JP2008266233A - Insecticide composition for thermal transpiration and volatilization rate-enhancing agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means for enhancing a volatilization rate of an N-methylcarbamate compound when used under heating. <P>SOLUTION: The insecticide composition for thermal transpiration comprises the N-methylcarbamate compound and an ether compound having vapor pressure at 25°C of not higher than 1×10<SP>-5</SP>Pa. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an insecticide composition for heat evaporation that improves the volatilization rate of an N-methyl carbamate compound and the volatilization rate improver of the compound.

N-methyl carbamate compounds are used as active ingredients of insecticides, but they are poor in stability, and particularly in the case of heat transpiration agents that are heated during use, the volatilization rate decreases due to thermal decomposition. is there.
Therefore, improvement of the stability of the N-methyl carbamate compound has been studied conventionally. For example, a phosphoric acid ester or a phosphorous acid ester is added to improve thermal stability (see Patent Document 1). It is known to suppress degradation over time by adding phenols (see Patent Document 2).

JP 56-92802 (page 1-4) Japanese Patent Laid-Open No. 7-206812 (page 1-4)

These prior arts are only to improve the stability of N-methyl carbamate compounds, and are not considered to improve the decrease in volatilization rate that occurs when heating is used during use. I can't.
In recent years, it has been found that by using phosphoric acid, the thermal decomposition of the N-methyl carbamate compound can be suppressed and the volatilization rate can be further improved (see Japanese Patent Application Laid-Open No. 2003-226602). Depending on the component, it was necessary to consider the influence of pH variation due to phosphoric acid. However, no other effective technique is known, and there is still room for study on the above-mentioned problem.
Therefore, the present invention newly provides means for improving the volatilization rate of N-methyl carbamate compounds when heating is used during use.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have included an effective amount of a specific ether compound when heating and using an N-methyl carbamate compound, thereby reducing the volatilization rate. It has been found that it can be remarkably improved and that the volatilization rate of the ether compound itself can be sufficiently obtained.
That is, the present invention is achieved by the following configurations (1) to (6).
(1) An insecticide composition for heat evaporation comprising an N-methyl carbamate compound and an ether compound having a vapor pressure of 1 × 10 ⁻⁵ Pa or less at 25 ° C.
(2) The insecticide composition for heat evaporation according to (1), wherein the ether compound is a compound represented by the following formula (1).
[In formula (1), R1 is a hydrocarbon group or halogenated hydrocarbon group having 1 to 2 carbon atoms, R2 is — (CH ₂ ) ₃ — or — (CH ₂ —O—CH ₂ ) —, and X is hydrogen. Atom or halogen, Y represents a carbon atom or a silicon atom. ]

(3) The insecticide composition for heat evaporation according to (1) or (2), wherein the N-methyl carbamate compound is propoxur.
(4) The insecticidal composition for heat evaporation according to any one of (1) to (3), wherein the ether compound is etofenprox.
(5) The insecticide composition for heat evaporation according to any one of (1) to (4), wherein the composition is heated to 200 to 400 ° C.
(6) A volatilization rate improver for an N-methyl carbamate compound, wherein an active compound is an ether compound having a vapor pressure at 25 ° C. of 1 × 10 ⁻⁵ Pa or less.

  According to the present invention, the volatilization rate of the N-methyl carbamate compound can be remarkably improved when it is heated at the time of use. Therefore, the pest control effect of the compound itself can be obtained by using it as an insecticide composition for heat evaporation. Can be obtained stably and sufficiently.

The insecticidal composition for heat evaporation of the present invention (hereinafter also referred to as “composition”) has an N-methyl carbamate compound (hereinafter also referred to as “compound A”) and a vapor pressure at 25 ° C. of 1 × 10 ^{− It} contains an ether compound (hereinafter also referred to as “compound B”) of ⁵ Pa or less as an active ingredient.

  Examples of the compound A of the present invention include one or more of oxamyl, mesomil, methiocarb, aldicarb, metocarb, propoxur, carbosulfan, bendiocarb, xylylcarb, macbar, carbaryl, etiophencarb, isoprocarb, fenobucarb and the like. It is done. Of these, propoxles that can significantly improve the volatilization rate are preferred.

  Compound A is preferably blended in the composition of the present invention so as to be 1 to 10% by mass, more preferably 1 to 5% by mass. If content is 1-10 mass%, since the volatilization improvement rate by the compound B is remarkable and the outstanding control effect with respect to various pests can be acquired, it is preferable.

Compound B of the present invention is an ether compound having a vapor pressure at 25 ° C. of 1 × 10 ⁻⁵ Pa or less, preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ Pa. Among these, a pyrethroid compound having a chemical structure in which an acid component and an alcohol component have an ether bond is preferable, and this structural skeleton is presumed to be related to the function and effect of the present invention. Furthermore, a compound represented by the following formula (1) is preferable. If the vapor pressure is within the above range, the volatilization rate of Compound A can be improved.

In the formula (1), R 1 represents a hydrocarbon group having 1 to 2 carbon atoms or a halogenated organic group, preferably an ethyl group or BrF ₂ C—. R 2 represents — (CH ₂ ) ₃ — or — (CH ₂ —O—CH ₂ ) —, preferably — (CH ₂ —O—CH ₂ ) —. X represents a hydrogen atom or a halogen, and the halogen is preferably a fluorine atom. Y represents a carbon atom or a silicon atom. Thus, compound B does not have an acid-derived oxygen atom (ester, carboxyl, carbonyl, etc.) but has an etheric oxygen atom, thereby contributing to an improvement in the volatilization rate of the N-methyl carbamate compound. It is considered a thing.

Specific examples of the compound B, etofenprox (vapor pressure at ^{25 ℃: 8.13 × 10 -7 Pa} ), halfenprox (vapor at 25 ° C. pressure: 7.79 × ¹⁰ -7 Pa), silafluofen ( One type or two or more types of vapor pressure at 20 ° C .: 2.5 × 10 ⁻⁶ Pa, vapor pressure at 25 ° C .: 5.2 × 10 ⁻⁶ Pa (cox diagram value), and the like can be given. Of these, etofenprox, which has a remarkable effect of improving the volatilization rate, is preferable.

  Compound B is preferably blended in the composition of the present invention so as to be 1 to 20% by mass, more preferably 5 to 15% by mass. If content is 1-20 mass%, since the volatilization rate with respect to the compound A can be improved notably and the outstanding control effect with respect to various pests can be acquired, it is preferable.

  Furthermore, as a compounding ratio of the compound A and the compound B in the composition of the present invention, it is preferable that the mass ratio is compound A: compound B = 1 to 5: 5 to 15. By setting it as the said compounding ratio, the volatilization rate of compound A and B is fully obtained by interaction of each compound, and can bring about activity with respect to a wider range of pests.

  As an optimal aspect in the composition of this invention, it is good to contain in a composition as propoxol 1-5 mass% and etofenprox 5-15 mass%.

The composition of the present invention can contain various desired components as long as the effects of the invention are exhibited. For example, insecticide chrysanthemum extract, natural pyrethrin, praretrin, imiprothrin, phthalthrin, allethrin, transfluthrin, bifenthrin, resmethrin, phenothrin, ciphenothrin, permethrin, cypermethrin, cyfluthrin, deltamethrin, fenpropatoline, empenthrin, profluthrin, profluthrin, profluthrin, etc. Compounds, fenitrothion, diazinon, marathon, pyridafenthione, prothiophos, oxime, chlorpyrifos, dichlorvos and other organophosphorus compounds, carbaryl, thiodicarb and other carbamate compounds, methoxadiazone and other oxadiazole compounds, fipronil and other phenylpyrazole compounds, Sulfonamide compounds such as amidoflumet, dinotefuran, imida Neonicotinoid compounds such as loprid, insect growth control compounds such as metoprene, hydroprene, pyriproxyfen, pyrrole compounds such as chlorfenapyr, rotenone, diet, P-menthane-3,8-diol, ethyl-butylacetylamino Examples include pest control ingredients such as propionate, hydroxyanisole, benzyl alcohol, mint oil, citronella oil, eucalyptus oil, geranium oil, and mosquito weeds.
In addition, efficacy enhancers such as piperonyl butoxide, sinepirin 222, S421, IBTA, deodorants and deodorants such as lauryl methacrylate, mint oil, orange oil, essential oil, fragrances such as various terpene compounds, butylhydroxyanisole, butylhydroxy Stabilizers such as toluene, Irganox 1076 (trade name), Irganox 1010 (trade name), retention agents such as piperonyl butoxide, n-butyl stearate, polyethylene glycol, polypropylene glycol, volatilization improvers such as phosphoric acid, etc. Can be mentioned.
These components can be blended in accordance with the purpose, but may be blended so as to be 0.1 to 20% by mass with respect to the preparation for heat transpiration.

  The composition of the present invention is formulated as a granule, a tablet, a pellet, a paste, a gel, a block, etc. using one or more of the above-mentioned various components, binders, solvents and the like. do it.

  Examples of the binder include animal and vegetable powders such as starch, wheat flour and silk powder, sugars such as glucose, sucrose and lactose, cellulose such as carboxymethyl cellulose, hydroxypropyl cellulose and hydroxyethyl cellulose, polyethylene glycol, and mixtures thereof. Can be mentioned.

  Examples of the solvent include water, ethanol, propanol, glycerol and other alcohols, paraffins and other hydrocarbons, propylene glycol, ethylene glycol and other glycols, N-methylpyrrolidone, propylene carbonate and the like, and mixtures thereof. Can be mentioned.

  The composition of the present invention is used as, for example, a hydrothermal exothermic heat transpiration agent, and is composed of a granule containing Compound A and Compound B together with a foaming agent and the like.

  Examples of the foaming agent include azodicarbonamide, benzenesulfonylhydrazine, P-toluenesulfonylhydrazine, P, P′-oxybis (benzenesulfonylhydrazine), dititrosopentanemethylenetetramine, N, N′-dinitroso-N, N ′. -Dimethylterephthalamide, trihydrazinotriazine, azobisisobutyronitrile, 4,4'-azobiscyanovaleric acid, t-butylazoformamide, 2,4-bis (azosulfonyl) toluene, 2,2 ' -Azobisisobutyramide, methyl-2,2'-azobisisobutyrate, 2- (carbamoylazo) isobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile and the like.

In addition, the foaming temperature can be adjusted by using Cd-stearate, Ca-stearate, Zn-stearate, Zn-octate, ZnO, Sn-malate, ZnCO ₃ , urea, chromium yellow, carbon black, etc. in combination with a foaming agent. May be.

  The composition of the present invention is preferably used by evaporating the active ingredient in the air by heating to 200 to 400 ° C, more preferably 300 to 400 ° C.

When used as a hydrothermal exothermic type heat transpiration agent, for example, an insecticide B for heat transpiration used in the form of a self-heating device 1 as shown in FIG.
The self-heating device 1 includes a cylindrical outer container 2 with a bottom, and a hydrothermal substance A is accommodated from the bottom to the side. The outer container 2 has a plurality of water holes at the bottom, and the water holes are closed by a member having water permeability, for example, a nonwoven fabric sheet 3. Further, the inside of the outer container 2 is partitioned into two spaces by a partition member 4. The partition member 4 is cylindrical and has a bottom that is substantially hollow hemispherical, and its side wall is disposed concentrically with the peripheral wall of the outer container 2.

  The hydrothermal exothermic substance A is filled in a space formed by the peripheral wall of the outer container 2, the partition member 4, and the nonwoven fabric sheet 3, and the heat transpiration agent B is accommodated inside the partition member 4. Further, the upper open surface of the outer container 2 is covered with a lid member 6 in which a plurality of openings are formed in a region corresponding to the upper open surface of the partition member 4. It is blocked by a hot-melt resin film 7 having vent holes.

  As the hydrothermal substance A, it is preferable to use a substance that generates heat to about 300 to 400 ° C. in about 50 to 80 seconds after contact with air or oxygen, for example, calcium oxide, magnesium chloride, iron Examples thereof include a mixture of powder and an oxidizing agent, a mixture of sodium sulfide and iron carbide, and the like. In such an exothermic system, it is preferable to use 1 to 10 times the amount of hydropyrogenic substance with respect to the preparation for heat transpiration, and specifically, 50 to 300 g of hydropyrogenic substance with respect to 5 to 100 g of the preparation for heat transpiration. Should be used as a guide. Further, water may be added so as to be 0.2 to 2 times by weight with respect to the hydrothermal substance.

  Therefore, in use, when the self-heating device 1 is placed in the container 20 containing the water W, the water W flows into the outer container 2 through the water passage hole, and further penetrates the nonwoven fabric sheet 3 and comes into contact with the hydrothermal substance A. Then, the heat-evaporating preparation B is heated by the reaction heat generated at that time, and the chemical is volatilized together with the pyrolysis gas of the organic foaming agent. Released. Further, since the heat-melting resin film 7 is thermally melted by heat radiation from the preparation B for heat transpiration and contact with the volatilized drug, the volatilized drug becomes smoke from a relatively early stage of transpiration, and the lid member 6 is opened. It is efficiently discharged outside through the section.

  Instead of the hydrothermal exothermic type, it may be used as a heating transpiration agent such as an ignition type such as a jet agent or a rod agent, a chemical reaction type such as an air oxidation exothermic agent, or an electric heating type. Further, without using a foaming agent, the composition of the present invention may be used as the heat transpiration agent B in a desired shape by impregnating or kneading an inorganic carrier such as talc, pearlite, or silicic anhydride.

  The present invention has been described in detail with reference to a hydrothermal exothermic type heat transpiration agent. However, as long as the effects of the present invention are exhibited, the present invention is not limited to this as long as the preparation is heated at the time of use. For example, it may be a mat preparation such as a flat plate shape, a cylindrical shape, or a tablet shape that is evaporated by being heated by an electric heater or the like. Moreover, the aspect which put preparations, such as a gel agent and a paste agent, in the heat-resistant case may be sufficient.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
<Test sample>
The powder having the composition shown in Table 1 was put in a mixer and sufficiently stirred, and then put in a mixer so as to have a ratio of 20 parts by mass of water to 100 parts by mass of the powder and kneaded for 10 minutes. Thereafter, granules of 3 mm in diameter and 5 mm in length were formed by an extruding granulator, and moisture of the sample was removed by a drier to produce specimen granules.

<Test method>
The self-heating device shown in FIG. 1 was used to store 10 g of the sample so as to be 65 g of calcium oxide, and 22 ml of water was added to the calcium oxide to generate heat, and the sample was evaporated by heating. The heating temperature was 300 to 400 ° C. The evaporated propoxle was collected on silica gel for 15 minutes by a collector, and the silica gel was immersed in 800 ml of acetone and subjected to ultrasonic extraction for 30 minutes. The extract was subjected to suction filtration, an internal standard substance (diisopropyl phthalate) was added to the filtrate, quantitative analysis was performed with a gas chromatograph, and the volatilization rate (%) was determined by the following formula.
Formula: Volatilization rate (%) = (Analysis value of volatilization amount of propoxle / propoxal content in 10 g of specimen) × 100

<Test results>
The test results are shown in Table 2. As shown in Comparative Example 1, when only compound A (propoxl) of the present invention was evaporated by heating, the volatilization rate was 45.0%, whereas as shown in Examples 1 and 2, It was confirmed that the volatilization rate of Compound A was remarkably improved to 76.9% and 71.0% by compounding Compound B (ethofenprox) of the present invention. As shown in Reference Example 1, when only a compound that was not an ether compound having a vapor pressure at 25 ° C. of 1 × 10 ⁻⁵ Pa or less was blended, the volatilization rate of Compound A could not be improved.

<Biological test>
Using the insecticidal composition for heat transpiration of Example 2, effects on various pests were confirmed. Ten resistant German cockroaches (female adults) were placed in a plastic cup with a diameter of 13 cm, and two test specimens with a lid with a direct 3 cm hole were prepared. Two test specimens were similarly prepared for black wagtails (female adults).
Two test specimens were prepared, in which 100 to 200 mushroom mites were put in a petri dish with a diameter of 9 cm and a height of 5 cm. Two test specimens were prepared in the same manner for mites.
Two test specimens were prepared, in which a filter paper was put on one bottom of a glass cylinder having a diameter of 6 cm and a height of 20 cm, and 10 cat fleas were placed in the cylinder with this face down.

A test specimen was prepared by storing 10 g of the insecticidal composition for heat evaporation of Example 2 in the partition member 4 in the self-heating device of FIG. In the 8 tatami test room (volume 32 m ³ ), as shown in FIG. 2, each test specimen of the insecticide composition and the test insect is installed, and the heat transpiration is performed in the same manner as the method for measuring the volatilization rate. went. After 2 hours of exposure, the time from the start of smoking until half knocked down (KT50 (min)), the knockdown rate after 2 hours (KD (%)), and the lethality rate after 48 hours (%) Asked. The test was repeated twice and the average value was obtained.

  As a result of the test, as shown in Table 3, it was confirmed that the insecticidal composition for heat transpiration of the present invention stably and sufficiently obtained an excellent control effect against various pests.

It is sectional drawing which shows one use form of the preparation for heat transpiration. It is a schematic diagram which shows the installation relationship of the test sample in a biological test laboratory.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Self-heating device 2 Outer container 3 Nonwoven fabric sheet 4 Partition member 6 Lid member 7 Heat-melt film 20 Container A Hydrothermal substance B Heating transpiration preparation W Water

Claims (6)

An insecticide composition for heat evaporation comprising an N-methyl carbamate compound and an ether compound having a vapor pressure at 25 ° C. of 1 × 10 ⁻⁵ Pa or less. The insecticidal composition for heat evaporation according to claim 1, wherein the ether compound is a compound represented by the following formula (1).
[In formula (1), R1 is a hydrocarbon group or halogenated hydrocarbon group having 1 to 2 carbon atoms, R2 is — (CH ₂ ) ₃ — or — (CH ₂ —O—CH ₂ ) —, and X is hydrogen. Atom or halogen, Y represents a carbon atom or a silicon atom. ]

  The insecticidal composition for heat evaporation according to claim 1 or 2, wherein the N-methyl carbamate compound is propoxur.   The insecticidal composition for heat evaporation according to any one of claims 1 to 3, wherein the ether compound is etofenprox.   The insecticide composition for heat evaporation according to any one of claims 1 to 4, wherein the composition is heated to 200 to 400 ° C. A volatilization rate improver for an N-methyl carbamate compound, wherein an active compound is an ether compound having a vapor pressure at 25 ° C. of 1 × 10 ⁻⁵ Pa or less.

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