JPS61180704A - Stabilized insecticidal and agricultural granular composition - Google Patents

Abstract

PURPOSE:The titled composition, obtained by adding polyvinyl alcohol to a specific sulfenylcarbamate derivative as an insecticidally active component, and making an unfired substance hold the component, having the stable active component for a long period, and available at a low cost. CONSTITUTION:A stabilized insecticidal and agricultural granular composition obtained by adding polyvinyl alcohol and if necessary urea to a sulfenylcarbamate derivative expressed by the formula [R<1> and R<2> are 1-8C alkyl, 3-6C cycloalkyl, 1-4C alkoxy 1-4C alkyl, phenyl, benzyl, -X-COOR<3> (X is 1-6C alkylene; R<3> is 1-8C alkyl, 3-6C cycloalkyl, -Y-CN (Y is X), etc.] as an insecticidally active component, and making an unfired substance such as bentonite, diatomaceous earth or talc hold the component. EFFECT:The active component is sufficiently stable even in formulation by hydration, and the activity not interior to that of the conventional formulation in biological effect is exhibited. The mixing formulation with another pharmaceutical which could not be formulated is possible.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to stabilized insecticidal pesticide granule compositions.

(Prior Art) In recent years, many sulfenyl carbamate derivatives have been developed and are being put into practical use as insecticidal carbamate agents with high insecticidal activity and low toxicity to warm-blooded animals, and are attracting attention. For example, in JP-A-50-48137, 2,3-dihydro-2,2-dimethylbenzo7ran-7-yl N-(
N,N-dibutylaminosulfenyl)
2,2-dimethylbenzo7ran-7-yl N-(N-″
Alkyl-N-ethoxycarbonylethylaminosulfenyl) N-methylcarbamate, etc., have been disclosed and are known as excellent low-toxicity insecticides that are highly effective against various pests and diseases in rice and field crops and have a wide insecticidal spectrum. However, it is also known that when these excellent insecticidal active ingredients are supported on powdered or granular mineral carriers, which are commonly used for formulation, and the formulation is made by adding water, the active ingredients are severely degraded. It is being It is generally said that decomposition by mineral carriers is influenced by the water content, pH 1 basic displacement capacity, surface acidity, etc. of the carrier used. For this reason, various studies have been made and patent applications have been made regarding the formulation of these sulfenyl carbamate derivatives with the aim of preventing the decomposition of the active ingredients. For example, US Patent 4
, 281,014 discloses a method of stabilization using an epoxy compound, and JP-A-59-51206 and JP-A-59-55807 disclose a method of using a mineral carrier calcined at 1000° C. or higher. It is shown.

However, in the former method, a sufficient stabilizing effect cannot be obtained unless a large amount of an epoxy compound is used, and therefore it is necessary to select a mineral substance with high oil absorption capacity.

On the other hand, in the latter method, the use of calcined minerals is well known as an agricultural carrier, but sufficient stability cannot be obtained unless calcined at a high temperature of 1000°C or higher, resulting in a narrow range of carrier selection (and cost It is high and has some drawbacks.

(Problems to be Solved by the Invention) An object of the present invention is to provide an inexpensive and stable insecticidal/pesticide granule composition that can easily be used to select mineral carriers.

(Means for Solving the Problems) The present invention provides an insecticidal active ingredient of the general formula [wherein R' and R2 may be the same or different, a Cl-6 alkyl group, a C3-6 cycloalkyl group, a (C , ~4) 7-alkyl group, phenyl group, substituted 7-enyl group, pencil group, substituted benzyl group, -X-COOR
3 group, -Y-CN group, and the substituents include a halogen atom, C=, s-furkyl group, CI, :l-furkoxy group, and X and Y are 01 to . is a straight-chain or branched alkylene group, R3 represents a C1-8 furkyl group, or a C3,@9 chloroalkyl group. Further, R' is the above group, R21J
Stabilization characterized by adding polyvinyl alcohol and optionally further urea to a sulfenyl carbamate derivative represented by ] representing a ni COOR4 group, R'it C+ to af) furkyl group and retaining it in an uncalcined mineral material. The present invention relates to an insecticidal pesticide granule composition.

An example of the sulfenyl carbamate derivative used in the present invention is as follows.

・2,3-dihydro-2,2-trimethylbenzo7ran-7-yl N-(N-ethoxycarbonylethyl-N-isopropyl 7-minosulfenyl) N-methylcarbamate (Compound 1) ・2,3-dihydro-2,2 -tumethylbenzofuran-fuyl N-(N,N-bis(ethoxycarbonylmethyl)aminosulfenyl]N-methylcarbamate (
Compound 2) ・2,3-dihydro-2,2-tumethylbenzo7ran-7-yl N-(N,N-dibutylaminosul7enyl)N-methylcarbamate (Compound 3)・[(2,2
-2methyl-2,3-dihydrobenzo7ranyl-7-oxy)-(N-methylamino)-carbonyl]-[n-
Butoxy-(N'-methylamino/)-carbonyl]-sulfide (Compound 4) The amount of the above-mentioned sulfenyl carbamate derivative can vary within a wide range, but 1 to 20% by weight is usually appropriate as a pesticide II component. .

The degree of saponification and degree of polymerization of the polyvinyl alcohol used in the present invention are not particularly limited, but the degree of saponification is 70
Polyvinyl alcohol with a polymerization degree of 200 to 3,500 is preferable, and a specific example is polyvinyl alcohol 205 (manufactured by Clan Co., Ltd., saponification degree of 87 to 3,500).
89 mol%, degree of polymerization 500-600], polyvinyl alcohol 224CC strain), saponification degree 87-89 mol%, degree of polymerization 2400-2500), and the like. The amount of polyvinyl alcohol blended varies depending on the type of sulfenylcarbamate (W) conductor used, the amount blended, etc., but it is usually 0.1 to 10% by weight, preferably 0.5 to 5% by weight in the composition. be.

In the present invention, urea can be used depending on the case. That is, if the amount of polyvinyl alcohol blended is too low to provide sufficient stability of the active ingredient, urea can be blended in an amount of 0.01 to 0.5% by weight based on the composition for stabilization.

The mineral carrier used in the present invention is not limited as long as it is commonly used for agricultural chemicals.
Examples include bentonite, clay, talc, zeolite, calcium carbonate, diatomaceous earth, and the like.

The composition of the present invention can be prepared by adding polyvinyl alcohol and optionally urea to a sulfenyl carbamate derivative as an active ingredient, adding a mineral carrier and an appropriate amount of water, and kneading the mixture, followed by granulation into an appropriate particle shape. . In addition, a sulfenyl carbamate derivative is dispersed in an aqueous polyvinyl alcohol solution by mechanical means to produce an oil-in-water type dispersible composition, and then polyvinyl alcohol is further added to this as necessary, and the mixture is kneaded with a mineral carrier. It can also be granulated into granular shapes.

(Effect of the invention) The active ingredient of the composition of the present invention thus obtained is stable over a long period of time, and when formulated with only a normal mineral carrier, almost no decomposition is observed even under conditions where it decomposes by 20% or more. I couldn't. In particular, the active ingredients of the composition of the present invention are sufficiently stable even when formulated with water, which was previously unthinkable.

Furthermore, the biological effect of the composition of the present invention is comparable to that of conventional preparations, and the present invention has a wider range of applications, such as making it possible to formulate mixed preparations with other drug waste, which was not possible with conventional preparations. Ta.

(Examples) The present invention will be explained in more detail below using Examples, Reference Examples, and Test Examples.

Reference Example 1 Compound 1 (42.4g), 2g of urea, 30g of 1
0% by weight polyvinyl alcohol 224 aqueous solution, 25.6
g of water were combined and mixed for 5 minutes at room temperature using a stirrer at 10,000 revolutions per minute. An oil-in-water type dispersible composition was obtained in which the total particle size was 10 μm or less and the average particle size was 3 μm.

Example 1 12.6 g of the oil-in-water dispersible composition obtained in Reference Example 1 was preliminarily mixed with diatomaceous earth 201 (20 g) and Tenryu bentonite (
20g) and talc GTA (52g) were added to the mixed carrier and mixed. To this, 12.5 g of a 20% polyvinyl alcohol 205 aqueous solution and an appropriate amount of water were added and kneaded.

The proportion of polyvinyl alcohol (PVA) in the composition is 3
Weight%. The kneaded product was passed through an extrusion granulator equipped with a screen with a diameter of 1 mm to form a granulated preparation. The granulated granules were dried with hot air at 50°C to -60°C all day and night.

Example 2 20% polyvinyl alcohol 205 aqueous solution 158 was added to compound 4&+ 1 (5.32 g), and the mixture was added to a carrier in which diatomaceous earth 201 (20 g), Tenryu bentonite (20 g), and talc GTA (52 g) were mixed in advance. Ta. An appropriate amount of water was added to this and kneaded. The kneaded product was passed through an extrusion granulator equipped with a screen having a diameter of 11 m to form a granulated preparation. The granulated granules were dried with hot air at 50 to 60°C all day and night.

Example 3 15 g of a 20% polyvinyl alcohol 205 aqueous solution was added to Compound 3 (5.32 g), and the mixture was added to a carrier in which sunbentonite (42 g), Kunimine clay (25 g), and calcium carbonate N S 100 (25 g) were mixed in advance. Combined. An appropriate amount of water was added to this and kneaded. The kneaded product was passed through an extrusion granulator equipped with a screen of diameter III@ to form a granulated preparation. Granulated granules are 5
It was dried with hot air at 0 to 60°C all day and night.

Examples 4-10 Granules of Examples 4-10 were produced in the same manner as Examples 1-3. Table 1 shows the types and amounts of active ingredients, minerals, polyvinyl alcohol, and amount of urea.

Test example 1 The granules of Examples 1 to 10 were then subjected to stability tests.

Each granule was stored at 50°C for 7 and 30 days, and the decomposition rate of the active ingredient was measured. As a comparative test example, the decomposition rate was measured when polyvinyl alcohol of the same composition was not included. The decomposition rate was measured by high performance liquid chromatography. The results are shown in Table 2, and it can be seen that the composition of the present invention is very stable.

No. 1 Table Table 2 (that's all)

Claims (5)

[Claims] (1) As insecticidal active ingredients, there are general formulas▲mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 and R^2 may be the same or different.C_1_
~_8 alkyl group, C_3_-_6 cycloalkyl group,
(C_1_~_4) Alkoxy (C_1_~_4) represents an alkyl group, phenyl group, substituted phenyl group, benzyl group, substituted benzyl group, -X-COOR^3 group, -Y-CN group, and the substituents include: Halogen atom, C_1_~
_3 alkyl group, C_1_-_3 alkoxy group, X, Y are C_1_-_6 linear or branched alkylene groups, R^3 is C_1_-_8 alkyl group, C_3_-_6
Represents a cycloalkyl group. Also, R^1 is the above group, R^2 is -COOR^4 group, and R^4 is C_1_~_
8 represents an alkyl group. A stabilized insecticidal pesticide granule composition characterized in that polyvinyl alcohol is added to the sulfenyl carbamate derivative represented by the following formula and retained in an uncalcined mineral substance. (2) The composition according to claim 1, wherein urea is added together with polyvinyl alcohol. (3) R^1 is -CH_2CH_2COOC_2H_5
, R^2 is an isopropyl group. (4) The composition according to claim 1, wherein R^1 and R^2 are n-butyl groups. (5) The composition according to claim 1, containing 0.1 to 10% by weight of polyvinyl alcohol.