WO2000072674A1

WO2000072674A1 - High-concentration pesticide solid formulation

Info

Publication number: WO2000072674A1
Application number: PCT/JP2000/003376
Authority: WO
Inventors: Kinji Tanizawa; Masakazu Tomioka; Tsuyoshi Hirata; Hiroshi Sabi
Original assignee: Sankyo Company, Limited
Priority date: 1999-05-27
Filing date: 2000-05-26
Publication date: 2000-12-07

Abstract

A high-concentration pesticide solid formulation obtained by wet pulverizing a suspension containing a high-concentration pesticide effective ingredient, compounded with a polyalkylene glycol type nonionic surfactant having ethylene glycol and propylene glycol in a block-like form in a molecule thereof, and kneading and granulating the obtained suspension.

Description

Specification

High concentration pesticide solid preparation [Technical field]

The present invention provides a suspension (slurry) containing a high concentration of a pesticidal active ingredient by blending a polyalkylene glycol-type nonionic surfactant containing a block of ethylene dalicol and propylene dalicol in the molecule. High-concentration pesticide solid preparation obtained by wet-grinding and kneading and granulating the obtained suspension, a method for producing and using the same, and dispersing the high-concentration pesticide solid preparation into a water-soluble film or sheet. And a method for using the same.

[Background technology]

Conventionally, pesticides have been formulated in various dosage forms, for example, powders, wettable powders, emulsions and granules, and sprayed on the water surface, soil and plants for the convenience of use.

Conventionally, solid agricultural chemicals have been mainly crushed by dry milling using a dit mill or hammer mill, but recently, the number of extremely poorly soluble active ingredients has increased, so finer crushing is often required. It has come. However, conventional dry pulverization cannot cope with such fine pulverization. Therefore, recently, wet pulverization using an atritor, a bead mill, or the like has been increasingly used.

In recent years, there has been a tendency to avoid powdery dosage forms and dosage forms containing organic solvents, due to environmental concerns and growing awareness of farmers' health. Also, for example, the aging of farmers, the shift to part-time jobs, and the increased burden on women's labor have led to a need for labor-saving spraying of pesticides.

Based on these facts, the flowable agent for dusting without dispersion, the flowable agent for paddy fields that can be processed without using a machine, and the so-called 1 kg granule that increases the active ingredient content in granules to reduce the amount of spraying as a formulation In addition, dosage forms such as granular wettable powders with little dusting have come to be used frequently.

However, since 1 kg granules and hydratable granules have a higher content of active ingredients than conventional so-called 3 kg granules, especially when the active ingredients are pulverized by a wet method, they have a high concentration. If the suspension containing the active ingredient cannot be pulverized, there is a disadvantage that the amount of kneading water becomes too large at the time of granulation and granulation cannot be performed.

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. And paddy field pesticide preparations) (JP-A-3-173802) have been commercialized, and these are also called jumbo preparations or pack preparations.

Examples of such preparations for throwing into paddy fields include: (1) a large effervescent tablet directly thrown into a paddy field (Japanese Patent Laid-Open No. 6-170503); and (2) a small effervescent tablet is divided into water-soluble films. Wrapped in a paddy and thrown into a paddy field (Japanese Patent Laid-Open No. Hei 5-33991)

(3) A water-soluble carrier such as potassium chloride is granulated together with a water-soluble film-forming polymer, and the pesticidal active ingredient is contained in the granulated water-soluble film. (Japanese Unexamined Patent Publication No. Hei 5-782807), ④Agrochemical solid preparation prepared to float and spread on the water surface is packaged in a water-soluble film and thrown into a paddy field (JP-A-6-336) (Patent Document 4; Japanese Patent Application Laid-Open No. 5-339103), and an oil preparation having water surface spreading property is packed in a water-soluble container and thrown into a paddy field.

The primary purpose of these agricultural chemicals for throwing in paddy fields is to save energy and energy.To achieve this, it is necessary to reduce the amount of the product and the number of thrown products per unit area as much as possible. is necessary. Also, in particular,

The production of the pesticide for rice paddy throwing into paddy fields involves a process of packaging in small sachets, which tends to increase production costs.To reduce costs, make a high-content formulation and treat it in unit area. It is necessary to reduce the number of sachets and the number of sachets to be thrown. For this reason, it is necessary to wet-pulverize the suspension with the highest possible content, but the wet-grinding using a conventionally known surfactant has never been able to grind a satisfactory content. In other words, when a surfactant that has been conventionally used for wet grinding of a suspension is used as it is for wet grinding of a suspension containing a high concentration of a pesticidal active ingredient, the suspension agglomerates and becomes uneven. There is a concern that adverse effects may occur, such as the production rate of the suspension being reduced due to reduced suspension discharge rate from the mill, resulting in inconsistent quality of the slurry or the inability to pulverize due to the increased viscosity of the suspension. Was done. As a result, the quality of It has been desired to develop a method capable of wet-grinding the highest possible content of suspension without affecting it.

On the other hand, since these paddy rice field preparations are applied topically, unless the active ingredient is rapidly diffused from the point where they are thrown, harmful effects and uneven efficacy due to unevenness of the active ingredient are likely to occur. However, defects such as the effect on residual crops due to residual active ingredients are likely to occur. For this reason, it is necessary to formulate a paddy field pesticide formulation that floats on water, mix it with an appropriate water surface spreader, and spread the formulation from the drop point as soon as possible. However, water-spreading agents formulated for this purpose are easily affected by surfactants used for other purposes, and depending on the type of surfactant used, the spreadability of the drug product on the water surface deteriorates. Often, Therefore, it is necessary to select a surfactant which does not cause such spreading inhibition as much as possible.

DISCLOSURE OF THE INVENTION In view of the above-mentioned situation, the present inventors can wet-pulverize a pesticidal active ingredient at a concentration as high as possible in a suspended state, and particularly produce a pesticide preparation for throwing into paddy fields. In such a case, a thorough study was conducted in search of a pulverization aid that would not adversely affect the spreadability of the formulation on the water surface when thrown into a paddy field. As a result, by blending (preferably in a small amount) a polyalkylene glycol type nonionic surfactant containing ethylene glycol and propylene glycol in the form of a block in the molecule, a suspension containing a high concentration of the pesticide active ingredient can be obtained. Suspension liquid can be pulverized with low viscosity without gelling, and it does not adversely affect the water surface spreader contained in paddy rice throwing pesticide prepared by kneading and granulating the obtained pulverized suspension. The present inventors have found that the paddy field pesticide preparation exhibits good spreadability, and completed the present invention. The present invention

A suspension containing a high concentration of pesticidally active ingredients was obtained by blending a polyalkylene glycol-type nonionic surfactant containing a block of ethylene glycol and propylene dalicol in the molecule, and was obtained by wet grinding. By mixing and granulating the suspension High concentration pesticide solid preparation obtained,

A suspension containing a high concentration of pesticidally active ingredients is obtained by blending a polyalkylene glycol-type nonionic surfactant containing a block of ethylene dalicol and propylene dalicol in the molecule, and wet-pulverizing the suspension. A method for producing the high-concentration agricultural chemical solid preparation, which comprises kneading and granulating the suspension.

Paddy field pesticide formulation in which the high-concentration pesticide solid formulation is packaged in a water-soluble film or sheet,

A method of using the above-mentioned high-concentration pesticide solid formulation by transferring it from the ridge into a paddy field, a method of using the above-mentioned high-concentration pesticide solid formulation by pouring the irrigation water from the water mouth of the paddy field,

A method of using the above pesticide formulation for paddy field pouring and pouring with irrigation water from a mouth of the paddy field.

This is a use method in which the pesticide preparation for paddy field injection is injected from a ridge into a paddy field. In the present invention, "a polyalkylene dalicol-type nonionic surfactant containing ethylene dalicol and propylene glycol in a molecule in a molecule" includes, for example, higher alcohols, alkylphenols, fatty acids, higher aliphatic amines or Ethylene oxide (hereinafter referred to as E0) and propylene oxide (hereinafter referred to as P0) are added to the hydroxyl group, carboxyl group, amino group or amide group of fatty acid amides in the molecule. Thus, it is a polyalkylene dalicol type non-ionic surfactant containing these in a block form, and the hydroxyl group at the terminal to which E0 or P0 is added may be a hydroxyl group, or may be a suitable alcohol (such as The alcohol may be, for example, a linear or branched unsaturated or saturated aliphatic alcohol having 1 to 18 carbon atoms, Suitably, it is a straight-chain or branched-chain saturated aliphatic alcohol or oleyl alcohol having 6 to 12 carbon atoms, or may form an ether, or an organic acid (the organic acid is For example, it may be a linear or branched unsaturated or saturated fatty acid having 1 to 18 carbon atoms, preferably a linear or branched saturated fatty acid having 6 to 12 carbon atoms. Fatty acid or oleic acid) or an inorganic acid (the inorganic acid may be, for example, sulfuric acid or phosphoric acid). When forming an ether or ester, the terminal When there are a plurality of hydroxyl groups, each hydroxyl group may optionally form an ether bond or an ester bond. In addition, surfactants having a form in which E0 or P0 is added in a block-like manner at both ends with a polyalkylene glycol interposed therebetween, such as the following compounds (1) and (2), are also included in the molecule of the present invention. It is included in the polyalkylene glycol type nonionic surfactant containing ethylene glycol and propylene glycol in a block shape.

The polyalkylene glycol type nonionic surfactant 1 containing ethylene glycol and propylene glycol in a block in the molecule of the present invention preferably has the following formula:

CH ₃

R ¹ 0— (CH ₂ CH ₂ 0) _x1 — (CH ₂ CHO) _y1 ― (CH ₂ CH ₂ 0) _x2 — H ( ¹ ) '

CH,

R ¹ 0— (CHCH ₂ 0) _y1 — (CH ₂ CH ₂ 0) _x1 — (CH ₂ CHO) _y2 — H (2)

[Wherein, R ¹ represents a hydrogen atom, a higher alcohol residue, an alkyl phenol residue, an aryl fuynol residue, a fatty acid residue, a higher aliphatic amide residue or a fatty acid amide residue, and xl, x 2, X 3 and X 4 each independently represent an integer of 4 or more and 900 or less, yl, y 2, y 3 and y 4 each independently represent an integer of 16 or more and 130 or less (preferably Is an integer of 16 or more and 70 or less.) ]

(1) to (4).

In the present invention, the higher alcohol residue is a straight or branched chain having 4 to 18 carbon atoms. A branched alcohol residue, for example, a butyl alcohol residue, a hexyl alcohol residue, an ethylhexyl alcohol residue, a lauryl alcohol residue or an oleyl alcohol residue; It is an alcohol residue or a radical alcohol residue.

In the present invention, the alkylphenol residue is a phenol residue in which the same or different 1 to 3 linear or branched alkyl groups having 3 to 9 carbon atoms are bonded, for example, tributylphenol The residue may be a methylhexylphenol residue or a nonylphenol residue, and is preferably a noylphenol residue.

In the present invention, the arylphenol residue has 1 to 3 styryl groups bonded thereto, and 1 or 2 identical or different linear or branched alkyl groups having 1 to 4 carbon atoms bonded thereto. And may be, for example, a monostyrylphenol residue, a distyrylphenol residue, a tristyrylphenol residue or a distyrylcresol residue, preferably a tristyrylphenol residue. .

In the present invention, the fatty acid residue is a saturated or unsaturated fatty acid residue having 2 to 18 carbon atoms, for example, an acetic acid residue, a butyric acid residue, a lauric acid residue or an oleic acid residue. It is preferably a lauric acid residue.

In the present invention, the higher aliphatic amine residue is a saturated or unsaturated aliphatic amine residue having 4 to 18 carbon atoms, for example, hexylamine residue, ethylhexylamine residue, laurylamine residue. Or a oleylamine residue, preferably a lauramine or oleylamine residue.

In the present invention, the fatty acid amide residue is a saturated or unsaturated fatty acid amide residue having 4 to 18 carbon atoms, such as a butyric acid amide residue, a lauric acid amide residue, or oleic acid. It may be an amide residue, preferably a lauric acid amide residue.

Generally, the compounds (1) and (2) are those in which R ¹ is a hydrogen atom and are nonionic surfactants called a pluronic type, and the compounds (3) and (4) are called a tetronic type Nonionic surfactant. The relationship between the compounds (1) and (2) and the compounds (3) and (4) is such that the addition positions of E0 and P0 are reversed. These compounds are surfactants commonly used as auxiliaries for pesticides, have low toxicity, are less harmful, have less environmental impact, It has features such as being less affected by pH.

In the compounds (1) and (2), R ¹ is preferably a hydrogen atom.

The polyalkylene dalicol type nonionic surfactant containing ethylene dalicol and propylene dalicol in the molecule used in the present invention in a block shape is more preferably a polyalkylene glycol type nonionic surfactant. The molecular weight of the propylene dalicol portion (P0 added portion) is 2000 to 400, and the molecular weight of the ethylene dalicol portion (E0 added portion) with respect to the molecular weight of the propylene dalicol portion (P0 added portion) It is a polyalkylene glycol type nonionic surfactant having a ratio of 0.05 to 10 times, and even more preferably, the molecular weight of the propylene glycol portion of the polyalkylene glycol type nonionic surfactant is 25. The ratio of the molecular weight of the ethylene glycol moiety to the molecular weight of the propylene glycol moiety is 0.000 to 350.

The compound (1) is ¹ to 4 times, and R ¹ is a hydrogen atom. Particularly preferably, the molecular weight of the propylene dalicol moiety is 2700 to 3200, and the propylene glycol moiety is The ratio of the molecular weight of the ethylene glycol moiety to the molecular weight of

The compound (1) above, wherein R ¹ is a hydrogen atom.

In addition, the above molecular weight may represent not only the molecular weight of one molecule but also the average molecular weight of a plurality of molecules.

When the above-mentioned surfactant is added to a suspension containing the pesticidal active ingredient, the viscosity of the suspension does not increase even if the concentration of the pesticidal active ingredient is high, and a considerably high concentration suspension is used as described below. The suspension can be wet-pulverized, and the resulting suspension can be kneaded and granulated to produce a high content of granules. In addition, even when these surfactants are added to granules that float and spread on the water surface, they only have a small degree of hindrance to the action of the water surface spread agent used at the same time. It can be blended with paddy field throwing pesticide formulations that are packaged in water-soluble films.

The amount of the polyalkylene glycol-type nonionic surfactant containing ethylene dalicol and propylene dalicol in a block in the molecule used in the present invention varies depending on the combination of the pesticidal active ingredient and the surfactant. It is usually a small amount in the suspension to be milled, preferably 0.05 to 10% by mass, more preferably 0.01 to 3% by mass. /. And even more preferably 0.05 to 2% by mass, Preferably, 0.08 to 1 mass ⁰ /. And most preferably 0.1 to 0.5% by mass. Although the effect of the present invention can be obtained when the content is more than 10% by mass, it is not preferable in view of economy.

In the present invention, the above-mentioned nonionic surfactant is suspended in water together with the active ingredient of the pesticidal active ingredient, and further, if necessary, together with a grinding aid such as a dispersing agent or a wetting agent. It can be crushed in the same way.

The wet pulverizer used for such wet pulverization is generally a pulverizer used for wet pulverization of pesticides, for example, an attrition mill such as an attritor; a vertical mill such as an apex mill, a dyno mill, and a sand mill. It can be a horizontal bead mill; a hammer mill such as a wet atomizer; or a colloid mill, preferably an atrition mill or a bead mill.

The pesticidal active ingredient used in the present invention is generally used as a pesticide, and is not particularly limited as long as the drug substance is solid at room temperature. For example, ordinary pesticides, fungicides, herbicides, or plant regulators (Preferably, a fungicide or a herbicide, more preferably, a herbicide). Preferably, the stability to water is not extremely poor, and the solubility in water is high. No or melting point higher than 30 ° C.

The insecticides used in the present invention include, for example, trichlorfon, monocrotophos, acephate, canolevofuran, bensnorepap, buprofezin, methorne canoleb, propoxure, imidacloprid, acetamiprid, milbemectin, carbaryl, chlorfluaz Ron, dimethylvinphos or pyrimidifen, preferably buprofezin, imidacloprid, acetamiprid, milbemectin or pyrimidifen.

The fungicides used in the present invention include, for example, fusalide, iprodione, probenazole, isoprothiolane, tricyclazole, pyroquilon, carpropamide, oliburite, azoxystrobin and 7-fluoro-1,2,5. , 6-Tetrahydro-14H-pyrro [3.2.1-j] Quinoline-141-one and other blast agents; diclomedin, flutolanyl, mepronil, tifluzamide, flametopyr, 2- (4-phenol) Orophenyl) 1- (1H-1,2,4-1triazole-11-yl) -13-Trimethylsilylpropan-12-ol, peniculon, etc. Other fungicides such as clofphthalam, benomyl, metalaxyl, maneb, zineb, thiadiazine, thiuram, polycarbamate, capyatan, TPN, thiophanatemethyl, vinclozolin, fluazinam, PCNB, triazine, chlorothaloninole and carboxin, Preferably, it is fusalide, probenazole, isoprothiolane, carpropamide, olibulite, azoxystrobin, diclomedin, flutranil, tifluzamide, flametopyr or techmouth phthalam.

Examples of the herbicides used in the present invention include, for example, pyrazolate, benzofenap, birazoxifen, pyribuchicarp, bromobutide, mefenacet, bensnoreflon-methinole, chronolenitrofen, clometoxifene, dimelon, bifenoxazirazone, naprooxadizone, naprooxadizone, naprooxadizone Pirate, dichopyr, imazos noreflon, quinoclamin, MCPA, 2, 4-D, MCPB, kink mouth rack, bilazosulfuron monoethinole, pentoxazone, teni / claw, cumino ^^, sinosnoreflon, simetrin, Sihalofop-Butinore, Etobenzad, Cahuens Tronoré, Ethoxysnoreflon, Azimsnorefuron, Cyclosulfamuron, Indanofa , Pyriminobac-methinole, oxadiclomefon, 4- (2-chlorophenyl) 1,5-cyclohexyl-1,4,5-dihydro Ν-ethyl-5-oxo-1 1 Η-tetrazole-1-carboxyamide (Ν Β Α 06 1), benzobicyclone (SB 500), methyl N— [4- (benzothiazole-2-ylmethoxy) -12-methylphenyl] potassium and methyl N— [4- (benzo Oxazole-2_ylmethoxy) 1-2-methinolephenyl] paddy field herbicides such as phorbamate; or upland fields such as trifnorellarin, linuron, diperon, metrivudine, promethrin, simazine, pendimethalin, aioxur, arlacrol and bromasil. Or a non-cropland herbicide, preferably pyrazolate, benzofenap, virazoxyfe , Piribuchikalp, Bromobutide, Mefenacet, Bensnoleflon-Methinole, Daimron, Oxazianoreginore, Imazosnolefin, Birazosnolefron-etinole, Pentoxazone, Cafuenstronole, Inethoxysulfuron, Inethoxysulfuron Oxadiclomephone, NBA061 or Benzovisik.

The plant regulator used in the present invention includes, for example, Inabenfide, Parkou Butorazo Or Nikonazol.

In the present invention, “wet grinding of a high-concentration suspension” is a wet grinding of a suspension having a concentration of an agricultural chemical active ingredient that exceeds the limit of the concentration that can be ground using an ordinary surfactant.

The concentration of the pesticidal active ingredient in the suspension to be wet-pulverized varies depending on, for example, the physical properties of the pesticidal active ingredient and the presence and type of grinding aids such as dispersants and wetting agents. 0% by mass, the higher is more efficient. The wet pulverization of the present invention is 80 mass depending on the combination of the pesticidally active ingredient and the nonionic surfactant used. / ₀ than are possible grinding of high concentration suspensions, for example, it is possible to grind the suspension Nigoeki is 8 5 wt% pesticide active ingredient, in this case, of course agrochemical active ingredient is 3 0 Grinding of the suspension, which is 880% by weight, is also possible. The concentration of the pesticidal active ingredient in the suspension that can be wet-pulverized differs depending on the type of pesticidal active ingredient.For example, when pyrazolate is used as the pesticide active ingredient, the conventional method requires that the pesticide content be in the suspension. The content is at most 60 to 65%, the use of diclomedine is at most 50%, and the use of pyrimidiphene is at most 45%, whereas the wet-millable pesticide of the present invention is The maximum concentration of active ingredient in suspension is 85% for virazolate, 70% for diclomedine and 65% for pyrimidifen, as described below. In the present invention, it is necessary to select and use a dispersant used in wet pulverization that does not compete with other components. Examples of the dispersant used in the wet milling include lignin sulfonate, (alkyl) naphthalene sulfonate and its condensate, phenol sulfonate and its condensate, styrene sulfonate condensate, maleic acid and styrene Salts of condensates with 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, maleic anhydride and methyl vinyl ether Nonionic surfactants with common ethylene oxides, such as copolymer salts, alkyl benzene sulfonates, dialkyl resulfosuccinates, lauryl sulfate salts, polyoxyethylene alkylaryl ether sulfates Sulfuric acid ester, polyoxyethylene alkyl aryl ether phosphate ester Such phosphate esters of nonionic surfactants with conventional ethylene O wherein de, and these sulfates and phosphate esters with a suitable cation Anionic surfactants such as neutralized salts; or phosphates such as sodium tripolyphosphate, sodium hexametaphosphate, and in many cases, are preferably anionic surfactants. Surfactants used in these dispersants are often effective as wetting agents. Further, in the present invention, a suitable one of nonionic, cationic and amphoteric surfactants can be used as a dispersant during wet pulverization.

The mixing amount of the above-mentioned dispersant or the above-mentioned dispersant and the wetting agent is usually 0.01 to 30% by mass in the suspension at the time of wet pulverization, and preferably 0.03 to 30% by mass. The content is preferably from 10 to 10% by mass, more preferably from 0.1 to 5% by mass.

As will be described later, when the high-concentration pesticide solid preparation of the present invention is subjected to so-called frame spraying or sprinkling treatment, and when the pesticide formulation for paddy field injection of the present invention is spouted or cast, the pesticide preparation is locally dispersed in the paddy field. It is necessary to spread the granules on the water surface with the power of the water surface spreader to exert the effect on the entire paddy field.However, if a large amount of the above dispersant is used, the water surface The spreading agent and the above-mentioned dispersant may antagonize. Therefore, as the dispersant used in the present invention, it is necessary to select and use a surfactant that does not antagonize the water surface spreader and the like.

The high-concentration pesticidal solid preparation of the present invention has a force S that can add other auxiliaries and liquid active ingredients, etc., as needed, during wet pulverization of the pesticidal active ingredient. It is necessary to select and use components that do not antagonize.

The suspension obtained by wet-grinding the solid pesticidal active ingredient thus obtained is, for example, an appropriate bulking agent, binder, disintegrant / dispersant, wetting agent, granulation improver, stabilizer, efficacy enhancer, drug It is mixed with a harm reducing agent, a floating agent, a water surface spreader, and other dry-ground active pesticide active ingredients, and if necessary, kneaded by adding water. Wet granulation can be performed using a granulator. However, these extenders, binders, disintegration agents *, dispersants, wetting agents, granulation improvers, stabilizers, potency enhancers, safeners, suspending agents and other active ingredients of agricultural chemicals do not compete with each other. Other pesticide active ingredients that have been dry-ground must be selected for use. For other reasons, such as when the active pesticide is extremely unstable in water and cannot be wet-ground, it must be dry-ground. In this case, the dry pulverized product can be mixed with other auxiliaries and kneaded and granulated with the above suspension. The extender used in the present invention is not particularly limited as long as it is generally used as a carrier for agricultural chemicals. For example, fine particles of mineral substances such as clay, calcium carbonate, diatomaceous earth, amorphous silicon dioxide, talc and bentonite; Plant powders such as starch, wood flour, ogatazu, coffee bean powder, tub flour, cellulose powder, microcrystalline cellulose, rice husk powder, rice bran, bran and coconut husk powder; water-soluble water such as urea, potassium chloride, ammonium sulfate and borate Or a water-soluble saccharide such as sugar, lactose and glucose, and is preferably a mineral fine powder or a vegetable powder.

The amount of the extender used varies depending on the type and amount of the other auxiliaries, but is usually 0.1 to 80 mass in the high-concentration agricultural solid preparation. /. And preferably 1 to 50% by mass.

The high-concentration pesticide solid preparation of the present invention can contain a binder for imparting hardness to the preparation when the high-concentration pesticide solid preparation is prepared by granulating a powder material. The binder used depends on whether the high-concentration pesticide solid preparation should disintegrate in water or not, but if it is preferable to disintegrate, for example, dextrin having a relatively low molecular weight can be used. , Polyvinylpyrrolidone, salts of polyacrylic acid or salts of carboxymethylcellulose, polyvinyl alcohol, ligninsulfonic acid salts with relatively low molecular weight and low testability, water-soluble polymer substances such as gum arabic or bentonite Etc., preferably a low molecular weight dextrin, a low molecular weight carboxymethyl cellulose salt, a lignin sulfonic acid salt, or a bentonite, preferably a non-disintegrating one. Examples include starch; water-soluble starch, dextrin, pregelatinized starch, and various other starches. A conductor; or a relatively high molecular weight polyvinylpyrrolidone, a salt of polyacrylic acid, a salt of carboxymethylcellulose or polyvinyl alcohol, preferably a water-soluble starch, dextrin, pregelatinized starch or other starch derivative. is there.

The amount of the binder to be used varies depending on the composition of the formulation, the granulation method, the size of the granules, and the like, but it is usually 0.1 to 30% by mass in the high-concentration solid agricultural chemical formulation. Is 0.5 to 20% by mass.

The high-concentration agricultural chemical solid preparation of the present invention can contain a disintegrating / dispersing agent for disintegrating the particles in water and suspending / dispersing the active ingredient in water. Disintegration agent used Is often, preferably, an anionic surfactant. The disintegrating and dispersing agents used can be common, and these disintegrating and dispersing agents are often useful as wetting agents. The disintegrating and dispersing agents and wetting agents are not limited to these, and nonionic, cationic or zwitterionic surfactants may be suitable. In addition, starch, carboxymethylcellulose, carboxymethylated starch and their salts, crosslinked products of polybutylpyrrolidone, microcrystalline cellulose, superabsorbent resins and the like having a property of absorbing water and expanding can be used as a disintegrant. Can be used.

These disintegrating and dispersing agent, the amount of the disintegrant or wetting agent is usually a high concentration agrochemical solid formulation, 0. 0 1-3 0 weight ⁰ /. It is preferably from 0.3 to 20% by mass, and more preferably from 0.05 to 10% by mass.

In the present invention, a granulation enhancer can be used to improve the granulation of the high-concentration agricultural chemical solid preparation. The granulating agent used may be a surfactant generally used as a granulating agent in pesticide granules or a material having a viscosity that imparts plasticity to the composition. Nonionic surfactants such as aryl ethers, polyoxyethylene alkyl esters, and polyoxyethylene aryl aryl ethers; sodium salts of dialkyl sulfosuccinates, and sodium salts of alkyl benzene sulfonic acid Anionic surfactants; mineral fines such as bentonite; starch derivatives such as dextrins and arsenic starch; natural gums such as gum arabic; cellulose derivatives such as sodium salt of carboxymethylcellulose; And water-soluble, such as sodium salt of polyacrylic acid It can be a synthetic polymer, preferably an anionic surfactant or bentonite.

The amount of the granulation enhancer to be used varies depending on the type of the granulation enhancer and the kind and amount of other auxiliaries. % By mass, and preferably 0.05 to 20% by mass. /. And more preferably 0.1 to 10% by mass.

The high-concentration agricultural chemical solid preparation of the present invention can contain a stabilizer, if necessary, for stabilization of the pesticidal active ingredient or physical stability in the high-concentration agricultural chemical solid preparation. Stabilizers used include, for example, pH regulators, antioxidants, light stabilizers and solid acid There may be a body base activity remover.

The amount of the stabilizer to be used is usually 0.01 to 5% by mass, and preferably 0.01 to 2% by mass, in the high-concentration solid agricultural chemical formulation. /. It is.

The high-concentration agricultural chemical solid preparation of the present invention may contain an efficacy enhancer such as, for example, piperonyl butoxide, as necessary, in order to maximize the efficacy of the agricultural chemical active ingredient. In addition, the high-concentration agricultural chemical solid preparation of the present invention can contain a safener if necessary. These potency enhancers and safeners can be used by selecting appropriate ones according to the pesticidal active ingredient.

The compounding amount of the potency enhancer or safener used depends on the type and amount of the pesticidal active ingredient.The amount is usually 0.1 to 10 times the amount of the pesticidal active ingredient, and preferably 0 to 10 times. 5 to 5 times the amount.

The high-concentration pesticide solid preparation of the present invention may be used as it is or may be formed into a paddy throw-in preparation, and may be locally treated without uniformly treating the pesticide throughout the paddy field, for example, in a frame treatment, a spout treatment, and a throw-in treatment described below. In the case of chemical treatment, a water-floating agent can be included to spread the solid formulation on the surface of the water and spread the active agricultural chemical throughout the paddy field. The water-floating agent used is, for example, mineral substances such as foamed shirasu, foamed perlite, foamed pumice and calcined vermiculite; plant materials such as konolek, wood flour and cellulose; foamed synthetic resins such as styrofoam; Synthetic resin powder such as; plastic hollow body (for example, Matsumoto Microsphere F30E); synthetic resin granule; or a mixture thereof, preferably cork, wood powder, and foamed silica. , Foamed pumice, fired vermiculite, foamed perlite, foamed synthetic resin, synthetic resin powder or plastic hollow body.

The amount of the water-floating agent used depends on, for example, the type and formulation of the water-floating agent and the particle size of the solid product, but may be any amount sufficient to allow the high-concentration pesticide solid product to float on the water surface. , a high concentration agrochemical solid formulation, 0.0 1-9 0 wt% Deari, preferably, a 0.1 to 7 0 wt%, more preferably, 0.5 to 6 0 mass ⁰ It is. The high-concentration agricultural chemical solid preparation of the present invention can contain a water surface spreader to improve the spread of the high-concentration agricultural chemical solid preparation on the water surface. Examples of the water surface spreader used include (co) polymers of carboxylic acids such as acrylic acid and maleic acid, acrylic acid, and maleic acid. Polycarboxylic acid-type polysoaps such as sodium, potassium, ammonium and other polymer salts obtained by copolymerizing styrene snorenoic acid, vinyl groups, etc. with the above carboxylic acid; potassium sodium stearate Stones such as dialkyl sodium snolefosuccinate, sodium dodecylbenzenesulfonate, sodium laurinoleate, perfluoroalkylcarboxylate, α-olefinsulfonic acid salt, α-sulfofatty acid salt, oleyl Other anionic surfactants such as salts of methyl tauride; polyoxyethylene alkyl aryl ethers, polyoxyethylene aryl aryl ethers, polyoxyethylene alkynole esters, alkyl esters of sonolebitan Alkylene oxide like Nonionic surfactants of the type added with silicone; various nonionic surfactants such as silicone surfactants and acetylene surfactants; these nonionic surfactants are esters of phosphoric acid or sulfuric acid, and in some cases, Surfactants neutralizing them with a suitable solvent; surfactants containing a fluorine atom in the molecular structure; liquid paraffin, naphthenic and aromatic high-boiling solvents, low-viscosity polybutene, Mineral oils such as machine oils; silicone oils; various vegetable oils; resins such as rosin; camphor white oil; α-pinene; camphor; or naphthalene, preferably sodium dialkyl sulfosuccinate, Olefin sulfonic acid salt, α-sulfo fatty acid salt, oleyl methyl tauride salt, silicone surfactant, acetylene surfactant, molecular structure Surfactants containing fluorine atoms or liquid paraffin, naphthenic and aromatic high-boiling solvents.

Among these, acetylene-based surfactants, silicone-based surfactants, and surfactants containing a fluorine atom in the molecular structure are particularly good as water surface spreaders. When a general surfactant is used in combination, the water surface spreadability often decreases, and it is desirable that the amount of the surfactant be kept to a minimum. However, the polyalkylene dalycol type nonionic surfactants containing ethylene glycol and propylene glycol in the molecule of the present invention in a block form (particularly, pull-mouth nick-type and tetronic-type surfactants) are not limited to these water surface spreading. It has the characteristic that it has no adverse effect on the vehicle.

The amount of the water surface spreader used is, for example, the type and content of the pesticidal active ingredient, the type and content of the water surface spreader and the formulation and formulation of the other components, such as the type and amount. Usually, it is 0.01 to 10% by mass, and preferably 0.1 to 5% by mass in the high-concentration agricultural chemical solid preparation. /. And more preferably 0.2 to 3 mass. /. It is. The high-concentration agricultural chemical solid preparation of the present invention can be prepared by the following method.

The high-concentration agricultural chemical solid preparation of the present invention can be obtained by kneading and granulating a high-concentration suspension of an agricultural chemical active ingredient that has been wet-pulverized by the above-mentioned method together with other auxiliaries. The granulator used can be, for example, an extrusion granulator such as a side-pressing, pre-pressing or basket type, a mixing granulator, a tumbling granulator, a fluidized-bed granulator and a spray dryer. If foam contains shirasu or foamed perlite, pressurizing them strongly may collapse the balloon and reduce buoyancy.If cork is contained, pressurizing the foam will reduce buoyancy. Therefore, a granulator that does not require strong pressure or shearing force is preferred.

The obtained wet granules are subjected to, for example, drying, sizing, and sieving steps to obtain target granules.

In the case of the granulation method, if the granule obtained is too large, drying of the granules becomes difficult.Particularly, when the high-concentration pesticide solid preparation of the present invention is a water-floating granule, the granule is The surface of the water is susceptible to the effects of the wind.If the particles are hydratable, if the particles are too large, the dispersion of the active pesticide in water will be slow.If the particles are too fine, the workability for dispensing will deteriorate. It is usually from 0.1 to 5 mm, preferably from 0.3 to 3 mm, and more preferably from 0.5 to 2 mm, as it may cause dusting during use. . The shape of the particles is not particularly limited, and may be, for example, a columnar shape, a spherical shape, and an irregular shape.

The apparent specific gravity of the high-concentration pesticide solid preparation of the present invention is usually 0.000 when the high-concentration pesticide solid preparation is a water-floating granule in terms of ease of handling, productivity, and ease of floating on the water surface. It is from 0.5 to 0.50, preferably from 0.2 to 0.45, and more preferably from 0.25 to 0.40.

When a liquid pesticidal active ingredient, a liquid pesticidal active ingredient or a low-melting pesticidal active ingredient is used, the high-concentration pesticide solid preparation of the present invention may be dissolved in a solvent or an emulsifier if necessary to prepare a concentrated preservative. A mix can be prepared and absorbed into the granules obtained by the above method to produce the mixture. The concentrated premix can optionally contain, for example, a water surface spreader, a stabilizer, an emulsifier, a dispersant, a wetting agent, and a solvent. Also, The pesticidal active ingredient is absorbed together with other auxiliaries into a carrier having a high oil-absorbing property, such as amorphous synthetic silica, diatomaceous earth, calcium silicate, a highly oil-absorbing resin and a highly oil-absorbing dextrin, or If a solid solution is formed with a resin, chemical substance or other solid pesticide active ingredient that is compatible with the ingredient, and this is crushed, it can be handled in the same manner as a solid pesticide active ingredient. Further, the high-concentration pesticidal solid preparation of the present invention provides a solid pesticidal active ingredient when a solid pesticidal active ingredient and a liquid pesticidal active ingredient, a liquid pesticidal active ingredient, or a low-melting pesticidal active ingredient are used simultaneously. The ingredients and other pesticidal active ingredients are ground together to prepare a so-called suspension emulsion, which is mixed and kneaded with other raw materials in the same manner as the above-mentioned suspension of the solid raw material, and granulated. It is possible to manufacture.

When the high-concentration agricultural chemical solid preparation of the present invention is produced by an absorption method, the previously prepared granules are charged into the above-mentioned stirring mixer, and the liquid or liquefied agricultural chemical active ingredient or a concentrated premix thereof is mixed with stirring. In addition, a method of absorbing is common. The premix can optionally contain, for example, a water surface spreader, a solvent, an emulsifier, and a stabilizer.

The high-concentration agricultural chemical solid preparation of the present invention may contain a solvent, if necessary, to dilute the liquid drug substance or to make the low-melting drug substance liquid. The solvents used are soluble in the drug substance, do not affect the stability of the drug substance, have a high boiling point, low toxicity and low flammability, and include, for example, paraffinic, aromatic and High-boiling solvents such as naphthenes; fatty acids obtained from various animal and vegetable oils such as oleic acid, maleic acid, fumaric acid and coconut oil used as plasticizers; esters such as phthalic acid, adipic acid and phosphoric acid; And vegetable oils such as rapeseed oil; or animal oils such as whale oil and sardine oil. In general, many pesticides have specific gravity of 1 or more. In such a case, it is desirable to use a solvent having a specific gravity of less than 1 and a low viscosity in order to keep the emulsified particles in the water for as long as possible and to diffuse them widely in paddy fields. In this sense, the solvent used is preferably liquid paraffin or low molecular weight polybutene.

The amount of solvent used depends on the type and physical properties of the pesticidal active ingredient, but should be as small as possible as long as it does not affect the stability over time or physical properties of the solid preparation. For 1 part, the amount is 0.1 to 50 parts, preferably 0.2 to 10 parts. The high-concentration 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 selecting an emulsifier for an emulsion. Can be selected and used according to the type and physical properties. The emulsifier used is different from a usual emulsifier and does not artificially stir when a pesticidal solid preparation is used. Therefore, the emulsifier preferably has a self-emulsifying property as much as possible and performs fine emulsification.

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.

When the high-concentration pesticide solid preparation of the present invention is manufactured by the coating method, previously prepared grain nuclei are charged into a stirring mixer, and if necessary, a liquid binder is added to wet the surface of the grain nuclei. Thereafter, 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 nucleus with the pesticidal active ingredient. The stirring mixer used can be, for example, a Nauta mixer, a ribbon blender, a rotary blender or a V-type mixer, preferably a low-speed mixer with less crushing of particles.

When producing water-spreading granules by the coating method or the absorption method, the effect of the water-surface spreading agent is more effectively exerted when it is present in the outermost layer. Therefore, it is desirable to add the water surface spreader at the end after coating or absorbing the pesticidal active ingredient and other auxiliaries. As described above, when the high-concentration pesticide solid preparation of the present invention is manufactured using the granulation method, the coating method, and the absorption method, the necessary steps among the steps of granulation, coating, and absorption are performed at one time. It may be carried out in two or more stages as necessary.For example, a part of the active pesticide is kneaded and granulated to obtain a floating granule, and the remaining pesticide is effective. The water-spreading agent may be coated or absorbed on the surface of the buoyant granules prepared by the granulation method, and the coating method and the absorption method may be applied to the same formulation. You may. The high-concentration agricultural chemical solid preparation of the present invention can be used as follows. The high-concentration agricultural chemical solid preparation of the present invention can be, for example, a granule, a granular wettable powder or a fine granule, and is preferably a granule or a granular wettable powder.

When using the high-concentration pesticide solid formulation of the present invention as a paddy field pesticide, the high-concentration pesticide of the present invention When pesticide solid preparations are granules, they can be evenly sprayed into the paddy field from the ridge without using a machine or using a spraying machine, as in the case of general granules. In addition, the high-concentration agricultural chemical solid preparation of the present invention can be subjected to a transfer treatment (frame treatment) from a ridge to a paddy field, a pouring treatment along with an inflow of irrigation water from a water mouth portion of a paddy field (water mouth treatment), or an appropriate water solubility. Separate into films and throw the resulting packages into paddy fields from the ridge.

(Throwing treatment), it is possible to spray pesticides without uniform spraying and without using a spraying machine. Further, when the high-concentration pesticide solid preparation of the present invention is a water-dispersible granule, the water-dispersible granule is diluted with a small amount of water at the time of use to prepare a suspension. Similarly to the above, pesticides can be sprayed by, for example, uniform spraying in a paddy field, frame treatment, water mouth treatment, and air spraying using a helicopter or the like.

Even when the high-concentration pesticide solid preparation of the present invention is used as a pesticide other than for paddy fields, when the high-concentration pesticide solid preparation of the present invention is granules, the granules can be uniformly dispersed in the same manner as general granules. It can be used as a high-concentration small amount of sprayable granules for labor-saving spraying. When the high-concentration agricultural chemical solid preparation of the present invention is a water-dispersible granule, the water-dispersible granule is diluted with water at the time of use to prepare a suspension, and the suspension is prepared in the same manner as the flowable. For example, it is also possible to spray the pesticide by uniform spraying on soil or foliage and aerial spraying using a helicopter or the like.

When the high-concentration pesticide solid preparation of the present invention is used as a package of a preparation for injection treatment, the water-soluble film is a film that dissolves or disperses in water and has spreadability. The raw material of the film may be, for example, polyvinyl alcohol or a derivative thereof, a pullulan film or a polyethylene oxide or a derivative thereof, and is preferably spreadable water-soluble paper, and more preferably, a polyvinyl alcohol or a derivative thereof. Film or sheet (hereinafter abbreviated as PVA film).

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 and 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, the degree of polymerization of the raw material polyvinyl alcohol is too high or the saponification degree is low. If it is too high, it will be difficult to dissolve in cold water. The thickness of the water-soluble film depends on the strength of the film and the dissolution time, but is usually 20 to 80 m, preferably 30 to 50 m.

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 pack, preferably 20 to 100 g, more preferably 25 to 100 g. ~ 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. Throwing it into the water two to three meters away is sufficient.

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 exterior of the package for throwing into a paddy field is, for example, paper, resin, a bag or box or bottle made of metal, wood, etc., which is made by attaching aluminum foil or depositing aluminum foil or silica to these. Preferably, it is a bag made of paper, resin, or those obtained by laminating aluminum foil on these or by depositing aluminum or silica.

The water-floating pesticidal solid preparation of the present invention, when it is a granular wettable powder or granules for uniform application, or when it is not packaged in a water-soluble film, even when it is subjected to a frame treatment or a mouth opening treatment, the above-mentioned packaging is used. Package in the same bag, box or bottle as the package.

The solid water-floating pesticide solid formulation of the present invention is stable over time in terms of physical properties with respect to moisture absorption, and therefore does not require attention to moisture absorption as compared to formulations containing a foaming agent. However, the water-soluble film will break if exposed to water. It is desirable to use a finished exterior.

[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 mass.

(Test Example 1)

Pulverization experiment of pyrazolate slurry

According to the formulation shown in Table 1 below, a pyrazolate slurry was prepared by mixing the pyrazolate drug substance, Surfinol TGE, NE291Pg, pull mouth nick P103 and water. A lighter filled with 3/16 inch steel balls 17 kg MA I N S — X type

3 kg of the above slurry was added to a wool (manufactured by Mitsui Mining Co., Ltd.) and pulverized at 200 rpm for 1 hour. After the completion of pulverization, the slurry was discharged from the attritor, and the weight of the slurry that could be taken out by natural discharge was measured to determine the yield relative to the charged amount, which was defined as the discharge rate. In addition, the dispersion state of the obtained slurry is indicated by a symbol, Δ indicates that the slurry is completely dispersed, Δ indicates that some aggregate is observed, and X indicates that an aggregate is formed and is difficult to stir. The results are shown in Table 1. table 1

Formulation, viscosity and discharge rate of pyrazolate slurry Experiment Pyrazolé-Surfino-NE2 9 Pluronic 'Water Discharge rate Slurry No. ¹ ) Nore TGE ² ) 1 PG ³ ) P 1 0 3 4)

(%) Dispersion state

1 70. 0% 0.5% 0 0.4% 29.1% 98 〇

2 70. 0% 0.5% 0 0.8% 28.7% 96 〇

3 75.0% 0.5% 0 0.8% 23.7% 95 〇

4 80. 0% 0.5% 0 0.8% 18.7% 96 〇

5 85. 0% 0.5% 0 0.8% 13.7% 95 〇 (Comparison) 65.0% (low concentration) 0.δ% 0.4% 0 34.1% 97 〇

7 (comparison) 70.0% 0.5% 0.4% 0 29.1% 88 Δ

8 (Comparison) 70.0% 0.5% 0 0 84 △

9 (comparison) 75.0% 0.5% 0.4% 0 24.1% 86 Δ

10 (comparison) 80.0% 0.5% 0.4% 0 19.1% 85 X pyrazolate 93.2%, moisture 6%

²⁾ Nissin Chemical Co., Ltd., surfactant mixture

³⁾ 70% of sodium salt of getyl hexyl sulfosuccinate manufactured by Nippon Emulsifier Co., Ltd.

⁴⁾ BAS F, pull nick type surfactant, molecular weight of P0 part is 3100, molecular weight of E0 part is 1 850

The slurries containing 70-75% pyrazolate obtained in Experiment Nos. 1-5 incorporating the pull-mouth nick p103 were completely dispersed and had high emissions. In particular, in Experiment No. 5, the 85% high-concentration slurry could be ground. On the other hand, the slurry containing 70% of pyrazolate obtained in Experiment No. 8 from which the pull-mouth nick P 103 was removed had a low discharge rate, and as the number of milling batches increased, the quality of the slurry increased. It was not stable.

In addition, the slurry containing 70% or more of pyrazolate obtained in Experiment Nos. 7, 9 and 10 containing NE 291 PG instead of Pluronic P 103 showed a little or considerable coagulation, The rate was low and the quality of the slurry was not stable as the number of grinding batches increased. In addition, the slurry obtained from Experiment No. 10 was not sufficiently kneaded with the powder carrier during granulation, and white kamako was conspicuous in the kneaded product. It should be noted that the slurry containing NE291PG in place of Pluronic P103 and wet-milled to completely disperse and exhibit a high emission is the concentration containing at most 65% pyrazolate (Experiment No. 6). When the pyrazolate concentration was 70%, the dispersion state and discharge of the slurry were inferior (Experiment No. 7). (Test Example 2)

Crushing experiment of pyrazolate slurry

A mixture of pyrazolate drug substance (70.0%), Surfynol TGE (0.5%), surfactant (0.4%) selected from Table 2 below, and water (29.1%) is mixed with a virazolose slurry. And 3 kg of the above slurry was added to a vessel of an atritor MA1 NS-X type (manufactured by Mitsui Mining Co., Ltd.) filled with 17 kg of a 3/16 inch steel ball, and pulverized at 200 rpm for 1 hour. After pulverization, the slurry was discharged from the attritor, and the weight of the slurry that could be taken out by natural discharge was measured to determine the yield relative to the charged amount, which was defined as the discharge rate. The viscosity of the obtained slurry was measured with a B-type viscometer. Table 2 shows the results. Table 2

Viscosity and discharge rate of surfactant and pyrazolate slurry containing it. Surfactant

Viscosity Emission rate

No. Compound name E0 part molecule] P0 part molecular weight (mPa'S) (%)

(Pull nick type)

1 Pull mouth nick L35 950 950 60 90

2 Pull nicks 42 430 1200 53 92

3 epang 450 1200 1200 48 93

4 Pull mouth nick L63 850 1800 49 92

5 epang 710 220 2000 44 94

6 epang 720 500 2000 45 94

7 Epan 740 1333 2000 40 94

8 Epan 750 2000 2000 45 94

9 Epan 785 11 333 2000 52 93

10 Pull mouth nick P84 1900 2300 43 95 1 Pull mouth nick P85 2300 2300 46 95

Pull mouth nick 92 950 2700 42 96

Epan u 102 775 3100 47 96

Epang u 103 1330 3100 41 98

5 epang u l05 3100 3100 43 95

6 epang u 108 12 400 3100 56 94

7 Pull mouth nick 17R2 550 1600 50 92

8 Pull mouth nick 17R4 1050 1600 48 93

9 Pull mouth nick 25R2 800 2300 48 94

0 Pull mouth nick 31R1 350 2900 48 93

(Tetronic type)

1 Tetronic 701 400 3200 47 93

2 Tetronic 704 2300 3200 42 95

3 Tetronic 901 500 4200 49 93

4 Tetronic 904 2500 4200 59 94

5 Tetronic 908 20 800 4200 63 93

6 Tetronic 90R4 2840 4400 63 92

7 Tetronic 150R1 800 7200 51 92 8 No additive 260 84 Note) Pull mouth nick and Tetronic are trade names of BAS F

Evan is a trade name of Daiichi Kogyo Co., Ltd.

As is clear from Table 2, the viscosity of the slurry containing the surfactant of the present invention was lower than that of the slurry without addition, and the discharge rate was good.

(Example 1)

1-g P granules manufactured using a slurry obtained by wet-grinding with blended pull nicks P 1 Q 3 Calfin 600 (manufactured by Adachi Lime Industry Co., Ltd., calcium carbonate powder, 48.2 parts), bentonite powder (Takashun Toyoko, 22.0 parts), AMICOL No. 1 (manufactured by Nisseki Chemical Co., Ltd., dextrin, 3.0 parts) and cellogen 5A (sodium salt of carboxymethylcellulose, 0.5 part, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in an eder, and then the slurry described in Test Example 1 as Experiment No. 1 (29.0 parts) and Tokisanon GR31 A (5.0 parts) were added and kneaded, and the mixture was granulated using an extruder EXK1 (Fuji Baudal Co., 0.9 mm screen). . It was dried at 105 ° C. using a fluidized bed drier and sieved into 1.0 to 0.5 mm sections to prepare base grains. The obtained base granules (95.08 parts) were charged into a Nauta mixer, a pretilachlor base material (96.0%, 4.92 parts) was added, mixed, and absorbed by the base particles to obtain 1 kg of granules. . This granule contains 18% pyrazolate and 4.5% pretilachlor, and is a so-called 1kg granule applied to paddy fields with 1kg per 10a.

(Comparative Example 1)

1kg granules manufactured using slurry pulverized without blending P1Q3

In Example 1, an attempt was made to obtain a 1 kg granule in the same manner as in Example 1, except that the slurry used was changed to 31.2 parts of the slurry described in Test Example 1 as Experiment No. 6. However, when the slurry was added to the powder mixture and kneaded, the granules extruded from the screen adhered to each other to form large lumps, did not flow in the fluidized bed dryer, and produced satisfactory granules. I couldn't get it. This means that the amount of granules calculated from the amount of virazolate required per 10 a is larger than 1 kg, and that 1 kg of pyrazolate cannot be produced.

(Example 2)

Paddy field throw-in pesticide formulation manufactured using wet-milled slurry containing Pull Mouth Nick P 103

Cork powder (0.2-0.5 mm division, 13.36 parts), bentonite powder (6.0 parts), cellogen 5A (8.0 parts), Surfynol 104S (3.0 parts) And ta Mol PP (manufactured by BAS F, sodium salt of a condensate of phenol sulfonic acid, 3.0 parts) was mixed in a kneader, and then a slurry (84. 5 parts), Toxanone GR31A (5.0 parts) and kneading water (small amount) are added and kneaded, and 1.2 mm using Twin Dome Gran (Fuji Baudal Co., Ltd., extrusion granulator). And extruded through a screen. The obtained granules were dried using a fluidized-bed dryer at 70 ° C., and sized with 2 mm and 0.5 mm sieves to obtain granules. The resulting granules are water spreadability of floating granules in a _c-obtained granules Haiseron C one 200 containing 63% Birazoreto (Nichigo Film Co., Ltd., PVA film, thickness 40 m) Then, the desired amount of agricultural chemical for throwing into paddy fields was obtained. This formulation is a paddy field pesticide formulation that processes 10 packs per 10 a.

(Comparative Example 2)

Throw-in pesticide formulation for paddy field, which was manufactured using wet-milled slurry without blending with Pull-out Nick P 103

In Example 2, in order to obtain granules having a pyrazolate content of 63%, 104 parts of the slurry was required in place of the slurry described in Test Example 1 as Experiment No. 6 in Test Example 1, and the kneading water was required. The granulation was difficult due to too much, and therefore, the desired agricultural chemical for throwing in paddy fields could not be obtained.

The content of granules that could be obtained using this slurry was limited to 47.3%. In this case, to make the same amount of the active ingredient as in Example 2, it was necessary to treat 400 g of the granules per 10 a. Compared to the pesticide formulation for paddy field injection of Example 2 which has the same active ingredient in 300 g, the pesticide formulation for paddy field injection of this example is also economical in terms of raw material cost, packaging cost, fare, etc. It is also disadvantageous in terms of portability and labor.

(Example 3)

Granular wettable powder manufactured using a slurry obtained by wet-milling with the blend of Pull Mouth Nick P 103

Nipseal NA (Nippon Silica Co., Ltd., amorphous silica, 5.0 parts), Palllex NP (Nippon Paper Industries Co., Ltd., sodium lignin sulfonate, 10.0 parts), Test Example 1 was prepared by mixing Neogen Powder (made by Daiichi Kogyo Seiyaku Co., Ltd., sodium dodecylbenzenesulfonate, 2.0 parts) and dried potato starch (Matsuya Chemical Co., Ltd., 18.42 parts). Then, the slurry (79.53 parts) described as Experiment No. 5 and kneading water (small amount) were added and kneaded. Next, the mixture was granulated with a 0.7 mm screen using a basket type granulator (L-15 type, manufactured by Kikusui Seisakusho Co., Ltd.), and then dried in a blow dryer set at 70 ° C. The obtained granules were sieved with a lmm to 0.3 mm sieve to obtain a granular wettable powder containing 63% of virazolate. This drug can be used in the same manner as flowables, by diluting 300 g per 10a into a small amount of water.

(Comparative Example 3)

Granular wettable powder manufactured using a wet-milled slurry without blending p103

When the slurry used in Example 3 was changed to the slurry described in Experiment No. 6 in Test Example 1, the kneading water became too large, and a granular wettable powder having an active ingredient content of 52.5% at the maximum was used. However, it was not possible to obtain the desired granular wettable powder.

In order to obtain the same amount of active ingredient as in Example 3 using the water dispersible granules, it was necessary to treat 360 g of the granules per 10 a. Compared with 300 g of the granular wettable powder of Example 3 having the same active ingredient, the granular wettable powder of this example is disadvantageous in terms of economy and convenience in use.

(Example 4)

Granular hydration m manufactured using a slurry that is wet-ground with Evan u 103

Mongard API (99.0%, 70.7 parts), Demol EP (Kao Corporation, carboxylic acid polysoap, 1.5 parts), Hytenol 12 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene) Alkyl ether sulfate ester ammonium salt (0.15 parts), epan u103 (0.8 parts) and water (26.85 parts) were mixed and wet milled under the same conditions as in Test Example 1. A slurry containing 70% of diclomedine was obtained. Nipsi NA (10.0 parts), Kaolin (6.85 parts), Vanirex N (8.0 parts) and Neogen Powder (2.0 parts) are mixed in a speed box, and then further The obtained slurry (1000.0 parts) was added, mixed and granulated. After the obtained granules were dried in a blow dryer at 70 ° C., a 0.2 to 0.7 mm section was sieved to obtain a granular wettable powder containing 70% of diclomedin. This wettable powder in granular form can be diluted with a small amount of water and used as a flying agent for aerial application.

(Comparative Example 4)

Conjugate granulated wettable powder manufactured using wet-milled slurry without blending u103

In the wet pulverization of Example 4, the mixture except for Evan u103 was tried to be wet pulverized in the same manner as in Example 4, but the viscosity of the slurry containing 70% of diclomedine was increased, and pulverization was impossible. Therefore, the desired granular wettable powder could not be obtained. In order to wet-pulverize the mixture except for Evan u 103, it is necessary to reduce the amount of Monguard original material to 50.5 parts and increase the amount of water to 47.85 parts compared to Example 4. Therefore, the concentration of pulverizable medicinal medine was limited to 50%. Granulation was carried out in the same manner as in Example 4 using this 50% diclomedin slurry, whereby a granular wettable powder containing 35% diclomedine was obtained. Table 3 shows a composition comparison between Example 4 and Comparative Example 4. “One” in the table indicates that no component was added. Table 3

Composition of wettable powder in granules Ingredient Example Content in Example 4 Content in Comparative Example 4 Slurry Monguard original substance 70.7 parts 50.5 parts

(Dichromedin content in slurry) (70.0%) (50.0%)

Demol EP 1.5 parts 1.5 parts Hytenol 1 2 0.15 parts 0.1 5 parts Epan U 1 03 0.8 parts

Water 26.85 咅 ^ 47.85 咅 [5 In granular wettable powder The above slurry 1000.0 parts 70 0 parts

(Dichromedin content in wettable powder) (70 · 0%) (35 0%)

Nipseal N A 10.0 parts 100 parts Kaolin 6.85 parts 43 49 parts Nilex N 8.0 parts 80 parts Neogen powder 2.0 parts 20 parts

(Example 5)

Granulated hydrated pyrimidifen drug substance (99.5%, 65.33 咅, Epane u102 (1.0 parts), Newcol 291) prepared by using wet-milled slurry containing Evan u102 PG (manufactured by Nippon Emulsifier Co., Ltd., sodium salt of dialkyl sulfosuccinate, 0.8 part) and water (32.87 parts) are mixed, and Dynomill KDL type (600 ml, continuous vessel, 480 ml, 1 mm diameter) Filled with glass beads, wet-pulverized using a rotation speed of 3000 rpm and a supply speed of 200 m1Z) to obtain a slurry containing 65% of pyrimidifen.Nipsil NA (18.0 parts), Tamol PP (8.0 parts), neogen powder (2.0 parts), AMICOL No. 1 (3.0 parts) and kaolin (7.03 parts) were mixed in a liquid mixer, and then the resulting slurry was obtained. — Add (92.3 1 part), knead, and use extruder EXD 1 (0.7 mm screen) The mixture was dried in a fluidized bed drier (blast temperature 70 ° C) and sieved in a range of 0.2 to 0.8 mm to obtain a water dispersible granule containing 60% of pyrimidifen. The wettable powder can be diluted with water and used as an acaricide spray.

(Comparative Example 5)

Evan u-102 Condyles attempted to be manufactured using wet-ground slurry without blending Granular wettable powder

In the wet pulverization of Example 5, the mixture excluding Evan u102 was subjected to wet pulverization in the same manner as in Example 5, but the viscosity of the slurry containing 65% of pyrimidifen was increased, so that pulverization was impossible. Therefore, the desired granular wettable powder was not obtained.

In order to wet-pulverize the mixture except for epan u 102, it is necessary to reduce the amount of the pyrimidifune bulk material to 45.23 parts and increase the amount of water to 53.97 parts as compared with Example 5. Yes, millable pyrimidifen concentration was limited to 45%. Granulation was carried out in the same manner as in Example 5 using this 45% slurry of pyrimidifen, and a granular wettable powder containing 35% of pyrimidifen was obtained. Table 4 shows a composition comparison between Example 5 and Comparative Example 5. “One” in the table indicates that no component was added. Table 4

Composition of granulated wettable powder Ingredients Content in Example 5 Content in Comparative Example 5 Slurry Pyrimidifen drug substance 65.33 parts 45.23 parts

(Pyrimidiphene content in slurry) (65.0%) (45.0%)

Epan U 102 1.00 copies

Niuco Ile 29 I PG 0.80 parts 0.80 parts Water 32.87 parts 53.97 parts Slurry in granular wettable powder 92 31 parts 77 8 parts

(Pyrimidiphene content in wettable powder) (600%) (350%) Nipseal NA 180 parts 180 parts Tamonore PP 0 parts 80 parts Neogen powder 20 parts 20 parts AMICOL No. 1 30 parts 30 parts Power Olin 7 03 parts 33 1 9 parts [Industrial applicability]

According to the present invention, it has become possible to produce a solid preparation containing a high concentration of a solid agricultural chemical active ingredient finely pulverized by wet pulverization. As a result, it was possible to reduce the weight of pesticide formulations, and it was possible to save labor and costs in terms of production and transportation. In terms of distribution and use, it is easy to handle and greatly contributes to the development of agriculture.

Claims

The scope of the claims

1. A suspension containing a high concentration of pesticidally active ingredients by wet blending with a polyalkylene glycol-type nonionic surfactant containing ethylenedaricol and propylene glycol in blocks in the molecule. A high-concentration agricultural chemical solid preparation obtained by kneading and granulating the suspension obtained.

2. The polyalkylene glycol type non-ionic surfactant has the following formula

CH ₃

R ¹ 0— (CH ₂ CH ₂ 0) _x1 — (CH ₂ CHO) _y1 — (CH ₂ CH ₂ 0) _x2 — H (1)

CH ₃ CH ₃

R ¹ 0— (CHCH ₂ 0) _y1 (CH ₂ CH ₂ 0) _x1 — (CH ₂ CHO) _y2 — H (2)

[Wherein, R ¹ represents a hydrogen atom, a higher alcohol residue, an alkyl phenol residue, an aryl: phenol residue, a fatty acid residue, a higher aliphatic amide residue or a fatty acid amide residue, and xl , X2, x3 and x4 each independently represent an integer of 4 or more and 900 or less, and yl, y2, y3 and y4 each independently represent an integer of 16 or more and 130 or less. The high-concentration agricultural chemical solid preparation according to claim 1, which is one or more non-ionic surfactants selected from the group consisting of compounds (1) to (4) represented by the formula:

3. The high-concentration agricultural chemical solid preparation according to claim 2, wherein R ¹ is a hydrogen atom.

4. The polyalkylene glycol type nonionic surfactant has the following formula

CH ₃

HO— (CH ₂ CH ₂ 0) _x1 — (CH ₂ CHO) _y1 ― (CH ₂ CH ₂ 0) _x2 — H ( ¹ )

[Wherein, x 1 and x 2 each independently represent an integer of 4 or more and 900 or less, and y lttl represents an integer of 6 or more and 70 or less. ]

2. The high-concentration agricultural chemical solid preparation according to claim 1, which is a non-ionic surfactant comprising a compound represented by the formula:

5. The molecular weight of the propylene dalicol portion of the polyalkylene glycol-type nonionic surfactant is from 2000 to 400, and the ratio of the molecular weight of the ethylene glycol portion to the molecular weight of the propylene dalicol portion is 5. 5. The solid high-concentration pesticide formulation according to any one of claims 1 to 4, which is 0.05 to 10 times.

6. The molecular weight of the propylene glycol part of the polyalkylene dalicol type nonionic surfactant is 2500 to 350, and the ratio of the molecular weight of the ethylene glycol part to the molecular weight of the propylene dalicol part is 6. The high-concentration agricultural chemical solid preparation according to any one of claims 1 to 4, which is 0.1 to 4 times.

7. The molecular weight of the propylene glycol portion of the polyalkylene glycol-type nonionic surfactant is from 270 to 320, and the ratio of the molecular weight of the ethylene glycol portion to the molecular weight of the propylene dalicol portion is 0. The high-concentration solid agricultural chemical preparation according to any one of claims 1 to 4, which is 2 to 1-fold.

8. The high-concentration solid agricultural chemical formulation according to any one of claims 1 to 7, comprising a water-floating agent.

9. The water-floating agent is Konorek, wood flour, foamed shirasu, foamed pumice, fired vermiculite, foamed perlite, foamed synthetic resin, synthetic resin powder or plastic hollow body. 9. The high-concentration agricultural chemical solid preparation according to claim 8.

10. The high-concentration solid agricultural chemical formulation according to any one of claims 1 to 9, comprising a water surface spreader.

11. The high-concentration agricultural chemical solid preparation according to claim 10, wherein the water surface spreader is an acetylene-based surfactant, a silicon-based surfactant, or a fluorine-based surfactant.

12. A polyalkylene glycol-type nonionic surfactant containing ethylenedaricol and propylenedaricol in the form of a block in the molecule is blended, and a suspension containing a high concentration of the pesticidal active ingredient is wet-milled. 12. The method for producing a high-concentration agricultural chemical solid preparation according to any one of claims 1 to 11, wherein the obtained suspension is kneaded and granulated.

13. An agricultural chemical formulation for throwing in a paddy field, wherein the high-concentration agricultural chemical solid product according to any one of claims 1 to 11 is packaged in a water-soluble film or sheet.

14. A method for transferring the high-concentration solid agricultural chemical product according to any one of claims 1 to 11 from a ridge into a paddy field.

15. Use of the high-concentration agricultural chemical solid product according to any one of claims 1 to 11 by pouring the irrigation water into the paddy field along with the inflow of irrigation water.

16. A method of using the agricultural chemical formulation for paddy field injection according to claim 13 by pouring it together with irrigation water from a mouth of the paddy field.

17. A method for injecting the pesticide formulation for paddy field injection according to claim 13 into a paddy field from a ridge.