JPS6379805A - Insecticidal spray agent - Google Patents

Abstract

PURPOSE:To obtain an insecticidal spray agent by filling contents consisting of an insecticidal formulated concentrate containing pyrethroid based compound and organic phosphorus agent and incombustible propellant containing dimethyl ether in a pressure-resistant vessel equipped with a special valve. CONSTITUTION:An insecticidal spray agent obtained by filling contents consisting of <=10% formulated concentrate containing a blend of a compound expressed by the formula (X is CH3 or Cl; R is H or CN) with an organic phosphorus agent, e.g. fenitrothione, and >=90% incombustible propellant containing 2-25% dimethyl ether, particularly a blended gas of flon 11 with flon 12 and dimethyl ether in a pressure-resistant vessel equipped with a special valve having a jetting nozzle of 0.4-1.0mm diameter under 3.0-7.0kg/cm<2>/25 deg.C internal pressure. The above-mentioned valve is capable of spraying the total amount of the contents at >=0.7ml/sec ratio and excellent in the viewpoint of fine dividing and diffusivity. The above-mentioned insecticide has remarkable insecticidal effect particularly on cockroaches resistant to pyrethroids.

Description

Detailed Description of the Invention The present invention provides a mixture of a compound represented by 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 an organic phosphorus agent. The contents consisting of 10% or less of the insecticidal stock solution and 90% or more of a nonflammable propellant containing 2 to 25% dimethyl ether are heated to an internal pressure of 3.0 to 7.0 Kg/c.
An insecticide characterized by comprising a pulp that is filled into a pressure-resistant container at rd/25°C, diffuses the contents as fine particles, and sprays the entire amount of the contents at a rate of 0.7 d or more per second. Regarding propellants.

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

Until now, it has been considered difficult to develop resistance to these pyrethroids, and in fact, there has been no problem in terms of pest control in Japan. Considering the emergence of sexual lineages and the tenacity shown by living organisms to ensure the survival of their species, it is considered appropriate to take measures based on the possibility of resistance development in Japan as well. Moreover, the development of these pyrethroid resistances is not dependent on the metabolic system, but involves a mechanism based on reduced neural sensitivity, and as a result, the phenomenon of pyrethroid cross-resistance has appeared. It has become important to develop applications, including the mixed use of pyrethroids and drugs with different physiological effects, such as pyrethroids and carbamates.

Therefore, the present inventors investigated a mixture of the pyrethroid represented by the general formula (1) and an organic phosphorus agent, and as a result of extensive research, it was found that when this mixture is used as an aerosol-type insecticidal propellant, the synergistic effect Not only is it effective, but it is also extremely superior in terms of resistance measures.
The composition containing 5% dimethyl ether improves the solubility and stability of the active ingredient, as well as the fineness of the contents during injection.
The present invention was completed based on the discovery that it is extremely useful in terms of diffusibility and the like.

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

In addition, all pyrethroids have two asymmetric carbon atoms in the acid moiety, and when R is a cyano group! has one asymmetric carbon in
Although there are optical isomers based on these, each isomer or a mixture thereof is naturally included in the present invention.

(1) 3'-phenoxybenzyl chrysanthemate (
Phenothrin) (233'-phenoxy-α'-cyanobenzyl chrysansemate (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, examples of the organic phosphorus agent used in the present invention include fenitrothion, diazinon, chloropyrifos, pyridafenthione, propafos, and DDVP.

Examples include, but are not limited to, bromophos.

Particularly useful fenitrothion is liquid at room temperature and is less soluble in paraffinic solvents than insecticidal ingredients such as cypyrethroid compounds.

The present inventors investigated the combination of the above-mentioned pyrethroids and organic phosphorus agents in various types, and as a result, discovered that the combination of the above-mentioned pyrethroid and organic phosphorus agent was most advantageous for application to an aerosol insecticide spray.

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

1. Either mix the insecticidal component with a combustion agent and eject the insecticide by using the combustion heat and smoke of the combustion agent, or pack the insecticide component and organic foaming agent together and heat the mixture indirectly to generate organic foam. The mechanism is such that the agent is thermally decomposed and the agent is converted to aX by the action of the thermal decomposition gas, and when the insecticidal component comes into contact with high temperatures, loss due to thermal decomposition is unavoidable.

Since it is mixed with a base material rich in 2 activities, stability over time may not be obtained depending on the properties of the insecticidal component.

3. Methods that involve combustion pose a risk of fire.

The present invention is a high-concentration, short-time space treatment agent designed to eliminate these drawbacks.

To explain the present invention in more detail, the content composition is a mixture of an insecticidal stock solution and a nonflammable propellant in a weight ratio of 10% or less for the insecticidal stock solution and 90% or more for the propellant. The solvent for preparing the stock solution is not particularly limited, but as for the propellant, it is recommended to contain 2 to 25% dimethyl ether to improve the solubility and stability of the active ingredient, or to improve the fineness of the contents during ejection.
Required from the viewpoint of diffusivity, etc.

In the summer, a container with a diameter of α3mm or more, preferably α4~1
．． By equipping a special pulp with an omm injection port, the internal pressure is 3.0 to 7.0 KW/di/1 at 25°.
It became possible to spray the entire amount of the contents at a rate of 0.7 d or more per second.

In addition, when we compared the distribution of the insecticidal ingredients that settled in the treated area after spraying with the smoke agent type, we found that the insecticide propellant of the present invention type had better dispersibility, cracks, gaps, etc. It was confirmed that the type of the present invention has excellent permeability into space, and the recovery rate of the insecticidal component calculated from the amount of deposited sediment is several orders of magnitude higher than the smoke type.

This is because, among the insecticidal ingredients, the organic phosphorus agent particularly used in the present invention has poor thermal stability, and therefore, when applied to a smoking agent, there is a large loss due to thermal decomposition during heating.

By using the insecticidal propellant of the present invention obtained in this manner, for example, a 100-volume one, a room of 6 to 10 tatami mats can be easily treated in a short time of less than 3 minutes without fear of fire, and it also eliminates cockroaches, flies, etc. It has extremely great practical advantages, such as its high extermination effect on indoor pests such as mosquitoes, bed bugs, and mites.

In particular, the insecticidal effect on cockroaches that have developed resistance to pyrethroids is remarkable, and the effect of the mixture in the insecticidal propellant of the present invention goes beyond simply adding the lethal power of the organic phosphorus agent, and provides a highly synergistic effect. This finding is completely unexpected from the conventional application of fumigants.

Various solvents can be used in the present invention, such as alcohols, ketones, ethers, esters, petroleum, halogenated hydrocarbons, and 7-halogenated hydrocarbons, but depending on the solubility of the active ingredient. , or from the viewpoint of quick drying after injection and toxicity, for example, acetone, methyl ethyl ketone,
It is preferable to use one or a mixed solvent of ethanol and ingropanol.

On the other hand, the propellant is 2 to 25% dimethyl ether, in addition to various fluorocarbon gases, nitrogen gas,
A combination of carbon dioxide gas or liquefied petroleum is used, and the composition is within the range of nonflammable gases.

A particularly useful propellant is a gas mixture of 70 N 11, 70 N 12 DEG dimethyl ether, where the 70 N 11 also serves as a solvent for the active ingredient or as a pressure regulator for the insecticidal propellant.

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

The injection valve provided in the container has an injection port with a diameter of 0.3 mm or more, but the internal pressure is 3.0 to 7.0 Ky/cri.
The shape is not particularly limited as long as it is possible to inject 0.7 or more contents per second at 725°C. For example, if you install several injection ports, set the injection angle at any angle other than upward, or rotate the injection ports to spray evenly into the room, the contents will be removed even when the injection starts. It is useful to have a device that delays the actual injection of the drug so that the person does not inhale the drug during use.

In addition, in the present invention, the efficacy enhancers of the above-mentioned insecticides such as pipero-2-lup toxide, octachlorodipropyl ether, imbornyl thiocyanoacetate, N-(2-ethylhexyl)-hycyclo[2°2.1]-hepta-5 −
En-2,3-dicarboximine F, N-(2-ethylhexyl)-1-isopropyl-4-methylbicyclo(
2,2,2) Oct-5-ene-2,3-dicarboximide and β-butoxy-β'-thiocyanodiethyl ether and insect repellent DEET, R-11. R-
326, dibutyl succinate, dibutyl 7 tallate,
Dimethyl 7-talate and the like can also be used in combination.

In addition to the above, stabilizers, fragrances, fungicides, acaricides or other insecticides such as pyrethroids such as allethrin, flamethrin, phthalthrin, empenthrin, 5-methoxy-3-(2-methoxyphenyl)-1,3 ,4-
It is also possible to mix a carbamate agent of oxadiazolin-2-one, etc., and a multipurpose composition with excellent effects can be obtained.

The insecticidal propellant of the present invention can be used indoors not only for susceptible pests but also for organic phosphorus agent, carbamate agent resistant or Kd
Various r-type pests such as flies.

It is particularly useful for exterminating mosquitoes, cockroaches, bedbugs, mites, etc., but it is also useful for exterminating grain storage pests such as the Japanese stag beetle, and aphids in plastic haxes.

It can also be applied to control agricultural pests such as scale insects and armyworms.

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

Example Insecticidal ingredients, solvents, and propellants having the composition shown in the table below were filled into a 100 Goaerosol container, a pulp having a diameter of α6 mm was attached to the injection port, and a protective cap was placed on the container to obtain an insecticidal propellant.

(Unit: g) The following propellant was prepared as a control for the insecticidal propellant of the present invention.

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

As a result of the test, the insecticidal component solubility of the propellant of the present invention was excellent, while the propellant without DME [1*
] and (1-L) formulation containing LPG instead of DME, oil act of insoluble matter was observed, demonstrating the usefulness of DME gas.

Experimental example & area 16rr? In a room with a height of 15 m, the present insecticidal propellant and a conventional smoke agent were applied, and the diffusibility of the insecticidal components and their permeability into objects were compared.

In other words, the center of the room is the injection point, 1.5 m.

Two 20σ square glass plates were placed at a distance of 2.5 m (one was left in the oven, and the other glass plate was placed in a 20c+n cubic cardboard box with a 0.5 x 10 cm band-shaped slit on the top). 20 hours later, the amount of sedimentation of the insecticidal component was measured.

The test samples were the insecticidal propellants El), [2], (1*) of the present invention prepared in the examples, and a commercially available organic foaming agent type smoking agent [Smoke-1] that was replaced with the insecticidal ingredient of the same formulation. [Smoking-2] was used.

Upper row: 2-converted amount h″v/rr? (lower row: Organophosphorus agent 9 value) The parentheses indicate the recovery rate relative to the theoretical sedimentation amount.

As a result of the test, the insecticidal propellant of the present invention had a distance of 1.5 m.

& 5m points, approximately 5% compared to the theoretical sedimentation amount.
It showed a high recovery rate of 0% (open) and had superior dispersion power compared to [1*] prescription and smoke agents.

In the case of smoking agents, it was confirmed that the recovery rate of organic phosphorus agents was particularly poor and the decomposition loss due to heat was large, and that dimethyl ether contributed to improving the diffusion power by comparing formulations [1] and [1*].

Furthermore, the processing time of the insecticidal propellant of the present invention is the same as that of a smoke agent, and its ability to penetrate between objects is excellent, so it has been recognized that it is extremely efficient.

Experimental Example 3゜ Place clothing boxes in the four corners of the room used in Experimental Example 2 with an area of 16 tref and a height of 2.5 m, and in each box about 20 susceptible and pyrethroid-resistant German cockroaches (female) were placed.
Each animal was released in two locations. A wooden shelter was installed inside the clothing box.

The test sample was sprayed from the center of the room and kept for 24 hours.
After exposure, the German cockroaches were collected and the mortality rate after 72 hours was examined, and the results were as follows.

(moe-1), (!-5) atsure ('shi, (1)
, [5] and the same test results showed that the insecticidal propellant of the present invention had a remarkable insecticidal effect on susceptible and 'resistant German cockroaches (11) and the control (5), [6].
] From the comparison, it was found that the mixture of pyrethroids and organic phosphorus agents was not observed in smoke agents.

Furthermore, from a comparison of [1] and [1*], it was found that dimethyl ether used as a propellant in the present invention is also useful in developing efficacy.

Example 2 Similarly to Experimental Example 1, a 100-aerosol container was filled with insecticidal ingredients, solvents, and propellants with the compositions shown in the table below, and the pulp and actuator were placed so that the injection port was installed at an upward angle of 45°. The insecticidal propellant of the present invention is obtained by attaching a protective cap to the compound A; 5-methoxy-3-(2-methoxyphenyl)-1,3,4-oxadiazolin-2.
- On procedure amendment (method) % formula % 1. Indication of the case Patent Application No. 113296 of 1985 2. Title of the invention Insecticidal propellant 3. Person making the amendment Relationship with the case Patent applicant address (residence) Osaka 5, Tosabori, Nishi-ku, Osaka City, Date of amendment order

Claims (1)

[Claims] General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼... (I) (In the formula, X represents a methyl group or a chloro atom, and R represents a hydrogen atom or a cyano group. ) and 90% or more of a nonflammable propellant containing 2 to 25% dimethyl ether, under an internal pressure of 3.0 to 7. .0kg/cm
^2/An insecticidal injection characterized by being filled into a pressure-resistant container at 25°C, dispersing the contents as fine particles, and equipped with a valve that sprays the entire amount of the contents at a rate of 0.7 ml or more per second. agent.