JP3535429B2 - Pesticide composition for water application - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-applied pesticide containing one or more kinds of pesticide active ingredients, a surfactant consisting of α-olefin sulfonate, etc. and a grain nucleus having an apparent specific gravity of less than 1. The present invention relates to a composition and a method for producing the composition.

[0002]

2. Description of the Related Art As general pesticide formulations, powders, granules,
Wettable powders, water solutions, flowables, liquids, emulsions and the like are known. Of these, spraying agents such as wettable powders, water solutions, and emulsions are mainly used in upland fields and non-agricultural fields. The emulsion has problems such as environmental pollution due to solvents and emulsifiers and fire hazard due to organic solvents. In addition, many pesticide active ingredients are difficult to dissolve in water, and it is often difficult to formulate them into liquid formulations. For these reasons, the use of aqueous or oily suspension formulations (flowables) or dry flowables, which are less problematic, has recently been increasing.

On the other hand, as a water surface application agent for paddy fields, powder,
Granules and the like can be mentioned, and conventionally, granules have been mainly used.
Granules are generally applied in an amount of 3 to 4 kg per 10 ares, but in recent years, demands for labor-saving spraying of agricultural chemicals have increased, and development of small-scale spraying agents for reducing the application rate of agricultural chemicals is required. However, when trying to reduce the application amount of the granule, the content of the pesticide active ingredient in the granule is inevitably increased and the number of particles per unit area is reduced. These are factors that directly affect the biological effects of pesticide active ingredients and phytotoxicity to crops, and it is required to treat pesticide formulations as uniformly as possible over the entire paddy field. However, in order to evenly distribute the recently developed 1 kg granules to the flooded sewage paddy,
Since it requires a certain amount of skill and experience, and in some cases, a spraying device, it is not always satisfactory as a dosage form for labor saving.

Therefore, in the field of water surface application agents for paddy fields, there are many developments of aqueous suspension preparations for the purpose of labor saving and efficiency improvement during spraying. This formulation differs from aqueous suspension formulations used in upland fields, non-agricultural fields, etc., because it is dripped or poured directly from the container into the paddy field without diluting the formulation.
Since it does not require special spraying equipment and the amount to be treated is as small as 200 ml to 1 liter per 10 ares, it has the characteristics of being light and easy to handle, and depending on the area of the field, it can be transferred from the ridge (so-called frame). Processing),
Since it is a preparation that can be processed by simply irrigating it from the water mouth when entering water (so-called water mouth treatment), and is an extremely labor-saving treatment, the market is expanding rapidly after its launch. However, since the aqueous suspension preparation is a preparation in which an agrochemical active ingredient is dispersed or emulsified in water, it has a problem that it is difficult to apply it to an agrochemical active ingredient which is easily hydrolyzed.

Further, in recent years, as a preparation in consideration of labor saving and environmental protection of pesticide spraying, a preparation for paddy field throwing (pack preparation) in which solid preparations such as tablets, ball-shaped preparations and granules are packaged in water-soluble paper such as water-soluble film. Or the development of jumbo agents) is progressing rapidly. Although such a formulation has the advantage of being able to easily treat pesticides for paddy fields, it does not undergo uniform treatment like the conventional treatment of granules and powders, and when these solid formulations are poured into water, the formulation becomes Since the pesticide active ingredient will be dispersed on the surface of the soil and will be dispersed here in the paddy water without foaming or foaming here, undissolved raw material particles will settle around the dropping point and the dissolved pesticide will be dissolved. Since the active ingredient also forms a high-concentration solution near the surface of the soil at the dropping point, it is easily adsorbed on the soil. Therefore, even if the solid solubility of these solid formulations in water-soluble paper such as water-soluble film is high, the pesticide active ingredient in the paddy field throwing formulation has a high concentration of the pesticide active ingredient in the soil near the dropping point of the formulation. However, depending on the field conditions, the weather conditions, etc., there is a drawback that the non-uniform pesticide active ingredient may cause phytotoxicity and non-uniformity of efficacy, and adverse effects on the subsequent crops. In order to eliminate such uneven distribution of pesticide active ingredients as much as possible,
BACKGROUND ART Conventionally, a water surface application agent has been developed in which a foaming agent is mixed with a solid agent to disintegrate and disperse the solid agent as soon as possible, and the pesticide active ingredient is diffused by the foaming power of the foaming agent. As such a foaming agent, an organic acid and a carbonate are used, and a mechanism in which both react in the presence of water to generate carbon dioxide has been used. However, pesticide formulations containing effervescent agents have the drawback that some of the organic acids and carbonates in the formulation react during storage to easily generate gas, which causes the packaging to swell and to be used. Problems such as weak foaming often occurred. In particular,
Even if the water temperature of the paddy field is low, the water surface application agent needs to disperse the pesticide active ingredient in water by the foaming power, dissolve and diffuse as soon as possible, and form a uniform treatment layer on the soil surface. There was a concern that the reduction would result in insufficient diffusion of the pesticide active ingredient, causing the above-mentioned drawbacks.

For this reason, recently, some proposals have been made regarding a water surface application agent containing no foaming agent. For example, a pesticidal active ingredient is dissolved in an organic solvent or the like, and a water-spreading oily substance is kept as it is or is retained in a solid substance to be packaged in a water-soluble film (JP-A-5-78207). , Consisting of a glass hollow body having an average particle diameter of 250 μm or less and a water-soluble polymer
A particle size of 600 μm containing 100 g (Japanese Patent Application Laid-Open No. 5-58804), an agrochemical active ingredient, an inorganic floating substance having an average particle size of 250 μm or less, and a high boiling point solvent.
10 to 100 g of the following solid composition is packaged in a water-soluble polymer film (Japanese Patent Laid-Open No. 5-78204), and a pesticide active ingredient and air / water interfacial tension are added to a grain nucleus having an apparent specific gravity of less than 1. A floating granular insecticide composition in which a substance to be changed is coated with an oily substance (Japanese Patent Laid-Open No. 5-155703), a pesticide active ingredient is adsorbed on a carrier composed of granular pumice or fluke, and coated with a higher fatty acid. (Japanese Patent Publication No. 44-8600), floating granules in which an insecticide is fixed to burned perlite with polybutene (Japanese Patent Publication No. 47-1240), and a drug effective against rice sclerotia is levitated above the rice field water. Granule (Japanese Patent Publication No. 48-1179), foamed perlite loaded with insecticide and water repellent (Japanese Patent Publication No. 48-1181), emulsion of herbicide supported on inorganic carrier floating in water Tighten the granules (JP-B-48-1
No. 182), a granular pesticide composition that floats in water by supporting a cellulose ether or a polycarboxylic acid type polymer surfactant as a spreading agent (JP-B-48-15612), a pesticide main agent and a solid carrier containing polyoxygen. Water-floating solid formulation containing alkylene silicone (Japanese Patent Publication No. 64-2570)
No. 2), a biologically active ingredient is attached to an inorganic or organic porous body or hollow body with a synthetic resin or gypsum, and the holes communicating with the outside are closed to form a hollow body, and the specific gravity is 1.0 or less, and the particle size is Those prepared to 5 mm or less (Japanese Patent Publication No. 2-563
No. 23) and a liquid undiluted solution containing an active ingredient and an emulsifier adsorbed on a thermally expanded rock powder granule (Japanese Patent Publication No. 3-76).
No. 281) has been proposed. However, these preparations are no different from the conventional granules and powders in terms of the spraying method and cannot reduce the spraying labor.

[0007] Further, for the purpose of labor-saving spraying of pesticide formulations,
Investigations on water-floating granules have been made. A composition in which a preparation containing an active ingredient of an agricultural chemical and calcined vermiculite or expanded perlite, expanded shirasu, cork, and an acetylene-based surfactant is wrapped in a water-soluble film (JP-A-6-33).
6403), granules or tablets in which a powder base having a specific gravity of 1 or less with the agrochemical active ingredient and a surfactant having a large interfacial tension reducing ability are uniformly dispersed (Japanese Patent Application Laid-Open No. 7-233002), and the agrochemical active ingredient has a specific gravity of 1 or less. Agrochemical formulation in which the grain nuclei of the above are coated with a surfactant having a large ability to reduce the interfacial tension and an oily substance (Japanese Patent Laid-Open Publication No. H9-96952).
183701) and the like are published. However, these methods do not always have sufficient water surface spreadability in practical use. That is, in practical situations, algae, rice husks and other suspended matter may cover the water surface of the paddy field.In such a case, even if the above-mentioned water surface application agent is treated, the agrochemical formulation can be sufficiently suspended and spread. However, there is a case in which there is a floating material that cannot be seen well from the shore in the paddy field where it seems that there is no floating material. In such a case, it was considered that the above-mentioned water surface application agent was treated, and a sufficient floating spread of the pesticide formulation could not be obtained.

[0008]

Therefore, there has been a demand for an agrochemical formulation that can sufficiently spread and spread the aquatic surface on a water surface even in a paddy field where a small amount of suspended matter is present.

That is, it requires no special equipment for spraying, is labor-saving, is safe for the sprayer and the environment, is easy to process in containers, and has insufficient drug efficacy and chemical damage due to segregation of active ingredients of agricultural chemicals. There has been a demand for a pesticide formulation that is not afraid, has excellent floating and spreading properties on the water surface even with a few obstacles, and is stable over time, and a treatment method therefor.

In view of the above situation, the present inventors have conducted diligent studies aiming at the development of a pesticide formulation satisfying the above conditions and a treatment method thereof, and as a result, the specific surfactant and the apparent specific gravity are less than 1. Pack the pesticide composition in a specific form using the grain nuclei, etc. in an appropriate container with a transfer port and transfer it directly into the paddy field, or disperse the pesticide composition in water or dissolve it in water. By subdividing into a film to be divided into sachets, and throwing it into the paddy field, the pesticide composition can spread and spread the rice field water well, and the pesticide active ingredient can be well distributed throughout the rice field water. And completed the present invention.

[0011]

The present invention provides one or more pesticide active ingredients, one or more surfactants selected from the following compound groups, and a grain nucleus having an apparent specific gravity of less than 1. A surface-applied agrochemical composition containing, wherein the compound group is an α-olefin sulfonate, an α-sulfo fatty acid salt and an oleylmethyl tauride salt, and a nonvolatile substance liquid at room temperature. The present invention relates to a pesticidal composition for water surface application which may contain, and a treatment method and a production method thereof.

When the surface-applied pesticide composition of the present invention is applied to a submerged paddy field, as the surfactant is dissolved, the surface-applied pesticide composition self-diffuses in various directions on the water surface, and the pesticide active ingredient is Disperses quickly and uniformly in the surface water. Further, the water-applied pesticide composition of the present invention, because the release rate of the pesticide active ingredient into water is very fast, even if the granules are blown by the residual wind on the water surface, the pesticide active ingredient is already blown before it is blown. Since it has been released, it has an extremely preferable characteristic in practical use that it has no effect on the manifestation of its action and effect.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The agrochemical active ingredient used in the present invention is, for example, a herbicide, an insecticide, a fungicide, an acaricide, a plant regulator, etc., and its physical properties are not particularly limited. However, as herbicidal active ingredients, for example, bensulfuron-methyl, azimsulfuron, imazosulfuron, pyrazosulfuron-ethyl, ethoxysulfuron, shinosulfuron, cyclosulfamuron, chlorsulfuron, chlorimuron-ethyl, neofensulfuron-methyl, flazas Luflon, sulfometuron methyl, primisulfuron methyl, rimsulfuron, dimepiperate, mefenacet, pretilachlor, molinate, pyributicarb, tenilchlor, esprocarb, butamiphos, bromobutide, dimeron, cafenstrol, cyhalofop-butyl, ben Fenup, pyrazolate, pyrazoxifene, benfresate, benchocarb, epoprodan, quinoclamin (ACN), cimetrin, dimetamethrin, pentoxazone, edbenzanide, dithiopyr, butachlor, oxadiaargyl, naproanilide, cinmethrin, (2,4-dichlorophenoxy) acetic acid (2,4-D) ) And its alkyl ester or its salt, 4- (4-chloro-o-tolyloxy) butyric acid (MC
PB), oxadichromefone, 4- (2-chlorophenyl) -N-cyclohexyl-4,5-dihydro-N-ethyl-5-oxo-1H-tetrazole-1-carboxamide (NBA-061), MT-128, 3, -(2
-Chloro-4-methylsulfonylbenzoyl) -4-phenylthiobicyclo [3.2.1] -3-octene-2
-One (SB-500), 2- [2- (3-chlorophenyl) -2,3-epoxypropyl] -2-ethylidene-1,3-dione (MK-243), 1- (2-chlorobenzyl) Examples include 3- (α, α-dimethylbenzyl) urea (JC-940) and bentazone.

The insecticidal active ingredient may be a persistent insecticide having a systemic migration property and an insecticide effective against water-dwelling insects such as rice weevil and rice dwarf beetle. For example, silafluofene, cycloprotoline, etophene. Prox, isoxathion, ethyl thiomethone, imidacloprid, nitenpyram, acetamiprid and the like can be mentioned.

The bactericidal active ingredient may be any bactericidal agent having osmotic transferability and effective against persistent blast and blight, such as carpropamide, pyroquilon, isoprothiolane, probenazole, iprobenphos, tricyclazole, fipronil, Flutolanil, flametopyr (S-658), mepronil, tifluzamide (MON-
240), (RS) -2- (4-fluorophenyl)-
1- (1H-1,2,4-triazol-1-yl)-
3-trimethylsilylpropan-2-ol (F-15
5), teclophthalam, benomyl and the like.

Examples of the plant regulator include maleic hydrazide and salts thereof, abscisic acid, calcium peroxide and psychocell.

The pesticide active ingredient used in the present invention may be one or more of the above herbicides, insecticides, fungicides, acaricides, plant regulators and the like.

The proportion of the pesticidal active ingredient used in the present invention is not particularly limited, but it is usually 1 to 90% in the pesticidal granular composition for surface application (hereinafter,% relating to the blending amount unless otherwise specified). Represents the percentage with respect to the mass), preferably 10 to 80%, more preferably 2
It is 0 to 70%.

Α- which is a surfactant used in the present invention
Olefin sulfonate is a sulfonated product using crude oil (petroleum) as a raw material, has excellent biodegradability, is extremely safe for skin and eyes, is stable against acid and alkali, It has characteristics that are friendly to people and the environment, such as excellent in hard water resistance. For example, α of C _{12 to} C ₁₆
-Olefin sulfonates.

The salt of α-olefin sulfonate is not particularly limited, and examples thereof include sodium, potassium, calcium, ammonium and various amine salts, and the sodium, ammonium or calcium salt is preferable.

Specific examples of the α-olefin sulfonate used in the present invention include, for example, Liporan LB-44.
0, Lipolan LB-840, Lipolan PJ-400, K
Lipolan PJ-400, Lipolan PB-800, Dt-
95 (above, manufactured by Lion Corporation. Trade name), M-38
01, M-3801G (above, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name), HostapurOSB (produced by Hoechst Japan Co., Ltd., trade name), and the like,
It is not limited to these.

Α- which is a surfactant used in the present invention
The sulfo fatty acid salt is a sulfonated product of natural oils and fats, and examples thereof include C _{10 to} C ₁₄ α-sulfo fatty acid salts.

The salt of α-sulfofatty acid salt is not particularly limited, but examples thereof include sodium, potassium, calcium, ammonium and various amine salts, and the sodium, ammonium or calcium salt is preferable.

Specific examples of the α-sulfo fatty acid salt used in the present invention include FA-615B and FA-61.
6B, FA-617B (above, manufactured by Lion Corporation, trade name) and the like can be mentioned, but the invention is not limited thereto.

The salt of the oleylmethyl tauride salt which is a surfactant used in the present invention is not particularly limited, but examples thereof include sodium, calcium, potassium and ammonium salts, and the sodium or calcium salt is preferable. .

Specific examples of the oleylmethyl tauride salt used in the present invention include, for example, Diapon T powder (manufactured by NOF CORPORATION), Hostapon T powder (manufactured by Hoechst Japan Co., Ltd.) and Ar.
koponT powder (manufactured by Hoechst Japan Co., Ltd.
Product names, etc. can be mentioned, but the invention is not limited thereto.

As the surfactant used in the present invention,
Preferred is an α-olefin sulfonate or an α-sulfo fatty acid salt.

The blending ratio of the surfactant used in the present invention is usually 0.01 to 40%, preferably 0.1 to 30%, more preferably 1 to 40% in the surface-applied pesticide composition. 20%. The surfactant used in the present invention may be used alone or in combination of two or more.

In addition to the above surfactants, other water surface spreaders may be added to the water surface application pesticide formulation, if necessary. Other water surface extenders include, for example, copolymers of carboxylic acids such as acrylic acid and maleic acid, and sodium salts, potassium salts and ammonium salts of those obtained by copolymerizing styrene sulfonic acid, vinyl group and the like. Polysulfonic acid type polysoap; soaps such as sodium oleate and potassium stearate; anionic surfactants such as sodium dialkylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, perfluoroalkylcarboxylates; poly Oxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, silicone surfactants, acetylene surfactants, pluronic type surfactants, etc. ON-surfactant; polyoxyethylene alkylaryl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, etc., are used as phosphoric acid or sulfuric acid esters, and in some cases, they are neutralized with a suitable alkali. Surfactants; Fluorine-containing fluorinated surfactants; various cationic surfactants; zwitterionic surfactants; liquid paraffin and naphthene-based high-boiling solvents; low-viscosity polybutene, silicone oil, machine oil, and other minerals. Oils; various animal and vegetable oils; various resins such as pine resin; camphor white oil; α-pinene; camphor; and naphthalene, and the like, but preferably acetylene-based surfactants, silicone-based surfactants or fluorine-based surfactants It is a surfactant.

The above-mentioned acetylene-based surfactants include acetylene alcohol, acetylene diol, and surfactants obtained by adding alkylene oxide to these.

Acetylene alcohol has the general formula HOCR
¹ R ² —C≡CH (wherein R ¹ and R ² are the same or different and each represents a C _{1 to} C ₈ alkyl group), and R ¹ is a methyl group or R ² is an isobutyl group, Surfynol 61, R ¹ and R ² are both methyl groups are Olfine B, and R ¹ is a methyl group and R ² is an ethyl group are commercially available under the trade name of Olphin P. .

Acetylenediol has the general formula HOCR ¹
R ² -C≡C-CR ¹ R ² OH (R ¹ and R ² are the same or different and each represents a C _{1 to} C ₈ alkyl group), and R ¹ is a methyl group. And R ² is an ethyl group, Surfynol 82, R ¹ is a methyl group and R ² is an isobutyl group is Surfynol 104, and R ¹ and R ² are both methyl groups are commercially available under the trade name of Olfine Y Has been done.

The surfactant obtained by adding alkylene oxide to the above acetylene alcohol or the above acetylene diol is, for example, a surfactant obtained by adding ethylene oxide and propylene oxide to the above acetylene alcohol or the above acetylene diol. As the alkylene oxide added, for example, surfynol 104 added with ethylene oxide is surfinol 400 series, surfinol 104 (wax-like) and amorphous silicon dioxide 4
A powdery premix obtained by mixing and pulverizing at a ratio of 0:60 is commercially available under the trade name of Surfynol 104S (both are manufactured by Aero Products and sold by Nisshin Chemical Co., Ltd.).

The silicone-based surfactant is obtained by introducing polyethylene oxide or polypropylene oxide or both into a part of the methyl groups at the terminals and side chains of dimethylpolysiloxane, and in some cases, the terminal hydroxyl group is etherified with an alkyl group. Is a nonionic surfactant whose main component is a modified polyether-modified silicone oil,
For example, trade names such as Silgard series (manufactured by Dow Corning Silicone Co., Ltd.), Silwet series (manufactured by Nippon Unicar Co., Ltd.), silicone oil KF series (manufactured by Shin-Etsu Chemical Co., Ltd.), and kinetic (manufactured by Helena Chemical Co., Ltd.) It is commercially available.

The fluorinated surfactant is a usual anion,
Nonion, a cation or a zwitterionic surfactant is a surfactant in which some or all of the hydrogen atoms of the surfactant have been replaced with fluorine atoms, and is known for its excellent surface tension lowering power,
For example, Unidyne series (manufactured by Daikin Industries, Ltd.), Megafac series (manufactured by Dainippon Ink and Chemicals, Inc.), Covergent series (manufactured by Neos Co., Ltd.), Surflon series (manufactured by Asahi Glass Co., Ltd.), Ftop It is sold under the product names such as (manufactured by Tochem Products Co., Ltd.).

The amount of the other water surface spreader used in the present invention is determined by the type and content of the agrochemical active ingredient, the type of surfactant and other water surface spreader, and the type and content of the other ingredients. Although it varies depending on the formulation and dosage form, it is usually 0.1 to 10%, preferably 0.3 to 5%, and more preferably 0.5 to 3% in the pesticidal composition for water surface application.

The grain nuclei having an apparent specific gravity of less than 1 used in the present invention are not particularly limited as long as they are particles having a property of floating in water. For example, hollow vermiculite, foamed shirasu, foamed perlite and the like are hollow. Mineral carrier; plant carrier such as cork; granular material such as synthetic resin foam such as styrofoam and molded granules containing one or more of them and imparting the property of floating in water, Preferably,
It is calcined vermiculite, expanded perlite or cork.

The pesticidal composition for surface application of the present invention is, for example,
A pesticide active ingredient, a particle nucleus having an apparent specific gravity of less than 1, 1 or 2 or more of the above-mentioned surfactants and, if necessary, other auxiliaries can be mixed and then dried or wet granulated to be produced. .

The grain nuclei of the present invention have an apparent specific gravity of less than 1 (ie, in other words, float on the water surface). The apparent specific gravity of the grain nuclei can be measured, for example, by the following method.

The surface of a standard sieve of 2380 μm is placed 20 cm above the upper end of a metal cylindrical receiver having a diameter of 50 mm and an internal volume of 100 ml. Grain nuclei sample for measuring apparent specific gravity is sifted little by little, and almost all of it is gently scraped off with a brush, and continued until the cone rises from the upper edge of the receiver. Correctly scrape the surface, weigh the sample (g), and calculate the apparent specific gravity by the following formula.

[0041]

[Formula 1] Apparent specific gravity = W ÷ 100 When granules having an apparent specific gravity of less than 1 are formed into a pesticidal composition for water surface application by granulation, the compounding amount of the granule nuclei is such that the pesticide composition for water surface application is in water. It is sufficient if the amount of floating in the, the type and grade of grain nuclei, the type of pesticide active ingredient and the type of other auxiliaries, compounding amount, etc., the floating surface pesticide composition of the present invention To give,
It is 0.1 to 40%, preferably 1 to 25% in the pesticidal composition for water surface application of the present invention. Regarding the particle size of the particle nuclei, if the particle size is too large, there is a high possibility that granulation will not be possible, and usually 80% or more of the particle nuclei are 200 to 600 μm.
Category, and preferably 90% or more of the grain nuclei are 200 to
Enters the 600 μm section.

The pesticidal composition for surface application of the present invention is, for example,
It can be produced by supporting an agrochemical active ingredient or the like on a grain nucleus having an apparent specific gravity of less than 1, or by coating the surface of the grain nucleus having an apparent specific gravity of less than 1 with the agrochemical active ingredient or the like.

When the pesticidal active ingredient or the like is carried on the grain nuclei having an apparent specific gravity of less than 1, the blending amount of the grain nuclei is sufficient as long as the pesticidal composition for surface application floats on the water surface. The type and grade of the grain nuclei, the type of the pesticide active ingredient and the type of other auxiliaries, depending on the compounding amount, etc., in order to impart the floating property to the water-applied pesticide composition of the present invention, usually,
10 to 90% in the pesticidal composition for water surface application of the present invention,
It is preferably 20 to 70%. Regarding the grain size of the grain nuclei, if there are many grain nuclei with a grain size smaller than 0.6 mm, they tend to sink in water, or the grains disintegrate too quickly. In addition to being easily blown, it takes time for the particles to disintegrate and disperse, and the particles disintegrate and disperse in the area where they are blown, causing segregation of the active ingredient of the agricultural chemicals.
It enters into the 4.760 mm section.

When the surface of the grain nuclei having an apparent specific gravity of less than 1 is coated with a surfactant or the like, the pesticidal composition for water surface application of the present invention can be applied to, for example, the grain nuclei having an apparent specific gravity of less than 1, or A non-volatile substance that is liquid at room temperature is used for a granulated product containing a particle nucleus having a specific gravity of less than 1, a part or all of the pesticide active ingredient and, if necessary, other auxiliaries, one or two kinds. It can be produced by coating the above-mentioned surfactant or one or more kinds of the above-mentioned surfactant and the remaining agrochemical active ingredient.

In the case of impregnating a grain core having an apparent specific gravity of less than 1 with a surfactant or the like, the pesticidal composition for water surface application of the present invention can be used, for example, in a grain nucleus having an apparent specific gravity of less than 1 or A non-volatile substance that is liquid at room temperature, one or two or more of the above, in a granulated product containing a particle nucleus having a specific gravity of less than 1, a part or all of the pesticide active ingredient and, if necessary, other auxiliaries. It can be produced by impregnating a surfactant and the remaining pesticide active ingredient.

The non-volatile substance which is liquid at room temperature used in the present invention has no adverse effect such as particle growth and decomposition on the pesticide active ingredient, and has the apparent specific gravity of less than 1 on the surface of the pesticide active ingredient evenly. A solvent having a high boiling point, a low toxicity, a high flash point, a low viscosity, a specific gravity of less than 1 and a low dissolving power for an agricultural chemical active ingredient is preferable, for example, a low boiling point. Viscous liquid paraffin, chlorinated paraffin, isoparaffin, machine oil, polybutene, paraffin-based, naphthene-based, aromatic-based high-boiling point mineral oils; vegetable oils such as coconut oil, soybean oil and rapeseed oil; whale oil, sardine oil Animal oils such as; Silicone oil, oleic acid, coconut oil fatty acid, maleic acid, fumaric acid, phthalic acid, various esters of dicarboxylic acid such as adipic acid, trib; Plasticizers such as various esters of phosphoric acid such as ruphosphate and trischloroethyl phosphate; glycols such as ethylene glycol, diethylene glycol, butanediol and various esters and ethers thereof; ε-caprolactone, γ-butyrolactone, etc. Examples thereof include lactones; N-methylpyrrolidone; and various liquid surfactants. Preferred are ethers of glycols or alkyl lactate esters, specifically, hexyl glycol (HeG, ethylene glycol monohexyl). Ether, Nippon Emulsifier Co., Ltd.), hexyl diglycol (HeDG, diethylene glycol monohexyl ether, Nippon Emulsifier Co., Ltd.), 2
Ethylhexyl glycol (EHG, ethylene glycol mono-2-ethylhexyl ether, Nippon Emulsifier Co., Ltd.), 2-ethylhexyl diglycol (EHDG, diethylene glycol mono-2-ethylhexyl ether, Nippon Emulsifier Co., Ltd.), methyl lactate, ethyl lactate, butyl lactate, etc. Can be mentioned.

The blending amount of the non-volatile substance which is liquid at room temperature used in the present invention varies depending on the kind of the pesticide active ingredient, the kind of other auxiliaries, the blending amount, etc., and is suitable for the surface-applied pesticide composition of the present invention. In order to impart water surface floating spreadability, it is usually 1 to 60%, and preferably 5 to 40% in the water surface application pesticide composition.

The binder used for forming the granules in the present invention is a grain nucleus having an apparent specific gravity of less than 1, and if necessary, other auxiliaries, agrochemical active ingredients, surfactants and other water surface expansion agents. A mixture of a spreading agent or the like is used for molding a granule, and for example, dextrin, polyvinyl alcohol, polyvinylpyrrolidone, a salt of carboxymethyl cellulose, methyl cellulose, gum arabic, polyethylene glycol and its derivatives, tab powder, bentonite, etc. Can be mentioned, and, for example,
Lignin sulfonate, carboxylic acid and sulfonic acid type polysoap can be used also as a dispersant, and bentonite and lignin sulfonate can be used as a bulking agent because they are relatively inexpensive, which is particularly useful.

As the binder used in the present invention,
In particular, bentonite and sodium salt of carboxymethyl cellulose have a strong binding force, can control the disintegration time of particles in water, and have a swelling property themselves, so that once disintegrated, the granules can be completely removed. It has the advantage that it can be disintegrated. The compounding amount of the binder used in the present invention is the type of the binder, the type of the particle nucleus having an apparent specific gravity of less than 1, the composition and the manufacturing method, the formulation of the agrochemical granules, the method of making and the shape, the type of the agrochemical active ingredient. Although it depends on the formulation, such as physical properties, physical properties, and types and blending amounts of other auxiliaries, in the case of bentonite, it is usually 3 to 70%, preferably 5 to 30% in the surface-applied agrochemical composition of the present invention. In the case of other binders, it is 0.1 to 30%, preferably about 0.5 to 20%.

The pesticidal composition of the present invention may contain other auxiliary agents for various purposes. Other auxiliaries include disintegrants, dispersants, wetting agents, extenders, solvents, emulsifiers, water repellents, particle growth inhibitors and stabilizers.

Examples of the disintegrant or dispersant used in the present invention include lignin sulfonate, (alkyl) naphthalene sulfonate and its condensate, phenol sulfonate and its condensate, and styrene sulfonate. Substance, a salt of a condensation product of maleic acid and styrene sulfonic acid,
Salts of carboxylic acid condensates such as acrylic acid and maleic acid,
Alkylbenzene sulfonate, dialkyl sulfosuccinate, lauryl sulfate salt, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkyl aryl ether sulfate salt, polyoxyethylene alkyl ether phosphate ester and its salt, polyoxyethylene alkyl Examples include, but are not limited to, anionic surfactants such as aryl ether phosphates and salts thereof, and phosphates such as sodium tripolyphosphate and sodium hexametaphosphate. Many of these disintegrants or dispersants are also useful as wetting agents.

The extender used in the present invention is used for diluting the pesticide active ingredient to prepare an amount which is easy to throw, and examples thereof include bentonite, talc, clay, diatomaceous earth,
In addition to fine mineral powders commonly used as pesticide carriers such as amorphous silicon dioxide, calcium carbonate, magnesium carbonate, resin powders such as vinyl chloride, chlorinated polyethylene, chlorinated polypropylene, glucose, sugar, lactose, etc. Sugars, carboxymethyl cellulose and its salts, starch and its derivatives, microcrystalline cellulose, wood flour, sawdust, rice bran, bran, chaff powder, coffee bean powder,
Cellulose powder, organic substances such as licorice powder, and water-soluble inorganic salts such as sodium sulfate, ammonium sulfate, and potassium chloride, and urea can be given. In particular, wood flour and sawdust are inexpensive, lightweight, and have the advantage of easily floating grains in water. There is an advantage.

The solvent used in the present invention is added as needed when diluting a liquid pesticidal active ingredient or making a low melting point pesticidal active ingredient into a liquid, has a high boiling point and low toxicity, and is flammable. A high boiling point solvent is selected and used, for example, a paraffin-based, aromatic-based, or naphthene-based high-boiling-point solvent agent; fatty acids obtained from various animals and plants such as oleic acid, maleic acid, fumaric acid, and coconut oil; Examples thereof include esters such as adipic acid and phosphoric acid; vegetable oils such as coconut oil and rapeseed oil; and animal oils such as whale oil and sardine oil.

The emulsifier used in the present invention is used, if necessary, in addition to the disintegrant or dispersant of the present invention described above, in order to emulsify a liquid pesticide active ingredient or a solution of the pesticide active ingredient in water. The emulsion can be selected and used in the same manner as in the case of selecting an emulsifier for an emulsion according to the usual pesticide active ingredient and solvent.

The water repellent used in the present invention is compounded mainly for suppressing the elution of the active ingredient of the agricultural chemical to spread it over the water surface as much as possible and then to dissolve it in water when the active ingredient of the agricultural chemical is highly water-soluble. Examples thereof include fatty acid salts such as magnesium stearate, calcium stearate and sodium oleate, higher alcohols such as stearyl alcohol, higher fatty acids such as stearic acid, silicone oil and its derivatives, fluorine-based surfactants and cationic interfaces. Activators, hydrophobic silica, liquid paraffin, machine oil and the like can be mentioned.

The grain growth inhibitor or stabilizer used in the present invention is blended, if necessary, depending on the properties of the agricultural chemical active ingredient. In addition, a dye, a bittering agent, and various other auxiliaries can be blended in the pesticide composition for water surface application, if necessary.

In order to produce the agrochemical composition for surface application of the present invention, when the agrochemical active ingredient is solid, the agrochemical active ingredient is usually finely pulverized by a dry method or a wet method, and the obtained agrochemical active ingredient is pulverized. Is mixed with a particle nucleus having an apparent specific gravity of less than 1, a surfactant and other auxiliary agents, and then formulated into a granule by a dry or wet granulation method. The wet molding machine used includes an extrusion granulator, a mixing granulator, a fluidized bed granulator and a tumbling granulator, and the dry molding machine includes a roller compactor, a tableting machine and a briquetting machine. And a hydraulic molding machine.

When the water-applied agrochemical composition of the present invention is formulated into granules, the granules having an apparent specific gravity of less than 1 and other necessary auxiliaries are mixed, and the pesticide is effective by using the above molding machine. A so-called "base grain" that does not contain an ingredient or contains only a part of the active ingredient may be preliminarily adjusted, and the pesticide active ingredient may be coated or absorbed with the rest of the other ingredients, and all ingredients After mixing in advance, it may be directly molded into granules using the above-mentioned molding machine.

When a liquid pesticidal active ingredient or a liquid pesticidal active ingredient is used, it is absorbed by a carrier having an apparent specific gravity of less than 1 or an oil-absorbing ability, and thereafter, a solid pesticide active ingredient is used. In the same manner as granules, or by pre-molding granules and other auxiliaries less than 1 into granules, by absorbing or coating liquid pesticide active ingredient or liquid pesticide active ingredient The pesticidal composition for surface application of the present invention can be obtained.

Regarding the particle size of the pesticidal composition for water surface application of the present invention, if the particle size is smaller than 0.6 mm, it tends to sink in water or the particles disintegrate too quickly.
The larger it is, the easier it is to be blown by the wind,
Since it takes time to disintegrate and disintegrate the particles and cause disintegration and dispersion at the location where the particles are blown, segregation of the active ingredient is usually required.
It is necessary that 0% or more falls within the range of 0.710 mm to 4.760 mm.

The thus obtained water-applied pesticide composition of the present invention is directly transferred into the paddy field from a box, bottle, bag or the like having a suitable transfer port, or is packaged in a water-soluble film to form a ridge. Throw in from etc. The water-applied pesticide composition of the present invention liberates the pesticide active ingredient while spreading on the water surface, so that it does not have to be uniformly sprayed into the paddy field like a common granule, and is appropriately sprayed into the paddy field from the ridge or the like. If processed, a sufficient biological effect can be obtained. The water-soluble film used in the present invention is a film or sheet having a property of being dissolved or dispersed in water, and its constituent material is, for example, one made of polyvinyl alcohol or its derivative, polyvinyl alcohol fiber. (For example, non-woven fabric), pullulan film, carboxymethylcellulose sodium salt and cellulose, polyethylene oxide and derivatives thereof, and the like. Particularly, a film made of polyvinyl alcohol or a derivative thereof. (Hereinafter, abbreviated as PVA film) itself has the property of being easily dispersed or dissolved in water to spread the water-applied pesticide composition of the present invention on the water surface.

The PVA film used in the present invention is obtained by filming polyvinyl alcohol having a degree of polymerization of 1000 to 2000 and a degree of saponification of 85 to 95% together with a small amount of a plasticizer, a stabilizer and the like. It also includes a film containing a small amount of a copolymer such as a carboxylic acid in the polymer. The thickness of the PVA film is usually 25 to 70 μm as a result of considering the film strength and the dissolution time.
And preferably 30 to 50 μm. Also, P
Advantageously, the edges of the VA film are heat sealable.

In the case of packaging in the above PVA film, 1
The weight of the package is usually 1 as a result of considering the ease of throwing.
It is 0 to 200 g, preferably 20 to 60 g, and the number of packets can be usually 2 to 40 per 10 ares to exert a sufficient biological effect, and preferably 4 ~ 20.

The "spreadability index" in the present specification is a numerical value of spreadability on the water surface of the pesticidal composition applied on the water surface in the range of 0 to 15 points (maximum 15 points), and the score is large. The better the water surface spreadability is, preferably 5 or more,
It is more preferably at least 7 points, and even more preferably at least 9 points. The test method of water surface spreadability is as follows.

25 L of tap water was put into a tou of 4 m in length and 14 cm in width, and 2 g of Sumicelco (manufactured by Sumikin Bussan Co., Ltd., powdered rice husks) assuming obstacles (floats) on the rice field water. Is evenly treated on the water surface. After standing still, 280 mg of the surface-applied pesticide composition was put into a point 10 cm from one end of the tou, and the time after which the pesticide composition of each surface-applied pesticide reached 1.5 m, the longest arrival from the point. The distance and the state of expansion after 5 minutes from the visual inspection are visually inspected, judgment is made according to the evaluation criteria shown in Table 1 below, and the expansion indexes of the respective items are summed to obtain the respective expansion indexes. When the spreadability of conventional pesticide formulations is evaluated in this test system, the spreadability on the water surface is less than 5 points, but when the pesticide composition for water surface application of the present invention is similarly evaluated, the spread index is 9 points. As above, it can be seen that the pesticidal composition for water surface application of the present invention has far superior water surface spreadability as compared with the prior art.

[0066]

[Table 1] Spreadability evaluation items and evaluation criteria ―――――――――――――――――――――――――――――――――――― Evaluation Item Judgment criteria Evaluation point ―――――――――――――――――――――――――――――――――――― 1.5m Arrival time 2 minutes or more 0 1 minute or more, less than 2 minutes 1 30 seconds or more, less than 1 minute 2 20 seconds or more, less than 30 seconds 3 10 seconds or more, less than 20 seconds 4 less than 10 seconds 5 ―――――――――――――――― ―――――――――――――――――――――― Longest reach less than 0.5m 0 0.5m or more, less than 1.0m 1 1.0m or more, less than 1.5m 2 1.5m or more, less than 2.0m 3 2.0m or more, less than 2.5m 4 2.5m or more, less than 3.0m 5 3.0m or more, less than 3.5m 6 3.5m or more 7 ――――― ――――――――― ――――――――――――――――――――― Expanded state after 5 minutes of processing The extended tip is returned to the processing point 0 0m from the longest reaching point 1m or more 1 Longest reaching Less than 1m returned from point 2 Not returned from longest reach point 3 ―――――――――――――――――――――――――――――――――――― Total 15 ―――――――――――――――――――――――――――――――――――――― The following are examples, comparative examples and test examples. The present invention will be described more specifically with reference to the following, but the present invention is not limited thereto. The following parts mean parts by weight.

[0067]

【Example】

[0068]

[Example 1] Granules Bensulfuron-methyl drug substance (purity 99.47%) 5.3
0 part, Kafenstrol raw drug (purity 98.39%) 2
0.88 parts and Daimlon drug substance (purity 99.4%) 3
6.18 parts were mixed, and this mixture was mixed with a jet mill (SK
-Jet Oh Mizer 0101 type, Seishin Enterprise Co., Ltd.) to obtain a premixed powder. 62.36 parts of the premix powder, sun extract P252
(Lignin sulfonate manufactured by Nippon Paper Industries Co., Ltd.) 7.5
0 part, M-3801G (Daiichi Kogyo Seiyaku Co., Ltd., α-
Olefin sulfonate) 3.42 parts, Neoperex No6F powder (Kao Corporation, alkylbenzene sulfonate) 0.68 parts, Amycol No. 5.48 parts of 1 (manufactured by Nippon Starch Chemical Co., Ltd., starch), 10.28 parts of bentonite (manufactured by Neolite Kosan Co., Ltd.) and 10.28 parts of cork (apparent specific gravity: 0.04 to 0.09) were mixed, This is kneader (Fuji Sangyo Co., Ltd. FM-NW-
5 type), 18 parts of water was added and kneaded. The obtained kneaded product was used for dome gran (Fuji Paudal Co., Ltd., DG
-L1 type, screen 1.0 mmφ) and extruded and granulated. The obtained granules are blown into a shelf type dryer (blast temperature 90
(C)) for 2 hours, then sieved to 850-1410 μm, 5% bensulfuron-methyl, cafenstrol 2
A granule containing 0% and Daimlon 35% was obtained.

[0069]

[Example 2] Granules Bensulfuron-methyl drug substance (purity 99.4%) 2.73
Part, CAPEFENT TROLL drug substance (purity 98.3%) 11.
37 parts, Daimlon drug substance (purity 99.4%) 24.09
Department, Olfin STG-E (manufactured by Nisshin Chemical Industry Co., Ltd.,
2,4,7,9-Tetramethyl-5-decyne-4,7-
Diol mixture) 0.5 part, KP1436 (Kao Corporation, polyoxyethylene phenylphenol ether phosphate) 0.4 part, Pearlex NP (Nippon Paper Manufacturing Co., lignin sulfonate) 5.64 parts and 55.27 parts of water was mixed, and the mixture was crushed with an attritor (manufactured by Mitsui Mining Co., Ltd.) to obtain a slurry. Toxanone GR31A was added to 95 parts of the obtained slurry.
(Sanyo Kasei Co., Ltd., polyacrylate) was added in an amount of 5 parts and further mixed and stirred to prepare a slurry 2. Cork 22.0 parts, serogen 5A (Daiichi Kogyo Seiyaku Co., Ltd.,
Carboxymethyl cellulose) 8.0 parts, Roca help B
439 (Mitsui Kinzoku Kogyo KK, expanded perlite)
7.0 parts, Pearlex NP (manufactured by Nippon Paper Industries Co., Ltd.,
Lignin sulfonate) 6.0 parts, wood flour (Neolite Kosan Co., Ltd.) 7.0 parts, M-3801G (Daiichi Kogyo Seiyaku Co., α-olefin sulfonate) 3.0
Department, Surfynol 104S (manufactured by Nisshin Chemical Co., Ltd.)
3.0 parts and bentonite 16.0 parts were mixed in a kneader, and 65.94 parts of the slurry 2 was added and kneaded. The obtained kneaded product was dome gran (screen 1.2).
(mmφ) and extruded and granulated. After drying the obtained granulated product with a blast shelf type dryer (blast temperature 70 ° C.), 4760 to
Sieving to 710 μm, bensulfuron methyl 1.7%,
A granule containing 7.0% of cafenstrol and 15% of Daimlon was obtained.

[0070]

[Example 3] Granule F-155 drug substance (purity 96.7%) 77.56 parts, M-
3801G 10.0 parts and Carplex # 1120
(Shionogi Pharmaceutical Co., Ltd., white carbon) 12.4
4 parts were mixed, and this mixture was ground by a jet mill to obtain a premix powder containing 75% of F-155. Hilcon SI-600 (calcined vermiculite, manufactured by Hilushi Chemical Co., Ltd., 0.6 mm undercut product, apparent specific gravity: 0.1) 51.5 parts were put into a Nauta mixer, and Daphne Oil SY-15 (Idemitsu Kosan Co., Ltd. (Manufactured by the company) to add 35 parts to moisten the surface of the particles, and then add 12.0 parts of the premix powder to mix and coat the surface of the particles, and further to add Surfynol 104S.
By adding 1.5 parts and mixing, the surface of the granules was coated to obtain granules containing 9.0% of F-155.

[0071]

[Example 4] Granule F-155 drug substance (purity 96.7%) 77.56 parts, M-
3801G 10.0 parts and Carplex # 1120
12.44 parts were mixed and this mixture was ground by a jet mill to obtain a premix powder containing 75% of F-155. 51.5 parts of Hilcon SI-600 (calcined vermiculite, manufactured by Hilushi Chemical Co., Ltd., 0.6 mm undercut product) were charged into a Nauter mixer, and E
HDG (manufactured by Nippon Emulsifier Co., Ltd., diethylene glycol mono-2-ethylhexyl ether) (35 parts) is added to moisten the surface of the particles, and then the premix powder 1
2.0 parts was added and mixed to coat the surface of the particles. Furthermore,
By adding 1.5 parts of Surfynol 104S and mixing, the surface of the particles was coated to obtain granules containing 9.0% of F-155.

[0072]

Example 5 Granule F-155 drug substance (purity 96.7%) 77.56 parts, Liporan PJ-400 (manufactured by Lion Corporation, α-olefin sulfonate) 10.0 parts and Carplex # 11
20 (Shionogi Pharmaceutical Co., Ltd., white carbon) 1
2.44 parts were mixed, and this mixture was ground by a jet mill to obtain a premix powder containing 75% of F-155. 51.5 parts of Hilcon SI-600 was charged into a Nauta mixer, 35 parts of EHDG was added to moisten the surface of the particles, and then 12.0 parts of the premix powder was added and mixed to coat the surface of the particles. Further, 1.5 parts of Surfynol 104S was added and mixed to coat the surface of the granules to obtain granules containing 9.0% of F-155.

[0073]

Example 6 77.56 parts of Granule F-155 drug substance (purity 96.7%), 10.0 parts of Hostapon T powder (Hoylst Japan KK, oleylmethyl tauride salt) and Carplex # 1120 12 0.44 parts were mixed, and this mixture was ground by a jet mill to obtain a premix powder containing 75% of F-155. Hilcon SI-600 5
Charge 1.5 parts into a Nauta mixer and use EHDG 35
Parts to wet the surface of the granules, then 12.0 parts of the premix powder is added and mixed to coat the surface of the granules,
Further, 1.5 parts of Surfynol 104S was added and mixed to coat the surface of the particles, and F-155 was added to 9.0.
% Granules were obtained.

[0074]

Example 7 Granule F-155 drug substance (purity 96.7%) 77.56 parts, Ho
stapler OSB (manufactured by Hoechst Japan Ltd.,
Oleyl methyl tauride salt) (10.0 parts) and Carplex # 1120 (12.44 parts) were mixed, and the mixture was ground by a jet mill to obtain a premix powder containing 75% of F-155. Hilcon SI-600
Charge 51.5 parts into a Nauta mixer and use EHDG
35 parts was added to moisten the surface of the granules, then 12.0 parts of the premix powder was added and mixed to coat the surface of the granules, and 1.5 parts of Surfynol 104S was further added and mixed to form the granules. Was coated on the surface of to obtain granules containing 9.0% of F-155.

[0075]

Example 8 Granule F-155 drug substance (purity 96.7%) 77.56 parts, FA
-617B (Lion Co., α-sulfo fatty acid salt)
10.0 parts and Carplex # 1120 12.44
Parts are mixed and the mixture is crushed by a jet mill,
A premix powder containing 75% F-155 was obtained.
51.5 parts of Hilcon SI-600 was charged into a Nauta mixer, 35 parts of EHDG was added to moisten the surface of the particles, and then 12.0 parts of the premix powder was added and mixed to coat the surface of the particles. , And Surfynol 10
4S 1.5 parts were added and mixed to coat the surface of the particles, and F-
A granule containing 9.0% of 155 was obtained.

[0076]

[Example 9] Granules Pyroquilone drug substance (purity 97.2%) 87.45 parts, M-
6801 parts of 3801G and 6.55 parts of Carplex # 80D (manufactured by Shionogi & Co., Ltd., white carbon) were mixed, and this mixture was crushed by a hammer mill (manufactured by Fuji Paudal Co., Ltd.) to contain 85% of pyroquilon. I got a premix. Hilcon SI-6003 3.09 parts was charged into a Nauta mixer, and 36 parts of Super Oil C (manufactured by Nippon Petrochemical Co., Ltd.) was added to moisten the surface of the particles,
Then, 29.41 parts of the premix is added and mixed to coat the surface of the particles, and further, Surfynol 104S
1.5 parts was added and mixed to coat the surface of the granules to obtain granules containing 25% of pyroquilon.

[0077]

Example 10 Granules Pyroquilon drug substance (purity 97.2%) 87.45 parts, M-
3801G 6 parts and Carplex # 80D 6.5
5 parts were mixed, and this mixture was ground with a hammer mill to obtain a premix containing 85% of pyroquilon.
33.09 parts of Hilcon SI-600 were charged into a Nauta mixer, 36 parts of EHDG was added to moisten the surface of the particles, and then 29.41 parts of the premix was added and mixed to coat the surface of the particles, Furthermore, Surfynol 104
1.5 parts of S was added and mixed to coat the surface of the granules to obtain granules containing 25% of pyroquilon.

[0078]

[Comparative Example 1] Granules Bensulfuron-methyl drug substance (purity 99.47%) 5.3
0 part, Kafenstrol raw drug (purity 98.39%) 2
0.88 parts and Daimlon drug substance (purity 99.4%) 3
6.18 parts were mixed, and this mixture was pulverized by a jet mill to obtain a premix powder. 62.36 parts of the premix powder, 7.50 parts of Sunextract P252, 0.68 part of Neoperex No6F powder, Amycor No. 15.48 parts and bentonite 23.98 parts were mixed, this was moved to the kneader, water 18 parts was added, and it kneaded. The obtained kneaded product was extruded and granulated with a dome gran (screen 1.0 mmφ). The obtained granulated product was dried for 2 hours by a ventilation shelf type dryer (blast temperature 90 ° C.) and then sieved to 850 to 1410 μm, and 5% of bensulfuron-methyl, 20% of cafenstrol and Daimlon 3 were obtained.
A granule containing 5% was obtained.

[0079]

[Comparative Example 2] Granules Bensulfuron methyl drug substance (purity 99.47%) 5.3
0 part, Kafenstrol raw drug (purity 98.39%) 2
0.88 parts and Daimlon drug substance (purity 99.4%) 3
6.18 parts were mixed, and this mixture was pulverized by a jet mill to obtain a premix powder. 62.36 parts of the premix powder, 7.50 parts of Sunextract P252, 0.68 part of Neoperex No6F powder, Amycor No. 15.48 parts, bentonite 13.7 parts and cork 10.28 parts are mixed and transferred to a kneader to prepare water 1
8 parts were added and kneaded. The obtained kneaded product was extruded and granulated with a dome gran (screen 1.0 mmφ).
The obtained granulated product is blown into a shelf dryer (blast temperature 90 ° C.)
After drying for 2 hours, the mixture was sieved to 850 to 1410 μm to obtain granules containing 5% bensulfuron-methyl, 20% cafenstrol and 35% dimuron.

[0080]

[Comparative Example 3] Granules Bensulfuron-methyl drug substance (purity 99.47%) 7.2
3 parts, raw material of cafenstrol (purity 98.39%) 2
8.50 parts and Daimlon drug substance (purity 99.4%) 4
9.36 parts were mixed, and this mixture was ground by a jet mill to obtain a premix powder. 62.36 parts of the premix powder, 7.50 parts of Sun Extract P252, M
-3801G 3.42 parts, Neoperex No6F powder 0.68 parts, AMICOL No. 15.48 parts of bentonite and 20.56 parts of bentonite were mixed, transferred to a kneader, added with 8 parts of water, and kneaded. The obtained kneaded product,
It was extruded and granulated with a dome gran (screen 1.0 mmφ). The obtained granulated product is dried for 2 hours in a fan tray dryer (blast temperature 90 ° C.) and then sieved to 850 to 1410 μm, containing 5% bensulfuron methyl, 20% cafenstrol and 35% dimeron. A granule was obtained.

[0081]

Comparative Example 4 Granule Bensulfuron Methyl Raw Material (Purity 99.4%) 2.73
Part, CAPEFENT TROLL drug substance (purity 98.3%) 11.
37 parts, Daimlon drug substance (purity 99.4%) 24.09
Part, Olfin STG-E 0.5 part, KP1436
0.4 parts, Pearlex NP 5.64 parts and water 5
After mixing 5.27 parts, this mixture was ground with an attritor to obtain a slurry. In 95 parts of the obtained slurry,
5 parts of Toxanone GR31A was added, mixed and stirred,
This was Slurry 2. Serogen 5A 8.0 parts, Roca help B439 7.0 parts, Pearlex NP 6.0 parts,
7.0 parts of wood powder, 3.0 parts of Surfynol 104S and 41.0 parts of bentonite were mixed in a kneader, and 65.94 parts of the slurry 2 was added and kneaded. The obtained kneaded product was extruded and granulated with a dome gran (screen 1.2 mmφ). The obtained granulated product is dried with a blast shelf type dryer (blast temperature 70 ° C.) and then 710 to 4760 μm
The mixture was sieved to give granules containing 1.7% of bensulfuron methyl, 7.0% of cafenstrol and 15% of dimuron.

[0082]

Comparative Example 5 Granule Bensulfuron Methyl Raw Material (Purity 99.4%) 2.73
Part, CAPEFENT TROLL drug substance (purity 98.3%) 11.
37 parts, Daimlon drug substance (purity 99.4%) 24.09
Part, Olfin STG-E 0.5 part, KP1436
0.4 parts, Pearlex NP 5.64 parts and water 5
After mixing 5.27 parts, this mixture was ground with an attritor to obtain a slurry. In 95 parts of the obtained slurry,
5 parts of Toxanone GR31A was added, mixed and stirred,
This was Slurry 2. 22.0 parts of cork, 5A of serogen
8.0 parts, Roca Help B439 7.0 parts, Pearlex NP 6.0 parts, wood flour 7.0 parts, Surfynol 10
After mixing 3.0 parts of 4S and 19.0 parts of bentonite in a kneader, 65.94 parts of the slurry 2 was added,
Kneaded The obtained kneaded product was extruded and granulated with Dome Gran (screen 1.2 mmφ). After drying the obtained granulated product in a ventilation shelf type dryer (airflow temperature 70 ° C.), 7
The mixture was sieved to 10 to 4760 μm to obtain granules containing 1.7% of bensulfuron methyl, 7.0% of cafenstrol and 15% of dimuron.

[0083]

[Comparative Example 6] Granule Bensulfuron-methyl drug substance (purity 99.4%) 2.73
Part, CAPEFENT TROLL drug substance (purity 98.3%) 11.
37 parts, Daimlon drug substance (purity 99.4%) 24.09
Part, Olfin STG-E 0.5 part, KP1436
0.4 parts, Pearlex NP 5.64 parts and water 5
After mixing 5.27 parts, this mixture was ground with an attritor to obtain a slurry. In 95 parts of the obtained slurry,
Toxanone GR31A (5 parts) was added, and the mixture was stirred to give a slurry 2. Serogen 5A 8.0 parts, Roca help B439 7.0 parts, Pearlex NP 6.0 parts, wood flour 7.0 parts, M-3801G 3.0 parts, Surfynol 104S 3.0 parts and bentonite 38.0 parts. After mixing in a kneader, 65.94 parts of the slurry 2 was added and kneaded. The obtained kneaded product was extruded and granulated with Dome Gran (screen 1.2 mmφ). The obtained granulated product was dried with a blast shelf type dryer (blast temperature of 70 ° C.) and then sieved to 710 to 4760 μm to obtain 1.7% of bensulfuron methyl, 7.0% of cafenstrol and 15% of dimeron. The containing granules were obtained.

[0084]

Comparative Example 7 77.56 parts of granule F-155 drug substance (purity 96.7%) and 22.44 parts of Carplex # 1120 were mixed, and this mixture was ground by a jet mill to give 75 parts of F-155.
% Premixed powder was obtained. Hilcon SI-6
00 51.5 parts was charged into a Nauta mixer, 35 parts of Daphne Oil SY-15 was added to moisten the surface of the particles, and then 12.0 parts of the premix powder was added and mixed to coat the surface of the particles. In addition, Surfynol 10
Add 1.5 parts of 4S and mix to coat on the surface of the dragon.
A granule containing 9.0% of -155 was obtained.

[0085]

[Comparative Example 8] 87.45 parts of granulated pyroquilon drug substance (purity 97.2%) and Carplex # 80D12.55 part were mixed, and this mixture was ground with a hammer mill to prepare a premix containing 85% of pyroquilon. Got Hilcon No. 1 33.09
Part is charged into a Nauta mixer, and Super Oil C 3
6 parts was added to moisten the surface of the grain, and then 29.41 parts of the premix was added and mixed to coat the surface of the grain. Next, 1.5 parts of Surfynol 104S was added and mixed to coat the surface of the granules to obtain granules containing 25% of pyroquilon.

[0086]

[Test Example 1] Spreadability test of granules 25 L of tap water was put in a tou with a length of 4 m and a width of 14 cm, and Sumiselco (manufactured by Sumikin Bussan Co., Ltd.) , Powdered rice husks) 2g
Was treated so as to be uniform on the water surface. After standing, Examples 1 to
280 mg of the granules described in 10 and Test Examples 1 to 8 were charged at a point 10 cm from one end of the tou, and the time required for reaching 1.5 m from the charging point of each granule after charging, the longest reaching from the charging point The distance and the spread state 5 minutes after the injection were visually inspected, judged according to the evaluation criteria shown in Table 1 above, and the spread indexes of the respective items were summed to obtain each spread index. The results are shown in Table 2. The symbol-in the table means that the granules did not spread.

[0087]

[Table 2]   Spreadability test of granules ―――――――――――――――――――――――――――――――――――― Test granule 1.5m arrival time Spreading distance (m) 5 minutes after processing Spreading index ―――――――――――――――――――――――――――――――――――― Example 1 45 seconds 2.4 No change 9 Example 2 57 seconds 2.6 No change 9 Example 3 27 seconds 2.4 No change observed 9 Example 4 19 seconds 3.1 No change 13 Example 5 27 seconds 2.6 No change 10 Example 6 28 seconds 2.8 No change 11 Example 7 27 seconds 2.8 No change 11 Example 8 28 seconds 2.4 No change 10 Example 9 28 seconds 2.4 No change observed 10 Example 10 15 seconds 3.1 No change 13 ------------------ Comparative Example 1 − − − 0 Comparative Example 2 2 minutes or more 0.2-0 Comparative Example 3 ---- 0 Comparative Example 4 − − − 0 Comparative Example 5 2 minutes or more 0.8 No change 4 Comparative Example 6 ---- 0 Comparative Example 7 2 minutes or more 0.7 Return of particles less than 1 m 3 Comparative Example 8 2 minutes or more 0.5 Return of particles less than 1 m 3 ――――――――――――――――――――――――――――――――――――

[0088]

[Table 3]   Spreadability test of granules ―――――――――――――――――――――――――――――――――――― Test granule Spreading state ―――――――――――――――――――――――――――――――――――― Examples 1 to 10 Show good water surface spreadability and disperse in water immediately after spread. ------------------ Comparative Example 1 Grains settled immediately after charging and did not spread Comparative Example 2 Grain does not settle, but it hardly spreads and is dispersed in water Comparative Example 3 Grain settled immediately after charging and did not spread Comparative Example 4 Grains settled immediately after being charged and did not spread. Comparative Example 5 The water surface is expanded, but the expansion speed is slow and the expansion power is weak. Comparative Example 6 Grain settled immediately after charging and did not spread Comparative Example 7 The water surface is expanded, but the expansion speed is slow and the expansion power is weak. Comparative Example 8 The water surface is expanded, but the expansion speed is slow and the expansion power is weak. ――――――――――――――――――――――――――――――――――――

[0089]

[Test Example 2] Paddy Field Throwing Test of Throwing Formulation A paddy field of about 27 mx 28 m was filled with water and the water depth was kept at 5 cm. 50 g of the granules of Examples 7 and 8 and Comparative Example 8 were wrapped in a non-woven fabric which was a water-soluble film and heat-sealed to give a throw-in preparation. Each thrown formulation was thrown into a paddy field, and the bag breaking time of the film, the time when all the grains came out of the film (total scattering time), and the area of the spread part of the grains were examined. The results are shown in Table 4. The wind speed during the treatment was 4 m / sec.

[0090]

[Table 4] ―――――――――――――――――――――――――――――――――――― Test Preparation Film Breaking Time Total Time Spread area (m ² ) ―――――――――――――――――――――――――――――――――――― Example 7 16 seconds 3 minutes 30 seconds 104 Example 8 20 seconds 3 minutes 30 seconds 361 ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― ― Comparative example 8 18 seconds 2 minutes 30 seconds 42 ――――――――― ―――――――――――――――――――――――――――

[0091]

EFFECTS OF THE INVENTION As is clear from the above test examples, the pesticide composition for water surface application of the present invention has a very good water surface spreading and floating property even on the water surface where obstacles are present, and moreover, it can be used in the paddy field. By simply throwing it in from above, it has far superior water surface spreadability compared to conventional water-floating pesticide granules, and even if there are a few obstacles, it is possible to disperse the pesticide active ingredient uniformly over the entire paddy field. Is.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masakazu Tomioka 1041 Yasu-cho, Yasu-gun, Shiga Sankyo Co., Ltd. (56) References JP-A-7-101805 (JP, A) JP-A-6-336403 (JP) , A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A01N 25/00-25/34

Claims (22)

(57) [Claims] Claims: 1. One or more pesticide active ingredients, one or more surfactants selected from the following compounds, and a hollow mineral substance carrier having an apparent specific gravity of less than 1 and a plant carrier.
Body, synthetic resin foam or one or more of these
A pesticidal composition for water surface application, which has a molded particle nucleus having a property of floating in water and has excellent water surface spreadability, wherein the compound group is α-olefin sulfonate, α-sulfone salt. It is a group consisting of fatty acid salts and oleylmethyl tauride salts. 2. The pesticidal composition for water surface application according to claim 1, wherein the pesticidal active ingredient is a herbicide, insecticide, fungicide, acaricide or plant regulator. 3. The surface-applied pesticide composition according to claim 1, wherein the content ratio of the pesticidal active ingredient is 1 to 90% in the surface-applied pesticide granular composition. 4. The α-olefin sulfonate is C12-
A C16 α-olefin sulfonate salt.
4. A pesticide composition for water surface application according to any one of 1 to 3. 5. The water-applied pesticide composition according to any one of claims 1 to 3, wherein the α-sulfofatty acid salt is a C10-C14 α-sulfofatty acid salt. 6. The salt according to claim 4, wherein the salt is a sodium, potassium, calcium, ammonium or amine salt.
The agrochemical composition for water surface application described in. 7. The pesticidal composition for water surface application according to claim 1, wherein the oleylmethyl tauride salt is a sodium, calcium, potassium or ammonium salt of oleylmethyl tauride. 8. The surface-applied pesticide composition according to claim 1, wherein the content of the surfactant in the surface-applied pesticide composition is 0.01 to 40%. 9. The agrochemical composition for surface application according to any one of claims 1 to 7, wherein the content of the surfactant is 0.1 to 30% in the agrochemical composition for surface application. 10. The surface-applied pesticide composition according to claim 1, wherein the content of the surfactant in the surface-applied pesticide composition is 1 to 20%. 11. The water-applied pesticide composition according to any one of claims 1 to 10, further comprising another water surface extender. 12. The pesticide composition for water surface application according to claim 1, wherein the other water surface spreading agent is an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant. object. 13. hollow mineral apparent specific gravity I der less than 1
Carrier, plant carrier, synthetic resin foam or one or more of these
Is a molded product that contains two or more types and has the property of floating in water.
The grain nuclei have an apparent specific gravity of less than 1
Light, foam Shirasu, foam perlite, cork, foam
The surface-applied pesticide composition according to any one of claims 1 to 12, which is styrene or a molded particle nucleus containing one or more of these and imparting a property of floating in water. 14. A non-volatile substance which is liquid at room temperature is contained.
The surface-applied pesticide composition according to any one of claims 1 to 13 . 15. The agricultural chemical composition for surface application according to claim 14 , wherein the non-volatile substance which is liquid at room temperature is an ether of a glycol or an alkyl lactate ester. 16. The spreadability index is 5 points or more.
A pesticide composition for water surface application according to any one of items 1 to 15 . 17. A box provided with a suitable transfer port for the pesticide composition for water surface application according to any one of claims 1 to 16 .
A method of treating pesticides by transferring the waste directly from the bottle or bag into the paddy field. 18. A method for treating a pesticide, which comprises packaging the water-applied pesticide composition according to any one of claims 1 to 16 in a water-soluble film and throwing it from a ridge. 19. The method for treating agricultural chemicals according to claim 18 , wherein the weight of each packet is 10 to 200 g. 20. agrochemical active ingredient, apparent specific gravity Oh less than 1
Hollow mineral carrier, plant carrier, synthetic resin foam or
Contains one or more of these and has the property of floating in water.
Characterized in that dry or wet granulation is carried out after mixing with a given shaped particle nucleus, one or more kinds of surfactants selected from the following compound group and other auxiliary agents if necessary. Item 17. A method for producing a pesticidal composition for water surface application according to any one of Items 1 to 16 , wherein the compound group is a group consisting of α-olefin sulfonate, α-sulfo fatty acid salt and oleyl methyl tauride salt. is there. 21. A hollow mineral having an apparent specific gravity of less than 1.
Carrier, plant carrier, synthetic resin foam or one or more of these
Is a molded product that contains two or more types and has the property of floating in water.
A non-volatile substance that is liquid at room temperature is added to the granules containing the granules having an apparent specific gravity of less than 1 or a part or all of the pesticide active ingredient and other auxiliary agents if necessary. make use of,
It is characterized by coating one or more surfactants selected from the following compound group, or one or more surfactants selected from the following compound group and the remaining agrochemical active ingredients. The method for producing a pesticidal composition for water surface application according to any one of claims 14 to 16 , wherein the compound group comprises α-olefin sulfonate, α-sulfo fatty acid salt and oleyl methyl tauride salt. It is a group. 22. A hollow mineral having an apparent specific gravity of less than 1.
Carrier, plant carrier, synthetic resin foam or one or more of these
Is a molded product that contains two or more types and has the property of floating in water.
A non-volatile substance that is liquid at room temperature, in a granule containing an agglomerate having an apparent specific gravity of less than 1, a part or all of the pesticide active ingredient and, if necessary, other auxiliaries, Claims characterized by impregnating one or more kinds of surfactants selected from the following compound group and the remaining agrochemical active ingredients:
The method for producing the pesticidal composition for water surface application according to any one of 14 to 16 , wherein the compound group is a group consisting of α-olefin sulfonate, α-sulfo fatty acid salt and oleylmethyl tauride salt. .