TW200938085A - Method for manufacturing pesticide granules - Google Patents

Abstract

This invention provides a method for manufacturing pesticide granules, which includes: blending water with a mixture of pesticide active components, plastic hollow micro bodies, surfactant, adhesive and calcium carbonate (CaCO3); proceeding an extrusion-granulation process to make granules; and drying the granules. Furthermore, the content of water in the composition after blending is 15-25 wt%, and the content of CaCO3 in the mixture before blending with water is 30-90 wt%. The quantity of CaCO3 takes up a proportion of 15-30 parts by weight with respect to 1 part by weight of the plastic hollow micro-cells. The pesticide granules obtained by the manufacture method of this invention have excellent floatability on the water, the diffusion property and so on to be suitable for a use in rice field. This manufacture method can be used in the industry to efficiently make pesticide granules.

Description

200938085 IX. Description of the Invention: The present invention relates to a method for producing a pesticide granule and a method for producing the pesticide granule encapsulated in a water-soluble film. [Prior Art] It is known to apply a pesticide granule containing a flotation aid and a specific gravity less than 1 in a rice field and to float and spread the applied pesticide granule on the water surface, thereby spreading the active ingredient of the pesticide throughout the rice field. Methods. Further, a method of inserting a pesticide granule into a packaged agricultural chemical preparation obtained by encapsulating a granule of a pesticide in a water-soluble film or the like to spread the pesticidal active ingredient throughout the rice field is also known. Japanese Patent Publication No. 2006-257082 discloses a pesticide granule for rice fields containing a condensed heterocyclic sulfonium urea compound and praczolin nitrile as a pesticidal active ingredient, but due to production conditions or The ratio of the mixing ratio of each component may cause problems such as insufficient water surface floating property and diffusibility of the produced agrochemical granules, or the fact that the granules adhere to each other during production, and cannot be efficiently produced. SUMMARY OF THE INVENTION The present invention provides a method for producing a pesticide granule which is excellent in industrial efficiency and smoothly produces a surface floating agrochemical granule excellent in floatability and diffusibility on a water surface. The invention relates to a method for producing a pesticide granule, which comprises mixing a pesticidal active ingredient, a plastic micro hollow body, a surfactant, a binder and a carbonated mixture with water, extruding and granulating, and drying and granulating. And 136,839.doc 200938085 Further, by adjusting the amount of water and calcium carbonate to a specific range, it is possible to industrially efficiently produce a surface floating agrochemical granule excellent in floatability and diffusibility on the water surface. . That is, the present invention is as follows. r A method for producing a pesticide granule, which comprises extrusion kneading a mixture comprising a pesticidal active ingredient, a plastic micro hollow body, a surfactant, a binder, and a calcium carbonate, and drying and granulating And the content of water in the composition obtained after the kneading is 15 to 25% by weight, and the content of the carbonic acid dance in the mixture with water is 3 〇 to 9 〇 by weight, and the amount of calcium carbonate is relatively It is a ratio of 15 to 3 parts by weight based on the weight of the plastic micro hollow body i. 2. The method for producing a pesticide granule according to the above 1, wherein the method of drying the granules in the granules of the granules is 0"" weight 0 / 〇. 3. The granules of the pesticides according to the above 1 or 2 The method for producing a pesticide granule according to any one of the above items 1 to 3, wherein the binder is carboxymethylcellulose sodium. a method for producing a pesticide granule, which comprises mixing a mixture of a pesticide active ingredient, a plastic micro hollow body, a surfactant, a binder, a carbonated fish and a bentonite with water, extruding and granulating, and drying the granulated product; Further, the content of water in the composition obtained after the kneading is 15 to 25% by weight, and the content of the carbonic acid in the mixture before mixing with water is 30 to 90% by weight, and the amount of carbonic acid is about a small amount relative to the plastic. The ratio of parts by weight is 15 to 3 parts by weight. 136839.doc 200938085 6 · A method for producing a pesticide granule comprising a pesticide active ingredient, a plastic micro hollow body, a surfactant, a condensed phosphate, and a binder Agent and carbonic acid The mixture is kneaded with water, subjected to extrusion granulation, and the granulated product is dried; and the content of water in the composition obtained after the kneading is 15 to 25% by weight, and mixed with water, /tc< The content of the carbonic acid is about 3 to 90% by weight, and the amount of the carbonic acid is 15 to 30 parts by weight relative to 1 part by weight of the plastic micro hollow body. 7. The manufacturing method of the pesticide preparation, which is manufactured A packaged pesticide preparation in which a pesticide granule obtained by the production method according to any one of the above 1 to 6 is encapsulated in a water-soluble film. [Embodiment] The present invention relates to a method for producing a pesticide granule. The invention comprises a pesticide active ingredient, a plastic micro hollow body, a surfactant, a binder and calcium carbonate, and further comprises a mixture of bentonite and/or condensed phosphate mixed with water ("mixing step") for extrusion granulation. ("granulation step"), and drying the granulated material ("drying step") The active ingredient of the agricultural chemical is not particularly limited, and various herbicides, plant growth regulators, killing agents, insecticidal agents which are previously known can be used. Further, the agrochemical active ingredient may be used singly or in combination of two or more kinds. Examples of the active ingredient compound of the herbicide include (4) continuous sacral gland ( Lfonylurea) herbicide, (b) urethane (3) plus (10) (4) herbicide (C) chloroacetanilide herbicide, (d) triazme herbicide, (4) guanamine Or urea (4) herbicide 136S39.doc 200938085 agent, (f) other herbicide active ingredient compound. Herbicides can be used alone or in combination of 2 or more. As an active ingredient of the continuous urea herbicide (a) Representative examples of the compound include compounds represented by the following formula (I): Ν < γ Q - S02NHC0NH~~^ \ (|)

Z

[wherein Q represents a condensed heterocyclic group represented by the following formula (Q1), (Q2), (Q3) or (Q4):

(wherein R1 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a lower alkyl group which may be substituted by a halogen atom, a lower alkoxy group which may be substituted by an i atom, a lower alkylthio group, a lower alkyl sulfinic group; a mercapto group, a lower alkylsulfonyl group, an amine group, a lower alkylamino group or a dilower alkylamino group; R2 represents a hydrogen atom, a halogen atom or a lower alkyl group which may be substituted by a halogen atom; and r3 represents hydrogen 136839.doc 200938085 Atom, an elemental atom, a cyano group, a nitro group, a lower alkyl group which may be substituted by a fang atom, a cycloalkyl group of 3 to 6 members which may be substituted by a halogen atom or a lower alkyl group, may be substituted by a crypto atom a lower alkenyl group, a lower alkynyl group which may be substituted by a fang atom, a lower alkoxy group which may be substituted by a _ atom, a lower alkylthio group, a lower alkyl group, a lower alkyl group, an amine group, Lower alkylamino or di-lower alkylamino); γ and z are the same or different and represent a lower alkyl group which may be substituted by a halogen atom, a lower alkoxy group which may be substituted by a ?I atom or a dentate atom] .

The so-called "lower" in the lower alkyl, lower dilute, lower alkoxy, lower disulfide, and the like in the formula (I) means that the hydrocarbon moiety is i or 2 to 6 carbon atoms (preferably One or two to four carbon atoms). Examples of the halogen atom include fluorine, gas, and bromine as the above, μ, (iv) W, and mortar. Examples of the "lower alkyl group" include a linear or branched alkyl group having a carbon number of 4, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a second group. Examples of the "lower alkoxy group" include a chain or a branched alkoxy group having a carbon number of 丨4, such as a methoxy group, an ethoxy group, a propoxy group or a different group. Propyloxy, tert-butoxy and the like. Examples of the "lower alkenyl group" include a vinyl group, a propylene group, a 2-propenyl group, a propylene group, a 2-butenyl group, a tributyl group, a uranium group, and the like. Examples of the "lower alkynyl group" include an ethynyl group, a "propyne group 2: a fast group, a butyl group, a 2-buty group, and the like. Examples of the "3 to 6 member": cyclohexyl group include a cyclopropyl group. , cyclobutyl, cyclopentyl, cyclohexyl. The condensed heterocyclic group represented by the table can be enumerated as 'type _ no', saliva [l, 2-b]. (4) and 136839.doc 200938085 [1,2_a] pyridazole, represented by formula (Q3), pyridazole, represented by formula (Q3), pyrazole, represented by formula (Q4) And [丨, 5^]thiazolyl. As a R car, it is a porphyrinogen + or a lower-formity base which can be replaced by a functional atom. Among them, a gas atom is preferred. As r2, it is preferred. a chlorine atom, a halogen atom or a lower alkyl group which may be substituted by a halogen atom, more preferably a hydrogen atom. As R3, a chlorine atom, a dentate atom, a lower-grade calcination which can be substituted by a pixel atom is preferred. a cycloalkyl group of 3 to 6 members which may be substituted by a dentate atom or a lower alkyl group, a lower alkoxy group which may be substituted by a functional atom, a lower alkylthio group, a lower alkyl sulfinyl group, a lower alkyl sulfonate Base a lower alkylamino group or a di-lower alkylamino group, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 3 to 6 members. Preferred as γ and Z. It is a lower alkyl group which may be substituted by a fang atom or a lower alkoxy group which may be substituted by a halogen atom, and more preferably a methoxy group. Specific examples of the compound which is an active ingredient of the urethroline herbicide (a) , for example, bensulfuron-methyl, pyrazosulfuron-ethyl, azimsulfuron, and 醯% long (3111!'〇8111!>111*〇11), Examples of the compound of the active ingredient of the urethane-based herbicide (b) include di-allate, butabut, and wilford ( Tri-allate), phenmedipham, chlorbufam, asulam, phenisopham, benthiocarb, mollus, and grass Esprocarb), pyributicarb, dimepiperate, swep, etc. as acetophenone Specific compound of herbicide (c) active ingredient 136839.doc •10- 200938085 Examples, examples include: propachlor, metazachlor, alachlor, acetochlor, Metalachlor, butachlor, pretilachlor, thenylchlor, and the like. Specific examples of the compound of the active ingredient of the three-till herbicide (d) include simazine, atrazine, propazine, cyanazine, and grass killing. Specific examples of the compound which is an active ingredient of a guanamine-based or urea-based herbicide (e), such as ametryn, simetryn, dimethametryn, or prometryn, may be mentioned. : isoxaben, beta than diflufenican, diuron, linuron, fluometuron, difenoxuron, methyl kill Methyldymron, isoproturon, isouron, tebuthiuron, methabenzthiazuron, propanil, mefenacet, kepu (clomeprop), naproanilide, bromobutide, dymron, cumyluron, etobenzanid, and the like. Further, specific examples of the compound of the active ingredient of the other herbicide (f) include bentazone, tridiphane, indanofan, amitrol, and 0-seat. Carfentrazone-ethyl, sulfentrazone, fenchlorazole-ethyl, fentrazamide, isoxaflutole, 136839.doc 200938085

Clomazone, maleichydrazide, pyridate, chloridazon, norflurazon, pyrithiobac, bromacil, special Terbacil, metribuzin, oxaziclomefone, 环庚草谜((^1111161;1171丨11), oxalic acid (£1111111〇1(^&€: -卩611171), °5丨1>cinidon-ethyl,flumioxazin,fluthiacet-methyl,azafenidin,benfuresate ), oxadiazon, oxadiargyl, pentoxazone, cyhalofop-butyl, benzene_cafenstrole, scent (pyriminobac-methyl), bispyribac-sodium, pyrimisulfan, mouth bite pyribenzoxim, pyrifalid, indanofan, algae-killing ACN, quinoclamine), benzobicyclon, dithiopyr, dalapon, grass (chlorthiamid), three "penoxsulam, etc. As an active ingredient compound of a plant growth regulator, for example, hymexazol, paclobutrazol, and uniconazole- P), inabenfide, prohexadione-calcium, etc., as an active ingredient compound of a bactericide, for example, a compound of a multi-functional sulfur-based bactericide (captan) )), the active ingredient compound of organophosphorus bactericide (IBP, iprobenfos, EDDP, edifenphos, tolclofos-methyl 136839.doc -12- 200938085, etc.) , an active ingredient compound of a benzimidazole-based fungicide (benomyl, carbendazim, thiophanate-methyl, etc.), an active ingredient compound of a guanamine-based bactericide ( Mepronil, fluolanil, thifluzamide, furametpyr, tecloftalam, pencycuron, carpropamid, double gas A compound of an active ingredient of a mercaptoalanine-based fungicide (metalaxyl, etc.), an active ingredient of an azole-based fungicide (triflumizole, ipconazole) , pefurazoate, prochloraz, etc., methoxy acrylic acid bactericide active ingredient compounds (azoxystrobin, metominostrobin, etc.), antibiotics sterilization Active ingredient compounds (validamycin A, bloomipin-S, kasugamycin, polyoxins, etc.), active ingredients of other fungicides (phthalide, probenazole, isoprothiolane, tricyclazole, pyroquilon, ferimzone, benzopyrene acibenzolar-S-methyl), diclomezine, oxolinic acid, phenazine oxide, tetrachloroisophthalonitrile (TPN, tetraprodophthalonitrile), iprodione, etc. Wait. Examples of the active ingredient compound of the insecticide include organic phosphorus compounds (fenthion, fenitrothion, pirimiphos-methyl, diazinon, and quinalphos). ), 136839.doc -13- 200938085 isoxathion, pyridaphenthion, chlorpyrifos-methyl, vamidothion, malathion, phenthoate, large Dimethoate, disulfoton, monocrotophos, tetrachlorvinphos, chlorfenvinphos, propaphos, acephate, three gas pine (trichlorfon), a 'pinkone (EPN), pyraclofos, etc.), amino phthalic acid vinegar compounds (carbaryl, metolcarb, isoprocarb, butyl extinction) Bacteria (BPMC, fenobucarb), Andan e (propoxur), XMC (macbal), carbofuran, carbosulfan, benfuracarb, cough line (furathiocarb), nano Methomyl, thiodicarb, etc., synthetic pyrethroid compounds (cycloprothrin, etofenprox, etc.), neretoxin compounds (peedan) (cartap), benzultap, thiocyclam, etc., new compounds (imidacloprid, nitenpyram, acetamiprid, race) Thiamethoxam, thiacloprid, dinotefuran, clothianidin, etc., other active compounds of insecticides (buprofezin, tebufenozide) ), fipronil, ethiprole, etc.). Examples of the active ingredient compound of the acaricide include: hexythiazox, pyridaben, fenpyroximate, tebufenpyrad, chlorfenapyr, and killing. Worm 136839.doc -14- 200938085 (etoxazole), pyrimidifen and the like. Examples of the active ingredient compound of the nematicide agent include fosthiazate and the like. As the active ingredient of the agricultural chemical, an active ingredient compound of the herbicide is particularly preferable. Further, as a pesticidal active ingredient, 2 is usually used. If the solubility of the water under the armpit is 50 mg/ml or less, it is preferably in the range of 〇_00〇〇1 to 1 〇 mg/ml, and ^ particularly preferably in the range of 0·0001 to 1 mg/ml. The present invention is particularly effective for a solid pesticide active ingredient having a small water solubility, that is, a water-insoluble solid pesticide active ingredient. The amount of the active ingredient of the agricultural chemical is usually from 0.1 to 45% by weight in the mixture before mixing with water, preferably from 2 to 4% by weight, more preferably from 0.5 to 30% by weight. The plastic hollow hollow system used in the present invention is a small hollow outer casing made of plastic. The plastic micro-hollow system is used to impart ❷ buoyancy to the manufactured pesticide granules, so its apparent specific gravity is less than one. Examples of the material of the outer shell of the plastic micro hollow body include a vinylidene dioxide-acrylonitrile resin, an acrylonitrile resin, and an acrylic resin, and the particle diameter thereof is usually about 300 μm. For the plastic hollow body, it is usually used as a mixture with water as a specific example. 'Matsumoto Microsphere F-30E (Matsumoto Oil & Fat Pharmaceutical Co., Ltd., ι〇% by weight 20~120 μηη partial ethylene ethylene _ acrylonitrile resin micro hollow body and 9 〇 wt% water mixture), Matsum 〇t〇Micr〇sphere F 8〇E (Matsumoto Oil Pharmaceutical Co., Ltd. trade name, 丨 5 wt% The particle size is 20~150 μηη partial 136839.doc -15- 200938085 a mixture of a vinyl chloride-acrylonitrile resin micro hollow body and 85% by weight of water). As for the plastic micro hollow, the amount of use is usually 0. 5~5 by weight 4% of the mixture before mixing with water. Preferably, it is 5 to 3 wt%, more preferably about 1 to 3 wt%. If the amount of the plastic hollow micro-body to be used is too small, the floating property of the floating surface pesticide granule is likely to be insufficient, and if it is too large, the k-grain property is decreased and the amount of the pesticide active ingredient or the surfactant is relatively decreased. It is easy to cause a decrease in the efficacy or diffusivity of the pesticide. In the present invention, the type of the surfactant is not particularly limited. (4) A polyacid surfactant or a nonionic surfactant is used. The surfactants may be used singly or in combination of two or more. Examples of the polyacid-lowering surfactant include a salt of a copolymer of maleic acid and styrene acid, a salt of a copolymer of isobutyl or diisobutyl and a cis-butane diacid, and a salt. A salt of a copolymer of butenedioic acid and acrylic acid, or a polyacrylic acid. As the salt, for example, a metal salt such as a sodium salt or a salt-removing salt, an alkaline earth metal salt such as a calcium salt or a magnesium salt, or an ammonium salt can be mentioned. The nonionic surfactant may, for example, be a B-ethyl glycol-based interfacial agent. Specific examples thereof include polyoxyethylene acetylene glycol (trade name "Olfin ElOlO" (manufactured by Nissin Chemical Industry Co., Ltd.), etc., as a nonionic interface active component, and a calcined diol derivative may also be used. The alkanediol derivative is a compound generally represented by the following formula (Π). ' Η〇~ίΑΐ~0^·Χ1~(·〇—A2 士 Ο Ο») Here, X1 represents a divalent saturated hydrocarbon group having a carbon number of 6 to 14, ... and 8 2 respectively 136839.doc •16· 200938085 An alkyl group having a carbon number of 2 to 4, wherein m and η each represent an integer "wherein, the sum of m and η is any one of integers 1 to 7. When m is an integer of 2 or more, each A1 may be mutually The same or different, when η is an integer of 2 or more, each A2 may be the same or different from each other. Examples of the divalent saturated hydrocarbon group having a carbon number of 6 to 14 in X1 include 1,6-hexamethylene, 1,7-heptamethylene, and 1,8-octamethylene. , 1,9-nonamethylene, 1,10-decamethylene, 1,11-undecamethylene, 1,12-dodecamethylene, 1 , 13-tridecamethylene, 1,14-tetradecamethylene, a linear alkyl group having a carbon number of 6 to 14; 2-butyl-2-ethyl, 1 , 3-butyl-2-ethyltrimethylene, 2,4-diethyl-1,5-diethylpentamethylene, 2-methyl-1,8-exexin A branched chain extension group having a carbon number of 6 to 14 such as 2-methyloctamethylene. Particularly preferred as X1' is a branched extension base having a carbon number of 6 to 14. Further, a divalent saturated hydrocarbon group having a carbon number of 9 or 10 in X1' is also preferable. Examples of the stretching group having a carbon number of 2 to 4 in A1 and A2 include, for example, ethylene, pr〇pyiene, ι, 3_trimethylene, 1,4. - a straight-bonded or branched-chain extended alkyl group such as tetramethylene. The HLB (Hydrophile_Lipophile Balance) of the diol derivative represented by the formula (II) is preferably in the range of 6 to 14, more preferably in the range of 8 to 12. 136839.doc -17- 200938085 The decanediol derivative represented by the formula (η) can be produced by a known method, for example, by the following method: in the presence of sodium hydroxide or hydroxide The epoxy group having a carbon number of 2, such as epoxy epoxide, propylene bromide, and tetrahydrogen bite, is subjected to a sequential addition reaction with a diol having a carbon number of 6 to 14 (house diol or the like). As for the amount of surfactant used, it is passed in a mixture before mixing with water. It is preferably 〇 2 to 8 by weight. /. It is better to 〇 5~7 wt% or so. In the present invention, it is preferred to use a condensed phosphoric acid or a salt thereof to supplement the function of the surfactant as a dispersing agent. The condensed phosphoric acid refers to a linear polymer phosphoric acid formed by dehydration condensation of orthophosphoric acid.

Hn+2Pn〇3n+l (H=2, 3, 4·······) is expressed. Specifically, it means polyphosphoric acid such as diphosphoric acid (pyrophosphate), triphosphate (tripolyphosphoric acid), or tetraphosphoric acid. Further, examples of the salt of the condensed phosphoric acid include an alkali metal salt such as a sodium salt or a potassium salt, an alkaline earth metal salt such as a calcium salt or a magnesium salt, and an ammonium salt. As the condensed phosphoric acid or a salt thereof, an alkali metal tripolyphosphate such as sodium tripolyphosphate is particularly preferable. In the case of using condensed phosphoric acid or a salt thereof, it is usually used in an amount of 〇1 to 1% by weight, preferably 0.2 to 8% by weight, more preferably 〇.5, in a mixture before mixing with water. ～7% by weight 'and further preferably about 2 to 6% by weight. In the present invention, it is preferred to use a nonionic surfactant such as a polycarboxylic acid surfactant or a polyoxyethylene acetylene glycol, or a condensed phosphoric acid or a salt thereof in combination, and the total amount of use thereof is Mixture with water before mixing 136839.doc • 18 - 200938085 Zhongtong 10 is 1~30% by weight, preferably 3~20% by weight. /. More preferably, it is about 5 to 15% by weight. In the present invention, 'the binder may, for example, be a cellulose derivative such as a salt of a methine cellulose (a sodium salt or the like), a polyethylene glycol or a derivative thereof, sodium alginate, a celery gum, or a gum arabic. Such as water soluble polymers. Among these, it is fortunate that a cellulose derivative such as a sodium salt of carboxymethyl cellulose is used. The amount of the binder to be used is usually 0. U by weight 0% by weight of the mixture before mixing with water, preferably from 2 to 8 % by weight, more preferably from 1 to 8 % by weight. In the present invention, as for the amount of carbonated cerium, it is usually 30 to 90% by weight in the mixture before mixing with water. /〇, preferably 4〇~8〇% by weight, more preferably 50~75% by weight. Further, the amount of use of strontium carbonate is 15 to 30 times, preferably 2 to 3 times, the amount of the plastic hollow body to be used by weight. In the present invention, in addition to calcium carbonate, an extender may be further used. Examples of the extender include organic acids (citric acid, succinic acid, maleic acid, etc.) or salts thereof, urea, and sugars [lactose]. Lac water-soluble carrier such as (lactose), glucose, sucrose, etc., plant powder (such as soybean meal, tobacco powder, wheat flour, wood flour, etc.), mineral powder or inorganic powder (such as kaolin, bentonite, acid clay, clay, etc.) Class, talc, Shoushan stone, talc, diatomaceous earth, 'mica, Shixi soil, oxidized Ming, sulfur, activated carbon, gasification oblique, sulfuric acid recorded, carbon. Sodium hydrogen hydride, sodium sulfate, magnesium carbonate, etc.). Of these, particularly good is the expansion

Run the soil. V In the present invention, calcium carbonate and other extenders are generally used in a particle size of from 1 to 50 μm η, preferably from about 5 to 30 μπ1. As for the total amount of the extender, it is usually 136,839.doc •19·200938085 is 60 to 90% by weight of the mixture before mixing with water, preferably 65 to 85 weight 0/〇. In the present invention, 'other than the above components', other additives such as a preservative, a granulating agent, a disintegrating agent, a dispersing agent, an emulsifier, a solvent, a stabilizer, a coloring matter and the like may be added as needed. In the kneading step, a pesticidal active ingredient, a plastic micro hollow body, a surfactant, a binder, and calcium carbonate are contained, and a mixture of bentonite and/or condensed phosphate or the like may be further mixed with water. Here, the content of water in the composition obtained after the kneading is 15 to 25% by weight, and the content of calcium carbonate in the mixture before mixing with water is 3 to 9% by weight, and the amount of calcium carbonate is relative to the plastic. Tiny hollow body! The ratio of the parts by weight to 15 parts by weight to 3 parts by weight. Example 0 The content of water in the composition obtained after the kneading means the total amount of the water contained in each component and the water added in the kneading step. If the water content is small, the water repellency of the obtained granules of the pesticide is lowered, and the granulation property at the time of granulation is lowered. • On the other hand, if the water content is high, granulation is carried out at the time of granulation. The problem that the granules are attached to each other and it is difficult to obtain a uniform kneaded material. The kneading can be carried out using a conventional kneading device such as a stirring mixer, such as a vertical granulator (VERTICAL GRANULATOR). The components may be separately supplied to the kneading device, but it is preferred that the solid components are put into the kneading device in advance and mixed, and then the liquid component containing water is added thereto and kneaded. In the granulation step, the composition obtained in the kneading step is subjected to extrusion granulation. The extrusion granulation can be carried out using a conventional extrusion granulator such as an extrusion granulator equipped with a 136839.doc • 20· 200938085 2 mesh. The extruded kneaded material was cut into a suitable length. The screen mesh diameter is usually 〇 3 to 1 〇 mm, preferably about 5 5 5 mm. The grain length of the extruded granules is usually 〇5 to 1 〇坩坩, preferably about 2 to 5 mm. • Dry the granules in a dry step. The granules obtained by the above granulation step can be directly supplied to the drying step, and if necessary, the granules can be supplied to the drying step.干燥 Drying can be carried out using a common drying device such as a flow layer dryer. Drying can also be carried out under reduced pressure. The pesticide granules obtained after drying have a water content of usually from 1 to 2% by weight. After the drying step, it can be stepped through the sieve. The superiority of the surface floatability and diffusibility of the agrochemical granules thus obtained is used as a granule for pesticides in rice fields. As with ordinary pesticide preparations, the agricultural granules can be dispersed by ordinary methods such as hand-spreading and mechanical dispersion. It can also be distributed from Tian Hao and others.上述 The above pesticide granules can also be encapsulated in a water-soluble film to form a packaged agricultural music preparation. The term "water-soluble film" refers to a film that is dissolved or dispersed in water, for example, it can be listed as: "polyethylene glycol or its derivatives, polytriglucose, salt of methyl sulphate (10), etc.), water-soluble fiber A film or sheet formed by cutting organisms, polyethylene oxide or its derivatives. Among them, a film or sheet formed of polyethylene glycol or a derivative thereof is preferred. As a method of encapsulating a pesticide granule in a water-soluble film, a general method such as packaging a granule of a pesticide with a water-soluble hydrazine and filling a granule of a pesticide with a water-soluble film in a bag of 136839.doc - 21 · 200938085 can be used. Typically, 5 to 100 g of pesticide granules are packaged per package. The packaged pesticide preparation thus obtained is also suitable for use as a rice field agricultural medicine, and is particularly suitable for being input into rice fields from the field. [Examples] Hereinafter, the present invention will be described in more detail by way of examples. However, the invention is not limited to the examples. The materials used in the examples and comparative examples are as follows. (Pesticide active ingredient: refer to the following formula) Compound A: Essence (water solubility: 0.31 mg/ml (pH 7)) Compound B: 1-(2-gas-6-n-propylimidazo[l, 2-b]嗒耕-3-ylsulfonyl)-3-(4,6-dioxaxypyrimidin-2-yl)urea (water solubility 0.15 mg/ml (pH 7)) Compound C : benzophenone oxime (water solubility is 〇·〇〇 25 mg/ml (pH 7)) Compound D: benzobicyclo ketone (water solubility 0.000052 mg/ml (pH 7))

CI

N

N

SO2NHC0NH—^ N N /〇CH3 och3 (A)

N

CI

S N

N

O2nhconh—^ N /〇CH3 och3 (B) CH2CH2CH3 136839.doc -22- 200938085

/CON(CH2CH3)2 .(C)

(D) 界面 (surfactant) Polyoxyethylene acetylene glycol (trade name "Olfin E1010", manufactured by Nissin Chemical Industry Co., Ltd.) Polyacrylic acid sodium (trade name "Toxanon GR-31A", manufactured by Sanyo Chemical Industry Co., Ltd.) (Binder) Sodium carboxymethyl cellulose (trade name "Cellogen 7A", manufactured by Daiichi Kogyo Co., Ltd.) (plastic micro hollow body) Product name "Microsphere F-80E" (content: 15% by weight; /; moisture: 85 wt%), manufactured by Matsumoto Oil & Fats Co., Ltd. (extender) Calcium carbonate (trade name "Northeast Tankal (# 250)", manufactured by Toho Corporation) Boiler (trade name "Kunigel VI", manufactured by Kunimine Industries, Inc.) Others) 136839.doc •23· 200938085 Trimeric sodium hydride examples 1 to 5 and comparative examples 1 to 6 Using a vertical granulator (VG-25 type, manufactured by Powrex), the ratio shown in Table 1 below will be used. Pesticide active ingredient, tripolysodium silicate, binder, plastic micro hollow body and extender for 2 minutes, then add a mixture of water, Olfin E1010 and Toxon GR-31A in vertical granulator Mixed trainingThe granules obtained were granulated using a basket granulator (200 mm in diameter and 1.5 mm in diameter - manufactured by Fuji Paudal Co., Ltd.), and the granules were granulated by hand until the granule length became about 3 mm, and then , using a small dryer (manufactured by Fuji Industrial Co., Ltd.) to dry at 6 ° C. 'Use a sieve (2000 μηη, 850 μηη does not pass) to screen the obtained particles to obtain a pesticide pellet. Agent. In addition, the "weight ratio" in Table 1 (the weight of the calcium carbonate / the weight of the plastic micro hollow body), "the total amount of water added (weight / /)) is the water added by the mixing and the added The ratio of the total amount of water contained in the Microsphere F-80E to the total composition obtained after the kneading. Further, the % by weight of the carbonic acid series is the ratio of the content of barium carbonate in the mixture before mixing with water. Evaluation test The granulation property, the surface floatability, and the diffusibility of the granules of each of the agrochemical granules obtained in the examples and the comparative examples were evaluated. Further, the moisture content (% by weight) in the agrochemical granules was measured. The results are shown in Table 1. Further, in Comparative Example 5, since the granulated product which can be supplied to the test of the floating property of the water surface and the diffusibility of the granules was not obtained, the test of the surface floating property and the diffusibility of the granules was not carried out. 136839.doc 200938085 * (granulation property) The granulation property at the time of granulation was evaluated based on the following criteria. ◎: The granules formed into a cylindrical shape were quickly extruded from the sieve mesh, and the kneaded materials hardly adhered to each other. • 〇: The granules are successfully extruded from the screen and some of the granules are visible. The kneaded materials hardly adhered to each other. △: The granules cannot be smoothly extruded from the sieve, and most of the granules can be seen in the fragmentation section. The kneaded materials hardly adhered to each other. χ. The granules extruded from the sieve mesh are clearly attached to each other. (Water surface floating) Add water temperature of 2〇〇C2 3 degree hard water 3〇〇 claws in a 300 mL beaker [, into which the above-mentioned granules 〇·5 g are put, and the particles are counted in a few seconds. Number of. This test was carried out 5 times to calculate the total number of grains. (Particle diffusibility) 4 〇g of each granule obtained above was packaged with a water-soluble film (trade name "KwaMy Φ Vhiyl〇n Film VF_HP4000", manufactured by Kuraray Co., Ltd.) to obtain each packaged pesticide preparation (water-soluble package). ). The agricultural preparation was dropped at room temperature into a paddy field containing water having a water depth of 5 cm. The diffusibility of the particles was evaluated according to the following reference. : Within 3 minutes after the release of the water-soluble film from the water-soluble film, the particles are uniformly dispersed throughout the rice field.粒· The particles are uniformly dispersed throughout the rice field for more than 3 minutes from the start of release of the water-soluble film and less than 丨 hours. △: After the particles are released from the water-soluble film, the particles are bonded to each other, and it takes more than one hour to uniformly disperse the particles 136839.doc -25- 200938085 throughout the rice field. X: The adhesion of the particles to each other is remarkable, so the particles cannot be uniformly dispersed throughout the rice field. (Measurement of moisture content) The moisture content of each granule was measured by the following measurement apparatus and measurement conditions. Measurement equipment: Infrared moisture meter "FD-610" (Kett Electric Laboratory Co., Ltd.) • Measurement sample amount: about 5 g • Measurement conditions: drying loss at 60 ° C for 1 minute Act 136839.doc 26- 200938085

i< VO inch CN CO CN ΓΟ 72.5 72.5 o 34.5 18.7 〇>50 〇00 〇in inch<N ΓΟ CN ro 17.3 71.1 o 26.5 28.1 X NDND 00 inch inch CS Ο C*^ ¢^) CN m Ό 20.5 20.5 沄m 22.4 20.6 〇>50 X »^Η m inch<N Ο) cn m CS m CN m 56.6 56.6 o 00 ϊ-Η 23.7 < X CN 1-H (N inch (N 〇\ cn m CS vo CN 60.2 o 25.8 11.2 <>50 〇a\ ο inch CS ON CO m cs m <N 60.2 o to 25.8 12.7 〇>50 〇Example CO (N 17.3 VO ON v〇o 26.5 24.2 〇(Ν 〇00 d inch inch <N m (N VO 17.3 〇\ om 26.5 22.5 〇CS 〇rn cn inch<N m CN v〇17.3 σ\ v〇v〇o 26.5 20.6 〇〇〇<N inch CN a\ CO m CS m cs vo 60.2 o »n 25.8 〇〇〇od inch oi Os m uS CN m VO <NV〇60.2 o 25.8 17.6 〇 inch 〇Oj Compound A (parts by weight) Compound B (parts by weight) Compound c (parts by weight) Compound D (parts by weight) 01fmE1010 (parts by weight) Toxanon GR-31A (parts by weight) 〇611 (^6117 parts by weight) Microsphere F-80E (parts by weight) (parts by weight) (% by weight) Bentonite (parts by weight) Sodium tripolyphosphate (parts by weight) Weight ratio Total water addition (% by weight) Granulating surface floatability (Parts) Water content of the diffusing granules of the granules (weight) %) Calcium carbonate 136839.doc -27- 200938085 [Industrial Applicability] According to the production method of the present invention, the amount of water and calcium carbonate used can be adjusted to a specific range by the abdomen a ^ product. The surface floating agrochemical granules which are excellent in basic properties such as floatability and diffusibility on the water surface are produced efficiently and smoothly, and do not cause a problem in the granulation step or the like. In addition, it is possible to industrially produce a bag-like pesticide preparation for rice field treatment in which the agrochemical granules having excellent basic properties such as floatability and diffusibility on the water surface are contained in a water-soluble film. 136839.doc -28 ·

Claims (1)

200938085, X. Application for patents: - A method for the manufacture of a pesticide granule, which will contain a pesticide active ingredient, (4) a tiny hollow body, a surfactant, a binder, and a carbon black complex / water mixing Extrusion granulation, and drying the granules; and, the content of water in the composition after the kneading is 15 to 25 weights ❹ / ❹, and the content of calcium carbonate in the mixture mixed with water is 30 〜 90 % by weight, and the ratio of calcium carbonate to 15 parts by weight to 1 part by weight of the plastic micro hollow body. 2. The method for producing a pesticide granule according to the item, wherein the drying is carried out so that the content of water in the granule of the pesticide reaches 〇1 to 2% by weight. 3. The method for producing a pesticide granule according to claim 1 or 2, wherein the ten surfactant is a polyoxo acid surfactant. 4. The method for producing a pesticide granule according to claim 4, wherein the binder is sodium hyaluronate. A method for producing a pesticide granule, which comprises mixing a pesticidal active ingredient, a plastic micro hollow body, a surfactant, a binder, a mixture of carbonic acid and bentonite with water, extruding and granulating, and drying and granulating And, the content of water in the composition obtained after the kneading is wt%, the content of calcium carbonate in the mixture before mixing with water is 3〇~9〇% by weight, and the amount of calcium carbonate is relatively small relative to the plastic. The body weight fraction is a ratio of 15 to 30 parts by weight. 6. A method for producing a pesticide granule comprising: mixing a pesticidal active ingredient, a plastic micro hollow body, a surfactant, a condensed phosphonium salt, a binder, a mixture of a carbonated feed and a bentonite with water, and extruding Granules, and 136839.doc 200938085 Dry granules; and 'The content of water in the composition obtained after mixing is 15 to 25 weight. /. The content of calcium carbonate in the mixture before mixing with water is 30 to 90% by weight, and the amount of calcium carbonate is 15 to 30 parts by weight based on the weight of the plastic micro hollow body. 7. A method of producing a packaged pesticide preparation, which comprises encapsulating a pesticide granule obtained by the method of claim 于 in a water-soluble film. 136839.doc 200938085 VII. Designation of Representative Representatives (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the characteristics that best show the invention. Chemical formula: (none) 136839.doc