JPH01190609A - Aqueous insecticidal aerosol - Google Patents

Abstract

PURPOSE:To obtain an aqueous insecticidal aerosol not inferior to a recipe of a conventional propellant gas (fluorocarbon gas), by blending an insecticidal formulated concentrate prepared by adding a lower alcohol to a specific insecticidal ingredient with water and dimethyl ether in a specific proportion and filling the resultant mixture in a pressure-resistant vessel. CONSTITUTION:An aqueous insecticidal aerosol obtained by filling contents consisting of 5-20vol.% insecticidal formulated concentrate prepared by adding a lower alcoholic solvent (preferably ethyl alcohol or isopropyl alcohol) to a mixture of a pyrethroid based compound (e.g., Phenothrin(R) or Permethrin(R)) expressed by the formula (X is CH3 or Cl; R is H or CN) with a carbamate based compound or organophosphorus agent, 15-30vol.% water and 50-90vol.% dimethyl ether or a propellant obtained by adding liquefied petroleum gas to the dimethyl ether in a pressure-resistant vessel having a valve for spraying >=95vol.% contents at >=0.5ml per sec rate under 3.0-7.0kg/ cm<2>/25 deg.C and diffusing the contents as fine particles.

Description

Detailed Description of the Invention The present invention relates to a compound represented by the general formula (I) (wherein X represents a methyl group or a chromium atom, and R represents a hydrogen atom or a cyano group) and a carbamate-based compound or an organic 5 to 20% by volume of an insecticidal stock solution made by adding a lower alcoholic solvent to a mixture of phosphorous agents, and 15 to 20% by volume of water.
30% by volume and 50-90% by volume of a propellant consisting of dimethyl ether/'v or dimethyl ether plus liquefied petroleum gas.
The contents consisting of are heated to an internal pressure of 3.0 to 7. OKtt/
dV Filled into a pressure-resistant container at 25°C, the content is diffused as fine particles, and the pulp is sprayed at a rate of 0.5 d or more per second to eject 95% or more of the content.・For insects and propellants.

The pyrethroid compound represented by the general formula CI) exhibits an extremely excellent insecticidal effect against various sanitary pests and agricultural and horticultural pests, while its toxicity against bleeding 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 control in Japan, but houseflies in northern Europe and the diamondback moth in Southeast Asia have developed resistance to pyrethroid agents. Considering the emergence of new strains 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 decreased neurosensitivity, and as a result, the phenomenon of pyrethroid cross-resistance has appeared, and as a solution to this phenomenon, organophosphate It has become important to develop applications including the mixed use of pyrethroids and drugs with different physiological effects, such as carbamate agents.

When the present inventors applied a mixture of the pyrethroid of general formula (I) and a carbamate compound or an organic phosphorus agent as an aerosol type insecticidal propellant, not only the synergistic effect but also the
Having found that the invention is extremely superior in terms of resistance, he has already applied for several patents listed below. Since the intention was to develop a biogenic insecticidal propellant, the propellant gas was mainly chlorofluorocarbon gas.

However, in recent years, the problem of ozone layer depletion caused by fluorocarbon gases has been brought into focus, and in view of the situation where the use of fluorocarbon gases in aerosol products should be restricted, the present inventors have investigated the use of fluorocarbons other than fluorocarbons, such as fluorocarbons and liquefied petroleum gas. As a result of intensive research into the development of an insecticidal propellant using propellant gas, we have developed an insecticidal stock solution containing 5-20% by volume of insecticidal ingredients plus a lower alcohol-μ solvent, 15-30% by volume of water, and liquefied into dimethyl ether or dimethyl ether. The contents consisting of 50 to 90% by volume of propellant to which petroleum gas has been added are heated to an internal pressure of 3
．． 0 to 7.0 Kg/ciV The insecticidal propellant filled in a pressure container at 25°C satisfies the explosiveness and flammability conditions stipulated in the regulatory regulations, as well as Kg, internal pressure, injection amount, and aerosol particle content. They discovered that there was no inferiority in terms of size, stability of insecticidal ingredients, etc. compared to conventional propellant gas formulations, and based on these findings, they completed the present invention.

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, any pyrethroid has two asymmetric carbon atoms in the acid moiety, and if R is a cyano group, it further has one asymmetric carbon,
There are optical isomers based on these, and each isomer or a mixture thereof is naturally included in the present invention.

(1) 3'-phenoxybendi chrysanthemate (phenothrin) (2) 3'-phenoxy α'-cyanobendi
Chrysanthemate (Saifninotrin) (3) 3'-phenoxybenzyl 2,2-dimethyl-3-(2,2-dichlorovinycyclopropanecarboxylate (permethrin) (4) 3'=
7z Tsukishi 4”-V7/Benge lv2.2-Dimethi/
l/-3-(2,2-dichlorovinyl→cyclozolobanka μboxylate (cype μmethrin)) On the other hand, among the carbamate compounds used in the present invention, particularly useful 3-(2-methoxypheny/l /)-5-
Methoxy-1,3,4-oxadiazo-/L'-2-one is a recently developed product that is solid at room temperature (m, p,
77'C) Compared to insecticidal ingredients such as acacia and pyrethroid compounds, it has the property of being less soluble in buffin-based solvents and alcohol-based solvents.

Further, examples of organic phosphorus agents include fenitrothion, pyridafenthione, diazinon, clopyrifos, propaphos, etc., but are not limited to these.

The present inventors investigated various types of combinations of the above-mentioned pyrethroids and carbamate compounds or organic phosphorus agents, and as a result, discovered that application to aqueous air-seal type insecticidal propellants is most advantageous.

That is, conventionally commonly used insecticidal methods include the air seal type and the 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 a combustion agent and blow out the insecticide by using the combustion heat and smoke of the combustion agent, or mix the insecticide component and organic foaming agent in a bag, and heat the mixture indirectly to generate organic foam. The mechanism is such that the insecticide is thermally decomposed and fumigated by the action of the pyrolysis gas, but when the insecticidal component comes into contact with high temperatures, loss due to thermal decomposition is unavoidable.

2. Stability over time may not be achieved depending on the properties of the insecticidal component because it is mixed with a highly active base material.

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 5 insecticidal stock solutions.
~20% by volume, 15-30% by volume of water, and 50% by volume of propellant.
It is blended at a ratio of 90% by volume.

As the solvent for preparing the stock solution, lower alcohol solvents are suitable from the viewpoint of solubility of the insecticidal component, compatibility with water and propellant, and quick drying after spraying, among which ethyl alcohol and isopropyl alcohol are suitable. Suitably used.

In addition, in the present invention, the efficacy enhancers of the above insecticides, such as viberoni ρ butoxide, octachlorosideropiate~, "thiocyanoacetic acid isoboμ2#, N-(2-x
Chill heki! /A/)-bisik' (2e2e1]-hept-5-ene-2,3-cica boximide, N-(2
-ethylhexy/I/)-1-isopropy/L'-4-
Methi p-bicyclo(2,2,2)oct-5-ene-2,
3-dicarboximide and β-butoxy-β'-thiocyanodiethyl ether p and the insect repellent DEET, R-11. R-326. Dibutyl succinate, dibutyl phthalate, dimethyl phthalate, etc. can also be used in combination.

In addition to the above, stabilizers, fragrances, fungicides, acaricides, and other insecticides such as allethrin and flamethrin.

Pyrethroid agents such as Futar/L'Surin and Embensuline, or hydroprene and methoprene.

1-Methyl/l/-1-(2-pyridyloxy)-2-(
It is also possible to mix insect growth disruptors such as 4-phenoxyphenoxy)ethane, and a multipurpose composition with excellent effects can be obtained.

The present invention is characterized in that 15 to 30% by volume of water is blended so that it falls within the range of weak flammability or less in the flammability classification specified in Ministry of International Trade and Industry Notification No. 557 of the High Pressure Gas Control Act. In other words, if the water content is less than 15% by volume, the flammability will be equivalent to strong twisting, making it unsuitable as a household insecticide;
It has become clear that when the amount exceeds 0% by volume, problems arise in terms of solubility of the insecticidal component or compatibility with the solvent and the propellant gas.

Further, as the propellant, dimethyl ether or a mixed gas of dimethyl ether and liquefied petroleum gas is used, and is blended in an amount of 50 to 90% by volume. If the amount is less than 50% by volume, it is necessary to make the injection port extremely large in order to obtain an injection amount of 0.5 d or more per second, and it is difficult to atomize and diffuse the spray particles, making it difficult to achieve the desired high concentration. Not suitable for short-term processing. In addition, when using a mixed gas, the ratio of liquefied petroleum gas to dimethyl ether is preferably 40% or less by volume from consideration of flammability.

The material of the container used for the insecticidal 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 100 to 200 can is usually suitable. .

In the case of water preparations, in order to prevent corrosion of the container due to water content, a rust preventive agent such as thorium benzoate may be added as appropriate, if necessary.

The propellant valve installed 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 Kg/cd/2.
The shape is not particularly limited as long as it is possible to inject 0.5 g or more of the content per second at 5°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 uniformly into the room, or set the injection port to start. Providing a device that delays the actual ejection of the contents is useful in that the drug is not inhaled by the person during use.

The insecticidal propellant of the present invention thus obtained, for example 100ne
If you use a 2.5-inch container, you can easily treat a 6-8 tatami room in less than 4 minutes without worrying about fire, and it is highly effective in exterminating pests inside the house, making it more practical. The benefits are extremely large.

In particular, the insecticidal effect on cockroaches that have developed resistance to pyrethroids is remarkable. This finding is completely unexpected from conventional smoke application.

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 has been confirmed that the type of the present invention has excellent permeability into space, and the recovery rate of insecticidal ingredients calculated from the amount of sedimentation deposited in history is several times higher than the smoke type.

This is because among the insecticidal ingredients, carbamate agents or organic phosphorus agents particularly used in the present invention have poor thermal stability.
This is because when applied to smoking agents, there is a large loss due to thermal decomposition during heating.

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 brown elephants and aphids in greenhouses.

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.

Test Example 1 Pemethrin 1.2g and 3-(2
-methoxyphenylene/L/)-5-methoxy-1,2゜4
-Oxadiazolin-2-one 0.4g in ethanol-ρ
100WI! with the composition shown in the table below of insecticidal stock solution dissolved in water, water, and propellant gas. Air Sea! The compatibility, EC (explosiveness), flame (flammability), and spray condition of the insecticidal propellant obtained by filling an aluminum can and attaching a pulp with a nozzle diameter of 0.5 mm were as follows. It was like that.

(Note) In the table, EC indicates the explosive concentration in the explosive test, and flame indicates the flame length in the flammability test.

As a result of the test, if the proportion of water is less than 15% by volume (control propellant 1), the flammability is unsuitable, while if it exceeds 30% by volume (control propellant 2), the compatibility and spray condition are unsuitable. There was a problem.

Furthermore, when the ratio of propellant gas was low (control propellant 3), the spray condition was not good, and when the insecticidal stock solution was less than 5% by volume (control propellant 4), the solubility of the insecticidal component was poor.

Therefore, it has been revealed that only the insecticidal propellant of the present invention, which contains the insecticidal stock solution, water, and propellant gas in a specific ratio, meets all conditions such as compatibility, flammability, and spray condition.

Test Example 2 Insecticidal ingredients, solvent, water, and propellant were used in the composition shown in the table below.
0-Fill into an aerosol container, the diameter of the injection port is 0.4 m
Attach the valve of m to membrane compound A15-methoxy-3
-(2-Methoxyphenylene/L/)-1,2,4-oxadiazolin-2-one Compound B; l-Methylv-1-(2-pyridyloxy)
-2-(4-phenoxyphenoxy)ethane In a room with an area of 16 trf and a height of 2.5 m, this insecticide propellant,
A control propellant and a conventional smoke agent were applied, and the diffusivity of the insecticidal ingredient, penetration between objects, and insecticidal efficacy were compared.

In other words, the center of the room is the injection point, and the distance is 1.5 m and 12.5 m.
Place two 20cm square glass plates at a distance of
After 20 hours, the amount of sedimentation of the insecticidal component was measured.

The amount of adhesion is expressed as the recovery rate (insecticidal component pyrethroid) relative to the theoretical sedimentation amount.

In addition, clothing boxes were placed in the four corners of the room, and sensitive and pyrethroid-resistant German cockroaches (approximately 20 cockroaches each) were released in two locations each.

A wooden shelter was installed inside the clothing box.

After being exposed to the spray for 24 hours, the German cockroaches were collected and the mortality rate after 72 hours was investigated, and the results were as follows.

As a result of the test, the propellant of the present invention showed a high recovery rate of more than 50% of the theoretical sedimentation amount at both 1.5 m and 2.5 m points, and the insecticidal efficacy was also extremely high.
In the case of sump/l/44 containing 0 volume % or more, the reach distance of the chemical solution was short, the diffusivity was inadequate, and the dryness after treatment was poor.

On the other hand, in the case of smoking agents, there is a large decomposition loss due to heat, so
Both the recovery rate of the attached amount and the insecticidal efficacy were inferior, confirming the usefulness of the insecticidal propellant of the present invention.

Example Similar to Test Example 2, a 100WI aerosol container was filled with insecticidal ingredients, solvents, and propellants with the compositions shown in the table below, and the valve and actuator were removed so that the injection port was installed upward at 45 degrees. A protective cap was then placed on the product to obtain an insecticidal propellant of the present invention.

Two sprays were sprayed at a cafeteria in about 40th Street, and the density of cockroaches after treatment was investigated using an adhesive trap. Ta.

(Unit: ig) Compound A, Compound B: Represents the same compounds as in Test Example 2.

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 a mixture of a carbamate compound or an organic phosphorus agent, a lower alcohol solvent is added to the insecticidal stock solution (5 to 20% by volume), and water is 15 to 20% by volume.
The contents consisting of 30% by volume and 50 to 90% by volume of dimethyl ether or a propellant prepared by adding liquefied petroleum gas to dimethyl ether were heated to an internal pressure of 3.0 to 7.0 Kg/cm^2.
An insecticidal propellant that is filled into a pressure-resistant container at /25°C and equipped with a valve that diffuses the contents as fine particles and sprays 95% or more of the contents at a rate of 0.5 ml or more per second. .