JP2002363003A - Sustained-release pesticide granules and their application method - Google Patents

Abstract

(57) Abstract: A sustained-release pesticide granule of the present invention comprises a pesticidally active ingredient, a thermoplastic resin (A) and polyvinyl alcohol (B), iron powder or copper powder (C) mixed uniformly. It is characterized by being done. According to the present invention, a sustained-release pesticide granule which suppresses initial dissolution when the pesticide active ingredient elutes from the pesticide granule and gradually starts dissolving the active ingredient after a certain period of time, and the granule It is possible to provide an application method using the same, whereby even when the crop is applied with the sustained-release pesticide granules according to the present invention at the initial stage of growth, the original control effect of the pesticide active ingredient is reduced. Therefore, it is possible to maintain the effect and reduce phytotoxicity to crops. Further, such a sustained-release pesticide granule is simple and economical to produce because no special dissolution control means is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sustained-release pesticide granule and a method for applying the same. More specifically, the present invention relates to a sustained-release pesticide granule obtained by uniformly mixing a thermoplastic resin, a water-soluble polymer, iron powder, or copper powder with a pesticide granule containing an agricultural chemical active ingredient, and a method for applying the same.

[0002]

BACKGROUND OF THE INVENTION Conventionally, in pesticide granules,
The harm to agricultural crops by pesticidal active ingredients has become a problem, and the sustainability of the effects of pesticidal active ingredients has been an issue in terms of labor saving in agricultural work. To solve these points,
Various studies have been made on pesticide granules that can control the amount of the pesticidally active ingredient eluted into water.

For example, granules obtained by coating a core containing a pesticide active ingredient with a thermoplastic resin film (Japanese Patent Publication No. 01-5002), a coating layer is provided on a core containing a pesticide active ingredient, and the active ingredient is gradually released. (Japanese Patent Publication No. 01-4483), a granule provided with a means for preventing film unevenness at the time of conversion, and a granule wherein a core containing an agricultural chemical active ingredient is coated with a water-insoluble oligomer or polymer (Japanese Patent Publication No. 02-57047) ), Granules comprising a mixture of a sulfonylurea-based herbicidal active ingredient, activated carbon, paraffin wax and a mineral carrier (JP-A-63-135504).
Publication), a soluble glass component is eluted from granular foam glass to form pinholes, and then the pinholes of foam glass particles are impregnated with a liquid of perfume, fertilizer, and herbicide. Japanese Unexamined Patent Publication (Kokai) No. 63-176337), an agricultural chemical obtained by directly adhering or immobilizing a fine powder of a hydrophobic substance on the particle surface of a solid agricultural active ingredient (Japanese Patent Application Laid-Open No. 01-13).
No. 16302).

[0004] Furthermore, a granule obtained by impregnating a hydrophobic oily liquid on the surface of a non-disintegratable pesticide granule in water and coating it with a hydrophobic fine powder (Japanese Patent Application Laid-Open No. 02-286602), On the surface of a non-oil-absorbing particulate carrier, granules comprising bentonite, a pesticidally active ingredient and calcium chloride, which can be disintegrated in a preferable state in water (JP-A-03-106802), and an absorbent fine powder containing an insecticidally active ingredient, etc. Coated granules (Japanese Patent Application Laid-Open No. 03-7202), granules obtained by granulating a powder mixture containing a polyglycerin fatty acid ester and an agrochemically active ingredient, wherein the polyglycerin fatty acid ester Granules provided with a control means for changing HLB (Japanese Patent Laid-Open No. 05-237), absorbent fine powder containing an agricultural chemical active ingredient, or non-oil-absorbing granules by an agricultural chemical active ingredient When the carrier is coated, granules using a mixture of a water-soluble adhesive and a water-insoluble adhesive as an adhesive for coating (Japanese Patent Application Laid-Open No. 04-352701) and a cellulose powder containing 10% or more of cellulose powder. Granules comprising a pesticidal active ingredient coated with an active particulate carrier (Japanese Patent Application Laid-Open No. 05-17302), a pesticidal active ingredient and bentonite as essential components, and a mixture of poval, vinyl acetate resin emulsion, etc. and water as a binder Granules obtained by coating non-disintegrating particles with a composition containing
No.-906), a multilayered pesticide comprising a double coating layer formed on the surface of a granular carrier containing an agricultural chemical active ingredient (JP-A-06-9303, JP-A-06-93).
04, JP-A-06-72805, JP-A-0-72805
6-80514) and the like.

[0005] However, the pesticide granules according to the prior art described above are not always satisfactory in terms of the production method being complicated, the effect of reducing the pesticidal effect of the pesticide active ingredient on the crops and the effect of controlling the pesticides. When the pesticide granules are applied to the initial crops, there is a problem that phytotoxicity to the crops is strongly exhibited and the control effect is not persistent.

[0006] Therefore, it can be produced by a simple production method, and even when applied to crops in the early growth stage, the phytotoxicity of the pesticidally active ingredient to the crops can be reduced, and the effect can be sustained without lowering the original control effect. There has been a demand for the development of pesticide granules capable of improving the properties.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art as described above, and when the pesticidal active ingredient is eluted from the pesticide granule, the initial elution is suppressed, and after a certain period of time elapses. It is an object of the present invention to provide a novel pesticide granule that gradually starts dissolving the active ingredient and an application method using the granule.

[0008]

SUMMARY OF THE INVENTION The sustained-release pesticide granule according to the present invention is obtained by uniformly mixing an active ingredient of a pesticide, a thermoplastic resin (A) and polyvinyl alcohol (B), iron powder or copper powder (C). It is characterized by. It is desirable that the thermoplastic resin (A) is selected from a styrene-acrylate copolymer, a vinyl acetate copolymer and a urethane resin.

It is desirable that the amount of the iron powder or the copper powder (C) is 10 to 200 parts by weight based on 100 parts by weight of the thermoplastic resin (A) and the polyvinyl alcohol (B).
It is also desirable that the pesticidal active ingredient is 3-allyloxy-1,2-benzisothiazole-1,1-dioxide (probenazole). The method for applying the sustained-release pesticide granule of the present invention comprises the above-mentioned sustained-release pesticide granule in which the pesticidal active ingredient is 3-allyloxy-1,2-benzisothiazole-1,1-dioxide (probenazole). It is characterized by being applied at the time of sowing.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the sustained-release pesticide granules according to the present invention and the method of applying the same will be described in detail. The sustained-release pesticide granule according to the present invention is obtained by uniformly mixing an agricultural chemical active ingredient, a thermoplastic resin (A), a polyvinyl alcohol (B), and a metal powder (C) which is an iron powder or a copper powder. First, the pesticidal active ingredient will be described.

The weight percentage and weight ratio in the present invention are calculated from the dry weight of the whole composition. Agrochemical active ingredient The pesticidal active ingredient contained in the sustained-release pesticide granule according to the present invention comprises one or more pesticidal active ingredients and / or one or more fungicidal active ingredients, or one or more herbicidal active ingredients.

The content of the pesticidal active ingredient used in the present invention is not particularly limited, but is generally 0.01 to 90% by weight, preferably 0.1 to 60% by weight of the whole preparation.
% By weight is desirable. Depending on the kind of the pesticidal active ingredient, it may be blended at an appropriate content so that the required application rate per 10 ares is obtained. Such insecticidal, fungicidal and herbicidal active ingredients are not particularly limited, but include the following. In addition, these pesticide active ingredient names are "Agrochemical Handbook 1994 Edition".
(Published by the Japan Plant Protection Association).

As the pesticidal active ingredient used in the present invention, it is preferable to use the following bactericidal active ingredient, probenazole. Insecticidal active ingredient As the insecticidal active ingredient used in the present invention, CYAP,
MPP, MEP, ECP, pirimiphosmethyl, diazinon, quinalphos, isoxathion, viridafenthione, chlorlipyphosmethyl, chlorpyrifos, ESP,
Bamidothion, marathon, PAP, dimethoate, formotion, thiometon, ethyl thiometon, hosalon,
PMP, DMTP, prothiophos, sulprophos, profenophos, pyraclophos, DDVP, monocrotophos, BRP, CVMP, dimethylvinphos, CVP, propaphos, acephate, isofenphos, DEP, E
PN, Ethion, NAC, MTMC, MIPC, BPM
C, PHC, XMC, Ethiophenecarb, Bendiocarb, Pirimicarb, Carbosulfan, Benfuracarb, Mesomyl, Oxamyl, Thiodicarb, Alanicarb, Allesulin, Resmethrin, Tefluthrin, Bifenthrin, Permethrin, Cypermethrin, Cyhalothrin, Cyfluthrin, Fenpromethrin , Cycloprothrin, fenvalerate, flucitrinate, fluvalinate, etofenprox, cartap, thiocyclam, bensultap, diflubenzuron, teflubenzuron, chlorfluazuron, flufenoxuron, tebufenozide, deprofezin, phenoxycarb, benzoepine, imidacloprid, meta Aldehyde, isoprothiolane, DBEDC, pyrethrum, delis, sulfate Chin, machine oil, DCV, BT,
CPCBS, Kelsen, Phenisobromolate, Tetradifone, BPPS, Quinomethionate (quinoxaline), Amitraz, Benzomate, Phenothiocarb,
Hexitiazox, fenbutatin oxide, dienochlor, fenpyroximate, debufenpyrad, fluazinam, pyridaben, clofenthedine, DPC (dinocap), milbemectin, bialaphos, DCIP, methyl isothiocyanate, dazomet, monacrosporium fimatopagum, steinanema capocapoepoe, and steinanema capopaepoe. , Mesulfenphos, phosthiazate, levamisole hydrochloride, carbam, carbam sodium and the like.

The fungicidal active ingredient used in the present invention includes inorganic copper (copper sulfate, quicklime, basic calcium copper sulfate, basic copper sulfate, basic copper chloride, cupric hydroxide, copper ammonium complex salt) ), Organic copper, copper nonylphenol sulfonate, DBE
DC, copper terephthalate, sulfur, zineb, maneb, manzeb, ambam, polycarbamate, organic sulfur nickel salt, propineb, ziram, thiuram, thiadiazine, captan, sulfenic acid, TPN, fusaride, IB
P, EDDP, tolclofosmethyl, pyrazophos, fosetyl, thiophanatemethyl, benomyl, carbendazole, thiabendazole, iprodione, vinclozolin, procymidone, fluoroimide, oxycarboxine, mepronil, flutranil, teclophthalam, pencyclon, metalaxyl, oxadixyl, triazimefon, buternil micron, buternil micron Hexaconazole, propiconazole, diphenoconazole, ipconazole, imibenconazole, triflumizole, prochloraz, pefurazoate, fenarimol, pyrifenox, triforine, organic arsenic (MAF, MAF
A), dithianone, quinoxaline, DPC, dimethylimol, flusulfamide, benzazole, diclomedine, triazine, ferimzone, fluazinam, dietofencarb, probenazole, isoprothiolane,
Tricyclazole, pyroquilon, oxolinic acid, iminoctadine acetate, propamocarb hydrochloride, sodium alginate, blasticidin S, kasugamycin,
Examples include polyoxin, validamycin A, streptomycin, oxytetracycline, mildiomycin, machine oil, carbam, PCNB, hydroxyisoxazole, echromezol, dazomet, chloroneb, metasulfocarb, methyl isothiocyanate, and the like.

Herbicidal active ingredients The herbicidal active ingredients used in the present invention include 2,4P
A, MCP, MCPB, MCPP, Triclovir, Fenothiol, Clomeprop, Naproanilide, Fenoxapropethyl, Fluazifop, Quizalofopethyl, CNP, Clomethoxynil, Bifenox, I
PC, Fenmedifam, MBPMC, Benthiocarb, Orthovencarb, Esprocarb, Molinate,
Dimepiperate, bilibuticarb, DCPA, alachlor, butachlor, pretilachlor, metolachlor, tenylchlor, bromobutide, mefenacet,
Napropamide, difenamide, propizamide, isoxaben, ashram, DCMU, linuron, siduron, daimulon, methyldaimuron, carbbutyrate,
Isouron, thiazafluron, ethidimuron, tebuthiuron, bensulfuron-methyl, pyrazosulfuron-ethyl, fluzasulfuron, thifensulfuron-methyl, imazosulfuron, metsulfuron-methyl, CAT, atrazine, simethrin, amethrin, promethrin, dimethmethrin, cyanazine, hexazinone , Terbasil, bromacil, renacil, PAC, bentazone, dazomet, pyridate, oxadiazon, pyrazolate, pyrazoxifene, benzofenab, paraquat, diquat, trifluralin, bethrosin,
Prodiamine, pendimethalin, MDBA, MDBA
Sodium salt, picloram, imazapyr, imazaquin ammonium salt, dithiopyr, TCTP, DPA, tetrapion, piperophos, amiproposmethyl, butamiphos, SAP, glyphosate, glyphosate ammonium salt, glyphosate trimesium salt, glyphosate sodium salt, bialaphos, glufosinate , Ioxynil, DBN, DCBN, alloxydim, sethoxydim,
ACN, chlorphthalim, cinmethylin, benfresate, carbum, maleic hydrazide, chlorate, cyanate and the like.

Thermoplastic resin (A) The thermoplastic resin (A) used in the present invention comprises 1 to 10% by weight of the whole pesticide granule. Such a thermoplastic resin (A) is not particularly limited, but may be an acrylic resin, a vinyl chloride resin, a urethane resin, a styrene resin.
Acrylic copolymer resin, styrene-acrylate copolymer resin, vinyl acetate copolymer resin, vinyl acetate
Ethylene copolymer resin, vinyl acetate-acrylic copolymer resin, vinyl acetate-ethylene-acrylic copolymer resin,
Vinyl acetate-ethylene-vinyl chloride copolymer resin, etc., preferably styrene-acrylate copolymer resin, vinyl acetate copolymer resin, vinyl acetate-ethylene copolymer resin, more preferably vinyl acetate copolymer resin It is desirable to use a polymer resin.

The thermoplastic resin (A) used in the present invention
Consists of one or more selected from the above resins. Polyvinyl alcohol (B) The polyvinyl alcohol (B) used in the present invention comprises 0.5 to 10% by weight of the whole pesticide granule.

The polyvinyl alcohol used in the present invention has a polymerization degree of 500 to 2500, preferably 10 to 2500.
It is desirably 00 to 2000, and has a saponification degree of 85 mol% or more and less than 100 mol%, preferably 95 mol% or more and less than 100 mol%. Examples of such polyvinyl alcohol include, for example, partially saponified Gohsenol GL-05.
S (Nippon Gosei Co., Ltd., average polymerization degree 500,
Degree of saponification 85.5 to 89.0 mol%), Gohsenol G
H-17 (trade name of Nippon Gohsei Co., Ltd., average degree of polymerization 1
700, a saponification degree of 86.5 to 89.0 mol%) or a completely saponified type gohsenol NL-05 (trade name, manufactured by Nippon Gohsei Co., Ltd., average degree of polymerization 500, saponification degree 98.
5 mol% or more), Gohsenol NH-14 (trade name, manufactured by Nippon Gohsei Co., Ltd., average polymerization degree 1400, saponification degree 9)
8.0 mol% or more), Gohsenol NH-18 (trade name, manufactured by Nippon Gohsei Co., Ltd., average degree of polymerization 1800, degree of saponification 98.0-99.0 mol%) Gohsenol NH-20
(Nippon Gosei Co., Ltd., average polymerization degree 2000,
Saponification degree of 98.5 to 99.4 mol%), and the like, but not limited thereto, and there is no problem even if one or two or more of these are used in combination. In the present invention, polyvinyl alcohol can also be used as a binder.

Iron powder or copper powder (C) The metal powder used in the present invention, such as iron powder or copper powder (C), is oxidized by the presence of water molecules, and its volume is increased. It is preferable because it has breaking properties. In particular, it is desirable to use iron powder having a remarkable volume expansion.
Metal powders such as nickel, chromium, aluminum, and the like, in which rust hardly spreads over the entire metal and has small volume expansion, are not preferred for the purpose of the present invention.

The iron powder or copper powder (C) is used in an amount of 10 to 200 parts by weight based on 100 parts by weight of the thermoplastic resin (A) and the polyvinyl alcohol (B).
It is desirable that the amount be from 14 to 200 parts by weight, more preferably from 14 to 170 parts by weight. When the iron or copper (C) used in the present invention is in the above-mentioned numerical range, the initial release of the pesticide active ingredient from the pesticide granule is suppressed, and the elution of the active ingredient is gradually started after a certain period of time. A pesticide granule can be obtained.

The iron or copper (C) used in the present invention is
It is appropriately selected and used depending on the type and amount of the pesticidal active ingredient to be used and the type and amount of the thermoplastic resin used. The size of the metal powder particles is 10 to 100 in particle size.
It is 0 μm, preferably 10 to 100 μm. [Other Components] In addition, in the sustained-release pesticide granule of the present invention, a surfactant, a binder, a carrier, a physical property improver, and the like can be appropriately added in addition to the above components.

The components will be described below. Surfactants As the surfactant used in the present invention, nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants commonly used in agricultural chemical formulations are used, and particularly, Although it is not limited, one or more kinds of surfactants specifically exemplified below can be used.

The nonionic surfactant used in the present invention includes alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ester,
Examples thereof include polyoxyethylene sorbitan alkylate, polyoxyethylene phenyl ether polymer, polyoxyethylene alkylene aryl phenyl ester, polyoxyethylene alkylene glycol, and polyoxyethylene polyoxypropylene block polymer.

Examples of the anionic surfactant include lignin sulfonate, alkyl aryl sulfonate dialkyl sulfosuccinate, polyoxyethylene alkyl aryl ether sulfate, alkyl naphthalene sulfonate, polyoxyethylene styryl phenyl ether sulfate and the like. Can be Examples of the cationic surfactant and the amphoteric surfactant include an alkylamine salt, a quaternary ammonium salt alkylbetaine, and an amine oxide.

Binders The binders other than polyvinyl alcohol that can be used in the present invention are not particularly limited, but include the following binders, for example, starch, dextrin, carboxymethylcellulose, polyvinylvirolidone, sodium alginate, ligninsulfonic acid. Sodium, calcium ligninsulfonate and the like can be used.

Carrier The carrier that can be used in the present invention is not particularly limited, and examples thereof include clay, silica, talc, bentonite, calcium carbonate, pumice, diatomaceous earth, vermiculite, perlite, and crystalline silica. One or more selected from among them can be used.

Other Additives The sustained-release pesticide granules of the present invention may contain a solid organic acid or the like which promotes oxidation of the added metal powder. Examples of the solid organic acid include succinic acid, DL-malic acid, tartaric acid, citric acid and the like. Further, the granules of the present invention may contain components such as stabilizers for pesticidal active ingredients, physical property improvers, pigments and dyes.

The sustained-release pesticide granule according to the present invention suppresses the initial dissolution when the pesticide active ingredient elutes from the granule into water.
The elution of the active ingredient is gradually started after a certain period of time. In the present invention, the "initial dissolution" refers to the dissolution of the pesticide active ingredient in water up to 5 days after the pesticide granule has been put into water, and the "certain period" after a certain period has elapsed.
Similarly, it refers to the period from when the pesticide granule is put into water until 5 days have passed.

In the pesticide granule containing the metal powder according to the present invention, the dissolution rate of the pesticide active ingredient in water is 15% or less, preferably 10% or less from the time of introduction into water to the fifth day (initial dissolution). And after 15 to 77 days, preferably 1
It is desirably 100% after 5 to 63 days. In the present invention, the term "sustained-release pesticide granules" refers to pesticide granules having the above-mentioned dissolution pattern.

When the dissolution rate of the pesticidal active ingredient in water is in the above range, the original control effect of the pesticidal active ingredient can be maintained even when the sustained-release pesticide granule according to the present invention is applied at an early stage of growing a crop. The effect can be maintained without lowering, and the phytotoxicity of the agricultural chemical active ingredient to the crop can be reduced. If the rate of dissolution of the pesticidal active ingredient in water is greater than 15% from day 5 in the water (initial dissolution), phytotoxicity occurs in the early stage of growth of the crop, and the initial dissolution is within the above range. Even if the dissolution rate in water reaches 100% by the 14th day, the effect of the pesticidal active ingredient cannot be maintained, and even if the initial dissolution is within the above range, the dissolution in water is not sufficient. If the rate becomes 100% after the 77th day, the original control effect of the pesticidal active ingredient is reduced, which is not preferable.

The method for preparing such a sustained-release pesticide granule is not particularly limited, and it can be prepared by a conventionally known method. Specifically, it is preferable to prepare by the following steps 1-3. Step 1: The pesticidal active ingredient, thermoplastic resin, iron powder, amorphous silica, surfactant and carrier and, if desired, other adjuvants are mixed together by a hammer mill to obtain a solid powdery raw material composition. .

Step 2: After adding an aqueous solution of polyvinyl alcohol and an appropriate amount of water to the raw material composition in the form of powder and kneading the mixture, the kneaded product is put into a basket-type extrusion granulator and granulated. Obtain the composition. Step 3: The granular composition is flow-dried, and then sieved to have a target particle size distribution, whereby the sustained-release pesticide granule of the present invention can be obtained.

The sustained-release pesticide granule according to the present invention has a production particle size of usually 0.6 to 2.0 mm, preferably 0.8 to 2.0 mm.
Preferably, it is 1.5 mm. The above-mentioned method of measuring the dissolution rate in water was performed as follows. In a beaker having a size of 1000 ml, 500 ml of 3rd hard water is put (water depth: 6 cm), and the sustained-release pesticide granules of the present invention are uniformly dispersed in water. The beaker was left in a dark room at 20 ° C., and water was sampled at regular intervals from three places (5 cm deep), and the concentration of probenazole contained in the water was measured by liquid chromatography and eluted into hard water three times. The elution amount of the pesticide active ingredient was calculated.

The dissolution rate when the pesticide active ingredient contained in the test granule is completely eluted into 500 ml of water in a beaker is defined as 100, and the dissolution rate of the pesticide active ingredient is determined from the dissolution rate measured at regular intervals. Calculated. Method for Applying Sustained-Release Pesticide Granules The method for applying the sustained-release pesticide granules according to the present invention is not particularly limited, and can be used in a method in which ordinary pesticide granules are applied. Examples of such methods include a method of applying rice at the time of sowing, a method of applying pesticide granules to the water surface simultaneously with rice planting in paddy field application, and a method of applying the pesticide granules to the water surface after rice planting in paddy field application.

The sustained-release pesticide granules of the present invention preferably use probenazole as the pesticidal active ingredient, and such sustained-release pesticide granules can be used by the above-mentioned application method, particularly when sowing rice. It is useful to use this method. Here, when sowing rice, specifically, when the coated pesticide granules are applied simultaneously with the seeds in the application of rice seedlings in a nursery box or paddy field, or beforehand mixed with a sustained-release pesticide granule in the seedling cultivation soil It refers to the case of doing.

[0036]

According to the present invention, there is provided a sustained-release pesticide granule which suppresses the initial dissolution of the pesticidal active ingredient from the pesticide granule and gradually starts dissolving the active ingredient after a certain period of time. Can be provided.

[0037]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “parts” all means parts by weight.

[0038]

Example 1 24.0 parts of probenazole as a pesticide active ingredient (bactericide), 5.0 parts of white carbon as amorphous silica, 0.2 parts of sodium lauryl sulfate as surfactant, clay 64. 8 parts were mixed and pulverized with a hammer mill to obtain 94.0 parts of a uniform powder mixture. To this, polyvinyl alcohol (Gohsenol NH-18 (trade name of Nippon Gosei Co., Ltd.)) as a binder
2.0 parts were dissolved after heating in water, and then added. Further, a styrene-acrylate copolymer (Polysol AP-
Solid content of 4710 (trade name of Showa Polymer Co., Ltd.)
A liquid obtained by mixing 0 parts with 3.0 parts of iron powder (reagent) and an appropriate amount of water were added and kneaded sufficiently. The obtained kneaded product was granulated by a basket-type extrusion granulator, and was fluid-dried, and then sized by sieving to obtain a sustained-release pesticide granule of the present invention.

The content (% by weight) of each component in the sustained-release pesticide granules is summarized in Table 1 below.

[0040]

Example 2 The amount of clay contained in the powder mixture prepared in Example 1 was reduced to 62.8 parts,
2.0 parts were obtained. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was heated and dissolved in water and then added to make 3.0 parts of a styrene-acrylate copolymer and 3.0 parts of iron powder (reagent). The mixed liquid and an appropriate amount of water were added and sufficiently kneaded, and a sustained-release pesticide granule of the present invention was prepared in the same manner as in Example 1.

Content of each component of sustained release pesticide granule (% by weight)
Are summarized in Table 1 below.

[0042]

Example 3 The content of clay contained in the powder mixture prepared in Example 1 was reduced to 60.8 parts, and powder mixture 9
0.0 parts were obtained. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was heated and dissolved in water and then added to make 5.0 parts of a styrene-acrylate copolymer and 3.0 parts of iron powder (reagent). The mixed liquid and an appropriate amount of water were added and sufficiently kneaded, and a sustained-release pesticide granule of the present invention was prepared in the same manner as in Example 1.

Content of each component of sustained release pesticide granule (% by weight)
Are summarized in Table 1 below.

[0044]

Example 4 In the same manner as in Example 1, 94.0 parts of a powder mixture was obtained. 1. Add polyvinyl alcohol to the obtained powder mixture.
After dissolving 0 parts in water with heating, the mixture is added to make styrene-acrylate copolymer 3.0 parts, iron powder (reagent)
A liquid mixed with 1.0 part and an appropriate amount of water were added and sufficiently kneaded, and a sustained-release pesticide granule of the present invention was prepared in the same manner as in Example 1.

Content of each component of sustained release pesticide granule (% by weight)
Are summarized in Table 1 below.

[0046]

Example 5 The content of clay contained in the powder mixture prepared in Example 1 was reduced to 60.8 parts, and powder mixture 9
0.0 parts were obtained. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was dissolved after being heated in water, and then added to 3.0 parts of a styrene-acrylate copolymer, and 5.0 parts of iron powder (reagent). The mixed liquid and an appropriate amount of water were added and sufficiently kneaded, and a sustained-release pesticide granule of the present invention was prepared in the same manner as in Example 1.

Content of each component of sustained-release pesticide granules (% by weight)
Are summarized in Table 1 below.

[0048]

Example 6 The content of clay contained in the powder mixture prepared in Example 1 was reduced to 58.8 parts,
8.0 parts were obtained. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was heated and dissolved in water, and then added to make 5.0 parts of a styrene-acrylate copolymer, and 5.0 parts of iron powder (reagent). The mixed liquid and an appropriate amount of water were added and sufficiently kneaded, and a sustained-release pesticide granule of the present invention was prepared in the same manner as in Example 1.

Content of each component of sustained-release pesticide granule (% by weight)
Are summarized in Table 1 below.

[0050]

EXAMPLE 7 The powder mixture prepared in Example 1 contained 66.8 parts of clay, and the powder mixture was 96.0 parts.
Got a part. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was heated and dissolved in water, and then added.
The liquid mixture of 1.0 part of the acrylate copolymer, 1.0 part of iron powder (reagent) and an appropriate amount of water were added and kneaded well. Sustained-release pesticide granules were prepared.

Content of each component of sustained release pesticide granule (% by weight)
Are summarized in Table 1 below.

[0052]

Example 8 The content of clay in the powder mixture prepared in Example 1 was 62.8 parts and the powder mixture was 92.0 parts.
Got a part. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was heated and dissolved in water, and then added.
The acrylate copolymer was adjusted to 5.0 parts, a liquid mixed with 1.0 part of iron powder (reagent) and an appropriate amount of water were added, and the mixture was sufficiently kneaded. Sustained-release pesticide granules were prepared.

Content (% by weight) of each component of sustained-release pesticide granule
Are summarized in Table 1 below.

[0054]

Example 9 The content of clay in the powder mixture prepared in Example 1 was 62.8 parts, and the powder mixture was 92.0 parts.
Got a part. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was heated and dissolved in water, and then added.
1.0 part of acrylate copolymer and copper powder (reagent)
A liquid mixed with 5.0 parts and an appropriate amount of water were added and sufficiently kneaded, and a sustained-release pesticide granule of the present invention was prepared in the same manner as in Example 1.

Content of each component of sustained release pesticide granules (% by weight)
Are summarized in Table 1 below.

[0056]

Example 10 The content of clay in the powder mixture prepared in Example 1 was 62.6 parts,
8 parts were obtained. 2.0 parts of polyvinyl alcohol was added to the obtained powder mixture after heating and dissolving in water, and 3.0 parts of a styrene-acrylate copolymer, 3.0 parts of iron powder (reagent) and citrate were added. A liquid obtained by mixing 0.2 part of an acid and an appropriate amount of water were added and kneaded well, and a sustained-release pesticide granule of the present invention was prepared in the same manner as in Example 1.

Content (% by weight) of each component of sustained-release pesticide granule
Are summarized in Table 1 below.

[0058]

Example 11 The content of clay in the powder mixture prepared in Example 1 was 62.8 parts,
0 parts were obtained. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was added as a binder after heating and dissolving in water, and further added. A vinyl acetate copolymer (Polysol SH-5) was further added.
02 (solid content of Showa Polymer Co., Ltd.) 3.0
Parts, a liquid obtained by mixing 3.0 parts of iron powder (reagent) and an appropriate amount of water were added and sufficiently kneaded, and a sustained-release pesticide granule of the present invention was prepared in the same manner as in Example 1.

Content of each component of sustained-release pesticide granules (% by weight)
Are summarized in Table 1 below.

[0060]

Example 12 The content of clay in the powder mixture prepared in Example 1 was 62.8 parts,
0 parts were obtained. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was added as a binder after heating and dissolving in water, and further added thereto. A urethane resin (Superflex 126) was further added.
(Solid content of (Daiichi Kogyo Seiyaku Co., Ltd.)) 3.0 parts,
A liquid obtained by mixing 3.0 parts of iron powder (reagent) and an appropriate amount of water were added and kneaded sufficiently, and a sustained-release pesticide granule of the present invention was prepared in the same manner as in Example 1.

Content of each component of sustained-release pesticide granule (% by weight)
Are summarized in Table 1 below.

[0062]

Comparative Example 1 Probenazole drug substance 24.0 as fungicide
Parts, 5.0 parts of white carbon as amorphous silica, 0.2 parts of sodium lauryl sulfate as a surfactant, and 68.8 parts of clay as a carrier were mixed and ground together with a hammer mill, and 98.0 parts of a uniform powder mixture. I got In addition, polyvinyl alcohol (Gohsenol NH-1) was used as a binder.
8 (trade name of Nippon Gosei Co., Ltd.) was added after heating and dissolving in water, and an appropriate amount of water was further added thereto and kneaded well. The obtained kneaded product was granulated by a basket-type extrusion granulator, and was fluid-dried, and then sieved to obtain a pesticide granule.

The content (% by weight) of each component in the pesticide granules is summarized in Table 1 below.

[0064]

Comparative Example 2 The clay content of the powder mixture prepared in Comparative Example 1 was reduced to 65.8 parts, and the powder mixture 9
5.0 parts were obtained. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was added after heating and dissolving in water, and further, a styrene-acrylate copolymer (Polysol AP-4710 (trade name of Showa Polymer Co., Ltd.)) was added. (3) Solids) 3.0 parts of a liquid and an appropriate amount of water were added and sufficiently kneaded, and a pesticide granule was prepared in the same manner as in Comparative Example 1.

The content (% by weight) of each component of the pesticide granules is summarized in Table 1 below.

[0066]

Comparative Example 3 The content of clay contained in the powder mixture prepared in Comparative Example 1 was reduced to 53.8 parts,
3.0 parts were obtained. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was heated and dissolved in water, and then added. Further, 3.0 parts of a styrene-acrylate copolymer was added.
A liquid obtained by mixing 12.0 parts of iron powder and an appropriate amount of water were added and sufficiently kneaded, and the obtained powder mixture was prepared in the same manner as in Comparative Example 1 to prepare pesticide granules.

The content (% by weight) of each component in the pesticide granules is summarized in Table 1 below.

[0068]

Comparative Example 4 The content of clay contained in the powder mixture prepared in Comparative Example 1 was reduced to 62.8 parts, and powder mixture 9
2.0 parts were obtained. To the obtained powder mixture, 2.0 parts of polyvinyl alcohol was heated and dissolved in water, and then added. Further, 3.0 parts of a styrene-acrylate copolymer was added.
A liquid obtained by mixing 3.0 parts of nickel powder (reagent) and an appropriate amount of water were added and sufficiently kneaded, and the resulting powder mixture was prepared in the same manner as in Comparative Example 1 to prepare pesticide granules.

The content (% by weight) of each component in the pesticide granules is summarized in Table 1 below. Next, Test Examples 1 to 3 demonstrate that the sustained-release pesticide granules of the present invention exhibit a sustained-release property of the active ingredient and further exhibit a phytotoxicity-reducing action without reducing the control effect of the active ingredient. Test Example 1 ( Aqueous dissolution test of pesticide active ingredient) 500 ml of 3rd hard water in a beaker of 1000 ml in size
(Water depth 6 cm), Examples 1 to 12 and Comparative Example 1
42 mg of a pesticide granule prepared according to 4 are uniformly dispersed in water. The beaker was left in a dark room at 20 ° C., and water was sampled from three places at a depth of 5 cm at regular intervals. The concentration of probenazole in the water sample was measured by liquid chromatography, and the whole eluted in the water in the beaker. The elution amount of probenazole was calculated.

When the total amount of probenazole in the test granules was completely eluted into 500 ml of water in the beaker, the concentration of propenazole was 20 ppm, and the elution rate was calculated from the elution amount measured at regular intervals. The test results obtained are shown in Table 1 below.

[0071]

[Table 1]

As is clear from the results in Table 1, Example 1
The sustained-release pesticide granules of the present invention obtained in Steps (1) to (12), 1 to 5 days after being put into water, probenazole, which is an active ingredient of pesticide, starts to elute in water, and the active ingredient elutes. When started, it was confirmed that the pesticidal active ingredient of the sustained-release pesticide granule was completely eluted (100%) in water after 15 to 77 days. In other words, it is confirmed that the sustained-release pesticide granules of the present invention obtained in Examples 1 to 12 receive the suppression of dissolution of the pesticide active ingredient, particularly the suppression of initial dissolution, and show a quadratic curve dissolution pattern. Was.

On the other hand, the granules containing neither the thermoplastic resin nor the metal powder of Comparative Example 1 start eluting the active ingredient immediately after being put into water, and after 5 days from being put in water, the pesticide The elution rate of the active ingredient was 37%, and no suppression of the initial elution was observed. The granules of Comparative Example 2 containing the thermoplastic resin and no iron powder, and the granules of Comparative Example 4 containing the thermoplastic resin and the nickel powder were poured into water because the elution of the pesticide active ingredient was strongly suppressed. Even after 77 days, the active ingredient was not completely eluted (100%).

The granules of Comparative Example 3 in which iron powder was added in an unnecessarily large amount were granules containing a required amount of iron powder (Example).
In comparison with that, no inhibition of the dissolution was observed in the initial stage, and the dissolution rate was 100% after 14 days from the introduction into water, and the dissolution of the component was not persistent. According to the following Test Examples 2 and 3, when the sustained-release pesticide granule of the present invention containing probenazole as an active ingredient was mixed with a seedling cultivation medium used for raising rice seedlings, the effect of reducing or preventing the damage to paddy rice caused by probenazole was demonstrated. Prove that you have. It also proves that it has the effect of controlling rice blast for a long period of time.

Test Example 2 (Influence on the Growth of Rice Seedlings) 100 g and 50 g of the sustained-release pesticide granules of the present invention were added to 4 liters of conventionally used seedling cultivation soil and mixed well. A seedling cultivation soil mixed with the sustained-release pesticide granules of Examples 1 to 3 was placed in a standard seedling raising box (width 30 cm × length 60 cm × height 3).
cm) 1 box is filled with an equivalent amount of 3 liters as floor soil, and rice seeds (variety: Nipponbare) which have been subjected to normal seed disinfection and preliminary treatment are sown on the floor soil, and the agrochemical granules are further added. The mixed culture was covered in an amount equivalent to 1 liter per standard seedling.

The seedling raising box was allowed to stand in a germination chamber at 32 ° C. for 2 days to promote germination of the seeded rice seeds. The seedling raising box after the budding treatment was moved into a glass greenhouse to perform seedling management. The germination rate of rice seeds was determined by using a seedling box having a 1/10 area of a standard seedling box, sowing 400 seeds per seedling box, and sowing 2 seeds.
The number of emergence was confirmed and calculated after 1 day and 7 days. The budding was performed according to the above conditions.

In this test, one 1/10 seedling raising box was used per test plot, and the test was repeated five times, and the average value was calculated. The results are shown in Table 2. For seedling growth in the seedling raising box after sowing, 180 g was seeded per box using a standard seedling raising box. The budding was performed according to the above conditions. The seedling raising box after the budding treatment was greened in an artificial weather chamber in which 50% of natural light at 20 ° C. was shielded from light for one day, and then moved to a transparent acrylic resin greenhouse. Seedling management was carried out for 21 days after sowing, and plant height, leaf age and rooting degree were examined. This test was repeated three times with one standard seedling raising box per test plot.

The plant height was measured with respect to 100 samples in total, one sample from each test plot, and the average value of three repetitions was calculated.
showed that. The leaf age was determined as one sample per sample from each test group, and measured for a total of 100 samples, and the average of three repetitions was calculated. Further, the degree of rooting was objectively investigated 21 days after sowing in comparison with the untreated section. The results are shown in Table 2.

For comparison, a granule containing probenazole of Comparative Example 1 but having no initial dissolution control (Comparative Example 1) was treated in the same manner as above to obtain a comparative group, and the pesticide granule containing probenazole was completely removed. An untreated test plot was designated as a non-treated plot.

[0080]

[Table 2]

As can be seen from the results in Table 2 above, Example 1
In the nursery box treated with the sustained-release pesticide granules in which the initial dissolution of ~ 3 was suppressed (invention plot), the germination rate of the seeded paddy showed 90% or more, and the germination rate with the untreated plot was reduced. There was no big difference. In addition, the seedling growth after sowing did not differ from the untreated plot, and a healthy seedling that could be transplanted to Honda was obtained 21 days after sowing.

On the other hand, in the comparative group to which probenazole granules (Comparative Example 1) which had not been subjected to the initial elution suppression treatment were applied, the rice growth was inferior and the seedling growth was lower than in the invention group and the untreated group. It was clear that it was bad and caused phytotoxicity. Test Example 3 (Rice blast control effect) 50 g of the sustained-release pesticide granule of the present invention was added to 4 liters of a conventionally used culture medium for raising seedlings and mixed well. The seedling cultivation soil mixed with the pesticide granules is placed in a standard seedling raising box (width 30 cm × length 6).
0 cm × 3 cm height) A box is filled with an equivalent amount of 3 liters as floor soil, and rice seeds (variety: Koshihikari) which have been subjected to normal seed disinfection and preliminary treatment are sown on the floor soil. The soil mixed with the pesticide granule was covered with an equivalent amount of 1 liter per standard seedling.

The seedling raising box was allowed to stand for 2 days in a germination chamber at 32 ° C. to promote germination. The seedling raising box after the budding treatment was moved into a vinyl greenhouse, and the seedling raising was managed for 21 days after sowing. In a paddy field where blast occurs naturally every year, a test plot having an area of 60 m ² (3 m × 20 m) was made in one plot, and the seedlings raised by the above method were transplanted with a rice transplanter (invention plot). In the investigation of the incidence of rice blast, 50 days and 60 days after transplantation, the number of lesions in the top three leaves of each strain was examined for 150 strains in each test plot. For comparison, the seedlings treated with the probenazole granules prepared by the method of Comparative Example 1 and not subjected to the initial dissolution suppression treatment and the probenazole granules prepared without the metal powder by the method of Comparative Example 2 were used. The seedlings treated with the agent were similarly transplanted (comparative plot). The effect of each treatment group was calculated from the control value (%) based on the comparison with the number of lesions in a seedling transplantation group without treatment with probenazole granules (untreated group). The results are shown in Table-3.

[0084]

[Table 3]

As can be seen from the results shown in Table 3, in the inventive plots using the sustained-release pesticide granules of the present invention (Examples 1 to 3), rice blast caused by natural infection was observed for a long time after transplantation in paddy fields. It was shown that the onset was almost completely or substantially controlled. On the other hand, in the control plots (Comparative Examples 1 and 2), the control effect against blast was insufficient.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshiaki Tamura 5-30-27 Tai, Tamano-shi, Okayama Prefecture (72) Inventor Motohiro Hiramatsu 5-20-3 Asahi-cho, Atsugi-shi, Kanagawa Prefecture (72) Invention Person Shinji Yonemura 1-8-11-205 Fukuta 1-8-11-205 Okada, Atsugi City, Kanagawa Prefecture 4H011 AA01 AB01 AC01 BB10 BC18 BC19 BC20 DC05 DC06 DF01 DF02 DH02 DH19 DH27

Claims (5)

[Claims] (1) A sustained-release pesticide granule comprising a homogeneous mixture of an agricultural chemical active ingredient, a thermoplastic resin (A), polyvinyl alcohol (B), iron powder or copper powder (C). 2. The sustained-release pesticide granule according to claim 1, wherein the thermoplastic resin (A) is selected from a styrene-acrylate copolymer, a vinyl acetate copolymer and a urethane resin. 3. The weight ratio of the iron powder or the copper powder (C) is 10 to 200 parts by weight based on 100 parts by weight of the thermoplastic resin (A) and the polyvinyl alcohol (B). The sustained-release pesticide granule according to claim 1 or 2. 4. The active ingredient for pesticides is 3-allyloxy-1,2.
The sustained-release pesticide granule according to any one of claims 1 to 3, which is -benzoisothiazole-1,1-dioxide (probenazole). 5. A method for applying a sustained-release pesticide granule, which comprises applying the sustained-release pesticide granule according to claim 4 at the time of sowing rice seeds.