WO2013176162A1 - Substance particulaire à base de nitrate d'ammonium pour agent générateur de gaz, son procédé de production, et pastille d'agent générateur de gaz - Google Patents

Substance particulaire à base de nitrate d'ammonium pour agent générateur de gaz, son procédé de production, et pastille d'agent générateur de gaz Download PDF

Info

Publication number
WO2013176162A1
WO2013176162A1 PCT/JP2013/064161 JP2013064161W WO2013176162A1 WO 2013176162 A1 WO2013176162 A1 WO 2013176162A1 JP 2013064161 W JP2013064161 W JP 2013064161W WO 2013176162 A1 WO2013176162 A1 WO 2013176162A1
Authority
WO
WIPO (PCT)
Prior art keywords
ammonium nitrate
gas generating
generating agent
granular material
water
Prior art date
Application number
PCT/JP2013/064161
Other languages
English (en)
Japanese (ja)
Inventor
勝美 加藤
英子 東
勝之 中野
清一郎 永山
恒佑 熊谷
祐介 塚原
祐典 和田
有司 和田
Original Assignee
日本化薬株式会社
旭化成ケミカルズ株式会社
独立行政法人産業技術総合研究所
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 日本化薬株式会社, 旭化成ケミカルズ株式会社, 独立行政法人産業技術総合研究所 filed Critical 日本化薬株式会社
Publication of WO2013176162A1 publication Critical patent/WO2013176162A1/fr

Links

Images

Classifications

    • 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
    • C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
    • C06B31/30—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with vegetable matter; with resin; with rubber
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0091—Elimination of undesirable or temporary components of an intermediate or finished product, e.g. making porous or low density products, purifying, stabilising, drying; Deactivating; Reclaiming

Definitions

  • This technology relates to an ammonium nitrate granular material for a gas generating agent and a method for producing the same. More specifically, the present invention relates to an ammonium nitrate granular material for a gas generating agent that is excellent in moisture resistance and mainly contains ammonium nitrate.
  • Ammonium nitrate which is known as a component of gas generating agents for automobile airbags, has poor handleability due to its high hygroscopicity, and low pellet strength when used as a pellet containing such ammonium nitrate. It has been pointed out that the strength changes when stored for a long time.
  • Patent Document 1 describes a gas generant composition in which a residue generated during combustion is small by limiting a polymer compound acting as a fuel and a binder to a specific polymer compound.
  • a general method for molding a gas generating agent is a method in which the composition is added to water or an organic solvent, followed by evaporation to dryness, extrusion molding, or molding by a tableting machine.
  • the gas generant pellets obtained by the molding method may vary in strength and may change over time.
  • Patent Document 2 describes a safe and highly reliable ammonium nitrate gas generating agent by containing aminotetrazole.
  • a water-soluble binder is described as an excipient, but since it is added from the viewpoint of maintaining the shape of the molded body, it is selected only from the viewpoint of its moldability, It is not selected to improve the hygroscopicity of ammonium nitrate.
  • Non-Patent Document 1 introduces a method of coating ammonium nitrate particles with a polymer by developing a technique called atmospheric pressure glow plasma.
  • this polymer coating method it is difficult to find conditions for stably spheroidizing and polymer coating, and it is necessary to improve productivity.
  • the raw materials for gas generating agents used in automobile airbags are required to have stability against changes in the temperature and humidity of vehicles used in various environments.
  • ammonium nitrate undergoes a phase change (phase transition between solid phases) between room temperature and about 100 ° C.
  • Patent Document 3 describes a gas generating composition in which a potassium salt of a water-soluble polymer serves as both a phase stabilizer and a binder, so that it is not necessary to add a phase stabilizer separately.
  • the use of the potassium salt of the water-soluble polymer described in the document is also used as a binder as described above, and the molding of the gas generating agent is also an extrusion molding or a compression molding by a tableting machine.
  • the pellets obtained by the above method are required to be further improved in terms of strength and aging.
  • JP 2000-103691 A Japanese Patent Laid-Open No. 10-130086 JP 2009-137819 A
  • ammonium nitrate has four phase transition points (around 35 ° C., 80 ° C., 125 ° C., and 160 ° C. in the temperature range of 20 ° C. to 200 ° C. Others are known to have a phase transition point between solid phases), and the volume changes due to the phase transition between the solid phases.
  • the temperature inside the car can easily exceed 50 ° C in the summer, and the temperature change during the day and night straddles this ammonium nitrate phase transition point (around 35 ° C and in some cases around 80 ° C). Become. Therefore, when a material that causes such a phase change is used as a raw material, the pellet may undergo a phase change with a change in temperature or humidity, whereby the volume may increase or decrease, and the pellet may crack. If the pellet is crushed due to the crack or strength change, it may cause an unexpected gas generation behavior, which may hinder safety.
  • phase-stabilized ammonium nitrate obtained by adding a phase stabilizer such as potassium salt such as potassium nitrate or potassium perchlorate or copper compound such as copper oxide is known. Yes.
  • the phase-stabilized ammonium nitrate by this phase stabilizer suppresses the phase transition around 20 ° C to 100 ° C.
  • an object of the present invention is to provide a method for producing an ammonium nitrate granular material for a gas generating agent that is excellent in moisture resistance and has phase stability in a wide temperature range.
  • Ammonium nitrate-containing liquid is prepared by dissolving or dispersing ammonium nitrate and a water-soluble polymer and / or a water-dispersible polymer in a solvent containing water as a main component, and the ammonium nitrate-containing liquid is spray-dried.
  • ⁇ 3> The method for producing an ammonium nitrate granular material for a gas generating agent according to ⁇ 1> or ⁇ 2>, wherein the solid concentration of the ammonium nitrate-containing liquid is 5% by weight or more and 65% by weight or less.
  • ⁇ 4> The ammonium nitrate granular material for gas generating agent according to any one of ⁇ 1> to ⁇ 3>, wherein the ratio of ammonium nitrate to the total amount of solids in the ammonium nitrate-containing liquid is 70 wt% or more and 99.9 wt% or less. Manufacturing method.
  • ⁇ 5> The ratio according to any one of ⁇ 1> to ⁇ 4>, wherein a ratio of the water-soluble polymer and the water-dispersible polymer to the total amount of the solid in the ammonium nitrate-containing liquid is 0.1 wt% or more and 20 wt% or less.
  • ammonium nitrate granular material for gas generating agent ⁇ 6> Ammonium nitrate for gas generating agent according to any one of ⁇ 2> to ⁇ 5>, wherein the ratio of the phase stabilizer to the total amount of solids of the ammonium nitrate-containing liquid is 1% by weight to 20% by weight A manufacturing method of granular materials.
  • ⁇ 7> The method for producing ammonium nitrate granular material for gas generating agent according to any one of ⁇ 1> to ⁇ 6>, wherein the water-soluble polymer is a carboxymethyl cellulose salt.
  • ⁇ 8> The method for producing an ammonium nitrate granular material for a gas generating agent according to any one of ⁇ 1> to ⁇ 7>, wherein the water-dispersible polymer is a latex.
  • ⁇ 9> The method for producing an ammonium nitrate granular material for a gas generating agent according to any one of ⁇ 2> to ⁇ 8>, wherein the phase stabilizer is potassium nitrate and / or potassium perchlorate.
  • Ammonium nitrate and a water-soluble polymer and / or water-dispersible polymer are dissolved or dispersed in a solvent containing water as a main component to prepare an ammonium nitrate-containing liquid, and obtained by spray drying the ammonium nitrate-containing liquid.
  • Ammonium nitrate granular material for gas generating agents characterized in that ⁇ 11> The ammonium nitrate granular material for gas generating agent according to ⁇ 10>, wherein the shape of the ammonium nitrate granular material for gas generating agent is a substantially spherical particle.
  • ⁇ 12> The ammonium nitrate granular material for gas generating agent according to ⁇ 11>, wherein the mode particle diameter of the substantially spherical particles is 1 ⁇ m or more and 200 ⁇ m or less.
  • ⁇ 13> The ammonium nitrate granular material for a gas generating agent according to any one of ⁇ 10> to ⁇ 12>, wherein the ammonium nitrate granular material for a gas generating agent does not have a phase transition in a temperature range from room temperature to 150 ° C. or less.
  • ammonium nitrate for a gas generating agent that is excellent in moisture resistance and has little phase transition between solid phases. Since the ammonium nitrate granular material for gas generant obtained by the production method of the present invention is excellent in moisture resistance and has few phase transitions between solid phases, when the gas generant using this is used as a pellet, the pellet has strength. And the volume change is small.
  • the ammonium nitrate of the present invention can be suitably used particularly for automobile airbags.
  • the ammonium nitrate granular material for a gas generating agent of the present invention is excellent in handleability because it integrates a polymer that functions as a binder when forming a gas generating agent pellet or the like.
  • the conceptual diagram of the spray dryer apparatus which performs spray drying is shown. It is a SEM photograph image (low magnification) of the ammonium nitrate granular material concerning this invention. It is a SEM photograph image (high magnification) of the ammonium nitrate granular material concerning this invention.
  • the SEM photograph image of an ammonium nitrate reagent is shown.
  • the SEM photograph image of the conventional ammonium nitrate granular material is shown.
  • the hygroscopic measurement result of the ammonium nitrate granular material concerning this invention is shown.
  • the DSC measurement result of the ammonium nitrate granular material concerning this invention is shown.
  • the DSC measurement result of the conventional ammonium nitrate granular material is shown.
  • the DSC measurement result of the ammonium nitrate granular material concerning this invention is shown.
  • the DSC measurement result of the ammonium nitrate granular material concerning this invention is shown.
  • an ammonium nitrate-containing liquid is prepared by dissolving or dispersing ammonium nitrate and a water-soluble polymer and / or a water-dispersible polymer in a solvent containing water as a main component, and the ammonium nitrate-containing liquid is spray-dried to produce ammonium nitrate.
  • the present invention relates to a method for producing an ammonium nitrate granular material for a gas generating agent to obtain a granular material.
  • ammonium nitrate granular material it is obtained by dissolving or dispersing ammonium nitrate and a water-soluble polymer and / or water-dispersible polymer in a solvent containing water as a main component to prepare an ammonium nitrate-containing liquid, and spray-drying the ammonium nitrate-containing liquid. It relates to the ammonium nitrate granular material.
  • an ammonium nitrate granular material having excellent moisture-proof property can be obtained, which is useful when the ammonium nitrate granular material is used for a gas generating agent.
  • the production method of the present invention will be described in detail.
  • ammonium nitrate is used as an oxidizing agent in the gas generating agent.
  • the ammonium nitrate used in the present invention is not particularly limited with respect to purity and use, and it is preferable to use a high-purity ammonium nitrate.
  • it since it may be dissolved in a solvent, it may be either powdery or granular, but a powdery form that is easy to dissolve is preferred.
  • the ammonium nitrate-containing liquid contains a water-soluble polymer and / or a water-dispersible polymer as essential components together with ammonium nitrate.
  • the water-soluble polymer used in the present invention means a polymer that has many hydrophilic groups in the molecule and dissolves in water.
  • a linear water-soluble polymer having no cross-linked structure is preferably used.
  • the molecular weight of the water-soluble polymer is not particularly limited as long as it is a water-soluble physical property, but from the viewpoint of the production efficiency of ammonium nitrate particulates, the weight average molecular weight is 5,000 or more and 500,000 or less. Is preferred.
  • water-soluble polymer used in the present invention examples include polyvinyl alcohol, carboxymethyl cellulose ammonium, sodium carboxymethyl cellulose, polyethylene glycol, polypropylene glycol, polyvinyl ether, polymaleic acid copolymer, polyethylene imide, polyvinyl pyrrolidone, polyacrylamide, and polyacrylic.
  • examples thereof include sodium acid, ammonium polyacrylate, dextrin and hydrates thereof, and guar gum.
  • the use of polyvinyl alcohol, carboxymethyl cellulose salt, or polyacrylate as the water-soluble polymer is preferable because an ammonium nitrate granule excellent in phase stability can be obtained.
  • Particularly preferred are polyvinyl alcohol, carboxymethyl cellulose ammonium or ammonium polyacrylate.
  • polyvinyl alcohol used in the present invention it is preferable to use linear polyvinyl alcohol that does not have a crosslinking structure formed by a carboxylic acid crosslinking agent, an acetal crosslinking agent, a metal chelating agent, or the like.
  • polyvinyl alcohol it is preferable to use polyvinyl alcohol having a degree of polymerization of 100 or more and 5,000 or less, or polyvinyl alcohol having a weight average molecular weight of 5,000 or more and 200,000 or less.
  • carboxymethyl cellulose salt is preferable because a granular material having very excellent phase stability can be obtained.
  • carboxymethylcellulose salt ammonium salt and sodium salt are preferable. Particularly preferred is carboxymethyl cellulose ammonium.
  • a polyacrylate because a granular material having excellent phase stability can be obtained.
  • ammonium salt and sodium salt are preferable. Particularly preferred is ammonium polyacrylate.
  • the water-dispersible polymer used in the present invention means a polymer dispersed and mixed in water.
  • a polymer aqueous solvent dispersant obtained by emulsifying fine particles of a polymer dispersed and mixed in water using an appropriate emulsifier. , Generally called latex).
  • an ammonium nitrate-containing liquid is prepared using a dispersion of such a water-dispersible polymer in a latex state, the mixing ability in the step of making an ammonium nitrate-containing liquid is improved, and the resulting moisture absorption of ammonium nitrate for a gas generating agent is improved.
  • a dispersion liquid (polystyrene latex) in which the polymer is a polystyrene fine particle or a dispersion liquid (styrene-butadiene copolymer latex) in which the polymer is a styrene-butadiene copolymer fine particle.
  • Polymer fine particles such as polystyrene fine particles and styrene-butadiene copolymer fine particles are not particularly limited, but polymer fine particles having a particle diameter of 0.01 ⁇ m to 100 ⁇ m are preferably used. More preferred are polymer fine particles having a particle diameter of 0.01 ⁇ m to 1.0 ⁇ m.
  • a water-dispersible polymer dispersion in which these polymer fine particles are dispersed in an aqueous medium at a content of 20 to 80% by mass is used.
  • the water-dispersible polymer is generally defined in terms of physical properties by the viscosity of the dispersion dispersed in an aqueous medium.
  • the water-dispersible polymer dispersion used in the present invention is mixed with other components and mixed with ammonium nitrate. From the viewpoint of production efficiency when producing granular materials, it is preferable to use those having a viscosity of 10 to 50,000 mPa ⁇ s.
  • Styrene-butadiene copolymer latex using styrene-butadiene copolymer fine particles has the properties of an emulsion rubber adhesive having high rubber elasticity and adhesive strength.
  • the water-dispersible polymer contains 20 to 80% by weight of styrene-butadiene copolymer fine particles having a particle size of 0.01 ⁇ m to 1.0 ⁇ m in an aqueous medium, and the viscosity of the dispersion dispersed in the aqueous medium is
  • a particularly preferred example is the use of a styrene-butadiene copolymer in a latex state of 30 to 10,000 mPa ⁇ s.
  • the water-dispersible polymer is preferably used in a latex state, and in particular, a polystyrene latex or a styrene-butadiene copolymer latex is used. It is preferable because very excellent moisture resistance can be obtained.
  • the ammonium nitrate-containing liquid only needs to contain a water-soluble polymer or a water-dispersible polymer, and a plurality of water-soluble polymers or water-dispersible polymers may be used in combination.
  • hydrophobic polymer other than the water-soluble polymer or water-dispersible polymer (other polymer) may be contained within the range not impairing the object of the present invention.
  • the solvent in the ammonium nitrate-containing liquid is a solvent containing water as a main component.
  • “with water as the main component” means that the ratio of water is 50% by weight or more, preferably 80% by weight or more (including 100% by weight) with respect to the total amount of the solvent. Since ammonium nitrate, which is the main raw material of the gas generating agent, is highly reactive, and the solvent is dried by spray drying, use of a highly reactive solvent may cause a safety problem. This is particularly problematic when combustible organic solvents are the main component. On the other hand, in the manufacturing method of this invention, since water is the main component, there exists an advantage that such a problem does not arise.
  • solvents such as alcohol can be added to the solvent to adjust the solubility and dispersibility of the solid content.
  • alcohol methyl alcohol, ethyl alcohol, butyl alcohol, or the like can be used as the alcohol.
  • phase stabilizer In the production method of the present invention, an ammonium nitrate phase stabilizer may be further added to the ammonium nitrate-containing liquid. By including the phase stabilizer, the phase change derived from ammonium nitrate is further suppressed in the produced ammonium nitrate granular material.
  • phase stabilizers include potassium nitrate, potassium perchlorate, potassium chlorate, potassium permanganate, potassium chromate, potassium dichromate, potassium chloride, potassium sulfate, potassium oxalate, sodium nitrate, chloride Examples include ammonium, copper nitrate, cesium nitrate, and cesium chloride.
  • potassium salts such as potassium nitrate and potassium perchlorate are particularly preferable.
  • potassium nitrate is preferably used because it has a large phase stabilizing effect even in a small amount.
  • a phase stabilizer is added to ammonium nitrate, since the phase stabilizer and ammonium nitrate are soluble in water, they are often dissolved in water and then evaporated to dryness to obtain phase-stabilized ammonium nitrate.
  • the phase stabilizer can be mixed and produced for spray drying without performing evaporation to dryness.
  • an additive other than the above-mentioned solid component such as ammonium nitrate may be added to the ammonium nitrate-containing liquid as long as the object of the present invention is not impaired.
  • additives include additives that are added for the purpose of improving the reactivity when the produced ammonium nitrate granular material is used as a gas generating agent (for example, strontium nitrate, basic copper nitrate, etc.). Nitrates, ammonium dinitramide, etc.) and additives that improve solubility and dispersibility when dissolved in a solvent.
  • the ammonium nitrate-containing liquid in the production method of the present invention contains ammonium nitrate, a water-soluble polymer, a water-dispersible polymer, a solid substance such as a phase stabilizer and additives that are added as necessary, and water. Consists of a solvent as a main component.
  • the solid concentration in the ammonium nitrate-containing liquid is preferably 5% by weight to 65% by weight, and more preferably 10% by weight to 30% by weight.
  • the solid when calculating the solid concentration referred to herein includes ammonium nitrate, a water-soluble polymer, a water-dispersible polymer, a phase stabilizer added as necessary, an additive, and other polymers. Including. When the solid concentration is too low, the production efficiency of the ammonium nitrate granular material obtained when spray drying is performed may be low, or it may be difficult to dry due to too much water content. If the solid concentration is too high, the solution viscosity may be unsuitable for spray drying, and the resulting ammonium nitrate particulates may not have sufficient characteristics.
  • the ratio of ammonium nitrate to the total amount of solids in the ammonium nitrate-containing liquid is 70 wt% or more and 99.9 wt% or less. More preferably, it is 70 to 98 weight%.
  • the ratio of the water-soluble polymer and the water-dispersible polymer to the total amount of solids in the ammonium nitrate-containing liquid is 0.1% in terms of both the reactivity as an oxidizing agent and the moisture-proof and phase-stability improving effects. % To 20% by weight is preferable. When the amount is less than 0.1% by weight, the characteristics of the ammonium nitrate particulate matter may not be sufficiently improved. When the amount exceeds 20% by weight, the amount of ammonium nitrate is reduced, so Reactivity may be reduced.
  • the weight of the polymer is preferably 1% by weight or more and 15% by weight or less, more preferably 1% by weight or more and 12% by weight or less.
  • the ratio of the phase stabilizer to the total amount of solids in the ammonium nitrate-containing liquid is 1% by weight or more and 20% by weight or less. Preferably, it is 3 to 15% by weight.
  • phase-stabilized ammonium nitrate obtained by mixing a phase stabilizer and ammonium nitrate in advance can also be used as the ammonium nitrate and phase stabilizer of the present invention.
  • the production method of the ammonium nitrate-containing liquid is not particularly limited, and its constituent components, ammonium nitrate, a water-soluble polymer and / or a water-dispersible polymer, and other components as necessary are dissolved in a solvent containing water as a main component. What is necessary is just to disperse.
  • Examples of the mixing method include a method of stirring with a stirrer and a method of stirring by applying ultrasonic vibration.
  • the mixing order is arbitrary as long as there is no particular problem such as reaction or precipitation, and any two or more components of the ammonium nitrate-containing liquid are mixed in advance, and then the remaining components are mixed. Or you may mix all at once.
  • the ammonium nitrate-containing liquid is obtained by spray drying the ammonium nitrate-containing liquid.
  • spray drying is a technique for producing a dry powder by spraying a solution or dispersion to be dried into a gas and drying it rapidly.
  • the production method of the present invention has one of the features of drying by spray drying, and ammonium nitrate, a water-soluble polymer, and a water-dispersible polymer as compared with conventional drying methods such as extrusion molding and compression molding by a tableting machine. Therefore, it is possible to obtain an ammonium nitrate granular material having excellent moisture resistance and phase stability.
  • a solution (a solution containing ammonium nitrate in the present invention) is atomized by a nozzle (nozzle spray method) or a centrifugal spray method (rotary atomizer method) and brought into contact with hot air, and dried instantaneously.
  • nozzle spray method any type of nozzle may be used, but general examples include a rotary disk nozzle and a single-fluid pressure swirl nozzle. Alternatively, a two-fluid nozzle or an ultrasonic nozzle may be used.
  • the particle diameter can be adjusted by adjusting the shape and rotation speed of the disk.
  • the gas used for spray drying may be a general gas selected when spray drying such as air or nitrogen.
  • An inert gas such as nitrogen can be selected for safety.
  • the drying temperature in the spray drying is not limited as long as water, which is the main solvent, can be dried.
  • the shape and particle size of the ammonium nitrate granular material to be manufactured can be controlled mainly by spray drying conditions. It is preferable to adjust the spray droplet size and the drying conditions so that the ammonium nitrate granular material has a substantially spherical particle having a suitable shape and a suitable particle size range.
  • the drying temperature can be controlled by adjusting either the hot air temperature and / or the chamber temperature in the spray dryer, but there may be differences between these temperatures.
  • the chamber temperature is usually lower, and the overall temperature is controlled by adjusting the hot air temperature and air volume. Specifically, the hot air temperature is usually in the range of 80 ° C. to 200 ° C., and the temperature in the chamber is usually in the range of 50 ° C. to 150 ° C.
  • the ammonium nitrate granular material for a gas generating agent according to the present invention is preferably formed into a substantially spherical particle by adjusting the spray drying conditions. What is necessary is just to observe an external appearance with the optical microscope and the electron microscope about the shape of a granular material.
  • the ammonium nitrate and the polymer and the phase stabilizer added as appropriate are dried in a sufficiently mixed state, so that the purpose is moisture proof and phase stability. The characteristics can be achieved more.
  • the particle diameter of the substantially spherical particles is 1 to 200 ⁇ m, preferably 5 to 100 ⁇ m, when observed with an optical microscope or an electron microscope.
  • the mode particle diameter is measured by image analysis of ammonium nitrate granular material in the observed image.
  • the mode particle size is larger than this, the solution diffusion conditions during spray drying and the viscosity of the solution itself are not appropriate, and it is considered that the solution is dried with a large particle size. Since the granular material obtained under such conditions is not suitable for the drying process, it may not exhibit the desired moisture resistance and phase stability. If the mode particle size is smaller than this, the solids concentration in the solution during spray drying may be low, or the amount of polymer may be insufficient, resulting in low production efficiency or characteristics such as moisture resistance and phase stability. May not be enough.
  • the ammonium nitrate granular material for gas generating agent of the present invention preferably has no phase transition point in the temperature range from room temperature to 100 ° C., and more preferably does not exhibit a phase transition point at a temperature of 120 ° C. or less. In particular, it is preferable not to have a phase transition point in a temperature range of 150 ° C. or lower.
  • the ammonium nitrate granular material of the present invention preferably has no phase transition point even in a low temperature range of ⁇ 50 ° C. to 25 ° C. That is, it preferably does not exhibit a phase transition point in a temperature range of ⁇ 50 ° C. or more and 100 ° C.
  • phase transition point in a temperature range of ⁇ 50 ° C. or more and 120 ° C. or less, and particularly preferably. No phase transition point is exhibited in the temperature range of ⁇ 50 ° C. or higher and 150 ° C. or lower.
  • “having no phase transition point” means that no endothermic peak is observed in differential scanning calorimetry (DSC). DSC measurement conditions will be described later in Examples.
  • ammonium nitrate granular material for gas generating agent of the present invention exhibits physical properties with extremely low crystallinity.
  • the ammonium nitrate granular material of the present invention shows a clear diffraction peak by powder X-ray diffraction measurement, but its low crystallinity is recognized by showing its peak intensity very weakly.
  • ammonium nitrate granular material of the present invention is suitably used as an oxidizing agent for a gas generating agent used for an air bag or the like. In such applications, it is usually used in the form of pellets.
  • the ammonium nitrate granular material for gas generating agent according to the present invention By using the ammonium nitrate granular material for gas generating agent according to the present invention to produce a gas generating agent pellet, it is possible to obtain a gas generating agent having high strength and less occurrence of cracks in use environments such as for airbags. it can.
  • the ammonium nitrate granular material for gas generating agent according to the present invention is used as one of the oxidizing agents, and further, fuel, other oxidizing agents, binders, combustion accelerators, pressure index adjusting agents, additives, etc. It can be pelletized by a known method such as mixing, extrusion molding or compression molding.
  • the composition of the raw material for the gas generating agent includes the polymer and other additives that can be a fuel in the ammonium nitrate granular material according to the present invention, and is adjusted according to the component ratio.
  • the concentration of ammonium nitrate itself is about 40 to 90% by weight.
  • ammonium nitrate For ammonium nitrate (“AN”), a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
  • KN Potassium nitrate
  • Wako Pure Chemical Industries, Ltd. a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
  • KP potassium perchlorate
  • Wako Pure Chemical Industries, Ltd. a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
  • Water-soluble polymer / water-dispersible polymer As water-soluble polymers, polyvinyl alcohol (polymerization degree 400) (“PVA- (A)”), polyvinyl alcohol (polymerization degree 2000) (“PVA- (B)”), sodium carboxymethylcellulose (“CMCN”), carboxymethylcellulose Ammonium (“CMCA”) was used. “PVA- (A)”, “PVA- (B)”, “CMCN”, “CMCA” manufactured by Wako Pure Chemical Industries, Ltd. were used.
  • PAA ammonium polyacrylate solution
  • aqueous solution manufactured by Wako Pure Chemical Industries, Ltd., and had a viscosity of 70 to 110 mPa ⁇ s as a solution and an evaporation residue of 44% by mass in the solution.
  • SB latex “L-1638” manufactured by Asahi Kasei Chemicals Corporation, which is a modified styrene-butadiene latex (hereinafter “Latex”), was used.
  • Example 1 to 12 Comparative Example 1
  • the ammonium nitrate-containing liquids of Examples 1 to 12 and Comparative Example 1 were prepared with the compositions shown in Table 1.
  • the ammonium nitrate granular material was obtained by spray-drying the ammonium nitrate described later.
  • Example 13 to 16 Using the solids described above, the same dissolution operation as in Comparative Example 1 and Examples 1 to 12 was performed, and the ammonium nitrate-containing liquids of Examples 13 to 16 were prepared with the compositions shown in Table 2. The ammonium nitrate granular material was obtained by spray-drying the ammonium nitrate described later.
  • Table 3 shows the yield and water content of the ammonium nitrate granules.
  • the yields in Table 3 are the yields of the powder obtained from the lower part of “Drying Chamber” in FIG. Moreover, a granular material can also be obtained from “Cyclone separator” in FIG. 1, and when combined, the yield is about 60 to 90%.
  • the ammonium nitrate granular material used as the comparative examples 2 and 3 was obtained by the following method.
  • An ammonium nitrate reagent (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) not according to the present invention was used as Comparative Example 2.
  • ammonium nitrate, potassium nitrate, and carboxymethyl cellulose ammonium were mixed at a ratio of 90 parts by weight: 10 parts by weight: 3 parts by weight, respectively, and a 20% by weight aqueous solution was dried in a constant temperature bath for a whole day (evaporation drying).
  • the granular material obtained by solidification) was used as Comparative Example 3.
  • FIG. 3 is an enlarged image of the SEM image shown in FIG.
  • the obtained ammonium nitrate granular material was substantially spherical.
  • the sample having a high polymer concentration in the solution tended to have a large particle size.
  • the relatively large particles of about 50 ⁇ m or more have a hollow inside, and the inside is filled with smaller diameter particles, but both the large particles and the small particles inside as a whole, The appearance is substantially spherical.
  • Table 4 shows the result of measuring the particle size of the photographed particles (arbitrary 500 particles) and calculating the particle size distribution. From Table 4, it can be confirmed that most of the particles obtained by the spray drying method of the present example are present in the range of 10 to 50 ⁇ m.
  • FIG. 4 shows an SEM observation image of Comparative Example 2 not according to the present invention. Moreover, the SEM observation image of the comparative example 3 is shown in FIG. These were clearly different in shape from the ammonium nitrate granules of the present invention.
  • Example 1 (PVA- (A)), Example 3 (PVA- (A)), Example 4 (PVA- (B)), Example 5 (PVA- (B)), Example 6 (CMCN), Example 7 (CMCN), Example 8 (CMCA), Example 9 (CMCA), Example 10 (Latex), and Example 11 (Latex) were obtained by spray drying.
  • the ammonium nitrate granular material was left in a constant temperature bath at 90 ° C. for a whole day and night to dry the sample.
  • each was stored in a desiccator prepared at a humidity of 40 RH%, and the moisture absorption was measured from the change in weight before and after storage.
  • the storage temperature was 30 ° C., and an aqueous potassium carbonate solution was placed in the desiccator (bottom) to maintain the humidity at 40 RH%.
  • the ammonium nitrate granular material according to the present invention has improved moisture resistance compared to the polymer-free sample of Comparative Example 1.
  • the ammonium nitrate granular material prepared using Latex according to Examples 10 and 11 has a moisture absorption amount of about 1/10 of that of the sample to which no polymer was added, indicating that the moisture resistance is high.
  • the granular material obtained by using the PVA-based polymer has an improved moisture absorption rate compared with the conventional ammonium nitrate alone, the moisture absorption is slightly larger than that of the granular material using other polymers. The nature is low.
  • Example 1 PVA- (A)
  • Example 4 PVA- (B)
  • Example 6 CMCN
  • Example 8 CMCA
  • Example 10 Latex
  • Example 2 which is AN alone
  • Example 1 Example 4, Example 6, Example 8, Example 10, Example 12, which are ammonium nitrate granular materials according to the present invention
  • CMCA CMCA
  • a peak derived from a phase transition between 125 ° C. at a solid phase, which cannot be suppressed only by adding KN was not observed.
  • DSC measurement of Example 12 without addition of KN was performed, a phase transition around 125 ° C. was confirmed, but other phase transitions observed with AN alone were not observed.
  • the phase transition can be suppressed without adding a phase stabilizer
  • the phase transition between solid phases can be further suppressed by adding a phase stabilizer.
  • FIG. 8 shows DSC measurement results of Comparative Example 1, Comparative Example 2, Comparative Example 3, and Example 8.
  • Comparative Example 2 which is an AN alone, as described above, endothermic peaks derived from interphase transitions were observed at 35 ° C., 80 ° C., and 125 ° C., respectively.
  • Comparative Example 1 which is an ammonium nitrate granular material obtained by spray drying without using a polymer, no endothermic peak at 100 ° C. or lower is observed, but as described above, this granular material has high hygroscopicity.
  • Comparative Example 3 which is a granular material obtained from a mixture of AN, KN and polymer by a conventional drying method not according to the present invention does not have a sufficient effect of improving the phase stability. As represented by Example 8, it can be seen that the present invention can achieve phase stability superior to conventional phase stability.
  • FIG. 9 shows DSC measurement results of Example 13 and Example 14.
  • FIG. 10 shows DSC measurement results of Example 15 and Example 16.
  • Examples 13 and 14 using ammonium polyacrylate as the water-soluble polymer no endothermic peak was observed at 100 ° C. or lower, and phase stabilization was achieved.
  • Example 15 and Example 16 which used potassium perchlorate as a phase stabilizer did not have the endothermic peak resulting from the phase transition between solid phases at 80 degreeC, and the phase transition between solid phases was suppressed.
  • an ammonium nitrate granular material for a gas generating agent which is excellent in moisture resistance and phase stability and has improved handleability.
  • Molding pellets using this gas generant ammonium nitrate granule is expected to prevent cracking because of its excellent moisture-proofing and phase stability, and strength change over conventional pellets, and volume change due to temperature changes is small. Therefore, it can be suitably used for a vehicle-mounted airbag or the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Air Bags (AREA)

Abstract

Cette invention concerne une substance particulaire à base de nitrate d'ammonium pour agent générateur de gaz, ayant d'excellentes propriétés de résistance à l'humidité et de stabilité de phase, et son procédé de production, ledit procédé de production comprenant la préparation d'un liquide contenant le nitrate d'ammonium dans lequel le nitrate d'ammonium et un polymère aqueux ou un polymère susceptible de dispersion dans l'eau sont dissous ou complètement dispersés dans un solvant principalement constitué d'eau, et le séchage par atomisation du liquide contenant le nitrate d'ammonium.
PCT/JP2013/064161 2012-05-22 2013-05-22 Substance particulaire à base de nitrate d'ammonium pour agent générateur de gaz, son procédé de production, et pastille d'agent générateur de gaz WO2013176162A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012116928 2012-05-22
JP2012-116928 2012-05-22

Publications (1)

Publication Number Publication Date
WO2013176162A1 true WO2013176162A1 (fr) 2013-11-28

Family

ID=49623848

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/064161 WO2013176162A1 (fr) 2012-05-22 2013-05-22 Substance particulaire à base de nitrate d'ammonium pour agent générateur de gaz, son procédé de production, et pastille d'agent générateur de gaz

Country Status (2)

Country Link
JP (1) JP2014001128A (fr)
WO (1) WO2013176162A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130086A (ja) * 1996-10-23 1998-05-19 Nippon Kayaku Co Ltd エアバッグ用ガス発生剤
JP2000086378A (ja) * 1998-07-13 2000-03-28 Nof Corp ガス発生剤組成物及びその成形物並びに成形物の製造方法
JP2001031490A (ja) * 1999-07-19 2001-02-06 Asahi Chem Ind Co Ltd 粒状爆薬
JP2002060293A (ja) * 2000-08-17 2002-02-26 Nippon Kayaku Co Ltd 耐水性粒状爆薬組成物
JP2002097095A (ja) * 2000-09-22 2002-04-02 Nof Corp ガス発生剤
JP2011516395A (ja) * 2008-04-10 2011-05-26 オートリブ エーエスピー，インコーポレイティド 高性能ガス発生組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6431597B1 (en) * 2000-05-26 2002-08-13 Trw Inc. Reduced smoke gas generant with improved mechanical stability

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130086A (ja) * 1996-10-23 1998-05-19 Nippon Kayaku Co Ltd エアバッグ用ガス発生剤
JP2000086378A (ja) * 1998-07-13 2000-03-28 Nof Corp ガス発生剤組成物及びその成形物並びに成形物の製造方法
JP2001031490A (ja) * 1999-07-19 2001-02-06 Asahi Chem Ind Co Ltd 粒状爆薬
JP2002060293A (ja) * 2000-08-17 2002-02-26 Nippon Kayaku Co Ltd 耐水性粒状爆薬組成物
JP2002097095A (ja) * 2000-09-22 2002-04-02 Nof Corp ガス発生剤
JP2011516395A (ja) * 2008-04-10 2011-05-26 オートリブ エーエスピー，インコーポレイティド 高性能ガス発生組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Funmu Kansoho ni yoru Shosan Ammonium no Boshitsuka", JAPAN EXPLOSIVES SOCIETY 2012 NENDO NENKAI KOEN YOSHISHU, no. 62, 24 May 2012 (2012-05-24), pages 133 - 134 *

Also Published As

Publication number Publication date
JP2014001128A (ja) 2014-01-09

Similar Documents

Publication Publication Date Title
Ma et al. Core–shell structured nanoenergetic materials: preparation and fundamental properties
Ayoman et al. Synthesis of CuO nanopowders by high-energy ball-milling method and investigation of their catalytic activity on thermal decomposition of ammonium perchlorate particles
JP5770675B2 (ja) 硫化リチウムの製造方法
Hu et al. Ammonium perchlorate encapsulating nanothermites as high energetic composites: Preparation, thermal decomposition and combustion properties
US20080181844A1 (en) Method for the production of Mg (OH)2 nanoparticles
Chen et al. Enhancing the combustion performance of metastable Al@ AP/PVDF nanocomposites by doping with graphene oxide
KR102068386B1 (ko) 나노 입자의 합성 방법
WO2017208916A1 (fr) Matériau actif d'électrode négative de batterie, batterie, et procédé de production de matériau actif d'électrode négative de batterie
JPH07206568A (ja) 点火薬造粒物の製造方法
Zhang et al. Electrostatic interactions for directed assembly of high performance nanostructured energetic materials of Al/Fe2O3/multi-walled carbon nanotube (MWCNT)
KR20170098270A (ko) 우수한 유동성을 갖는 알칼리 금속 중탄산염 입자
TW201502066A (zh) 金屬錫－碳複合體、其製造方法、利用其而得之非水系鋰二次電池用負極活性物質、含其之非水系鋰二次電池用負極及非水系鋰二次電池
KR101510528B1 (ko) 분무건조 공정에 의한 응집체 구조의 리튬 이차 전지용 전극활물질 분말의 제조방법 및 이로부터 제조된 전극활물질 분말
Zhao et al. Influence of tailored CuO and Al/CuO nanothermites on the thermocatalytic degradation of nitrocellulose and combustion performance of AP/HTPB composite propellant
US9850180B1 (en) Method for manufacture of amorphous energetics
US9126846B2 (en) Method of synthesizing metal composite oxide and metal composite oxide obtained by same
WO2013176162A1 (fr) Substance particulaire à base de nitrate d'ammonium pour agent générateur de gaz, son procédé de production, et pastille d'agent générateur de gaz
Cudziło et al. Preparation and characterization of energetic nanocomposites of organic gel–inorganic oxidizers
Ghanta et al. Solution phase chemical synthesis of nano aluminium particles stabilized in poly (vinylpyrrolidone) and poly (methylmethacrylate) matrices
Yan et al. Insensitive energetic materials containing two-dimensional nanostructures as building blocks
Nagayama et al. Moisture proofing of spray dried particles comprising ammonium nitrate/potassium nitrate/polymer
Zhang et al. A new strategy for the fabrication of high performance reactive microspheres via energetic polyelectrolyte assembly
Ching et al. Synthesis of highly monodisperse porous manganese oxide spheres using a butyric acid microemulsion
EP3222704B1 (fr) Savon de fer, son procédé de production ainsi que composition de résine thermoplastique contenant ce savon de fer
JP4711744B2 (ja) チタン酸バリウム粉末の製法およびチタン酸バリウム粉末

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13794342

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13794342

Country of ref document: EP

Kind code of ref document: A1