CN1353572A - Floating solid pesticide preparations - Google Patents

Abstract

Floating solid pesticide preparations which contain one or more water surface spreaders comprising C2-4 alkylene oxide adducts of C4-10 alkyl-alcohols and derivatives thereof and an active pesticide ingredient.

Description

Water surface floating agricultural chemical solid preparation

technical field

The present invention relates to a solid preparation of water surface floating agricultural chemicals, which contains one or more water surface spreading agents selected from C _4-10 alkyl alcohol, C _2-4 alkylene oxide adducts and derivatives thereof , and active ingredients of agrochemicals; an agrochemical preparation coated with a water-soluble film suitable for spreading in paddy fields; and a method of controlling harmful organisms occurring in paddy fields using these agrochemical preparations.

Background technique

Agrochemicals used in rice fields are usually provided in various formulations such as powders, wettable powders, emulsions and granules for easy application on water or rice. However, in recent years, from the standpoint of aging of farmers, part-time employment, and increased burden on female workers, labor saving for applying agricultural chemicals has been demanded.

Therefore, there is a tendency to use flowable formulations that do not require machinery or so-called "1-kg-granules" with an increased active ingredient content, thus reducing the amount of formulation that needs to be applied. However, flow preparations are accompanied by a problem depending on the direction of the wind, and it may happen that droplets fall on the user during use. Disposal of empty bottles after use is also a problem. On the other hand, 1-kg-granules have drawbacks such as the necessity to use application equipment and difficulty in uniform spreading.

Recently, there has been proposed (in Japanese Published Unexamined Patent Application No. Hei 3-173802) a labor-saving agrochemical formulation (that is, an agrochemical formulation to be cast in rice fields) by The agrochemical solid preparation is obtained by wrapping a layer of water-soluble film. The preparation does not need to enter the paddy field, but can show its effect only by throwing it from the ridge into the paddy field. There has been a commercial sale called "Jumbo" or "Throw-in-packherbicide".

This preparation that is sprinkled into the paddy field is known: (1) a large effervescent tablet is sprinkled into the paddy field (Japanese Published Unexamined Patent Application No. Hei 6-107503), (2) a Small foaming tablets coated with a water-soluble film are sprinkled in paddy fields (Japanese Published Unexamined Patent Application No. Hei 5-339106), (3) a pack of preparations is sprinkled in paddy fields, the The preparation is prepared by granulating a water-soluble carrier such as potassium chloride and a high-molecular-weight substance that can form a water-soluble film, adding the active ingredients of agricultural chemicals to the obtained granules, and then coating the mixture with a water-soluble film (Japan Published Unexamined Patent Application No.Hei5-78207), (4) throwing a pack of agrochemical solid preparation into rice fields, which is made to float and spread on the water surface and is covered with a water-soluble film ( Japanese published unexamined patent application No.Hei 6-336403), and (5) drop the container of the oily preparation filled with water flow expansibility into the paddy field (Japanese published unexamined patent application No.Hei5- 339103).

The agricultural chemical formulation sprinkled into the paddy field has a high content of active ingredients of the agricultural chemical, and is applied topically. If they cannot diffuse the active ingredient from the casting site quickly, the agricultural chemical will cause damage to rice crops or uneven efficacy due to insufficient diffusion of the active ingredient of the agricultural chemical. Sometimes, the active ingredients of agrochemicals left in the field can be potentially dangerous and have adverse effects on subsequent crops.

As an agrochemical solid formulation that is prepared to float and disperse on the water surface and to diffuse its active ingredient of the agrochemical, there are disclosed, for example (1) a formulation that floats by using a surface-floatable carrier (Japanese Patent Publication No.Sho 48-15613, Japanese Patent No.Sho 47-1240), (2) a preparation (Japanese Patent Publication No.Sho 44-8600) with pumice or vermiculite with special water absorption capacity as carrier, ( 3) A granule formulation formed with a volatile insecticide compound (Japanese Patent Laid-Open No. Sho 49-11421), (4) A formulation on a solid carrier containing carbamate, an agrochemical active ingredient and an organic compound having a partition coefficient of 102 or more in water (Japanese Published Unexamined Patent Application No. Hei 2-174702), and (5) an organic compound containing a fungicide, herbicide or plant growth regulator Composition as active ingredient, solid carrier and oil (Japanese Published Unexamined Patent Application No. Hei 3-193705).

Even by so-called "frame application" from the ridge of the field without entering the paddy field, the above-mentioned solid formulations of agrochemicals show high efficacy because the rice seedlings in the field are small and there are no obstacles when used in the paddy field If there are floating weeds, algae and oily phases, the granules are dispersed by the force of the wind and spread over the entire water surface. When the power of the wind cannot be used because the rice seedlings grow tall or there are obstacles on the water surface such as floating weeds, algae, and oily phases, the granules are not easy to disperse alone, and sometimes cannot show sufficient biological efficacy due to the localization of active ingredients Or sometimes make pesticides harmful to rice crops. In this case, similar to conventional granules, it is necessary to apply into paddy fields, which is not preferable from the viewpoint of labor saving.

Focusing on overcoming the above-mentioned problems, in the preparation of floating solid insecticides, it has been tried to use acetylenic surfactants as water surface spreading agents, and then the resulting preparation is wrapped with a water-soluble film with water surface spreadability, or try to use Silicone surfactant or fluorosurfactant or dialkyl sulfosuccinate as water spreading agent (Japanese Published Unexamined Patent Application No. Hei 6-336403, Japanese Published Unexamined Patent application No.Hei8-99802, or Japanese Patent Publication No.2766973). According to these techniques, however, there are some obstacles on the water surface as described above, or sufficient spreading is not always obtained when the rice seedlings are treated after they have grown tall.

Contents of the invention

The present inventors conducted extensive investigations on water-surface-floating solid formulations of agricultural chemicals having excellent water-surface spreadability. As a result, a water surface floating agrochemical solid formulation containing one or more water surface spreading agents selected from the group consisting of C _4-10 alkyl alcohols, C _2-4 alkylene oxide adducts and derivatives thereof has been found , even when applied to a paddy field with some obstacles on the water surface and/or where the rice has grown tall, exhibits excellent spreadability out of the water surface, leading to the completion of the present invention.

The invention provides a solid preparation of water surface floating agricultural chemicals, which contains one or more water surface spreading agents selected from _C4-10 alkyl alcohol, _C2-4 alkylene oxide adducts and derivatives thereof , and active ingredients of agrochemicals; an agrochemical formulation suitable for spraying in paddy fields, which is covered with a water-soluble film; and a method of controlling harmful organisms occurring in paddy fields using the same.

In the present invention, "C _4-10 alkyl alcohol" refers to a straight or branched chain alcohol having 4-10 carbon atoms. Examples may include butanol, pentanol, hexanol, heptanol, octanol, nonanol, isononanol, decanol, and ethylhexanol, among which linear or branched alcohols having 6 to 10 carbon atoms are preferred, and more Octanol, ethylhexanol and isononanol are preferable, and ethylhexanol and isononanol are more preferable.

In the present invention, "C _2-4 alkylene oxide" refers to a linear or branched chain alkylene oxide having 2-4 carbon atoms. Examples may include ethylene oxide, propylene oxide and butylene oxide, with ethylene oxide and propylene oxide being preferred.

In the present invention, "C _2-4 alkylene oxide adduct of C _4-10 alkyl alcohol" refers to adding the above-mentioned "C _2-4 alkylene oxide" to the above-mentioned "C _4- The compound obtained on the hydroxyl group of ₁₀ alkyl alcohols. When a plurality of alkylene oxides are added, the order of addition is not limited.

The "C _2-4 alkylene oxide adduct of C _4-10 alkyl alcohol" is preferably represented by the following formula (I):

R ¹ O-(AO) _m -(BO) _n -H (I)[Wherein, R ¹ represents C _4-10 alkyl, A represents the group represented by the formula: -CH ₂ CH ₂ -, B represents the formula: -CH ₂ -CH(CH ₃ )- the group shown, m represents 0-30 and n represents 0-30, provided that m and n do not represent 0 at the same time, and when n is 0, m is 2 or more , or when neither m nor n represent 0, the mAO and nBO parts are connected to each other in any order. ]

In the above formula, "m" and "n" respectively represent the numbers of oxirane groups and propylene oxide groups added to one compound (I). It may also refer to the average number of each oxirane group and propylene oxide group added to many compounds (I).

In the present invention, "derivatives of C _2-4 alkylene oxide adducts of C _4-10 alkyl alcohols" may be, for example, phosphoric acid esters, salts of phosphoric acid esters, sulfuric acid esters, salts of sulfuric acid esters Or C _1-10 alkyl ether, various "C _4-10 alkyl alcohol C _2-4 alkylene oxide adducts" exemplified above, among which phosphoric acid esters and salts thereof are preferred.

In the present invention, "phosphate esters" include monoesters, diesters and triesters, and a mixture of such esters is preferred.

The "salt" of the present invention is not particularly limited as long as it is commonly used as an agricultural chemical. Examples include alkali metal salts such as sodium salt, potassium salt and lithium salt; amine salts such as ammonium salt, triethanolamine salt and isopropylamine salt, and alkaline earth metal salts such as calcium salt and barium salt, among which ammonium salt and alkali metal salt are preferred salts, more preferably ammonium, sodium and potassium salts.

In the present invention, "C _1-10 alkyl ether" is obtained by adding a C _2-4 alkylene oxide of a straight chain or branched chain alkyl group having 1-10 carbon atoms to the above-mentioned "C _4-10 alkyl alcohol". obtained by linking the oxygen atom of the terminal hydroxyl group of the compound". Examples include methyl ether, diethyl ether, propyl ether, isopropyl ether, butyl ether, pentyl ether, hexyl ether, heptyl ether, octyl ether, ethyl hexyl ether, nonyl ether, isononyl ether and decyl ether, of which ethyl hexyl ether is preferred and isononyl ether.

In the present invention, compound (1a) represented by the following formula (I) is more preferable as "C _2-4 alkylene oxide adduct of C _4-10 alkyl alcohol", wherein:

R ¹ represents C _6-10 alkyl (more preferably octyl, ethylhexyl or isononyl, more preferably ethylhexyl or isononyl), A represents the group represented by the formula: -CH ₂ CH ₂ -, B Representative formula: the group represented by -CH ₂ -CH(CH ₃ )-, m represents 0-15 (more preferably 0-10), n represents 0-15 (more preferably 0-10), provided that m and n are not While representing 0, and when n is 0, m is a number of 2 or more, or when neither m nor n represent 0, the connection order of mAO and nBO parts is not limited.

Particularly preferred compound (1b) represented by formula (I) is used as a water surface spreading agent, wherein R ¹ represents ethylhexyl or isononyl, m represents 0-10, n represents 0-10, and the condition is that m and n do not represent at the same time 0, and when n is 0, m is a number of 2 or more; its phosphoric acid ester or the ammonium salt, sodium salt or potassium salt of said phosphoric acid ester; most preferably the compound (1c) represented by formula (I), Wherein ^R represents ethylhexyl or isononyl, m represents 2-8, n represents 0-8, its phosphoric acid ester or the sodium salt of said phosphoric acid ester.

As the water surface spreading agent of the present invention, commercially available ones can be used. Alternatively, if not commercially available, it can be prepared by a similar method as described in "Novel Surfactants" (Hiroshi Horiguchi, published by Sankyo Publishing Co., 1975).

The amount of the water surface spreading agent in the solid preparation is usually 0.1-50% by weight, preferably 0.5-30% by weight, more preferably 1-20% by weight.

The active ingredient of the agricultural chemical of the present invention is not particularly limited as long as it can be used in rice fields. It can be liquid or solid. Examples may include insecticides, fungicides, herbicides and plant growth regulators.

Examples of insecticides include systemic insecticides such as isoxazophos, diazinon, diphorate, propafon, trichlorfon, dimethoate, monocrotophos, acephate, gram Budweiser, carbosulfan, thiacycline, cartap, insecticide, carbosulfan, furosecarb, buprofezin, butylbencarb, methiocarb, propoxam, mimaphid, Nitrapyridine and acetamiprid; and pyrethroids, such as pyrethrin, etofenprox, and pyrethrin, are effective against insects that live in or near water, such as the rice weevil and the rice slugworm, Among them, imidazolid, nitrapyridine, acetamiprid, pyrethrin, etofenproxil and betasil are preferred.

Examples of fungicides may include fungicides for the prevention of rice blast, such as thiabendazole, ricebendazole, isofradazine, tricyclazole, pyroxaquinone, chlorocyclopropamide, anthranilamide, azuridine Esters and 7-fluoro-1,2,5,6-tetrahydro-4H-pyrrolo[3.2.1-i.j]quinolin-4-ones; fungicides against sheath blight, e.g. Amines, bromfenazole, furazolin and 2-(4-fluorophenyl)-1-(1H-1,2,4-triazol-1-yl)-3-trimethylsilylpropane -2-alcohol; and tecloftal; and benomyl, among which thiabendazole, rice blastazim, pyroquinone, chlorocyclopropanamide, anthranilamide, azoxystrobin, 7-fluoro-1, 2,5,6-tetrahydro-4H-pyrrolo[3.2.1-i.j]quinolin-4-one, fluoramide, bromfluconazole, furazolin, 2-(4-fluorophenyl)- 1-(1H-1,2,4-Triazol-1-yl)-3-trimethylsilyl-propan-2-ol and chlorophyllin.

Examples of herbicides include paddy herbicides such as pyrazolid, methazaldone, pyrazolone, barnyard, bromobutyramid, methafos, mefenacet, bensulfuron, saponin Phosphorus, deschloramine, pretilachlor, dicarban, cloquat, chlornitramide, vanillon, chlorpyramid, chlorpyramid, oxadiazole, propargyloxazone, methazone, and oxazone , difenfos, dipyrazon, difenben, dithiopyr, pyrisulfuron, furazone, algaquinone, ciprofen, MCPA or its salts, such as its sodium and potassium salts or MCPA Esters, 2,4-D or its salts, such as sodium and potassium salts or esters of 2,4-D, MCPB or its salts, such as sodium and potassium salts or esters of MCPB, quinclorac, Pyrazosulfuron, pentoxazone, thiefentralam, cumyluron, fensulfuron, sizazone, meprofen, cyhalofop-butyl, ethiprofen, cafenstrole, ethoxysulfuron, tetrazole Huanglong, ciprosulfuron, indanofan, oxazone, chloroxazone, 4-(2-chlorophenyl)-N-cyclohexyl-4,5-dihydro-N-ethyl-5-oxo -1H-tetrazole-1-carboxamide (fentrazamide, NBA061), [3(2-chloro-4-methylsulfonylbenzoyl)-4-phenylthio]bicyclo[3.2.1]octane-3 -en-2-one (benzobicyclon, SB500), methyl N-[4-(benzothiazol-2-ylmethoxy)-2-methylphenyl] carbamate and methyl N-[4 -(Benzoxazole)-2-methylphenyl]carbamate, among which pyrazolate, metazazone, pyrazolone, barnyard, bromobutyramid, mefenacet, benzyl Rimisulfuron, samponiphos, desachlor, pretilachlor, vanillon, propargyl oxazone, imisulfuron, pyrazosulfuron, pentoxafen, thiefentrachlor, and procitrame , cyhalofop-butyl, cafenstrole, ethimethuron, tetrazosulfuron, indanofan, fentrazamide (NBA061), benzobicyclon, methyl N-[4-(benzothiazol-2-ylmethoxy)-2-methyl phenyl]carbamate and methyl N-[4-(benzoxazol-2-ylmethoxy)-2-methylphenyl]carbamate.

Examples of plant growth regulators include tributamide, paclobutrazol, uniconazole and imconazole, among which tributamide and paclobutrazol are preferred.

In addition to the water surface spreading agent and the active ingredients of the agrochemical, the solid formulation of the agrochemical of the present invention may also contain a floating agent, another water surface spreading agent, a breaking and dispersing agent, a wetting agent, a binder, a diluent , granulation improver, solvent, emulsifier, stabilizer and grinding aid, and other additives.

The solid formulation of the agricultural chemical of the present invention may contain a floating agent in order to improve its buoyancy on the surface of water. Any floating agent may be used as long as it can float the solid formulation of the agricultural chemical on the water surface. Examples include minerals such as expanded Shirasu, expanded perlite, expanded pumice, and tempered vermiculite; plant-based such as cork, wood flour, and cellulose; expanded synthetic resins such as expanded styrene; synthetic resin powders such as polyvinyl chloride powder ; Plastic foams such as "Matsumoto microsphere F30E" ; Synthetic resins in granular form, and mixtures thereof. Among them, expanded Shirasu, expanded perlite, expanded pumice, calcined vermiculite, cork, wood powder, expanded synthetic resin, synthetic resin powder, and plastic foam are preferable.

Although the amount of floating agent used in the present invention varies with the kind of floating agent used and the type of formulation or the particle size of the solid formulation of agricultural chemicals, the amount sufficient to float the solid formulation of agricultural chemicals on the water surface is satisfactory. . Usually, the amount added to the solid formulation of agrochemicals is 0.01-90% by weight, preferably 0.1-70% by weight, more preferably 0.5-60% by weight.

In the present invention, it is possible to add various surfactants as auxiliary agents. When added, the surfactant may act as an additional water spreading agent, breaking and dispersing agent, wetting agent, binder, granulation improving agent or emulsifier. Polymers or organic solvents can be used for many purposes depending on their properties.

In the solid formulation of the agricultural chemical of the present invention, another water surface spreading agent may be added together with the above water surface spreading agent in order to further improve the spreadability on the water surface. Examples of additional water spreading agents include polycarboxylic acid polysoaps, for example, (co)polymers of carboxylic acids such as acrylic acid and maleic acid, and polymer salts, such as carboxylic acids such as acrylic acid and maleic acid with Sodium, potassium or ammonium salts of styrene sulfonic acid or vinylic copolymers; soaps, such as sodium oleate and potassium stearate; other anionic surfactants, such as sodium dialkyl sulfosuccinate, Sodium dialkylbenzenesulfonate, sodium lauryl sulfate, and perfluoroalkyl carboxylates; other nonionic surfactants, such as polyoxyethylene alkylaryl ethers, polyoxyethylenes having at least 11 carbon atoms Alkyl ethers, polyoxyethylene alkyl esters and alkyl esters of sorbitan; nonionic silicone surfactants; nonionic acetylene surfactants and nonionic pluronic-type surfactants; by Surfactants obtained by converting the nonionic surfactants exemplified above into their corresponding phosphate or sulfate salts, neutralized if necessary with a suitable base; fluorinated surfactants; mineral oils such as liquid chain Alkanic, naphthenic or aromatic high-boiling solvents, low-viscosity polybutenes and machine oils; silicone oils; various vegetable oils; resins, such as turpentine; camphor oil; α-pinene, camphor; and naphthalene, among which nonionic Acetylene surfactants and various mineral oils.

Although the amount of additional water surface spreading agent used in the present invention varies depending on the nature or addition method of the water surface spreading agent, the nature or amount of the active ingredient of the agricultural chemical or the floating agent, the nature or amount of other additives, or the formulation type, it is usually added to the agrochemical solid preparation in an amount of 0.01-50 wt%, preferably 0.1-40 wt%, more preferably 0.2-30 wt%.

The solid formulation of the agricultural chemical of the present invention may contain a crushing and dispersing agent for crushing the granule in water and suspending or dispersing the active ingredient of the agricultural chemical in the water. It tends to be preferable to use anionic surfactants as breaking and dispersing agents. Examples include lignosulfonates, (alkyl)naphthalenesulfonates and their condensates, dobesylates and their condensates, salts of styrenesulfonic acid condensates, maleic acid and benzene Salts of condensates of vinylsulfonic acid, salts of condensates of carboxylic acids such as acrylic acid or maleic acid, salts of polyacrylates, salts of copolymers of acrylic acid and maleic acid, maleic anhydride and methylvinyl Ether copolymer salts, alkylbenzene sulfonates, dialkyl sulfosuccinates, lauryl sulfates, polyoxyethylene alkyl aryl ether sulfates, polyoxyethylene aryl aromatic Ether sulfates, polyoxyethylene alkyl aryl ether phosphates, polyoxyethylene aryl aryl ether phosphates, and salts of such sulfates or phosphates by neutralizing them with suitable cations Among the obtained salts, lignosulfonates, condensation products of (alkyl)naphthalenesulfonates, condensation products of dobesylates, condensation products of styrenesulfonates, maleic acid Salts of condensates of acid and styrenesulfonic acid, salts of condensates with carboxylic acids such as acrylic acid or maleic acid, salts of polyacrylates, salts of copolymers of acrylic acid and maleic acid, maleic anhydride and formaldehyde salts of copolymers of vinyl ethers, and dialkyl sulfosuccinates. Many of these surfactants used as disintegrating and dispersing agents are also effective wetting agents. In addition, phosphates such as sodium phosphate and sodium hexametaphosphate; suitable species selected from nonionic surfactants, cationic surfactants, and amphoteric surfactants; and compounds that have water-absorbing properties and thus swell, such as starch, Carboxymethyl cellulose and carboxymethylated starch and its salts, cross-linked polyvinylpyrrolidone, microcrystalline cellulose and resins with high water absorption can also be used as crushing and dispersing agents.

The amount of the crushing and dispersing agent or the amount of the crushing and dispersing agent and the wetting agent is usually 0.01-30% by weight, preferably 0.03-20% by weight, more preferably 0.05-10% by weight in the agrochemical solid formulation.

The solid formulation of the agricultural chemical of the present invention may contain a binder to make the granule hard when the granule is prepared by granulating the powder raw material, or to firmly coat the active ingredient of the agricultural chemical on the surface of the granule core.

Examples of binders for the former purpose include water-soluble starch derivatives such as dextrin and α-starch with relatively low molecular weight; water-soluble high-molecular weight substances such as polyvinylpyrrolidone, polyacrylates, carboxymethyl Salts of cellulose, polyvinyl alcohols of relatively low molecular weight and low saponification value, lignosulfonates, and gum arabic; and fine powders of kaolin minerals such as bentonite.

The amount of binder used for the former purpose varies depending on the components of the formulation, the method of preparation or the particle size of the granules; usually it is 0.1-30% by weight, preferably 0.5-20% by weight in the solid formulation of agrochemicals .

Examples of binders used for the latter purpose include both the above-mentioned solid binders and the following slightly volatile oily binders. In the present invention, such binders are dissolved in solvents such as water or volatile organic solvents. Then, the surface of the particle core can be coated with the agrochemical active ingredient by using the solution followed by removal of the solvent by evaporation, or it can be coated with the aid of a slightly volatile oily adjuvant or a liquefied binder. , leaving the binder in the agrochemical solid formulation without evaporating. The latter method of leaving the binder in the solid formulation of the agrochemical is advantageous because the drying step can be omitted.

When the solvent is evaporated after the application of the active ingredient, it is economical to use as little binder as possible. It is usually added in an amount of 0.01-20% by weight, preferably 0.1-10% by weight, more preferably 0.2-5% by weight. As a solvent for the binder, water is preferred.

When leaving the binder in the agrochemical solid formulation, any binder capable of uniformly coating the active ingredient of the agrochemical on the surface of the granule core may be used. An oily binder that has no side effects on the active ingredients of agrochemicals, such as neither affecting particle growth nor decomposing the active ingredients, is preferable. For example, a solvent having a high boiling point, low toxicity, low flammability and low viscosity, a specific gravity of less than 1, and not easily dissolving active ingredients of agrochemicals therein is preferable. Examples of such binders may include mineral oils such as low viscosity liquid paraffins, chlorinated paraffins, isoparaffins, motor oils, polybutenes and paraffinic, naphthenic or aromatic high boiling point solvents; vegetable oils such as coconut oil , soybean oil and rapeseed oil; animal oils, such as whale oil and sardine oil; silicone oil and its derivatives; plasticizers, for example, esters of monocarboxylic acids such as oleic acid or coconut fatty acid, dicarboxylic acids such as maleic acid , esters of fumaric acid, phthalic acid or adipic acid, and phosphate esters such as tributyl phosphate and triethyl phosphate; glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, Propylene glycol, butylene glycol, and hexylene glycol; lactones such as ε-caprolactone and γ-butyrolactone; N-alkylpyrrolidones; and various liquid surfactants; and mixtures thereof. Among them, binders that are relatively cheap, have no side effects on active ingredients, are stable, and have low volatility are preferred, and mineral oils such as liquid paraffin, motor oil, and polybutene, monocarboxylic acid esters, and dicarboxylic acid esters are more preferred. .

Although the amount of the binder remaining in the agrochemical solid formulation varies depending on the properties of the binder, the properties or physical characteristics of the active ingredients of the agrochemical or the properties or amounts of other additives, it is usually The amount in the formulation is 1-50% by weight, preferably 3-40% by weight, more preferably 5-35% by weight.

There is no particular limitation on the diluent used in the solid formulation of the agricultural chemical in the present invention, as long as it can be generally used as a carrier of the agricultural chemical. Examples may include minerals such as clay, calcium carbonate, diatomaceous earth, amorphous silica, and talc; and vegetable powders such as starch, wood flour, sawdust, coffee bean powder, Makko (Machilus thunbergii) based powder, fiber Vegetarian powder, microcrystalline cellulose, chaff powder, rice bran, wheat bran and coconut cake flour, among which amorphous silica, talc and wood flour are preferred.

Although the amount of the diluent varies depending on the nature or amount of other additives, it is generally 0.1-80% by weight, preferably 1-50% by weight, more preferably 2-40% by weight in the agrochemical solid formulation.

The solid formulation of the agricultural chemical of the present invention may contain a granulation improver in order to improve the granulation performance of the agricultural chemical granule. The granulation improver used in the present invention is not particularly limited as long as it is a generally used granulation improver such as a surfactant or a compound capable of imparting plasticity to the composition. Examples include nonionic surfactants such as polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters and polyoxyethylene aryl aryl ethers; anionic surfactants such as dialkyl sulfosuccinic acid Sodium salts and sodium salts of alkylbenzenesulfonic acids; mineral fine powders, such as bentonite; starch derivatives, such as dextrin and alpha-starch; natural gums, such as acacia; cellulose derivatives, such as carboxymethylcellulose and sodium salts of water-soluble synthetic polymers such as polyvinyl alcohol and polyacrylic acid, among which sodium salts of bentonite and carboxymethyl cellulose are preferred.

Although the amount of the granulation improver used in the present invention varies depending on the properties of the granulation improver, or the properties or amounts of other additives, it is usually 0.01-30% by weight, preferably 0.05-25% by weight in the solid formulation of agrochemicals. % by weight, more preferably 0.1-20% by weight.

The solid preparation of agricultural chemicals of the present invention may contain a solvent for balanced release of liquid agricultural chemical active ingredients or dissolution of low melting point agricultural chemical active ingredients. The solvent used for the above purpose preferably has a high boiling point, low toxicity and high flammability. In the case where the specific gravity of the active ingredient of the agrochemical is 1 or more, a solvent with a specific gravity of less than 1 and low viscosity can be selected in order to keep the emulsified particles in water for as long as possible and spread them widely in the paddy field. Examples may include high boiling alkanic, aromatic or naphthenic solvents; oleic, maleic, fumaric and fatty acids obtained from various animal and vegetable oils such as coconut oil, phthalic, adipic or phosphoric acids esters; vegetable oils such as coconut oil and rapeseed oil; and animal oils such as whale oil and sardine oil, among which liquid paraffin and low molecular weight polybutene are preferred.

The amount of the solvent used to dilute or dissolve the active ingredient of the agricultural chemical therein varies depending on the properties or physical characteristics of the active ingredient of the agricultural chemical. The amount of the solvent is preferably as small as possible, with the proviso that the storage stability or physical properties of the solid formulation of the agrochemical are not adversely affected. It is usually 0.1-50 parts, preferably 0.2-10 parts, relative to 1 part of the active ingredient of the agrochemical to be diluted or dissolved.

C _2-4 alkylene oxide adducts of C _4-10 alkyl alcohols can be used as solvents to dilute or dissolve active ingredients of agrochemicals therein.

The solid formulation of the agricultural chemical of the present invention may contain an emulsifier in order to emulsify the active ingredient of the agricultural chemical in water. Selection of such an emulsifier is similar to selection of an emulsifier for an emulsifiable concentrate, depending on the properties or physical characteristics of the agrochemical active ingredient or solvent. Emulsifiers capable of spontaneous emulsification are recommended, since solid formulations of agrochemicals in water are not manually stirred at the time of use. In addition, an emulsifier capable of fine emulsification is preferable.

The amount of the emulsifier used in the present invention is usually 0.01-10 parts, preferably 0.03-3 parts, relative to 1 part of the liquid to be emulsified, the liquid to be emulsified contains liquid agrochemical active ingredients or diluted with a solvent or dissolved in a solvent Active ingredients of agricultural chemicals.

If necessary, the solid formulation of the agricultural chemical of the present invention may contain a stabilizer in order to stabilize the active ingredient of the agricultural chemical in the formulation or to stabilize its physical properties. Examples of stabilizers may include pH adjusters, antioxidants, light stabilizers, volatilization inhibitors, solid acid activity inhibitors, colorants, and desiccants.

The agrochemical solid formulation of the present invention may contain abrasives, if necessary, in order to improve grindability or to prevent powder from sticking to equipment when dry-grinding active ingredients. Examples of abrasives include synthetic amorphous silica, talc and various particulate minerals, among which synthetic amorphous silica and talc are preferred.

When the active ingredient of the agrochemical is solid, the agrochemical solid formulation of the present invention can be prepared by grinding, if necessary, mixed with a water surface spreading agent, a crushing and dispersing agent, a wetting agent, a diluent, a stabilizer and an abrasive Grind together. And the resulting powder premix is applied to the core of the floating granules by means of a suitable binder. Alternatively, when the active ingredient of the agricultural chemical is in a liquid state, it can be prepared by absorbing the liquid into the cores of particles floating in water, or when the active ingredient of the agricultural chemical is in a solid state or even in a liquid state, by Or the liquid is dissolved in a suitable solvent, optionally adding suitable crushing and dispersing agents, wetting agents, emulsifiers, stabilizers or other auxiliary agents, and then absorbing the solution into the core of the floating particles.

The solid formulation of agricultural chemicals of the present invention can be obtained by the following method.

When the active ingredient of the agricultural chemical of the present invention is in a solid state, the active ingredient of the agricultural chemical having a large particle size can be allowed to settle at the position where the formulation is applied in the paddy field. Long-term local deposition of active ingredients of agricultural chemicals may cause troubles such as decreased potency or agricultural chemicals will damage the rice crop. The active ingredient of the agricultural chemical of the present invention must exhibit its efficacy by dissolving and diffusing into the water of the paddy field immediately after being applied to the paddy field. Even if the solubility in water is high, the active ingredients of solid agrochemicals must be ground finely to some extent. Active ingredients with only low water solubility require a finer grinding in particular. Grind with the aforementioned abrasives or other auxiliaries if necessary. The active ingredient of the solid preparation can then be ground by dry grinding with a hammer mill or a jet mill, or by wet grinding with a sand mill or an attritor.

Since the dry-ground agrochemical active ingredient is very fine and has a low apparent specific gravity, it is easy to separate from the floating agent or other additives, which tends to cause uneven dispersion of the agrochemical active ingredient in the agrochemical formulation. In this case, the method of continuously feeding the slurry containing the active ingredient of the wet-milled agrochemical together with the additive, kneading the mixture and granulating the mixture, as described later, is preferable, Because it hardly causes uneven dispersion of active ingredients of agricultural chemicals.

After wet milling, the active ingredients of agrochemicals are dried with a spray dryer, etc., and then pulverized; or absorbed into a suitable carrier with oil-absorbing capacity, such as synthetic amorphous silica, diatomaceous earth, calcium silicate or super oil-absorbing resin, It is then dried and pulverized if necessary. The powder thus obtained can be treated in a similar manner to dry-ground agrochemical active ingredients. In addition, the agricultural chemical granules of the present invention can be produced by wet granulation after kneading a wet grinding slurry containing the active ingredient of the agricultural chemical and a small amount of water for kneading and other solid auxiliary agents.

When the active ingredient of the agrochemical is liquid, dissolved or has a low melting point, it may be dissolved in a solvent or an emulsifier if necessary, and then absorbed into the surface floating carrier or the core of the granule. Alternatively, it can also be absorbed into a carrier with oil-absorbing properties together with other additives, such as synthetic amorphous silica, diatomaceous earth, calcium silicate, high oil-absorbing resin or high oil-absorbing dextrin, or in resin , chemical or another solid agrochemical active ingredient that can dissolve the agrochemical active ingredient to form a solid solution, followed by treatment in a manner similar to the above-mentioned solid agrochemical active ingredient.

The agrochemical active ingredient thus obtained is subjected to various processes such as mixing, grinding, kneading, granulation, drying, shaping, coating and/or absorption together with other additives, thereby preparing the agrochemical solid formulation of the present invention .

When the agrochemical solid formulation of the present invention is a powder, it can be prepared by mixing the active ingredient of the agrochemical with a water surface spreading agent and other additives, and if necessary, passing through an appropriate grinder such as a hammer mill or an air mill Grind preparation.

When the active ingredient of the agrochemical of the present invention is a granule, for example, it can be prepared by granulating a powdered raw material using a granulator (granulation method), and the active ingredient of the agrochemical can be granulated with the aid of an appropriate binder. Prepared by coating on the core of pre-prepared floating particles (coating method), it can also be prepared by dissolving the active ingredients of agricultural chemicals in a suitable solvent, and then absorbing the obtained solution into the core of pre-prepared floating particles ( absorption method).

In the present invention, when the agrochemical solid preparation is a granule prepared by a granulation method, if necessary, the active ingredient of the agrochemical can be mixed with other additives in advance to form a concentrated premix, and the obtained premix can be mixed with The other components are combined, then granulated, dried and sieved. Examples of the granulator may include a horizontal or box-type extrusion granulator, a mixing granulator, a rolling granulator, a fluidized bed granulator, and a spray dryer, among which an extrusion granulator is preferable. If the component contains expanded Shirasu or expanded perlite, application of high pressure may rupture their cavities, possibly reducing buoyancy. Applying high pressure also reduces their buoyancy if they contain cork. In this case, therefore, it is preferable to use a granulator without high pressure or shear.

When the solid formulation of the agricultural chemical of the present invention is a granule prepared by a coating method, it can be prepared by loading the core of the floating granule prepared in advance into the agitating mixer, and if necessary, wetting the granule with a liquid binder. After the surface of the granule, the concentrated premix of the active ingredient of the agricultural chemical is added and the resulting mixture is stirred and mixed, so that the active ingredient of the agricultural chemical is coated on the surface of the granule core. As the agitating mixer, a low-speed mixer that crushes fewer particles is preferable. Examples include Nauta mixers, screw mixers, tumble mixers, and V-shaped mixers, among which Nauta mixers and screw mixers are preferred. If necessary, spreaders, water flotation agents, additional water spreaders, breaking and dispersing agents, wetting agents, diluents, granulation improvers, solvents, emulsifiers or stabilizers may be added to the concentrated premix agent.

When the agrochemical solid preparation of the present invention is a granule prepared by an absorption method, it is usually possible to add the liquid or dissolved agrochemical active ingredient under stirring by loading the core of the floating granule prepared in advance into the above-mentioned agitating mixer. Or a concentrated premix thereof, whereby the agrochemical active ingredients are absorbed into the core of the granules. If necessary, water spreaders, solvents, emulsifiers or stabilizers can be added to the premix.

When the water surface floating particles are prepared by the coating method or the absorption method, the effect of the particles having the water surface spreading agent on the outermost layer is remarkable. This means that the water surface spreading agent is preferably added last, after coating or absorbing the cores of the granules with the active ingredients of the agrochemicals and other adjuvants. In the granulation, coating and absorption method, the necessary steps of granulation, coating and absorption can be carried out simultaneously or, if necessary, in at least two steps. For example, a part of the active ingredient of agricultural chemicals is completely granulated to form a nucleus of floating particles, and then the remaining part of the active ingredient of agricultural chemicals is coated thereon. The water spreader can be applied or absorbed onto the surface of the floating particles prepared by the granulation method. It is also possible to produce the preparations both by coating and by absorption.

The cores of the granules used in the coating or absorption process may be those prepared in a similar manner to the granulation process granules, or those prepared from some raw materials. Alternatively, a water surface flotation agent such as cork, expanded Shirasu, calcined vermiculite, expanded perlite, expanded pumice, or expanded synthetic resin adjusted to have an appropriate particle size may be used as the nucleus of the particles.

The particle size of the water-floating agricultural chemical granules of the present invention is usually 0.1-5 mm, preferably 0.3-3 mm, more preferably 0.5-2 mm. A particle diameter exceeding the above range makes it difficult to dry the granules when prepared by a granulation method. In addition, such particles are susceptible to wind on the surface of the water. A large particle size is therefore not preferred.

The water-floating agricultural chemical granules of the present invention obtained by granulating powdered raw materials may be decomposable or non-decomposable when applied to water.

There is no particular limitation on the shape of the particles of the surface-floating agricultural chemical, and they may be, for example, cylindrical, spherical or irregular.

From the viewpoints of easy handling, production and water surface buoyancy, the apparent specific gravity of the water surface floating agricultural chemical granules of the present invention is usually 0.15-0.50, preferably 0.20-0.45, more preferably 0.25-0.40.

The water surface floating agricultural chemical solid preparation of the present invention contains high concentration of active ingredients of the agricultural chemical, so it must be dispersed, dissolved and diffused rapidly in water after being spread on the water surface. When particles containing high concentrations of active ingredients of agrochemicals are deposited in soil, local accumulation of active ingredients of agrochemicals occurs at the deposition point due to insufficient dispersion, dissolution, and diffusion, and these particles may cause damage or decrease in efficacy of agrochemicals . If the agrochemical active ingredient is floating on the water surface for a long time without being released from the particles, there is a potential danger of wind drifting it.

The water-floating agrochemical solid formulation of the present invention can be uniformly applied to rice fields, similar to conventional granules. In addition, due to its excellent spreadability on the water surface, (1) it can be sprinkled into the paddy field from the field ridge after being covered with a water-soluble film (spreading application), (2) it can be scattered into the water of the paddy field along the field ridge (frame application) ), or (3) the nationalized formulation of water surface floating agrochemicals or its kit can be used at the water inlet of the paddy field when water is released, and it is dispersed in the water of the paddy field with irrigation water (water inlet application). Even in a field where there are some obstacles on the water surface or a tall rice crop grows, the active ingredient of the agrochemical can be uniformly dispersed in the water of the paddy field so as to produce sufficient biological effects without causing damage of the agrochemical.

A water soluble film for packaging for drop application is a film that is soluble or dispersible in water. Examples of materials for the water-soluble film may include polyvinyl alcohol and its derivatives, pullulan film, and polyethylene oxide and its derivatives, among which polyvinyl alcohol and its derivatives are preferable.

The non-spreadable water-soluble film wrapped on the water surface floating agricultural chemical solid preparation of the present invention will hinder the spreading of the water surface floating agricultural chemical solid preparation. In this case, since the water surface spreading agent is dissolved in water before the water surface floating agrochemical solid formulation is fully dispersed, thereby losing its spreading ability, the water surface spreadability of the packaged preparation is not as good as that applied without packaging. Water surface floatability on water surface Water surface spreadability of solid formulations of agrochemicals. In this case, the active ingredient of the agrochemical is confined to a narrow range near the point of application, which may lead to adverse results. The water-soluble film is therefore preferably spreadable with a water-soluble coating.

A spreadable water-soluble coating is a film or sheet that itself is easily dispersed or dissolved in water, and has the ability to spread a water-floatable solid formulation of agrochemicals onto the water surface. Examples may include various films and sheets made of polyvinyl alcohol or derivatives thereof (the film or sheet will hereinafter be abbreviated as "PVA film").

The PVA film is obtained by forming a layer of film or sheet from polyvinyl alcohol with a polymerization degree of 500-2000 and a saponification rate of 80-98% together with a small amount of plasticizer and stabilizer. It includes films containing copolymers, or films or sheets containing small amounts of carboxylic or sulfonic acids in the polymer.

Water-soluble films must have high mechanical strength and low-temperature resistance and be water-soluble. As a raw material, it is not preferable to use polyvinyl alcohol having an excessively high degree of polymerization or saponification rate because the resulting film is not easily soluble in cold water. Although the thickness of the water-soluble film varies depending on film strength or dissolution time, it is usually 20-80 µm, preferably 30-50 µm.

The water-soluble film can be edge-sealed with starch at the end, but the edge-sealed with starch will have problems in processability, and in addition, the part of the edge-sealed with starch sometimes becomes difficult to dissolve in water. Water-soluble films that can be heat-sealed are therefore preferred.

The weight of the medicine package used for sprinkle application in paddy field is usually 10-200g per package, preferably 20-100g, more preferably 25-60g. Even children, women or the elderly can easily drop a bale of this weight to a target point that is 15m or less from where they are standing. Dropping sachets heavier than the above-mentioned weights becomes a burden for them, making it difficult for them to deal with large paddy fields. On the other hand, a charge lighter than the above range is affected by the wind, making it difficult to scatter it to the target point.

Because the water surface floating agrochemical solid preparation of the present invention spreads widely on the water surface, it does not need to be cast and sprinkled very far in a rice field of a conventional size, and it is sufficient to sprinkle it on the water surface 2-3m away from the field ridge.

Using too many packages requires too much labor for casting, which is undesirable to save labor. In addition, it is not cost-effective. On the other hand, if the amount of the drug package is too small, there will be a potential danger that the solid formulation of the floating agricultural chemical on the water surface will not be sufficiently dispersed. The number of medicine packs necessary for the paddy field application is usually 1-30 packs, preferably 2-20 packs, per 10-acre paddy field.

The drug pack used in paddy field sprinkle application is packaged in a bag, box or bottle made of paper, resin, paper or resin laminated with aluminum foil, or paper or resin deposited with silica, metal or wood.

When the solid formulation of the water surface floating agricultural chemical of the present invention is used for frame application or water inlet application, the drug pack can also be packaged in a similar manner as above.

From the standpoint of physical properties, the water-floating agrochemical solid formulation of the present invention has stability against moisture absorption even over time. Therefore, compared with formulations containing foaming agents, there is no need to consider the hygroscopicity of the formulation, but the water-soluble film breaks when it comes into contact with water, thus requiring the use of waterproof packaging.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention is described in further detail by way of Examples, Comparative Examples and Experimental Examples. However, it should be borne in mind that the invention is not limited to or by them. All "parts" specifications are by weight.

(Example 1-18)

Spreadable floating particles on the water surface

A mixture of 24 parts of pyroquinone commercial product, 3 parts of talc (Japanese Pharmacopoeia) and 1 part of "Carplex#80" (synthetic amorphous silica; product of Shionogi Co., Ltd.) was used in "SAMPLE-MILL" (hammer mill ; Fuji Paudal Co., Ltd. manufacture) grinding, thus obtaining the pyroquinone premix. The water surface spreading agent shown in Table 1 and "Carplex #80" were mixed separately in a ratio of 1:1, followed by grinding with a SAMPLE-MILL, thereby obtaining a premix containing 50% of the water surface spreading agent.

35 parts of "Hilcon No.S-1" (calcined vermiculite, grade 3-0.5mm; product of Hiruishi Chemical Industry) was added to a screw mixer, and 33 parts of "Super oil C" (natural liquid paraffin; product of Nippon Oil Company, Ltd.) and wet the particle surface with it. Then, add 28 parts of the premixed material of pyroquinone and mix it, and use it to coat the surface of the granule, then add and mix 4 parts by weight of the premixed material of 50% water surface spreading agent, premix with this spreading agent The material was coated on the surface of the granules, thereby obtaining floating granules containing 24% pyroquiquinone spreadable on the water surface.

In Table 1, Et, 2-Et-C ₆ H ₁₃ , Iso-C ₉ H ₁₉ , EO, PO and -(EO) ₃ -(PO) ₅ -(EO) ₂ - represent ethyl, 2-ethyl ylhexyl, isononyl, groups represented by the formula -CH ₂ -CH ₂ -O-, groups represented by the formula -CH ₂ -CH(CH ₃ )-O-, and 3 moles of ethylene oxide, 5 Moles of propylene oxide and 2 moles of ethylene oxide were added separately to the groups in the order mentioned. In the column listing derivatives, the symbol "-" means that the water surface spreading agent is compound (I), the meaning of the term "ether" is that the surface spreading agent is an ether derivative of compound (I), and the term " Phosphate ester ammonium salt" means that the water surface spreading agent is the ammonium salt of the phosphate ester of compound (I).

Table 1 Water Surface Spreading Agent R ¹ O-(AO) _m -(BO) _n -H (1) Example No. Water Surface Spreading Agent

R ¹ -(AO) _m -(BO) _n - derivative 1 C ₆ H ₁₃ -(EO) ₂ - -2 2-Et-C ₆ H ₁₃ -(EO) ₂ - -3 2-Et-C ₆ H ₁₃ -(EO) ₂ - 2-Ethylhexyl ether 4 2-Et-C ₆ H ₁₃ -(EO) ₅ - -5 2-Et-C ₆ H ₁₃ -(EO) ₃ - Diethyl ether 6 2-Et -C ₆ H ₁₃ -(EO) ₃ -(PO) ₅ -(EO) ₂ - -7 2-Et-C ₆ H ₁₃ -(EO) ₁₅ -(PO) ₃ - -8 iso-C ₉ H ₁₉ -(EO) ₂ -(PO) _7.2 -(EO) _5.3 - -9 2-Et-C ₆ H ₁₃ -(EO) ₂ - Ammonium Phosphate 10 2-Et-C ₆ H ₁₃ -(EO) ₂ - Phosphate Sodium Salt 11 2-Et-C ₆ H ₁₃ -(EO) ₂ - Phosphate Triethanolamine Salt 12 2-Et-C ₆ H ₁₃ -(EO) ₂ - Phosphate 13 2-Et-C ₆ H ₁₃ -(EO) ₂ - Phosphate Calcium Salt 14 2-Et-C ₆ H ₁₃ -(EO) ₂ - Sulfate Ammonium Salt 15 2-Et-C ₆ H ₁₃ -(EO) ₂ - Sulfate Potassium Salt 16 C ₄ H ₉ -(EO) ₂ -(PO) ₁ -Phosphate isopropylamine salt 17 C ₆ H ₁₃ -(EO) ₂ -(PO) ₁ -Phosphate triethanolamine salt 18 Iso-C ₉ H ₁₉ -( EO) ₂ -(PO) _7.2 -(EO) _5.3 - Sodium Phosphate

In embodiment 1, 2, 9, 10 or 12, use commercially available product (Nippon Nyukazai Co., Ltd.) as water surface spreading agent. The water surface spreading agents in other examples can be prepared, for example, by methods similar to those described in "Novel Surfactants" (written by Hiroshi Horiguchi, published by Sankyo Publishing Co. in 1975).

(Example 19)

Floating granules spreadable on water surfaces and sachets in paddy fields

In a "Nauta mixer" (manufactured by Hosokawamicron Corporation), 42 parts of expanded Shirasu (0.3-1.0 mm) were charged, and 25 parts of "Super Oil C" were added while mixing to wet the surface of the pellets. Then, add and mix 28 parts of the roquiquinone premix as described in Examples 1-18, use it to coat the surface of the granules, then add and mix 5 parts of the 50% water surface spread as described in Example 8 A premix of the agent was used to coat the surface of the granules, thereby obtaining floating granules containing 24% of roquiquinone spreadable on the water surface.

The floating particles thus obtained were packaged into 50 g packs with "Hi-Selon C200" (PVA film thickness 40 μm, product of Nippon Gohsei Film Co., Ltd.), thereby obtaining a spray pack for paddy fields.

(Example 20)

Floating powder formulations that can be spread on water surfaces and sachets in paddy fields

Charge 47.5 parts of expanded Shirasu (0.03-0.15 mm) and 22.5 parts of polyvinyl chloride powder in a Ldige mixer (manufactured by Matsuzaka Co., Ltd), and then add 25 parts of pretilachlor industrial product and 5 parts of Example The mixed solution of the water surface spreading agent described in 17 was mixed to obtain a floating powder preparation containing 25% pretilachlor and spreadable on the water surface.

The thus-obtained powder formulation was packaged in "Hi-Selon 200" into a 30-g pack, whereby a spray pack for paddy fields was obtained.

(Example 21)

Floating granule formulations spreadable on water surfaces and sachets in paddy fields

In 36.15 parts of water, 63 parts of pyrazolate commercial product and 0.85 part of "Newcol 291PG" (sodium diethylhexyl sulfosuccinate; product of Nippon Nyukazai Co., Ltd.) were suspended. The resulting suspension was ground with "DYNO-MILL" (bead mill; manufactured by Shinmaru Enterprises Corp.) to yield a finely ground product containing 63% of pyrazole ester. 2.5 parts of "Toxanone GR31A" (acrylic type dispersant; product of Sanyo Chemical Industries, Ltd.) was added to 57.14 parts of the finely ground product, and mixed to obtain a pyrazolide slurry. In a kneader, 14 parts of cork (0.2-0.5 mm grade), 7 parts of bentonite (trademark Hodaka; product of Hojun Kogyo Co., Ltd.), 7 parts of "Cellogen 7A" (carboxymethyl cellulose Sodium salt; a product of Dai-ichi Kogyo Seiyaku Co., Ltd.) and 14.52 parts of wood flour (a product of Neoraito Kosan Co., Ltd.). After diluting with a small amount of water, 58.64 parts of the above-mentioned pyrazolide slurry was added to the mixture and kneaded, and then extruded through the A 1.5mm sieve. The wet granules thus obtained were dried at 100° C. by a fluidized bed dryer, and sieved through a sieve of 4.76 to 1.20 mm, whereby concentrated pyrazolide granules were obtained. Charge 80 parts of the resulting concentrated granules in a Nauta mixer, then add a mixed solution of 15 parts of butachlor commercial products and 5 parts of the water surface spreading agent described in Example 18 and mix to absorb them into the granules , thus obtaining a water-spreadable floating granule formulation containing 36% pyrazolid and 15% butachlor.

The thus-obtained floating granule preparation was packaged in "Hi-Selon C200" into 50-g packs, whereby a spray pack for paddy fields was obtained.

(comparative examples 1-4)

floating particles on water

Each of Comparative Examples 1-4 obtained floating particles spreadable on the water surface in a similar manner to Example 1, except that the water surface spreading agent of Table 2 was used instead of the water surface spreading agent of Example 1. Table 2 Water Surface Spreading Agent Comparative Example No. Water Surface Spreading Agent

1 "Surfinol 104"

(surfactant for alkynes; from Nisshin Chemical Industry

Co., Ltd)

2 "Silguard 309"

(Silicone-type surfactant; from Dow Corning Toray

Silicone Co., Ltd.)

3 "UNIDYNE DS101"

(Fluorine-type surfactant; manufactured by Daikin Industries, Ltd.)

4 "Newcol 291PG"

          (Sodium diethylhexyl sulfosuccinate; obtained from

Nippon Nyukazai Co., Ltd.) (comparative example 5)

Floating powder formulations spreadable on water and sachets in paddy fields

Except that "Newcol 291PG" was used instead of the water surface spreader described in Example 20, a floatable powder formulation spreadable on the water surface and a spray bag in a paddy field could be prepared in a similar manner to those described in Example 20.

(Test Example 1)

Spreadability of active ingredients of agrochemicals on water with obstacles

Pour water into a 25.5 cm wide and 32 cm long plastic container to a depth of 2 cm. After the water surface becomes calm, spread 0.25g of wood flour evenly on the water surface so that it covers the entire surface. In the center of the water surface, 0.1 g each of the floating particles spreadable on the water surface obtained in Examples 1-18 and the floating particles spreadable on the water surface obtained in Comparative Examples 1-4 were applied. Take pictures of the state of the water surface after applying it for one minute, measure the number of cracks produced by the progress of the particles between the wood powder on the water surface, and the ratio of the unobstructed water surface area (5% as a unit) where the wood powder is pushed away, and thus determine the Spreadability on water with obstacles. The results are shown in Table 3.

Table 3 Spreadability test granules of active ingredients of agrochemicals when there are obstacles on the water surface Spreadability

Number of cracks formed on water surface Unobstructed water surface where wood flour was pushed away

Example ratio ( %) Example 1 4 50 Example 4 55 Example 4 55 Example 4 4 50 Examples 5 55 Example 6 5 55 Example 8 6 75 Example 9 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 70 Example 10 5 65 Example 11 4 60 Example 12 7 75 Example 13 4 65 Examples 15 5 60 Examples 16 60 Examples 17 4 60 Examples 18 5 75 Comparison Example 1 1 2 25 Comparative Example 2 3 3 30 Comparative Example 3 1 10 Comparative Example 4 2 1 5

Compared with the floating particles of Comparative Example, the floating particles of the present invention showed excellent spreadability even when there were obstacles on the water surface.

(Test Example 2)

Distribution of active ingredients of agrochemicals in the presence of obstacles on the water surface

Make a 90cm wide, 7m long and 10cm deep shelf out of styrofoam and place it horizontally in a wind-free space. A black vinyl sheet was glued on the inner surface of the rack and filled with water to a depth of 5 cm. Sprinkle 20g of wood powder evenly on the water surface through a sieve with an opening diameter of 0.5mm. After the water surface was calm, 3.15 g each of the floating particles spreadable on the water surface obtained in Example 19 and the floating particles spreadable on the water surface of Comparative Example 2 were applied from a position 10 cm from the edge of the shelf. Five minutes after application, measure the distance from the point of application to the point at the front where the wood flour is pushed away by the particle. In addition, after 3, 7 and 24 hours, as shown in Fig. 1, the concentration of each agrochemical active ingredient in the water at the center b and 2.5 cm deep at a and c at both ends of 50 cm from the longitudinal center line was measured. The distribution of active ingredients of agrochemicals is thus studied. The results are shown in Table 4.

Table 4: Distribution of active ingredients of agrochemicals with obstacles on the water surface

Concentration of pyroquinone in water from application point to wood agrochemicals (ppm)

The test particles of the concentration of the active ingredient at the point where the powder is pushed away The distance of the measurement position After 3 hours of treatment

7 24

Hours Example 19 Hours 5.8 A A 3.62 3.02 2.80

B 3.07 2.81 2.53

A 0.05 0.65 1.58 Comparative Example 2.9 A A 8.49 6.35 5.8

2 B 0.04 1.31 1.83

C 0 0 0 0.04

When there are obstacles on the water surface, the effective distribution speed of the agricultural chemicals in the water surface floating particles of the present invention is faster than that of the water surface floating particles of the comparative example, indicating that the agricultural chemicals in the water surface floating particles of the former are more effective in water. The uniformity of active ingredients of chemicals is superior.

(Test Example 3)

Distribution and herbicidal effect of active ingredients of agrochemicals in the presence of obstacles on the water surface

Rice seedlings were transplanted into paddy fields divided into 10 m x 10 m. After seven days, the water depth was adjusted to 5 cm, and 100 g of wood powder was evenly sprinkled in each field with "Mizet Duster" (a small duster manufactured by Arimitsu Industry Co. Ltd.), and the water surface was covered with wood powder. The sacks in the paddy fields obtained in Example 20 and Comparative Example 5 were sprinkled into the center of each field, and the way the particles were dispersed was observed. Ten minutes after application, when the dispersal of the granules has reached its limit, the unobstructed water surface where the wood flour is pushed away by the granules is measured. In addition, 24 hours after the application, as shown in Figure 2, water was taken from the point 3 of the paddy field and points 1, 2, 4, and 5 at a distance of 1 m from the four corners, and the concentration of the active ingredient of the agrochemical in the water was analyzed and determined . The results are shown in Table 6.

table 5

Distribution test of the active ingredient of the agrochemical in the field when there is an obstacle on the water surface. The active ingredient of the agrochemical on the unobstructed water surface. After 24 hours, the shape and area (m ² ) of the spraying bag for pretilachlor, the measurement position of the concentration Concentration (ppm) Example 20 7 Starfish, 1 (windward) 1.03

20 2 1.45

3(center) 2.80

...

                                                                                

                                                                                                                                                           

3 (center) 6.23

4 0.72

                                                                                                                  ,

After 40 days of treatment with the drug pack, the herbicidal effect against Echinochloa crusgalli was studied. Echinochloa crusgalli had been pre-sown at points 1-5 when transplanting rice weeds. Treated with the kit of Example 20, Echinochloa crusgalli was not found anywhere in the test area. On the contrary, in the test area treated with the drug pack of Comparative Example 5, a small amount of weeds remained at points 1 and 4 facing the wind during the treatment.

As described above, the active ingredient of the agrochemical in the spraying kit of Example 20 spread well on the water surface where the water surface was obstructed. One day after application, it spread almost evenly over the entire paddy field, and showed excellent herbicidal action. On the contrary, even after one day of application, the concentration of the agrochemical active ingredient of the spraying kit obtained in Comparative Example 5 did not become uniform, and the herbicidal effect was inferior to those of the kit of Example 20 in addition.

(Test Example 4)

Herbicidal effect test in field with algae

Rice seedlings are planted in a rice field with an area of 30 acres. Ten days after planting, it was confirmed that algae appeared in about one-third of the area of the paddy field, and 1500 g of the spreadable floating particles on the water surface obtained in Example 21 were applied, respectively, by the water inlet application method (a method of applying particles by mixing the particles with irrigation water) The method of applying agrochemicals by injecting them together from the water inlet of the paddy field), the frame application method (when walking along the ridges on both sides of the paddy field, spread two 750g granules at a distance of about 50cm from the two long ridges to apply Agrochemical method) and the method of casting and applying the 30 bags of 50g obtained in Example 21 (when walking along the ridge on both sides of the paddy field, sprinkle each 15 bags of medicine to a distance of two long Field ridge about 7m, to apply the method of agricultural chemicals) application. After 40 days of application, observe and study the herbicidal effect on three lines, two lines each 3m away from the long ridge and the center line. Almost no weeds remained in each test plot, which indicated that the herbicidal effect was significantly high.

[industrial applicability]

The agrochemical solid formulation of the present invention has excellent spreadability on the water surface, even if the water surface of the paddy field is covered with algae or floating weeds; and its active ingredients of the agrochemical are evenly spread in the paddy field. Even when agrochemicals are used to treat paddy fields with rice seedlings or paddy fields with the aforementioned obstacles, the effects of the active ingredients of the agrochemicals can be fully exhibited. So farmers can use these solid formulations of agrochemicals without any scruples. In addition, the spraying drug pack of the present invention used for paddy field distribution can be used under the above-mentioned unfavorable conditions, and thus greatly contributes to labor saving in paddy field agriculture.

[Brief description of the drawings]

[Fig. 1] Illustrates the measurement positions of the active ingredients of agrochemicals in Test 2.

[Fig. 2] Illustrates the measurement position of the active ingredient of the agrochemical in Test 3.

[ Fig. 3 ] An illustration of the agrochemical application method in Test 4.

Claims (16)

1. A water surface floating agricultural chemical solid preparation, which contains one or more water surface spreading agents selected from C _2-4 alkylene oxide adducts and derivatives thereof of C _4-10 alkyl alcohols, and active ingredients of agrochemicals. 2. The water surface floating agrochemical solid formulation of claim 1, wherein the water surface spreading agent is one or more water surface spreading agent compounds selected from compounds represented by the following formula (1): R ¹ O-(AO) _m -(BO) _n -H (1)[Wherein, R ¹ represents C _4-10 alkyl, A represents the group represented by the formula: -CH ₂ CH ₂ -, B represents the formula: -CH ₂ CH(CH ₃ )-The group shown, m represents 0-30 and n represents 0-30, provided that m and n do not represent 0 at the same time, and when n is 0, m is 2 or greater number, or when neither m nor n represent 0, the mAO and nBO moieties are attached to each other in any order], the phosphate ester of the compound, the sulfate ester of the compound, the salts of said ester and the C _1-10 of the compound Alkyl ether. 3. The water surface floating agricultural chemical solid formulation of claim 2, wherein R ¹ represents C _6-10 alkyl. 4. The water-floatable agricultural chemical solid formulation according to claim 2 or 3, wherein m represents 0-10, and n represents 0-10. 5. The water surface floating agricultural chemical solid formulation of claim 2, wherein R ¹ represents ethylhexyl or isononyl, m represents 0-10, and n represents 0-10, the phosphoric acid ester of the compound, or the phosphoric acid ester ammonium, sodium or potassium salts. 6. The water surface floating agricultural chemical solid formulation of claim 2, wherein R ¹ represents ethylhexyl or isononyl, m represents 2-8, and n represents 0-8, the phosphoric acid ester of the compound or the phosphoric acid ester sodium salt. 7. The water surface floating agricultural chemical solid preparation according to any one of claims 1 to 6, which further contains a water surface floating agent. 8. The water surface floating agricultural chemical solid preparation according to claim 7, wherein the water surface floating agent is expanded Shirasu, expanded perlite, expanded pumice, calcined vermiculite, cork, wood powder, expanded synthetic resin, synthetic resin powder or plastic foam . 9. The water-floatable agricultural chemical solid preparation according to any one of claims 1-8, wherein the diameter of the particles is 0.1-5 mm. 10. A drug bag for paddy fields, which is prepared by packaging the water-floatable agricultural chemical solid preparation according to any one of claims 1-9 with a water-soluble film. 11. The drug bag for paddy fields according to claim 10, wherein the water-soluble film is a film or sheet made of polyvinyl alcohol or a derivative thereof. 12. The drug bag for paddy fields according to claim 10 or 11, wherein the weight of the drug bag is 10-200 g per bag. 13. A method of controlling harmful organisms present in a paddy field, which comprises spreading 1 to 30 packages of the spraying kit according to any one of claims 10 to 12 in a paddy field having an area of 10 acres. 14. A method of controlling harmful organisms appearing in a paddy field, which comprises dispersing the solid preparation of water-surface-floating agrochemicals according to any one of claims 1 to 9 into the water of the paddy field along the ridge of the paddy field. 15. A method of controlling harmful organisms appearing in a paddy field, comprising using the water surface floating agrochemical solid formulation of any one of claims 1-9 for injecting water into a water inlet of the paddy field, and combining the formulation with Irrigation water is distributed into the rice fields together. 16. A method of controlling harmful organisms appearing in a paddy field, which comprises using the spraying kit according to any one of claims 10 to 12 for injecting water into the inlet of the paddy field, and combining the effective ingredients of the agricultural chemicals with the irrigation The water is scattered together in the water of the rice field.

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