JPH07121847B2 - Insecticide propellant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a compound of general formula (I) as an insecticidal active ingredient. (Wherein, X represents a methyl group or a chloro atom, and R represents a hydrogen atom or a cyano group), or a pyrethroid selected from the group consisting of an organic phosphorus agent, a carbamate agent, and an insect growth disturbing agent. 3 to 20% by weight of a pesticidal stock solution containing 1 or 2 kinds of the pesticidal active ingredient or a mixture of the pesticidal active ingredient or a synergist with kerosene or an alcohol-based solvent. Methane 40-75% by weight, dimethyl ether 20
50 wt%, and the contents of the pressure made by blending in a proportion of 0% liquefied petroleum gas 0.8~5.0kg / cm ² at 20 ° C., the inner pressure of 4.0~6.5kg / cm ^2/25 ℃ And a valve for injecting 95% or more of the content at a rate of 0.7 ml or more per second, according to 1.

Conventionally commonly used insecticidal methods include an aerosol type and a smoke agent type, but the former is limited to a small space and the latter has various drawbacks as described below.

1. Mix the insecticidal component with the combustion agent to eject the drug by the combustion heat and smoke of the combustion agent, or mix and pack the insecticidal component and the organic foaming agent and indirectly heat the mixture to form the organic foaming agent. It has a mechanism of thermally decomposing and fumigating the drug by the action of the thermally decomposing gas, and when the insecticidal component is exposed to a high temperature, the loss due to the thermal decomposition is unavoidable.

2. Stability over time cannot be obtained depending on the nature of the insecticidal component because it is mixed with a highly active base material.

3. There is a risk of fire in the method involving combustion.

The present inventors have continued to study aerosol type insecticidal propellants aiming at high-concentration short-time spatial treatment as an insecticidal method for eliminating these drawbacks, and previously disclosed some useful inventions.

However, in these insecticidal propellants, CFC 11 and CFC 12 are mainly used as a propellant gas, and in consideration of the recent air pollution problem of CFC gas. At times, there is an urgent need to develop alternative injection gases.

The present inventors focused on monochlorodifluoromethane (hereinafter referred to as “F22”), which is a CFC gas with rapid decomposition in the environment and has little concern about ozone layer depletion from the above-mentioned circumstances. As a result of repeated various studies, the insecticidal stock solution, F22, and dimethyl ether and liquefied petroleum gas having a pressure at 20 ° C of 0.8 to 5.0 Kg / cm ^{2 at} a specific amount ratio described below are insecticidal propellants. In addition to satisfying the explosive and flammable conditions stipulated in the regulations of the law, the insecticidal injection of conventional injection gas prescriptions is also taken into consideration in terms of internal pressure, injection amount, aerosol particle size, insecticidal component stability, container corrosiveness, etc. The inventors have found that they are no better than the agents, and have completed the present invention based on these findings.

That is, the insecticidal propellant of the present invention, based on the total amount,
3-20% by weight of an insecticidal active ingredient, or a mixture of this and a synergist, in kerosene or an alcohol-based solvent, 40 to 75% by weight of F22 as a propellant, and 20 to 50% of dimethyl ether. Wt% and pressure at 20 ° C
Liquefied petroleum gas of 0.8 to 5.0 kg / cm ² was blended at a rate of 0 to 10% by weight, and a valve for injecting the content at a rate of 0.7 ml or more per second was provided.

In the present invention, when the insecticidal stock solution is 20% by weight or more, in order to obtain an injection amount of 0.7 ml or more per second, it is necessary to extremely enlarge the injection port, and it is difficult to atomize or diffuse the injection particles. , Not suitable for the intended high-concentration short-time treatment.

F22 does not have explosiveness and flammability, and has good injection performance, but if it is blended at 75% by weight or more, the internal pressure is high and it is dangerous considering the pressure resistance of the container. On the other hand, when the content is 40% by weight or less, the requirements of the regulations of regulation are not satisfied in terms of explosiveness and flammability.
Dimethyl ether is useful not only as a propellant gas, but in terms of solubility and stability of the active ingredient, and because it has the effect of suppressing corrosion or rusting of the container due to water derived from the insecticidal stock solution or propellant gas, 20 to 50% by weight is blended. 50
Exceeding weight% is dangerous in terms of explosiveness.

Blending of liquefied petroleum gas having a pressure at 20 ° C. of 0.8 to 5.0 Kg / cm ² is not an essential requirement, but it is explosive even if 0 to 10 wt% of the composition of F22 and dimethyl ether is replaced with this.
Satisfactory results can be obtained in terms of flammability and internal pressure.

That is, the present invention blends the insecticidal stock solution in an amount of 3 to 20% by weight, F22 as a propellant in an amount of 40 to 75% by weight, dimethyl ether in an amount of 20 to 50% by weight, and liquefied petroleum gas in an amount of 0 to 10% by weight. The upper limit of the internal pressure to the general high-pressure gas safety regulation (Ministry of International Trade and Industry Ordinance No. 53), Article 12, paragraph 27, (h) "In the production of aerosol, the internal pressure of the container becomes 8 kg / cm ² or less at a temperature of 35 ° C ..." In addition to lowering, it succeeded in obtaining satisfactory results in all aspects of spray explosiveness, flammability, and spray condition. Insecticides propellant of the present invention is filled in a pressure vessel at an internal pressure of 4.0~6.5Kg / cm ^2/25 ℃, comprising a valve for injecting more than 95% of the contents further at a rate of more than 0.7ml per second It is characterized by

If the injection amount is 0.7 ml / sec or more, the shape of the valve, button, etc. is not particularly limited, but for example, a special valve having an injection port with a diameter of 0.3 mm to 1.0 mm is preferably used. In addition, several injection ports can be attached, the injection angle can be set at any angle other than above, or the injection port can be rotated to evenly spray inside the room. It is useful to provide a device that delays the actual injection in that humans do not inhale the drug during use.

The active ingredient of the insecticidal propellant according to the present invention is represented by the general formula (I) (In the formula, X represents a methyl group or a chlorine atom, and R represents a hydrogen atom or a cyano group.), Or a synthetic pyrethroid represented by the same and an organic phosphorus agent (fenitrothion, diazinon, chloropyrifos, pyridaphenthion, DDVP).
Etc.), carbamate agents (NAC, BPMC, propoxer,
5-methoxy-3- (2-methoxyphenyl) -1,2,4
-Oxadiazolin-2-one and the like] or an insect growth disturbing agent [hydroprene, methoprene, 1-methyl-1- (2-pyridyloxy) -2- (4-phenoxyphenoxy) ethane and the like] 1 or 2
It is a mixture with seeds.

The insect growth disturbing agent has a completely different mechanism of action from the nervous system insecticides such as the above-mentioned pyrethroid agent, and its mixed use is extremely useful as a measure against resistance, but the onset of efficacy is generally slow. Therefore, in the case of expecting a rapid effect against pyrethroid-resistant pests, it is appropriate to mix a pyrethroid agent with an organophosphorus agent or a carbamate agent, and if an insect growth disturbing agent is further added, the best insecticidal effect can be obtained over a long period of time. it can. Further, the acid component of the general formula (I) has two asymmetric carbons, and when R is a cyano group, there is one asymmetric carbon, and optical isomers based on these asymmetric carbons exist. The isomers or mixtures thereof are naturally included in the present invention.

Examples of the compound represented by formula (I) are shown below.

(1) 3'-phenoxybenzyl chrysanthemate (phenothrin) (2) 3'-phenoxy-α'-cyanobenzyl chrysanthemate (cyphenothrin) (3) 3'-phenoxybenzyl 2,2-dimethyl-3
-(2,2-Dichlorovinyl) cyclopropanecarboxylate (permethrin) (4) 3'-phenoxy-α'-cyanobenzyl 2,2
-Dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate (cypermethrin) Further, in the present invention, piperonyl butoxide, octachlorodipropyl ether, thiocyanoacetic acid, which is a potentiator of the above insecticide, is used. Isobornyl, N- (2-ethylhexyl) -bicyclo [2,2,1] -hepta-5-ene-2,3
-Dicarboximide, N- (2-ethylhexyl) -1
-Isopropyl-4-methylbicyclo [2,2,2] oct-5-ene-2,3-dicarboximide and β-butoxy-β'-thiocyanodiethyl ether may be added to enhance the insecticidal efficacy. And pest repellents such as Diet, R-11, R-326, dibutyl succinate,
Dibutyl phthalate, dimethyl phthalate, etc. can also be mixed. In addition to the above, stabilizers, fragrances, germicides,
It is also possible to obtain a versatile composition having excellent effects by mixing an acaricide or another insecticide.

As a solvent used for preparing the insecticidal stock solution of the present invention, kerosene or an alcohol-based solvent is suitable from the viewpoint of solubility of the active ingredient, quick-drying property after spraying, toxicity and the like.

As long as the properties and performance of the composition are not impaired,
Of course, other kinds of solvents such as ketones, ethers, esters, halogenated hydrocarbons may be mixed.

For example, when the insecticidal active ingredient is the general formula (I) or a mixture of the same with an aliphatic ester-based insect growth disturbing agent, a kerosene-based solvent is suitable, while when an organic phosphorus agent or a carbamate agent is mixed, ethanol or isopropanol is used. Are suitable, but are not limited to this range.

By using the insecticide propellant of the present invention thus obtained, for example, 100 ml volume, a room of 6 to 10 tatami mats can be easily treated in a short time within 3 minutes without worrying about fire, and in addition to susceptible pests and resistance It is highly effective against indoor pests such as sex pests such as flies, mosquitoes, cockroaches, bedbugs and mites, as well as stored-grain pests such as elephants and agricultural pests such as aphids, scale insects, and armyworms in greenhouses. It is also possible, and the practical advantage is extremely large.

In addition, after spraying, the distribution of the insecticidal components settled in the treated area was examined in comparison with the smoke agent type, and the insecticide propellant of the present invention showed not only the diffusion amount but also cracks, narrow spaces such as gaps. It was confirmed that the type of the present invention is superior to the smoking agent type in terms of the recovery rate of the insecticidal component calculated from the settling agent, which is excellent in permeability.

Next, examples and test examples of the present invention will be shown, but the present invention is not limited to the following examples unless the gist thereof is exceeded.

Test Example 1 As a pesticidal active ingredient, 1.35 g of vermethrin and 0.4 g of hydroprene were dissolved in kerosene, and a propellant gas was filled in a 100 ml aerosol container with the composition shown in the table below. With respect to the insecticidal propellant obtained by attaching the above, the internal pressure, EC (explosiveness), frame (flammability), and spray state were tested, and the results were as follows.

As a result of the test, when the ratio of the insecticidal undiluted solution exceeds 20% by weight (control propellant 1), the injection amount or the state of contamination by the spray solution is not good, and the mixing ratio of F22 exceeds 75% (control propellant 2). ), There was a problem in terms of safety. If the F22 ratio is less than 40% by weight, or if the dimethyl ether mixing ratio is
If it exceeds 50% by weight (control propellants 3, 4), it is not suitable in terms of explosiveness.

Test Example 2 An insecticidal propellant was obtained by filling a 100 ml aerosol container with the insecticidal component, solvent and propellant in the composition shown in the table below, and attaching a valve having a diameter of injection port of 0.6 mm.

Compound A; 5-methoxy-3- (2-methoxyphenyl)
-1,2,4-oxadiazolin-2-one compound B; 1-methyl-1- (2-pyridyloxy) -2
-(4-phenoxyphenoxy) ethane In a room with an area of 16m ² and a height of 2.5m, the insecticide propellant, the control propellant and the conventional smoke agent were applied, and the insecticidal component was diffused and penetrated between the objects. , And compared the insecticidal efficacy.

In other words, with the center of the room as the injection point, two 20 cm square glass plates at each of the distances of 1.5 m and 2.5 m (one is open as it is, the other glass plate is 0.5 x 10c on the top surface).
A 20 cm cubic ball box provided with m-shaped slits was placed), and after 20 hours, the amount of the deposited insecticidal components was measured.

The adhered amount is indicated by the recovery rate (insecticidal component pyrethroid) with respect to the theoretical sedimentation amount.

In addition, clothing boxes were placed in the four corners of the room, and about 20 susceptible and pyrethroid-resistant German cockroaches (♀) were released in each of the two locations. In addition, in the clothes box,
A wooden shelter was installed.

After exposing it to the jet for 24 hours, collect the German cockroach,
When the mortality rate after 72 hours was examined, it was as follows.

As a result of the test, the propellant of the present invention showed a high recovery rate of 50% or more with respect to the theoretical sedimentation amount at both 1.5 m and 2.5 m points, and the insecticidal effect was also extremely high, but the insecticidal stock solution was 20% by weight or more. In the compounded sample No. 4, the reaching distance of the chemical solution was short and there was a problem in diffusibility.

On the other hand, in the case of smoke agents, the decomposition loss due to heat is large,
It was confirmed that the usefulness of the insecticidal propellant of the present invention was poor because the collection rate of adhered amount and the insecticidal efficacy were poor.

Example As in Test Example 2, a 100 ml aerosol container was filled with the insecticidal component, solvent and propellant in the composition shown in the table below, and a valve and an actuator were attached so that the injection port was installed in the direction of upward 45 °. A protective cap was put on to obtain an insecticidal propellant of the present invention.

^Two cockroaches were sprayed in a cafeteria of about 40 m ^{2 and} the density of the cockroaches after treatment was investigated using a sticky trap. The number of cockroaches captured per day was less than 1 over 45 days for all prescriptions. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area A01N 43:82) (A01N 53/08 43:40) (A01N 53/00 508 C 43:82) (A01N 53/00 508 A 43:40)

Claims (1)

[Claims] 1. A general formula (I) as an insecticidal active ingredient. (Wherein, X represents a methyl group or a chloro atom, and R represents a hydrogen atom or a cyano group), or a pyrethroid selected from the group consisting of an organic phosphorus agent, a carbamate agent, and an insect growth disturbing agent. 3 to 20% by weight of a pesticidal stock solution containing 1 or 2 kinds of the pesticidal active ingredient or a mixture of the pesticidal active ingredient or a synergist with kerosene or an alcohol-based solvent. Methane 40-75% by weight, dimethyl ether 20
50 wt%, and the contents of the pressure made by blending in a proportion of 0 to 10% by weight liquefied petroleum gas 0.8~5.0kg / cm ² at 20 ° C., the inner pressure of 4.0~6.5kg / cm ^2/25 An insecticidal propellant characterized by comprising a valve for injecting 95% or more of the content at a rate of 0.7 ml or more per second filled in a pressure resistant container at ℃.