WO2023167222A1 - Composition d'agent générateur de gaz - Google Patents

Composition d'agent générateur de gaz Download PDF

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Publication number
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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WO
WIPO (PCT)
Prior art keywords
gas generant
weight
generant composition
less
gas
Prior art date
Application number
PCT/JP2023/007486
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English (en)
Japanese (ja)
Inventor
諭史 吉田
陽次 藤▲崎▼
隼人 古上
Original Assignee
株式会社ダイセル
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社ダイセル filed Critical 株式会社ダイセル
Publication of WO2023167222A1 publication Critical patent/WO2023167222A1/fr

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Classifications

    • 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
    • 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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Air Bags (AREA)

Abstract

L'invention concerne une composition d'agent générateur de gaz comprenant les composants (a) à (c) suivants, la température de combustion calculée sur la base d'une composition comprenant les composants (a) à (c) suivants étant de 1680K ou plus : (a) nitrate de guanidine ; (b) nitrate basique de cuivre ; et (c) cyanurate de mélamine.
PCT/JP2023/007486 2022-03-03 2023-03-01 Composition d'agent générateur de gaz WO2023167222A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022032715 2022-03-03
JP2022-032715 2022-03-03

Publications (1)

Publication Number Publication Date
WO2023167222A1 true WO2023167222A1 (fr) 2023-09-07

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004067424A (ja) * 2002-08-05 2004-03-04 Daicel Chem Ind Ltd メラミンシアヌレートを含むインフレータ用ガス発生剤組成物
WO2010134466A1 (fr) * 2009-05-21 2010-11-25 ダイセル化学工業株式会社 Composition génératrice de gaz
US20130248062A1 (en) * 2012-03-23 2013-09-26 Trw Airbag Systems Gmbh Gas generating composition
WO2014061397A1 (fr) * 2012-10-18 2014-04-24 株式会社ダイセル Composition d'agent générant du gaz, et générateur de gaz mettant en œuvre celui-ci

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004067424A (ja) * 2002-08-05 2004-03-04 Daicel Chem Ind Ltd メラミンシアヌレートを含むインフレータ用ガス発生剤組成物
WO2010134466A1 (fr) * 2009-05-21 2010-11-25 ダイセル化学工業株式会社 Composition génératrice de gaz
US20130248062A1 (en) * 2012-03-23 2013-09-26 Trw Airbag Systems Gmbh Gas generating composition
WO2014061397A1 (fr) * 2012-10-18 2014-04-24 株式会社ダイセル Composition d'agent générant du gaz, et générateur de gaz mettant en œuvre celui-ci

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