JPH0735323B2 - Insecticide propellant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has the general formula (I) (Wherein X represents a methyl group or a chloro atom, and R represents a hydrogen atom or a cyano group) and 3-
Insecticidal stock solution 5 in which a mixture of (2-methoxyphenyl) -5-methoxy-1,3,4-oxadiazol-2-one (hereinafter referred to as compound A) is dissolved in a ketone or alcohol-based solvent. 10% or less and 2 to dimethyl ether
An internal pressure of 3.0 ~ with a content of 25% and non-combustible propellant 90 ~ 95% containing 50 ~ 95% of Freon gas.
Insecticidally filled in a pressure vessel at 7.0kg / cm ^2/25 ℃, with diffuse the contents as fine particles, characterized by comprising a valve for injecting the total amount of the contents at a rate of more than 1ml per second Regarding propellant.

The pyrethroid compound represented by the general formula (I) exhibits an extremely excellent insecticidal effect against various sanitary pests and agricultural and horticultural pests, while it has low toxicity to warm-blooded animals and is already used in households.
It is widely used as an insecticide for epidemics and agriculture.

To date, the development of resistance to these pyrethroids has been difficult, and in fact, there are no cases of actual control problems in Japan, but pyrethroid resistance to house flies in northern Europe and diamondback moth in Southeast Asia. Given the emergence of strains and the highness of organisms showing in the field of species survival, it would be appropriate to deal with the possibility of resistance development in Japan as well. Moreover, in these pyrethroid resistance development, the involvement of the mechanism based on the decrease in nerve sensitivity was observed regardless of the metabolic system, and as a result, the phenomenon of pyrethroid cross resistance has emerged.
It has become important to develop applications in terms of application including mixing of pyrethroids with drugs having different physiological actions, such as organic phosphorus agents and carbamate agents.

Therefore, the present inventors investigated a mixture of the pyrethroid of the general formula (I) and the compound A of the carbamate agent, and conducted intensive studies. As a result, when the mixture was used as an aerosol-type insecticide propellant. In addition to its synergistic effect, it is extremely superior in terms of resistance measures. Furthermore, a composition containing 2 to 25% of the total amount of dimethyl ether as a propellant and 50 to 95% of a chlorofluorocarbon gas is used. , Solubility of the active ingredient,
The inventors have found that they are extremely useful in terms of stability, miniaturization of contents at the time of jetting, diffusibility, etc., and completed the present invention.

The pyrethroid of the general formula (I) used as an active ingredient in the present invention is already known and is a solid or liquid at room temperature. The example of the compound is shown below.

It should be noted that any pyrethroid has two asymmetric carbons in the acid moiety, and one more asymmetric carbon when R is a cyano group,
Optical isomers based on these exist, but each isomer or a mixture thereof 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 (permethrin) (4) 3'-phenoxy-α'-cyanobenzyl 2,2
-Dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate (cypermethrin) On the other hand, the carbamate compound A used in the present invention was recently developed and is a solid at room temperature (mp77).
C.), and is less soluble in paraffinic solvents than insecticidal components such as pyrethroid compounds.

As a result of examining various combinations of the above-mentioned pyrethroid and compound A for each dosage form, the present inventors have found that application to an aerosol-type insecticidal spray is the most advantageous.

That is, as an insecticidal method which has been generally used conventionally, there are 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 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 invention is a high-concentration short-time spatial treatment agent designed to eliminate these drawbacks.

The present invention will be described in more detail. The content composition is such that the insecticidal stock solution and the non-combustible propellant are mixed in the insecticidal stock solution amount of 5 to 10% and the propellant amount of 90 to 95% by weight. As the stock solution preparation solvent, a ketone-based or alcohol-based solvent is mainly used in view of the solubility of the compound A, while a propellant contains dimethyl ether in an amount of 2 to 25% and a chlorofluorocarbon gas in an amount of 50 to 50%. It is essential to contain 95% from the viewpoints of solubility and stability of the active ingredient, miniaturization of contents at the time of ejection, and diffusibility.

Furthermore, the container has a diameter of 0.3 mm or more, preferably 0.4 to 1.0 mm.
By providing a special valve with the injection port, the total amount of the contents at a rate of more than 1ml it became possible injection per second at an internal pressure of 3.0~7.0kg / cm ^2/25 °.

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

This is because, among the insecticidal components, the compound A, which is particularly used in the present invention, has poor thermal stability, so that when it is applied to a smoke agent, the loss due to thermal decomposition during heating is large.

By using the insecticidal propellant of the present invention thus obtained, for example, 100 ml volume, a room of 6 to 8 tatami can be easily treated in a short time within 3 minutes without fear of fire, and cockroaches, flies, mosquitoes. It has a great practical advantage by exerting a high extermination effect against domestic pests such as bedbugs, bedbugs and mites.

In particular, the insecticidal effect on cockroaches that have developed resistance to pyrethroids is remarkable, and the effect of the admixture in the insecticidal propellant of the present invention is not limited to merely adding the lethality of compound A, but provides a high synergistic effect. The findings are totally unexpected from the application of conventional smoke agents.

In the present invention, a solvent mainly composed of alcohols and ketones is used, and ethers, esters, petroleum, halogenated hydrocarbons, fluorinated halogenated hydrocarbons and the like may be added thereto. Absent. From the viewpoint of solubility of the active ingredient, quick-drying property after injection, toxicity, etc., for example, one containing acetone, ethanol, isopropanol or a mixed solvent is preferably used.

On the other hand, the propellant is based on dimethyl ether 2 to 25%, on which CFC11, CFC12, CFC134-
a, Freon 142-b, etc. Freon-based gas ... Nitrogen gas,
Carbon dioxide gas or liquefied petroleum is combined and used as a composition contained in the range of nonflammable gas.

A particularly useful propellant is a mixed gas of CFC11, CFC12 and dimethyl ether. In this case, CFC11 also serves as a solvent of the active ingredient or as a pressure regulator of the insecticide propellant.

The size of the container of the insecticidal propellant of the present invention is appropriately determined according to the intended application space, but a can of 100 to 200 ml is usually suitable.

The injection valve comprising a container, has a diameter 0.3mm or more injection ports, the internal pressure 3.0~7.0kg / cm ^2/25 ℃ inject 1ml more content per second if possible, its shape is particularly Not limited. For example, several injection ports are attached, the injection angle is set to any angle other than above, or the injection port is rotated to devise a uniform spray in the room. It is useful to provide a device that delays the actual injection in that humans do not inhale the drug during use.

Further, in the present invention, piperonyl butoxide, octachlorodipropyl ether, isobornyl thiocyanoacetate, N- (2-ethylhexyl) -bicyclo [2,2,1] -hepta which are the above-mentioned insecticide efficacy enhancers. 5-en-
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 pest repellents such as Diet, R-11, R-326, dibutyl succinate, dibutyl phthalate and dimethyl phthalate can also be mixed.

In addition to the above, stabilizers, fragrances, fungicides, acaricides or other insecticides such as allethrin, flamethrin, phtalthrin, and pyrethroids such as empensulin, fenitrothion, DDVP, diazinon, and organic phosphorus agents such as propaphos are mixed. It is also possible to obtain a multipurpose composition having excellent effects.

INDUSTRIAL APPLICABILITY The insecticide propellant of the present invention is used indoors as well as susceptible pests, as well as organophosphorus agents, carbamate agents resistant or Kdr.
It is especially useful for the control of various insect pests such as flies, mosquitoes, cockroaches, bedbugs, mites, etc., but also for the control of stored-grain pests such as elephants and agricultural pests such as aphids, scale insects, and gall midges in a greenhouse. You can also do it.

Next, examples and experimental 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.

Example A 100 ml aerosol container was filled with the insecticidal component, solvent and propellant in the composition shown in the table below, a valve having a diameter of the injection port of 0.6 mm was attached, and a protective cap was further covered to obtain an insecticidal propellant.

Compound A; 3- (2-methoxyphenyl) -5-methoxy-1,3,4-oxadiazol-2-one The following propellants were prepared as a control of the insecticidal propellant of the present invention.

Experimental Example 1. The insecticidal propellant prepared in the same manner as in Example except that a pressure-resistant glass bottle was used instead of the aerosol container was stored in a refrigerator at -5 ° C, and after 2 weeks, a liquid state was observed to determine the solubility of the insecticidal component. The examination revealed the following.

As a result of the test, the propellant of the present invention has excellent solubility in insecticidal components, while DME is not mixed with the propellant [1 ^* ].
In addition, precipitation of insoluble matter was observed in the [1-L] formulation containing LPG instead of DME, and the usefulness of DME gas was confirmed.

Experimental Example 2. In a room having an area of 16 m ² and a height of 2.5 m, the present insecticidal propellant and a conventional smoke agent were applied, and the diffusivity of insecticidal components and the permeability between objects were compared.

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 sedimented and attached insecticidal components was measured.

As the test sample, the insecticide propellant of the present invention [1], [2], [1 ^* ] prepared in Examples and a commercially available organic foaming agent-type smoke agent [smoked-1 ]
[Smoked-2] was used.

Adhesion amount It is the value converted to, and () shows the recovery rate against the theoretical sedimentation amount.

As a result of the test, the insecticidal propellant of the present invention showed a high recovery rate of about 50% (open) with respect to the theoretical sedimentation amount at both 1.5m and 2.5m points, and [1 ^* ] formulation and smoking agent Compared with the diffusion power.

In the case of smoking agents, the recovery rate of carbamate agent (Compound A) was particularly poor, and the decomposition loss due to heat was large, and the comparison of [1] and [1 ^* ] formulations confirmed the contribution of dimethyl ether to the improvement of diffusion power. It was

Further, it was confirmed that the treatment time of the insecticidal propellant of the present invention was extremely efficient because the penetrating force between the objects was excellent regardless of the smoking agent.

Experimental example 3. Place a clothing box in each of the four corners of a room with an area of 16 m ² and a height of 2.5 m used in Experimental example 2, and in each of them, there are about 20 sensitive and pyrethroid-resistant German cockroaches (♀), 2 in each. I released it. A wooden shelter was installed in the clothes box.

The test sample was sprayed from the center of the room, exposed for 24 hours, the German cockroach was collected, and the mortality rate after 72 hours was examined.

As a result of the test, the insecticidal propellant of the present invention showed a remarkable insecticidal effect against susceptible and resistant German cockroaches, [1]
From the comparison between [5] and [6] of the control, it was confirmed that the synergistic effect of mixing the pyrethroid agent and the carbamate agent (Compound A) is characteristic of the insecticidal propellant type and not seen with the smoke agent. Was given. Further, from the comparison between [1] and [1 ^* ], it was confirmed that the dimethyl ether used as the propellant in the present invention is also useful in manifesting the effect.

Example 2 Similar to Example 1, a 100 ml aerosol container was filled with the insecticidal component, solvent and propellant according to the composition shown in the table below, and a valve having a diameter of the injection port of 0.6 mm was attached and further covered with a protective cap to form a book. Invented insecticide propellant obtained Compound A; 3- (2-methoxyphenyl) -5-methoxy-1,3,4-oxadiazol-2-one

Claims (1)

[Claims] 1. A general formula (I) (Wherein X represents a methyl group or a chloro atom, and R represents a hydrogen atom or a cyano group) and 3-
Insecticidal stock solution 5-10% prepared by dissolving a mixture of (2-methoxyphenyl) -5-methoxy-1,3,4-oxadiazol-2-one in a ketone or alcohol-based solvent.
If, comprises 2-25% dimethyl ether, and the contents comprising a nonflammable propellant 90% to 95%, including 50% to 95% of the gas of fluorocarbon, the inner pressure 3.0~7.0kg / cm ^2/25 ℃ The pressure-resistant container to disperse the contents as fine particles and
An insecticidal propellant characterized by comprising a valve for injecting the entire amount of the content at a rate of 1 ml or more per second.