JP5700816B2 - Smoke-type insecticide, smoke-type insecticide, insecticide method - Google Patents

Description

  The present invention relates to a smoke-type insecticide, a smoke-type insecticide and an insecticide method using the smoke-type insecticide.

In order to control sanitary pests such as flies, mosquitoes and cockroaches, molds, bacteria, and the like, indoor and in-vehicle spaces are treated with a smoke agent (fumigant).
The smoke agent is a solid preparation mainly composed of an exothermic base in which various combustion agents or foaming agents are mixed and an active ingredient such as an insecticide. As the exothermic base, nitrocellulose, azodicarbonamide, p, p′-oxybis (benzenesulfonylhydrazide), N, N′-dinitrosopentamethylenetetramine and the like are generally used.
When the smoke agent is heated at the time of use, the exothermic base burns or decomposes to generate smoke (gas and fine particles), and the active ingredient is released and diffused into the air by the action of this smoke and heat (hereinafter, It is called volatilization.) Therefore, the active ingredient can be spread throughout the space in a short time, and pests can be controlled.

The soot agent is heated by direct heating method in which a part of the soot agent is directly heated to cause a self-combustion reaction or by the hydration heat of the heating agent such as calcium oxide. An indirect heating method is used in which heating is performed to a certain temperature. For example, smoke generated by self-combustion of a combustion base by heating a smoke base composition containing a combustion base such as azodicarbonamide and an insecticidal component by an indirect heating method using hydration heat of calcium oxide, etc. Smoke apparatuses that volatilize active ingredients with (gas and fine particles generated by thermal decomposition) have been proposed (for example, Patent Documents 1 and 2) and are put into practical use.
However, although smoke agents containing a combustion base such as azodicarbonamide are excellent in volatilizing ability of active ingredients, there is a problem that white precipitates and the like are contaminated by generated smoke.

On the other hand, as an insecticide used by volatilizing an active ingredient by heating, a liquid one in which the active ingredient is dissolved in a solvent has been proposed. Such an insecticide is housed in a device equipped with a liquid absorbent wick, absorbed by the liquid absorbent wick, and the active ingredient is volatilized by heating the liquid absorbent wick. The heating temperature is lower than that in the case of the smoke agent, and is usually 135 ° C. or lower (for example, Patent Documents 3 to 4).
Although this type of insecticide does not contain a pyrogenic base, it is difficult to cause contamination, but the volatility of an active ingredient is lower than that of a smoke agent. Therefore, depending on the active ingredient, there is a problem that the active ingredient that can be used is limited because it does not volatilize, and it takes time to diffuse throughout the space even if volatilized. In addition, since the volatilized state of the active ingredient cannot be visually recognized, there is a problem that it is difficult to confirm whether or not the processing is finished.

Japanese Patent Publication No.58-28842 Japanese Patent Publication No.59-49201 Japanese Patent Laid-Open No. 7-69805 JP 2009-232915 A

  The present invention has been made in view of the above circumstances, and is a low-contamination and a smoke-type insecticide capable of efficiently volatilizing an active ingredient, and a smoke-type insecticide using the smoke-type insecticide An object is to provide an apparatus and an insecticidal method.

As a result of intensive studies to solve the above problems, the present inventors have obtained the following knowledge.
When a glycol-based composition is heated at 150-450 ° C. instead of the exothermic base of the current smoke agent, white smoke is generated as in the case of the current smoke agent, and exothermic Since fine particles generated by combustion or decomposition of the base are not included, white precipitates derived from the exothermic base can be prevented, and contamination can be reduced. However, compared with the case where an exothermic base is used, there is a problem that the active ingredient is easily thermally decomposed during heating. When thermal decomposition occurs, the amount volatilized in an effective state (undecomposed state) decreases (volatilization efficiency decreases), and the insecticidal efficacy decreases. In particular, in the case of an active ingredient having a relatively low heat resistance such as an oxadiazole compound or a carbamate compound, thermal decomposition is remarkable and hardly volatilizes.
The present invention has been found as a result of studies to suppress thermal decomposition of this active ingredient, and has the following aspects.
[1] containing (A) glycol, (B) an insecticidal active ingredient, and (C) at least one selected from ascorbic acid compounds and phenolic antioxidants ,
The ascorbic acid compound is ascorbic acid, sodium ascorbate, disodium ascorbate phosphate, magnesium ascorbate phosphate, disodium ascorbate sulfate, ascorbyl glucoside, ascorbyl monopalmitate, ascorbyl dipalmitate, Is at least one selected from the group consisting of ascorbyl monostearate, erythorbic acid and sodium erythorbate,
The phenolic antioxidant is dibutylhydroxytoluene, butylhydroxyanisole, p-hydroxyanisole, tocopherol, nordihydroguaiaretic acid, tert-butylhydroquinone, butyl gallate, propyl gallate, octyl gallate, dodecyl gallate , At least one selected from the group consisting of trihydroxybutylphenone, catechin, anthocyanin, rutin, ellagic acid, chlorogenic acid, lignan, curcumin, lutein, zeaxanthin, fucoxanthin and astaxanthin,
The content of the (A) glycol is 50 to 90% by mass,
Content of the said (B) insecticidal active ingredient is 1-20 mass%,
Wherein (C) ascorbic acid compound and at least one content selected from phenolic antioxidants, from 1 to 20% by mass Ru fumigant type insecticide.
[ 2 ] The mass ratio (C / B) to the active ingredient (B) of at least one selected from the (C) ascorbic acid compound and the phenolic antioxidant is 0.2 to 10. The smoke-type insecticide according to [1] or [2].
[ 3 ] A smoke type insecticidal apparatus in which the smoke type insecticide according to [1] or [2] and a heat generating part that generates heat of 150 to 450 ° C are arranged via a heat transfer part.
[ 4 ] An insecticidal method comprising heating the smoke-type insecticide according to [1] or [2] at 150 to 450 ° C.

  According to the present invention, it is possible to provide a smoke-type insecticide that is low-contamination and capable of efficiently volatilizing an active ingredient, a smoke-type insecticide apparatus and an insecticide method using the smoke-type insecticide.

It is a schematic sectional drawing explaining an example of a structure of a smoke type insecticidal apparatus.

≪Smoke type insecticide≫
The smoke type insecticide of the present invention comprises (A) glycol (hereinafter referred to as component (A)), (B) an insecticidal active ingredient (hereinafter referred to as component (B)), (C) an ascorbic acid compound and And at least one selected from phenolic antioxidants (hereinafter referred to as “component (C)”).
The smoke type insecticide of the present invention can be heated at a high temperature of about 150 to 450 ° C. during use, and the component (B) can be volatilized in the space to be treated in a short time. Similar to the agent, white smoke is visible. That is, when the heating is performed, the component (A) is vaporized and ejected into a space such as a room. Since the vapor of the component (A) works in the same manner as the smoke of the conventional smoke agent, the component (B) is volatilized in the entire space to be treated in a short time. Moreover, the thermal decomposition of the (B) component at the time of the said heating is suppressed by containing (C) component. Therefore, the volatilization efficiency of the component (B) is high and exhibits an excellent control effect against pests such as flies, mosquitoes, cockroaches, and ticks. Further, even if it is smoke-like, it does not contain fine particles generated by combustion or decomposition of the exothermic base, unlike the smoke of the current smoke smoke agent, so that contamination by white sediment can be prevented.

[(A) component]
“Glycol” is a dihydric alcohol having two hydroxyl groups in the molecule, and is also called a diol. When glycol is heated at 150 to 450 ° C., white smoke is generated in the same manner as the current smoke agent, and it is used as a smoke generating substrate in the present invention.
The component (A) is not particularly limited, and the component (B) has volatility, solubility / dispersibility, and usage among those used in pharmaceuticals, quasi drugs, cosmetics, miscellaneous goods, industrial products, and the like. It is appropriately selected in consideration of the heating temperature at the time.
The boiling point of the component (A) is preferably 150 to 300 ° C, and more preferably 170 to 300 ° C, from the viewpoint of the temperature at which the active ingredient is volatilized.

As a preferred component (A), one hydroxyl group is added to each of two carbon atoms of an aliphatic hydrocarbon having 2 or more carbon atoms and an etheric oxygen atom (—O—) inserted between carbon atoms. A compound having a bonded structure is exemplified.
In the compound, the aliphatic hydrocarbon may be saturated or unsaturated. The aliphatic hydrocarbon may be a chain, a ring, or a combination thereof, and is preferably a chain. In the case of a chain, the aliphatic hydrocarbon may be linear or branched. When cyclic, the aliphatic hydrocarbon may be monocyclic or polycyclic.
More specifically, examples of such a compound include compounds represented by the following general formula (A1) or (A2).
HO—R ¹ —OH (A1)
HO— (R ² O) _n —H (A2)
[Wherein, R ¹ and R ² are each independently a divalent aliphatic hydrocarbon group having 2 or more carbon atoms, and n is an integer of 2 or more. ]

In formula (A1), the number of carbon atoms of the divalent aliphatic hydrocarbon group in R ¹ is preferably 2 to 18, more preferably 2 to 4, and still more preferably 3 or 4. R ¹ is particularly preferably a propylene group.
The compound represented by the formula (A2) is a so-called polyether.
In formula (A2), examples of R ² include the same groups as R ¹ , an ethylene group or a propylene group is preferable, and an ethylene group is particularly preferable.
n is preferably from 2 to 14, and more preferably from 2 to 4.

Examples of the compound represented by the general formula (A1) include ethylene glycol, propylene glycol, 1,3-butylene glycol, trans-2-butene-1,4-diol, 2-butyne-1,4-diol, 2,5-hexanediol, 2-methyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2,4-heptanediol, 2 , 2-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-2-butyl-1,3-propanediol, isoprene glycol, trimethylene glycol, 1,4-butane Diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1, 16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, 1,20-icosanediol, 1,2-octanediol, 1,2-decanediol, Examples include 1,2-dodecanediol, 1,2-tetradecanediol, 1,2-hexadecanediol, 1,2-octadecanediol, and the like.
Examples of the compound represented by the general formula (A2) include diethylene glycol, triethylene glycol, polyethylene glycol having an average molecular weight of 200 to 20000, dipropylene glycol, tripropylene glycol, and polypropylene glycol having an average molecular weight of 300 to 2000. .
Polyethylene glycol having an average molecular weight of 200 to 20000 is also referred to as macrogol. Polyethylene glycol 200 (average molecular weight 190 to 210), polyethylene glycol 300 (average molecular weight 280 to 320), polyethylene glycol 400 (average molecular weight 380 to 420), polyethylene Glycol 600 (average molecular weight 570-630), polyethylene glycol 1000 (average molecular weight 950-1050), polyethylene glycol 1500 (equal mixture of polyethylene glycol 300 and polyethylene glycol 1540), polyethylene glycol 1540 (average molecular weight 1290-1650), polyethylene Glycol 2000 (average molecular weight 1850-2150), polyethylene glycol 4000 (average molecular weight 2600-38) 0), polyethylene glycol 6000 (average molecular weight 7300-9300), polyethylene glycol 10000 (average molecular weight 9,300 to 12,500), and polyethylene glycol 20000 (average molecular weight 15500 to 20000) and the like.
For these polyethylene glycols, for example, commercially available products available from Sanyo Chemical Industries, Ltd. or NOF Corporation can be used. Commercially available products of polyethylene glycol are usually given the above numerical values (200, 300, etc.), and depending on the product, for example, polyethylene glycol # 1000, there may be a # between the polyethylene glycol and the numerical value. .
In addition, the average molecular weight of said polyethyleneglycol shows the average molecular weight of quasi-drug raw material specification 2006, and is a value by the measuring method of quasi-drug raw material specification 2006.
Examples of the polypropylene glycol having an average molecular weight of 300 to 2000 include those having a polymerization degree of 4 to 34. Examples of such polypropylene glycol include Newpol PP-400, PP-1000, PP-2000 (Sanyo Chemical Industries, Ltd.). (Commercially available) can be used.
In addition, the average molecular weight of polypropylene glycol is a number average molecular weight, and is a value obtained from a hydroxyl value.
As the component (A), among the above, propylene glycol, dipropylene glycol, tripropylene glycol, and 1,3-butylene glycol are preferable.

The component (A) contained in the smoke type insecticide of the present invention may be one type or two or more types.
In the smoke type insecticide of the present invention, the content of the component (A) is preferably 50 to 90% by mass and more preferably 60 to 85% by mass with respect to the total mass of the smoke type insecticide. There exists a possibility that (B) component may not fully volatilize that it is less than 50 mass%. When it exceeds 90% by mass, the content of the component (B) and the component (C) is relatively decreased, so that the component (B) is not sufficiently volatilized and the insecticidal effect may be insufficient.

[Component (B)]
The insecticidal active ingredient of the component (B) is not particularly limited, and is appropriately selected from the insecticidal ingredients that have been conventionally blended in smoke agents in consideration of the type of harmful pests to be controlled.
For example, representative insecticidal components include, but are not limited to, oxadiazole compounds, carbamate compounds, pyrethroid compounds, organophosphorus compounds, neonicotinoid compounds, and the like. Among these, at least one selected from oxadiazole compounds, carbamate compounds, and pyrethroid compounds is preferable from the viewpoint of safety to the human body. In particular, it is preferable to contain at least one selected from an oxadiazole-based compound and a carbamate-based compound because it is easily thermally decomposed and is excellent in suppression of thermal decomposition due to the blending of the component (C) and the accompanying improvement in volatilization rate.

Examples of the oxadiazole compound include methoxadiazone.
Examples of carbamate compounds include propoxur and carbaryl.
The pyrethroid compound may be any one of pyrethrin, a natural insecticidal component contained in pesticide chrysanthemums, chrysanthemum extract obtained by extracting dried flowers of pesticide chrysanthemum with a solvent, and a synthesized pyrethrin analog (synthetic pyrethroid). As long as it is an ester compound comprising an alcohol moiety, it is not particularly limited whether it is a natural product or a synthetic product. Specifically, a licorice extract, pyrethrin (for example, trade name manufactured by Sumitomo Chemical Co., Ltd .: pyrethrin), allethrin (for example, commercial name manufactured by Sumitomo Chemical Co., Ltd .: pinamine), dl · d-T80-alleslin (for example, Sumitomo) Chemical brand name: Pinamin Forte), phthalthrin (for example, Sumitomo Chemical brand name: Neopinamine), dT80-phthalthrin (for example, Sumitomo Chemical brand name: Neopinamine) Forte), Resmethrin (for example, trade name: Chryslon, manufactured by Sumitomo Chemical Co., Ltd.), d-T80-Resmethrin (for example, trade name: Chryslon Forte, manufactured by Sumitomo Chemical Co., Ltd.), d-T80-Framethrin (for example, Sumitomo Chemical) Product name: Pinamin-D Forte), phenothrin (for example, manufactured by Sumisho Agro International Co., Ltd.) (Trade name: Smithlin), permethrin (for example, trade name: Exmine) manufactured by Sumitomo Chemical Co., Ltd., d-T80-cyphenothrin (for example, trade name: Gokyrat manufactured by Sumitomo Chemical Co., Ltd.), d · d-T- Cifenotrin (for example, trade name: Gokyrat S manufactured by Sumitomo Chemical Co., Ltd.), d · d-T80-praretrin (for example, trade name: Etokku manufactured by Sumitomo Chemical Co., Ltd.), EZ-empentrin (for example, Sumitomo Chemical Co., Ltd.) Product name: Vaporthrin, imiprothrin (for example, product name: Pral, manufactured by Sumitomo Chemical Co., Ltd.), transfluthrin (for example, product name: Biothrin, manufactured by Sumitomo Chemical Co., Ltd.), metfluthrin (for example, Sumitomo Chemical (for example) Co., Ltd. product name: Eminence).
Since the volatilization improving effect due to the blending of component (C) is remarkable, methoxadiazone is preferable among oxadiazole compounds, propoxur is preferable among carbamate compounds, and d, d-T-cyphenothrin among pyrethroid compounds. At least one selected from phenothrin is preferred.

The component (B) contained in the smoke type insecticide of the present invention may be one type or two or more types.
In the smoke type insecticide of the present invention, the content of the component (B) is preferably 1 to 20% by mass and more preferably 5 to 15% by mass with respect to the total mass of the smoke type insecticide. If it is less than 1% by mass, the insecticidal effect may be insufficient. If it exceeds 20% by mass, the contents of the component (A) and the component (C) are relatively reduced, and the volatilization efficiency of the component (B) may be reduced. Moreover, the solubility and degradability to (A) component may be impaired, and formulation may become difficult. Moreover, since the insecticidal effect hardly changes even if it exceeds 20 mass%, it is not preferable from an economical viewpoint.

[Component (C)]
In the component (C), ascorbic acid compounds include ascorbic acid, isomers thereof, derivatives thereof, salts thereof and the like. The isomer includes erythorbic acid. As the derivatives, those generally proposed as vitamin C derivatives can be used, and examples thereof include higher fatty acid esters, phosphate esters, and sulfate esters of ascorbic acid or erythorbic acid. As the higher fatty acid, a fatty acid having 16 to 18 carbon atoms is preferable, and examples thereof include palmitic acid and stearic acid. Examples of the salt include sodium salt, calcium salt, potassium salt, magnesium salt, phosphate, sulfate and the like.
Specific examples of ascorbic acid compounds include ascorbic acid, sodium ascorbate, disodium ascorbate phosphate, magnesium ascorbate phosphate, disodium ascorbate sulfate, glucoside ascorbate, ascorbyl monopalmitate, dipalmitin Ascorbyl acid, ascorbyl monostearate, erythorbic acid, sodium erythorbate and the like can be mentioned.
Among these ascorbic acid compounds, ascorbic acid, sodium ascorbate, and magnesium ascorbyl phosphate are preferable, and ascorbic acid is particularly preferable from the viewpoint of the volatilization rate of the insecticidal active ingredient.

The phenolic antioxidant refers to a compound having an antioxidant ability in a group (phenolic compound) group having an aromatic ring to which a hydroxyl group is bonded. Depending on the number of hydroxyl groups bonded to the aromatic ring, monovalent, divalent, Classified as trivalent. The number of aromatic rings contained in one molecule may be 1 or 2 or more, preferably 1 to 3. In addition, the phenol compound more than bivalence is also called a polyhydric phenol compound (polyphenol compound).
Having antioxidation ability means having the ability (reduction action) to be oxidized by itself in order to prevent the object from being oxidized.
Examples of the monohydric phenol compound having antioxidant ability include dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), p-hydroxyanisole, tocopherol and the like. Examples of the dihydric phenol compound having antioxidant ability include nordihydroguaiaretic acid and tert-butylhydroquinone. Examples of the trivalent phenolic compound having antioxidant ability include butyl gallate, propyl gallate, octyl gallate, dodecyl gallate, and trihydroxybutylphenone.
Examples of polyphenol compounds having antioxidant ability other than the above include catechin, anthocyanin, rutin, ellagic acid, chlorogenic acid, lignan, curcumin, lutein, zeaxanthin, fucoxanthin, astaxanthin and the like.
Of these phenolic antioxidants, dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, and octyl gallate are preferred, and dibutylhydroxytoluene and propyl gallate are particularly preferred from the viewpoint of the volatilization rate of the insecticidal active ingredient.

(C) component contained in the smoke type insecticide of this invention may be 1 type, or 2 or more types.
In the smoke type insecticide of the present invention, the content of the component (C) is preferably 1 to 20% by mass, more preferably 2 to 20% by mass, and more preferably 3 to 15% with respect to the total mass of the smoke type insecticide. More preferred is mass%. If it is less than 1% by mass, the volatilization efficiency of the component (B) may be reduced. If it exceeds 20% by mass, there may be problems such as solubility, making formulation difficult.

  In this invention, it is preferable that mass ratio (C / B) with respect to (B) component of (C) component in a smoke type insecticide is 0.2-10, It is 0.2-7. Is more preferable, and 0.3 to 5 is more preferable. When the mass ratio is less than 0.2, the thermal decomposition of the component (B) cannot be sufficiently suppressed, and the volatilization efficiency of the component (B) may be reduced. Even if the mass ratio exceeds 10, the volatilization efficiency hardly changes.

The smoke type insecticide of the present invention may further contain water for the purpose of further reducing contamination.
As water, purified water, ion exchange water, distilled water, or the like can be used.
The water content is preferably 50% by mass or less, more preferably 20% by mass, and particularly preferably 10% by mass or less based on the total mass of the smoke-type insecticide. When the amount of water is 50% by mass or less, the specific heat of the steam generated during heating is sufficiently small, so that dense smoke is generated.

The smoke type insecticide of the present invention may contain other components other than the above components (A) to (C) and water as long as the effects of the present invention are not impaired. Examples of the other components include repellents, bactericides, preservatives, deodorants, surfactants, gelling agents, essential oils, and fragrances.
The smoke type insecticide of this invention can be prepared by mixing said each component.

≪Insecticidal method≫
As described above, the smoke-type insecticide of the present invention is heated at 150 to 450 ° C. to generate white smoke and the component (B) is volatilized. When the smoke type insecticide of the present invention is heated in a space such as indoors or in a vehicle, the component (B) is volatilized in the space in a short time by the smoke, and the insecticidal effect against pests is exhibited. Is done.
The heating temperature of the smoke-type insecticide is 150 to 450 ° C, preferably 170 to 400 ° C, and more preferably 190 to 400 ° C. By heating at 150 ° C. or higher, the generated vapor of component (A) can be ejected in the form of smoke, and component (B) can be diffused throughout the space to be treated. Within this range, the higher the heating temperature, the shorter the time for the component (B) to diffuse throughout the space, and the diffusion range becomes wider. When the heating temperature is 450 ° C. or lower, the thermal decomposition of the component (B) is sufficiently suppressed by the component (C), so that the volatilization efficiency is improved.

The heating of the smoke-type insecticide is preferably carried out by an indirect heating method because of its excellent anti-contamination effect. The indirect heating method is a method known as one of the heating methods for smoke agents, and the temperature (thermal energy) required for the pyrolysis of the exothermic base without burning the smoke agent is changed to the heat transfer part ( For example, it is the method of supplying through the wall (side wall, bottom wall, etc.) of the container which accommodated the said smoke agent. That is, in the case of the present invention, it is preferable to supply the temperature (thermal energy) necessary for vaporizing the component (A) via the heat transfer section without burning the smoke-type insecticide.
The heating unit is not particularly limited, and a heating unit conventionally used for the indirect heating method can be used. For example, a method in which a substance that generates heat in contact with water is brought into contact with water and the reaction heat is used, a metal and a metal oxide or an oxidizer having a lower ionization tendency than the metal are mixed (for example, iron powder and an oxidizer ( Heat generated by energizing the heat sinks and heating elements used in conventional electric mosquito mats and liquid mosquito traps. The method of using, etc. are mentioned. Among these, from the viewpoint of practicality, a method of bringing a substance that generates heat upon contact with water into contact with water and utilizing the reaction heat thereof is preferred, and a method of utilizing the reaction heat between calcium oxide and water is more preferred.
Examples of substances that generate heat upon contact with water include calcium oxide, magnesium chloride, aluminum chloride, calcium chloride, and iron chloride. For example, when calcium oxide and water are reacted, heat of about 200 to 400 ° C. is generated.
Heating by the indirect heating method can be carried out, for example, by incorporating the smoke-type insecticide of the present invention into a container conventionally used in an indirect heating method smoke device.

Examples of the insecticidal target of the insecticidal method of the present invention include insects such as flies, mosquitoes, cockroaches and mites.
The target space for performing the insecticidal treatment according to the present invention is not particularly limited as long as it can be sealed, and examples thereof include indoors (bathrooms, living rooms, closets, etc.), vehicles, and the like.
What is necessary is just to set suitably the usage-amount of a smoke type insecticide according to the floor area made into object. Usually, 0.1 to 2.0 g is preferable per 1 m ² , and 0.2 to 1.5 g is more preferable.
The treatment time (time for sealing the target space after the start of heating) is not particularly limited, preferably 1 hour or more, and more preferably 2 hours or more.

≪Smoke type insecticidal device≫
The smoke type insecticidal apparatus of the present invention is one in which the smoke type insecticide of the present invention and a heat generating part that generates heat of 150 to 450 ° C. are arranged via a heat transfer part.
The configuration of the smoke type insecticide of the present invention may be the same as the configuration of a known indirect heating type smoke device except that the smoke type insecticide of the present invention is used instead of the smoke agent.
One embodiment of the smoke type insecticidal apparatus of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a schematic cross-sectional view illustrating the configuration of the smoke type insecticidal apparatus 1 of the present embodiment.
The smoke-type insecticidal apparatus 1 includes an outer container 10, an inner container 20 provided inside the outer container 10, a heat generating unit 30 provided between the outer container 10 and the inner container 20, and an inner container 20. It is comprised roughly with the smoke-type insecticide 40 accommodated.
As the smoke type insecticide 40, the smoke type insecticide of the present invention is used.

The heat generating portion 30 is formed by filling a substance that generates heat upon contact with water (for example, calcium oxide). The filling amount of the substance can be determined in consideration of the amount of heat necessary for generating steam from the smoke type insecticide 40. Examples of the substance that generates heat upon contact with water include the same substances as mentioned in the description of the insecticidal method, and calcium oxide is preferable.
In addition, although the example filled with the substance which generate | occur | produces heat in contact with water was shown here, this invention is not limited to this. For example, a partition material may be disposed in the heat generating portion 30 to form a plurality of independent compartments, and each compartment may be filled with a metal and a metal oxide or oxidizer having a lower ionization tendency than the metal.

The inner container 20 functions as a container that accommodates the smoke-type insecticide 40 and also functions as a heat transfer section that transmits the heat energy generated in the heat generating section 30 to the smoke-type insecticide 40.
The material of the inner container 20 may be any material having heat conductivity, and examples thereof include metal, plastic, paper, and the like.

The outer container 10 includes a main body 12, a lid portion 14, and a bottom portion 16.
The material of the main body 12, the lid portion 14, and the bottom portion 16 is a material having heat resistance that does not cause deformation due to heat generated in the heat generating portion 30 or high-temperature steam generated from the smoke-type insecticide 40, for example, Metal, ceramic, paper, etc. are mentioned.
The main body 12 has a substantially cylindrical shape, the inner diameter thereof is larger than the outer diameter of the inner container 20, and the height is higher than the height of the inner container 20. Thereby, when the inner container 20 is installed in the outer container 10, a gap is formed between the side wall and the bottom wall of the inner container 20.
The lid portion 14 has a hole through which steam passes, and examples thereof include a mesh, a punching metal, and a lattice frame.
The bottom portion 16 is made of a material having a hole that transmits water and does not transmit a material that constitutes the heat generating portion 30 (a material that generates heat upon contact with water), such as a nonwoven fabric or a mesh. As a result, water can enter the heat generating portion 30 from the bottom portion 16 during use to generate heat.
The structure of the bottom portion 16 is determined according to the configuration of the heat generating portion 30. For example, when the heat generating portion 30 is filled with a metal and a metal oxide or an oxidizer having a lower ionization tendency than the metal, The structure of the bottom portion 16 may be impermeable to water.

An insecticidal method using the smoke type insecticidal apparatus 1 will be described.
First, the smoke type insecticidal apparatus 1 is installed in the target space. Next, the heat generating unit 30 generates heat according to the mechanism of the heat generating unit 30. For example, when the heat generating part 30 filled with calcium oxide is provided, the bottom part 16 of the outer container 10 is immersed in water. Thereby, the water which permeated from the bottom part 16 reacts with calcium oxide in the heat generating part 30, and heat of about 200 to 400 ° C. is generated. This heat is transmitted to the smoke-type insecticide 40 through the side wall and the bottom wall of the inner container 20, and the temperature of the smoke-type insecticide 40 rises to generate the vapor of component (A). The component (B) diffuses through the hole of the lid 14 together with the generated vapor. Thus, the insecticidal effect can be obtained by diffusing the component (B) in the target space.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
The raw materials used in the following examples are as follows.
Propylene glycol: manufactured by Kanto Chemical Co., Inc.
Dipropylene glycol: manufactured by Kanto Chemical Co., Inc.
Tripropylene glycol: manufactured by Kanto Chemical Co., Inc.
Metoxadiazone: manufactured by Sumitomo Chemical Co., Ltd.
Permethrin: manufactured by Sumitomo Chemical Co., Ltd.
d · d-T-cyphenothrin: manufactured by Sumitomo Chemical Co., Ltd.
Propoxl: Sumisho Agro International Co., Ltd.
Ascorbic acid: manufactured by Kanto Chemical Co., Inc.
Ascovir palmitate: Wako Pure Chemical Industries, Ltd.
BHT: manufactured by Kyodo Pharmaceutical.
N-Propyl gallate: manufactured by Kanto Chemical Co., Inc.
Sodium sulfite: manufactured by Kanto Chemical Co., Inc.

<Examples 1-22, Comparative Examples 1-2>
A liquid smoke type insecticide was prepared by mixing and dissolving the components shown in Tables 1 to 3.
In Tables 1 to 3, the unit of the blending amount of each component is mass%, and water was added so that the total amount was 100 mass%.
50 g of calcium oxide is filled in a tin can used in Lion's “Valsan starting with water” 12.5 g, a dedicated bottom lid is attached, and 5 g of the smoke-type insecticide of each case is placed in the inner container. A smoke-type insecticidal device.
Each smoke type insecticidal device was evaluated as follows. The results are shown in Tables 1-3.

(Evaluation method)
[Volatilization rate]
18 mL of water was placed in a plastic cup having a diameter of 8 cm and a height of 4 cm, and the plastic cup was placed in the center of a test chamber having an internal volume of 6.38 m ³ (6380 L). The smoke type insecticidal apparatus of each example was installed in this plastic cup. White smoke started to appear 1 minute after installation.
Five minutes after the start of the generation of white smoke, the air in the test chamber was stirred with a fan. After stirring, 20 L of air in the test chamber was passed through the recovery column using a vacuum pump, and the active ingredient (component (B)) volatilized in the test chamber was adsorbed. As the recovery column, chromatographic silica gel (Wakogel C-100, manufactured by Wako Pure Chemical Industries, Ltd.) was used.
Next, after the active ingredient was adsorbed, acetone was passed through the recovery column, and the passed acetone was recovered. Thus, the active ingredient adsorbed on the silica gel for chromatography was eluted. Using the collected acetone as a sample, the amount of active ingredient X (g) in the sample was quantified by gas chromatography (GC). The volatilization rate (%) was calculated from the quantitative result and the amount Y (mass%) of the active ingredient in the smoke type insecticide by the following formula.
In Examples 20 to 22 where a plurality of active ingredients were used in combination, the volatilization rate (%) was determined for each active ingredient.

From the calculated volatilization rate (%), the volatilization efficiency of the active ingredient was evaluated according to the following criteria.
[Evaluation criteria]
A: Volatilization rate is 35% or more.
○: Volatilization rate of 15% or more and less than 35%.
Δ: Volatilization rate of 5% or more and less than 15%.
X: Volatilization rate is less than 5%.

<Examples 23 to 34>
A liquid smoke type insecticide was prepared by mixing and dissolving the components shown in Table 4.
In Table 4, the unit of the blending amount of each component is mass%, and water was added so that the total amount was 100 mass%.
50 g of calcium oxide is filled in a tin can used in Lion's “Valsan starting with water” 12.5 g, a dedicated bottom lid is attached, and 5 g of the smoke-type insecticide of each case is placed in the inner container. A smoke-type insecticidal device.
About each smoke type insecticidal apparatus, the volatilization rate (%) of the active ingredient was measured similarly to Examples 1-22. The results are also shown in Table 4. As shown in Table 4, the volatilization rate of the active ingredients was as good as 20% or more.

  DESCRIPTION OF SYMBOLS 1 ... Smoke type insecticidal apparatus, 10 ... Outer container, 12 ... Main body, 14 ... Cover part, 16 ... Bottom part, 20 ... Inner container, 30 ... Heat generating part, 40 ... Smoke type insecticide

Claims (4)

(A) glycol, (B) an insecticidal active ingredient, and (C) at least one selected from ascorbic acid compounds and phenolic antioxidants ,
The ascorbic acid compound is ascorbic acid, sodium ascorbate, disodium ascorbate phosphate, magnesium ascorbate phosphate, disodium ascorbate sulfate, ascorbyl glucoside, ascorbyl monopalmitate, ascorbyl dipalmitate, Is at least one selected from the group consisting of ascorbyl monostearate, erythorbic acid and sodium erythorbate,
The phenolic antioxidant is dibutylhydroxytoluene, butylhydroxyanisole, p-hydroxyanisole, tocopherol, nordihydroguaiaretic acid, tert-butylhydroquinone, butyl gallate, propyl gallate, octyl gallate, dodecyl gallate , At least one selected from the group consisting of trihydroxybutylphenone, catechin, anthocyanin, rutin, ellagic acid, chlorogenic acid, lignan, curcumin, lutein, zeaxanthin, fucoxanthin and astaxanthin,
The content of the (A) glycol is 50 to 90% by mass,
Content of the said (B) insecticidal active ingredient is 1-20 mass%,
Wherein (C) ascorbic acid compound and at least one content selected from phenolic antioxidants, from 1 to 20% by mass Ru fumigant type insecticide. The mass ratio (C / B) to the (B) insecticidal active ingredient of at least one selected from the (C) ascorbic acid compound and the phenolic antioxidant is 0.2 to 10. The smoke type insecticide described. A smoke type insecticidal apparatus in which the smoke type insecticide according to claim 1 or 2 and a heat generating part that generates heat of 150 to 450 ° C are arranged via a heat transfer part. An insecticidal method comprising heating the smoke-type insecticide according to claim 1 or 2 at 150 to 450 ° C.

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