JPH0557964B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to an agricultural oil-in-water type dispersible insecticide composition, and more specifically, the insecticidal ingredient is [In the formula, Ar is

[Formula] Group or

[Formula] represents a group. R ₁ and R ₂ are the same or different and are a C _1-8 alkyl group, a C _3-6 cycloalkyl group, a phenyl group, a substituted phenyl group, -X-
COOR represents a ₃ group or a -Y-CN group, where X and Y are each a C _1-6 alkylene group, and R ₃ is a C _1-8
represents an alkyl group or a _C3-6 cycloalkyl group. Alternatively, R ₁ is a C _1-8 alkyl group or benzyl group, and R ₂ is

[Formula] represents a group, where R ₄ represents a C _1-8 alkyl group. ] This invention relates to an agricultural oil-in-water dispersible insecticide composition containing a sulfenyl carbamate derivative as a main ingredient. BACKGROUND ART Emulsions and powdered wettable powders are known as conventional agrochemical formulations for liquid spraying. Emulsions are made by dissolving insecticidal ingredients in organic solvents using surfactants, but because they contain surfactants and organic solvents, there are problems with toxicity and irritation to humans and animals, and chemical damage to crops. Also, it is difficult to handle because of the foul odor and risk of ignition due to the organic solvent. On the other hand, powdered wettable powders consist of an insecticidal component, an inorganic carrier, and a dispersant, and do not use organic solvents, so they do not have any disadvantages due to organic solvents. It is difficult to handle because it scatters, and the prepared spray solution is also unstable and inevitably causes sedimentation of the inorganic carrier.
There is a problem in that it is difficult to spray in small amounts at high concentrations during aerial spraying. In recent years, JP-A-55-17301, JP-A-55-
Publication No. 124707, Japanese Patent Publication No. 56-49303, Japanese Patent Publication No. Sho
No. 56-49307, JP-A-56-120608, JP-A-58-192810, and JP-A-58-118501, etc. disclose methods using water as a base material and suspending hydrophobic insecticidal components in the form of fine particles. Dispersed suspension compositions have been proposed. All of these compositions have a phosphorus-based insecticidal component or a synthetic pyrethroid insecticidal component as a main ingredient, and contain polyvinyl alcohol, a thickener, and other additives. On the other hand, sulfenyl carbamate derivatives represented by the general formula [] are disclosed in JP-A-50-48137, JP-A-57-200377, JP-A-58-92655,
It is disclosed in Japanese Patent Application Laid-Open No. 53-11863, etc., and has been developed as a useful insecticide because of its high insecticidal activity and low toxicity to warm-blooded animals. Therefore, making these sulfenyl carbamate derivatives represented by the general formula [] into an oil-in-water dispersible composition compensates for the drawbacks of the conventional formulations shown above, makes it possible to spray small amounts at high concentrations, and is safer. It has the advantage of being used as a seed treatment agent and is useful. However, it is known that the sulfenyl carbamate derivative represented by the general formula [] generally has poor storage stability, particularly in water. In order to improve stability, tertiary amines or epoxy compounds are added to conventional formulations such as emulsions and wettable powders. When you adjust the
During long-term storage, it gels and loses its dispersibility, and when an oil-in-water dispersion composition is prepared without the addition of an epoxy compound or stabilizer, the insecticidal component decomposes by about 10 to 30% during long-term storage. This is unsatisfactory and the desired composition cannot be obtained. Structure of the Invention The present inventors have studied to prepare an oil-in-water type dispersible insecticide composition with good dispersibility and good storage stability of insecticidal ingredients, and as a result, the intended purpose was achieved by adding urea. The present invention was completed based on this discovery. That is, the present invention provides an agricultural oil-in-water dispersible insecticide characterized by comprising 1 to 70% by weight of a sulfenyl carbamate derivative represented by the above general formula [], 1 to 20% by weight of polyvinyl alcohol, urea, and the remainder water. The invention relates to a drug composition. An example of the sulfenyl carbamate derivative used in the present invention is as follows. Γ2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-ethoxycarbonylethyl-N-isopropylaminosulfenyl)N-methylcarbamate (compound 1) Γ2,3-dihydro-2,2 -dimethylbenzofuran-7-yl N-[N,N-bis(ethoxycarbonylmethyl)aminosulfenyl]N
-Methylcarbamate (compound 2) Γ2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N,N-dibutylaminosulfenyl)N-methylcarbamate (compound 3) ΓS-methyl N[[ N-methyl (N-isobutyl-N-ethoxycarbonylethylaminothio)
Carbamoyl]oxy]thioacetimidate (compound 4) ΓS-methyl N[[N-methyl (N-benzyl-
N-ethoxycarbonylethylaminothio)carbamoyl]oxy]thioacetimidate (compound 5) ΓO-butylO'-(2,3-dihydro-2,2-
dimethylbenzofuran-7-yl)N,N'-
Dimethyl N,N'-thiodicarbamate (compound 6) The amount of the above sulfenyl carbamate derivative contained in the composition of the present invention is usually 1 to 70% by weight,
Preferably it is 10 to 60% by weight. If the amount of the sulfenyl carbamate derivative is less than 1% by weight, it is not practical because a large amount of polyvinyl alcohol is required to maintain the dispersion stability of the composition. The amount of sulfenyl carbamate derivative
If it exceeds 70% by weight, the resulting composition will have a high viscosity, making it difficult to use and impractical. The degree of saponification and degree of polymerization of the polyvinyl alcohol used in the present invention are not particularly limited, but polyvinyl alcohol with a degree of saponification of 70 to 90 mol% and a degree of polymerization of 200 to 3,500 is preferable. Polyvinyl alcohol 205 [Kuraray Co., Ltd.]
Saponification degree 87-89 mol%, polymerization degree 500-600], polyvinyl alcohol 224 [Kuraray Co., Ltd., saponification degree 87-89
mole %, degree of polymerization 2400 to 2500], etc. The blending amount of polyvinyl alcohol is as follows:
Although it varies depending on the amount, type, etc. of the sulfenyl carbamate derivative used, it is usually 1 to 20% by weight, preferably 1.5 to 12% by weight. When the amount of polyvinyl alcohol is less than 1% by weight,
The dispersion stability of the composition deteriorates, making long-term storage difficult. Contains 20% polyvinyl alcohol by weight
If it is more than that, the viscosity becomes high and it is not practical. It is necessary to add urea to the composition of the present invention in order to maintain the stability of the insecticidal component. The amount of urea blended is 0.5 to 10% by weight, preferably 1 to 5% by weight. If the amount of urea added is less than 0.5% by weight, the storage stability of the insecticidal ingredient will deteriorate, and if the amount of urea is less than 0.5% by weight,
The above method is not economical because there is no change in storage stability. If other stabilizers such as epoxy compounds are added to the composition of the present invention, even higher effects may be exhibited. Specific examples of the epoxy compound include soybean oil epoxidized product, phenyl glycidyl ether, glycidol, and the like. The composition of the present invention does not need to contain a thickener or a surfactant, but may be added if necessary. Thickeners used include, for example, sodium polyacrylate, ammonium polyacrylate, carboxymethyl cellulose sodium salt,
Examples include hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, gelatin, starch, casein, sodium alginate, guar gum, locust bean gum, and xanthan gum. Examples of the surfactants used include alkyl sulfates, alkylbenzene sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, sorbitan fatty acid esters, polyoxyethylene fatty acid esters, and oxyethylene. Examples include oxypropylene block polymers, polyoxyethylene alkylamines, alkyl betaines, and the like. The blending amount of these thickeners and surfactants is usually 5% by weight or less in the composition of the present invention. The composition of the invention is prepared by dispersing liquid particles of a sulfenyl carbamate derivative in an aqueous mixture of polyvinyl alcohol and urea by mechanical means. For example, if necessary, heat the sulfenyl carbamate derivative to a liquid state, then disperse and suspend it in an aqueous solution of polyvinyl alcohol and urea at a temperature between room temperature and 70°C using an ultra-high-speed homogenizer such as the Swiss Kinematica Polytron. It is manufactured by converting Stirring time is 5-10
Within minutes, the average particle size is 1-5μ, and all individual particles are
Continue until it becomes 10μ or less, preferably 5μ or less.
It is also possible to add surfactants and finally mix in appropriate amounts of thickeners. When using the composition of the present invention, it is possible to use it undiluted, or dilute it at a low dilution of several to several tens of times, or dilute it at a high dilution of 1000 to 2000 times. A carrier or water is used for dilution to achieve a predetermined concentration depending on the purpose. The composition of the present invention can be used as a foliar spray, either undiluted or after dilution.
Used as a soil treatment agent, seed treatment agent, etc. Effects of the Invention The composition of the present invention thus obtained has good dispersibility and stability of the insecticidal component over a long period of time, and has biological effects comparable to those of conventional formulations, and furthermore, has a biological effect comparable to that of conventional formulations. It has advantages not found in That is, the composition of the present invention has a concentration ranging from a low concentration to 70% by weight.
It is possible to formulate highly concentrated formulations, and since no organic solvents are used, there is no phytotoxicity to crops, there is little irritation to the eyes and skin, it is non-flammable, and there is little staining or damage to the paint, which is almost impossible with conventional emulsions. Even water containing a high concentration of inorganic salts can be used as dilution water. EXAMPLES The present invention will be explained in more detail with reference to Examples, Test Examples, and Reference Examples below. Example 1 22.2 g of compound 1 (active ingredient content 90%), 3 g of urea, 50 g of 10% by weight polyvinyl alcohol 224
The aqueous solution and 24.8 g of water were combined and mixed for 5 minutes at room temperature using a Polytron R◯ at 10,000 revolutions per minute. A micrograph showed that all the particles were 10μ or less, and the average particle size was 3μ. The resulting composition had good water dilutability. The composition was placed in a sealed container and left at 50°C for 30 days, but no separation of an oil layer was observed and it remained stable. Example 2 66.6 g of compound 1 (active ingredient content 90%), 3 g of urea, 20 g of 10% by weight polyvinyl alcohol 205
The aqueous solution and 10.4 g of water were combined and mixed for 5 minutes at room temperature using a Polytron R◯ at 10,000 revolutions per minute. Microscopic photographs showed that all particles were less than 10μ and the average particle size was 2μ. The resulting composition had good water dilutability. Put the composition in a sealed container
Although it was left at 50°C for 30 days, no separation of an oil layer was observed and it remained stable. Example 3 42.4 g of compound 5 (active ingredient content 94%), 2 g of urea, 30 g of 10% by weight polyvinyl alcohol 224
The aqueous solution and 25.6 g of water were combined and mixed for 5 minutes at 50° C. using a Polytron R◯ at a rotational speed of 10,000 rpm. Microscopic photographs showed that all particles were less than 10μ and the average particle size was 3μ. The resulting composition had good water dilutability. Put the composition in a sealed container
Although it was left at 50°C for 30 days, no separation of an oil layer was observed and it remained stable. Examples 4-12 Compositions of Examples 4-12 were produced in the same manner as Examples 1-3. The blending ratio of the composition and the stability of the composition are shown in the table.

【table】

[Table] In the table, stability at 50°C for 30 days is defined as "good" when the composition is placed in a sealed container and left at 50°C for 30 days without separation of the oil layer. Also, what is water dilutability?
When the composition was added to a beaker containing water at a dilution rate of 100 to 1000 times and stirred with a magnetic stirrer, the composition was rated as "good" if it was uniformly dispersed within 30 seconds. Reference example 1 22.2g of compound 1 (active ingredient content 90%), 50g of
10% by weight polyvinyl alcohol 224 aqueous solution and
27.8 g of water was combined and mixed for 5 minutes at room temperature using a Polytron R◯ at 10,000 revolutions per minute. A micrograph showed that all the particles were 10μ or less, and the average particle size was 3μ. The resulting composition had good water dilutability. Place the composition in a sealed container and heat at 50℃ for 30 minutes.
Although it was left for several days, no separation of the oil layer was observed. Reference example 2 56.8g of compound 3 (active ingredient content 88%), 30g of
10% by weight polyvinyl alcohol 205 aqueous solution, 5g
of soybean oil epoxide and 8.2g of water,
Rotation speed 10000 per minute using Polytron R○ at room temperature
Mixed by rotation for 5 minutes. A micrograph showed that all the particles were 10μ or less, and the average particle size was 2μ. The resulting composition had good water dilutability. The composition was placed in a sealed container and left at 50°C for 30 days, but no separation of the oil layer was observed. Reference example 3 44.4g of compound 1 (active ingredient content 90%), 25g of
20% by weight polyvinyl alcohol 205 aqueous solution, 8g
of triethanolamine and 22.6 g of water,
Rotation speed 10000 per minute using Polytron R○ at room temperature
Mixed by rotation for 5 minutes. A micrograph showed that all the particles were 10μ or less, and the average particle size was 3μ. The resulting composition had good water dilutability. When the composition was placed in a sealed container and left at 50°C for 30 days, the composition gelled and was unusable. Test Example 1 The storage stability of the insecticidal ingredients in the compositions obtained in the above Examples and Reference Examples was tested. The composition was placed in a sealed container and left to stand at 40°C and 50°C for 30 days, then the insecticidal component was measured and the decomposition rate was calculated. The table shows the decomposition rate of each composition.

[Table] As shown in the table, the insecticidal ingredients in the compositions of Examples 1 to 12 to which urea was added were stable, but those of Reference Examples 1 and 2 were unstable and were virtually unusable. Test Example 2 The bioefficacy of the composition obtained in Example was compared with a conventional dosage form composition containing the same active ingredient by a spraying test. Comparative examples of insecticidal activity are shown in the table.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, Ar represents a [formula] group or a [formula] group. R ₁ and R ₂ are the same or different and are a C _1-8 alkyl group, a C _3-6 cycloalkyl group, a phenyl group, a substituted phenyl group, -X-
COOR represents a ₃ group or a -Y-CN group, where X and Y are each a C _1-6 alkylene group, and R ₃ is a C _1-8
represents an alkyl group or a _C3-6 cycloalkyl group. Alternatively, R ₁ represents a C _1-8 alkyl group or a benzyl group, R ₂ represents a [Formula] group, and R ₄ represents a C _1-8 alkyl group. ] Sulfenyl carbamate derivatives 1-
70% by weight, polyvinyl alcohol 1-20% by weight,
An agricultural oil-in-water dispersible insecticide composition comprising 0.5 to 10% by weight of urea and water. 2. The composition according to claim 1, wherein 2 Ar is a [Formula] group, R ₁ is a -CH ₂ CH ₂ COOC ₂ H ₅ group, and R ₂ is an isopropyl group. 3. The composition according to claim 1, wherein Ar is a [Formula] group, and R ₁ and R ₂ are both n-butyl groups. 4. The composition according to claim 1, wherein Ar is a [Formula] group, R ₁ is a -CH ₂ CH ₂ COOC ₂ H ₅ group, and R ₂ is a benzyl group. 5. The composition according to claim 1, wherein Ar is a [Formula] group, R ₁ is a -CH ₂ CH ₂ COOC ₂ H ₅ group, and R ₂ is an isobutyl group. 6 The degree of polymerization of polyvinyl alcohol is 200 to 3500,
The composition according to claim 1, having a degree of saponification of 70 to 90 mol%.