JP2598938B2 - Water-based insecticide propellant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a compound represented by the general formula (I) (Wherein X represents a methyl group or a chlorine atom, and R represents a hydrogen atom or a cyano group).
Insecticidal stock solution containing a mixture of (2-methoxyphenyl) -5-methoxy-1,3,4-oxadiazol-2-one or an organic phosphorus agent and an alcoholic solvent having 2 to 3 carbon atoms.
Volume%, water 15-30 volume%, dimethyl ether or dimethyl ether plus liquefied petroleum gas propellant 60-90
The contents consisting of volume%, the inner pressure 3.0~7.0kg / cm ^2/25
Fill the pressure-resistant container at ℃, diffuse the contents as fine particles and 95% of the contents at a rate of 0.5 ml or more per second.
The present invention relates to an insecticide propellant comprising a bubble for jetting the above.

The pyrethroid compound represented by the general formula (I) has an extremely excellent insecticidal effect on various sanitary pests and agricultural and horticultural pests, but has low toxicity to warm-blooded animals and has already been used for household, epidemics and agricultural pesticides. It is widely used for practical use.

To date, it has been considered difficult to develop resistance to these pyrethroids.In fact, there has been no actual problem in Japan in controlling pests, but pyrethroid-resistant pyrethroids have been found in northern European fly and Conaga in Southeast Asia. Given the emergence of phylogeny and the height of organisms showing in the place where species survive, it is appropriate in Japan to deal with the possibility of developing resistance. Moreover, the development of pyrethroid resistance involves the involvement of a mechanism based on neuronal sensitivity regardless of the metabolic system, and as a result, the phenomenon of pyrethroid cross-resistance has emerged.
It has become important to develop in terms of application including mixing pyrethroids with agents having different physiological actions, such as organic phosphorus agents and carbamate agents.

The present inventors have found that when a mixture of a pyrethroid of the general formula (I) and a carbamate-based compound or an organophosphorus agent is applied as an aerosol-type insecticide propellant, not only is the synergistic effect, but also extremely excellent in terms of resistance measures. The following several patents have already been filed, but in the above-mentioned inventions, all of the above-mentioned inventions were intended to develop a non-flammable insecticide propellant. The injection gas was mainly composed of Freon gas. However, in recent years, the ozone layer depletion problem of CFCs has been highlighted, and in view of the situation that the use of CFCs in aerosol products should be restricted, the present inventors have proposed injection gases other than CFCs, such as dimethyl ether and liquefied petroleum gas. As a result of intensive studies on the development of the insecticide propellant used, a pesticide solution containing a lower alcohol solvent and a pesticidal component, 5 to 20% by volume, water 15 to 30% by volume, and dimethyl ether or dimethyl ether added with liquefied petroleum gas. the contents consisting of propellant 60 to 90 volume%, the inner pressure 3.0~7.0Kg / cm ^2/25 insecticide propellant filled in a pressure vessel at ℃ is defined enforcement regulations has been explosive and flammable conditions And the internal pressure, injection amount, size of aerosol particles, stability of insecticide, etc. are comparable to those of the conventional injection gas formulation. And in which the present invention has been completed based on these findings.

The pyrethroid of the general formula (I) used as an active ingredient in the present invention is already known and is fixed or liquid at ordinary temperature. The compound examples are shown below.

In addition, each pyrethroid has two asymmetric carbons in the acid portion, and one more asymmetric carbon when R is a cyano group, and there are optical isomers based on these, and each isomer or The mixture is naturally included in the present invention.

(1) 3'-phenoxybenzyl chrysanthemate (phenothrin) (2) 3'-phenoxy-α'-cyanobenzyl chrysanthemate (cyphenothrin) (3) 3'-phenoxybenzyl 2,2-dimethyl-3
-(2,2-dichlorovinyl) cyclopropanecarboxylate (vermethrin) (4) 3'-phenoxy-α'-cyanobenzyl 2,2
-Dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate (cybermethrin) On the other hand, among the carbamate compounds used in the present invention, particularly useful 3- (2-methoxyphenyl) -5-methoxy -1,3,4-oxadiazol-2-one is a recently developed substance that is solid at normal temperature (mp 77 ° C) and is more susceptible to paraffinic solvents and alcoholic solvents than insecticides such as pyrethroid compounds. It has the property of being hardly soluble in solvents.

Examples of the organic phosphorus agent include, but are not limited to, fenitrothion, pyridafenthion, diazinon, chlorpyrifos, and propaphos.

The present inventors have studied the combinations of the above pyrethroids with carbamate-based compounds or organic phosphorus agents for various dosage forms, and as a result, have found that application to aqueous aerosol-type insecticidal propellants is most advantageous.

That is, the aerosol type or the smoker type is generally used as a conventional insecticide method, but the former is limited to a small space, and the latter has various disadvantages as described below.

1. Mix the insecticide component with the burning agent and blow out the medicine by the combustion heat and smoke of the burning agent, or mix and pack the insecticide component and the organic blowing agent and indirectly heat the mixture to remove the organic blowing agent. It has a mechanism of pyrolyzing and fumigating the drug by the action of the pyrolysis gas. When the insecticide is exposed to high temperatures, loss due to the thermal decomposition is inevitable.

2. Because it is mixed with a substrate having high activity, stability over time cannot be obtained depending on the properties of the insecticidal component.

3. There is a danger of fire in a method involving combustion. The present invention is a high-concentration, short-time spatial treatment agent designed to eliminate these disadvantages.

To explain the present invention in more detail, the content composition is formulated in the ratio of 5 to 20% by volume of the pesticide stock solution, 15 to 30% by volume of water, and 60 to 90% by volume of the propellant.

As the solvent for preparing the undiluted solution, lower alcohol solvents are suitable from the viewpoints of solubility of the insecticidal component, water, compatibility with the propellant, and quick drying after spraying, among which ethyl alcohol,
Isopropyl alcohol is preferably used.

In the present invention, piperonyl butoxide, octachlorodipropyl ether, isobornyl thiocyanoacetate, N- (2-ethylhexyl) -bicyclo [2,2,1] -hepta, which is an efficacy enhancer of the above insecticide, is used. 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 and the insect repellent deet, R-11, R-326, dibutyl succinate, dibutyl phthalate, Dimethyl phthalate can also be used.

In addition to the above, stabilizers, fragrances, fungicides, acaricides, and other insecticides such as pyrethroids such as allethrin, framethrin, phthalthrine, and embensulin, or
It is possible to mix insect growth disrupting agents such as hydroprene, methoprene, 1-methyl-1- (2-pyridyloxy) -2- (4-phenoxyphenoxy) ethane, etc. Obtainable.

The present invention is characterized in that 15 to 30% by volume of water is blended in the flammability category specified in the Ministry of International Trade and Industry Notification No. 557 of the High Pressure Gas Control Law so as to fall within the range of low flammability. That is, if the water content is 15% by volume or less, the flammability is equivalent to strong flammability and is not suitable as a household insecticide.
It is evident that when the ratio exceeds the above, a problem occurs in the solubility of the insecticidal component or the compatibility with the solvent and the propellant gas.

As the propellant, dimethyl ether or a mixed gas obtained by adding liquefied petroleum gas to dimethyl ether is used, and is mixed at 60 to 90% by volume. If it is less than 60% by volume,
In order to obtain an injection amount of 0.5 ml or more per second, the injection port needs to be extremely large, and atomization and diffusion of spray particles are difficult, so that it is not suitable for the intended high-concentration short-time processing.
When using a mixed gas, the ratio of liquefied petroleum gas to dimethyl ether is 40%
The following is preferred.

The material of the container used for the insecticide propellant of the present invention is generally made of tin or aluminum, and its size is appropriately determined depending on the intended application space, but a can of 100 to 200 ml is usually suitable. In the present agent, a rust inhibitor such as sodium benzoate may be appropriately added, if necessary, in order to prevent corrosion of the container caused by containing water. The propellant valve provided in the container has an injection port with a diameter of 0.3 mm or more.
The shape is not particularly limited as long as the contents can be sprayed at a rate of 0.5 ml or more per ^{second at} 3.0 to 7.0 kg / cm 2/25 ° C. For example, several injection ports are installed, the injection angle is set at an arbitrary angle other than the upper direction, or the injection ports are rotated to devise a uniform spray into the room. It is useful to provide an arrangement that delays the actual injection in that humans do not inhale the medicine during use.

By using the insecticide propellant of the present invention thus obtained, for example, a 100 ml volume, a room of 6 to 8 tatami mats can be easily treated without fear of fire in a short time of 4 minutes or less, and it can be used for house pests. Practical merits are extremely large by exhibiting a high extermination effect.

In particular, the insecticidal effect on the cockroaches that have developed resistance to pyrethroids is remarkable, and the effect of the mixture in the insecticide propellant of the present invention is not limited to simply adding the lethality of the carbamate or organophosphorus agent, and a high synergistic effect The finding that they provide is entirely unexpected from the application of conventional smokers.

Also, after spraying, the distribution of the insecticidal components that settled
When examined in comparison with the smoker type, the insecticide propellant of the present invention is excellent not only in diffusivity but also in permeability to narrow spaces such as cracks and gaps, and furthermore, insecticide calculated from the amount of sedimentation In terms of the recovery of the components, it was confirmed that the type of the present invention was several stages better than the type of the smoker.

This is because, among the insecticidal components, the carbamate agent or the organic phosphorus agent particularly used in the present invention has poor thermal stability, and when applied to a smoke agent, the loss due to thermal decomposition during heating is large.

The insecticide propellant of the present invention is suitable for indoor use, not only susceptible pests but also organic phosphorus, carbamate resistant or Kd
It is especially useful for controlling various pests such as flies, mosquitoes, cockroaches, bed bugs, mites, and the like, but also for controlling stored pests such as black elephants and agricultural pests such as aphids, scale insects, and armyworms in plastic greenhouses. It can also be applied.

Next, examples and experimental examples of the present invention will be described, but the present invention is not limited to the following examples unless it exceeds the gist.

Test Example 1 1.2 g of vermethrin and 3- (2-
(Methoxyphenyl) -5-methoxy-1,2,4-oxadiazolin-2-one 0.4 g of an insecticidal stock solution dissolved in ethanol, water, and propellant gas were placed in a 100 ml aerosol aluminum can with the composition shown in the table below. The insecticide propellant obtained by filling and attaching a valve having a jet port diameter of 0.5 mm was tested for compatibility, EC (explosive), flame (flammability), and spray condition. .

As a result of the test, when the water ratio is 15% by volume or less (Control Propellant 1), the flammability is unsuitable. On the other hand, when the water ratio exceeds 30% by volume (Control Propellant 2), the compatibility and the spray state are poor. There was a problem.

In addition, when the rate of injection gas is low (control propellant 3),
When the spray state was not good and the stock solution of insecticide was 5% by volume or less (Control Propellant 4), the solubility of the insecticidal component was poor.

Therefore, it was clarified that only the pesticidal propellant of the present invention in which the pesticidal solution, water, and the propellant gas were blended in a specific amount ratio met all conditions such as compatibility, flammability, and spray state.

Test Example 2 Insecticidal components, solvents, water, and propellants were used in the composition shown in the table below.
The mixture was filled in a 0 ml aerosol container, and a valve having a nozzle having a diameter of 0.4 mm was attached to obtain an insecticide propellant.

The insecticide propellant, the control propellant and the conventional smoker were applied in a room having an area of 16 m ² and a height of 2.5 m, and the diffusivity of the insecticidal component, the permeability between objects, and the insecticidal efficacy were compared.

In other words, the center of the room is the injection point, and two glass plates of 20 cm square are placed at a distance of 1.5 m and 2.5 m, respectively (one is open and 0.5 x 1
A 20-cm cubic cardboard box provided with a 0-cm band-shaped slit was placed), and after 20 hours, the sedimentation adhesion amount of the insecticidal component was measured.

The amount of adhesion is shown by the recovery rate (the insecticidal component pyrethroid) with respect to the theoretical sedimentation amount.

In addition, put clothes boxes in the four corners of the room, and put in them sensitive and pyrethroid-resistant German cockroaches (♀) about 20
Each animal was released in two places. A wooden shelter was installed in the dressing box.

After being exposed for 24 hours, the German cockroach was recovered and the mortality after 72 hours was examined. The results were 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 the 1.5m and 2.5m points, and the insecticidal effect was extremely high. In sample No.4, the reach of the chemical was short,
Diffusivity was unsuitable, and there was a problem in drying properties after treatment.

On the other hand, in the case of the smoke agent, since the decomposition loss due to heat is large, both the recovery rate of the attached amount and the insecticidal efficacy are inferior, and the usefulness of the insecticide propellant of the present invention was confirmed.

Example In the same manner as in Test Example 2, a pesticidal component, a solvent, and a propellant were filled in a 100-ml aerosol container with the composition shown in the following table, and a valve and an actuator were attached so that the injection port was installed in an upward 45 ° direction. The insecticidal propellant of the present invention was obtained by covering with a protective cap.

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

Claims (1)

(57) [Claims] 1. The compound of the general formula (I) (Wherein X represents a methyl group or a chlorine atom, and R represents a hydrogen atom or a cyano group);
Insecticidal stock solution containing a mixture of (2-methoxyphenyl) -5-methoxy-1,3,4-oxadiazol-2-one or an organic phosphorus agent and an alcoholic solvent having 2 to 3 carbon atoms.
Volume%, water 15-30 volume%, dimethyl ether or dimethyl ether plus liquefied petroleum gas propellant 60-90
The contents consisting of volume%, the inner pressure 3.0~7.0kg / cm ^2/25
Fill the pressure container at ℃, diffuse the contents as fine particles, and at the rate of 0.5 ml or more per second 95
% Insecticide, comprising a bubble for injecting at least 100%.