JPH0774130B2 - Liquid type heat-penetrating insecticide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to an aqueous insecticide for liquid heat evaporation, which is applied to a system in which an insecticide is evaporated by heating at 100 to 180 ° C.

[Conventional technology]

Heretofore, (1) so-called mosquito coil and (2) electric mosquito mat have been popular as a method for heating and evaporating a drug for the purpose of insecticidal action.

In recent years, the method of dipping a porous liquid-wicking core in a drug solution and heating the upper part of the core to heat and evaporate the drug does not require replacement of a mat or the like each time, and the effect is stable for a long time. It has been receiving attention again for the reason.

This method has been known for quite some time, for example
Although the method of direct heating is described in Japanese Patent Laid-Open No. 432501/25081, the method of indirect heating generally tends to be adopted since the decomposition of the drug is severe in the case of direct heating. As an indirect heating method, a method of heating by interposing a felt or the like between the liquid absorption core and the heating element is used.
No. 12459, JP-B No. 46-22585, and a method of heating the absorbent core and the heating element with a certain distance from each other is JP-B-43-26274, JP-B-44-8361, It is described in JP-B-45-14913 and JP-B-45-29244.

However, the thing at that time had a difficulty in the above-mentioned sustainability due to the clogging of resin etc., and as a result, its advantage was not recognized and it was not accepted in the market compared with the above-mentioned mosquito coil and mosquito mat. Was there.

Recently, a heat evaporation method using this type of absorbent core has been actively developed, and various proposals have been made regarding drug formulation and improvement of material and composition of the absorbent core. For example, Japanese Patent Publication Sho 61-23
Japanese Patent No. 163 discloses a drug prepared by dissolving allethrin or an isomer thereof as an insecticide in a hydrocarbon solvent having a specific high boiling point range, and JP-A-63-48201 discloses the number of carbon atoms. 12 to 18 aliphatic hydrocarbons with pesticides
Attempts have been described to incorporate antioxidants that do not substantially evaporate at heating temperatures of 110-140 ° C.

Although these conventional chemical agents for heating and evaporation have some tentative results in terms of transpiration and usability, they are all oil-based oils, and they are highly flammable and can avoid the danger of fire. The current situation is that there are none.

[Problems to be Solved by the Invention]

The present invention has been made for the purpose of eliminating the risk of the conventional heat-evaporating agent against fire, and providing a liquid heat-evaporating agent which is excellent in all aspects such as transpiration property, insecticidal effect, and safety for humans and animals. It is a thing.

[Means for Solving the Problems]

As a result of intensive studies conducted by the present inventors to achieve the above-mentioned object, it was found that, surprisingly, an aqueous insecticide containing a specific surfactant instead of an oil agent can be preferably used. Completed the invention.

By the way, as an aqueous insecticide containing a pyrethroid, some spray preparations have already been developed, but they have been put into practical use only in Japan. Moreover,
Its active ingredient is limited to phenothrin and permethrin, and surfactants such as polyoxyethylene polystyryl phenyl ether and alkylbenzene sulfonate that are mixed in these preparations are generally non-volatile and 100-180
None of them evaporated when heated to ℃. From such a situation, it has been generally considered that when an aqueous insecticide is used for heat evaporation, the aqueous insecticide loses its balance and cannot perform its evaporation function.

However, the present inventors have paid attention to a low boiling point surfactant,
When a heat transpiration test was carried out by preparing an aqueous insecticide using these, it can be said that the transpiration of the active ingredient can be maintained constant for a long period of time without disturbing the balance of the composition of the ingredients, especially in the method using the absorbent core. It became clear.

That is, the present invention provides (a) a pyrethroid compound as an active ingredient in an amount of 0.3 to 10.
0% by weight, (b) 1 of the surfactant that evaporates at a heating temperature of 100-180 ℃
The present invention relates to an aqueous pesticide for heat-evaporation, which comprises 10.0 to 70.0% by weight of one or more kinds and (c) water.

As an active ingredient of the liquid insecticide for liquid heat evaporation of the present invention, a pyrethroid compound is used from the viewpoint of safety, and 0.3 to 10.0% by weight is compounded alone or in combination.

For example, the following insecticides can be exemplified, but of course the invention is not limited thereto.

a) d1-3-allyl-2-methylcyclopent-2-en-4-one-1-yl d-cis / trans-chrysanthemate (trade name; pinamine forte: manufactured by Sumitomo Chemical Co., Ltd.) b ) (S) -2-Methyl-4-oxo-3- (2-propynyl) cyclopent-2-enyl d-cis / trans-chrysanthemate (generic name; plaresulin) c) 5-propargyl-2-furylmethyl d-cis /
Trans-chrysanthemate (trade name; Pinamine D Forte: manufactured by Sumitomo Chemical Co., Ltd.) d) 1-ethynyl-2-methyl-2-pentenyl d-
Cis / trans-chrysanthemate (generic name; empentrin) e) d-3-allyl-2-methylcyclopent-2-en-4-on-1-yl d-trans-chrysanthate (trade name; exulin) : Manufactured by Sumitomo Chemical Co., Ltd.) f) 5-benzyl-3-furylmethyl d-cis / trans-chrysanthate (trade name; Krislon Forte: manufactured by Sumitomo Chemical Co., Ltd.) g) 3-phenoxybenzyl d-cis / trans-chrysanthemate (generic name; phenothrin) h) 3-phenoxybenzyl 2,2-dimethyl-3-
(2,2-Dichlorovinyl) cyclopropanecarboxylate (generic name; permethrin) i) 3-allyl-2-methyl-cyclopent-2-en-4-one-1-yl 2,2,3,3-tetra Methylcyclopropanecarboxylate (generic name; terrareslin) j) 1-ethynyl-2-methyl-2-pentenyl 2,2
-Dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate k) 3-phenoxybenzyl 2- (4-ethoxyphenyl) -2-methylpropyl ether (generic name; etofenprox) l) dimethyl (4 -Ethoxyphenyl) {3- (3-
Phenoxy-4-fluorophenyl) propyl} silane m) 2-methyl-2- (4-ethoxyphenyl) -5
-(3-phenoxy-4-fluorophenyl) pentane Among these, the insecticides a) to d) are preferable in terms of their industrial availability, efficacy, safety and transpiration property, and among them, the insecticide c) is excellent. There is.

The present invention comprises 10.0 to 70.0% by weight of one or more surfactants which evaporate at the heating temperature of 100 to 180 ° C. in the above insecticide.
It is characterized by adding water and water to form an aqueous insecticide.

Among the above surfactants, preferred ones have a boiling point of 250 mm or less at 5 mmHg and / or the following conditions: Detector: Flame ionization type detector Separation tube: Silane-treated 125-150 μm gas chromatograph Diatomaceous earth coated with methyl silicon polymer at a ratio of 5% and packed in a glass column with an inner diameter of about 3 mm and a length of about 1 m Separation tube temperature; Operate the gas chromatograph at a constant temperature around 140 ° C to perform pyrethroid. When the retention time of the compound d1-3-allyl-2-methylcyclopent-2-en-4-one-1-yl d-cis / trans chrysanthemate was adjusted to 50 minutes, the main peak The retention time is within 80 minutes.

Incidentally, the surfactant in the present specification means one capable of stably maintaining a pyrethroid compound in an emulsified state in water or in a solubilized state regardless of the presence or absence of micelle formation,
In a broad sense, it also includes a solvent that is compatible with water and oil.

In general, the solubilized type aqueous insecticide is less likely to cause liquid phase separation and the like in comparison with the emulsified type and is superior in usability, and thus is suitable for the present insecticidal method.

Following formula I Suitable surfactants in the present _{invention: R-O- (C 3 H} 6 O) m (C 2 H 4 O) in n · H (I) (wherein, R 1 to 8 carbon atoms Represents an alkyl group of
And n represent an integer of 0 to 6. However, m + n is 1
It is an integer of 8. ) A nonionic polyoxyalkylene alkyl ether compound represented by the following formula II: (In the formula, R ′ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m and n represent an integer of 0 to 6, and m + n is an integer of 1 to 6.) Nonionic polyoxyalkylene phenyl ether compounds, and further the following formula III: R—COO— (CH ₂ CH ₂ O) _n · H (III) (wherein R and n have the same meanings as described above). A polyoxyethylene fatty acid ester represented by the following formula IV or
V: (Wherein R represents the same meaning as described above), and a polyhydric alcohol fatty acid partial ester represented by the following formula VI: (In the formula, 1, m and n represent an integer of 0 to 8, where 1 + n is an integer of 1 to 8.) polyoxyethylene polyoxypropylene glycol or polyoxyethylene polyhydric alcohol fatty acid Examples thereof include partial esters and fatty acid alkylolamides, but are not limited thereto.

Particularly preferred surfactants are those of the above formulas I and II, in which R represents an alkyl group having 3 to 8 carbon atoms, R'represents a hydrogen atom, and when either m or n is 0, the other is An integer of 2 to 5, or both m and n represent an integer of 2 or 3, which have sufficient solubilizing ability and are not so high in viscosity, and among these surfactants, Some of them, such as polyoxyethylene butyl ether (n = 2), are repellent to mosquitoes and are excellent in usability.

In ordinary production, it is obtained as a mixture of compounds having different degrees of polymerization, and m and n are often expressed as an average number of moles, but it goes without saying that both single products and mixtures are included in the present invention. .

In addition, if necessary, to the extent that these surfactants do not impair the characteristics of the present invention, a small amount of a cationic surfactant,
An anionic surfactant, a zwitterionic surfactant or an organic solvent may be blended.

Furthermore, the liquid insecticide for liquid heat evaporation of the present invention, if necessary, other insecticidal components such as organic phosphorus agents, carbamate agents,
Ingredients such as bactericides and repellents, or organic solvents such as stabilizers, synergists, dyes, fragrances or auxiliaries may be added as appropriate.

The liquid type heat-penetrating insecticide of the present invention thus obtained is applied to a method of evaporating the insecticide by heating at 100 to 180 ° C., but in particular, a part of the porous liquid absorbent core is contained in the chemical solution. It is suitable for a system in which the drug is absorbed by the immersion and the upper part of the core is heated to evaporate the absorbed drug.

As the heating method, either direct heating or indirect heating can be applied, but in consideration of the decomposition loss of the drug and the like, indirect heating is preferred. The first specific example applied to this method
Shown in the figure.

The water-based insecticide 1 of the present invention is injected into a plastic pharmaceutical liquid container 2 having excellent chemical resistance such as polypropylene, PET, polyvinyl chloride, etc., and after holding the liquid-absorbing core 3 in a hermetically sealed state via a suitable holder. It is stored in the heating evaporation device 4.

As a shape of the chemical liquid container 2, a cylindrical shape has been generally used, but for example, a recess is formed in the bottom,
If a groove or streak is provided on the cylindrical surface, or if it has a polygonal shape, it can be easily grasped by hand, and the storage operation in the evaporation device 4 can be performed easily, which is convenient.

In addition, the liquid absorbent core 3 is made of an inorganic substance such as calcium carbonate, magnesia, clay, talc, kaolin, diatomaceous earth, stone porcelain, porcelain substance, or an organic substance such as heat-resistant polymer substance, wood powder, pulp carbon powder, activated carbon or the like. It is possible to use a powder obtained by firing or hardening it with an appropriate binder, or a material such as felt, non-woven fabric, asbestos, wood, bamboo, etc., which allows liquid to flow through by a capillary phenomenon, etc. And is held in the liquid medicine container 2 in the form of a sealed plug.

Since the aqueous insecticide 1 of the present invention uses a surfactant having a relatively low boiling point, unlike the conventional surfactant, even if it is dipped in the absorbent core and allowed to absorb the liquid, the surfactant remains in the core. It has become clear that there is no risk of causing the accumulation of liquor, and thus the risk of causing problems such as separation of chemicals and clogging is small.

As a conventional method for storing the liquid medicine container 2 loaded with the liquid absorbent core 3 in the heating evaporation device 4, it is of course possible to mount the liquid medicine container 2 on this by providing a screw-on bottom lid as in the conventional method. Although it does not matter, the method of screwing the screw part engraved on the upper side of the drug solution container 2 into the holder provided inside the device can fix the drug solution container 2 to the device 4 more firmly than the former, preferable. Reference numeral 5 is a heating element installed around the heat receiving portion of the liquid absorbent core 3 with a gap, and 6 is a power cord connected to the heating element 5.
A so-called cordless type in which the plug terminal is fixed to the device 4 may be used, or a storage chamber for storing the power cord may be separately provided in the device 4. Reference numeral 7 is a protective cap placed on top of the heating element 5, which is preferably attached for safety. A transpiration port 8 is formed in the central portion, but its size and shape are arbitrary as long as the transpiration chemical solution is not excessively condensed and attached to the protective cap 7 or the device 4.

Further, the heating evaporation device is appropriately provided with a vent hole 9 so that the outside air can communicate with the outside through the gap between the heat receiving part of the liquid absorbent core 3 and the heating element 5.

The position of the vent hole 9 may be either the trunk or the bottom,
The bottom portion is more preferable in that a chimney-type action and effect that provides a stable evaporation function and a high drug diffusion force can be expected.

When the liquid insecticide 1 for liquid heating and evaporation of the present invention is applied to the above heating and evaporation device 4 and used with electricity, the insecticide 1 that has penetrated into the heat receiving portion of the liquid absorbent core 3 is indirectly heated by the heating element 5 and evaporated.
It exhibits an extremely high control effect against mosquitoes, flies, cockroaches, bed bugs, mites and the like.

Further, since the chemical solution of the present invention is an aqueous insecticide, it eliminates the danger of fire, unlike the conventional ones, and is very excellent in terms of odor and usability.

[Examples] Hereinafter, the present invention will be described based on Examples, but the present invention is not limited thereto.

Example 1 d1-3-allyl-2-methylcyclopent-2-ene-
4-on-1-yl d-cis / trans-chrysanthemate 1.5 parts, BHT 0.3 parts by blending the surfactant shown in the following Table 1 and dissolving, and then adding deionized water to the liquid water for heat evaporation An insecticide was prepared, and the properties and transpiration performance of the solution were investigated. The results are shown in Table 1.

As a control, the same test was performed using kerosene (having 13 to 15 carbon atoms) instead of the surfactant and water.

1) Properties of solution; separation of liquid phase, generation of turbidity, etc. were observed.

○: clear solution with no liquid phase separation △: slightly turbid solution with liquid phase separation 2) Evaporation performance: 35 g of the chemical solution was poured into a plastic bottle and diatomaceous earth was obtained by absorption. After loading the liquid core, the liquid core was set in the heating evaporation device (heating element temperature 135 ° C.) shown in FIG. The electricity was supplied for 12 hours every day, and the amount of drug transpiration was measured daily.

○: The amount of drug transpiration is constant Δ: The amount of drug transpiration slightly decreases over the course of time ×: The amount of drug transpiration sharply decreases over the course of day 3) N.D.

As a result of the test, when a high boiling point surfactant is used, or when 70% or more of the surfactant used in the present invention is blended, the amount of transpiration sharply decreases with time. There was a problem with the evaporation performance.

On the other hand, regarding the aqueous insecticide of the present invention, it can be said that it is more useful than the conventional agents based on kerosene in view of the fact that there is no particular problem with the properties of the solution and the transpiration performance and there is no flammability.

FIGS. 2 and 3 show the results of a gas chromatographic test conducted on some of the pyrethroid compounds and surfactants used in the present invention under the following conditions.

FIG. 2 shows a constant temperature condition and FIG. 3 shows a temperature rising condition.
C (Pinamine Forte), D (Pinamine Forte),
F (praresulin) is a pyrethroid compound, A (polyoxyethylene butyl ether, n = 2), B (polyoxyethylene hexyl ether, n = 3), E (polyoxyethylene octyl ether, n = 4) are used in the present invention. It is a suitable surfactant. However, for commercially available surfactants in which n is represented as the average number of moles, the main peak position corresponding to the fraction of the average number of moles is shown.

Constant temperature condition [Fig. 2] Detector: Hydrogen flame ionization type detector Separation tube: Glass column with inner diameter of about 3 mm and length of about 1 m filled with Chromosolve W impregnated with SE-30 at 5% packing Separation Tube temperature; constant temperature around 140 ° C As shown in Fig. 2, the vapor pressure was higher when the heat-evaporable pyrethroid pinamine forte (D) was adjusted to hold for about 50 minutes. The retention time of Pinamine D Forte (C) was about 30 minutes, and that of Praresulin (F), which had a slightly lower heat transpiration property than Pinamine Forte (D), was about 60 minutes.

When SE-30 is used as the packing material, it is generally said that the order of retention time corresponds to the boiling point (low → high) of the compound, and the boiling point of pinamine forte is about 190 ° C / 5mmH.
It is g.

On the other hand, the retention time of the polyoxyethylene butyl ether (n = 2), polyoxyethylene hexyl ether (n = 3), and polyoxyethylene octyl ether (n = 4) used for the aqueous insecticide of the present invention are respectively About 2
Min, approx. 10 min, approx. 50 min.
It was within 80 minutes.

Temperature rising conditions [Fig. 3] Detector, separation tube; same as constant temperature conditions Separation tube temperature: 100 ° C (maintained for 10 minutes) 100 to 260 ° C (heating rate of 3 ° C per minute) 260 ° C (maintained for 30 minutes) As shown in FIG. 3, when the holding operation of the pinamine forte (D) was adjusted to about 40 minutes under the temperature rising condition, the holding time of each compound was closer to that of the constant temperature condition of, The retention time of Pinamine D Forte (C) is about 35 minutes,
Praresulin (F) was about 42 minutes.

On the other hand, polyoxyethylene butyl ether (n = 2),
The retention times of polyoxyethylene hexyl ether (n = 3) and polyoxyethylene octyl ether (n = 4) are about 5 minutes, about 25 minutes, and about 40 minutes, respectively, and the retention time of the main peak is 60 minutes. It was within the range.

That is, since the aqueous insecticide of the present invention uses a surfactant having a relatively low boiling point, it can be evaporated together with the pyrethroid compound, and there is no risk of accumulating in the absorbent core or causing a problem of clogging. Was confirmed.

Example 2 According to Example 1, an aqueous insecticide for liquid heat evaporation was prepared according to the following formulation, and the side surface of the core was heated to 120 ° C. and every predetermined time (1) insecticidal efficacy test using Culex pipiens and (2) The amount of transpiration of the insecticide was measured.

In (2), the silica gel packed column was trapped at regular intervals, the insecticide was extracted with acetone, and this was analyzed by glass chromatography.

The results are shown in Table 2. In the table, for (1) above, the initial value of the kerosene-based control drug was shown, and for (2), the initial value of each drug was 1.00, and the relative effective ratio was shown. .

As a result of the test, for the heat-transpiration aqueous insecticide of the present invention, the same transpiration performance and insecticidal efficacy as those of conventional kerosene-based agents can be obtained, and problems such as separation and clogging of the drug solution occur in the absorbent core. It was confirmed that not.

〔The invention's effect〕

As described in detail above, the water-based insecticide for liquid heating evaporation of the present invention eliminates the conventional danger of fire, and is excellent in all aspects such as transpiration property, insecticidal effect, and safety for humans and animals. Is.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view showing a specific example of a heating evaporation device suitable for applying the aqueous insecticide of the present invention. In the figure, 1 ... Aqueous insecticide for liquid heating evaporation 2 ... Chemical container, 3 ... Liquid absorption core 4 ... Heating evaporation device, 5 ... Heating element, 6 ... Power cord, 7 ... Protective cap 8 ... Evaporation port, 9 ... Vent port FIGS. 2 and 3 are graphs showing some gas chromatograms of the pyrethroid compound and the surfactant used in the present invention. FIG. FIG. 3 shows the temperature rising conditions. In the figure, A: polyoxyethylene butyl ether (n = 2) B: polyoxyethylene hexyl ether (n = 3) C: pinamine D forte D: pinamine forte E: polyoxyethylene octyl ether (n = 4) F ... Praresulin

Claims (5)

[Claims] (A) 0.3 to 10.0% by weight of a pyrethroid compound as an active ingredient, (b) a surfactant which evaporates at a heating temperature of 100 to 180 ° C.
A liquid type aqueous insecticide for heat evaporation, comprising 10.0 to 70.0% by weight of one or more kinds and (c) water. 2. The aqueous insecticide for liquid heat evaporation according to claim 1, wherein the surfactant to be blended has a boiling point at 5 mmHg of 250 ° C. or lower. 3. The surfactant to be blended is under the following conditions: Detector; Hydrogen flame ionization type detector Separation tube; Silane-treated 125 to 150 μm gas chromatograph diatomaceous earth containing 5% methyl silicon polymer. A glass column with an inner diameter of about 3 mm and a length of about 1 m packed with a coating of 1. Separation tube temperature; Operate the gas chromatograph at a constant temperature of around 140 ° C, and use the pyrethroid compound d1-3-allyl-2- When the retention time of methylcyclopent-2-en-4-on-1-yl d-cis / trans chrysanthemate is adjusted to 50 minutes, the retention time of the main peak is within 80 minutes. The aqueous insecticide for liquid heat evaporation according to claim 1 or 2, characterized in that. 4. The surfactant to be blended is represented by the following formula I: R—O— (C ₃ H ₆ O) _m · (C ₂ H ₄ O) _n · H (I) (wherein R is a carbon atom). Represents an alkyl group having 1 to 8 atoms, m
And n represent the integer of 0-6. However, m + n is 1
It is an integer of 6. ) 1 type or 2 types or more of the polyoxyalkylene alkyl ether type chemical compound represented by these), The water-based liquid insecticide for heat evaporation according to any one of claims 1 to 3. 5. The surfactant to be blended has the following formula II: (In the formula, R ′ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m and n represent an integer of 0 to 6, provided that m + n is an integer of 1 to 6). The polyoxyalkylene phenyl ether compound according to any one of claims 1 to 3, which is one or more polyoxyalkylene phenyl ether compounds.