WO2018066312A1 - Smoke generating composition and smoke generator - Google Patents

Smoke generating composition and smoke generator Download PDF

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Publication number
WO2018066312A1
WO2018066312A1 PCT/JP2017/032650 JP2017032650W WO2018066312A1 WO 2018066312 A1 WO2018066312 A1 WO 2018066312A1 JP 2017032650 W JP2017032650 W JP 2017032650W WO 2018066312 A1 WO2018066312 A1 WO 2018066312A1
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WO
WIPO (PCT)
Prior art keywords
component
smoke
generating composition
smoke generating
generator
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PCT/JP2017/032650
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French (fr)
Japanese (ja)
Inventor
中橋勝弘
小田愼吾
大路信之
黒田隆雄
樋口裕二
三村敦志
Original Assignee
株式会社ダイセル
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Publication of WO2018066312A1 publication Critical patent/WO2018066312A1/en

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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
    • 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)
    • C06D3/00—Generation of smoke or mist (chemical part)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41B—WEAPONS FOR PROJECTING MISSILES WITHOUT USE OF EXPLOSIVE OR COMBUSTIBLE PROPELLANT CHARGE; WEAPONS NOT OTHERWISE PROVIDED FOR
    • F41B15/00—Weapons not otherwise provided for, e.g. nunchakus, throwing knives
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H9/00—Equipment for attack or defence by spreading flame, gas or smoke or leurres; Chemical warfare equipment
    • F41H9/06—Apparatus for generating artificial fog or smoke screens
    • F41H9/08—Smoke-pots without propulsive charge, i.e. stationary
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H9/00—Equipment for attack or defence by spreading flame, gas or smoke or leurres; Chemical warfare equipment
    • F41H9/10—Hand-held or body-worn self-defence devices using repellant gases or chemicals

Definitions

  • the present invention relates to a smoke generating composition that can be used in a crime prevention device (smoke generator) and a smoke generator using the same.
  • Japanese Utility Model Laid-Open No. 57-194182 discloses a device for a smoke screen device with a security camera having a security smoke cylinder and a small security simple camera.
  • Utility model registration No. 2500591 discloses a device for a smoke screen device for crime prevention, but requires a gas tank filled with high-pressure gas, and carbon dioxide is exemplified as the gas.
  • Japanese Patent No. 3816867 describes a smoke screen generating device including an ignition device and a smoke generating agent.
  • a smoke generating agent a composition formed of zinc oxide, ammonium perchlorate, vinyl chloride, and calcium carbonate into a tablet shape is described (paragraph 0020).
  • the use of vinyl chloride monomer itself is prohibited because it is carcinogenic, and even vinyl chloride resin may generate harmful chlorine gas due to combustion. is there.
  • Japanese Patent Application Laid-Open No. 2003-306395 describes a white smoke rod-like body in which an oxidizer, white powder, and a combustor are bonded and formed into a rod shape with a curable resin and cured.
  • oxidizing agents such as ammonium perchlorate
  • white powders such as zinc oxide and zinc chloride
  • auxiliary substances such as starches, carbohydrates, and chlorinated rubber
  • unsaturated polyester resins that cure with a combination of curing agents
  • epoxy resins epoxy resins.
  • a white smoke rod-shaped body made of a thermosetting resin is described (paragraph numbers 0010 and 0011). In the description of Example 1, a rod-shaped body containing an unsaturated polyester resin (prepolymer) is molded and then cured.
  • the unsaturated polyester resin is thermally decomposed by the action of a combustor or an oxidant to generate gas, and at that time, white powder such as zinc oxide or zinc chloride is released to generate white smoke. It is thought that In this way, the white smoke source is white powder, and the gas source is generated by thermal decomposition of the thermosetting resin, so it is difficult to instantaneously generate a large amount of gas and diffuse the white powder. It is done.
  • Japanese Patent Application Laid-Open No. 2015-42603 discloses a gas and white smoke source containing (A) a smoke generating agent for generating a white smoke source, and (B) (B-1) fuel and (B-2) an oxidizing agent.
  • a smoke generating composition containing a gas generating agent for generating gas, wherein the white smoke source generated from the component (A) and the component (B) is scattered by the gas generated from the component (B).
  • a smoke generator composition is described. Summary of the Invention
  • the present invention provides a fuming agent composition that is excellent in visual blocking effect due to white smoke by generating a white smoke source, and has little harm and influence on the human body and the environment, and a smoke generator using the same. This is the issue.
  • the present invention is a smoke agent composition containing (A) fuel, (B) white smoke agent, and (C) an oxidizer, and the content ratio of component (A) and component (B) in the smoke agent composition
  • the smoke generating composition has a ratio (A) / (B) of greater than 1.
  • the fuel may be a saccharide
  • the white smoke agent may be one or more selected from waxes containing a paraffin compound and a polyalkylene glycol.
  • the present invention also provides a smoke generating composition containing (A) fuel, (B) white smoke agent, (C) oxidizing agent, and (D) isoalkyl alcohol.
  • the present invention also relates to a smoke generator using any one of the above smoke generating compositions.
  • the smoke generating composition of the present invention is excellent in visual blocking effect due to fuming by generating a white smoke source. For this reason, when the smoke generating composition of this invention is used for a crime prevention device (smoke generator), that is, since the smoke generator of this invention is excellent in the visual blocking effect by white smoke, the crime prevention effect is enhanced.
  • smoke generator smoke generator
  • FIG. 3 is an axial sectional view of a first member of a second closure used in FIG. 2.
  • FIG. 3 is an axial sectional view of an annular partition plate used in FIG. 2.
  • the smoke generating composition of the present invention contains fuel as the component (A).
  • the component (A) is a fuel (combustible agent) for generating white smoke.
  • the component (A) is preferably a saccharide from the viewpoint of obtaining a visual blocking effect by fuming.
  • component saccharides (A-1) monosaccharides such as glucose, galactose, fructose, mannose, ribose, deoxyribose, (A-2) disaccharides such as sucrose, lactose, maltose, trehalose, tulanose, cellobiose, (A-3) Polysaccharides such as starch, cellulose, glycogen, chitin, agarose and pectin.
  • the component (A) is preferably at least one selected from the components (A-1) and (A-2), more preferably (A-2), from the viewpoint of obtaining a visual blocking effect due to fuming.
  • the component (A-1) is preferably at least one selected from glucose, galactose and fructose, more preferably at least one selected from glucose and galactose from the viewpoint of obtaining a visual blocking effect due to fuming. Yes, more preferably galactose.
  • the component (A-2) is preferably at least one selected from sucrose and lactose, more preferably sucrose, from the viewpoint of obtaining a visual blocking effect due to fuming.
  • the component (A-3) is preferably at least one selected from starch, cellulose and glycogen, more preferably at least one selected from starch and cellulose, from the viewpoint of obtaining a visual blocking effect due to fuming. is there.
  • the component (A) is preferably at least one selected from glucose, galactose, fructose, sucrose and lactose, more preferably glucose, galactose and sucrose, from the viewpoint of obtaining a visual blocking effect due to fuming. 1 or more selected from galactose and sucrose, and more preferably sucrose.
  • the saccharide as the component (A) is preferably in the form of particles and contained in the smoke generating composition of the present invention, and the average particle size of the component (A) is preferably 300 ⁇ m from the viewpoint of a visual blocking effect due to fuming. More preferably, it is 400 ⁇ m or more, more preferably 450 ⁇ m or more, still more preferably 500 ⁇ m or more, preferably 1000 ⁇ m or less, more preferably 800 ⁇ m or less, still more preferably 650 ⁇ m or less, and still more preferably 600 ⁇ m or less.
  • the particle size may be measured using a laser diffraction / scattering method.
  • the smoke generating composition of the present invention contains a white smoke agent as the component (B).
  • the component (B) is a component (white smoke agent) that is vaporized (changes in state) by heat during operation to become a gas (white smoke source), and the gas is cooled to become droplets to become white smoke.
  • a white smoke agent a component that is vaporized (changes in state) by heat during operation to become a gas (white smoke source)
  • the gas is cooled to become droplets to become white smoke.
  • the component (B) is preferably at least one selected from waxes containing paraffin compounds and polyalkylene glycols from the viewpoint of obtaining a visual blocking effect due to fuming.
  • component (B) one or more selected from waxes containing paraffin compounds and polyalkylene glycols, (B-1) waxes containing paraffin compounds such as paraffin wax (main component: normal paraffin), microcrystalline wax (main component: isoparaffin, cycloparaffin), (B-2) Polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and the like can be mentioned.
  • the component (B) is preferably the component (B-1) from the viewpoint of safety and ease of handling.
  • the component (B-1) is preferably one or more selected from paraffin wax (main component: normal paraffin) and microcrystalline wax (main component: isoparaffin, cycloparaffin) from the viewpoints of safety and ease of handling. Yes, more preferably paraffin wax (main component: normal paraffin).
  • the component (B-1) is preferably at least one selected from normal paraffin, isoparaffin and cycloparaffin from the viewpoint of safety and ease of handling, and more preferably normal paraffin.
  • the component (B-2) is preferably at least one selected from polyethylene glycol and polypropylene glycol, more preferably polyethylene glycol, from the viewpoint of safety and ease of handling.
  • the component (B) is preferably at least one selected from paraffin wax, microcrystalline wax and polyethylene glycol from the viewpoint of safety and ease of handling, and more preferably paraffin wax.
  • the component (B) is preferably at least one selected from normal paraffin, isoparaffin, cycloparaffin and polyethylene glycol, more preferably normal paraffin, from the viewpoints of safety and ease of handling.
  • the smoke generating composition of the present invention contains an oxidizing agent as the component (C).
  • the component (C) is produced by instantly burning the fuel (combustible agent) that is the component (A) to generate a large amount of gas (a gas containing nitrogen gas or carbon dioxide) and changing the oxidant itself.
  • a smoke source can be generated.
  • Chlorates such as potassium chlorate and sodium chlorate
  • C-2 perchlorates such as strontium perchlorate, magnesium perchlorate, ammonium perchlorate, potassium perchlorate, sodium perchlorate
  • C-3) Nitrate salts such as strontium nitrate, potassium nitrate and sodium nitrate.
  • the component (C) is preferably the component (C-3) from the viewpoint of safety and ease of handling.
  • the component (C-1) is preferably potassium chlorate from the viewpoint of safety and ease of handling.
  • the component (C-2) is preferably potassium perchlorate from the viewpoints of safety and ease of handling.
  • the component (C-3) is preferably at least one selected from potassium nitrate and strontium nitrate, and more preferably potassium nitrate, from the viewpoints of safety and ease of handling.
  • the component (C) is preferably at least one selected from potassium chlorate, potassium perchlorate, strontium nitrate and potassium nitrate, more preferably perchloric acid, from the viewpoint of safety and ease of handling.
  • the smoke generator composition of the present invention contains isoalkyl alcohol as component (D).
  • D Since a component does not melt
  • D) component is mix
  • the component (D) is preferably at least one selected from isopropanol, isobutanol, isopentanol and isohexanol, more preferably isopropyl alcohol, from the viewpoint of not dissolving the particles of the component (A).
  • the content ratio of each component in the smoke composition of the present invention is as follows with respect to 100 parts by mass in total of the component (A), the component (B), and the component (C).
  • the component (A) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 25 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 60 parts by mass or less, more preferably. 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 35 parts by mass or less.
  • the component (B) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 12 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 18 parts by mass or less.
  • the component (C) is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, still more preferably 45 parts by mass or more, still more preferably 47 parts by mass or more, and preferably 70 parts by mass or less, more preferably 60 mass parts or less, More preferably, it is 55 mass parts or less, More preferably, it is 53 mass parts or less.
  • the ratio (A) / (B) of the content ratio of the component (A) to the component (B) is more than 1, preferably 1 from the viewpoint of obtaining a visual blocking effect due to fuming. .2 or more, more preferably 1.5 or more, still more preferably 1.8 or more, still more preferably 2 or more, and preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, still more preferably 3 or less.
  • the ratio (A) / (B) of the content ratio of the component (A) and the component (B) is 1.2 or more and 10 or less. In another embodiment, ratio (A) / (B) of the content rate of (A) component and (B) component is 2-10.
  • the content ratio of the component (D) in the smoke generating composition of the present invention is (A) with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C).
  • the content is preferably 1 ppm or more, and when the content ratio of the component (D) is increased, it is preferably 100 ppm or less, more preferably 50 ppm or less, from the viewpoint of hindering smoke generation.
  • the content rate of (D) component is 1 ppm or more and 100 ppm or less with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component.
  • the smoke generating composition of the present invention preferably contains a binder as the component (E) in addition to the components (A) to (C), or in addition to the components (A) to (D).
  • a component is a component used when shape
  • the component (E) includes at least one selected from guar gum, sodium carboxymethylcellulose (CMCNa), ethylcellulose, polyvinylpyrrolidone, polyacrylamide, starch and dextrin. It is 1 or more types chosen from methylcellulose sodium (CMCNa) and ethylcellulose, More preferably, it is ethylcellulose.
  • starch and ethyl cellulose which are (E) components can also be used as (A) component.
  • the content ratio of the component (E) is preferably 0.01 parts by mass or more with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C). More preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.7 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably. Is 2 parts by mass or less, more preferably 1.5 parts by mass or less.
  • the smoke generating composition of the present invention includes nitrocellulose, nitroguanidine, guanidine nitrate, dicyandiamide, melamine, melamine cyanurate, 5-aminotetrazole, and 5,5′-bistetrazole diammonium as a combustible other than the component (A).
  • the smoke generating composition of the present invention may contain a compound selected from the following (i) to (vi) from the viewpoint of achieving the effects of the present invention.
  • Metal oxides such as cupric oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide, bismuth oxide, silica, and alumina
  • metal hydroxide such as cobalt and iron hydroxide
  • metal carbonate such as cobalt carbonate and calcium carbonate
  • Metal oxide such as acid clay, kaolin, talc, bentonite, diatomaceous earth, hydrotalcite, or hydroxide
  • Metal acid salts such as sodium silicate, mica molybdate, cobalt molybdate, ammonium molybdate, etc.
  • Molybdenum disulfide calcium stearate, silicon nitride, silicon carbide, metaboric acid, boric acid, Boric
  • the smoke generating composition of the present invention can be used as a powder or granulated body, and can be formed into a molded body having a desired shape.
  • the average particle diameter of the smoke generating composition when used as a granulated material is preferably 550 ⁇ m or more, more preferably 1000 ⁇ m or more, and preferably 5000 ⁇ m or less, more preferably from the viewpoint of the visual blocking effect due to fuming. 3000 ⁇ m or less.
  • the particle size may be measured using a laser diffraction / scattering method.
  • the molded body can be formed into a single-hole or porous cylindrical molded body or prismatic molded body, disk-shaped molded body, or granular molded body.
  • a known method for producing a gas generant molded article for a gas generator used in an airbag apparatus can be applied.
  • paragraphs 0035 to 0037 of JP-A-10-87390, Examples The manufacturing method described in 1 can be applied.
  • the present invention provides a smoke generating composition
  • a smoke generating composition comprising (A) component, (B) component, and (C) component, or (A) component, (B) component, (C) component, and (D) component.
  • a manufacturing method is provided.
  • the method described for the smoke generating composition of the present invention can be appropriately applied to the method for producing the smoke generating composition of the present invention.
  • the smoke generator composition of the present invention When the smoke generator composition of the present invention is used in a smoke generator for a crime prevention device, for example, a smoke screen generator (smoke generator) shown in FIGS. 1 and 2, the smoke generator composition (powder or molded product) is 1 Can be stored in a smoke generator in one container.
  • the smoke generator of FIG. 1 the smoke composition contained in the smoke generator is ignited by an electric igniter to generate a combustion product, and a white smoke source is generated by contact with the white smoke agent. Can be made.
  • the smoke screen generator of FIG. 1 does not have an initiator.
  • the smoke screen generator (smoke generator) shown in FIG. 2 will be described below.
  • the inner peripheral surface of the peripheral wall portion 11 on the first end opening 10a side of the cylindrical housing 10 has a first annular step surface 12, and the thickness from the first annular step surface 12 to the first end opening 10a is thick.
  • the first tip peripheral wall portion 13 is thin.
  • the inner peripheral surface 13a of the first tip peripheral wall portion 13 has a screw portion.
  • the inner peripheral surface of the peripheral wall portion 11 on the second end opening 10b side of the cylindrical housing 10 has a second annular step surface 14, and the thickness from the second annular step surface 14 to the second end opening 10b is thick.
  • the second end peripheral wall portion 15 is thin.
  • the outer peripheral surface 15a of the second tip peripheral wall portion 15 has a screw portion.
  • the first end opening 10 a side of the cylindrical housing 10 is closed with a first closure 20.
  • the first closure 20 has a substantially cup shape and has a bottom surface portion 21 and a peripheral wall portion 22.
  • the bottom surface portion 21 has a convex portion 23 at the center, and a plurality of ignition product discharge holes 24 formed through the bottom surface portion 21 around the convex portion 23.
  • About 2 to 8 discharge holes 24 for the plurality of ignition products are formed at equal intervals in the circumferential direction.
  • a sealing tape may be provided in the discharge hole 24 at the bottom surface portion 21 as necessary to prevent spillage of the smoke generating composition and to take measures against humidity.
  • the peripheral wall portion 22 has a screw portion 22 a that can be screwed into the screw portion of the inner peripheral surface 13 a of the first tip peripheral wall portion 13.
  • An igniter 5 having an igniter collar 6 is attached to the internal space 25 of the first closure 20.
  • the igniter 5 is attached by screwing the igniter collar 6 into the inner peripheral wall surface 25 a of the first closure 20.
  • the ignition part 5 a of the igniter 5 is located in the internal space 25.
  • the second end 10 b side of the cylindrical housing 10 is closed with a second closure 30.
  • the second closure 30 is a combination of the first member 31 and the second member 40, but may be a single member.
  • the first member 31 includes an annular substrate 32 having a large outer diameter, an annular convex portion 33 having an outer diameter smaller than the annular substrate 32 formed on the annular substrate 32, and an annular substrate. It has an inner peripheral wall portion 34a, an outer peripheral wall portion 34b of the annular substrate, and an annular bottom surface portion 35.
  • the inner diameter of the annular protrusion 33 is larger than the inner diameter of the annular substrate 32.
  • the annular protrusion 33 is formed in the axial direction from the difference between the inner and outer diameters of the annular substrate 32 and the annular inner step surface 36a facing the axial direction on the inner peripheral wall 34a side of the annular substrate, that is, radially inward. Facing the outer peripheral wall 34b side of the annular substrate, that is, radially outside, has an annular outer stepped surface 36b.
  • the annular convex portion 33 Due to the difference between the inner diameter and outer diameter of the annular substrate 32, the annular convex portion 33 has an annular inner peripheral wall surface 37a facing inward in the radial direction (a direction orthogonal to the axial direction) and an annular outer peripheral wall surface facing outward in the radial direction. 37b.
  • a smoke screen source discharge port 38 defined by the inner peripheral wall portion 34a of the annular substrate is formed at the center of the first member 31 and inside the annular inner stepped surface 36a.
  • the first member 31 has an annular outer peripheral wall surface 37b in contact with the inner peripheral surface 10c of the cylindrical housing 10, an annular outer step surface 36b in contact with the second annular step surface 14, and an outer peripheral wall portion 34b of the annular substrate. Is fitted into the second end opening 10b of the cylindrical housing 10 in a state of being in contact with the second tip peripheral wall 15.
  • the second member 40 has a substantially cup shape, and has a peripheral wall portion 41 and a bottom surface portion 42 in which a through hole 43 is formed in the central portion.
  • the peripheral wall portion 41 has a screw portion 44 on the inner peripheral surface. is doing.
  • the inner diameter of the through hole 43 is larger than the inner diameter of the smoke screen source discharge port 38 and smaller than the outer diameter of the annular bottom surface portion 35.
  • the second member 40 is fixed by screwing the screw portion 44 into the outer peripheral surface 15a of the second tip peripheral wall portion 15. Since the bottom surface portion 42 of the second member 40 presses the annular bottom surface portion 35 of the first member 31 in the axial direction (the direction toward the first end opening 10a), the first member 31 is connected to the second member 40. It is fixed by being sandwiched between the second annular stepped surfaces 14.
  • a porous cylindrical body 50 in which a net is formed into a cylindrical shape is disposed.
  • the porous cylindrical body 50 has the first opening 50a side fitted into the convex portion 23 of the first closure 20 from the outside, and the second opening 50b side is connected to the annular inner step surface 36a and the annular inner step surface of the first member 31 of the second closure. It is in contact with the peripheral wall surface 37a. Since the porous cylindrical body 50 is fixed from both sides in the axial direction, it does not move before and during operation.
  • the cylindrical space between the inner peripheral surface 10 c of the cylindrical housing 10 and the porous cylindrical body 50 is a smoke generating agent composition storage chamber 55 in which the smoke generating composition 56 is stored.
  • the smoke generating composition 56 can be made into a dosage form having a desired shape such as a cylinder, a disk, a powder, or a granule.
  • a plurality of ignition product discharge holes 24 formed in the bottom surface portion 21 of the first closure 20 face the first end opening portion 10a side of the smoke generating composition containing chamber 55, and the second end opening portion.
  • the 10b side faces the first member 31 of the second closure 30.
  • the igniter 5, the porous cylindrical body 50, the smoke screen source discharge port 38, and the through hole 43 of the second member 40 are arranged so that the central axis thereof and the axis of the cylindrical housing 10 are coaxial.
  • the first annular partition plate 60 is sandwiched between the second opening 70 b of the first inner cylinder member 70 and the first opening 71 a of the second inner cylinder member 71. Has been placed.
  • the first annular partition plate 60 has a through hole 61a for passing the porous cylindrical body 50 and a first smoke screen source passage hole 61b for passing the smoke screen source during operation.
  • the second annular partition plate 62 is disposed in a state of being sandwiched between the second opening 71 b of the second inner cylinder member 71 and the first opening 72 a of the third inner cylinder member 72.
  • the second annular partition plate 62 has a through hole 62a through which the porous cylindrical body 50 passes and a second smoke screen source passage hole 62b through which the smoke screen source passes during operation.
  • the size of the first smoke screen source passage hole 61b and the second smoke screen source passage hole 62b may be smaller or larger than the smoke generating agent composition 56.
  • the number of the first smoke screen source passage holes 61b and the second smoke screen source passage holes 62b is not particularly limited, but about 4 to 20 with the same interval between the first annular partition plate 60 and the second annular partition plate 62. It can be formed in a dispersed manner.
  • the smoke generating agent composition storage chamber 55 includes a first chamber 55a, a second chamber 55b, and a third chamber in order from the first closure 20 side to the second closure 30 by the first annular partition plate 60 and the second annular partition plate 62.
  • the chamber 55c is divided.
  • the outer diameters of the first inner cylinder member 70, the second inner cylinder member 71, and the third inner cylinder member 72 are adjusted to such a size that they can be inserted into the cylindrical housing 10 and can contact the inner peripheral surface 10c. .
  • the annular step surface 11a is provided on the second closure 30 side by adjusting the thickness of the peripheral wall portion 11 of the cylindrical housing 10, and the second opening portion 72b side of the third inner cylinder member 72 is the annular step surface 11a.
  • the smoke generating agent composition storage chamber 55 is fixed in the axial direction by contacting the first opening 70 a side of the first inner cylinder member 70 with the first closure 20.
  • the security device includes a sensor and an electric igniter, and contains a smoke generating composition, and is used by being attached to an indoor ceiling or wall.
  • the smoke generating composition may be accommodated together in one accommodation room provided in the security device.
  • the senor When a trespasser enters the room, the sensor detects it and activates the electric igniter to generate combustion products (mixed with flames and high-temperature gas). Thereafter, a white smoke source is generated by the contact between the combustion product and the white smoke agent of component (B).
  • the white smoke agent of component (B) is ejected from the crime prevention device in a state of being changed into gas (white smoke source) by the combustion product (heat) of the electric igniter, and is cooled in the air after being ejected. Changes to smoke (droplets).
  • the component (A) and the component (C) are also ignited and combusted in contact with the combustion product.
  • the fuel (combustible agent) as the component (A) is burned by the action of an oxidant, and instantly generates a high-temperature gas including nitrogen gas, carbon dioxide gas, and the like.
  • the (C) component oxidizing agent burns the (A) component fuel (combustible), and the oxidizing agent itself is a source of white smoke such as sodium chloride, potassium chloride, magnesium chloride, potassium oxide, potassium carbonate, etc. Changes to white smoke as a fine powder.
  • disassembly of (B) component can also be accelerated
  • the white smoke generated from the component (B) is ejected vigorously by the action of the gas generated from the component (A). Uniformly and rapidly. And since white smoke is jetted and diffused from the security device into the room in this way, threats are made against the intruder, the visibility of the intruder is hindered, and the action is deterred or delayed. Action is deterred, prevented, or restrained.
  • Examples 1-9, Comparative Examples 1-5 A smoke generator composition molded body comprising each component shown in Table 1 was produced in the same manner as a known method for producing a gas generant molded body.
  • the smoke agent compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were formed into powders as they were, and the smoke agent compositions of Examples 7 to 9 were granulated to have an average particle size of 2000 ⁇ m. Was formed into a molded body.
  • the smoke generator composition was used as a cylindrical molded body having an outer diameter of 10 mm, a length of 10 mm, and a mass of 0.2 g.
  • the first smoke screen generator shown in FIG. 1 is filled with 70 g of the smoke composition composition (smoke generator 1), and the second smoke screen generator shown in FIG. 2 is filled with 140 g of the smoke composition composition. (Smoke generator 2) was used.
  • the difference between the smoke screen generator 1 and the smoke screen generator 2 is only the presence or absence of an initiator (the smoke screen generator 2 has an initiator).
  • a smoke screen generator was placed at the center of the floor of a transparent glass container of 30 m 3 (length 6 m, width 2.5 m, height 2 m). The inside of the container was maintained at room temperature (20 ° C.). Set the device on the light receiving side of the transmittance measuring device along the long side wall of the corners of the long side and short side of the container, and place it on the light emitting side at a position 50 cm away from the light receiving side device in the long side direction. The device was set.
  • non-combustible means that the smoke generating agent composition did not burn and white smoke was not generated even when the ignition device of the smoke screen generator was operated.
  • Examples 10-12, Comparative Examples 6-8 ⁇ Manufacture of smoke generator composition> A smoke generator composition molded body comprising the respective components shown in Table 2 was produced in the same manner as a known method for producing a gas generant molded body. That is, the smoke former composition molded bodies of Examples 10 to 12 were produced by the following method.
  • Example 10 to 12 The components (A) and (B) are added to a solution (EC-vehicle, manufactured by Nisshin Kasei Co., Ltd.) in which 2% by mass of ethyl cellulose as the component (E) is dissolved in isopropyl alcohol as the component (D). The mixture was stirred with a conductive spatula until it could be visually confirmed that the mixture was uniformly mixed. Thereafter, the component (C) was added and stirred while confirming the mass until the isopropyl alcohol content volatilized to 10% by mass or less of the total mass.
  • EC-vehicle manufactured by Nisshin Kasei Co., Ltd.
  • the smoke generator composition molded body was put into a dryer and dried at a drying temperature of 40 ° C. for 5 hours or more.
  • the smoke generator composition used was granulated to have an outer diameter of 1 mm, a length of 2 mm, and a mass of 0.05 g.
  • the smoke former composition molded bodies of Comparative Examples 6 to 8 were produced by the following method.
  • (Comparative Example 6) Add the (A) component and the (B) component to a solution in which 2% by mass of the carboxymethyl cellulose, which is the (E) component, is dissolved in water. Stir. Thereafter, the component (C) was added, formed into granules, put into a dryer, and dried at a drying temperature of 20 ° C. for 20 hours or more.
  • the smoke generator composition obtained was granulated to have an outer diameter of 2 mm, a length of 5 mm, and a mass of 0.5 g.
  • the component (A), the component (B), and the component (C) were stirred and mixed with a conductive spatula until it was confirmed that they were visually mixed uniformly.
  • the mixed smoke generating composition was weighed into a molding die, and the powder mixed product was compressed by a hydraulic press machine to form a powder compressed product.
  • the smoke generator composition obtained was formed into a cylindrical shape having an outer diameter of 10 mm, a length of 0.9 mm, and a mass of 0.9 g.
  • ⁇ Quantitative test of component (D)> The content of isopropyl alcohol as the component (D) in the smoke generating composition was quantified by the following method.
  • the smoke agent composition of Example 10 (927.2 mg) was immersed in methanol (20 mL, 7827.5 mg) for 2 days to extract isopropyl alcohol contained in the smoke agent composition.
  • methanol 20 mL, 7827.5 mg
  • the content of isopropyl alcohol was quantified with a calibration curve using a gas chromatogram mass spectrometer (GC / MS (SIM)) (manufactured by Shimadzu Corporation, gas chromatogram mass spectrometer), the obtained peak intensity was obtained.
  • GC / MS gas chromatogram mass spectrometer
  • the content of the component (D) in Examples 11 and 12 was determined based on the amount of the solution obtained by dissolving 2% by mass of ethyl cellulose in isopropyl alcohol used for the addition of the component (D) and the component (E). This is a value obtained by converting the amount added.
  • the smoke screen generator shown in FIG. 2 filled with 80 g of each smoke generating composition was used.
  • a smoke screen generator was placed at the center of the floor of a 30 m 3 (6 m long, 2.5 m wide, 2 m high) container. The inside of the container was maintained at room temperature (20 ° C.).
  • the device was set. 100 seconds after igniting the ignition device, irradiate light of each wavelength of 405 nm, 635 nm, and 785 nm from the device on the light-emitting side, detect it with the light sensor on the light-receiving side, and transmit it through the amplifier to the measuring instrument The rate was measured. The results are shown in Table 1. The smaller the transmittance, the higher the smoke screen density, and the better the visual blocking effect of white smoke.

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Abstract

Provided are a smoke generation composition, which generates a white smoke source and thus exhibits an excellent visual blocking effect using white smoke, and a smoke screen generator. The smoke generating composition comprises (A) a fuel, (B) a white smoke generator and (C) an oxidant, wherein the blending ratio of component (A) to component (B) [(A)/(B)] in the smoke generating composition exceeds 1. A smoke generating composition which comprises (A) a fuel, (B) a white smoke generator, (C) an oxidant and (D) an isoalkyl alcohol.

Description

発煙剤組成物及び発煙器Smoke composition and smoke generator
　本発明は、防犯装置（発煙器）に使用できる発煙剤組成物及びそれを用いた発煙器に関する。
背景技術 The present invention relates to a smoke generating composition that can be used in a crime prevention device (smoke generator) and a smoke generator using the same.
Background art
　建物内への侵入者に対する防犯装置として、煙を発生させる機能を有しているものが知られている。実開昭５７－１９４１８２号公報には、防犯用発煙筒と防犯小型簡易カメラを備えた防犯カメラ付煙幕装置の考案が記載されている。実用新案登録第２５００５９１号公報には防犯用煙幕装置の考案が記載されているが、高圧ガスが充填されたガスタンクを必須とするものであり、ガスとしては二酸化炭素が例示されている。 As a crime prevention device against intruders in the building, one having a function of generating smoke is known. Japanese Utility Model Laid-Open No. 57-194182 discloses a device for a smoke screen device with a security camera having a security smoke cylinder and a small security simple camera. Utility model registration No. 2500591 discloses a device for a smoke screen device for crime prevention, but requires a gas tank filled with high-pressure gas, and carbon dioxide is exemplified as the gas.
　特許第３８１６８６７号公報には、点火装置と発煙剤などを備えた煙幕生成装置が記載されている。発煙剤としては、酸化亜鉛、過塩素酸アンモニウム、塩化ビニル、炭酸カルシウムからなる組成物を錠剤状に成形したものが記載されている（段落番号００２０）。塩化ビニルモノマー自体は発癌性があるとして使用が禁止されているものであり、塩化ビニル樹脂であっても、燃焼により有害な塩素ガスを発生することが考えられるため、安全性の点で問題がある。 Japanese Patent No. 3816867 describes a smoke screen generating device including an ignition device and a smoke generating agent. As the smoke generating agent, a composition formed of zinc oxide, ammonium perchlorate, vinyl chloride, and calcium carbonate into a tablet shape is described (paragraph 0020). The use of vinyl chloride monomer itself is prohibited because it is carcinogenic, and even vinyl chloride resin may generate harmful chlorine gas due to combustion. is there.
　特開２００３－３０６３９５号公報には、酸化剤、白色粉末、助燃剤が硬化性樹脂により棒状に結着成形され、硬化されてなる白色発煙棒状体が記載されている。具体例として、過塩素酸アンモニウムなどの酸化剤、酸化亜鉛また塩化亜鉛などの白色粉末、澱粉質、炭水化物、塩化ゴムなどの助燃剤、硬化剤の併用により硬化する不飽和ポリエステル樹脂、エポキシ樹脂などの熱硬化性樹脂からなる白色発煙棒状体が記載されている（段落番号００１０、００１１）。実施例１の記載では、不飽和ポリエステル樹脂（プレポリマー）を含む棒状体を成形した後で硬化させている。 Japanese Patent Application Laid-Open No. 2003-306395 describes a white smoke rod-like body in which an oxidizer, white powder, and a combustor are bonded and formed into a rod shape with a curable resin and cured. Specific examples include oxidizing agents such as ammonium perchlorate, white powders such as zinc oxide and zinc chloride, auxiliary substances such as starches, carbohydrates, and chlorinated rubber, unsaturated polyester resins that cure with a combination of curing agents, and epoxy resins. A white smoke rod-shaped body made of a thermosetting resin is described (paragraph numbers 0010 and 0011). In the description of Example 1, a rod-shaped body containing an unsaturated polyester resin (prepolymer) is molded and then cured.
　棒状体にマッチで着火すると、助燃剤や酸化剤の作用により不飽和ポリエステル樹脂が熱分解してガスを生じさせ、そのときに酸化亜鉛また塩化亜鉛などの白色粉末を放出して白煙を生じさせるものと考えられる。このように白煙源は白色粉末であり、ガス源が熱硬化性樹脂の熱分解によるものであるから、瞬間的に多量のガスを発生させて白色粉末を拡散させることは困難であると考えられる。 When the rod-shaped body is ignited with a match, the unsaturated polyester resin is thermally decomposed by the action of a combustor or an oxidant to generate gas, and at that time, white powder such as zinc oxide or zinc chloride is released to generate white smoke. It is thought that In this way, the white smoke source is white powder, and the gas source is generated by thermal decomposition of the thermosetting resin, so it is difficult to instantaneously generate a large amount of gas and diffuse the white powder. It is done.
　特開２０１５－４２６０３号公報には、（Ａ）白煙源を発生するための発煙剤と、（Ｂ）（Ｂ－１）燃料と（Ｂ－２）酸化剤を含む、ガスおよび白煙源を発生するためのガス発生剤を含有する発煙剤組成物であって、（Ａ）成分と（Ｂ）成分から発生した白煙源が、（Ｂ）成分から発生したガスにより飛散されるものである、発煙剤組成物が記載されている。
発明の概要 Japanese Patent Application Laid-Open No. 2015-42603 discloses a gas and white smoke source containing (A) a smoke generating agent for generating a white smoke source, and (B) (B-1) fuel and (B-2) an oxidizing agent. A smoke generating composition containing a gas generating agent for generating gas, wherein the white smoke source generated from the component (A) and the component (B) is scattered by the gas generated from the component (B). A smoke generator composition is described.
Summary of the Invention
　本発明は、白煙源を発生させることで、白煙による視覚的な遮断効果に優れ、また、人体、環境への害・影響が少ない発煙剤組成物及びそれを用いた発煙器を提供することを課題とする。 The present invention provides a fuming agent composition that is excellent in visual blocking effect due to white smoke by generating a white smoke source, and has little harm and influence on the human body and the environment, and a smoke generator using the same. This is the issue.
　本発明は、（Ａ）燃料、（Ｂ）白煙剤、（Ｃ）酸化剤を含有する発煙剤組成物であって、発煙剤組成物中の（Ａ）成分と（Ｂ）成分の含有割合の比（Ａ）／（Ｂ）が、１超である、発煙剤組成物を提供する。一つの実施形態において、（Ａ）燃料は糖類であってよく、（Ｂ）白煙剤はパラフィン化合物を含むワックス類及びポリアルキレングリコールから選ばれる１種以上であってよい。 The present invention is a smoke agent composition containing (A) fuel, (B) white smoke agent, and (C) an oxidizer, and the content ratio of component (A) and component (B) in the smoke agent composition The smoke generating composition has a ratio (A) / (B) of greater than 1. In one embodiment, (A) the fuel may be a saccharide, and (B) the white smoke agent may be one or more selected from waxes containing a paraffin compound and a polyalkylene glycol.
　また本発明は、（Ａ）燃料、（Ｂ）白煙剤、（Ｃ）酸化剤、及び（Ｄ）イソアルキルアルコールを含有する、発煙剤組成物を提供する。 The present invention also provides a smoke generating composition containing (A) fuel, (B) white smoke agent, (C) oxidizing agent, and (D) isoalkyl alcohol.
　また本発明は、上記のいずれかの発煙剤組成物を用いた発煙器に関する。 The present invention also relates to a smoke generator using any one of the above smoke generating compositions.
　本発明の発煙剤組成物は、いずれも白煙源を発生させることで、発煙による視覚的な遮断効果に優れる。このため、本発明の発煙剤組成物を防犯装置（発煙器）に使用したとき、即ち本発明の発煙器は、白煙による視覚的な遮断効果に優れるため、防犯効果が高められる。 The smoke generating composition of the present invention is excellent in visual blocking effect due to fuming by generating a white smoke source. For this reason, when the smoke generating composition of this invention is used for a crime prevention device (smoke generator), that is, since the smoke generator of this invention is excellent in the visual blocking effect by white smoke, the crime prevention effect is enhanced.
本発明の発煙剤組成物を使用した第１の煙幕発生器の軸方向断面図。The axial sectional view of the 1st smoke generator using the smoke generating composition of the present invention. 本発明の発煙剤組成物を使用した第２の煙幕発生器の軸方向断面図。The axial sectional view of the 2nd smoke generator using the smoke generating composition of the present invention. 図２で使用している第２クロージャの第１部材の軸方向断面図。FIG. 3 is an axial sectional view of a first member of a second closure used in FIG. 2. 図２で使用している環状仕切り板の軸方向断面図。FIG. 3 is an axial sectional view of an annular partition plate used in FIG. 2.
　本発明の発煙剤組成物は、（Ａ）成分として、燃料を含有する。（Ａ）成分は、白煙を発生させるための燃料（可燃剤）である。 The smoke generating composition of the present invention contains fuel as the component (A). The component (A) is a fuel (combustible agent) for generating white smoke.
　（Ａ）成分は、発煙による視覚的な遮断効果を得る観点から、糖類が好ましい。（Ａ）成分の糖類としては、
（Ａ－１）グルコース、ガラクトース、フルクトース、マンノース、リボース、デオキシリボース等の単糖類、
（Ａ－２）スクロース、ラクトース、マルトース、トレハロース、ツラノース、セロビオース等の二糖類、
（Ａ－３）デンプン、セルロース、グリコーゲン、キチン、アガロース、ペクチン等の多糖類
が挙げられる。 The component (A) is preferably a saccharide from the viewpoint of obtaining a visual blocking effect by fuming. As (A) component saccharides,
(A-1) monosaccharides such as glucose, galactose, fructose, mannose, ribose, deoxyribose,
(A-2) disaccharides such as sucrose, lactose, maltose, trehalose, tulanose, cellobiose,
(A-3) Polysaccharides such as starch, cellulose, glycogen, chitin, agarose and pectin.
　（Ａ）成分は、発煙による視覚的な遮断効果を得る観点から、好ましくは（Ａ－１）成分及び（Ａ－２）成分から選ばれる１種以上であり、より好ましくは（Ａ－２）成分から選ばれる１種以上である。 The component (A) is preferably at least one selected from the components (A-1) and (A-2), more preferably (A-2), from the viewpoint of obtaining a visual blocking effect due to fuming. One or more selected from components.
　（Ａ－１）成分としては、発煙による視覚的な遮断効果を得る観点から、好ましくはグルコース、ガラクトース及びフルクトースから選ばれる１種以上であり、より好ましくはグルコース及びガラクトースから選ばれる１種以上であり、更に好ましくはガラクトースである。 The component (A-1) is preferably at least one selected from glucose, galactose and fructose, more preferably at least one selected from glucose and galactose from the viewpoint of obtaining a visual blocking effect due to fuming. Yes, more preferably galactose.
　（Ａ－２）成分としては、発煙による視覚的な遮断効果を得る観点から、好ましくはスクロース及びラクトースから選ばれる１種以上であり、より好ましくはスクロースである。 The component (A-2) is preferably at least one selected from sucrose and lactose, more preferably sucrose, from the viewpoint of obtaining a visual blocking effect due to fuming.
　（Ａ－３）成分としては、発煙による視覚的な遮断効果を得る観点から、好ましくはデンプン、セルロース及びグリコーゲンから選ばれる１種以上であり、より好ましくはデンプン及びセルロースから選ばれる１種以上である。 The component (A-3) is preferably at least one selected from starch, cellulose and glycogen, more preferably at least one selected from starch and cellulose, from the viewpoint of obtaining a visual blocking effect due to fuming. is there.
　（Ａ）成分は、上記の中でも、発煙による視覚的な遮断効果を得る観点から、好ましくはグルコース、ガラクトース、フルクトース、スクロース及びラクトースから選ばれる１種以上であり、より好ましくはグルコース、ガラクトース及びスクロースから選ばれる１種以上であり、更に好ましくはガラクトース及びスクロースから選ばれる１種以上であり、より更に好ましくはスクロースである。 Among the above, the component (A) is preferably at least one selected from glucose, galactose, fructose, sucrose and lactose, more preferably glucose, galactose and sucrose, from the viewpoint of obtaining a visual blocking effect due to fuming. 1 or more selected from galactose and sucrose, and more preferably sucrose.
　（Ａ）成分である糖類は、粒子状で本発明の発煙剤組成物に含有することが好ましく、（Ａ）成分の平均粒径は、発煙による視覚的な遮断効果の観点から、好ましくは３００μｍ以上、より好ましくは４００μｍ以上、更に好ましくは４５０μｍ以上、より更に好ましくは５００μｍ以上、また、好ましくは１０００μｍ以下、より好ましくは８００μｍ以下、更に好ましくは６５０μｍ以下、より更に好ましくは６００μｍ以下である。粒径は、レーザー回折・散乱法を用いて測定してよい。 The saccharide as the component (A) is preferably in the form of particles and contained in the smoke generating composition of the present invention, and the average particle size of the component (A) is preferably 300 μm from the viewpoint of a visual blocking effect due to fuming. More preferably, it is 400 μm or more, more preferably 450 μm or more, still more preferably 500 μm or more, preferably 1000 μm or less, more preferably 800 μm or less, still more preferably 650 μm or less, and still more preferably 600 μm or less. The particle size may be measured using a laser diffraction / scattering method.
　本発明の発煙剤組成物は、（Ｂ）成分として、白煙剤を含有する。（Ｂ）成分は、作動時における熱により気化（状態変化）してガス（白煙源）となり、前記ガスが冷却されて液滴となって白煙となる成分（白煙剤）である。気化によって拡散する空間に白煙を均一濃度に分散させることができるほか、広範囲にわたって拡散させることができる。 The smoke generating composition of the present invention contains a white smoke agent as the component (B). The component (B) is a component (white smoke agent) that is vaporized (changes in state) by heat during operation to become a gas (white smoke source), and the gas is cooled to become droplets to become white smoke. In addition to being able to disperse white smoke at a uniform concentration in the space that diffuses by vaporization, it can be diffused over a wide range.
　（Ｂ）成分は、発煙による視覚的な遮断効果を得る観点から、パラフィン化合物を含むワックス類及びポリアルキレングリコールから選ばれる１種以上が好ましい。 The component (B) is preferably at least one selected from waxes containing paraffin compounds and polyalkylene glycols from the viewpoint of obtaining a visual blocking effect due to fuming.
　（Ｂ）成分である、パラフィン化合物を含むワックス類及びポリアルキレングリコールから選ばれる１種以上としては、
（Ｂ－１）パラフィンワックス（主成分：ノルマルパラフィン）、マイクロクリスタリンワックス（主成分：イソパラフィン、シクロパラフィン）等のパラフィン化合物を含むワックス類、
（Ｂ－２）ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール、等のポリアルキレングリコール
が挙げられる。 As the component (B), one or more selected from waxes containing paraffin compounds and polyalkylene glycols,
(B-1) waxes containing paraffin compounds such as paraffin wax (main component: normal paraffin), microcrystalline wax (main component: isoparaffin, cycloparaffin),
(B-2) Polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and the like can be mentioned.
　（Ｂ）成分は、安全性、取り扱い易さの観点から、好ましくは（Ｂ－１）成分である。 The component (B) is preferably the component (B-1) from the viewpoint of safety and ease of handling.
　（Ｂ－１）成分としては、安全性、取り扱い易さの観点から、好ましくはパラフィンワックス（主成分：ノルマルパラフィン）及びマイクロクリスタリンワックス（主成分：イソパラフィン、シクロパラフィン）から選ばれる１種以上であり、より好ましくはパラフィンワックス（主成分：ノルマルパラフィン）である。 The component (B-1) is preferably one or more selected from paraffin wax (main component: normal paraffin) and microcrystalline wax (main component: isoparaffin, cycloparaffin) from the viewpoints of safety and ease of handling. Yes, more preferably paraffin wax (main component: normal paraffin).
　また（Ｂ－１）成分としては、安全性、取り扱い易さの観点から、好ましくはノルマルパラフィン、イソパラフィン及びシクロパラフィンから選ばれる１種以上であり、より好ましくはノルマルパラフィンである。 The component (B-1) is preferably at least one selected from normal paraffin, isoparaffin and cycloparaffin from the viewpoint of safety and ease of handling, and more preferably normal paraffin.
　（Ｂ－２）成分としては、安全性、取り扱い易さの観点から、好ましくはポリエチレングリコール及びポリプロピレングリコールから選ばれる１種以上であり、より好ましくはポリエチレングリコールである。 The component (B-2) is preferably at least one selected from polyethylene glycol and polypropylene glycol, more preferably polyethylene glycol, from the viewpoint of safety and ease of handling.
　（Ｂ）成分は、上記の中でも、安全性、取り扱い易さの観点から、好ましくはパラフィンワックス、マイクロクリスタリンワックス及びポリエチレングリコールから選ばれる１種以上であり、より好ましくはパラフィンワックスである。また（Ｂ）成分は、上記の中でも、安全性、取り扱い易さの観点から、好ましくはノルマルパラフィン、イソパラフィン、シクロパラフィン及びポリエチレングリコールから選ばれる１種以上であり、より好ましくはノルマルパラフィンである。 Among these, the component (B) is preferably at least one selected from paraffin wax, microcrystalline wax and polyethylene glycol from the viewpoint of safety and ease of handling, and more preferably paraffin wax. The component (B) is preferably at least one selected from normal paraffin, isoparaffin, cycloparaffin and polyethylene glycol, more preferably normal paraffin, from the viewpoints of safety and ease of handling.
　本発明の発煙剤組成物は、（Ｃ）成分として、酸化剤を含有する。（Ｃ）成分は、（Ａ）成分である燃料（可燃剤）を瞬時に燃焼させて大量のガス（窒素ガスや二酸化炭素を含むガス）を発生させると共に、酸化剤自体が変化することで白煙源を生じさせることができる。 The smoke generating composition of the present invention contains an oxidizing agent as the component (C). The component (C) is produced by instantly burning the fuel (combustible agent) that is the component (A) to generate a large amount of gas (a gas containing nitrogen gas or carbon dioxide) and changing the oxidant itself. A smoke source can be generated.
　（Ｃ）成分としては、
（Ｃ－１）塩素酸カリウム、塩素酸ナトリウム等の塩素酸塩、
（Ｃ－２）過塩素酸ストロンチウム、過塩素酸マグネシウム、過塩素酸アンモニウム、過塩素酸カリウム、過塩素酸ナトリウム等の過塩素酸塩、
（Ｃ－３）硝酸ストロンチウム、硝酸カリウム、硝酸ナトリウム等の硝酸塩
が挙げられる。 As component (C),
(C-1) Chlorates such as potassium chlorate and sodium chlorate,
(C-2) perchlorates such as strontium perchlorate, magnesium perchlorate, ammonium perchlorate, potassium perchlorate, sodium perchlorate,
(C-3) Nitrate salts such as strontium nitrate, potassium nitrate and sodium nitrate.
　（Ｃ）成分は、安全性、取り扱い易さの観点から、好ましくは（Ｃ－３）成分である。 The component (C) is preferably the component (C-3) from the viewpoint of safety and ease of handling.
　（Ｃ－１）成分は、安全性、取り扱い易さの観点から、好ましくは塩素酸カリウムである。（Ｃ－２）成分は、安全性、取り扱い易さの観点から、好ましくは過塩素酸カリウムである。（Ｃ－３）成分は、安全性、取り扱い易さの観点から、好ましくは硝酸カリウム及び硝酸ストロンチウムから選ばれる１種以上であり、より好ましくは硝酸カリウムである。 The component (C-1) is preferably potassium chlorate from the viewpoint of safety and ease of handling. The component (C-2) is preferably potassium perchlorate from the viewpoints of safety and ease of handling. The component (C-3) is preferably at least one selected from potassium nitrate and strontium nitrate, and more preferably potassium nitrate, from the viewpoints of safety and ease of handling.
　（Ｃ）成分は、上記の中でも、安全性、取り扱い易さの観点から、好ましくは塩素酸カリウム、過塩素酸カリウム、硝酸ストロンチウム及び硝酸カリウムから選ばれる１種以上であり、より好ましくは過塩素酸カリウム、硝酸ストロンチウム及び硝酸カリウムから選ばれる１種以上であり、更に好ましくは過塩素酸カリウム及び硝酸カリウムから選ばれる１種以上であり、最も好ましくは硝酸カリウムである。 Among the above, the component (C) is preferably at least one selected from potassium chlorate, potassium perchlorate, strontium nitrate and potassium nitrate, more preferably perchloric acid, from the viewpoint of safety and ease of handling. One or more selected from potassium, strontium nitrate and potassium nitrate, more preferably one or more selected from potassium perchlorate and potassium nitrate, and most preferably potassium nitrate.
　一つの実施形態において、本発明の発煙剤組成物は、（Ｄ）成分としてイソアルキルアルコールを含有する。（Ｄ）成分は、発煙剤組成物を製造する際に、（Ａ）成分を溶解しないため、（Ａ）成分の粒子形状を維持することができる。（Ｄ）成分は、（Ａ）成分の粒子形状を維持して、発煙剤組成物を製造することを目的として配合される。 In one embodiment, the smoke generator composition of the present invention contains isoalkyl alcohol as component (D). (D) Since a component does not melt | dissolve (A) component when manufacturing a smoke generating composition, it can maintain the particle shape of (A) component. (D) component is mix | blended for the purpose of maintaining the particle shape of (A) component and manufacturing a smoke generating composition.
　（Ｄ）成分としては、（Ａ）成分の粒子を溶解させない観点から、好ましくはイソプロパノール、イソブタノール、イソペンタノール及びイソヘキサノールから選ばれる１種以上であり、より好ましくはイソプロピルアルコールである。 The component (D) is preferably at least one selected from isopropanol, isobutanol, isopentanol and isohexanol, more preferably isopropyl alcohol, from the viewpoint of not dissolving the particles of the component (A).
　一つの実施形態において、本発明の発煙剤組成物中、各成分の含有割合は（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計１００質量部に対して、次の通りである。 In one embodiment, the content ratio of each component in the smoke composition of the present invention is as follows with respect to 100 parts by mass in total of the component (A), the component (B), and the component (C).
　（Ａ）成分は、好ましくは１０質量部以上、より好ましくは２０質量部以上、更に好ましくは２５質量部以上、より更に好ましくは３０質量部以上、また、好ましくは６０質量部以下、より好ましくは５０質量部以下、更に好ましくは４０質量部以下、より更に好ましくは３５質量部以下である。 The component (A) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 25 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 60 parts by mass or less, more preferably. 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 35 parts by mass or less.
　（Ｂ）成分は、好ましくは１質量部以上、より好ましくは５質量部以上、更に好ましくは１０質量部以上、より更に好ましくは１２質量部以上、また、好ましくは３０質量部以下、より好ましくは２５質量部以下、更に好ましくは２０質量部以下、より更に好ましくは１８質量部以下である。 The component (B) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 12 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 18 parts by mass or less.
　（Ｃ）成分は、好ましくは３０質量部以上、より好ましくは４０質量部以上、更に好ましくは４５質量部以上、より更に好ましくは４７質量部以上、また、好ましくは７０質量部以下、より好ましくは６０質量部以下、更に好ましくは５５質量部以下、より更に好ましくは５３質量部以下である。 The component (C) is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, still more preferably 45 parts by mass or more, still more preferably 47 parts by mass or more, and preferably 70 parts by mass or less, more preferably 60 mass parts or less, More preferably, it is 55 mass parts or less, More preferably, it is 53 mass parts or less.
　本発明の発煙剤組成物中、（Ａ）成分と（Ｂ）成分の含有割合の比（Ａ）／（Ｂ）は、発煙による視覚的な遮断効果を得る観点から、１超、好ましくは１．２以上、より好ましくは１．５以上、更に好ましくは１．８以上、より更に好ましくは２以上、そして、好ましくは１０以下、より好ましくは８以下、更に好ましくは５以下、より更に好ましくは３以下である。 In the smoke generating composition of the present invention, the ratio (A) / (B) of the content ratio of the component (A) to the component (B) is more than 1, preferably 1 from the viewpoint of obtaining a visual blocking effect due to fuming. .2 or more, more preferably 1.5 or more, still more preferably 1.8 or more, still more preferably 2 or more, and preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, still more preferably 3 or less.
　一つの実施形態において、（Ａ）成分と（Ｂ）成分の含有割合の比（Ａ）／（Ｂ）は、１．２以上１０以下である。別の実施形態において、（Ａ）成分と（Ｂ）成分の含有割合の比（Ａ）／（Ｂ）は、２以上１０以下である。 In one embodiment, the ratio (A) / (B) of the content ratio of the component (A) and the component (B) is 1.2 or more and 10 or less. In another embodiment, ratio (A) / (B) of the content rate of (A) component and (B) component is 2-10.
　一つの実施形態において、本発明の発煙剤組成物中、（Ｄ）成分の含有割合は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計１００質量部に対して、（Ａ）成分の粒子を溶解させない観点から、好ましくは１ｐｐｍ以上、そして、（Ｄ）成分の含有割合が多くなると、発煙作動時の妨げになる観点から、好ましくは１００ｐｐｍ以下、より好ましくは５０ｐｐｍ以下である。一つの実施形態において、（Ｄ）成分の含有割合は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計１００質量部に対して、１ｐｐｍ以上１００ｐｐｍ以下である。 In one embodiment, the content ratio of the component (D) in the smoke generating composition of the present invention is (A) with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C). From the viewpoint of not dissolving the component particles, the content is preferably 1 ppm or more, and when the content ratio of the component (D) is increased, it is preferably 100 ppm or less, more preferably 50 ppm or less, from the viewpoint of hindering smoke generation. In one embodiment, the content rate of (D) component is 1 ppm or more and 100 ppm or less with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component.
　本発明の発煙剤組成物は、（Ａ）成分～（Ｃ）成分に加え、または（Ａ）成分～（Ｄ）成分に加え、（Ｅ）成分として、バインダーを含有することが好ましい。（Ｅ）成分は、発煙剤組成物を所望形状に成形するときに使用する成分である。 The smoke generating composition of the present invention preferably contains a binder as the component (E) in addition to the components (A) to (C), or in addition to the components (A) to (D). (E) A component is a component used when shape | molding a smoke generating composition in a desired shape.
　（Ｅ）成分としては、グアガム、カルボキシメチルセルロースナトリウム（ＣＭＣＮａ）、エチルセルロース、ポリビニルピロリドン、ポリアクリルアミド、デンプン及びデキストリンから選ばれる１種以上が挙げられ、結合性、取り扱い易さの観点から、好ましくはカルボキシメチルセルロースナトリウム（ＣＭＣＮａ）及びエチルセルロースから選ばれる１種以上であり、より好ましくはエチルセルロースである。 The component (E) includes at least one selected from guar gum, sodium carboxymethylcellulose (CMCNa), ethylcellulose, polyvinylpyrrolidone, polyacrylamide, starch and dextrin. It is 1 or more types chosen from methylcellulose sodium (CMCNa) and ethylcellulose, More preferably, it is ethylcellulose.
　なお、（Ｅ）成分であるデンプン及びエチルセルロースは、（Ａ）成分としても使用可能である。 In addition, the starch and ethyl cellulose which are (E) components can also be used as (A) component.
　本発明の発煙剤組成物中、（Ｅ）成分の含有割合は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計１００質量部に対して、好ましくは０．０１質量部以上、より好ましくは０．１質量部以上、更に好ましくは０．５質量部以上、より更に好ましくは０．７質量部以上、また、好ましくは５質量部以下、より好ましくは３質量部以下、更に好ましくは２質量部以下、より更に好ましくは１．５質量部以下である。 In the smoke generating composition of the present invention, the content ratio of the component (E) is preferably 0.01 parts by mass or more with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C). More preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.7 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably. Is 2 parts by mass or less, more preferably 1.5 parts by mass or less.
　本発明の発煙剤組成物は、（Ａ）成分以外の可燃剤として、ニトロセルロース、ニトログアニジン、硝酸グアニジン、ジシアンジアミド、メラミン、メラミンシアヌレート、５－アミノテトラゾール、５，５’－ビステトラゾールジアンモニウム塩、シリコーンオイル及びクエン酸三カリウムから選ばれる可燃剤を含有してもよい。但し、これらは本願の効果の一つである人体への害・影響の軽減を考慮すると、含まないことが好ましい。 The smoke generating composition of the present invention includes nitrocellulose, nitroguanidine, guanidine nitrate, dicyandiamide, melamine, melamine cyanurate, 5-aminotetrazole, and 5,5′-bistetrazole diammonium as a combustible other than the component (A). You may contain the combustible chosen from salt, silicone oil, and tripotassium citrate. However, it is preferable not to include these in consideration of the reduction of harm and influence on the human body, which is one of the effects of the present application.
　本発明の発煙剤組成物は、本発明の効果を奏する観点から、下記（ｉ）～（ｖｉ）から選ばれる化合物を含有してもよい。
（ｉ）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
（ｉｉ）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
（ｉｉｉ）炭酸コバルト、炭酸カルシウム等の金属炭酸化物
（ｉｖ）酸性白土、カオリン、タルク、ベントナイト、ケイソウ土、ヒドロタルサイト等の金属酸化物又は水酸化物の複合化合物
（ｖ）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
（ｖｉ）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 The smoke generating composition of the present invention may contain a compound selected from the following (i) to (vi) from the viewpoint of achieving the effects of the present invention.
(I) Metal oxides such as cupric oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide, bismuth oxide, silica, and alumina (ii) aluminum hydroxide, magnesium hydroxide, hydroxide Metal hydroxide such as cobalt and iron hydroxide (iii) Metal carbonate such as cobalt carbonate and calcium carbonate (iv) Metal oxide such as acid clay, kaolin, talc, bentonite, diatomaceous earth, hydrotalcite, or hydroxide (V) Metal acid salts such as sodium silicate, mica molybdate, cobalt molybdate, ammonium molybdate, etc. (vi) Molybdenum disulfide, calcium stearate, silicon nitride, silicon carbide, metaboric acid, boric acid, Boric anhydride, etc.
　本発明の発煙剤組成物は、粉末体又造粒体として使用することができ、また所望形状の成形体にすることができる。造粒体として使用する場合の発煙剤組成物の平均粒径は、発煙による視覚的な遮断効果の観点から、好ましくは５５０μｍ以上、より好ましくは１０００μｍ以上、そして、好ましくは５０００μｍ以下、より好ましくは３０００μｍ以下である。粒径は、レーザー回折・散乱法を用いて測定してよい。 The smoke generating composition of the present invention can be used as a powder or granulated body, and can be formed into a molded body having a desired shape. The average particle diameter of the smoke generating composition when used as a granulated material is preferably 550 μm or more, more preferably 1000 μm or more, and preferably 5000 μm or less, more preferably from the viewpoint of the visual blocking effect due to fuming. 3000 μm or less. The particle size may be measured using a laser diffraction / scattering method.
　成形体は、単孔または多孔を有する円柱状成形体または角柱状成形体、ディスク状成形体、粒状成形体に形成することができる。成形方法としては、公知のエアバッグ装置で使用するガス発生器用のガス発生剤成形体の製造方法を適用することができ、例えば、特開平１０－８７３９０号公報の段落番号００３５～００３７、実施例１に記載の製造方法を適用することができる。 The molded body can be formed into a single-hole or porous cylindrical molded body or prismatic molded body, disk-shaped molded body, or granular molded body. As the molding method, a known method for producing a gas generant molded article for a gas generator used in an airbag apparatus can be applied. For example, paragraphs 0035 to 0037 of JP-A-10-87390, Examples The manufacturing method described in 1 can be applied.
　すなわち本発明は、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分、または（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分を混合する、発煙剤組成物の製造方法を提供する。また一つの実施形態においては、上記のようにバインダーとして（Ｅ）成分を混合してよい。 That is, the present invention provides a smoke generating composition comprising (A) component, (B) component, and (C) component, or (A) component, (B) component, (C) component, and (D) component. A manufacturing method is provided. Moreover, in one embodiment, you may mix (E) component as a binder as mentioned above.
　本発明の発煙剤組成物の製造方法は、本発明の発煙剤組成物について述べた事項を適宜適用することができる。 The method described for the smoke generating composition of the present invention can be appropriately applied to the method for producing the smoke generating composition of the present invention.
　本発明の発煙剤組成物を防犯装置用の発煙器、例えば図１、図２に示される煙幕発生器（発煙器）において使用するときは、発煙剤組成物（粉末状または成形体）を１つの容器に入れた状態で発煙器に収容することができる。例えば図１の発煙器では、そのようにして発煙器に収容された発煙剤組成物を電気式点火器で着火し、燃焼生成物を発生させ、白煙剤との接触によって白煙源を生じさせることができる。なお図２の煙幕発生器と異なり、図１の煙幕発生器はイニシエータを有しない。 When the smoke generator composition of the present invention is used in a smoke generator for a crime prevention device, for example, a smoke screen generator (smoke generator) shown in FIGS. 1 and 2, the smoke generator composition (powder or molded product) is 1 Can be stored in a smoke generator in one container. For example, in the smoke generator of FIG. 1, the smoke composition contained in the smoke generator is ignited by an electric igniter to generate a combustion product, and a white smoke source is generated by contact with the white smoke agent. Can be made. Unlike the smoke screen generator of FIG. 2, the smoke screen generator of FIG. 1 does not have an initiator.
　図２に示される煙幕発生器（発煙器）を以下に説明する。 The smoke screen generator (smoke generator) shown in FIG. 2 will be described below.
＜図２の煙幕発生器＞
　煙幕発生器１Ａは、筒状ハウジング１０内に発煙剤組成物５６および各部品が配置されている。 <Smoke screen generator in FIG. 2>
In the smoke screen generator 1 </ b> A, the smoke generating composition 56 and each component are arranged in the cylindrical housing 10.
　筒状ハウジング１０の第１端開口部１０ａ側の周壁部１１の内周面は第１環状段差面１２を有しており、第１環状段差面１２から第１端開口部１０ａまでは厚さの薄い第１先端周壁部１３になっている。第１先端周壁部１３の内周面１３ａはねじ部を有している。筒状ハウジング１０の第２端開口部１０ｂ側の周壁部１１の内周面は第２環状段差面１４を有しており、第２環状段差面１４から第２端開口部１０ｂまでは厚さの薄い第２先端周壁部１５になっている。第２先端周壁部１５の外周面１５ａはねじ部を有している。 The inner peripheral surface of the peripheral wall portion 11 on the first end opening 10a side of the cylindrical housing 10 has a first annular step surface 12, and the thickness from the first annular step surface 12 to the first end opening 10a is thick. The first tip peripheral wall portion 13 is thin. The inner peripheral surface 13a of the first tip peripheral wall portion 13 has a screw portion. The inner peripheral surface of the peripheral wall portion 11 on the second end opening 10b side of the cylindrical housing 10 has a second annular step surface 14, and the thickness from the second annular step surface 14 to the second end opening 10b is thick. The second end peripheral wall portion 15 is thin. The outer peripheral surface 15a of the second tip peripheral wall portion 15 has a screw portion.
　筒状ハウジング１０の第１端開口部１０ａ側は、第１クロージャ２０で閉塞されている。第１クロージャ２０は略カップ形状のものであり、底面部２１と周壁部２２を有している。底面部２１は中心部に凸部２３を有しており、凸部２３の周囲には、底面部２１を貫通して形成された複数の点火生成物の放出孔２４を有している。複数の点火生成物の放出孔２４は、周方向に均等間隔で２～８個程度形成されている。 The first end opening 10 a side of the cylindrical housing 10 is closed with a first closure 20. The first closure 20 has a substantially cup shape and has a bottom surface portion 21 and a peripheral wall portion 22. The bottom surface portion 21 has a convex portion 23 at the center, and a plurality of ignition product discharge holes 24 formed through the bottom surface portion 21 around the convex portion 23. About 2 to 8 discharge holes 24 for the plurality of ignition products are formed at equal intervals in the circumferential direction.
　また底面部２１においては放出孔２４に必要に応じてシールテープを設け、発煙剤組成物のこぼれ防止や、湿度対策をとることもできる。周壁部２２は、第１先端周壁部１３の内周面１３ａのねじ部に対してねじ込むことができるねじ部２２ａを有している。 In addition, a sealing tape may be provided in the discharge hole 24 at the bottom surface portion 21 as necessary to prevent spillage of the smoke generating composition and to take measures against humidity. The peripheral wall portion 22 has a screw portion 22 a that can be screwed into the screw portion of the inner peripheral surface 13 a of the first tip peripheral wall portion 13.
　第１クロージャ２０の内部空間２５には、点火器カラー６を有する点火器５が取り付けられている。点火器５は、第１クロージャ２０の内周壁面２５ａに対して点火器カラー６がねじ込まれることで取り付けられている。点火器５の着火部５ａは、内部空間２５内に位置している。 An igniter 5 having an igniter collar 6 is attached to the internal space 25 of the first closure 20. The igniter 5 is attached by screwing the igniter collar 6 into the inner peripheral wall surface 25 a of the first closure 20. The ignition part 5 a of the igniter 5 is located in the internal space 25.
　筒状ハウジング１０の第２端１０ｂ側は、第２クロージャ３０で閉塞されている。第２クロージャ３０は、第１部材３１と第２部材４０の組み合わせからなるものであるが、一つの部材からなるものにすることもできる。 The second end 10 b side of the cylindrical housing 10 is closed with a second closure 30. The second closure 30 is a combination of the first member 31 and the second member 40, but may be a single member.
　図２及び図３に示すように、第１部材３１は、外径の大きな環状基板３２、環状基板３２上に形成された、環状基板３２よりも外径の小さな環状凸部３３、環状基板の内周壁部３４ａ、環状基板の外周壁部３４ｂ、環状底面部３５を有している。環状凸部３３の内径は環状基板３２の内径よりも大きい。 As shown in FIGS. 2 and 3, the first member 31 includes an annular substrate 32 having a large outer diameter, an annular convex portion 33 having an outer diameter smaller than the annular substrate 32 formed on the annular substrate 32, and an annular substrate. It has an inner peripheral wall portion 34a, an outer peripheral wall portion 34b of the annular substrate, and an annular bottom surface portion 35. The inner diameter of the annular protrusion 33 is larger than the inner diameter of the annular substrate 32.
　環状凸部３３は、環状基板３２との内径および外径の差から、軸方向に面した、環状基板の内周壁部３４ａ側の、即ち半径方向内側の、環状内側段差面３６ａと、軸方向に面した、環状基板の外周壁部３４ｂ側の、即ち半径方向外側の、環状外側段差面３６ｂを有している。 The annular protrusion 33 is formed in the axial direction from the difference between the inner and outer diameters of the annular substrate 32 and the annular inner step surface 36a facing the axial direction on the inner peripheral wall 34a side of the annular substrate, that is, radially inward. Facing the outer peripheral wall 34b side of the annular substrate, that is, radially outside, has an annular outer stepped surface 36b.
　環状凸部３３は、環状基板３２との内径および外径の差から、半径方向（軸方向に直交する方向）内側に面した環状内側周壁面３７ａと、半径方向外側に面した環状外側周壁面３７ｂを有している。 Due to the difference between the inner diameter and outer diameter of the annular substrate 32, the annular convex portion 33 has an annular inner peripheral wall surface 37a facing inward in the radial direction (a direction orthogonal to the axial direction) and an annular outer peripheral wall surface facing outward in the radial direction. 37b.
　第１部材３１の中心部であり、環状内側段差面３６ａの内側には、環状基板の内周壁部３４ａによって画定された煙幕源排出口３８が形成されている。第１部材３１は、環状外側周壁面３７ｂが筒状ハウジング１０の内周面１０ｃに当接され、環状外側段差面３６ｂが第２環状段差面１４に当接され、環状基板の外周壁部３４ｂが第２先端周壁部１５に当接された状態で、筒状ハウジング１０の第２端開口部１０ｂに嵌め込まれている。 A smoke screen source discharge port 38 defined by the inner peripheral wall portion 34a of the annular substrate is formed at the center of the first member 31 and inside the annular inner stepped surface 36a. The first member 31 has an annular outer peripheral wall surface 37b in contact with the inner peripheral surface 10c of the cylindrical housing 10, an annular outer step surface 36b in contact with the second annular step surface 14, and an outer peripheral wall portion 34b of the annular substrate. Is fitted into the second end opening 10b of the cylindrical housing 10 in a state of being in contact with the second tip peripheral wall 15.
　第２部材４０は、略カップ形状のものであり、周壁部４１と中心部に貫通孔４３が形成された底面部４２を有しており、周壁部４１は内周面にねじ部４４を有している。貫通孔４３の内径は、煙幕源排出口３８の内径よりも大きく、環状底面部３５の外径よりも小さくなっている。 The second member 40 has a substantially cup shape, and has a peripheral wall portion 41 and a bottom surface portion 42 in which a through hole 43 is formed in the central portion. The peripheral wall portion 41 has a screw portion 44 on the inner peripheral surface. is doing. The inner diameter of the through hole 43 is larger than the inner diameter of the smoke screen source discharge port 38 and smaller than the outer diameter of the annular bottom surface portion 35.
　第２部材４０は、ねじ部４４が第２先端周壁部１５の外周面１５ａに対してねじ込まれることで固定されている。第２部材４０の底面部４２は、第１部材３１の環状底面部３５を軸方向（第１端開口部１０ａに向かう方向）に押さえつけているため、第１部材３１は、第２部材４０と第２環状段差面１４の間において挟み付けられることで固定されている。 The second member 40 is fixed by screwing the screw portion 44 into the outer peripheral surface 15a of the second tip peripheral wall portion 15. Since the bottom surface portion 42 of the second member 40 presses the annular bottom surface portion 35 of the first member 31 in the axial direction (the direction toward the first end opening 10a), the first member 31 is connected to the second member 40. It is fixed by being sandwiched between the second annular stepped surfaces 14.
　筒状ハウジング１０内には、網が筒状に成形された多孔筒状体５０が配置されている。多孔筒状体５０は、第１開口部５０ａ側が第１クロージャ２０の凸部２３に外側から嵌め込まれ、第２開口部５０ｂ側が第２クロージャの第１部材３１の環状内側段差面３６ａと環状内側周壁面３７ａに当接されている。多孔筒状体５０は、軸方向の両側から固定されているため、作動前および作動時においても動くことがない。 In the cylindrical housing 10, a porous cylindrical body 50 in which a net is formed into a cylindrical shape is disposed. The porous cylindrical body 50 has the first opening 50a side fitted into the convex portion 23 of the first closure 20 from the outside, and the second opening 50b side is connected to the annular inner step surface 36a and the annular inner step surface of the first member 31 of the second closure. It is in contact with the peripheral wall surface 37a. Since the porous cylindrical body 50 is fixed from both sides in the axial direction, it does not move before and during operation.
　筒状ハウジング１０の内周面１０ｃと多孔筒状体５０の間の筒状空間が、発煙剤組成物５６が収容された発煙剤組成物収容室５５である。発煙剤組成物５６は、円柱、ディスク形状、粉状、顆粒のような所望形状の剤型にすることができる。 The cylindrical space between the inner peripheral surface 10 c of the cylindrical housing 10 and the porous cylindrical body 50 is a smoke generating agent composition storage chamber 55 in which the smoke generating composition 56 is stored. The smoke generating composition 56 can be made into a dosage form having a desired shape such as a cylinder, a disk, a powder, or a granule.
　発煙剤組成物収容室５５の第１端開口部１０ａ側には、第１クロージャ２０の底面部２１に形成された複数の点火生成物の放出孔２４が面しており、第２端開口部１０ｂ側は第２クロージャ３０の第１部材３１に面している。 A plurality of ignition product discharge holes 24 formed in the bottom surface portion 21 of the first closure 20 face the first end opening portion 10a side of the smoke generating composition containing chamber 55, and the second end opening portion. The 10b side faces the first member 31 of the second closure 30.
　点火器５、多孔筒状体５０、煙幕源排出口３８および第２部材４０の貫通孔４３は、それらの中心軸と筒状ハウジング１０の軸が同軸になるように配置されている。 The igniter 5, the porous cylindrical body 50, the smoke screen source discharge port 38, and the through hole 43 of the second member 40 are arranged so that the central axis thereof and the axis of the cylindrical housing 10 are coaxial.
　図４に示すように、第１環状仕切り板６０が、第１内筒部材７０の第２開口部７０ｂと第２内筒部材７１の第１開口部７１ａとの間に挟み付けられた状態で配置されている。第１環状仕切り板６０は、多孔筒状体５０を通すための貫通孔６１ａと作動時に煙幕源を通すための第１煙幕源通過孔６１ｂを有している。 As shown in FIG. 4, the first annular partition plate 60 is sandwiched between the second opening 70 b of the first inner cylinder member 70 and the first opening 71 a of the second inner cylinder member 71. Has been placed. The first annular partition plate 60 has a through hole 61a for passing the porous cylindrical body 50 and a first smoke screen source passage hole 61b for passing the smoke screen source during operation.
　第２環状仕切り板６２が、第２内筒部材７１の第２開口部７１ｂと第３内筒部材７２の第１開口部７２ａとの間に挟み付けられた状態で配置されている。第２環状仕切り板６２は、多孔筒状体５０を通すための貫通孔６２ａと作動時に煙幕源を通すための第２煙幕源通過孔６２ｂを有している。 The second annular partition plate 62 is disposed in a state of being sandwiched between the second opening 71 b of the second inner cylinder member 71 and the first opening 72 a of the third inner cylinder member 72. The second annular partition plate 62 has a through hole 62a through which the porous cylindrical body 50 passes and a second smoke screen source passage hole 62b through which the smoke screen source passes during operation.
　第１煙幕源通過孔６１ｂと第２煙幕源通過孔６２ｂの大きさは、発煙剤組成物５６よりも小さくてもよいし、大きくてもよい。第１煙幕源通過孔６１ｂと第２煙幕源通過孔６２ｂの数は特に制限されないが、第１環状仕切り板６０と第２環状仕切り板６２のそれぞれに均等間隔をおいて４～２０個程度を分散して形成することができる。 The size of the first smoke screen source passage hole 61b and the second smoke screen source passage hole 62b may be smaller or larger than the smoke generating agent composition 56. The number of the first smoke screen source passage holes 61b and the second smoke screen source passage holes 62b is not particularly limited, but about 4 to 20 with the same interval between the first annular partition plate 60 and the second annular partition plate 62. It can be formed in a dispersed manner.
　発煙剤組成物収容室５５は、第１環状仕切り板６０と第２環状仕切り板６２により、第１クロージャ２０側から第２クロージャ３０に向かって順に第１室５５ａ、第２室５５ｂ、第３室５５ｃに分割されている。第１内筒部材７０、第２内筒部材７１および第３内筒部材７２の外径は、筒状ハウジング１０内に挿入でき、かつ内周面１０ｃに当接できる大きさに調整されている。 The smoke generating agent composition storage chamber 55 includes a first chamber 55a, a second chamber 55b, and a third chamber in order from the first closure 20 side to the second closure 30 by the first annular partition plate 60 and the second annular partition plate 62. The chamber 55c is divided. The outer diameters of the first inner cylinder member 70, the second inner cylinder member 71, and the third inner cylinder member 72 are adjusted to such a size that they can be inserted into the cylindrical housing 10 and can contact the inner peripheral surface 10c. .
　図３では、筒状ハウジング１０の周壁部１１の厚さを調整することで第２クロージャ３０側に環状段差面１１ａを設け、第３内筒部材７２の第２開口部７２ｂ側が環状段差面１１ａに当接され、第１内筒部材７０の第１開口部７０ａ側が第１クロージャ２０に当接されることで、発煙剤組成物収容室５５は軸方向に固定されている。 In FIG. 3, the annular step surface 11a is provided on the second closure 30 side by adjusting the thickness of the peripheral wall portion 11 of the cylindrical housing 10, and the second opening portion 72b side of the third inner cylinder member 72 is the annular step surface 11a. The smoke generating agent composition storage chamber 55 is fixed in the axial direction by contacting the first opening 70 a side of the first inner cylinder member 70 with the first closure 20.
　本発明の発煙剤組成物を防犯装置（発煙器）に使用したときの作動状態を説明する。防犯装置は、センサー、電気式点火器を備え、発煙剤組成物が収容されたものであり、室内の天井や壁に取り付けられて使用される。発煙剤組成物は、例えば防犯装置に設けられた一つの収容室内にまとめて収容されていてもよい。 The operating state when the smoke generating composition of the present invention is used in a crime prevention device (smoke generator) will be described. The security device includes a sensor and an electric igniter, and contains a smoke generating composition, and is used by being attached to an indoor ceiling or wall. For example, the smoke generating composition may be accommodated together in one accommodation room provided in the security device.
　室内に不法侵入者が入ったとき、センサーが感知することで電気式点火器を作動させて燃焼生成物（火炎や高温ガスなどが混在したもの）を発生させる。その後、燃焼生成物と（Ｂ）成分の白煙剤が接触することによって白煙源が生じる。 When a trespasser enters the room, the sensor detects it and activates the electric igniter to generate combustion products (mixed with flames and high-temperature gas). Thereafter, a white smoke source is generated by the contact between the combustion product and the white smoke agent of component (B).
　（Ｂ）成分の白煙剤は、電気式点火器の燃焼生成物（熱）によってガス（白煙源）に変化した状態で防犯装置から噴出され、噴出後に空気中で冷却されることで白煙（液滴）に変化する。 The white smoke agent of component (B) is ejected from the crime prevention device in a state of being changed into gas (white smoke source) by the combustion product (heat) of the electric igniter, and is cooled in the air after being ejected. Changes to smoke (droplets).
　白煙剤と燃焼生成物の接触と並行して、（Ａ）成分及び（Ｃ）成分も燃焼生成物と接触して着火燃焼される。（Ａ）成分である燃料（可燃剤）は、酸化剤の作用により燃焼して、窒素ガス、二酸化炭素ガスなどを含む高温ガスを瞬時に発生させる。 In parallel with the contact between the white smoke agent and the combustion product, the component (A) and the component (C) are also ignited and combusted in contact with the combustion product. The fuel (combustible agent) as the component (A) is burned by the action of an oxidant, and instantly generates a high-temperature gas including nitrogen gas, carbon dioxide gas, and the like.
　（Ｃ）成分である酸化剤は、（Ａ）成分である燃料（可燃剤）を燃焼させると共に、酸化剤自体は、塩化ナトリウム、塩化カリウム、塩化マグネシウム、酸化カリウム、炭酸カリウムなどの白煙源に変化して、微細な粉末のまま白煙となる。なおガス発生剤が燃焼するときの熱を使って（Ｂ）成分の分解を促進することもできる。 The (C) component oxidizing agent burns the (A) component fuel (combustible), and the oxidizing agent itself is a source of white smoke such as sodium chloride, potassium chloride, magnesium chloride, potassium oxide, potassium carbonate, etc. Changes to white smoke as a fine powder. In addition, decomposition | disassembly of (B) component can also be accelerated | stimulated using the heat | fever when a gas generating agent burns.
　本発明の発煙剤組成物を使用することで、（Ｂ）成分から生じた白煙が、（Ａ）成分から発生したガスの作用により勢いよく噴出されることから、白煙が濃くなり、室内に均一にかつ迅速に広範囲に拡散される。そして、このように防犯装置から室内に白煙が噴出され拡散されることで、侵入者に対して威嚇が行われ、侵入者の視界が妨げられ、行動が抑止または遅延されることから、犯罪行為が抑止乃至は防止、牽制される。
実施例 By using the smoke generating composition of the present invention, the white smoke generated from the component (B) is ejected vigorously by the action of the gas generated from the component (A). Uniformly and rapidly. And since white smoke is jetted and diffused from the security device into the room in this way, threats are made against the intruder, the visibility of the intruder is hindered, and the action is deterred or delayed. Action is deterred, prevented, or restrained.
Example
（Ａ）成分
　スクロース：大日本明治製糖株式会社製、粒径５００～６００μｍ
（Ｂ）成分
　パラフィンワックス：日本精蝋株式会社製、平均粒径１２０μｍ
（Ｃ）成分
　硝酸カリウム：大塚化学株式会社製、平均粒径６０μｍ Component (A) Sucrose: Dainippon Meiji Sugar Co., Ltd., particle size 500-600 μm
(B) Component Paraffin wax: Nippon Seiwa Co., Ltd., average particle size 120 μm
(C) Component Potassium nitrate: manufactured by Otsuka Chemical Co., Ltd., average particle size 60 μm
　＜透過率測定器＞
　（投光側の機器）
　機器名：可視光レーザー４０５ｎｍ，６３５ｎｍ，７８５ｎｍ（（株）キコー技研）
　型番（４０５ｎｍ）：ＭＬＸＡ－Ｄ１２－４０５－２０（ＣＮ４）
　型番（６３５ｎｍ）：ＭＬＸＡ－Ｄ１２－６３５－５（ＣＮ４）
　型番（７８５ｎｍ）：ＭＬＸＡ－Ｄ１２－７８５－７０（ＣＮ４）
　（受光側の機器）
　機器名：光センサ（日置電機（株））
　型番：９７４２－１０　
　（増幅器）
　機器名：光パワーメータ（日置電機（株））
　型番：３６６４
　（計測器）
　機器名：データ収集システム（（株）キーエンス）
　型番：ＮＲ－２０００ <Transmittance measuring instrument>
(Emission side equipment)
Device name: Visible light laser 405 nm, 635 nm, 785 nm (Kiko Engineering Co., Ltd.)
Model number (405 nm): MLXA-D12-405-20 (CN4)
Model number (635nm): MLXA-D12-635-5 (CN4)
Model number (785nm): MLXA-D12-785-70 (CN4)
(Receiving device)
Device name: Optical sensor (Hioki Electric Co., Ltd.)
Model number: 9742-10
(amplifier)
Device name: Optical power meter (Hioki Electric Co., Ltd.)
Model: 3664
(Measuring instrument)
Device name: Data collection system (Keyence Corporation)
Model number: NR-2000
実施例１～９、比較例１～５
　表１に示す各成分からなる発煙剤組成物成形体を公知のガス発生剤成形体の製造方法と同様にして製造した。なお、実施例１～６、比較例１～５の発煙剤組成物は粉末状体のものをそのまま成形体にし、実施例７～９の発煙剤組成物は平均粒径２０００μｍに造粒したものを成形体にした。発煙剤組成物は、外径１０ｍｍ、長さ１０ｍｍ、質量０．２ｇの円柱状成形体として使用した。 Examples 1-9, Comparative Examples 1-5
A smoke generator composition molded body comprising each component shown in Table 1 was produced in the same manner as a known method for producing a gas generant molded body. The smoke agent compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were formed into powders as they were, and the smoke agent compositions of Examples 7 to 9 were granulated to have an average particle size of 2000 μm. Was formed into a molded body. The smoke generator composition was used as a cylindrical molded body having an outer diameter of 10 mm, a length of 10 mm, and a mass of 0.2 g.
　得られた発煙剤組成物成形体を使用して、発煙状態を確認する試験をした。図１に示す第１の煙幕発生器に発煙剤組成物成形体７０ｇを充填したもの（煙幕発生器１）と、図２に示す第２の煙幕発生器に発煙剤組成物成形体１４０ｇを充填したもの（煙幕発生器２）を使用した。煙幕発生器１と煙幕発生器２の違いは、イニシエータの有無のみである（煙幕発生器２はイニシエータ有り）。 Using the obtained smoke generator composition molded body, a test for confirming the smoke generation state was conducted. The first smoke screen generator shown in FIG. 1 is filled with 70 g of the smoke composition composition (smoke generator 1), and the second smoke screen generator shown in FIG. 2 is filled with 140 g of the smoke composition composition. (Smoke generator 2) was used. The difference between the smoke screen generator 1 and the smoke screen generator 2 is only the presence or absence of an initiator (the smoke screen generator 2 has an initiator).
　３０ｍ３（縦６ｍ、横２．５ｍ、高さ２ｍ）の透明なガラス容器の床面の中心に煙幕発生装置を置いた。容器内は室温（２０℃）に維持した。容器の長辺と短辺の角部の長辺側の壁面に沿って透過率測定器の受光側の機器をセットし、受光側の機器から長辺方向に５０ｃｍ離れた位置に投光側の機器をセットした。 A smoke screen generator was placed at the center of the floor of a transparent glass container of 30 m 3 (length 6 m, width 2.5 m, height 2 m). The inside of the container was maintained at room temperature (20 ° C.). Set the device on the light receiving side of the transmittance measuring device along the long side wall of the corners of the long side and short side of the container, and place it on the light emitting side at a position 50 cm away from the light receiving side device in the long side direction. The device was set.
　点火装置を作動させてから１００秒後に、投光側の機器から４０５ｎｍ、６３５ｎｍ、７８５ｎｍの各波長の光を照射して、受光側の光センサで検出し、増幅器を介して計測器につなぎ透過率を測定した。結果を表１に示す。透過率が小さいほど煙幕濃度が高く、白煙による視覚的な遮断効果に優れることを意味する。 100 seconds after igniting the ignition device, irradiate light of each wavelength of 405 nm, 635 nm, and 785 nm from the device on the light-emitting side, detect it with the light sensor on the light-receiving side, and transmit it through the amplifier to the measuring instrument. The rate was measured. The results are shown in Table 1. The smaller the transmittance, the higher the smoke screen density, and the better the visual blocking effect of white smoke.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１中、「不燃」とは、煙幕発生器の点火装置を作動させても、発煙剤組成物が燃焼せず、白煙が発生しなかったことを意味する。 In Table 1, “non-combustible” means that the smoke generating agent composition did not burn and white smoke was not generated even when the ignition device of the smoke screen generator was operated.
実施例１０～１２、比較例６～８
＜発煙剤組成物の製造＞
　表２に示す各成分からなる発煙剤組成物成形体を公知のガス発生剤成形体の製造方法と同様にして製造した。即ち、実施例１０～１２の発煙剤組成物成形体は以下の方法により製造した。 Examples 10-12, Comparative Examples 6-8
<Manufacture of smoke generator composition>
A smoke generator composition molded body comprising the respective components shown in Table 2 was produced in the same manner as a known method for producing a gas generant molded body. That is, the smoke former composition molded bodies of Examples 10 to 12 were produced by the following method.
（実施例１０～１２）
　（Ｄ）成分であるイソプロピルアルコールに（Ｅ）成分であるエチルセルロースを２質量％溶解させた溶液（日新化成株式会社製、ＥＣ－ビヒクル）に（Ａ）成分、及び（Ｂ）成分を投入し、目視で均一に混合されていると確認できるまで、導電性スパチュラで撹拌した。その後、（Ｃ）成分を投入し、イソプロピルアルコールの含有量が全質量の１０質量％以下に揮発するまで、質量を確認しながら撹拌した。イソプロピルアルコールの含有量が全重量の１０質量％以下に到達後、発煙剤組成物成形体を乾燥機に入れて、乾燥温度４０℃で５時間以上乾燥を行った。発煙剤組成物は、外径１ｍｍ、長さ２ｍｍ、質量０．０５ｇとなるように造粒したものを使用した。 (Examples 10 to 12)
The components (A) and (B) are added to a solution (EC-vehicle, manufactured by Nisshin Kasei Co., Ltd.) in which 2% by mass of ethyl cellulose as the component (E) is dissolved in isopropyl alcohol as the component (D). The mixture was stirred with a conductive spatula until it could be visually confirmed that the mixture was uniformly mixed. Thereafter, the component (C) was added and stirred while confirming the mass until the isopropyl alcohol content volatilized to 10% by mass or less of the total mass. After the content of isopropyl alcohol reached 10% by mass or less of the total weight, the smoke generator composition molded body was put into a dryer and dried at a drying temperature of 40 ° C. for 5 hours or more. The smoke generator composition used was granulated to have an outer diameter of 1 mm, a length of 2 mm, and a mass of 0.05 g.
　また比較例６～８の発煙剤組成物成形体は以下の方法により製造した。
（比較例６）
　水に（Ｅ）成分であるカルボキシルメチルセルロースを２質量％溶解させた溶液に（Ａ）成分、及び（Ｂ）成分を投入し、目視で均一に混合されていると確認できるまで、導電性スパチュラで撹拌した。その後、（Ｃ）成分を投入し、粒状に成形後、乾燥機に入れて、乾燥温度２０℃で２０時間以上乾燥を行った。得られた発煙剤組成物は、外径２ｍｍ、長さ５ｍｍ、質量０．５ｇとなるように造粒したものを使用した。 Further, the smoke former composition molded bodies of Comparative Examples 6 to 8 were produced by the following method.
(Comparative Example 6)
Add the (A) component and the (B) component to a solution in which 2% by mass of the carboxymethyl cellulose, which is the (E) component, is dissolved in water. Stir. Thereafter, the component (C) was added, formed into granules, put into a dryer, and dried at a drying temperature of 20 ° C. for 20 hours or more. The smoke generator composition obtained was granulated to have an outer diameter of 2 mm, a length of 5 mm, and a mass of 0.5 g.
（比較例７）
　（Ａ）成分、（Ｂ）成分、（Ｃ）成分を、目視で均一に混合されていると確認できるまで、導電性スパチュラで撹拌混合した。混合した発煙剤組成物を成形金型に秤量して、油圧プレス機により粉体混合品を圧縮して粉体圧縮品の成形を行った。得られた発煙剤組成物は、外径１０ｍｍ、長さ０．９ｍｍ、質量０．９ｇとなるように円柱状に成形したものを使用した。 (Comparative Example 7)
The component (A), the component (B), and the component (C) were stirred and mixed with a conductive spatula until it was confirmed that they were visually mixed uniformly. The mixed smoke generating composition was weighed into a molding die, and the powder mixed product was compressed by a hydraulic press machine to form a powder compressed product. The smoke generator composition obtained was formed into a cylindrical shape having an outer diameter of 10 mm, a length of 0.9 mm, and a mass of 0.9 g.
（比較例８）
　（Ａ）成分、（Ｂ）成分、（Ｃ）成分を、目視で均一に混合されていると確認できるまで、導電性スパチュラで撹拌混合した。混合した発煙剤組成物は、そのまま粉体として使用した。 (Comparative Example 8)
The component (A), the component (B), and the component (C) were stirred and mixed with a conductive spatula until it was confirmed that they were visually mixed uniformly. The mixed smoke generating composition was directly used as a powder.
＜（Ｄ）成分の定量試験＞
　発煙剤組成物中の（Ｄ）成分であるイソプロピルアルコールの含有量は、以下の方法により定量した。実施例１０の発煙剤組成物９２７．２ｍｇをメタノール２０ｍＬ（７８２７．５ｍｇ）に２日浸漬し、発煙剤組成物に含まれているイソプロピルアルコールを抽出した。抽出液をガスクロマトグラム質量分析器（ＧＣ／ＭＳ（ＳＩＭ））（島津製作所社製、ガスクロマトグラム質量分析器）を用いて、検量線によりイソプロピルアルコールの含有量を定量したところ、得られたピーク強度は定量限界（信頼性の限界値）である６４ｐｐｍ未満であったが、定量結果は理論値として３２ｐｐｍであった。また実施例１１、１２の（Ｄ）成分の含有量は、（Ｄ）成分と（Ｅ）成分の添加に用いたイソプロピルアルコールにエチルセルロースを２質量％溶解させた溶液の添加量から実施例１の当該添加量を基準に換算して求めた値である。 <Quantitative test of component (D)>
The content of isopropyl alcohol as the component (D) in the smoke generating composition was quantified by the following method. The smoke agent composition of Example 10 (927.2 mg) was immersed in methanol (20 mL, 7827.5 mg) for 2 days to extract isopropyl alcohol contained in the smoke agent composition. When the content of isopropyl alcohol was quantified with a calibration curve using a gas chromatogram mass spectrometer (GC / MS (SIM)) (manufactured by Shimadzu Corporation, gas chromatogram mass spectrometer), the obtained peak intensity was obtained. Was less than 64 ppm which is the limit of quantification (reliability limit value), but the quantification result was 32 ppm as a theoretical value. In addition, the content of the component (D) in Examples 11 and 12 was determined based on the amount of the solution obtained by dissolving 2% by mass of ethyl cellulose in isopropyl alcohol used for the addition of the component (D) and the component (E). This is a value obtained by converting the amount added.
　得られた発煙剤組成物成形体を使用して、発煙状態を確認する試験をした。図２に示す煙幕発生器に各発煙剤組成物８０ｇを充填したものを使用した。　３０ｍ３（縦６ｍ、横２．５ｍ、高さ２ｍ）のコンテナの床面の中心に煙幕発生装置を置いた。容器内は室温（２０℃）に維持した。 Using the obtained smoke generator composition molded body, a test for confirming the smoke generation state was conducted. The smoke screen generator shown in FIG. 2 filled with 80 g of each smoke generating composition was used. A smoke screen generator was placed at the center of the floor of a 30 m 3 (6 m long, 2.5 m wide, 2 m high) container. The inside of the container was maintained at room temperature (20 ° C.).
　容器の長辺と短辺の角部の長辺側の壁面に沿って透過率測定器の受光側の機器をセットし、受光側の機器から長辺方向に５０ｃｍ離れた位置に投光側の機器をセットした。点火装置を作動させてから１００秒後に、投光側の機器から４０５ｎｍ、６３５ｎｍ、７８５ｎｍの各波長の光を照射して、受光側の光センサで検出し、増幅器を介して計測器につなぎ透過率を測定した。結果を表１に示す。透過率が小さいほど煙幕濃度が高く、白煙による視覚的な遮断効果に優れることを意味する。 Set the device on the light receiving side of the transmittance measuring device along the long side wall of the corners of the long side and short side of the container, and place it on the light emitting side at a position 50 cm away from the light receiving side device in the long side direction. The device was set. 100 seconds after igniting the ignition device, irradiate light of each wavelength of 405 nm, 635 nm, and 785 nm from the device on the light-emitting side, detect it with the light sensor on the light-receiving side, and transmit it through the amplifier to the measuring instrument The rate was measured. The results are shown in Table 1. The smaller the transmittance, the higher the smoke screen density, and the better the visual blocking effect of white smoke.
Figure JPOXMLDOC01-appb-T000002
 符号の説明
Figure JPOXMLDOC01-appb-T000002
 Explanation of symbols
　１Ａ　　煙幕発生器
　５　　　点火器
　１０　　筒状ハウジング
　１０ａ　第１端開口部
　１０ｂ　第２端開口部
　２０　　第１クロージャ
　３０　　第２クロージャ
　５０　　多孔筒状体
　５５　　発煙剤組成物収容室
　５６　　発煙剤組成物 DESCRIPTION OF SYMBOLS 1A Smoke generator 5 Igniter 10 Cylindrical housing 10a 1st end opening part 10b 2nd end opening part 20 1st closure 30 2nd closure 50 Porous cylindrical body 55 Fuming agent composition storage chamber 56 Fuming agent composition

Claims (18)

  1. 　（Ａ）燃料、（Ｂ）白煙剤、（Ｃ）酸化剤を含有する発煙剤組成物であって、
    　発煙剤組成物中の（Ａ）成分と（Ｂ）成分の含有割合の比（Ａ）／（Ｂ）が、１超である、発煙剤組成物。     A smoke generating composition containing (A) a fuel, (B) a white smoke agent, and (C) an oxidizing agent,
    The smoke generating composition, wherein the ratio (A) / (B) of the content ratio of the component (A) and the component (B) in the smoke generating composition is more than 1.
  2. 　（Ａ）成分と（Ｂ）成分の含有割合の比（Ａ）／（Ｂ）が、１．２以上１０以下である、請求項１に記載の発煙剤組成物。 The ratio (A) / (B) of the content ratio of the (A) component and the (B) component is 1.2 or more and 10 or less, The smoke generating composition according to claim 1.
  3. 　（Ａ）成分と（Ｂ）成分の含有割合の比（Ａ）／（Ｂ）が、２以上１０以下である、請求項２に記載の発煙剤組成物。 The ratio (A) / (B) of the content ratio of the (A) component and the (B) component is 2 or more and 10 or less, The smoke generating composition of Claim 2.
  4. 　（Ａ）燃料、（Ｂ）白煙剤、（Ｃ）酸化剤、及び（Ｄ）イソアルキルアルコールを含有する、発煙剤組成物。 A smoke generating composition containing (A) fuel, (B) white smoke agent, (C) oxidizing agent, and (D) isoalkyl alcohol.
  5. 　（Ａ）成分が糖類である、請求項１～４の何れか１項に記載の発煙剤組成物。 The smoke generating composition according to any one of claims 1 to 4, wherein the component (A) is a saccharide.
  6. 　（Ａ）成分が二糖類である、請求項５に記載の発煙剤組成物。 The smoke generating composition according to claim 5, wherein the component (A) is a disaccharide.
  7. 　（Ａ）成分がスクロースである、請求項６に記載の発煙剤組成物。 The smoke generating composition according to claim 6, wherein the component (A) is sucrose.
  8. 　（Ｂ）成分がパラフィン化合物を含むワックス類及びポリアルキレングリコールから選ばれる１種以上である、請求項１～７の何れか１項に記載の発煙剤組成物。 The smoke generating composition according to any one of claims 1 to 7, wherein the component (B) is at least one selected from waxes containing a paraffin compound and polyalkylene glycol.
  9. 　（Ｂ）成分がパラフィン化合物を含むワックス類である、請求項８に記載の発煙剤組成物。 The smoke generating composition according to claim 8, wherein the component (B) is a wax containing a paraffin compound.
  10. 　（Ｂ）成分が、パラフィンワックス及びマイクロクリスタリンワックスから選ばれる１種以上である、請求項９に記載の発煙剤組成物。 The smoke generating composition according to claim 9, wherein the component (B) is at least one selected from paraffin wax and microcrystalline wax.
  11. 　（Ｂ）成分が、ノルマルパラフィン、イソパラフィン及びシクロパラフィンから選ばれる１種以上である、請求項１０に記載の発煙剤組成物。 The smoke generating composition according to claim 10, wherein the component (B) is at least one selected from normal paraffin, isoparaffin, and cycloparaffin.
  12. 　（Ｂ）成分がノルマルパラフィンである、請求項１１に記載の発煙剤組成物。 The smoke generating composition according to claim 11, wherein the component (B) is normal paraffin.
  13. 　（Ｄ）成分がイソプロパノール、イソブタノール、イソペンタノール及びイソヘキサノールから選ばれる１種以上である、請求項１～１２の何れか１項に記載の発煙剤組成物。 The smoke generating composition according to any one of claims 1 to 12, wherein the component (D) is at least one selected from isopropanol, isobutanol, isopentanol and isohexanol.
  14. 　（Ｄ）成分がイソプロパノールである、請求項１３に記載の発煙剤組成物。 The smoke generating composition according to claim 13, wherein the component (D) is isopropanol.
  15. 　（Ｄ）成分の含有割合が、（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計１００質量部に対して、１００ｐｐｍ以下である、請求項１～３に従属しない請求項４～１４の何れか１項に記載の発煙剤組成物。 The content ratio of the component (D) is 100 ppm or less with respect to 100 parts by mass in total of the components (A), (B), and (C). The smoke generator composition according to any one of the above.
  16. 　（Ｄ）成分の含有割合が、（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計１００質量部に対して、１ｐｐｍ以上１００ｐｐｍ以下である、請求項１５に記載の発煙剤組成物。 The smoke generator composition according to claim 15, wherein the content ratio of the component (D) is 1 ppm or more and 100 ppm or less with respect to 100 parts by mass in total of the components (A), (B), and (C).
  17. 　（Ｄ）成分の含有割合が、（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計１００質量部に対して、５０ｐｐｍ以下である、請求項１５に記載の発煙剤組成物。 The smoke generator composition according to claim 15, wherein the content ratio of the component (D) is 50 ppm or less with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C).
  18. 　請求項１～１７の何れか１項に記載の発煙剤組成物を用いた発煙器。 A smoke generator using the smoke generating composition according to any one of claims 1 to 17.
PCT/JP2017/032650 2016-10-07 2017-09-11 Smoke generating composition and smoke generator WO2018066312A1 (en)

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