JP3024765B2 - Granular insecticidal composition - Google Patents

Description

The present invention relates to butyl 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N, N'-dimethyl-N, N-thiodicarbamate ( The present invention relates to a granular pesticidal composition in which isocyanate compound or an isocyanate compound and a hydroxyl group-containing compound are blended with the active ingredient, thereby reducing fish poison of flatiothiocarb.

[Conventional technology]

It is known that fratiothiocarb has an insecticidal activity against insects of the order Coleoptera and Lepidoptera, and can be applied to the control of pests on vegetable crops, cottonseed crops and fruit crops (Japanese Patent Application Laid-Open No. 53-53).
119863). However, fratiothiocarb is problematic for use in paddy fields due to its high toxicity to fish and shellfish.

Heretofore, as a method of reducing the toxicity of pesticides to fish and shellfish, a method of reducing fish toxicity by adding menadione bisulfite to a thiol carbamate herbicide (Japanese Patent Laid-Open No.
56-63905), a method of reducing fish toxicity by adding menadione bisulfite and a malonic acid derivative to a thiol carbamate herbicide (Japanese Patent Application Laid-Open No. 59-167507), a metal salt of a fatty acid and a silicon compound in an agricultural chemical formulation To reduce fish toxicity (JP-A-611-1), a method of reducing fish toxicity by blending an lipophilic pesticide active ingredient with an organic compound and the like (JP-A-171402). Are known.

[Problems to be solved by the invention]

The above items are methods for reducing fish toxicity of thiol carbamate herbicides, and the effect of reducing fish toxicity on the active ingredient of the present invention cannot be expected. Is a method of reducing fish toxicity in pesticide dust compositions,
The effect of the active ingredient cannot be expected for aquatic pests. In addition, the method uses a distribution rule of an active ingredient to water, and is strongly affected by temperature such as a water temperature at the time of use, so that there is a concern that the effect is not constant or the insecticidal effect is reduced.

The present inventors have conducted intensive studies on a method for providing a granular insecticidal composition capable of reducing fish toxicity of flatiothiocarb and killing agriculturally harmful pests.As a result, the addition of an isocyanate compound to the particulate composition containing fratiothiocarb Or by further adding a hydroxyl group-containing compound,
The present inventors have found that a granular insecticidal composition suitable for the purpose can be obtained, and completed the present invention.

[Means for solving the problem]

The granular pesticidal composition of the present invention contains furatiocarb as an active ingredient, and further contains an isocyanate compound or an isocyanate compound and a hydroxyl group-containing compound.

Next, the isocyanate compound and the hydroxyl group-containing compound used in the present invention will be described.

Although any isocyanate compound can be used in the present invention, a compound having a large number of isocyanato groups is particularly advantageous. They may be used alone or as a mixture of two or more. For example, an aliphatic diisocyanate compound such as hexamethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-
2,6-diisocyanate, diphenylmethane-4,4-diisocyanate, chlorophenylene-2,4-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4-diisocyanate, 4,4-diisocyanato-3,
Aromatic diisocyanate compounds such as 3-dimethyldiphenyl, 3-methyl-diphenylmethane-4,4-diisocyanate and phenylether diisocyanate;
1-methylcyclohexyl-2,4-diisocyanate,
1-methylcyclohexyl-2,6-diisocyanate,
Alicyclic diisocyanate compounds such as bis (isocyanatocyclohexyl) -methane; triisocyanate compounds such as 2,4,6-triisocyanatotoluene and 2,4,4-triisocyanatodiphenyl ether; (In the formula, n represents an integer of 1 or more.) Methylene-crosslinked polyphenylene polyisocyanate.

Further, as the hydroxyl group-containing compound, monohydric alcohols represented by the general formula R'OH (wherein R 'represents a linear or branched alkyl group having 1 to 12 carbon atoms). Formula _{HO- (CH 2) m-OH} ( wherein,
m shows the integer of 2-6. Dihydric alcohols represented by). Trihydric or higher alcohols such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol and pentaerythritol. Compounds obtained by condensing dicarboxylic acids such as adipic acid, sebacic acid, maleic acid and dimer acid with the dihydric or higher alcohols represented by the formula (1) and terminating in OH, and polyester-type polyols such as polymerized lactone glycol esters and linolenic acid glycerides. Polyether polyols such as polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, and poly (oxytetramethylene) glycol obtained by ring-opening polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and tetrahydrofuran. A polyether polyol obtained by addition or addition polymerization of an alkylene oxide represented by the formula (2) to the dihydric or higher alcohols represented by the formula (1).
General formula (Wherein, R ₂ represents a hydrogen atom or a methyl group, and R ₃ represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 12 carbon atoms substituted with a carboxyl group.) Polyol (average molecular weight: 500-10000).

These hydroxyl group-containing compounds may be used alone or in combination of two or more.

Next, the granular pesticidal composition of the present invention, if necessary, a diluent commonly used in formulating agricultural chemicals, a surfactant,
It is manufactured by blending auxiliary agents such as a binder, a stabilizer and a dye. Examples of the production method include the following methods, but are not limited thereto.

(1) A raw material obtained by adding and mixing and pulverizing white carbon, an isocyanate compound, or a hydroxyl group-containing compound to fratiothiocarb as a raw material, adding a diluent, a surfactant, a binder, an auxiliary agent, and the like as appropriate, and granulating the mixture. .

(2) An isocyanate compound or a hydroxyl group-containing compound is adsorbed on granules obtained by appropriately adding a diluent, a surfactant, a binder, an auxiliary agent, and the like to furatiocarb and producing the granulated product.

(3) A natural granular base or a granulated granular base is adsorbed with flatiothiocarb, an isocyanate compound, or a hydroxyl group-containing compound to produce the compound.

In this case, it is possible to mix and adsorb two or three kinds of furatiothiocarb, an isocyanate compound and a hydroxyl group-containing compound, and it is also possible to produce the compound by separately adsorbing alone. Here, examples of the diluent include clay, bentonite, talc, diatomaceous earth, pumice, white carbon,
Examples include carboxymethyl cellulose and starch. Examples of the surfactant include sodium alkylbenzenesulfonate, sodium ligninsulfonate and the like. Examples of the binder include polyvinyl alcohol and the like. Examples of the stabilizer include organic acids and inorganic acids.

The amount of flatiothiocarb to be added to the granular insecticidal composition cannot be determined in any way depending on the pest to be controlled, the application rate and the method of application, but is less than 20% by weight. The amount of the isocyanate compound used is determined in consideration of the content of the flatiothiocarb in the granular insecticidal composition, the method for producing the composition, the insecticidal effect, the degree of reduction of fish poison, and the like.
-20% by weight, preferably 0.5-10% by weight. The amount of the hydroxyl group-containing compound used is 0.1 to 20 with respect to the granular insecticidal composition.
%, Preferably 0.5 to 10% by weight. The ratio of the isocyanate compound and the hydroxyl group-containing compound is 1:20 to 20: 1,
Preferably it is in the range of 1:10 to 10: 1.

The addition of the isocyanate compound and the hydroxyl group-containing compound can be carried out by adding, for example, triethylenediamine as a catalyst.

Furthermore, it can also be manufactured by appropriately adding other pesticidal active ingredients by the above-mentioned manufacturing methods (1) to (3).

These pesticidal active ingredients are not particularly limited, but typical examples include 5-methyl-1,2,4-triazolo (3,4b) -benzothiazole (tricyclazole),
1,2,5,6-tetrahydro-4H-pyrrolo [3,2,1-ij] quinolin-4-one (pyroquinone), diisopropyl-1,3
Fungicides such as -dithiolan-2-ylidene-malonate (isoprothiolane), 3-allyloxy-1,2-benzothiazole-1,1-dioxide (probenazole),
2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate (carbofuran), 2,3-dihydro-2,2-dimethylbenzofuran-7-yl (dibutylaminothio) -N-methyl Carbamate (carbosulfan), 2,2-dimethyl-1,3-benzodioxol-
4-yl-N-methylcarbamate (bendiocarb), 0,0-3,5,6-trichloro-2-pyridyl-0,0-
Dimethyl phosphorothioate (chloropyrifosmethyl), 2-chloro-1- (2,4-dichlorophenyl) vinyldimethylphosphate (dimethylvinphos), 0.0-
Dimethyl-0- [3-methyl-4- (methylthio) phenylcoenyl] thiophosphate (MPP), 1,3-bis (carbamoylthio) -2- (N, N-dimethylamino)
Insecticides such as propane hydrochloride (Cartap), 2,4-bis (ethylamino) -6-methylthio-1,3,5-triazine (simethrin), S-ethylhexahydro-1H-azepine-1-carbothio Ethate (molinate), 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) acetanilide (butachlor), 2- (β-naphthyloxy) propionanilide (naproanilide), 4-
Herbicides such as (2,4-dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl-P-toluenesulfonate (pyrazolate) and SP-chlorobenzyldiethylthiocarbamate (benthiocarb).

The granular insecticidal composition reduced in fish venom obtained as described above can be used as an insecticide by spraying on a paddy field or soil, etc. in the same manner as a conventional granular pesticide composition. And control of dwarf beetles, dwarf beetles, etc. Furthermore, it can be used for controlling pests such as green worms, moths and aphids which are pests of vegetable crops.

〔Example〕

Next, the composition of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Parts and% in Examples are parts by weight and% by weight.

Example 1 White carbon (15 parts) was added to fratiothiocarb (5.3 parts).
Parts), bentonite (30 parts), pregelatinized starch (3 parts),
After adding and mixing clay (46.7 parts), an appropriate amount of water is added and kneaded. This is granulated by attaching a screen having a hole diameter of 0.8 mm to a granulator. After drying the granulated product, the granulated product is sized to obtain a base for kneading flatiocarb. The following crude mixture of polymethylene phenyl isocyanate (3 parts) and polypropylene glycol (average molecular weight: 750) (2 parts) were simultaneously added to the kneaded base for flatiothiocarb (95 parts) and uniformly adsorbed to contain 5% of flatiothiocarb. Obtain granules.

Polymethylene phenyl isocyanate Example 2 Clay (92 parts), bentonite (5 parts), pregelatinized starch (2.5 parts), sodium dodecylbenzenesulfonate (0.5 part) were mixed, and the mixture was mixed according to the kneading base granulation method of Example 1. A particulate free base containing no furatiocarb is obtained. The empty base (90.5 parts) was taken and mixed with furatiocarb (5 parts), the crude mixture of polymethylene phenyl isocyanate used in Example 1 (1.5 parts), and polypropylene glycol (average molecular weight 500-600) (3 parts). The particles are uniformly adsorbed to obtain granules containing 5% of fratiothiocarb.

Example 3 Furatiocarb (5 parts) was heated to 40 ° C.
After uniformly adsorbing on 1.0 mm granular pumice (91 parts), the crude mixture of polymethylene phenyl isocyanate used in Example 1 (2 parts) and polypropylene glycol (average molecular weight 1000) (2 parts) were uniformly added thereto. To obtain a granule containing 5% of furathiocarb.

Example 4 Furoficarb (5.5 parts) was supplemented with Hofite carbon (5 parts).
Parts), polyvinyl alcohol (3 parts), clay (86.5
After adding and mixing (parts), a kneaded base for flatiothiocarb is obtained according to the kneading base granulation method of Example 1. A mixture of 2,4-toluylene diisocyanate and a mixture of 2,6-toluylene diisocyanate (mixing ratio 8: 2) (5 parts) was uniformly adsorbed to the furatiocarb-kneaded base (91 parts), and further mixed with polyethylene glycol (average). A mixture of molecular weight 200) (3 parts) and glycerin (1 part) is uniformly adsorbed, and
% Granules are obtained.

Example 5 Fratiocarb (5 parts) and the following acrylic polyol (3 parts) were mixed with the free base (87 parts) used in Example 2 and uniformly adsorbed, followed by 1,5-naphthylene diisocyanate. (5 parts) is uniformly adsorbed to obtain granules containing 5% of fratiothiocarb.

Example 6 Pyroquilon (5.5 parts) was added to polyvinyl alcohol (4
Parts), bentonite (10 parts) and clay (80.5 parts) are added and mixed to obtain a pyroquilon kneaded base according to the granulating method of the kneaded base of Example 1. This pyroquilon kneading base (91 parts)
And glycerin-added crude mixture of fratiothiocarb (3 parts), polymethylenephenyl isocyanate (2 parts) and polypropylene glycol (average molecular weight 700 to 800)
(4 parts) is uniformly adsorbed to obtain a granule containing 5% of pyroquilone and 3% of flatiothiocarb.

Polymethylene phenyl isocyanate (tetramethylene pentaphenyl pentaisocyanate) Example 7 Tricyclazole (4.5 parts) was added to pregelatinized starch (3
Parts), bentonite (20 parts), sodium dodecylbenzenesulfonate (0.3 parts) and clay (72.2 parts) were added and mixed, and tricyclazole kneading base was added according to the granulation method of kneading base in Example 1. obtain. To this tricyclazole kneaded base (90 parts), furatiothiocarb (5 parts), the crude mixture of polymethylenephenylisocyanate used in Example 1 (2 parts), and the trimethylolpropane-added crude mixture of polyethylene propylene glycol (average molecular weight 500 ~ 60
0) (3 parts) was uniformly adsorbed and tricyclazole 4
% Granules containing 5% of fratiothiocarb.

Example 8 The following polymethylene phenyl isocyanate (8 parts) and white carbon (15 parts) were added to furathiocarb (3 parts).
Parts), bentonite (5 parts), and clay (69 parts) were added and pulverized to obtain granules containing 3% of flatiothiocarb according to the granulating method of the kneading base of Example 1.

Polymethylene phenyl isocyanate (nonamethylene decaphenyl decaisocyanate) Example 9 The polymethylene phenyl isocyanate used in Example 1 (10 parts), white carbon (20 parts), bentonite (30 parts), clay (35 parts) were used in furatiocarb (5 parts).
Is added and mixed and pulverized to obtain granules containing 5% of flatiothiocarb according to the granulating method of the kneading base of Example 1.

Next, effects of the present invention will be described with reference to test examples. In the test, the following drugs were manufactured and used for comparison.

Referential Example 1 White carbon (10 parts)
Parts), pregelatinized starch (2 parts), bentonite (5 parts),
After adding and mixing sodium dodecylbenzenesulfonate (0.3 parts) and clay (77.7 parts), a granule containing 5% of fratiothiocarb is obtained according to the granulating method of the kneading base of Example 1.

Reference Example 2 White carbon (5 parts) was added to furatiocarb (3 parts).
Parts), pregelatinized starch (2 parts), bentonite (5 parts),
After adding and mixing sodium dodecylbenzenesulfonate (0.3 parts) and clay (84.7 parts), a granule containing 3% of fratiothiocarb is obtained according to the granulating method of the kneading base of Example 1.

Reference Example 3 To flatiothiocarb (5 parts), sodium menadione bisulfite (1 part), white carbon (10 parts), polyvinyl alcohol (2 parts), bentonite (5 parts), and clay (77 parts) were added and mixed. According to the granulating method of the kneading base of Example 1, granules containing 5% of fratiothiocarb are obtained.

Reference Example 4 Methyl hydrogen polysiloxane (average molecular weight: 15,000) (1 part), magnesium stearate (5 parts), white carbon (5 parts) in furatiocarb (5 parts),
After adding and mixing polyvinyl alcohol (3 parts) and clay (81 parts), according to the granulating method of the kneading base of Example 1,
A granule containing 5% of fratiothiocarb is obtained.

Reference Example 5 Amyl oleate (5 parts) was added to furatiocarb (5 parts).
Parts), white carbon (10 parts), polyvinyl alcohol (3 parts) and clay (77 parts), and after mixing, according to the granulation method of the kneading base of Example 1, 5% of flatiothiocarb
Is obtained.

Test Example 1 Fish Poison Test for Carp (Part 1) Fish poison test for carp was performed on the granules of Examples 1, 2, 3, 5, 9 and Reference Examples 1, 3, 4, and 5. The test method is as follows.

<Fish poison test method> Test fish: carp (Cyprinus carpio), body length 4.8 ± 0.5cm body weight 2.8 ± 1.0g, 10 fish per group Test water: water temperature 22 ± 1 ℃, pH7.0 ± 0.4 dissolved oxygen (DO ) 7.0 ± 1.0mg / Water tank: Glass tank (29 × 60 × 36cm) Water volume: 50 Lighting: Lighting time was 12 hours from 7:00 am to 7:00 pm.

Illumination: At 250 cm above the floor, 250 Lux granules were weighed so that the active ingredient would have a predetermined concentration, and placed on the water surface, and the mortality after 48 hours and 96 hours was examined. Table 1 shows the test results.

Test Example 2 Fish Toxin Test on Carp (Part 2) The granules of Examples 6, 8 and Reference Example 2 were subjected to a fish toxin test on carp. The test method is the same as in Test Example 1, and the test fish and test water are as follows.

 Test fish: Carp (Cyprinus carpio), 4.3 ± 0.5cm long, 1.9 ± 0.7g long, 10 fish per group Test water: Water temperature 22 ° C ± 1 ° C, pH 7.5 ± 0.5 DO 8.0 ± 2mg / Test results are shown in Table-2. Shown in

Test Example 3 Fish Toxin Test for Shrimp Shrimp Fish toxin tests for prawns were performed on the granules of Examples 1, 2, and 4 and Reference Examples 1, 4, and 5. The test method is as follows.

<Fish poison test method> Test fish: Shrimp (Penaeus japonicus) Body length 1.5 ± 0.3cm, body weight 19 ± 9mg, 10 individuals per group Test water: groundwater, water temperature 22.0 ± 0.5 ℃ pH8.5 ± 0.3 DO 6.5 ± 0.3 mg / chlorine amount 19.3% Specific gravity 1.025 Water tank: Glass tank (29 × 60 × 36cm) Water quantity: 50 Lighting: Lighting time was 12 hours from 7:00 am to 7:00 pm.

Illuminance: 250 Lux granules at 85 cm above the floor are weighed so as to have a predetermined concentration, and are poured into the water surface.
The mortality at 48 and 96 hours was examined. Table 3 shows the test results.
Shown in

Test Example 4 Fish Toxin Test on Medaka Fish poison test was performed on the granules of Examples 1, 3, 5, 6, 7 and Reference Examples 1, 2, and 3. The test method is as follows.

<Fish venom test method> Test fish: medaka (Oryzias latipes), body length 2.6 ± 0.2cm, body weight 0.4 ± 0.1g, 10 groups per group Test water: water temperature 24 ± 1 ℃, pH7.3 ± 0.1, DO 7.5 ± 1.0 mg / water tank: glass tank (19 × 30 × 26 cm) Water volume: 5 Lighting: Lighting time was 12 hours from 7:00 am to 7:00 pm

Illumination: 250 Lux granules at 85 cm above the floor are weighed to a specified concentration and dropped onto the water surface.
The mortality at 48 and 96 hours was examined. Table 4 shows the test results.
Shown in

From the above results, it was confirmed that the particulate pesticidal composition for reducing fish poison according to the present invention and the particulate pesticide composition using the silicon compound and the fatty acid metal salt of Reference Example 4 reduce the toxicity to aquatic organisms including fish. Can be

Test Example 5 Insecticidal Test Against Adult Water Weevil Adults The following biological tests were performed using the granules of Examples 1, 2, 3, 4, 7, 9 and Reference Examples 1 and 4.

Test crop: 1.5-leaf stage rice grown in a nursery box (30 x 60 x 3 cm) (variety: Asahi Aichi) Chemical treatment: The day before transplantation, 50 g of sample granules were treated with the formulation per nursery box, and A 500 ml watering treatment was performed.

One day after the chemical treatment, rice was collected by a rice transplanter, and five stems of one strain were transplanted to a 1/5000 arel Wagner pot. After transplanting, the pot was placed on a covered bench to a depth of 3 cm. A wire mesh cylinder was wrapped every predetermined day, and 10 water weevil dwarf adults per pot were released per pot. Test 1
The ward was operated in three consecutive districts, and two days later, the mortality was determined by examining the life and death.

 The test results are shown in Table-5.

From the above results, it can be seen that the granular insecticidal composition of Reference Example 4 using the silicon compound and the fatty acid metal, which are effective in reducing fish toxicity, is inferior to the rice weevil, the rice weevil.

〔The invention's effect〕

The granular insecticidal composition of the present invention is an isocyanate compound, or by further adding a hydroxyl group-containing compound,
It has reduced the toxicity of fratiothiocarb to fish and shellfish and made it possible to use it against pests in paddy fields.
By adjusting the amount of the isocyanate compound or the hydroxyl group-containing compound according to the present invention, not only the toxicity to fish and shellfish can be reduced but also the pests can be suppressed for a long time. In addition, by mixing other pesticidal active ingredients at the time of production, it is possible to provide a granular pesticidal composition capable of controlling other diseases and weeds at the same time. The addition amount of the isocyanate compound used in the present invention or the hydroxyl group-containing compound is sufficient to obtain a sufficient effect with a relatively small amount, does not require a special step even at the time of production, and reduces the pesticidal efficacy of fratiothiocarb at a low agricultural level. When fully utilized, it is economical and can kill pests without destroying the environment.

Claims (2)

(57) [Claims] 1. A granular insecticidal composition comprising butyl 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N, N'-dimethyl-N, N'-thiodicarbamate as an active ingredient, an isocyanate compound A granular insecticidal composition characterized by adding 2. A granular insecticidal composition comprising butyl 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N, N'-dimethyl-N, N'-thiodicarbamate as an active ingredient, an isocyanate compound And a granular insecticidal composition characterized by adding a hydroxyl group-containing compound