WO2000060941A1

WO2000060941A1 - Floating solid pesticide preparations

Info

Publication number: WO2000060941A1
Application number: PCT/JP2000/002214
Authority: WO
Inventors: Kinji Tanizawa; Hiroshi Sabi; Masakazu Tomioka
Original assignee: Sankyo Company, Limited
Priority date: 1999-04-09
Filing date: 2000-04-06
Publication date: 2000-10-19
Also published as: JP2000351701A; CN1353572A; KR100766754B1; KR20020009588A

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

Specification

Water-floating pesticide solid formulation

[Technical field] The present invention provides ^ ~. C ₂ to c ₄ alkylene O key side adduct and water-floating agrochemical solid formulation containing one or more kinds of water extender agent and agrochemical active ingredient made from the derivatives of alkyl alcohols, minute it water-soluble film TECHNICAL FIELD The present invention relates to a packaged agricultural chemical for throwing into a paddy field and a method for controlling pests generated in a paddy field using the same.

[Background Art] Conventionally, paddy field pesticides have been formulated in various dosage forms, for example, powders, wettable powders, emulsions and granules, and sprayed on the water surface or rice body for convenience of use. However, in recent years, for example, from the viewpoints of aging and part-time jobs of farmers and increase in the labor burden of women, labor saving of pesticide application has been required.

For this reason, flowable preparations that can be processed without using a machine, and so-called 1 kg granules, which increase the active ingredient content in preparations and reduce the amount of application as preparations, have been increasingly used. However, the flowable agent has problems such as spraying to the sprayer at the time of treatment and empty bottle treatment depending on the wind direction, etc.In addition, 1 kg granular IJ requires, for example, a spraying device. And the disadvantages of uniform spraying.

Furthermore, recently, a solid agricultural chemical formulation is packaged in a water-soluble film, and this package can be processed simply by throwing from a ridge without entering a paddy field (that is, paddy field throwing). Pesticide formulation) has been proposed (Japanese Patent Laid-Open Publication No. 3-173802) and commercialized, and these are also called jumbo preparations or pack preparations.

Such preparations for throwing into paddy fields include, for example, (1) a product in which a large effervescent tablet is thrown into a paddy field as it is (Japanese Patent Laid-Open No. 6-170503); A package that is thrown into a paddy field (Japanese Patent Laid-Open No. 5-33910), ③ A water-soluble carrier such as potassium chloride is mixed with a water-soluble film-forming polymer. Both of these granules contain the pesticidal active ingredient, packaged in a water-soluble film, and thrown into a paddy field (Japanese Patent Application Laid-Open No. 5-72807). The prepared pesticide solid preparation is packaged in a water-soluble film, which is thrown into a paddy field (Japanese Patent Laid-Open No. 6-33643), and ⑤ water-spreading oil A container packed in a container and thrown into a paddy field (Japanese Patent Application Laid-Open No. 5-339103) is known.

Since these pesticide preparations for throwing into paddy fields have a high content of pesticidal active ingredients in the preparation and are applied topically, unless the active ingredients diffuse quickly from the point where they are thrown, harmful effects due to unevenness of the pesticide active ingredients are caused. In addition, in some cases, residual pesticide active ingredients may affect subsequent crops.

On the other hand, solid pesticide preparations that are prepared so as to float on the water surface for the purpose of diffusion of the pesticidal active ingredient include, for example, (1) those that are suspended using a water-suspendable carrier (Japanese Patent Publication No. 48-15). No. 613, Japanese Patent Publication No. 417-240), (2) Pumice or hillite having a specific water absorption capacity as a carrier (Japanese Patent Publication No. 44-860) ), (3) a volatile insecticidal compound granules using (Kokoku 4 9 - 1 1 4 2 1 No.), (4) and Kabame preparative pesticides active ingredient, the distribution coefficient for water 1 0 ² or more An organic compound held on a solid carrier (Japanese Unexamined Patent Publication No. 2-174702); and (5) a fungicide, a herbicide or a plant growth regulator, an active ingredient, and a solid A composition comprising a carrier and an oil (JP-A-3-193705 ′) has been disclosed.

However, when these pesticide solid preparations are treated under conditions where the rice is small and the surface of the water is free of obstacles such as weeds, algae and oil films, the particles are spread widely on the water surface, aided by the power of the wind. Therefore, the so-called frame spraying, which is sprayed from the ridge without entering the paddy field, also exhibits a high effect.However, after the rice grows large and the power of the wind cannot be used, obstacles such as weeds, algae, and oil slicks on the water surface When treated under certain conditions, the particles are unlikely to spread on their own and may not be able to exert sufficient biological effects, or may cause phytotoxicity due to the localization of the active ingredient. In such a case, as in the case of conventional granules, it is necessary to enter the paddy and spray it, which is not preferable in terms of reducing labor.

In order to solve these drawbacks, acetylene-based surfactants were used as a water surface spreader, and further attempts were made to package them in a water-soluble film with water surface spreadability. Attempts have been made to use silicon-based or fluorine-based surfactants or dialkylsulfosuccinates (Japanese Patent Application Laid-Open Nos. Hei 6-33640, Hei 8-99982, and Japanese Patent Publications). No. 2,676,733). However, even with these technologies, sufficient spreading may not be observed under the conditions where there are obstacles on the water surface as described above or under the treatment after the rice grows.

[Disclosure of the Invention]

The present inventors have a water spreadability of excellent water-floating agrochemical solid formulation results of銳意_{_{studied, C 4 ~ C 1 ()}} C 2 ~ C 4 alkylene O wherein de adducts of alkyl alcohols and derivatives thereof Water-floating pesticide solid preparations containing one or more water-spreading agents consisting of: The present inventors have found that the present invention exhibits expandability and completed the present invention.

The invention relates to C ₄ -C ₁ . C ₂ -C ₄ alkylene O key side adduct and water-floating agrochemical solid formulation containing one or more kinds of water extender agent and agrochemical active ingredient made from the derivatives of alkyl alcohols, minute it water-soluble film Provided are a packaged agricultural chemical for paddy field throwing and a method for controlling pests generated in a paddy field using the same.

In the present invention, "^-. Alkyl alcohol" is a straight-chain or branched-chain alcohol having 4 to 10 carbon atoms, such as butanol, pentanol, hexanol, heptanol, octanol, nonanol, It may be isononanol, decanol or ethylhexanol, preferably a linear or branched alcohol having 6 to 10 carbon atoms, more preferably octanol, ethylhexanol or isononanol, Even more preferably, it is ethylhexanol or isononanol.

In the present invention, the `` C ₂ -alkylene oxide '' is a linear or branched alkylene oxide having 2 to 4 carbon atoms, for example, ethylene oxide, propylene oxide or butylene oxide. Preferably, it is ethylene oxide or propylene oxide. In the present invention, the “C ₄ -Ci. C ₂ -C ₄ alkylene oxide adduct of alkyl alcohol” refers to the above-mentioned “^-. Alkyl alcohol” with the above-mentioned “C ₂ -C ₄ alkylene oxide” added to the hydroxyl group. However, when a plurality of alkylene oxides are added, the order of addition is arbitrary.

RC Ci of the present invention. The “C ₂ -C ₄ alkylene oxide adduct of alkyl alcohol” is preferably represented by the following general formula (I)

R'O- (AO) _m- (BO) _n -H (I)

[Where R ¹ is ^ ~. A represents an alkyl group; A represents a group represented by the formula _CH ₂ — CH ₂ _; B represents a group represented by the formula: —CH ₂ — CH (CH ₃ ); m represents 0 Represents 30 to 30; n represents 0 to 30; however, m and n are not simultaneously 0, and when n is 0, m is 2 or more, and both m and n are not 0 At this time, the order in which the m AO groups and the n BO groups are bonded is arbitrary. ]

It is a compound represented by these.

In the above formula, “m” and “n” represent the number of ethylene oxide and propylene oxide added to one compound (I), respectively, and the number of ethylene added to a plurality of compounds (I) It is also possible to represent the average of the numbers of oxoxide and propylene oxide.

"~. Derivatives of C ₂ -C ₄ alkylene O wherein de adducts of alkyl alcohol" in the present invention include, for example, the aforementioned "^ ~. C ₂ ~C ₄ 7 Ruki Ren O key side adducts of alkyl alcohol" A phosphoric acid ester, a phosphoric acid ester salt, a sulfuric acid ester, a sulfuric acid ester salt or It may be an alkyl ether, preferably a phosphoric acid ester or a salt thereof.

The “phosphate ester” in the present invention includes any of a monoester, a diester and a triester, and is preferably a mixture thereof.

In the present invention, the “salt” is not particularly limited as long as it is commonly used as a pesticide, and examples thereof include alkali metal salts such as sodium salt, potassium salt and lithium salt; ammonium salt, triethanolamine salt and potassium salt. An amine salt such as isopropylamine salt; or an alkaline earth metal salt such as calcium salt and barium salt, preferably an ammonium salt or an alkali metal salt, more preferably an ammonium salt. Salt, sodium salt or potassium salt.

In the present invention, “〇, to 〇 .. alkyl ether” refers to a compound having 1 carbon atom at the oxygen atom of the terminal hydroxyl group of the “C _{4 to} C .. alkyl alcohol C _{2 to} C ₄ alkylene oxide adduct”. To 1 oii in which a linear or branched alkyl group is bonded, for example, methyl ether, ethynoleatenole, propinoleatenole, isopropinoleatenole, butynooleatenole, pentinooleatenole, Hexinoleatenole, heptinoleatenole, octinole ethere, etinole hexinoleatenole, noninoleatenole, isononinoleate or decylether, preferably ethylethylhexyl or isonoelether. is there. In the present invention, the "adduct of -alkenyl alkoxide of -alkaryl alcohol" is more preferably the compound (I),

R ¹ is Ci. An alkyl group (more preferably an octyl, ethylhexyl or isononyl group, even more preferably an ethylhexyl or isononyl group), wherein A is represented by the formula —CH ₂ —CH ₂ — Group

A group represented by the formula: CH ₂ — CH (CH _{; i} ) —

m is 0 to 15 (more preferably 0 to 10), and n is 0 to 15 (more preferably 0 to 10), and m and n are simultaneously When n is not 0 and n is 0, m is 2 or more, and when both m and n are not 0, the order in which m A〇 groups and n BO groups are bonded is arbitrary. ,

The compound (la) represented by

Particularly preferably, in the compound (I), R ¹ is an ethylhexyl or isononyl group, m is 0 to 10, and n is 0 to 10. Yes, provided that m and n are not simultaneously 0, and when n is 0, m is 2 or more

(lb), a phosphate ester or an ammonium salt, a sodium salt or a potassium salt of the phosphate ester, and most preferably, in the compound (I), R ′ is an ethylhexyl or isononyl group. The compound (Ic) wherein m is 2 to 8 and n is 0 to 8 is prepared with its phosphate or its sodium salt.

As the water surface spreader of the present invention, a commercially available product can be used as it is, and even if it is not commercially available, for example, a new surfactant (Hiroku Horiguchi, Sankyo Shuppan, 1975) Issued) It can be manufactured according to the method described.

The amount of the water surface spreader used is usually from 0.1 to 50% by mass, preferably from 0.5 to 30% by mass, more preferably from 1 to 50% by mass in the solid agricultural chemical preparation. About 20% by mass.

The pesticidal active ingredient in the present invention is not particularly limited as long as it can be applied to the surface of water, and may be a liquid or a solid, and may be, for example, an insecticide, a fungicide, a herbicide, or a plant regulator.

The insecticides used are, for example, isoxathion, diazinon, disulfotone, propaphos, triconorephone, honoremothion, dimethoate, monochrome tophos, acephate, carbofuran, carbosulfan, thiocyclam, cynoletap, ventostap Systemic insecticides such as benflacab, beratocab, buprofezin, phenobucalp, metholcalp, propoxure, imidacloprid, ettembiram and acetamiprid; Synthetic pyrethroids that are effective against pests that live in water or near the surface of water, preferably imidacloprid, nittenbiram, acetamip Lido, cycloprothrin, etfenprox or sirafnolefen.

Fungicides used include, for example, probenazole, isoprothiolane, iprobenfos, tricyclazole, pyroquilon, carpropamide, olibulite, azoxystrobin and 7-fluoro-1,2,5,6-tetrahydro-4-tetrapyrrolate [3] . 2.1-i. J] Quimoty agents such as quinoline-141-one; flutranil, mepronil, thifluzamide, flametopyr and 2 _ (4-fluorophenyl) — 1— (1H—1, 2, 4- Triazol-1-yl) —3_trimethylsilylpropane-2-ol or the like; techopen phthalam; or benomyl, preferably probenazole, isoprothiolane, pyroquilon, carpropamide, Olivelite, azoxystrobin, 7-fluoro-1,2,5,6-tetrahydro-1 4H-pyro mouth [3.2. 1 — to j] quinolin-1 4-one, funoretranyl, thifluzamide, flametopyr, 2- (4-fluorophenyl) 1 1 (1H—1, 2, 4—triazono 1 1—inole) 1 3— Trimethylsilyl-propan-1-ol or techmouth phthalam. Herbicides to be used include, for example, pyrazolate, benzophenap, pyrazoxyphen, pyribticcanoleb, bromobutide, butamiphos, mefenacet, bensnoreff lon-methinolle, anilophos, butaclonole, plethyclanofen, thiovenclonomoleno, thiovenclonomoleno , Naproanilide, Oxaziazone, Oxaziazirgil, Bentazone, Molinate, Pirophos, Dimepirate, Esprocanoleb, Zicino pinore, Imazosnoreflon, Benfresate, Quinoclamine, Symmethylin, MCP A or sodium salt thereof Or esters such as 2,4-D or its sodium salt, potassium salt, etc., MCPB or Or its salts such as sodium salt, potassium salt, etc., kink mouth lac, virazosulfuronethyl, pentoxazone, turchlor, cuminoleron, sinosulfuron, simetrin, dimethamethrin, cyhalofop butyl, etobenzanide, cafuens Tronoré, Ethoxysnoreflon, Azimsnoreflon, Axinorenorfamuron, Indanophan, Pyriminobac methylone, Oxadiclomehon, 4- (2-chlorophenyl) 1-N-cyclohexyl _ 4,5-dihi Dro-N-ethyl-5-oxo-1H-tetrazole-1-carboxyamide (NBA061), [3- (2-chloro-14-methylsulfonylbenzoyl) -4-4-phenylthio] bicyclo [3. 2.1] oct-3-one-2-one (benzobicyclone, SB 500), methyl = N — [4— (Benzothiazole-1-ylmethoxy) -1-methylphenyl] capitarubate and methyl = N— [4— (Benzoxazole-12-ylmethoxy) -12-methylphenyl] captamate such as paddy field It can be a herbicide, preferably, pyrazolate, benzophenap, birazoxifen, pyribticanoleb, bromobutide, mefenacet, bensnoreflon-methyani, phos, butacrole, pretilaclonole, daimlone, oxadia Noreginole, Imazosnoleflon, Pyrazosnoleflon-Ietinore, Pentoxazone, Teninolecuronore, Dimetamethrin, Cyhalofopbutinole, Cahuenstronole, Ethoxysnoleflon, Azimsnoleflon, Indanophan, NBA061, Benzo Bicyclon, Mechinore N 1 [4— ( Benzothiazo-1-yl-2-ylmethoxy) -12-methylpheninole canolevamate or methyl N- [4- (benzoxazol-12-ylmethoxy) -12-methylphenyl] caprolumarate. The plant regulator used can be, for example, inabenfide, paclitaxel butrazole, diconazole or tripentenol, preferably inabenfide or paclobutrazole. The pesticidal solid preparation of the present invention includes, in addition to the water surface spreader and the pesticidal active ingredient, for example, a water surface floater, another water surface spreader, a disintegrating / dispersing agent, a wetting agent, a binder, a bulking agent, and a granulating agent. Other additives such as a performance improver, a solvent, an emulsifier, a stabilizer, and a grinding aid can be contained. The solid pesticide formulation of the present invention may further contain a water-floating agent to further improve the water-floating property. The water-floating agent may be any substance that allows the solid pesticide formulation to float on the surface of the water. For example, mineral substances such as effervescent shirasu, effervescent perlite, effervescent pumice and calcined vermiculite; Foamed synthetic resin such as styrofoam; synthetic resin powder such as polyvinyl chloride powder; plastic hollow body such as Matsumoto Mike Sufure-1 F30E; granular material of synthetic resin; or a mixture thereof. Foamed shirasu, foamed pearlite, foamed pumice, fired vermiculite, konolek, wood flour, foamed synthetic resin, synthetic resin powder or plastic hollow body.

The amount of the water-floating agent used depends on the type and formulation of the water-floating agent used, the size of the solid pesticide, etc.Agrochemical solid preparation It is sufficient if the amount is sufficient to float on the water surface. In the composition, the content is 0.01 to 90% by mass, and preferably 0.1 to 70% by mass. / ₀ , more preferably 0.5 to 60% by mass.

In the present invention, various surfactants can be contained as auxiliaries, and the surfactant used depends on the nature of the surfactant, other water surface spreaders, disintegrators, dispersants, wetting agents, binders, It can also act as a grain improver or emulsifier. Polymers and organic solvents can also be used for multiple purposes, depending on their properties.

The solid pesticide formulation of the present invention may further contain another water surface spreader in addition to the above-mentioned water surface spreader in order to further improve the spreadability on the water surface. Other water surface spreaders used are, for example, (co) polymers of carboxylic acids such as acrylic acid and maleic acid, and copolymers of carboxylic acids such as acrylic acid and maleic acid with styrene sulfonic acid and vinyl. Polycarboxylic acid type polysoaps such as polymer salts such as sodium salt, potassium salt and ammonium salt; sodium oleate potassium stearate Other anionic surfactants such as sodium dialkyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and perfluoroalkylcarboxylates; polyoxyethylene alkylaryls Other nonionic surfactants such as ethers, polyoxyethylene alkyl ethers having 11 or more carbon atoms, polyoxyethylene alkyl esters and anolequinoleestenole of sonolebitan; silicon-based nonionic surfactant; acetylene-based nonionic interface Surfactants and nonionic surfactants of the pluronic type; these nonionic surfactants are esters of phosphoric acid or sulfuric acid and, if necessary, neutralized with a suitable alkali; surfactants containing fluorine Surfactants; liquid paraffin, na Mineral oils such as ten-based and aromatic high-boiling solvents, low-viscosity polybutene and machine oils; silicone oils; various vegetable oils; resins such as rosin; camphor white oil; hippinene; camphor; And is preferably an acetylene-based nonionic surfactant or various mineral oils.

The amount of other water surface spreaders used depends on the type and amount of the water surface spreader, the type and amount of the pesticide active ingredient and the water surface floating agent, and the type and amount of other auxiliaries and the formulation. More usually, but usually 0.01 to 50 mass in solid agricultural chemicals. /. And preferably 0. To 40% by mass, more preferably 0.2 to 30% by mass.

The solid pesticidal formulation of the present invention can contain a disintegrating / dispersing agent for disintegrating the particles in water and suspending / dispersing the pesticidal active ingredient in water. In many cases, the disintegrant / dispersant used is an anionic surfactant. For example, lignin sulfonate, (alkyl) naphthalene sulfonate and its condensate, phenol sulfonate and its condensate, styrene sulfone Acid salt, salt of maleic acid and styrene sulfonic acid condensate, salt of carboxylic acid condensate such as acrylic acid and maleic acid, polyacrylic acid salt, salt of acrylic acid and maleic acid copolymer, anhydrous Maleic acid and methyl vinyl ether copolymer salt, alkyl benzene sulfonate, dialkyl sulfosuccinate, lauryl sulfate salt, polyoxyethylene alkyl aryl ether tersulfate, polyoxyethylene aryl aryl ether sulfate, Polyoxyethylene alkyl aryl ether Phosphate esters, polyoxyethylene aryl ether phosphates or their sulfates and phosphates May be an anionic surfactant such as a salt neutralized with a suitable cation, and is preferably a lignin sulfonate, a condensate of (anorekyl) naphthalene sulfonate, a condensate of phenol sulfonate, styrene sulfone Salts of condensates of acid salts, salts of condensates of maleic acid and styrene sulfonic acid, salts of carboxylic acid condensates such as acrylic acid and maleic acid, polyatalylic acid salts, salts of atarilic acid and maleic acid copolymer, maleic anhydride It is a salt of an acid and a methyl vinyl ether copolymer or a dialkyl sulfosuccinate. Many of the surfactants used in these disintegrating and dispersing agents are effective as wetting agents. Further, phosphates such as sodium phosphate and sodium hexametaphosphate; suitable nonionic, cationic and amphoteric surfactants; and starch, carboxymethyl cellulose, carboxymethylated starch and salts thereof, polyvinyl Those having a property of absorbing water and expanding, such as a bridge of pyrrolidone, microcrystalline cellulose and a superabsorbent resin, can also be used as a disintegrating / dispersing agent.

The amount of the disintegrant / dispersant / disintegrant / dispersant and wetting agent used is usually 0.01 to 30% by mass, preferably 0.03 to 20% by mass, in the pesticidal solid preparation. Mass ⁰ /. And more preferably 0.05 to 10%.

The solid pesticide formulation of the present invention contains a binder to impart hardness to the granules when granulating the powder raw material to prepare granules, or to coat the surface of the granule core with the pesticide active ingredient. can do.

The binder used for the former purpose is a water-soluble starch derivative such as dextrin and arsenic starch having relatively low molecular weight; polyvinylpyrrolidone, a salt of polyacrylic acid, a salt of carboxymethylcellulose; Water-soluble polymer substances such as polyvinyl alcohol, lignin sulfonic acid salt and gum arabic having a low content; or montmorillonite mineral powder such as bentonite.

The amount of the binder used for the former purpose varies depending on, for example, the composition of the formulation, the granulation method and the size of the granules, but is usually 0.1 to 30% by mass in the solid pesticide formulation. Is 0.5 to 20% by mass.

The binder used for the latter purpose may be the following non-volatile oily binder in addition to the solid binder described above. According to the present invention, the surface of the grain nucleus is coated with the pesticidal active ingredient by dissolving these binders in a solvent such as water or a volatile organic solvent. After that, the solvent may be evaporated, or it may be coated with an oily or liquefied binder that hardly volatilizes, and the binder may be left in the pesticide solid formulation without being evaporated. The method of leaving the binder in the solid pesticide formulation ^ is an advantageous method because the drying step can be omitted.

The amount of the binder used when the binder is evaporated after coating is preferably smaller in consideration of economy. Usually, the amount is 0.01 to 20% by mass in the solid pesticide formulation, Preferably, it is 0.1 to 10% by mass, more preferably 0.2 to 5% by mass. Water is suitable as the solvent for dissolving the binder.

The binder used when the binder is left in the pesticide solid preparation may be any as long as it can uniformly coat the surface of the grain core with the pesticide active ingredient. Preferred are oils which do not give water, for example, solvents having a high boiling point, low toxicity, low flammability and low viscosity, a specific gravity of less than 1 and a low solubility of the active agricultural chemicals. Such binders include, for example, mineral oils such as low viscosity liquid paraffin, chlorinated paraffin, isoparaffin, machine oil, polybutene, paraffinic, naphthenic and aromatic high boiling solvents; coconut oil, Vegetable oils such as soybean oil and rapeseed oil; animal oils such as whale oil and sardine oil; silicone oils and derivatives thereof; esters of monocarboxylic acids such as oleic acid and coconut oil fatty acids, maleic acid, fumaric acid, phthalate Plasticizers such as esters of dicarboxylic acids such as acid and adipic acid, and esters of phosphoric acid such as tributyl phosphate and triethyl phosphate; ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, butane Glycols such as diols and hexylene glycol; Lactones such as lactone and γ-butyrolactone; Ν-alkylpyrrolidone; various liquid surfactants; or mixtures thereof, preferably those which are relatively inexpensive and do not adversely affect the active ingredients And the binder itself is stable and has low volatility, and more preferably, liquid paraffin, mineral oil such as machine oil and polybutene, monocarboxylic acid ester or dicarboxylic acid ester.

The amount of the binder used when the binder is left in the pesticide solid formulation varies depending on the type of binder, the type and physical properties of the pesticide active ingredient, and the type and amount of other auxiliaries. In it, it is 1 to 50% by mass, preferably 3 to 40% by mass, and more preferably 5 to 35% by mass. The extender used in the solid pesticide formulation of the present invention is not particularly limited as long as it is generally used as a pesticide carrier, and examples thereof include clay, calcium carbonate, diatomaceous earth, amorphous silicon dioxide, and talc. Minerals; or plant powders such as starch, wood flour, oakakus, coffee bean powder, tub flour, cellulose powder, microcrystalline cellulose, rice husk powder, rice bran, bran and coconut powder; Or amorphous silicon dioxide, talc or wood flour.

The amount of the extender used varies depending on the type and amount of other auxiliaries, but is usually 0.1 to 80% by mass, preferably 1 to 50% by mass in the solid pesticide formulation. Yes, more preferably 2 to 40% by mass.

The solid pesticide formulation of the present invention can contain a granulation improver for improving the granulation property of the pesticide granule. The granulation improver used is not particularly limited as long as it imparts plasticity to a surfactant or a composition which is generally used as a granulation improver in pesticide granules, for example, polyoxyethylene alkyl. Nonionic surfactants such as aryl ethers, polyoxyethylene alkyl esters and polyoxyethylene arylaryl ethers; Anionic surfactants such as sodium salts of dialkyl sulfosuccinates and sodium salts of alkyl benzene sulfonic acids. Mineral fines such as bentonite; starch derivatives such as dextrin and a-starch; natural gums such as arabia gum; cellulose derivatives such as the sodium salt of carboxymethylcellulose; or polybutyl alcohol or polyacrylic acid. Like sodium salt It is a soluble synthetic polymer, preferably a Natoriumu salt of bentonite bets or local volume carboxymethyl cellulose.

The amount of the granulation enhancer to be used varies depending on the type of the granulation enhancer and the type and amount of other auxiliaries, but is usually 0.01 to 30% by mass in the solid agricultural chemical preparation. preferably, 0. 0 5 to 2 5% by weight Deari, more preferably a 0.1 to 2 0 mass ^_0/0. The solid pesticidal formulation of the present invention can contain a solvent for diluting the liquid pesticidal active ingredient or turning the low-melting pesticidal active ingredient into a liquid state. The solvent used for this purpose has a high boiling point and low toxicity and a high flash point.When the specific gravity of the pesticidal active ingredient is 1 or more, the emulsified particles are kept in water for as long as possible and diffused widely in paddy fields. In particular, a solvent having a specific gravity of less than 1 and a low viscosity is preferable, for example, a paraffin-based solvent, an aromatic solvent, and a solvent. High-boiling solvents based on phthalene; fatty acids obtained from various animals and plants such as oleic acid, maleic acid, fumaric acid and coconut oil; esters such as phthalic acid, adipic acid and diphosphoric acid; coconut oil and rapeseed oil Vegetable oil; or animal oil such as whale oil and sardine oil, preferably liquid paraffin or low molecular weight polybutene.

The amount of solvent used to dilute or dissolve the pesticidal active ingredient used depends on the type and physical properties of the pesticidal active ingredient, and should be as small as possible as long as it does not affect the stability over time or physical properties of the solid pesticide formulation. Usually, the amount is 0.2 to 50 parts, preferably 0.2 to 10 parts per part of the pesticidal active ingredient to be diluted or dissolved.

Also, C _{4 to} C,. Compounds obtained by adding a C ₂ -C ₄ alkylene oxide to an alkyl alcohol can also be used as a solvent for diluting or dissolving the pesticidal active ingredient.

The pesticidal solid preparation of the present invention can contain an emulsifier for emulsifying the pesticidal active ingredient in water, and such an emulsifier can be used in the same manner as the selection of the emulsifier for the emulsion. Unlike conventional emulsifiers, it does not agitate artificially when using solid agricultural chemicals, so it has good self-emulsifiability and fine emulsification as much as possible. .

The amount of the emulsifier to be used is usually 0.01 to 10 parts with respect to 1 part of the liquid to be emulsified consisting of the liquid pesticidal active ingredient or the pesticidal active ingredient diluted or dissolved in a solvent. There are 0.03 to 3 parts.

The solid pesticide formulation of the present invention can contain a stabilizer, if necessary, for stabilizing the pesticide active ingredient or stabilizing physical properties in the formulation. The stabilizers used can be, for example, pH regulators, antioxidants, light stabilizers, volatilization inhibitors, inhibitors of solid acid activity, pigments or desiccants.

The solid agricultural chemical preparation of the present invention can contain a grinding aid as necessary to improve the friability and prevent adhesion to equipment when the active ingredient is dry crushed. The grinding aid used can be, for example, amorphous synthetic silica, talc or various granular minerals, and is preferably amorphous synthetic silica or talc.

The solid pesticide preparation of the present invention, when the pesticidal active ingredient is a solid, is pulverized together with a water surface spreader, a disintegrating / dispersing agent, a wetting agent, a bulking agent, a stabilizer and a grinding aid, if necessary, to obtain The powder premix obtained is coated on the particle nuclei suspended in water using a suitable binder. In the case where the pesticidal active ingredient is a liquid, it may be left in a liquid state, or in the case where the pesticidal active ingredient is a solid or a liquid, if necessary, in an appropriate solvent. It can also be produced by dissolving and, if necessary, adding a suitable disintegrating / dispersing agent, a wetting agent, an emulsifying agent, and other auxiliaries such as a stabilizer, and absorbing the particles into floating particles in water. .

The solid agricultural chemical preparation of the present invention can be obtained as follows.

When the pesticidal active ingredient of the present invention is solid, if the pesticidal active ingredient has a coarse particle size, it will cause the pesticidal active ingredient to sediment densely at the input point of the paddy field, and the pesticidal active ingredient will be localized for a long period of time. This may cause inconveniences such as insufficient efficacy and phytotoxicity. The pesticidal active ingredient of the present invention must be dissolved and diffused in paddy water immediately after being put into a paddy field to exert its efficacy, and therefore, even if it has high solubility in water, it is a solid pesticide. It is necessary to pulverize the active ingredient to a certain degree, and those with low solubility in water require especially pulverization. For this reason, the solid active ingredient, if necessary, together with the above-mentioned grinding aids and other auxiliaries, for example, by dry grinding with a hammer mill and a jet mill; or by wet grinding with a sand mill and an attritor. Can be ground.

The dry-ground pesticide active ingredient is apt to be classified due to differences in particle size and provisional specific gravity from the water-floating agent and other auxiliaries, and the pesticide active ingredient is likely to be uneven in the solid pesticide formulation. In this regard, as will be described later, the method of kneading and granulating the slurry containing the wet-ground pulverulent pesticide active ingredient together with other auxiliaries causes the above-mentioned non-uniformity of the pesticide active ingredient. Difficult and suitable.

The wet-ground pesticidal active ingredient is dried by a method such as spray drying and then ground, or absorbed in a carrier having an appropriate oil-absorbing ability, such as amorphous synthetic silica, diatomaceous earth, calcium silicate, and a highly oil-absorbing resin. If necessary, it can be dried and pulverized and treated in the same way as dry-ground agrochemical active ingredients. Further, in the wet granulation, the slurry containing the pesticidally active ingredient which has been wet-ground is used together with the kneading water to knead and granulate to produce the pesticide granule of the present invention.

When using liquid agricultural chemical active ingredients, liquid agricultural chemical active ingredients or low-melting agricultural chemical active ingredients, dissolve them in a solvent or emulsifier, if necessary, and use a water-floating carrier. Alternatively, it can be absorbed by water-suspended grain nuclei, or together with other auxiliaries, an oil-absorbing carrier such as amorphous synthetic silica, diatomaceous earth, calcium silicate, highly oil-absorbing resin and highly oil-absorbing dextrin. Or a solid solution with a resin, a chemical substance, or another solid pesticidal active ingredient that is compatible with the pesticidal active ingredient, and can be handled in the same manner as the solid pesticidal active ingredient.

These pesticidal active ingredients, together with other auxiliaries, can be converted to the pesticidal solid preparation of the present invention through processes such as mixing, pulverization, kneading, granulation, drying, sizing, coating or absorption. .

When the solid pesticidal formulation of the present invention is a powder formulation, the active ingredient of pesticide, water surface spreader and other auxiliaries are mixed, and if necessary, a suitable pulverizer such as a hammer mill and an air mill. Can be produced by pulverization.

When the solid pesticide preparation of the present invention is a granule, for example, a method of granulating the raw material powder using a suitable granulator (granulation method), a method of appropriately binding to a previously prepared floating particle nucleus. To coat pesticidal active ingredient with pesticide (coating method), or to dissolve pesticide active ingredient in suitable solvent? Then, it can be manufactured by a method (absorption method) in which this is absorbed into a previously prepared floating particle nucleus.

When the pesticide solid preparation of the present invention is used to produce granules by a granulation method, the pesticide active ingredient, if necessary, is made into a concentrated premix with other auxiliaries in advance, and this is mixed with other ingredients, It can be produced by granulation, drying and sizing. The granulator used can be, for example, an extrusion granulator of the side-press or basket type, etc., a mixing granulator, a tumbling granulator, a fluidized-bed granulator or a spray dryer, preferably extrusion. It is a granulator. When foamed shirasu or foamed perlite is contained in the components, if these are strongly pressurized, the balloon may be crushed and the buoyancy may be reduced. Therefore, it is preferable to use a granulator that does not apply strong pressure or shearing force.

In the case of producing granules by the coating method, the pesticidal solid preparation of the present invention is prepared by charging a preliminarily prepared floating granule into a stirring mixer and, if necessary, adding a liquid binder to form the granules. After the surface is moistened, a concentrated premix of the pesticidal active ingredient is added, and the mixture is further stirred and mixed to coat the surface of the grain core with the pesticidal active ingredient. The disturbance used The stirring mixer is preferably a low-speed mixer with less crushing of particles, and may be, for example, a Nauta mixer, a ribbon blender, a rotary blender or a V-type mixer, preferably a Nauta mixer or a ribbon blender. . In the concentrated premix, if necessary, for example, a water surface spreader, a water surface floating agent, another water surface spreader, a disintegration agent, a dispersant, a wetting agent, a bulking agent, a granulation improver, Solvents, emulsifiers or stabilizers may be incorporated.

In the case of producing granules by the absorption method, the solid pesticidal formulation of the present invention is generally prepared by charging the previously prepared buoyant granules into the above-mentioned mixing mixer, and stirring the mixture to form a liquid or liquefied liquid. It can be produced by adding a pesticidal active ingredient or a concentrated premix thereof for absorption. In the premix, if necessary, for example, a water surface spreader, a solvent, an emulsifier, or a stabilizer can be blended.

In the case of producing a water-floating granule by a coating method or an absorption method, the effect of the water-surface spreader in the outermost layer can be more effectively exerted. Therefore, it is desirable that the water surface spreader be added last after coating or absorbing the pesticidal active ingredient and other auxiliaries. As described above, in the granulation method, the coating method, and the absorption method, the necessary steps of the granulation, coating, absorption, and the like may be performed at once, or may be divided into two or more steps as necessary. For example, a part of the pesticidal active ingredient may be kneaded and granulated to obtain a floating granule nucleus, which may be coated with the remaining pesticidal active ingredient. The surface of the granules may be coated or absorbed with a water surface spreader, and the coating method and the absorption method may be applied to the same preparation.

The grain nucleus used in the coating method or the absorption method may be a grain nucleus prepared by the same method as that for preparing the granules in the above granulation method or a grain nucleus prepared by removing a part of the raw material; A water-floating agent, such as cork, foamed shirasu, calcined vermiculite, foamed perlite, foamed pumice, or foamed synthetic resin, which has been prepared in advance to an appropriate particle size, may be used directly as the grain nucleus.

The particle size of the water-suspendable pesticide granule of the present invention is usually 0.1 to 5 mm, preferably 0.3 to 3 mm, and more preferably 0.5 to 2 mm. If the particle size is too large, it is difficult to dry the granules when the granules are produced, and the granules are easily affected by wind on the water surface, which is not preferable.

The water-floating pesticide granules of the present invention, when granules granulated from powder raw material, water When thrown, it does not matter whether it is disintegrable or non-disintegrable.

The shape of the water-floating pesticide granules of the present invention is not particularly limited, and may be, for example, columnar, spherical, or irregular.

The apparent specific gravity of the water-floating pesticide granules of the present invention is usually 0.15 to 0.50 in terms of ease of handling, productivity and ease of floating of the particles on the water surface, and is preferably 0.2 to 0.45, more preferably 0.25 to 0.40.

Since the solid pesticidal formulation having a water-floating surface of the present invention contains a high concentration of an active agricultural chemical, the active agricultural chemical must be dispersed, dissolved, and diffused in water immediately after spreading on the water surface. Insufficient dispersion, dissolution and diffusion, and the appearance of sedimentation of granules containing a high concentration of pesticidal active ingredient may cause localization of the pesticidal active ingredient at the point of sedimentation, which may cause phytotoxicity and insufficient efficacy. . In addition, if the pesticidal active ingredient is not released from the granules and stays on the water surface for a long time, there is a concern about the problem of wind storm.

The water-floating pesticidal solid preparation of the present invention can naturally enter a paddy field and be uniformly treated, as in the case of ordinary granules. Throw the film into sachets from the ridges (throwing treatment), (2) transfer into the rice fields along the ridges (frame treatment), or (3) place the solid formulation or the sachets on the water-floating pesticide into the paddy fields. When pouring water, it can be treated in the water mouth and diffused into the rice fields together with irrigation water (water mouth treatment), etc., and it can be treated in fields with some obstacles on the water surface, even in fields with large rice plants. The pesticidal active ingredient can be spread evenly throughout the paddy field, and can produce sufficient biological effects without causing phytotoxicity. A water-soluble film of a package for throwing into a paddy field is a film having a property of dissolving or dispersing in water. The raw material of the water-soluble film to be used can be, for example, polyvinyl alcohol or a derivative thereof, pullulan film or polyethylene oxide or a derivative thereof, and preferably polybutyl alcohol or a derivative thereof.

When the solid water-floating pesticide solid preparation of the present invention is packaged in a water-soluble film having no spreadability, the water-soluble film may hinder the spread of the water-floating pesticide solid preparation. In this case, the water surface spreader dissolves in the water before the solid water-susceptible pesticide solid spreads sufficiently and loses the spreading power. The spreadability of the sachet on the water surface is inferior to that of solid agricultural chemicals. In such a case, the pesticidal active ingredient may be localized in a narrow range near the drop point, and a favorable result may not be obtained. Therefore, the water-soluble film is preferably spreadable water-soluble paper.

The spreadable water-soluble paper itself is a film or sheet that easily disperses or dissolves in water and spreads the water-susceptible solid pesticide formulation on the water surface. The spreadable water-soluble paper used may be, for example, a film or sheet (hereinafter abbreviated as PVA film) made of polyvinyl alcohol or a derivative thereof.

The PVA film was formed into a film or a sheet of polyvinyl alcohol having a degree of polymerization of 500 to 200 and a saponification degree of 80 to 98% together with a small amount of a plasticizer and a stabilizer. And films or sheets containing a small amount of a copolymer such as carboxylic acid or sulfonic acid in the polymer.

A water-soluble film must have high mechanical strength and cold-resistance strength and be water-soluble.In that sense, if the degree of polymerization of the raw material polyvinyl alcohol is too high or the saponification degree is too high, It is not preferable because it becomes difficult to melt. The thickness of the water-soluble film depends on the film strength and dissolution time, but is usually from 20 to 80 μπι, and preferably from 30 to 50 / im.

The end of the water-soluble film may be sealed with glue, but there is a problem in workability, and the glued portion may be difficult to dissolve. In this regard, a material that can be heat-sealed is preferable.

The weight of the sachet for throwing into a paddy field is usually 10 to 200 g per 1 ° / ° C, preferably 20 to: LOO g, more preferably , 25 to 60 g. With this weight, even a child, woman or elderly person can easily throw the sachet into a target point within 15m. If the package is heavier than this, it will be difficult to throw it in and it will not be easy to process it over a large area.If the package is smaller than this, the package will reach the target point due to the wind. It becomes difficult to do. Since the solid pesticidal formulation floating on the water surface of the present invention spreads widely on the water surface and the active ingredient of the pesticide diffuses over a wide range, it is not necessary to forcibly throw the pesticide far away in a paddy field of normal size. It is enough to throw it into the water surface 2-3 m away. If the number of packages to be thrown into the paddy field is too large, the throwing requires labor and labor is not saved, and it is economically disadvantageous.If the number is too small, the spread of the solid pesticide formulation that floats on the water surface is not sufficient. There is a possibility that the number will be sufficient. Usually, the number is 1 to 30 and preferably 2 to 20 per 10 a of the paddy field.

The package for throwing into a paddy field shall be packaged in a bag, box or bottle made of paper, resin, aluminum foil or aluminum or silica deposited on them, metal or wood.

The solid water-floating pesticide solid preparation of the present invention can be packaged in the same manner as when the above-mentioned packaging is packaged, even when the solid water-floating pesticide solid preparation is subjected to a frame treatment or a mouth opening treatment.

The water-floating pesticidal solid preparation of the present invention is stable with respect to moisture absorption over time in terms of physical properties. Therefore, it is not necessary to pay more attention to moisture absorption than to a preparation containing a foaming agent. However, since a water-soluble film breaks when exposed to water, it is desirable to use an exterior that has been appropriately waterproofed.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited thereto. The following parts mean parts by weight.

(Examples 1 to 18)

Water surface spreadable granules

Combine 24 parts of pyroquilon drug substance, 3 parts of talc (Europe), and 1 part of Carplex # 80 (amorphous synthetic silica, manufactured by Shionogi & Co., Ltd.), and sample mill (Fuji Baudal Co., Ltd., hammer) Mill) to obtain a pyroquilon premix. In addition, each water surface spreader and Carplex # 80 shown in Table 1 below were mixed at a ratio of 1: 1 and pulverized by a sample mill to obtain 50% water surface spreader premix.

Hilcon S-1 (Hirishi Chemical Industry Co., Ltd., firing baking liquid 3-0.5 mm) 3 Put 5 parts in a ribbon blender and use Super Oil C (Nippon Oil Co., Ltd., coarse liquid paraffin 3) Add 3 parts and mix to wet the grain surface, then Add 28 parts of the above-mentioned pyroquilon premix, mix and coat the surface of the granules, and then add 4 parts of the above 50% water surface spreader premix, mix and coat the surface of the granules to obtain 24% of pyroquilon. Was obtained.

In Table 1 below, Et represents an ethyl group, 2-Et-C ₆ H ₁₃ represents a 2-ethylhexyl group, iso-C ₉ H ₁₉ represents an isononyl group, and E〇 represents a compound of the formula CH ₂ —CH ₂ — O—, a group represented by the formula—CH ₂ —CH (CH ₃ ) —O—, a group represented by — (E0) _3- (P0) _5- (E0) _2- Indicates a group in which 3 mol of ethylene oxide, 5 mol of propylene oxide and 2 mol of ethylene oxide are added in this order, and the symbol “-” in the derivative column indicates that the water surface expander is a compound (I) The symbol “ethyl ether” in the derivative column indicates that the water surface spreader is the ethyl ester of compound (I), and the symbol “phosphate ammonium salt” in the derivative column indicates the water surface spreader. This shows that the agent is an ammonium salt of a phosphoric acid ester of compound (I). table 1

Water surface expander

R'O— (AO) (BO) -H (I) Example Water surface expander

Number

-(A0) _m- (B0) _n -derivative

_{1 - (E0) 2 - 2} ^ -Et-C B h n - (E0) 2 - 3 - (E0) 2 - 2 Echinore to carboxymethyl Honoré ether Honoré _{4 2-Et-QH 1 -} (E0) 5 - 5 2-Et-CH, - ( E0) 3 - Engineering Chinoree one Tenore _{6 2-Et-C 6 H} 13 - (EO) 3 - (PO) 5 - (EO) 2 -

_{2 - Et - C fi H -} (E0) 15 - (P0) 3 -

_{iso-C Q H - (Ε0} ) 2 - (Ρ0) 7 2 -.. (Ε0) δ 3 - 2-Et-di-(E0) ₂ — phosphate ammonium salt 0 2-Et-C ₆ H _1- (E0) ₂ _ phosphate sodium salt

11 2-Et-C _fi H-(E0) ₂ -Phosphate triethanolamine salt

12 2-Et-H,-(E0) _2- Estenole phosphate

13-(E0) ₂ — Calcium phosphate ester salt

14 2-Et-CKH'.J-(E0) ₂ -sulfate ammonium salt

15-(E0) _2- Potassium sulfate salt

16-(E0) ₂ — (P0),-Phosphate isopropylamine salt

17-(E0) _2- (P0) _r Phosphate triethanolamine salt

_{18 ISO "- (E0) 2} - (P0) 7 2 - (ΕΟ);. Phosphate Toriumu salt Example 1, 2, 9, 1 0 and 1 2 Water extender agent according to the commercial product (Nippon Emulsifier Other surface extenders can be manufactured, for example, according to the method described in New Surfactant (Hiroku Horiguchi, Sankyo Publishing, published in 1975).

(Example 19)

Water-floating spreadable granules and sachets for throwing in paddy fields

2 parts of foamed white shirasu (0.3 to 1.0 mm) was placed in a Nauta mixer (manufactured by Hosokawa Micron Corporation), and mixed while adding 5 parts of super oil C25 to wet the grain surface. Add 28 parts of the pyroquilon premix described in 1 to 18 and mix to coat the grain surface, and then add 5 parts of the 50% water surface spreader premix described in Example 8 and mix to mix. By coating the surface, a water-floating spreadable granule containing 24% of pyrochilone was obtained.

The obtained water-spreading granules are subdivided into 50 g portions of Hythelon C 200 (a PVA film having a thickness of 40 μm, manufactured by Nichigo Film Co., Ltd.) to obtain a paddy throwing package.

(Example 20)

Water-floating spreadable powder preparation and sachet for throwing in paddy fields 47.5 parts of foamed shirasu (0.03 to 0.15 mm) and 22.5 parts of polyvinyl chloride powder were placed in a LeDige mixer (manufactured by Matsusaka Trading Co., Ltd.), and 25 parts of pretilachlor raw material and described in Example 17 By mixing while adding a mixed solution of 5 parts of a water surface spreader, a water surface spreadable powder formulation containing 25% of pretilachlor was obtained.

The obtained water-floating spreadable powder formulation was subdivided into 30 g portions of Hythelon C 200 to obtain a package for paddy throwing.

(Example 21)

Water-floating spreadable granules and sachets for throwing in paddy fields

63 parts of the pyrazolate drug substance and Newcol 29 1 PG (sodium salt of getylhexylsulfosuccinate, manufactured by Nippon Emulsifier Co., Ltd.) 0.85 parts are suspended in 36.15 parts of water. Using a bead mill (manufactured by Shinmaru Enterprises Co., Ltd.), a pulverized product containing 63% of pyrazolate was obtained. To 57.14 parts of the obtained pulverized product, 2.5 parts of Toxanone GR31A (manufactured by Sanyo Chemical Co., Ltd., acrylic acid-based dispersant) was added and mixed to obtain a vilasolate slurry. Cork (0.2-0.5mm class) 14 parts, bentonite (manufactured by Toyoshun Mining Co., Ltd., Hotaka) 7 parts, cellogen 7A (sodium salt of carboxymethyl cellulose, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 7 Part and wood flour (manufactured by Neolight Kosan Co., Ltd.) 14. Mix 52 parts in a kneader, knead with 59.64 parts of the above virazolate slurry diluted with a small amount of water and mix. It was extruded and granulated through a 1.5 mm screen by Gran (Fuji Baudal Co., Ltd., extrusion granulator). The obtained wet granules were dried at 100 ° C. using a fluidized bed drier and sieved with a sieve of 4.76 to 1.2 Omm to obtain a pyrazolate concentrated granule. 80 parts of the obtained concentrated granule is charged into a Nauta mixer, and a mixed solution of 15 parts of a butachlor raw material and 5 parts of a water surface spreader described in Example 18 is added, mixed, and absorbed. As a result, a water-floating spreadable granule containing 36% of pyrazolate and 15 ° C./o of butachlor was obtained.

The obtained water-spreading granules were subdivided into 50 g portions of Hythelon C 200 to obtain paddy throwing sachets. (Comparative Examples 1 to 4)

Water-floating granules

Each water-floating granule was obtained in the same manner as in Example 1 except that the water-surface spreading agent described in Example 1 was used instead of the water-surface expanding agent described in Example 1. Table 2

Water surface expander Comparative Example No. Water surface expander Surfino 1 0 4

(Acetylene-based surfactant, manufactured by Nissin Chemical Co., Ltd.)

(Silicon surfactant, manufactured by Toray Dow Corning Co., Ltd.)

(Fluorine-based surfactant, manufactured by Daikin Industries, Ltd.) Niuco Mono 291 PG (sodium salt of getylhexyl sulfosuccinate, manufactured by Nippon Emulsifier Co., Ltd.)

(Comparative Example 5)

Water-floating powder preparations and sachets for paddy throwing

In the same manner as in Example 20 except that Newcol 291 PG was used instead of the water surface spreader described in Example 2◦, a water-floating powder preparation and a package for paddy throwing were obtained. Was.

(Test Example 1)

Spreadability of active agricultural chemicals under dirty water surface conditions

Fill a 25.5 cm wide and 32 cm long plastic container with water to a depth of 2 cm It was adjusted. After the water surface was disturbed, 0.25 g of wood flour was evenly spread on the water surface, and the water surface was covered with wood flour. At the center of the water surface, 0.1 g of the water-surface-spreading granules of Examples 1 to 18 and Comparative Examples 1 to 4 were respectively charged. One minute after the introduction of the granules, a photograph of the surface of the water was taken and the number of cracks into which the granules entered by breaking the wood powder on the surface of the water and the area of the container where the wood flour was displaced by the introduction of the granules were removed. The ratio to the area (5% unit) was measured and the extensibility on the water surface was determined. The results are shown in Table 3. Table 3

Spreadability of active agricultural chemicals under dirty water surface Test granules Spreadability Number of cracks on water surface (number) Ratio of water surface on which wood flour was displaced (%) Example 1 450

Example 2 4 5 5

Example 3 4 5 5

Example 4 4 5 0

Example 5 4 5 5

Example 6 5 7 0

Example 7 5 5 5

Example 8 6 7 5

Example 9 6 7 0

Example 1 0 5 6 5

Example 1 1 4 6 0

Example 1 2 7 7 5

Example 1 3 4 6 5

Example 1 4 5 6 0

Example 1 5 5 6 0 Example 1 6 6 7 0

Example 1 7 4 6 0

Example 1 8 5 7 5 Comparative Example 1 2 2 5

Comparative Example 2 3 3 0

Comparative Example 3 1 1 0

Comparative Example 4 2 15 The water-spreading granules of the present invention exhibited excellent spreadability even under dirty water conditions, compared to the water-spreading granules of the Comparative Example.

(Test Example 2)

Uniformity of pesticide active ingredients under dirty water surface conditions

A frame with a width of 90 cm, a length of 7 m, and a depth of 10 cm was made of styrofoam and placed horizontally in a windless room. A black vinyl sheet was placed on the inner surface of the frame, and water was added to adjust the depth to 5 cm. 20 g of wood flour was evenly spread on the water surface through a sieve having an opening diameter of 0.5 mm. After the turbulence of the water surface was reduced, the water-surface-spreading granules of Example 19 and 3.15 g of Comparative Example 2 were each treated at a position 10 cm from the edge of the frame. did. Five minutes after the treatment, the distance from the input point to the tip where the wood flour was displaced by the introduction of the grains was measured, and 3 hours, 7 hours, and 24 hours after the treatment, as shown in Figure 1. in 5 0 cm distant points a and c from both ends of the center point b and the center line, depth 2.5 water agrochemical active ingredient concentration locations cm was measured, _c the results of the examination of homogeneity of the agrochemical active ingredient Are shown in Table 4. Table 4

Uniformity of active ingredients for pesticides under dirty water conditions Test granules Wood flour from granule input point Pesticide effectiveness Pyroquilone concentration in water (ppm) The concentration of the component that was displaced

Distance to the edge (m) Measuring position 3 hours 7 hours 24 hours after processing Example 1 9 5.8 a 3.6 2 3.0 2 2.80 b 3.07 7 2.8 1 2.53 c 0. 0 5 0. 6 5 1. 5 8 Comparative Example 2 2.9 a 8.49 6.3 5.5.8 5 b 0 .04 1. 3 1 1. 8 3 c 0 0 0. 04 The water-spreading granules of the present invention spread the pesticidal active ingredient under dirty conditions on the water surface more quickly and have better uniformity of the pesticidal active ingredient in water than the water-spreading granules of the comparative example. Met.

(Test Example 3)

Homogeneity and herbicidal effect of active pesticides in a field with dirty water

1 OmX We planted rice in a paddy field divided into 1 Om. After 7 days, adjust the water depth to 5 cm, and treat 100 g of wood flour per ward with a midget duster (small spreader, manufactured by Arimitsue Co., Ltd.) so that the water surface is wood flour. Covered. The sachets for paddy field throwing of Example 20 and Comparative Example 5 were put into the center of each section, and it was observed that the granules spread on the water surface. At the time when the spread became maximum 10 minutes after the treatment, the area where the wood flour was displaced was measured. Further, 24 hours after the treatment, as shown in Fig. 2, as shown in Fig. 2, paddy water was collected from the dropping point 3 and points 1, 2, 4, and 5 lm away from each corner, and the concentration of the pesticidally active ingredient in water was measured. Analyzed and determined. Table 6 shows the results. Table 5

Uniformity of pesticide active ingredients in fields with dirty water Test paddy throwing Wood flour dislodged Agricultural chemical active ingredient 24 Pre-packed packaging after 4 hours and area (m ² ) Concentration measurement position Lacrol concentration (ppm) Example 20 0 0 1 (windward) 1. 03

2 1.45

3 (center) 2.80

4 1.28

5 (leeward) 1.85

Comparative Example 5 2 linear, 3 1 (windward) 0.32

2 0.94

3 (center) 6. 23

4 0.72

5 (leeward) 1.03 Furthermore, 40 days after the paddy field throw-in packaging treatment, the herbicidal effect on the seeds of the seedlings, which had been sown in advance at the time of rice transplanting at the water sampling points 1 to 5, was examined. At no point, no outbreaks were found. On the other hand, in the treated section of Comparative Example 5, some residual weeds were observed at the points 1 and 4 that hit the windward during the treatment.

As described above, in the paddy throwing sachet of Example 20 of the present invention, in a field where the water surface is contaminated, the active ingredient of the pesticide spreads well in the paddy field, and after one day of treatment, the whole field is almost completely spread. Although it spread evenly and the herbicidal effect was good, the sachet of the paddy field of Comparative Example 5 was not uniform even after one day from the treatment, and the herbicidal effect was inferior to that of Example 20.

(Test Example 4)

Herbicidal effect test in a field where algae developed

We planted rice in a 30 a paddy field. After 10 days from the rice planting, it was confirmed that algae had been generated in about 1 Z3 of the paddy area, and as shown in Fig. 3, the water-spreading granules of Example 21 1 g in the water mouth treatment method (the method of treating pesticides in which granules are poured from the water mouth into the paddy field together with irrigation water) and the frame treatment method (750 g while walking on long ridges on both sides) A method for treating pesticides in which each granule is transferred to a point about 50 cm from the ridge and the package for paddy throwing of 50 g X 30 pack of Example 21 are thrown into the padding method (long ridges on both sides) While walking along the shore, a pack of 15 packs was applied using a method of treating pesticides that was thrown at a point about 7 m from the ridge. At 40 days after application, the herbicidal effect was observed and surveyed at 3 m from the ridges of both long ridges and in the center three rows. In all the test plots, very little weeds were found, and extremely high herbicidal effects were obtained.

[Industrial applicability] The solid pesticide formulation of the present invention has good water surface spreadability even in a paddy field with dirt on the water surface such as algae and floating grass, and also has good uniformity of the pesticide active ingredient in the paddy field. . For this reason, pesticide treatment after the rice grows large, and even in paddy fields with the above-mentioned obstacles, the effect of the pesticide active ingredient is fully exhibited, and a pesticide solid formulation that farmers can use with peace of mind. is there. Furthermore, the paddy throwing sachet of the present invention can be used under the above disadvantageous conditions, and greatly contributes to labor saving in paddy field agriculture.

[Brief description of drawings]

[Figure 1] Agricultural chemical active ingredient concentration measurement position in Test Example 2

[Figure 2] Agricultural chemical active ingredient concentration measurement position in Test Example 3

[Figure 3] Pesticide treatment method in Test Example 4

Claims

The scope of the claims

_{_{1. c 4 ~c 1 () c}} 2 ~c 4 alkylene O wherein de adducts of alkyl alcohols and consists derivative of that one or more kinds of the water surface extender, and water surface planktonic containing an agrochemical active ingredient Pesticide solid preparation.

2. The water surface expander has the general formula (I)

R'O- (AO) _m — (BO) _n -H (I)

[Wherein, R ¹ is. Represents an alkyl group,

A represents a group represented by the formula: CH ₂ — CH ₂ —,

B is a group represented by the formula: CH ₂ —CH (CH ₃ );

m represents 0 to 30; n represents 0 to 30; however, m and n are not simultaneously 0, and when n is 0, m is 2 or more; and m and n are When both are not 0, the bonding order of the m A〇 groups and the n BO groups is arbitrary. ]

, A phosphoric acid ester, a sulfuric acid ester thereof, a salt of the ester, and _one or more water-spreading compounds selected from the group consisting of C ₁ to C _{1 ()} alkyl ethers of the compound. 2. The water-floating pesticide solid preparation according to claim 1, which is:

3. R ¹ 3. The water-floating pesticidal solid preparation according to claim 2, which is an alkyl group.

4. The solid water-floating agrochemical preparation according to any one of claims 2 or 3, wherein m is 0 to 10 and n is 0 to 10.

5. A compound in which R ′ is an ethylhexyl or isononyl group, m is 0 to 10 and n force S is 0 to 10, a phosphate ester thereof, an ammonium salt, a sodium salt of the phosphate ester or 3. The water-floating agrochemical solid preparation according to claim 2, which is a potassium lime salt.

6. The compound according to claim ¹ , wherein R ¹ is an ethylhexyl or isononyl group, m is 2 to 8, and n is 0 to 8, a phosphoric ester thereof or a sodium salt of the phosphoric ester. Item 2. The solid water-floating pesticide preparation according to item 2.

7. The solid water-floating agrochemical solid preparation according to any one of claims 1 to 6, further comprising a water-floating agent.

8. The method according to claim 7, wherein the water-floating agent is foamed shirasu, foamed perlite, foamed pumice, fired vermiculite, cork, wood flour, foamed synthetic resin, synthetic resin powder, or plastic hollow body. Waterborne pesticide solid formulation.

9. The solid water-floating pesticide solid formulation according to any one of claims 1 to 8, wherein the solid water-floating pesticide solid formulation is a granule having a particle size of 0.1 to 5 mm. .

10. A package for paddy throwing in a paddy field, wherein the solid water-floating pesticide solid preparation according to any one of claims 1 to 9 is packaged in a water-soluble film.

11. The rice field throwing sachet according to claim 10, wherein the water-soluble film is a film or sheet made of polyvinyl alcohol or a derivative thereof.

12. The package for throwing rice in a paddy field according to claim 10 or 11, wherein the package has a weight of 10 to 200 g per pack.

13. The paddy throwing package according to any one of claims 10 to 12 is thrown into a paddy at a rate of 1 to 30 pieces per 10 a. A method of controlling pests.

14. The water-floating pesticide solid according to any one of claims 1 to 9 A method of controlling pests that occur in paddy fields by transferring the drug product along the ridge into paddy fields.

15. The water-floating pesticide solid formulation according to any one of claims 1 to 9 is treated at a water mouth when water is poured into a paddy field, and diffused into the paddy field together with irrigation water. How to control pests that occur in paddy fields.

16. The paddy field throwing sachet according to any one of claims 10 to 12 is treated at a water mouth when water is poured into the paddy field, and diffused into the paddy field together with irrigation water. A method of controlling pests that occur in paddy fields.