JP2000351701A - Water-floating pesticide solid formulation - Google Patents

Abstract

(57) [Abstract] [Problem] To obtain a water-floating pesticidal solid formulation that exhibits excellent water surface spreading properties even in the treatment of paddy fields with obstacles on the water surface or after the rice has grown. . The C ₄ -C ₁₀ alkyl alcohol is a C ₂ -C ₄ alkyl alcohol.
A solid water-floating agrochemical solid preparation comprising one or more water-surface spreaders composed of an alkylene oxide adduct and a derivative thereof and an agrochemical active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to one or more water surface spreaders comprising C ₂ -C ₄ alkyl alcohol adducts of C ₄ -C ₁₀ alkyl alcohols and derivatives thereof, and active ingredients for agricultural chemicals. The present invention relates to a water-suspendable solid pesticide formulation, a pesticide formulation for paddy throwing into a water-soluble film, and a method for controlling pests generated in paddy fields using the same.

[0002]

2. Description of the Related Art Conventionally, paddy agricultural chemicals have been formulated into various dosage forms, for example, powders, wettable powders, emulsions and granules, and sprayed on the water surface or rice body for convenience of use. But,
In recent years, for example, in view of the aging and part-time work of farmers and the increase in the labor burden of women, labor saving of pesticide application has been required.

[0003] For this reason, flowable agents which can be processed without using a machine, and so-called 1 kg granules, in which the content of the active ingredient in the preparation is increased to reduce the amount of application as a preparation, have been increasingly used. However, flowables, for example, depending on the direction of the wind, there is a problem of spraying to the sprayer at the time of processing and there is a problem of empty bottle processing, 1kg granules,
For example, it has the disadvantages of requiring spraying equipment and difficulties in uniform spraying.

[0004] Recently, a solid agricultural chemical preparation is packaged in a water-soluble film, and the package can be processed simply by throwing it from a ridge without entering a paddy field (ie, a paddy field). A throw-in pesticide formulation) has been proposed
No. 173802), which are commercially available, and are also called jumbo preparations or packs.

[0005] Such preparations for throwing in paddy fields include, for example, those in which large effervescent tablets are thrown into rice fields as they are (JP-A-6-107503), and those in which small effervescent tablets are packaged in a water-soluble film. Into a paddy field (Japanese Patent Laid-Open No. 5-339106), a water-soluble carrier such as potassium chloride granulated together with a water-soluble film-forming polymer, and a pesticidal active ingredient is contained in the water-soluble film. A package that is packaged and thrown into a paddy field (Japanese Patent Application Laid-Open No. 5-78207), and a pesticide solid preparation prepared so as to float and spread on the water surface is packaged in a water-soluble film and thrown into a paddy field ( JP-A-6-3
Japanese Patent Application Laid-Open No. 5-339103 discloses a method in which an oil having water surface spreadability is packed in a water-soluble container and thrown into a paddy field.

[0006] These pesticide preparations for throwing into paddy fields have a high content of the pesticidal active ingredient in the preparation and are applied topically. Therefore, unless the active ingredient diffuses promptly from the thrown point, the pesticide active ingredient becomes uneven. It is easy to cause phytotoxicity and nonuniformity of efficacy, and in some cases, residual agricultural chemical active ingredients may affect subsequent crops.

On the other hand, as an agricultural chemical solid preparation prepared so as to float and spread on the surface of water for the purpose of diffusing the active ingredient of agricultural chemicals, for example, (1) a pharmaceutical preparation which is suspended using a water-suspending carrier (Japanese Patent Publication No. No. 15613, JP-B-47-124
No. 0), (2) those using pumice or hillite having a specific water absorbing ability as a carrier (Japanese Patent Publication No. 44-8600),
(3) Granules using volatile insecticide compounds (Japanese Patent Publication No. 49-1)
No. 1421), (4) a carbamate-based pesticidal active ingredient and an organic compound having a partition coefficient to water of 10 ² or more held on a solid carrier (JP-A-2-17470).
No. 2) and (5) a composition comprising an active ingredient which is a fungicide, a herbicide or a plant growth regulator, a solid carrier, and an oil (JP-A-3-193705).

However, when these pesticidal solid preparations are treated under conditions where the rice is small and the water surface is free from obstacles such as weeds, algae and oil films, the particles are widely spread on the water surface with the help of the wind force. So, the so-called frame spraying, which is sprayed from the ridge without entering the paddy field, also exhibits a high effect, but after the rice grows large and the power of the wind cannot be used,
When treated under conditions where obstacles such as algae and oil slicks are present, the particles are unlikely to diffuse on their own and may not be able to exert a sufficient biological effect, or may cause phytotoxicity due to the localization of the active ingredient. In such a case, as in the case of the 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 such a drawback, an attempt has been made to use an acetylene-based surfactant as a water surface spreader, further package the water-soluble film having a water surface spreadability, and to use silicon as a water surface spreader. Attempts have been made to use surfactants or fluorine-based surfactants or dialkyl sulfosuccinates (JP-A-6-336403, JP-A-8-9980).
No. 2 and Japanese Patent Publication No. 2766973). However, even with these techniques, sufficient spreading may not be observed in the above-described conditions where there is an obstacle on the water surface or in the treatment after the rice grows.

[0010]

The present inventors have [0005] As a result of extensive studies on water spreadability of excellent water-floating agrochemical solid formulation, C ₂ -C ₄ alkylene oxide adduct of C ₄ -C ₁₀ alkyl alcohols Water-floating pesticide solid preparations containing one or more water-spreading agents consisting of products and their derivatives, even in the treatment of paddy fields with obstacles on the water surface or after the growth of rice The present invention has been found to exhibit excellent water surface spreadability.

[0011]

The present invention SUMMARY OF] is a C ₄ ~C ₁₀ C ₂ ~C ₄ alkylene oxide adduct and one or two or more water extender agent and agrochemical active ingredient made from the derivatives of alkyl alcohols Provided are a water-floating solid pesticide formulation, a pesticide formulation for throwing into a paddy field in which the solid formulation is packaged in a water-soluble film, and a method for controlling pests generated in paddy fields using the same.

In the present invention, "C ₄ -C ₁₀ alkyl alcohol" is a straight-chain or branched-chain alcohol having 4 to 10 carbon atoms, for example, butanol, pentanol,
It may be hexanol, heptanol, octanol, nonanol, isononanol, decanol or ethylhexanol, preferably a straight-chain or branched-chain alcohol having 6 to 10 carbon atoms, more preferably octanol, ethylhexanol or Isononanol, even more preferably ethylhexanol or isononanol.

In the present invention, "C ₂ -C ₄ alkylene oxide" is a linear or branched alkylene oxide having 2 to 4 carbon atoms, and may be, for example, ethylene oxide, propylene oxide or butylene oxide. Preferably, it is ethylene oxide or propylene oxide.

[0014] "C ₂ -C ₄ alkylene oxide adduct of C ₄ -C ₁₀ alkyl alcohol" in the present invention, the above hydroxyl group of "C ₄ -C ₁₀ alkyl alcohol""C ₂ -C ₄ alkylene oxide" However, when a plurality of alkylene oxides are added, the order in which the alkylene oxides are added is arbitrary.

The "C ₂ -C ₄ alkylene oxide adduct of a C ₄ -C ₁₀ alkyl alcohol" of the present invention is preferably represented by the following general formula (I):

[0016]

Embedded image R ¹ O— (AO) _m — (BO) _n —H (I) wherein R ¹ represents a C ₄ -C ₁₀ alkyl group, and A represents a compound of the formula —CH ₂ —CH ₂ Represents a group represented by-, B is a group represented by the formula -CH
₂ represents a group represented by —CH (CH ₃ ) —;
Represents 0, n represents 0 to 30, provided that m and n are not simultaneously 0, and when n is 0, m is 2 or more, and when both m and n are not 0, 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” are 1
The number of ethylene oxide and propylene oxide added to each of the compounds (I) is represented, and the average of the numbers of ethylene oxide and propylene oxide added to a plurality of compounds (I) can be represented.

[0018] "Derivatives of C ₄ -C ₁₀ alkyl C ₂ -C ₄ alkylene oxide adduct of alcohol" in the present invention include, for example, C ₂ -C ₄ alkylene oxide adduct of the above "C ₄ -C ₁₀ alkyl alcohols , A phosphate ester, a phosphate ester salt, a sulfate ester, a sulfate ester salt or a C ₁ -C ₁₀ alkyl ether, and preferably a phosphate ester or a salt thereof.

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

In the present invention, the "salt" is not particularly limited as long as it is generally used as an agricultural chemical. For example, alkali metal salts such as sodium salt, potassium salt and lithium salt; ammonium salt, triethanolamine salt and Amine salts such as isopropylamine salts; or alkaline earth metal salts such as calcium and barium salts, preferably ammonium salts or alkali metal salts, more preferably ammonium salts, sodium salts Salt or potassium salt.

In the present invention, the "C ₁ -C ₁₀ alkyl ether" refers to the "C ₂ -C ₁₀ alkyl alcohol of the C ₂ -C ₁₀ alkyl alcohol".
A C ₄ alkylene oxide adduct ”wherein a linear or branched alkyl group having 1 to 10 carbon atoms is bonded to an oxygen atom of a terminal hydroxyl group, for example, methyl ether,
It can be ethyl ether, propyl ether, isopropyl ether, butyl ether, pentyl ether, hexyl ether, heptyl ether, octyl ether, ethylhexyl ether, nonyl ether, isononyl ether or decyl ether, preferably ethylhexyl or isononyl ether. .

The "C ₂ -C ₄ alkylene oxide adduct of a C ₄ -C ₁₀ alkyl alcohol" of the present invention is more preferably the compound (I) wherein R ¹ is a C ₆ -C ₁₀ alkyl group. (more preferably, octyl, and ethylhexyl or isononyl group, even more preferably, ethylhexyl or isononyl group), a has the formula -CH ₂ -C
A group represented by H ₂ —, wherein B is a group represented by the formula —CH ₂ —CH (C
H ₃ ) —, wherein m is 0 to 15 (more preferably, 0 to 10), n is 0 to 15 (more preferably, 0 to 10), However, when m and n are not simultaneously 0 and n is 0, m is 2 or more;
And both n are not 0, m AO groups and n BO
Compounds represented by the formula (I)
a).

The water surface spreader of the present invention is particularly preferably the compound (I), wherein R ¹ is an ethylhexyl or isononyl group, m is 0-10, and n is 0-10.
Wherein m and n are not 0 at the same time, and when n is 0, compound (Ib) wherein m is 2 or more, a phosphoric ester thereof, or an ammonium salt of the phosphoric ester,
A sodium salt or a potassium salt; most preferably, in the compound (I), R ¹ is an ethylhexyl or isononyl group; m is 2 to 8;
8 is compound (Ic), its phosphoric ester or its sodium salt.

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

The amount of the water surface spreader used is usually from 0.1 to 50% by mass in the solid pesticide formulation,
It is 0.5 to 30% by mass, more preferably 1 to 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 the water, and may be liquid or 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,
Trichlorfon, formothion, dimethoate, monocrotophos, acephate, carbofuran, carbosulfan, thiocyclam, cartap, bensultap, benfracarb, flatiocarb, buprofezin, fenobucarb, metolcarb, propoxure, imidacloprid, nittenpyram and acetamiprid, etc. Or, cycloprothrin,
It can be a synthetic pyrethroid that is effective against pests that live in water or near the water surface, such as rice weevil and rice beetle such as etofenprox and silafluofen,
Preferably, it is imidacloprid, nittenpyram, acetamiprid, cycloprothrin, etofenprox or silafluofen.

The fungicides used are, for example, probenazole, isoprothiolane, iprobenfos, tricyclazole, pyroquilon, carpropamide, olivrite, azoxystrobin and 7-fluoro-1,2,2.
5,6-tetrahydro-4H-pyrrolo [3.2.1-
i. j] Imotic agents such as quinolin-4-one; flutranil, mepronil, thifluzamide, flametopyr and 2-
(4-Fluorophenyl) -1- (1H-1,2,4-
An antibacterial agent such as triazol-1-yl) -3-trimethylsilylpropan-2-ol; teclophthalam; or
It can be benomyl, preferably probenazole, isoprothiolane, pyroquilon, carpropamide, olibrite, azoxystrobin, 7-fluoro-1,2,5,5.
6-tetrahydro-4H-pyrrolo [3.2.1-i.
j] Quinolin-4-one, flutranyl, thifluzamide, flametopyr, 2- (4-fluorophenyl) -1
-(1H-1,2,4-triazol-1-yl) -3
-Trimethylsilyl-propan-2-ol or teclophthalam.

The herbicides to be used include, for example, pyrazolate, benzofenap, pyrazoxifene, pyributicarb, bromobutide, butamiphos, mefenacet, bensulfuron-methyl, anilofos, butachlor, pretilachlor, thiobencarb, chlornitrofen, clomethoxyphen, dimuron, bifenox, Naproanilide, oxadiazon, oxadialgyl, bentazone, molinate, piperophos, dimepiperate, esuprocarb, dithiopyr, imazosulfuron, benfresate, quinoclamin, cinmethylin, M
CPA or a salt or ester thereof such as a sodium salt or a potassium salt; 2,4-D or a salt or ester such as a sodium salt or a potassium salt; MCPB or a salt or ester such as a sodium salt or a potassium salt thereof; Lac, pyrazosulfuron-ethyl, pentoxazone, tenylchlor, cumyluron, sinosulfuron, simethrin, dimethamethrin, cyhalofop-butyl, etobenzanide, cafenstrole, ethoxysulfuron, azimusulfuron, cyclosulfamuron,
Indanophane, pyriminobac-methyl, oxadichromemephone, 4- (2-chlorophenyl) -N-cyclohexyl-4,5-dihydro-N-ethyl-5-oxo-1
H-tetrazole-1-carboxamide (NBA06
1), [3- (2-Chloro-4-methylsulfonylbenzoyl) -4-phenylthio] bicyclo [3.2.1]
Oct-3-en-2-one (benzobicyclone, SB
500), methyl = N- [4- (benzothiazole-2)
-Ylmethoxy) -2-methylphenyl] carbamate and methyl = N- [4- (benzoxazol-2-ylmethoxy) -2-methylphenyl] carbamate; Fenap, pyrazoxifene, pyributicarb, bromobutide, mefenacet, bensulfuron-methyl,
Anilofos, butachlor, pretilachlor, dimuron, oxadialgyl, imazosulfuron, pyrazosulfuron-ethyl, pentoxazone, tenylchlor,
Dimethamethrin, cyhalofop butyl, capfentrol, ethoxysulfuron, azisulfuron, indanophan, NBA061, benzobicyclon, methyl
N- [4- (benzothiazol-2-ylmethoxy)-
2-methylphenyl] carbamate or methyl N-
[4- (benzoxazol-2-ylmethoxy) -2
-Methylphenyl] carbamate.

The plant regulator used can be, for example, inabenfide, paclobutrazol, uniconazole or tripentenol, preferably inabenfide or paclobutrazol.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION In addition to a water surface spreader and an active pesticide active ingredient, the solid agricultural chemical preparation of the present invention includes, for example, a water surface floating agent, another water surface spread agent, a disintegrating / dispersing agent, a wetting agent, and a binder. , A bulking agent, a granulation improver, a solvent, an emulsifier, a stabilizer, and other assistants such as a grinding assistant.

The solid pesticide preparation 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 as long as it allows the solid pesticide formulation to float on the surface of the water, for example, foamed shirasu, foamed pearlite,
Mineral substances such as foamed pumice and calcined vermiculite; plant materials such as cork, wood flour and cellulose; foamed synthetic resins such as styrene foam; synthetic resin powders such as polyvinyl chloride powder; plastic hollow bodies such as Matsumoto Microsphere-F30E;
It can be granules of a synthetic resin; or a mixture thereof, and is preferably expanded shirasu, expanded perlite, expanded pumice, calcined vermiculite, cork, wood powder, expanded synthetic resin, synthetic resin powder, or a hollow plastic 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 formulation, and the like, but may be any amount sufficient to allow the solid pesticide formulation to float on the water surface. , 0.01 to 90 in the pesticide solid preparation
% By mass, preferably from 0.1 to 70% by mass,
More preferably, it is 0.5 to 60% by mass.

In the present invention, various surfactants can be contained as auxiliaries, and depending on the nature of the surfactants used, other surfactants for water surface spread, disintegrating / dispersing agents, wetting agents, binders , Can also act as a granulation improver or emulsifier. Also, polymers and organic solvents, due to their properties,
Can be used for multiple purposes.

The solid agricultural chemical preparation 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 water surface spreadability. Other water surface spreaders used are, for example, (co) polymers of carboxylic acids such as acrylic acid and maleic acid, and those obtained by copolymerizing styrenesulfonic acid and vinyl with carboxylic acids such as acrylic acid and maleic acid. Polycarboxylic acid type polysoaps such as sodium, potassium and ammonium salts; soaps such as sodium oleate and potassium stearate; sodium dialkylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate And other anionic surfactants such as perfluoroalkyl carboxylate; polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl ethers having 11 or more carbon atoms, polyoxyethylene alkyl esters and alkyl esters of sorbitan. And other nonionic surfactants; silicon-based nonionic surfactants; acetylene-based nonionic surfactants and nonionic surfactants of the pluronic type; these nonionic surfactants are esters of phosphoric acid or sulfuric acid, and may be Surfactants neutralized with an appropriate alkali; surfactants containing fluorine; liquid paraffin, naphthenic and aromatic high-boiling solvents, low-viscosity polybutenes and mineral oils such as machine oils; silicone oils; Vegetable oil; resins such as pine resin; camphor white oil; α-pinene; camphor; or naphthalene, preferably acetylenic nonionic surfactant or various mineral oils.

The amount of the other water surface spreader to be used depends on the type and amount of the water surface spreader, the type and amount of the pesticidal active ingredient and the water surface floating agent, and the type and amount of other auxiliaries. Although it depends on the dosage form, it is usually 0.0
1 to 50% by mass, and preferably 0.1 to 40% by mass.
And more preferably 0.2 to 30% by mass.

The solid pesticide preparation of the present invention is used for disintegrating particles in water and suspending / dispersing the pesticidal active ingredient in water.
A disintegrating / dispersing agent can be contained. In many cases, the disintegrating / dispersing agent used is preferably an anionic surfactant. For example, lignin sulfonate, (alkyl) naphthalene sulfonate and its condensate, phenol sulfonate and its condensate, styrene sulfone 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, polyacrylic acid salts, salts of acrylic acid and maleic acid copolymers, salts of maleic anhydride and methyl vinyl ether copolymers, alkylbenzene sulfonates, dialkyl sulfosuccinic acids Salt, salt of lauryl sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene aryl aryl ether sulfate,
It can be an anionic surfactant such as polyoxyethylene alkyl aryl ether phosphate, polyoxyethylene aryl aryl ether phosphate, or a salt obtained by neutralizing these sulfates or phosphates with a suitable cation. , Lignin sulfonate,
Condensates of (alkyl) naphthalenesulfonates, condensates of phenolsulfonates, condensates of styrenesulfonates, salts of condensates of maleic acid and styrenesulphonic acid, carboxylic acid condensations such as acrylic acid and maleic acid A salt of a polyacrylate, a salt of a copolymer of acrylic acid and maleic acid, a salt of a copolymer of maleic anhydride and methyl vinyl ether, or a dialkyl sulfosuccinate. Many of the surfactants used in these disintegrating / dispersing agents are effective as wetting agents. Further, phosphates such as sodium phosphate and sodium hexametaphosphate; suitable nonionic, cationic or amphoteric surfactants; and starch, carboxymethylcellulose, carboxymethylated starch and salts thereof, and crosslinked products of polyvinylpyrrolidone Also, those having a property of absorbing water and expanding such as microcrystalline cellulose and superabsorbent resin can be used as a disintegrating / dispersing agent.

The amount of the disintegrating / dispersing agent or the disintegrating / dispersing agent and the wetting agent used is usually 0.01 to 0.01% in the solid pesticide formulation.
To 30% by mass, preferably 0.03 to 20% by mass.
And more preferably 0.05 to 10%.

The pesticidal solid preparation of the present invention is used for imparting hardness to granules when granulating powder raw materials to prepare granules, or for coating the surface of the grain core with the pesticidal active ingredient. Agents can be included.

The binder used for the former purpose is a water-soluble starch derivative such as dextrin and pregelatinized starch having a relatively low molecular weight; polyvinylpyrrolidone, a salt of polyacrylic acid, a salt of carboxymethylcellulose, and a saponifier having a relatively low molecular weight. Water-soluble polymer substances such as polyvinyl alcohol, lignin sulfonic acid salt and gum arabic having a low ratio; 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 grains, but is usually 0.1 to 30% by mass in the solid pesticide formulation. Preferably, it is 0.5 to 20% by mass.

The binder used for the latter purpose may be, in addition to the above-mentioned solid binder, the following oily binder which is hardly volatile. The present invention may be used by dissolving these binders in a solvent such as water or a volatile organic solvent to coat the pesticidal active ingredient on the surface of the grain nucleus and then evaporate the solvent, It may be coated with a less volatile oily or liquefied binder and leave the binder in the solid pesticide formulation without evaporation. The method of leaving the binder in the pesticidal solid preparation 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 of the binder is 0.01 to 20% by mass in the solid pesticide preparation.
And preferably 0.1 to 10% by mass, and 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 pesticidal solid preparation may be any as long as it can uniformly coat the surface of the grain core with the pesticidal active ingredient.
Oily solvents that do not adversely affect the growth and decomposition of particles are preferred. For example, a solvent 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 chemical component is preferred. Such binders are, for example,
Mineral oils such as low viscosity liquid paraffin, chlorinated paraffin, isoparaffin, machine oil, polybutene, paraffinic, naphthenic and aromatic high boiling solvents; vegetable oils such as coconut oil, soybean oil and rapeseed oil; whale oil and Animal oils such as sardine oil; silicone oils and derivatives thereof; esters of monocarboxylic acids such as oleic acid and coconut oil fatty acids, esters of dicarboxylic acids such as maleic acid, fumaric acid, phthalic acid and adipic acid, and tributyl phosphate And plasticizers such as esters of phosphoric acid such as triethyl phosphate; glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, butanediol and hexylene glycol; lactones such as ε-caprolactone and γ-butyrolactone. N-alkylpyrrolidone; various liquid surfactants; or mixtures thereof, preferably those which are relatively inexpensive and do not adversely affect the active ingredient, the binder itself is stable and volatile 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 solid pesticide formulation varies depending on the kind of the binder, the kind and physical properties of the pesticidal active ingredient, and the kind and amount of other auxiliaries. 1 to 50% by mass in the pesticide solid formulation;
Preferably it is 3 to 40% by mass, more preferably 5 to 40% by mass.
35% by mass.

The extender used in the solid pesticide preparation 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 can be plant powders such as starch, wood flour, sawdust, coffee bean powder, tub flour, cellulose powder, microcrystalline cellulose, rice husk powder, rice bran, bran and coconut shell powder; Amorphous silicon dioxide, talc or wood flour.

The amount of the extender used depends on the type and amount of the other auxiliaries.
0.1 to 80% by mass, preferably 1 to 50% by mass
And more preferably 2 to 40% by mass.

The solid pesticide preparation of the present invention may contain a granulating agent for improving the granulating property of the pesticide granule. The granulating agent used is not particularly limited as long as it imparts plasticity to a surfactant or a composition generally used as a granulating agent in pesticide granules, for example, polyoxyethylene alkyl. Nonionic surfactants such as aryl ethers, polyoxyethylene alkyl esters and polyoxyethylene aryl aryl ethers; anionic surfactants such as sodium salts of dialkyl sulfosuccinates and sodium salts of alkyl benzene sulfonic acids; minerals such as bentonite Starch fines such as dextrin and pregelatinized starch; natural gums such as gum arabic; cellulose derivatives such as the sodium salt of carboxymethylcellulose;
Or, it may be a water-soluble synthetic polymer such as sodium salt of polyvinyl alcohol or polyacrylic acid, preferably,
Bentonite or sodium salt of carboxymethyl cellulose.

The amount of the granulation improver to be used varies depending on the type of the granulation improver and the kind and amount of other auxiliaries, but is usually 0.01 to 30% by mass in the pesticidal solid preparation. Yes, preferably 0.05 to 25% by mass, and more preferably 0.1 to 20% by mass.

The solid agricultural chemical preparation of the present invention may contain a solvent for diluting the liquid agricultural chemical active ingredient or for converting the low-melting agricultural chemical active ingredient to 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 to diffuse widely into paddy fields. Preferred are solvents having a specific gravity of less than 1 and a low viscosity, for example, high-boiling solvents of paraffinic, aromatic and naphthenic types; 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 phosphoric acid; vegetable oils such as coconut oil and rapeseed oil; or animal oils such as whale oil and sardine oil, preferably liquid paraffin or low molecular weight polybutene. .

The amount of the solvent used for diluting or dissolving the pesticidal active ingredient varies depending on the type and physical properties of the pesticidal active ingredient, and it is preferable that the amount is as small as possible as long as it does not affect the stability over time or the physical properties of the solid pesticide preparation. The amount is usually 0.1 to 50 parts, preferably 0.2 to 10 parts, per part of the pesticidal active ingredient to be diluted or dissolved.

In addition, C ₄ -C ₁₀ alkyl alcohol may be substituted with C ₂ -C ₁₀ alkyl alcohol.
Compounds to which C ₄ alkylene oxide has been added can also be used as a solvent for diluting or dissolving the pesticidal active ingredient.

The pesticidal solid preparation of the present invention may contain an emulsifier for emulsifying the pesticidal active ingredient in water.
Such an emulsifier can be selected according to the type and physical properties of the pesticidal active ingredient and the solvent in the same manner as when selecting the emulsifier for the emulsion. Since there is no need for agitation, it is preferable to use those which have as good a self-emulsifying property as possible and perform fine emulsification.

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

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

When the active ingredient is dry-pulverized, the solid agricultural chemical preparation of the present invention may contain a pulverizing aid as necessary in order to improve the pulverizability and prevent adhesion to equipment. . The grinding aid used can be, for example, amorphous synthetic silica, talc or various granular minerals, preferably amorphous synthetic silica or talc.

The pesticidal solid preparation of the present invention, when the active ingredient of the pesticide 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. Then, the obtained powder premix can be produced by coating the particle nuclei floating in water with a suitable binder, and when the pesticidal active ingredient is a liquid, it remains liquid. Alternatively, if the pesticidal active ingredient is a solid or liquid, it is dissolved in a suitable solvent if necessary, and if necessary, a suitable disintegrating / dispersing agent, a wetting agent, an emulsifier, a stabilizer, etc. Can also be produced by adding an auxiliary agent and absorbing the nuclei in the particle nuclei floating 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 a solid, if the pesticidal active ingredient has a coarse particle size, it will cause the pesticidal active ingredient to sediment densely at the point of introduction into the paddy field, and the pesticidal active ingredient will not be dispersed for a long period of time. Localization may cause inconveniences such as insufficient efficacy and phytotoxicity. The pesticidal active ingredient of the present invention dissolves and diffuses in paddy water immediately after being put into a paddy field,
It is necessary to exert its efficacy, and therefore, even if it has a high solubility in water, it is necessary to pulverize the solid pesticidal active ingredient to a certain extent, and if the solubility is low in water, it is particularly fine. Requires grinding. For this reason, if necessary, the solid active ingredient is pulverized together with the above-mentioned pulverizing aid and other auxiliary agents, for example, by dry pulverization with a hammer mill and a jet mill; or by wet pulverization with a sand mill and an attritor. be able to.

[0060] The dry-ground pesticidal active ingredient is liable to be classified due to the difference in particle size and temporary specific gravity from the water-floating agent and other auxiliaries, and the pesticidal active ingredient is likely to be uneven in the pesticidal solid preparation. In this regard, as will be described later, the slurry containing the wet-ground pulverulent active ingredient is supplied in a fixed amount together with other auxiliaries, and the method of kneading and granulating is less likely to cause unevenness of the pesticidal active ingredient as described above. Is preferred.

The wet-ground pulverulent active ingredient is dried by a method such as spray drying and then pulverized, or absorbed into a suitable oil-absorbing carrier such as amorphous synthetic silica, diatomaceous earth, calcium silicate and a highly oil-absorbing resin. Then, if necessary, it is dried and pulverized, and can be treated in the same manner as the dry-pulverized agricultural chemical active ingredient. Furthermore, at the time of wet granulation, the agricultural chemical granule of the present invention can be produced by kneading and granulating the slurry by using a slurry containing a pesticidally active ingredient that has been wet-ground together with kneading water.

When a liquid pesticidal active ingredient, a liquid pesticidal active ingredient or a low-melting pesticidal active ingredient is used, it may be dissolved in a solvent or an emulsifier, if necessary, to form a water-floating carrier or a water-floating water. It can be absorbed in the grain nucleus, or it can be absorbed together with other auxiliaries in an oil-absorbing carrier such as amorphous synthetic silica, diatomaceous earth, calcium silicate, high oil-absorbing resin and high oil-absorbing dextrin, or It forms a solid solution with a resin, a chemical substance or another solid pesticidal active ingredient 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, are subjected to the steps of mixing, crushing, kneading, granulating, drying, sizing, coating, or absorbing to give the pesticidal solid preparation of the present invention. it can.

When the solid pesticide preparation of the present invention is a powder preparation, the pesticidal active ingredient, a water surface spreader and other auxiliaries are mixed, and if necessary, a suitable pulverizing method such as a hammer mill or an air mill is used. It can be manufactured by crushing using a machine.

When the solid agricultural chemical preparation of the present invention is in the form of granules, for example, a method of granulating the raw material powder using a suitable granulator (granulation method) may be used to prepare a floating particle nucleus prepared in advance. A method of coating the pesticidal active ingredient with a suitable binder (coating method),
Alternatively, the active ingredient can be produced by dissolving the pesticidal active ingredient in a suitable solvent and absorbing the active ingredient in a previously prepared floating particle nucleus (absorption method).

The pesticidal solid preparation of the present invention comprises, when granules are produced by a granulation method, an active ingredient of a pesticide, if necessary,
It can be produced by preparing a concentrated premix with other auxiliaries in advance, mixing this with other components, granulating, drying and sizing. The granulator used can be, for example, an extrusion granulator such as a side-push or basket type, a mixing granulator, a tumbling granulator, a fluidized-bed granulator or a spray dryer, and is preferably extruded. It is a granulator. When foamed shirasu or foamed pearlite is contained in the component, if these are strongly pressurized, the balloon may be crushed and the buoyancy may be reduced.Also, when cork is contained, the buoyancy may be increased by strongly pressurizing them. It is preferable to use a granulator that does not receive strong pressure or shearing force because it decreases.

In the case of producing granules by the coating method, the pesticidal solid preparation of the present invention is prepared by charging a previously prepared buoyant granule nucleus into a stirring mixer and, if necessary, adding a liquid binder. After the surface of the agent 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 stirring mixer to be used 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, and preferably a Nauta mixer or a ribbon blender. Also, during the rich premix, if necessary, for example,
Water surface expander, water surface floating agent, other water surface expander,
Dispersants, wetting agents, extenders, granulation improvers, solvents, emulsifiers or stabilizers can 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 a previously prepared buoyant particle nucleus into the above-mentioned stirring mixer, and stirring the mixture to form a liquid or liquid. It can be produced by adding a concentrated pesticidal active ingredient or a concentrated premix thereof and absorbing it. During the premix, if necessary, for example,
Water spreaders, solvents, emulsifiers or stabilizers can be included.

In the case of producing granules having a water surface floating property by a coating method or an absorption method, the effect of the water surface spreader can be exhibited more effectively when it is present in the outermost layer. Therefore, it is desirable that the water surface spreader is added last after coating or absorbing the pesticidal active ingredient and other auxiliaries. in this way,
In the granulation method, the coating method, and the absorption method, the necessary steps among the steps of granulation, coating, and absorption may be performed at once, or may be performed in two or more steps as necessary. For example, a part of the pesticidal active ingredient is kneaded and granulated,
A floating granule may be obtained, and the remaining pesticidal active ingredient may be coated thereon.The surface of the floating granule prepared by the granulation method may be coated or absorbed with a water surface spreader, 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 can be a grain nucleus prepared by the same method as that for preparing the granules of the above granulation method or a grain nucleus prepared by removing a part of the raw materials. Alternatively, a water surface suspending agent such as cork, foamed shirasu, calcined vermiculite, foamed perlite, foamed pumice, foamed synthetic resin, or the like, which has been previously adjusted to an appropriate particle size, may be used as the grain nucleus as it is.

The particle size of the pesticidal particles having a water-floating property of the present invention is usually 0.1 to 5 mm, preferably 0.3 to 3 mm, more preferably 0.5 to 2 mm. If the particle size is too large, it is difficult to dry the particles when produced by a granulation method, and the granules are easily affected by wind on the water surface, which is not preferable.

When the water-floating pesticide granules of the present invention are granulated from powdered raw materials, they may be either disintegrable or non-disintegrable granules when thrown into water.

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 pesticide granules having a water-floating property of the present invention is usually from 0.15 to 0.50 in view of easiness of handling, productivity and floating of the grains on the water surface. Is 0.20 to 0.45, more preferably 0.25 to 0.
40.

Since the solid pesticidally water-susceptible formulation of the present invention contains a high concentration of the pesticidal active ingredient, the pesticidal active ingredient must be promptly dispersed, dissolved and diffused in water after spreading on the water surface. . Insufficient dispersion, dissolution and diffusion,
If granules containing a high concentration of the pesticidal active ingredient seem to settle, localization of the pesticidal active ingredient may occur at the point of sedimentation, which may cause harm or insufficient efficacy. In addition, if the pesticidal active ingredient is not released from the granules and floats on the water surface for a long time, there is a concern about the problem of wind blowing.

The solid formulation of the present invention can be applied to a paddy field and uniformly treated as in the case of ordinary granules. Throwing from a ridge etc. as a sachet on a water-resistant film (throwing treatment), transferring into a paddy field along the ridge (frame treatment), or applying the solid pesticide solid formulation or the sachet to a paddy field Can be treated at the water mouth when pouring, and then diffused into the paddy field along with irrigation water (water mouth treatment). Even in fields with some obstacles on the water surface or fields with large rice, pesticide is effective. The components can be spread evenly throughout the paddy field, and can produce sufficient biological effects without causing phytotoxicity.

The water-soluble film of the 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 used can be, for example, polyvinyl alcohol or a derivative thereof, pullulan film or polyethylene oxide or a derivative thereof, and is preferably polyvinyl alcohol or a derivative thereof.

When the solid water-floating pesticide solid preparation of the present invention is packaged in a non-spreading water-soluble film, the water-soluble film may hinder the spread of the water-floating pesticide solid preparation. is there. In this case, before the water-floating pesticide solid formulation is sufficiently diffused, the water-spreading agent dissolves in the water and loses its spreading power. The spreadability of the package on the water surface is inferior to that of the preparation. 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 a spreadable water-soluble paper.

The spreadable water-soluble paper itself is a film or sheet that has the property of easily dispersing or dissolving in water and spreading the water-floating agrochemical solid preparation on the water surface. The spreadable water-soluble paper used is, for example, a film or sheet (hereinafter referred to as PV) made of polyvinyl alcohol or a derivative thereof.
Abbreviated as A film. ).

The PVA film has a degree of polymerization of 500 to 20.
The polyvinyl alcohol having a degree of saponification of 80 to 98% is formed into a film or sheet with a small amount of a plasticizer and a stabilizer, and a small amount of a carboxylic acid or a sulfonic acid is contained in the polymer. And a film or sheet containing a copolymer such as

The water-soluble film needs to have high mechanical strength and cold-resistance strength and to be water-soluble, and in that sense, the polymerization degree of the raw material polyvinyl alcohol is too high,
If the saponification degree is too high, it becomes difficult to dissolve in cold water, which is not preferable. The thickness of the water-soluble film is usually from 20 to 80 μm, and preferably from 30 to 50 μm, depending on the film strength and the dissolution time.

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 film which can be heat-sealed is preferable.

The weight of the sachet for throwing into a paddy field is usually 10 to 200 g per pack, preferably 20 to 100 g, more preferably 25 to 100 g.
60 g. With such a weight, even a child, a woman or an elderly person can easily throw the sachet into a target point within 15 m. If the sachet is heavier, it will be difficult to throw it in and it will not be easy to process it over a large area.If the sachet is less than this, the sachet will reach the target point under the influence of the wind. Becomes difficult.

Since the solid formulation for pesticide floating on the water surface of the present invention spreads over a wide area on the water surface and the active ingredient of the pesticide diffuses over a wide range, it is not necessary to forcibly throw it into a paddy field of a normal size. It is enough to throw it into the water 2-3m away from the shore.

The number of packages to be thrown into a paddy field is
If the amount is too large, labor is required for throwing and labor is not saved, and it is economically disadvantageous. If the amount is too small, there is a possibility that the spread of the water-floating pesticide solid formulation may be insufficient, and usually, per paddy field 10a , 1 to 30, preferably 2 to 20
Individual.

The sachet for throwing into a paddy field is as follows:
Paper, resin, aluminum foil bonded to these, aluminum or silica vapor-deposited, metal, wood, etc. bag, box or bottle.

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 time in moisture absorption in terms of physical properties. Therefore, it is not necessary to pay attention to moisture absorption as compared with a preparation containing a foaming agent. However, since a water-soluble film breaks when exposed to water, it is desirable to use an exterior which has been subjected to a suitable waterproof treatment.

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.

[0090]

【Example】

[0091]

Examples 1 to 18 Water-Floating Spreadable Granules 24 parts of a pyroquilone bulk material, 3 parts of talc (Europe) and 1 part of Carplex # 80 (amorphous synthetic silica manufactured by Shionogi & Co., Ltd.) were mixed. And pulverized by a sample mill (a hammer mill manufactured by Fuji Paudal Co., Ltd.) to obtain a pyroquilon premix. Further, each water surface spreader shown in Table 1 below and Carplex # 80 were mixed at a ratio of 1: 1 and pulverized by a sample mill to obtain a 50% water surface spreader premix.

Hilcon S-1 (Hirishi Chemical Industry Co., Ltd., calcined vermiculite 3 to 0.5 mm section) 3
Put 5 parts in a ribbon blender, add 33 parts of Super Oil C (manufactured by Nippon Oil Co., Ltd., coarse liquid paraffin) and mix to wet the grain surface, then add and mix 28 parts of the above-mentioned pyroquilon premix. Coated on the grain surface,
Thereafter, 4 parts of the 50% water surface spreader premix was further added, mixed and coated on the particle surface to obtain a water surface spreadable granule containing 24% pyroquilone.

In Table 1, Et represents an ethyl group, 2-Et-C ₆ H ₁₃ represents a 2-ethylhexyl group, and iso-C ₉ H ₁₉
Represents an isononyl group, EO represents a group represented by the formula —CH ₂ —CH ₂ —O—, PO represents a group represented by the formula —CH ₂ —CH (CH ₃ ) —O—, and — (EO) _3- (PO) _5- (EO) _2- represents 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 a water surface spreader. Is the compound (I), the symbol "ethyl ether" in the derivative column indicates that the water surface spreader is the ethyl ether of the compound (I), and the symbol "ammonium phosphate ester" in the derivative column is Indicates that the water surface spreader is an ammonium salt of a phosphoric acid ester of compound (I).

[0094]

[Table 1] Water surface spreader

[0095]

Embedded image R ¹ O— (AO) _m — (BO) _n —H (I) ──────────────────────────── ──────── Example Water surface spreader No. ──────────────────────────────── 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 - ethyl 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 - phosphoric acid ester ammonium salt _{10 2-Et-C 6 H} 13 - (EO) 2 - sodium phosphates _{11 2-Et-C 6 H} 13 - (EO ) ₂ - phosphoric acid ester triethanol amine Salt _{12 2-Et-C 6 H} 13 - (EO) 2 - phosphoric acid ester _{13 2-Et-C 6 H} 13 - (EO) 2 - phosphoric acid ester 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 - phosphoric acid ester isopropylamine salt 17 _{C 6 H 13 - (EO)} 2 - (PO) 1 - phosphoric acid ester triethanolamine salt _{18 iso-C 9 H 19 -} (EO) 2 - (PO) 7.2 - (EO) 5.3 - phosphate ester sodium saltの Examples 1, 2, 9, 10 and 12 A commercially available product (manufactured by Nippon Emulsifier Co., Ltd.) was used as the water surface spreader. Other water surface spreaders can be produced, for example, according to the method described in New Surfactant (Hiroguchi Hiroshi, Sankyo Shuppan, published in 1975).

[0096]

Example 19 Water-Floating Spreadable Granules and Packaging for Paddy Field Throwing 42 parts of foamed shirasu (0.3 to 1.0 mm) was placed in a Nauta mixer (manufactured by Hosokawa Micron Corporation), and 25 parts of super oil C was added. Mix to wet the grain surface, then add 28 parts of the pyrochilone premix described in Examples 1-18, mix and coat the grain surface, and then further add the 50% water surface spreader premix described in Example 8. 5 parts of the mix was added, mixed and coated on the particle surface to obtain a water-surface-spreading granule containing 24% of pyroquilone.

The obtained water-surface-spreading granules are subdivided into 50 g portions of Hythelon C200 (a PVA film having a thickness of 40 μm, manufactured by Nichigo Film Co., Ltd.) to obtain a package for paddy throwing.

[0098]

Example 20 Water-Floatable Spreadable Powder Formulation and Packing for Throwing in Paddy Field 47.5 parts of foamed shirasu (0.03 to 0.15 mm) and 22.5 parts of PVC powder were mixed with a Reedige mixer (Matsusaka Trading Co., Ltd.) And 25 parts of a pretilachlor base material and 5 parts of a water surface spreader described in Example 17 were mixed while adding a mixed solution to obtain a water surface spreadable powder formulation containing 25% pretilachlor. .

[0099] The obtained water-surface-spreading spreadable powder preparation was subdivided into 30 g portions of Hycelon C200 to obtain a paddy throwing package.

[0100]

Example 21 Water-Floating Spreadable Granules and Packing for Throwing in Paddy Field 63 Parts of Pyrazolate Material and Newcol 291PG
0.85 parts (sodium salt of diethylhexyl sulfosuccinate, manufactured by Nippon Emulsifier Co., Ltd.) in 36.1 of water
The suspension was suspended in 5 parts, and the suspension was pulverized using a Dynomill (Beads Mill, manufactured by Shinmaru Enterprises) to obtain a pulverized product containing 63% of pyrazolate. 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 pyrazolate slurry. 14 parts of cork (0.2-0.5 mm section), 7 parts of bentonite (manufactured by Toyoko Mining Co., Ltd., Hotaka), 7 parts of cellogen 7A (sodium salt of carboxymethyl cellulose, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and wood 14.52 parts of powder (manufactured by Neolite Kosan Co., Ltd.) are mixed in a kneader, and a mixture obtained by further diluting 59.64 parts of the above pyrazolate slurry with a small amount of water is added and kneaded. Dome Gran (Fuji Powder Co., Ltd.) , Extrusion granulator) with a 1.5mm screen
The mixture was extruded and granulated. The obtained wet granules are dried at 100 ° C. using a fluidized bed drier, and 4.76 to 1.20 m
m to obtain a pyrazolate concentrated granule.
80 parts of the obtained thick granule is charged into a Nauta mixer,
To this, a mixed solution of 15 parts of butachlor raw material and 5 parts of the water surface spreader described in Example 18 was added, mixed and absorbed to obtain 36% of pyrazolate and butachlor 15
% Was obtained.

The obtained water-surface-spreading granules were subdivided into 50 g portions of Hycelon C200 to obtain a paddy throwing package.

[0102]

Comparative Examples 1 to 4 Water-floating granules Instead of the water-surface spreader described in Example 1, the following Table 2 was used.
Each water-floating granule was obtained in the same manner as in Example 1 except that the described water surface spreading agent was used.

[0103]

[Table 2] Water surface spreading agent ──────────────────────────────────── Comparative example number Water surface spreading Agent ──────────────────────────────────── 1 Surfynol 104 (Acetylene surfactant, Nissin 2 Silgard 309 (Silicon-based surfactant, manufactured by Toray Dow Corning Co., Ltd.) 3 Unidyne DS101 (Fluorine-based surfactant, manufactured by Daikin Industries, Ltd.) 4 Newcol 291PG (sodium of diethylhexyl sulfosuccinate) Salt, manufactured by Nippon Emulsifier Co., Ltd.)

[0104]

[Comparative Example 5] Water-floating powder formulation and sachet for throwing into a paddy field Water-floating was performed in the same manner as in Example 20 except that Newcol 291PG was used instead of the water-spreading agent described in Example 20. An aqueous powder preparation and a package for paddy throwing were obtained.

[0105]

Test Example 1 Spreadability of Agricultural Chemical Active Ingredients Under Water-Dirt Conditions Water was poured into a resin container having a width of 25.5 cm and a length of 32 cm to adjust the water depth to 2 cm. 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. In the center of the water surface, 0.1 g of the water-surface-spreading granules of Examples 1 to 18 and the water-surface-floating granules of Comparative Examples 1 to 4.
Respectively. One minute after the introduction of the granule, a photograph of the state of the water surface was taken, and the number of cracks into which the granule entered by breaking the wood powder on the surface of the water by the addition of the granule and the area of the container where the wood powder of the water surface was displaced were removed. Ratio to area (5% unit)
Was measured, and the extensibility on the water surface was determined. Table 3 shows the results.

[0106]

[Table 3] Spreadability of active agricultural chemicals under dirty water conditions 水──── Test granule Extensibility ────────────────────────────── Number of cracks on water surface (number) Wood flour Example of water surface ratio (%) that was displaced ──────────────────────────────────── Example 14 50 Example 2 4 55 Example 3 4 55 Example 4 4 50 Example 5 4 55 Example 6 5 70 Example 7 5 55 Example 8 6 75 Example 9 6 70 Example 10 5 65 Example 11 4 60 Example 12 7 75 Example 13 4 65 Example 14 5 60 Example 15 560 Example 16 670 Example 17 460 Example 18 5 75----------- − − − − − − Comparative Example 1 2 25 Comparative Example 2 3 30 Comparative Example 3 1 10 Comparative Example 4 2 15 ────────────────────────水 The water-spreading granules of the present invention show excellent spreadability even under dirty water conditions, compared to the water-spreading granules of Comparative Example. Was.

[0107]

Test Example 2 Uniformity of Agricultural Chemical Active Ingredients Under Water-Dirt Conditions In a windless room, a frame having a width of 90 cm, a length of 7 m and a depth of 10 cm was made of Styrofoam and placed horizontally. Spread a black vinyl sheet on the inner surface of the frame, pour water and
cm. 20 g of wood flour was uniformly spread on the water surface through a sieve having an opening diameter of 0.5 mm. After the water surface was disturbed, 3.15 g of the water-surface-spreading granule of Example 19 and 3.15 g of the water-surface-floating granule of Comparative Example 2 were each 10 c from the end of the frame.
m. 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. Also, three hours, seven hours, and 24 hours after the treatment, as shown in FIG. At the points a and c 50 cm away from the center point b and both ends on the center line, the concentration of the pesticidal active ingredient in water at a position at a depth of 2.5 cm was measured, and the uniformity of the pesticidal active ingredient was investigated. Table 4 shows the results.

[0108]

[Table 4] Uniformity of pesticide active ingredients under conditions where the water surface is dirty ─── Test granule From the granule input point to the wood flour Pesticide effective concentration of the component from which the pyroquilone concentration in water (ppm) was displaced ─────────────── Distance to the end (m) Measurement position 3 hours after treatment 7 hours 24 hours ──────────────────────────────────── Example 195 0.8a 3.62 3.02 2.80b 3.07 2.81 2.53c 0.05 0.65 1.58------------------ Comparative Example 2 2.9 a 8.49 6.35 5.85 b 0.04 1.31 1.83 c 00 0.04} ────────水 The water-spreading granules of the present invention spread the active agricultural chemical component under dirty conditions on the water surface more quickly than the water-floating granules of Comparative Example, and The uniformity of the pesticidal active ingredient was good.

[0109]

Test Example 3 Uniformity of Herbicidal Active Ingredients and Herbicidal Effect in a Field with Contaminated Water Surface Rice was planted in a paddy field divided into 10 mx 10 m. After 7 days, the water surface was adjusted to a depth of 5 cm, and 100 g of the wood powder per section was uniformly treated with a midget duster (small sprayer, manufactured by Arimitsu Kogyo Co., Ltd.) to cover the water surface with the wood powder. The sachets for paddy field throwing of Example 20 and Comparative Example 5 were put into the center of each section, and the manner in which the granules spread on the water surface was observed. 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, paddy water was collected from the dropping point 3 and points 1, 2, 4 and 5 which were 1 m away from each corner, and the concentration of the pesticide active ingredient in the water was analyzed. I asked. Table 6 shows the results.

[0110]

[Table 5] Uniformity of pesticide active ingredients in fields with dirty water surface ── Test paddy throwing Wood flour dislodged Pesticide active ingredient After 24 hours, packaging and area for pleating (m ² ) Concentration measurement position Lacrol concentration (ppm) ────────── ────────────────────────── Example 20 7 starfish, 201 (upwind) 1.03 2 1.45 3 (center) 2.80 4 1.28 5 (leeward) 1.85 Comparative Example 5 2 linear, 31 (upwind) 0.32 2 0.94 3 (center) 6.23 4 0.72 5 (leeward) 1.03 mm ──────────────────── Furthermore, 40 days after the paddy throwing sachet, the herbicidal effect on the seeds of the seedlings, which had been previously sown at the water sampling points 1 to 5 at the time of rice transplantation, was examined. Solid place, in Example 20-treated group, at any point, the occurrence of barnyardgrass was not observed. On the other hand, in the treated section of Comparative Example 5, slight residual grass was observed at the points 1 and 4 that hit the windward during the treatment.

As described above, the package for throwing rice in the paddy field according to the twentieth embodiment of the present invention has a good spread of active agricultural chemicals in the paddy field in a field where the water surface is dirty, and one day after the treatment, almost the entire field Although the herbicidal effect spread evenly and the herbicidal effect was good, the package for paddy throwing 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.

[0112]

[Test Example 4] Test on herbicidal effect in a field where algae developed Rice was planted in a paddy field having a size of 30a. Ten days after rice transplanting, it was confirmed that algae had been generated in about one-third of the paddy field area, and as shown in FIG.
0 g each of the water mouth treatment method (the method of treating pesticides in which the granules are poured from the water mouth into the paddy field together with the irrigation water) and the frame treatment method (while walking along the long ridge on both sides, apply 750 g of the granules from the ridge approximately A method for treating pesticides to be transferred to a point of 50 cm and the paddy throwing package 50 g of Example 21 ×
The 30 packs were applied by a throwing treatment method (a method of treating pesticides in which sacks of 15 packs were thrown into a point about 7 m from the ridge while walking on the long ridge on both sides). Forty days after the application, the herbicidal effect was observed and surveyed at a position 3 m from the ridges of both long ridges and three rows at the center. In each of the test plots, almost no residual grass was observed, and an extremely high herbicidal effect was obtained.

[0113]

Industrial Applicability The pesticidal solid preparation of the present invention has a good water surface spreadability even in a paddy field with dirt on the water surface such as algae and floating plants, and has good uniformity of the pesticidal active ingredient in the paddy field.
For this reason, pesticide treatment after the rice grows up, 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 sachet for paddy field throwing of the present invention can be used under the above-mentioned disadvantageous conditions, and greatly contributes to labor saving in paddy field agriculture.

[Brief description of the drawings]

FIG. 1 is a measurement position of the concentration of an agricultural chemical active ingredient in Test Example 2.

FIG. 2 shows a measurement position of the concentration of an agricultural chemical active ingredient in Test Example 3.

FIG. 3 shows a method of treating pesticides in Test Example 4.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Masakazu Tomioka 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga Prefecture Sankyo Stock Company In-house F-term (reference) 4H011 AA01 AB02 AB03 AC01 BA01 BA05 BB09 BC03 BC18 BC19 BC20 DA02 DA04 DB08 DC01 DC05 DD02 DH02 DH03 DH25

Claims (16)

[Claims] 1. A C ₂ -C ₄ alkyl alcohol of C ₄ -C ₁₀ alkyl alcohol.
A solid water-floating agrochemical solid preparation comprising one or more water-surface spreaders composed of an alkylene oxide adduct and a derivative thereof and an agrochemical active ingredient. 2. The method of claim 1, wherein the water surface spreader is represented by the general formula (I): R ¹ O- (AO) _m- (BO) _n -H (I) wherein R ¹ is C ₄ -C It indicates ₁₀ alkyl group, a is of the formula -CH ₂ -CH ₂ - represents a group represented by, B has the formula -CH
₂ represents a group represented by —CH (CH ₃ ) —;
Represents 0, n represents 0 to 30, provided that m and n are not simultaneously 0, and when n is 0, m is 2 or more, and when both m and n are not 0, The order in which the m AO groups and the n BO groups are bonded is arbitrary. A compound represented by, the phosphoric acid esters is their sulfuric esters and C ₁ -C one or more kinds of water spreadability compound selected from the group consisting of _C10 alkyl ethers of salts and a compound thereof ester The solid formulation of the water-floating pesticide according to claim 1. 3. The water-floating agrochemical solid preparation according to claim 2, wherein R ¹ is a C ₆ -C ₁₀ alkyl group. 4. The solid formulation according to claim 2, wherein m is from 0 to 10 and n is from 0 to 10. 5. A compound wherein R ¹ is an ethylhexyl or isononyl group, m is from 0 to 10, and n is from 0 to 10, a phosphoric ester thereof, or an ammonium salt, a sodium salt or a potassium salt of the phosphoric ester. Is,
The solid formulation for pesticidal water-floating water according to claim 2. 6. The compound according to claim 2, 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. 3. The water-floating pesticidal solid preparation according to 1.). 7. The solid water-floating agrochemical solid preparation according to claim 1, further comprising a water-floating agent. 8. The water-floating agent may be expanded shirasu, expanded perlite, expanded pumice, fired vermiculite, cork, wood flour,
The water-suspendable pesticide solid preparation according to claim 7, which is a foamed synthetic resin, a synthetic resin powder, or a hollow plastic body. 9. The water-floating pesticide solid preparation having a particle size of 0.1
The water-floatable pesticide solid preparation according to any one of claims 1 to 8, which is a granule having a particle size of 5 to 5 mm. 10. A package for throwing in a paddy field, wherein the solid formulation for floating water surface according to any one of claims 1 to 9 is packaged in a water-soluble film. 11. The package for throwing rice in a paddy field according to claim 10, wherein the water-soluble film is a film or sheet made of polyvinyl alcohol or a derivative thereof. 12. A package having a weight of 10 to 20 per pack.
The package for throwing rice in a paddy field according to claim 10, which is 0 g. 13. The package for paddy field throwing according to any one of claims 10 to 12, wherein 1 to 30 pieces per 10a.
A method of controlling pests that occur in paddy fields by throwing them into paddy fields. 14. A method for controlling pests generated in a paddy field, comprising transferring the solid pesticidal water-floating solid preparation according to any one of claims 1 to 9 into a paddy field along a ridge. 15. The method of claim 1, wherein the solid formulation having a water-floating pesticide according to any one of claims 1 to 9 is treated in a water mouth when water is poured into a paddy field, and diffused into the paddy field together with irrigation water. How to get rid of pests. 16. The paddy-throwing sachet according to any one of claims 10 to 12 is applied to a water port when water is poured into a paddy field, and diffused into the paddy field together with irrigation water. A method of controlling pests.