before combustion is divided by this elapsed time. The calculated numerical value was taken as the burning speed. Table 1 shows the test results of Examples and Comparative Examples when a pressure of 7 MPa was applied. Also, the pressure index was determined using the numerical value of the burning rate obtained under each pressure. Table 1 shows the results.
表１の実施例及び比較例の結果の比較から、硝酸グアニジンと塩基性硝酸銅を含有するガス発生剤組成物において、メラミンシアヌレートをさらに含有する場合には、ガス発生剤組成物の圧力指数を小さくすることができるのに加え、７ＭＰａ加圧化での燃焼速度を向上させられることが分かった。
From the comparison of the results of Examples and Comparative Examples in Table 1, it can be seen that in the gas generant composition containing guanidine nitrate and basic copper nitrate, when melamine cyanurate is further contained, the pressure index of the gas generant composition can be reduced, and the combustion rate at 7 MPa pressurization can be improved.
本開示によれば、高い燃焼温度、小さい圧力指数及び所望の燃焼速度を有するガス発生剤組成物を提供できる。
According to the present disclosure, it is possible to provide a gas generant composition having a high combustion temperature, a small pressure index and a desired combustion rate.
Claims (13)
- 以下の（ａ）～（ｃ）の成分を含むガス発生剤組成物であって、以下の（ａ）～（ｃ）からなる組成に基づき算出される燃焼温度が１６８０Ｋ以上である、ガス発生剤組成物。
（ａ）硝酸グアニジン
（ｂ）塩基性硝酸銅
（ｃ）メラミンシアヌレート A gas generating agent composition containing the following components (a) to (c), wherein the combustion temperature calculated based on the composition consisting of (a) to (c) below is 1680 K or higher. Composition.
(a) guanidine nitrate (b) basic copper nitrate (c) melamine cyanurate - 前記（ａ）硝酸グアニジンの含有量が３０重量％以上、６０重量％以下であり、
前記（ｂ）塩基性硝酸銅の含有量が４０重量％以上、６５重量％以下であり、
前記（ｃ）メラミンシアヌレートの含有量が０．５重量％以上１２重量％以下である、請求項１に記載のガス発生剤組成物。 The content of the (a) guanidine nitrate is 30% by weight or more and 60% by weight or less,
The content of the (b) basic copper nitrate is 40% by weight or more and 65% by weight or less,
2. The gas generant composition according to claim 1, wherein the content of (c) melamine cyanurate is 0.5% by weight or more and 12% by weight or less. - 前記（ａ）硝酸グアニジンの含有量が３２重量％以上、５５重量％以下である、請求項２に記載のガス発生剤組成物。 The gas generant composition according to claim 2, wherein the content of (a) guanidine nitrate is 32% by weight or more and 55% by weight or less.
- 前記（ｂ）塩基性硝酸銅の含有量が４３重量％以上、６０重量％以下である、請求項２に記載のガス発生剤組成物。 The gas generant composition according to claim 2, wherein the content of (b) basic copper nitrate is 43% by weight or more and 60% by weight or less.
- 前記（ｃ）メラミンシアヌレートの含有量が１重量％以上、１１重量％以下である、請求項２に記載のガス発生剤組成物。 The gas generant composition according to claim 2, wherein the content of (c) melamine cyanurate is 1% by weight or more and 11% by weight or less.
- 前記（ａ）～（ｃ）からなる組成に基づき算出される燃焼温度が１７００Ｋ以上である、請求項１～５のいずれか一項に記載のガス発生剤組成物。 The gas generant composition according to any one of claims 1 to 5, wherein the combustion temperature calculated based on the composition consisting of (a) to (c) is 1700K or higher.
- 前記（ａ）～（ｃ）からなる組成に基づき算出される燃焼温度が２０００Ｋ以下である、請求項１～６のいずれか一項に記載のガス発生剤組成物。 The gas generant composition according to any one of claims 1 to 6, wherein the combustion temperature calculated based on the composition consisting of (a) to (c) is 2000K or less.
- 圧力指数が０．３５以下である、請求項１～７のいずれか一項に記載のガス発生剤組成物。 The gas generant composition according to any one of claims 1 to 7, which has a pressure index of 0.35 or less.
- 圧力指数が０．２３以下である、請求項８に記載のガス発生剤組成物。 The gas generant composition according to claim 8, which has a pressure index of 0.23 or less.
- 圧力指数が０．０１以上である、請求項８に記載のガス発生剤組成物。 The gas generant composition according to claim 8, which has a pressure index of 0.01 or more.
- 前記成分（ａ）及び前記成分（ｂ）の合計量と、前記成分（ｃ）の重量比（（（ａ）＋（ｂ））／（ｃ））の範囲が、８以上１５０以下である、請求項１～１０のいずれか一項に記載のガス発生剤組成物。 The total amount of the component (a) and the component (b) and the weight ratio of the component (c) (((a) + (b)) / (c)) is in the range of 8 or more and 150 or less. The gas generant composition according to any one of claims 1-10.
- 前記成分（ａ）及び成分（ｂ）の合計量と、成分（ｃ）の重量比（（（ａ）＋（ｂ））／（ｃ））の範囲が、１１．６以上１２５以下である、請求項１１に記載のガス発生剤組成物。 The total amount of the component (a) and the component (b) and the weight ratio of the component (c) (((a) + (b)) / (c)) is in the range of 11.6 or more and 125 or less. 12. The gas generant composition of claim 11.
- 請求項１～１２のいずれか一項に記載のガス発生剤組成物を含む、インフレータ。
An inflator comprising the gas generant composition according to any one of claims 1 to 12.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004067424A (en) * | 2002-08-05 | 2004-03-04 | Daicel Chem Ind Ltd | Gas generator composition for inflator containing melamine cyanurate |
| WO2010134466A1 (en) * | 2009-05-21 | 2010-11-25 | ダイセル化学工業株式会社 | Gas generant composition |
| US20130248062A1 (en) * | 2012-03-23 | 2013-09-26 | Trw Airbag Systems Gmbh | Gas generating composition |
| WO2014061397A1 (en) * | 2012-10-18 | 2014-04-24 | 株式会社ダイセル | Gas-generating-agent composition and gas generator using same |
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2023
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|---|---|---|---|---|
| JP2004067424A (en) * | 2002-08-05 | 2004-03-04 | Daicel Chem Ind Ltd | Gas generator composition for inflator containing melamine cyanurate |
| WO2010134466A1 (en) * | 2009-05-21 | 2010-11-25 | ダイセル化学工業株式会社 | Gas generant composition |
| US20130248062A1 (en) * | 2012-03-23 | 2013-09-26 | Trw Airbag Systems Gmbh | Gas generating composition |
| WO2014061397A1 (en) * | 2012-10-18 | 2014-04-24 | 株式会社ダイセル | Gas-generating-agent composition and gas generator using same |
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