JP2017019677A - Smoking agent composition and smoking device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a smoking agent composition which can be used for a smoking screen generator for crime prevention.SOLUTION: There is provided a smoking agent composition containing (A) a fuel, (B) an oxidant and (C) a smoking source component selected from metal oxide and metal salt having refractive index of 1.8 or more, where burning temperature when burning the fuel of the (A) component and the oxidant of the (B) component is the melting point of the smoking source component of the (C) component or higher.SELECTED DRAWING: None

Description

  The present invention relates to a smoke generating composition and a smoke generating apparatus using the same.

  Smoke generators on the ceiling and walls of the room, etc., for the purpose of ensuring the time to capture people who have illegally entered stores and houses by visually blocking the escape route and causing mental confusion. May be attached.

Patent Document 1 describes a white smoke rod-shaped body in which an oxidizer, white powder, and a combustion aid are bound and formed into a rod shape by 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.
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.

Patent Literature 2 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.

In Patent Document 3, (A) a smoke generating agent for generating a white smoke source, and (B) (B-1) a fuel and (B-2) an oxidant containing gas and a white smoke source are generated. A smoke generating composition containing a gas generating agent, wherein the white smoke source generated from the component (A) and the component (B) is scattered by the gas generated from the component (B). Things are disclosed.
(A) Examples of smoke generating agents for generating a white smoke source include waxes and metal hydroxides. When waxes are used, the generated smoke has a sticky feeling. The crime prevention effect is high in terms of giving a sense of disgust, but there is room for improvement in that it takes time to clean later, and when a metal hydroxide is used, a coolant against the combustion of component (B) Therefore, there is room for improvement in that the combustion temperature is lowered and the jet pressure of white smoke may be affected.

JP 2003-306395 A Japanese Patent No. 3816867 JP2015-42603A

  This invention makes it a subject to provide the smoke generating composition which can produce | generate a quick white smoke quickly, and a smoke generator using the same.

The present invention is a smoke agent composition comprising (A) a fuel, (B) an oxidizer, and (C) a smoke source component selected from a metal oxide and a metal salt having a refractive index of 1.8 or more,
The fuel of the component (A) and the oxidant of the component (B) are combusted when the fuel of the component (A) and the oxidant of the component (B) are combusted. A smoke generating composition that is a combination that exceeds the melting point of the components, and a smoke generating device using the same are provided.

The smoke generating composition of the present invention can realize a high visual field shielding effect by generating dark white smoke in a short time.
Moreover, since the smoke generator composition of the present invention contains a smoke source component selected from a metal oxide and a metal salt having a refractive index of 1.8 or more as the component (C), the light scattering effect of the component (C) In an environment with light, the visual field blocking effect is further enhanced.

<(A) Fuel>
Examples of the fuel used in the present invention include hydrocarbon polymers such as HTPB (terminal hydroxyl group polybutadiene) and CTPB (carboxyl group terminal polybutadiene) in addition to nitrogen-containing organic compounds, and nitrogen-containing organic compounds are preferred.

As the nitrogen-containing organic compound, known ones can be used as the fuel for the gas generant composition, and examples thereof include at least one selected from tetrazole compounds, guanidine compounds, triazine compounds, and nitroamine compounds.
The tetrazole compounds are preferably 5-aminotetrazole, bitetrazole ammonium salt and the like.
The guanidine compound is preferably guanidine nitrate (guanidine nitrate), aminoguanidine nitrate, nitroguanidine, triaminoguanidine nitrate or the like.
The triazine compound is preferably melamine, cyanuric acid, ammelin, ammelide, ammeland and the like.
The nitroamine compound is preferably cyclo-1,3,5-trimethylene-2,4,6-trinitramine.

<(B) Oxidizing agent>
As the oxidizing agent used in the present invention, a known oxidizing agent for the gas generant composition can be used, and examples thereof include at least one selected from basic metal nitrates, nitrates, perchlorates and chlorates. .
The basic metal nitrate is at least selected from basic copper nitrate, basic cobalt nitrate, basic zinc nitrate, basic manganese nitrate, basic iron nitrate, basic molybdenum nitrate, basic bismuth nitrate, and basic cerium nitrate. One type is mentioned.

  Examples of nitrates include ammonium nitrates such as alkaline metal nitrates such as potassium nitrate and sodium nitrate, and alkaline earth metal nitrates such as strontium nitrate.

Perchlorate and chlorate are components that have an oxidation action and a combustion promotion action. Oxidation means that oxygen is generated and the fuel is oxidized. On the other hand, the combustion promoting action means an action for improving the ignitability of the smoke generating composition or an action for improving the combustion rate.
Examples of perchlorate and chlorate include at least one selected from ammonium perchlorate, potassium perchlorate, sodium perchlorate, potassium chlorate, and sodium chlorate.

  Perchlorate, chlorate, and nitrate change the fuel of component (A) and change to sodium chloride, potassium chloride, magnesium chloride, potassium oxide, potassium carbonate, etc. This is preferable because it also functions as a smoke source.

<(C) Smoke source component>
The component (C) used in the present invention contains a smoke source component selected from metal oxides and metal salts having a refractive index of 1.8 or more.
The smoke source component of component (C) is composed of one kind selected from metal oxides and metal salts having a refractive index of 1.8 or more, or a combination of two or more kinds.
When the refractive index is 1.8 or more, the light scattering effect is increased and a higher visual field shielding effect can be realized as compared with the case where the same amount as that having a smaller refractive index is used.
In the present invention, the component (C) is preferably composed of a smoke source component having a refractive index of 1.8 or more. However, from the viewpoint of production cost and the like, the smoke source component having a refractive index of 1.8 or more and a refractive index of 1 are used. It may be a mixture of smoke source components of less than .8.
When a mixture of a smoke source component having a refractive index of 1.8 or more and a smoke source component having a refractive index of less than 1.8 is used, the ratio of the smoke source component having a refractive index of 1.8 or more is 80% by mass or more. It is preferable.

  As the smoke source component having a refractive index of 1.8 or more of the component (C), those shown in Table 1 can be used, and among these, those having a refractive index of 1.9 or more are preferable.

The melting point of the smoke source component of component (C) is preferably 2250K or less. When using a material having a melting point exceeding 2250K, it is preferable to use a material having a low melting point.
The particle size of the component (C) of the smoke source is not particularly limited, and for example, a particle having a particle size of 0.5 μm or less can be used.

In the composition of the present invention, the content ratio of the component (A) and the component (B) causes darker smoke, so that the combustion temperature when the fuel of the component (A) and the oxidizing agent of the component (B) burn Are combined so as to be equal to or higher than the melting point of the smoke source component of component (C).
For example, when titanium oxide (rutile) (melting point 2120K) is used as the smoke source component of component (C), the combustion temperature of the fuel of component (A) and the oxidizing agent of component (B) is 2120K or higher, preferably 2120K. Combine so that the temperature exceeds.
Moreover, it is preferable that the difference (combustion temperature of a composition-melting | fusing point of (C) component) is 200K or less, from a viewpoint of producing | generating dark smoke (smoke screen), and the melting temperature of the combustion temperature of a composition and (C) component, More preferably, the difference is in the range of 100 to 200K.
If the combustion temperature of the fuel of component (A) and the oxidizing agent of component (B) is equal to or higher than the melting point of the smoke component of component (C), the component (C) is released into the air in a molten state during combustion, and then When solidified by being cooled in the air, particles (white smoke) are formed. For this reason, white smoke is produced | generated without depending on the particle diameter of (C) component used as a raw material, and sufficient shielding effect is acquired.

The combustion temperature of the fuel of component (A) and the oxidizing agent of component (B) is, for example, well known in gas generating agents (including fuel and oxidizing agent) used in gas generators of airbag devices. It can be obtained by theoretical calculation using a thermochemical equilibrium calculation simulation program.
In addition, about the combustion temperature of the gas generant composition used with a gas generator, it is shown also in the Example of many gazettes, When it shows a few examples, it is Unexamined-Japanese-Patent No. 2014-80340, Unexamined-Japanese-Patent No. 2014. In the examples of Japanese Patent No. 80338, Japanese Patent Application Laid-Open No. 2012-2111064, Japanese Patent Application Laid-Open No. 2012-211035, the combustion temperature of the gas generant composition containing fuel, oxidant, binder and various additives is obtained by calculation. Yes.

  In the composition of the present invention, the content ratio of the component (C) is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and more preferably 15 to 35% by mass in order to make the shielding effect easier to express. Is more preferable.

<Binder>
In this invention, a binder can be contained as needed.
As the binder, carboxymethylcellulose (CMC), carboxymethylcellulose sodium salt (CMCNa), carboxymethylcellulose potassium salt, carboxymethylcellulose ammonium salt, cellulose acetate, cellulose acetate butyrate (CAB), methylcellulose (MC), ethylcellulose (EC), hydroxy Ethyl cellulose (HEC), ethyl hydroxyethyl cellulose (EHEC), hydroxypropyl cellulose (HPC), carboxymethyl ethyl cellulose (CMEC), microcrystalline cellulose, polyacrylamide, polyacrylamide amination, polyacryl hydrazide, acrylamide / metal acrylate Copolymer, Copolymer of polyacrylamide / polyacrylic acid ester compound Polyvinyl alcohol, acrylic rubber, guar gum, starch, may be at least one selected from silicone.
In the composition of the present invention, the content of the binder is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, and further preferably 3 to 7% by mass.

The composition of the present invention can be molded into a desired shape, and can be formed into a single-hole cylindrical shape, a porous cylindrical shape, a disk shape, or an indeterminate shape.
These moldings are prepared by adding water or an organic solvent to the composition, mixing and extruding (single-hole cylindrical or porous cylindrical molding), compression-molding using a tableting machine, etc. (disk shape) ).
The single-hole columnar shape and the porous columnar shape may be either those in which the hole penetrates in the length direction or those in which the hole does not penetrate and forms a recess.
The composition of the present invention can also be a mixture of the (A) component, the (B) component molding and the powdery (C) component.

<Smoke generator>
The smoke generating composition of the present invention can be used as a smoke source (smoke screen generation source) of a smoke generation device (smoke screen generation device).
As the smoke generating device (smoke screen generating device), for example, known devices such as a smoke generator (FIGS. 1 to 5) of JP-A-2015-43143 and a smoke screen generator of Japanese Patent No. 3816867 can be used.

Next, an operation state when the smoke generating composition of the present invention is used in a smoke generating device (smoke screen generating device) will be described. The smoke generating device of the present invention can be used as a security device in combination with a sensor or the like.
The smoke generating device is a housing in which an electric igniter and a smoke generating composition are contained in a housing having a discharge port of a smoke source (smoke screen source), and is combined with a sensor or the like as necessary.
The smoke generating device is used by being attached to an indoor ceiling or wall.
For example, the smoke generating composition may be stored together in one storage chamber in the smoke generating apparatus, or the component (A), the component (B), and the component (C) may be stored in separate storage chambers. Good.

When a trespasser enters the room, an electric igniter is activated by sensing the sensor, and combustion products (flames, high-temperature gas, etc. are mixed by combustion of component (A) and component (B) ).
The combustion product comes into contact with the component (C) and melts, so that a smoke source derived from the component (C) is generated.
In addition, (B) the oxidant burns the fuel (A) and changes itself into a white smoke source such as sodium chloride, potassium chloride, magnesium chloride, potassium oxide, potassium carbonate, etc. White smoke remains.
When water vapor is generated by combustion, it is also cooled and changed into white smoke (droplets), which becomes a source of smoke generation.
And the smoke source derived from the component (C), the powder derived from the component (B), and the water vapor from the smoke generator into the room by the heat and high-temperature gas when the component (A) and the component (B) burn. It emits vigorously and cools, resulting in white smoke.

The white smoke released into the room is quickly diffused, threatening the intruder, hindering the view of the intruder, and deterring or delaying the behavior. Prevention and restraint.
Moreover, since the smoke generating composition used for the smoke generating device contains a smoke source component having a refractive index of 1.8 or more as the component (C), it is compared with the case where the same amount as that having a lower refractive index is used. As a result, the light scattering effect is increased, and a higher visual field shielding effect can be realized.
The effect of improving the shielding effect by the light scattering effect is effective even in a dim environment such as a crime prevention light (nightlight), but from the viewpoint of further enhancing the effect, the smoke generator is activated to diffuse white smoke. In addition, the illumination can be turned on.

Examples and comparative examples (combustion temperature calculation method)
Combustion temperature: Theoretical calculation was performed using a thermochemical equilibrium calculation simulation program.

(Method for producing composition sample for evaluation)
Each component was weighed with the composition shown in Table 2, passed twice through a sieve and thoroughly mixed, and then ion-exchanged water was added and mixed. This was dried at 110 ° C. for 16 hours and then pulverized.

(Shielding effect confirmation test)
0.2 g of the produced composition sample was placed on a wire mesh, and a solid fuel (main component methanol) was placed under the wire mesh.
An acrylic box (0.06 m ³ ) was put on these to seal the inside.
A transmittance measuring device (Kiko Giken MLXA-D12-785-70) was set and heated from the outside to ignite and burn the solid fuel.
The light transmittance at a wavelength of 785 nm was measured 9 minutes after the ignition of the solid fuel. The smaller the transmittance, the deeper the white smoke (smoke screen).

From the comparison between Example 2 and Example 4, the light transmittance was lower in Example 2 using titanium oxide having a small refractive index.
In comparison between Example 1 and Example 3, the light transmittance of Example 1 is high because the difference between the melting point of (C) and the combustion temperature (360K) of the composition becomes too large, and the inside of a small acrylic box. Then, it is considered that the white smoke was not generated because the component (C) in the molten state was not sufficiently cooled. However, when it is applied to an actual building having a larger space, it is considered to function sufficiently in practice because it is sufficiently cooled.

  The smoke generating composition of the present invention can be used as a security device.

Claims (6)

A smoke generator composition comprising (A) a fuel, (B) an oxidizer, and (C) a smoke source component selected from metal oxides and metal salts having a refractive index of 1.8 or more,
The fuel of the component (A) and the oxidant of the component (B) are combusted when the fuel of the component (A) and the oxidant of the component (B) are combusted. A smoke generating composition, which is a combination that exceeds the melting point of the components.   The smoke source component having a refractive index of 1.8 or more of the component (C) is titanium oxide (rutile type), titanium oxide (anatase type), chromium oxide (III), black iron oxide, zirconium oxide, silver chloride, zinc oxide, The smoke generating composition according to claim 1, which is selected from sodium chloride, aluminum oxide, potassium chloride and magnesium oxide.   The smoke generating composition according to claim 1 or 2, wherein the fuel is a nitrogen-containing organic compound selected from a tetrazole compound, a guanidine compound, a triazine compound, and a nitroamine compound.   The oxidant is selected from alkali metal halides or alkali metal perhalogenates, alkali metal nitrates, alkaline earth metal nitrates, etc., or ammonium nitrate. The smoke generator composition described in 1.   Furthermore, the smoke generating composition of any one of Claims 1-4 containing the binder.   A smoke generating apparatus in which the smoke generating composition according to any one of claims 1 to 5 is accommodated as a smoke generating source.