JPH037207A - Aqueous insecticide for heat evaporation and method for killing insect - Google Patents

Abstract

PURPOSE:To obtain an aqueous insecticide capable of canceling danger to fire and being excellent in all respects of evaporating property, insecticidal effects, safety to man and animal, etc., by blending a pyrethroid compound with a specific surfactant. CONSTITUTION:The aqueous insecticide for heat evaporation containing 0.3-10.0wt.% pyrethroid compound which is an active ingredient, 10.0-70.0wt.% one or two or more surfactants capable of evaporating at heating temperature of 100-180 deg.C and water. As the surfactant, polyoxyalkylenealkyl ether based compound expressed by formula I (R is 1-8C alkyl; M and n are 0-6) or polyoxyalkylenephenyl ether based compound expressed by formula II (R' is H or 1-3C alkyl), etc., are preferably used. A liquid absorbing wick is partly dipped into the insecticide to absorb the liquid of insecticide into the wick and insect is killed by heating the upper part of the wick at 100-180 deg.C to evaporate insecticide. The above-mentioned method is free from danger of fire and advantageous.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an aqueous insecticide for heat transpiration, which is applied to a method of evaporating the insecticide by heating at 100 to 180° C., and an insecticidal method.

[Prior Art] Conventionally, as methods for heating and evaporating chemicals for the purpose of killing insects, etc., (1) so-called mosquito coils and (2) electric mosquito repellent mats have been popular.

In recent years, a method in which a porous liquid-absorbing wick is immersed in a drug solution and the upper part of the wick is heated to evaporate the drug has been developed. It has been attracting attention again for a number of reasons.

This method has been known for a long time, and for example, a method using direct heating is described in Utility Model Publication No. 43-25081, but since direct heating causes rapid decomposition of the drug, indirect heating is generally used. There is a tendency for this method to be adopted.

As a method using indirect heating, there is a method of heating by interposing felt, etc. between the liquid absorbent wick and the heating element, as described in Utility Model Publication No. 36-1.
No. 2459 and Utility Model Publication No. 46-22585, and a method of heating the liquid absorbing wick and heating element by separating them at regular intervals is disclosed in Utility Model II? ! It is described in Japanese Utility Model Publication No. 43-26274, Japanese Utility Model Publication No. 44-8361, Japanese Utility Model Publication No. 45-14913, and Japanese Utility Model Publication No. 45-292445.

However, the products at that time had problems with long-term sustainability due to clogging of the resin, etc., and in the end, their advantages were not recognized compared to the above-mentioned mosquito coils and mosquito repellent cloaks, and they were not accepted in the market. It ended in

Recently, the development of heating evaporation methods using this type of liquid-absorbing wick has been actively conducted, and various proposals have been made for improving drug formulations, the material and composition of the liquid-absorbing wick.
No. 23163 discloses a drug in which allethrin or its isomer is dissolved in a hydrocarbon solvent having a specific high boiling point range as an insecticide, and Japanese Patent Application Laid-Open No. 63-48
No. 201 describes an attempt to blend an antioxidant, which does not substantially evaporate at a heating temperature of 110 to 140° C., to an aliphatic hydrocarbon having 12 to 18 carbon atoms together with an insecticide.

Although these conventional heating transpiration agents have shown some success in terms of evaporation performance and usability, they are all petroleum-based oil agents and are highly flammable and do not pose a danger to fire. The current situation is that there is no such thing.

[Problems to be Solved by the Invention] The present invention eliminates the danger of conventional heating transpiration agents against fire, and provides a heating transpiration agent that is excellent in all aspects, including transpiration performance, insecticidal efficacy, and safety for humans and livestock. This invention was developed for the purpose of providing an insecticidal method using the same.

(Means for Solving the Problems) In order to achieve the above object, the present inventors have conducted extensive research and have found that, quite unexpectedly, an aqueous insecticide containing a specific surfactant is suitable instead of an oil agent. The present invention was completed based on the discovery that the present invention can be used for the following purposes.

Several spray formulations have already been developed for water-based insecticides containing pyrethroids, but they have only been put into practical use in Japan. Moreover, its active ingredients are limited to phenothrin and permethrin,
In addition, surfactants such as polyoxyethylene polystylphenyl ether and alkylbenzene sulfonate that are blended into these preparations are generally non-reproductive and have a concentration of 100 to 18
Even when heated to 0°C, nothing evaporated. Under such circumstances, it has been generally believed that when an aqueous insecticide is used for heat transpiration, the balance of the aqueous insecticide is lost and the insecticide cannot perform its transpiration function.

However, the present inventors focused on low boiling point surfactants,
When we prepared water-based insecticides using these and conducted heat transpiration tests, we found that the transpiration of the active ingredients could be sustained over a long period of time without disrupting the balance of the component composition, especially in the method using a liquid-absorbing wick. 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) 10.0 to 70.0% by weight of one or more surfactants that evaporate at a heating temperature of 100 to 180°C, and (c) water. The present invention relates to a water-based insecticide for heat transpiration and an insecticidal method using the same.

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

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

a) 3-allyl-2-methylcyclopent-2-ene-
4-on-1-yl d-cis/trans-chrysanthemate (trade name: Pinamine Forte: manufactured by Sumitomo Chemical Co., Ltd.) b) (S)-2-Methyl-4-oxo-3-(
2-7"lopinyl) cyclopent-2-enyl d-cis/trans-chrysanthemate (-ship name: Prarethrin) c) 5-propargyl-2-furylmethyl d-cis/
Trans-chrysanthemate (trade name; Pinamine D Forte: Sumitomo Chemical Co., Ltd.) % formula % (-ship name; empenthrin) e) d-3-allyl-2-methylcyclopent-2-en-4-one- 1-yl d-trans-chrysanthemate (trade name; Exrin: manufactured by Sumitomo Chemical Co., Ltd.) f) 5-benzyl-3-furylmethyl d-cis/trans-chrysanthemate (trade name; Chrylonforte: (manufactured by Sumitomo Chemical Co., Ltd.) g) 3-phenoxybenzyl d-cis/trans-chrysanthemate (-ship name: phenothrin) h) 3-phenoxybenzyl 2,2-dimethyl-3-
(2,2-dichlorovinyl)cyclopropanecarboxylate (-ship name; permethrin) i) 3-allyl-2-methyl-cyclopent-2-en-4-one-1-yl 2.2.3°3-tetra Methylcyclopropanecarboxylate (-ship name: Terrarethrin) j) 1-ethynyl-2-methyl-2-pentenyl 2.
2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate k) 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylprotolyether (-i name; etofenbrox) 1) Dimethyl (4-ethoxyphenyl)(3-(3
-phenoxy-4-fluorophenyl)propyl)silane m) 2-methyl-2-(4-ethoxyphenyl)-
5-(3-phenoxy-4-fluorophenyl)pentane Among these, insecticides a) to d) are preferred in terms of their industrial availability, efficacy, safety, and transpiration properties, and among them, insecticide C) is excellent. ing.

The present invention provides the above insecticide with one or more surfactants that evaporate at a heating temperature of 100 to 180"C.
It is characterized by adding ~70.0% by weight and water to form an aqueous insecticide.

Among the above surfactants, preferred are those whose boiling point in 5-HH is 250°C or lower, and/or the following conditions: Detector; Flame ionization type detector separation tube; Silanized 125-150 μm gas chroma A glass column with an inner diameter of about 3 mm and a length of about 1 m was filled with diatomaceous earth coated with 5% methyl silicone polymer for gas chromatography at a constant temperature around 140°C. When the retention time of the pyrethroid compound dl.d-T80-allethrin was adjusted to 50 minutes, the retention time of the main peak was within 80 times.

In addition, the surfactant in this specification means a substance that can stably maintain a pyrethroid compound in water in an emulsified state or in a solubilized state regardless of the presence or absence of micelle formation.
In a broad sense, it also includes solvents that are compatible with water and oil.

Generally, solubilized type aqueous insecticides are less likely to cause liquid phase separation than emulsified type insecticides and are superior in terms of usability, so they are suitable for this insecticidal method.

As a surfactant suitable for the present invention, the following formula I: R-0-(C
3H6O)m(C2H40)n"H(1) (wherein, R represents an alkyl group having 1 to 8 carbon atoms, m and n are O
A nonionic polyoxyalkylene alkyl ether compound represented by the following formula (representing an integer of ~6), or the following formula (where Ro represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m and n represent integers of O to 6), a nonionic polyoxyalkylene phenyl ether system 1 represented by the following formula 1: R-Coo-(CH2CH20)7''H(m) (formula During,
R and n represent the same meanings as above.

), a polyoxyethylene fatty acid ester represented by the following formula ■ or ■: (in the formula, R represents the same meaning as above), a polyhydric alcohol fatty acid partial ester represented by the following formula ■: (in the formula , I, m and n represent integers of 0 to 8.

), polyoxyethylene polyhydric alcohol fatty acid partial ester, fatty acid alkylolamide, etc., but are not limited to these.

Particularly preferred surfactants are the above formulas (1) and (H), in which R represents an alkyl group having 3 to 8 carbon atoms, Ro represents a hydrogen atom, and when either m or n is O, the other is 2 an integer of ~5, or both m and n are 2
or an integer of 3, and these have sufficient solubilizing ability and are also excellent in usability because their viscosity is not so high.

In normal production, it is obtained as a mixture of compounds with various degrees of polymerization, and m and n are often expressed as average numbers of moles, but it is of course included in the present invention regardless of whether it is a single product or a mixture. .

If necessary, a small amount of a cationic surfactant,
Anionic surfactant, amphoteric surfactant or 8! A solvent may be added.

Furthermore, the aqueous insecticide for heat evaporation of the present invention may optionally contain other insecticidal ingredients such as organic phosphorus agents and carbamate agents, ingredients such as bactericides and repellents, or stabilizers, synergists, pigments, and fragrances. Alternatively, an organic solvent or the like as an auxiliary agent may be added as appropriate.

The thus obtained aqueous insecticide for heat transpiration of the present invention has 1
It is applied to the method of heating the insecticide to 00 to 180 degrees Celsius to weaken the insecticide, but in particular, immersing a part of the porous night wick in the chemical solution and making the wick absorb the chemical solution, as well as removing the insecticide from the cough wick. It is suitable for a method in which the absorbed drug is evaporated by heating the upper part.

As a heating method, both direct heating and indirect heating can be applied, but indirect heating is preferable in consideration of decomposition loss of the drug.
As shown in the figure.

The aqueous insecticide 1 of the present invention is injected into a plastic pharmaceutical liquid container 2 made of polypropylene, PET, polyvinyl chloride, etc. with excellent chemical resistance, and after holding the liquid absorbing core 3 in a sealed manner through a suitable holder. It is housed in a heating evaporation device 4.

Conventionally, the shape of the drug solution container 2 has generally been cylindrical;
If the cylindrical surface is provided with grooves or stripes, or if it is made into a polygonal shape, it is convenient because it is easy to hold by hand and can be easily stored in the evaporation device 4.

The liquid absorbent core 3 can be made of inorganic materials such as calcium carbonate, magnesia, clay, talc, kaolin, diatomaceous earth, gypsum, and porcelain materials, and organic materials such as heat-resistant polymer materials, wood flour, valve return powder, and activated carbon. Powder fired or hardened with a suitable binder, or felt, non-woven fabric, asbestos,
A material such as wood or bamboo that allows liquid to flow through by capillary action can be used, and is held in the drug solution container 2 in a sealed manner via a suitable holder.

Since the aqueous insecticide 1 of the present invention uses a surfactant with a relatively low boiling point, unlike conventional surfactants, even if the liquid-absorbing core is immersed and absorbed, the surfactant in the 8. It has been found that there is no accumulation of liquid, and therefore there is little risk of causing problems such as chemical separation or clogging.

Of course, as a method of storing the chemical solution container 2 loaded with the liquid absorption wick 3 in the heating evaporation device 4, it is possible to provide a screw-on bottom cover at the bottom and place the drug solution container 2 on top of this, as in the conventional method. However, a method in which a threaded part carved on the upper part of the liquid medicine container 2 is screwed into a holder provided inside the device allows the liquid medicine container 2 to be firmly fixed to the device 4 compared to the former method, and is more effective. Preferably, 5 is a heating element installed with a gap around the heat receiving part of the liquid absorbing core 3, and 6 is a power cord connected to the heating element 5, and the extension cord attachment is a type,
It may be a so-called cordless type in which the plug terminal is fixed to the appliance 4, or a storage chamber for storing the power cord may be provided in the appliance 4 separately. A transpiration port 8 is formed in the center of the cap, which is preferably attached for safety reasons.The size and shape of the evaporation port 8 are determined as long as the evaporation chemical solution does not excessively condense or adhere to the protective cap 7 or the device 4. Optional.

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

The position of the vent 9 may be either the trunk or the bottom, but
The bottom part is more preferable because it can be expected to have a chimney-like action effect that brings about stable transpiration function and high drug-diffusing power.

The aqueous insecticide 1 for heat transpiration of the present invention is applied to the heat transpiration equipment 4.
When the insecticide 1 penetrates into the heat-receiving part of the liquid-absorbing wick 3 and is energized, it is indirectly heated by the heating element 5 and transpires, resulting in an extremely high extermination effect against mosquitoes, flies, cockroaches, bed bugs, mites, etc. It is something that demonstrates the.

Furthermore, since the chemical solution of the present invention is an aqueous insecticide, it eliminates the risk of fire unlike conventional products, and is also excellent in terms of odor and usability.

〔Example〕

The present invention will be described below based on Examples, but the present invention is not limited thereto.

Example 1 3-allyl-2-methylcyclopent-2-ene-4-
1.5 parts of on-1-yl d-cis/trans-chrysanthemate and 3 parts of BHTo are mixed with the surfactants shown in Table 1 below, and after melting, deionized water is added to make an aqueous insecticide for heat evaporation. The solution was prepared and its properties and transpiration performance were investigated.

The results are shown in Table 1.

As a control, kerosene (
The same tests were conducted on those using carbon atoms (having 13 to 15 carbon atoms).

1) Properties of the t8 liquid; separation of liquid phase, formation of turbidity, etc. were observed.

O: Clear solution with no separation of liquid phase △: Slight separation of liquid phase, slightly cloudy solution 2) Transpiration performance; Chemical solution 3
After pouring 5 g into a plastic bottle and loading it with a liquid absorbent core obtained by firing diatomaceous earth, it was set in a heating evaporation device (heating element temperature: 135° C.) shown in FIG.

Electricity was applied for 12 hours every day, and the amount of drug evaporated was measured orally.

O... The amount of drug transpiration is constant Δ... The amount of drug transpiration decreases somewhat with the passage of days ×... The amount of drug transpiration decreases rapidly with the passage of days 3) N, D: Not able to be measured.

As a result of the test, it was found that when a high boiling point surfactant was used and when formula I
Even with the surfactant represented by , when 70% or more is blended, there are problems with transpiration performance, such as a rapid decrease in the amount of transpiration over time.

On the other hand, the aqueous insecticide of the present invention has no particular problems with its solution properties or transpiration performance, and considering its non-flammability, it can be said to be more useful than conventional kerosene-based agents.

Some of the pyrethroid compounds and surfactants used in the present invention were tested by gas chromatography under the following conditions, and the results are shown in FIGS. 2 and 3.

Figure 2 is for constant temperature conditions, and Figure 3 is for elevated temperature conditions.
C (Pinamin D Forte), D (Pinamin Forte),
F (prarethrin) is a pyrethroid compound, and A (polyoxyethylene butyl ether, n-2), B (polyoxyethylene hexyl ether, n-3), and E (polyoxyethylene octyl ether, n-4) are included in the present invention. It is a suitable surfactant. However, for commercially available surfactants where n is expressed as the average number of moles, the position of the main peak corresponding to the fraction of the average number of moles is shown.

■ Constant temperature conditions [Figure 2] Detector: Hydrogen flame ionization type detector Separation tube: Glass column with an inner diameter of about 3 m and a length of about 1 m.
Separation tube temperature filled with Chromosorp W impregnated with 5% filler 5E-30; constant temperature around 140°C As shown in Figure 2, the retention time of Pinamin Forte (D), a heat-transpirationable pyrethroid. When adjusting the retention time to be approximately 50 minutes, the retention time of Pinamin D Forte (C), which has a higher vapor pressure, is approximately 30 minutes, and that of Prarethrin (F), which has a slightly lower heat transpiration property than Pinamin Forte (D). case about 6
It was O minutes.

When using 5E-30 as a filler, it is generally said that the order of retention time corresponds to the boiling point of the compound (low → high), and by the way, the boiling point of Pinamine Forte is approximately 190
°C/5 maiHg.

On the other hand, the retention times of polyoxyethylene butyl ether (n-2), polyoxyethylene hexyl ether (n=3), and polyoxyethylene octyl ether (n-4) used in the aqueous insecticide of the present invention are The retention times of the main peaks were about 2 minutes, about 10 minutes, and about 50 minutes, all within a range of 80 times.

■ Temperature rising conditions [Figure 3] Detector 1 separated layer; ■ Separated layer temperature same as constant temperature condition; 100℃ (maintained for 10 minutes) 100-26O
℃ (temperature increase rate of 3℃ per minute) 26O℃ (maintained for 30 minutes) As shown in Figure 3, Pinamin Forte (D
) was adjusted so that the holding time was approximately 40 minutes,
The retention times of each of the compounds described above were close to each other compared to the constant temperature conditions (2), with the retention time of Pinamin Forte (C) being about 35 minutes and Prarethrin (F) being 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 approximately 5 minutes, approximately 25 minutes, and approximately 40 minutes, respectively, and the retention time of the main peak is 60 times It was within the range.

That is, since the aqueous insecticide of the present invention uses a surfactant with a relatively low boiling point, it can evaporate together with the pyrethroid compound, and there is no risk of it accumulating in the absorbent core or causing clogging problems. This was recognized.

Example 2 A water-based insecticide for heat transpiration was prepared according to the following formulation according to Example 1, and the side surface of the core was heated to 120 °C and tested at predetermined intervals for (1) insecticidal efficacy test using Culex pipiens and (2) )
The amount of transpiration of insecticide per hour was measured.

In (2), the insecticide was trapped with a silica gel-filled column at regular intervals, the insecticide was extracted with acetone, and this was analyzed with a gas chromatograph.

The results are shown in Table 2, where for (1) above, the initial value of the kerosene-based control drug is shown, and for (2), the initial value of each drug is shown as 1. It is expressed as relative effectiveness ratio as OO.

1) The numbers in the upper row of the table represent the results of the efficacy test, and the numbers in the lower row represent the results of the transpiration measurement.

As a result of the test, the aqueous insecticide for heat evaporation of the present invention obtained transpiration performance and insecticidal efficacy equivalent to that of conventional kerosene-based agents, but did not cause problems such as separation of the chemical solution and clogging in the liquid absorbent core. It has been confirmed that this is not the case.

〔Effect of the invention〕

As explained above in detail, the aqueous insecticide for heat transpiration of the present invention eliminates the danger of conventional fires, and is excellent in all aspects such as transpiration performance, insecticidal efficacy, and safety for humans and livestock. .

Therefore, the insecticidal method using this aqueous insecticide of the present invention also exhibits excellent effects.

[Brief explanation of the drawing]

FIG. 1 is a longitudinal sectional view showing an example of a heating evaporation device used for applying the aqueous insecticide of the present invention. In the figure, 1... Water-based insecticide for heat transpiration 2... Chemical solution container 3... Liquid absorbing wick 4... Heating transpiration device 5... Heating element 6... Power cord
7...Protective cap 8...Transpiration port
9...Vent Figures 2 and 3 are graphs showing gas chromatograms of some of the pyrethroid compounds and surfactants used in the present invention; Figure 2 is under constant temperature conditions, and Figure 3 is under elevated temperature conditions. It is under warm conditions. In the diagram, Funeral map C...Pinamin forte D...Pinamin forte

Claims (6)

[Claims] (1) (a) 0 pyrethroid compound as an active ingredient
．． 3 to 10.0% by weight, (b) 10.0 to 70.0% by weight of one or more surfactants that evaporate at a heating temperature of 100 to 180°C, and (c) water. A water-based insecticide for heat transpiration characterized by: (2) The aqueous insecticide for heat transpiration according to claim 1, wherein the surfactant blended has a boiling point of 250° C. or less at 5 mmHg. (3) The blended surfactant meets the following conditions: Detector;
Flame ionization type detector separation tube; silanized 125
A glass column with an inner diameter of about 3 mm and a length of about 1 m is filled with ~150 μm diatomaceous earth for gas chromatography coated with 5% methyl silicone polymer Separation tube temperature: Gas chromatography at a constant temperature around 140°C Manipulate the pyrethroid compound dl・d-T.
3. The aqueous insecticide for heat transpiration according to claim 1, wherein the retention time of the main peak is within 80 times when the retention time of 80-allethrin is adjusted to 50 minutes. (4) The surfactant to be blended has the following formula I: R-O-(C_3H_6O)_m・(C_2H_4O)
_n・H(I) (wherein, R represents an alkyl group having 1 to 8 carbon atoms, and m and n represent integers of 0 to 6), 1 of the polyoxyalkylene alkyl ether compounds The aqueous insecticide for heat transpiration according to any one of claims 1 to 3, characterized in that the aqueous insecticide is one or more types. (5) The surfactant to be blended has the following formula II: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R' represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, 4. The polyoxyalkylene phenyl ether compound represented by m and n represents an integer of 0 to 6. Water-based insecticide for heat transpiration. (6) A liquid-absorbing wick is partially immersed in the aqueous insecticide for heat transpiration according to any one of claims 1 to 5, and the insecticide is absorbed into the wick, and the upper part of the wick is An insecticidal method characterized by heating to ~180°C to evaporate the pyrethroid compound, surfactant, and water contained in the insecticide.