JP6681773B2 - Smoke agent composition - Google Patents

Description

  The present invention relates to a smoke agent composition.

  A smoke agent composition containing a pest control component and a combustion agent is widely used for controlling harmful insects such as flies, mosquitoes, and cockroaches indoors. Known examples of the combustion agent are azodicarbonamide (ADCA) and nitrocellulose (NC), which are self-reactive combustion agents. The use of the self-reactive combustion agent improves the volatility of the pest controlling component. However, when a self-reactive combustor is used, there is a problem that white deposits are accumulated after the treatment and indoors are contaminated.

  Therefore, a smoke agent composition containing an ascorbic acid compound has been proposed as a smoke agent composition capable of obtaining good volatility of pest control components without using a self-reactive combustion agent (( Patent Document 1).

JP, 2012-232922, A

  However, in the conventional smoke agent compositions such as Patent Document 1, the residual effect of the smoked pest control component after sedimentation is still insufficient, and the effect may not last for a long time. Further, in the smoke agent composition, it is important to maintain a high smoke rate even if the storage period is long, and further enhance the volatility of the pest control component.

  It is an object of the present invention to provide a smoke agent composition having a high smoke conversion rate of a pest controlling component even with a long storage period and excellent residual effect.

The present invention provides a smoking agent composition having the following constitution.
[1] (A) component: pest control component, (B) component: 4-isopropyl-3-methylphenol, (C) component: ascorbic acid compound, and (D) component: hydroxyethyl cellulose, hydroxyethyl methyl cellulose, A smoking agent composition containing hydroxypropyl cellulose, hypromellose, carmellose and salts thereof, carboxyvinyl polymer, vinylpyrrolidone / vinyl acetate copolymer, at least one selected from the group consisting of povidone, polyvinyl alcohol and starch. .
[2] The smoke agent composition according to [1], which does not contain a self-reactive combustion agent.
[3] The smoking agent composition according to [1] or [2], wherein the mass ratio B / A of the component (B) to the component (A) is 1/10 to 25/1.
[4] The smoking agent composition according to any one of [1] to [3], wherein the content of the component (C) is 1 to 40% by mass.
[5] The smoking agent composition according to any one of [1] to [4], which is a granule.

  INDUSTRIAL APPLICABILITY The smoke agent composition of the present invention has a high smoke conversion rate of the pest controlling component even when it is stored for a long period of time, and has an excellent residual effect.

In the present invention, the “granule” means a No. 3.5 sieve (opening size 5.60 mm) when 25 to 100 g is sieved according to the second method “sieving method” of the Japanese Pharmacopoeia. It means the agent that has passed and remains on the No. 16 sieve (opening size 1.0 mm).
The “powder” means an agent which passes through No. 18 sieve (opening size 850 μm) when 25 to 100 g is sieved according to the second particle size measurement method “sieving method” of the Japanese Pharmacopoeia.
The "self-reactive combustion agent" is an agent capable of volatilizing the component (A) and the like by its combustion heat. Examples of the self-reactive combustor include nitrocellulose, azodicarbonamide, p, p'-oxybis (benzenesulfonylhydrazide), N, N'-dinitrosopentamethylenetetramine and the like.

  The smoke agent composition of the present invention is a smoke agent composition containing components (A) to (D) described below. The smoking agent composition of the present invention is a heating type smoking agent composition in which smoke is generated by heating and the components are volatilized.

[(A) component]
The component (A) is a pest control component.
The component (A) is not particularly limited, and a component blended in a conventional smoke agent composition can be used and can be appropriately selected in consideration of the kind of harmful pests to be controlled. Specific examples of the component (A) include pyrethroid compounds, carbamate compounds, oxadiazole compounds, neonicotinoid compounds and the like. As the component (A), phenothrin, permethrin, pyrethrin, methoxadiazone, etofenprox, d.dT-cyphenothrin, propoxur, and dinotefuran are preferable.
As the component (A), one type may be used alone, or two or more types may be used in combination.

  The blending amount of the component (A) can be appropriately set according to the target pest, and is preferably 0.5 to 20% by mass, and preferably 1 to 10% by mass, based on the total mass of the smoking agent composition. When the blending amount of the component (A) is at least the lower limit value, the pest control effect can be easily obtained. When the blending amount of the component (A) is not more than the upper limit value, the blending amounts of the components (B) to (D) can be relatively increased, so that the smoke generation rate of the component (A) tends to be high. The residual effect is also improved.

[(B) component]
The component (B) is 4-isopropyl-3-methylphenol (IPMP). The component (B) has a function of volatilizing into white smoke together with the component (A) by heating and then settling and adhering to the room, thereby increasing the residual rate of the component (A) after the settling. That is, by blending the component (B) in the smoke agent composition, the residual effect of the component (A) after smoke treatment is improved, and the pest control effect lasts longer. Further, the component (B) also plays a role of improving the temporal stability of the component (C) in the smoke agent composition.
As the component (B), for example, IPMP of a grade usually used in cosmetics, quasi-drugs, miscellaneous goods and the like can be used.

The blending amount of the component (B) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass, based on the total mass of the smoking agent composition.
When the blending amount of the component (B) is at least the lower limit value, the residual effect of the component (A) after smoking is improved, and the effect is easily maintained for a long period of time. When the blending amount of the component (B) is not more than the upper limit value, sufficient granulation property during granule production can be easily obtained, and the granule can be produced more stably. Further, since the amount of heat required for smoking is prevented from becoming too high, the smoke conversion rate of the component (A) is improved.

  The mass ratio B / A of the component (B) to the component (A) is preferably 1/10 to 25/1, more preferably 1/1 to 10/1, still more preferably 2/1 to 8/1. When the mass ratio B / A is within the above range, the residual effect of the component (A) is further improved.

[(C) component]
The component (C) is an ascorbic acid compound. By blending the component (C) in the smoke agent composition, the initial smoke rate of the component (A) is improved. In addition, since the visibility at the time of smoking becomes good, it becomes easy for the user to recognize that smoking has started.

The ascorbic acid compound includes ascorbic acid and its isomers, ascorbic acid and its isomer derivatives, and ascorbic acid and its isomer salts. Examples of the isomer of ascorbic acid include erythorbic acid.
As the derivative of ascorbic acid and its isomer, those generally proposed as vitamin C derivatives can be used, and examples thereof include higher fatty acid esters, phosphoric acid esters, and sulfuric acid esters of ascorbic acid or erythorbic acid. As the higher fatty acid, a fatty acid having 16 to 18 carbon atoms such as palmitic acid and stearic acid is preferable.
Examples of salts of ascorbic acid and its isomers include sodium salt, calcium salt, potassium salt, magnesium salt, phosphate salt, and sulfate salt.

Specific examples of the component (C) include, for example, ascorbic acid, sodium ascorbate, disodium ascorbate phosphate, magnesium ascorbate phosphate, disodium ascorbate sulfate, ascorbate glucoside, and ascorbyl monopalmitate, Examples thereof include ascorbyl dipalmitate, ascorbyl monostearate, erythorbic acid, and sodium erythorbate. Among them, as the component (C), ascorbic acid, sodium ascorbate, and magnesium ascorbyl phosphate are preferable, and ascorbic acid is particularly preferable, from the viewpoint of the smoke generation rate of the component (A).
As the component (C), one type may be used alone, or two or more types may be used in combination.

  The blending amount of the component (C) is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and further preferably 5 to 30% by mass, based on the total mass of the smoke agent composition. When the blending amount of the component (C) is at least the lower limit value, the smoke generation rate of the component (A) tends to be sufficiently high, and thus the pest control effect is likely to be sufficiently exerted. When the blending amount of the component (C) is at most the upper limit value, the granulation property during granule production tends to be sufficiently high, and the granules can be produced more stably.

[(D) component]
The component (D) plays a role of improving the residual effect of the component (A) after the smoke treatment. Further, the component (D) makes it easier to form the smoke agent composition into granules, and the smoke conversion rate of the component (A) becomes higher.

The component (D) is selected from the group consisting of hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hypromellose, carmellose and salts thereof, carboxyvinyl polymer, vinylpyrrolidone / vinyl acetate copolymer, povidone, polyvinyl alcohol, and starch. At least one kind. Examples of salts of hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hypromellose and carmellose include sodium salt, calcium salt, potassium salt, magnesium salt, phosphate salt, sulfate salt and the like.
As the component (D), hypromellose and povidone are preferable from the viewpoint of the residual effect of the component (A).
As the component (D), one type may be used alone, or two or more types may be used in combination.

The blending amount of the component (D) is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and further preferably 1 to 5% by mass, based on the total mass of the smoke agent composition. . When the blending amount of the component (D) is at least the lower limit value, the excellent residual effect of the component (A) is likely to be obtained. In addition, the strength of the smoke agent composition tends to be sufficiently high, and it becomes easy to prepare a granule. When the blending amount of the component (D) is at most the upper limit value, granulation of the smoke agent composition will be easy.
In addition, the total compounding quantity of (A)-(D) component does not exceed 100 mass%.

[Arbitrary ingredients]
The smoke agent composition of the present invention may contain optional components in addition to the components (A) to (D). As the optional component, a known component used in the smoke agent composition can be used, and examples thereof include a fragrance, a surfactant, an excipient, an exothermic aid, a stabilizer, a potency enhancer, and an antioxidant. Can be mentioned.
As the optional component, one type may be used alone, or two or more types may be used in combination.

  The smoke agent composition of the present invention preferably does not contain a self-reactive combustion agent, since it has little effect on household goods and metal products and can suppress pollution after smoke treatment. Further, the self-reactive combustion agent may be contained as long as white precipitates are accumulated after the treatment so as not to pollute the inside of the room. The content of the self-reactive combustion agent may be the total amount of the smoke agent composition. 15 mass% or less is preferable with respect to mass, 10 mass% or less is more preferable, and 5 mass% or less is still more preferable.

[Granule]
The smoke agent composition of the present invention is preferably a granule from the viewpoint of the smoke generation rate of the component (A). When the smoke agent composition is made into granules, the agent becomes denser as compared with the case where it is made into a powder, heat is more easily transferred, and the temperature is raised efficiently, so that the smoke generation rate becomes higher. The smoking agent composition of the present invention may be in the form of powder.

When the smoke agent composition of the present invention is used as a granule, the average particle diameter is preferably 1 to 5 mm, more preferably 2 to 4 mm. If the average particle diameter is not less than the lower limit value, the smoke generation rate of the component (A) tends to be higher. When the average particle diameter is not more than the upper limit value, it is easy to granulate as a granule.
The average particle diameter is measured by the weight remaining on the sieve of each opening size, which is obtained by classifying 25 to 100 g through a sieve according to the second method of the Japanese Pharmacopoeia, “Sieving method”.

[Production method]
The method for producing the smoke agent composition of the present invention is not particularly limited, and, for example, the components (A) to (D) and, if necessary, optional components are mixed in a predetermined amount. When the smoke agent composition of the present invention is made into a solid preparation such as powder, granules, tablets, etc., a known production method can be adopted depending on the dosage form. For example, when the smoke agent composition of the present invention is used as granules, known granulation methods such as extrusion granulation method, compression granulation method, stirring granulation method, tumbling granulation method, fluidized bed granulation method, etc. The method can be adopted.

  In the case of the extrusion granulation method, for example, the components of the smoke agent are mixed by a kneader or the like, and an appropriate amount of solvent is further added and kneaded. Next, the obtained kneaded product is granulated using a pre-extrusion granulator or a lateral extrusion granulator equipped with a die having openings of a certain area, and dried. The obtained granulated product may be cut into a certain size using a cutter or the like before drying if necessary.

Examples of the solvent include water; alcohols such as ethanol, propanol and benzyl alcohol; paraffins such as liquid paraffin and n-paraffin; ethers such as butyldiglycol; esters such as isopropyl myristate; Examples thereof include polyhydric alcohol; N-methylpyrrolidone; propylene carbonate and the like.
As the solvent, one type may be used alone, or two or more types may be used in combination.

  The drying temperature may be appropriately determined depending on the solvent. For example, when water is used, it is preferably 60 to 90 ° C.

[how to use]
The method of using the smoke agent composition of the present invention is not particularly limited, and known methods can be used. Specifically, for example, a method of storing a smoke agent composition in an arbitrary container such as a metal container and a ceramic container, and starting the smoke treatment by indirectly heating the smoke agent composition is a method. Can be mentioned.

Examples of the method of indirectly heating the smoke agent composition include a method of housing the smoke agent in a metal container and heating the smoke agent through the metal container. As a heating method, a conventionally known method can be used, and examples thereof include the following method (a) and method (b), and the method (a) is preferable from the viewpoint of practicality.
(A) A method of utilizing a reaction heat by bringing a substance which is in contact with water and generates heat into contact with water.
(B) A method of mixing iron powder and an oxidizing agent (ammonium chlorate or the like), or a metal and a metal oxide or an oxidizing agent having a smaller ionization tendency than the metal, and utilizing the heat of oxidation reaction.

  Examples of the substance that generates heat upon contact with water include calcium oxide, magnesium chloride, aluminum chloride, calcium chloride, iron chloride and the like. Of these, calcium oxide is preferable.

The amount of the smoking agent composition used in one smoking treatment may be appropriately set according to the volume of the target space, preferably 0.1 to 5 g per 1 m ³ , and 0.5 to 3.5 g. More preferable.

[Effect]
In the smoke agent composition of the present invention described above, since the component (C) is combined with the component (A), the initial smoke rate of the component (A) is high and the storage period is long ( A sufficient smoke rate of the component A) is secured. Further, since the component (B) and the component (D) are further combined, the residual effect is excellent, and the component (A) is likely to remain after the smoke treatment, so that the pest control effect is likely to last for a long period of time. . Further, since the smoke agent composition of the present invention ensures a sufficient smoke conversion rate without blending a self-reactive combustion agent, it is possible to suppress pollution after smoke treatment.
From these, the smoke agent composition of the present invention, the generation of flammable gas in a closed state, to suppress the generation of dirt due to dust, and the provision of a preventive pest control effect is more desired. It is particularly effective for applications in small spaces such as tall, closets, and closets that are smaller than 6 tatami mats.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following description.
[Materials used]
The raw materials used in this example are shown below.
(Component (A))
Phenothrin: Product name "Smithlin", manufactured by Sumitomo Chemical Co., Ltd.
d-d-T-cyphenothrin: trade name "Gokirat S", manufactured by Sumitomo Chemical Co., Ltd.
Methoxadiazone: Product name "Elemic", manufactured by Sumitomo Chemical Co., Ltd.

(Component (B))
IPMP: 4-isopropyl-3-methylphenol, trade name "isopropylmethylphenol", manufactured by Osaka Kasei.

(Component (C))
VC: trade name "ascorbic acid", manufactured by BASF Japan Ltd.
VC-Na: trade name "sodium ascorbate", manufactured by Wako Pure Chemical Industries.

((D) component)
HPMC: Hypromellose, trade name "Metroses 60SH-50", manufactured by Shin-Etsu Chemical Co., Ltd.
PVP: Povidone, trade name "Polyvinylpyrrolidone K60", manufactured by Tokyo Chemical Industry.

(Combustion agent)
ADCA: Product name “Vinihall AC # 3-K7”, manufactured by Eiwa Chemical Industry.

(Excipient)
Clay: Product name "AX Kaolin", manufactured by Kanaya Kosan Co., Ltd.

[Example 1]
A predetermined amount of each component was weighed out in the proportions shown in Table 1, and sufficiently stirred and mixed by a kneader (S5-2G type manufactured by Moriyama). Next, 5% by mass of water was added to the mixture to knead them, and after granulating using a granulator having a die diameter of 2 mm (EXK-1 manufactured by Fuji Paudal Co., Ltd.), a dryer ( A smoking agent composition was obtained by drying at 80 ° C. for 2 hours with an RT-120HL manufactured by Alp.

[Examples 2 to 14]
A smoking agent composition was obtained in the same manner as in Example 1 except that the composition was changed as shown in Tables 1 and 2. The smoking agent compositions obtained in Examples 2 to 13 were granules, and the smoking agent compositions obtained in Example 14 could not be granulated and were in powder form.

[Comparative Examples 1 to 4]
A smoking agent composition was obtained in the same manner as in Example 1 except that the composition was changed as shown in Table 3. The smoking agent composition obtained in Comparative Examples 1, 2 and 4 was a granule, and the smoking agent composition obtained in Comparative Example 3 was a powder which could not be granulated.

[Manufacture of smoke type insecticide]
A metal can used for "Begin with water, Balsan 6-8 tatami mat" manufactured by Lion Co., Ltd. was prepared, and 5 g of the smoke agent composition immediately after the production of each example was filled in the smoke agent filling portion of the metal can, 50 g of calcium oxide was filled in the exothermic agent-filled portion to obtain a smoke-type insecticidal device.

[Smoke rate]
18 mL of water was put into a plastic cup having a diameter of 8 cm and a height of 4 cm, and the cup was placed at the center of the floor of a closed test chamber having an internal volume of 6.38 m ³ . Next, a smoke type insecticidal device was installed in the cup, the bottom surface was exposed to water, and the smoke treatment was started. Five minutes after the white smoke was generated, the air in the test chamber was stirred for 1 minute by a fan (manufactured by ORIX, MU1238A-11B). After the stirring, 20 L of air in the test chamber was passed through the recovery column using a vacuum pump to adsorb the smoked components in the test chamber. Silica gel for chromatography (Wakogel C-100, manufactured by Wako Pure Chemical Industries, Ltd.) was used for the recovery column. Next, 100 mL of acetone was passed through the recovery column to extract the adsorbed components, and the extraction solution was recovered in a 200 mL eggplant flask. Then, the extraction solution was completely evaporated to dryness with an evaporator (manufactured by Yamato Scientific Co., RE-46), and then an internal standard solution was added and dissolved to obtain a sample solution. The amount W ₁ (g) of the component (A) in the sample solution (in the collected indoor air) was quantified by gas chromatography (GC) to determine the amount W _{2 of the} component (A) in the smoking agent composition. From (mass%), the smoke rate was calculated by the following formula.
Smoke rate (%) = [W ₁ (g) / 20 (L)] × [100 / {5 (g) × W ₂ (mass%)}] × 6380 (L) × 100

For Kemurika rate, and Kemurika rate to Q ₁ smoke type insecticidal apparatus immediately after manufacturing, in a state sealed in a bag body made of aluminum used in manufactured by Lion Corporation "start with water Varsan 6-8 mats for" The smoke conversion rate Q ₂ of the smoke type insecticidal device after storage in a constant temperature bath at 50 ° C. for 1 month was measured. The smoke retention rate was calculated by the following formula and evaluated according to the following criteria.
Smoke rate maintenance rate (%) = [Q ₂ (%) / Q ₁ (%)] × 100
(Evaluation criteria)
⊚: The smoke rate maintenance rate is 90% or more.
◯: Smoke rate maintenance rate is 80% or more and less than 90%.
Δ: The smoke rate maintenance rate is 60% or more and less than 80%.
(Triangle | delta): The maintenance rate of smoke generation rate is 40% to less than 60%.
X: The smoke rate maintenance rate is less than 40%.
In addition, those having a smoke retention rate of 80% or more (⊚ and ◯) were judged to be good.

[Residual effect (floor settling amount)]
Two glass petri dishes for measuring sedimentation were placed side by side on the floor of a closed test chamber equivalent to 8 tatami mats. Separately, 18 mL of water was placed in a plastic cup having a diameter of 8 cm and a height of 4 cm, and the cup was placed in the center of the floor surface of the closed test chamber. Next, a smoke type insecticidal device was installed in the cup, the bottom surface was exposed to water, and the smoke treatment was started. After the sealed test chamber was closed for 2 hours after the generation of white smoke, two glass petri dishes for sedimentation measurement were collected.
Of the two glass petri dishes, the components settled in one glass petri dish were dissolved in 100 mL of acetone and collected in a 200 mL eggplant flask. Then, the solution was completely evaporated to dryness by an evaporator (RE-46, manufactured by Yamato Scientific Co., Ltd.), and then an internal standard solution was added and dissolved to obtain a sample solution. The sedimentation amount W ₃ (mg) of the component (A) in the sample solution was quantified by gas chromatography (GC). Further, the other glass petri dish was allowed to stand at room temperature (25 ° C.) for 2 weeks, and then the sedimentation amount W ₄ (mg) of the component (A) in the sample solution was quantified in the same manner as above.

The maintenance rate of the sedimentation amount was obtained by the following formula and evaluated according to the following criteria.
Maintenance rate of sedimentation amount (%) = [W ₄ (mg) / W ₃ (mg)] × 100
(Evaluation criteria)
⊚: The retention rate of sedimentation amount is 50% or more.
◯: The maintenance rate of sedimentation amount is 40% or more and less than 50%.
(Triangle | delta): The maintenance rate of sedimentation amount is 30% or more and less than 40%.
X: The maintenance rate of the sedimentation amount is less than 30%.
In addition, those with a retention rate of sedimentation amount of 50% or more (⊚ or ◯) were judged to have good residual effect.

[Indoor pollution]
Two hours after the start of smoking in the above-mentioned residual effect test, the glass petri dish installed on the floor of the closed test chamber was visually inspected, and indoor contamination was evaluated according to the following evaluation criteria.
(Evaluation criteria for indoor pollution)
⊚: No difference in surface condition is confirmed as compared with the glass petri dish before smoking.
◯: There is almost no difference in surface condition compared to the glass petri dish before smoking.
Δ: Compared with the glass petri dish before smoking, some contamination can be seen, but the difference is difficult to understand.
X: Contamination can be easily discriminated and adhesion of stains is obvious as compared with a glass petri dish before smoking.

  Tables 1 to 3 show the composition of the smoke agent composition of each example and the evaluation results of the smoke generation rate and the residual effect.

  As shown in Tables 1 to 3, in the smoke agent compositions of Examples 1 to 14 containing components (A) to (D), Comparative Example 1 containing no components (B) to (C). As compared with the smoking agent compositions of Nos. 4 to 4, the smoke retention rate of the component (A) was high, and the residual effect was also excellent. Further, the smoking agent compositions of Examples 1 to 14 were also suppressed from polluting the room after use.

Claims (5)

(A) component: pest control component,
(B) component: 4-isopropyl-3-methylphenol,
Component (C): Ascorbic acid, sodium ascorbate, disodium ascorbate phosphate, magnesium ascorbate phosphate, disodium ascorbate sulfate, ascorbate glucoside, ascorbyl monopalmitate, ascorbyl dipalmitate, monostearin. Acid ascorbyl, erythorbic acid, at least one selected from the group consisting of sodium erythorbate ,
And component (D): selected from the group consisting of hydroxyethyl cellulose, hydroxyethylmethyl cellulose, hydroxypropyl cellulose, hypromellose, carmellose and salts thereof, carboxyvinyl polymer, vinylpyrrolidone / vinyl acetate copolymer, povidone, polyvinyl alcohol, and starch. A smoke agent composition containing at least one of the following:   The smoke agent composition according to claim 1, which is free of self-reactive combustion agents.   The smoking agent composition according to claim 1 or 2, wherein the mass ratio B / A of the component (B) to the component (A) is 1/10 to 25/1.   The smoke agent composition according to any one of claims 1 to 3, wherein the blending amount of the component (C) is 1 to 40% by mass.   The smoke composition according to any one of claims 1 to 4, which is a granule.