TW201340869A - Emulsifiable granule obtainable by mixing an pesticidal emulsion with solid dispersant and extruding the resulting paste - Google Patents

Abstract

The present invention relates to a method for preparing an emulsifiable granule comprising the steps of (a) emulsifying water with a solution of a pesticide in a water-insoluble solvent, (b) contacting the emulsion resulting from step (a) and a solid dispersant containing a water-soluble polycarboxylate and a water-soluble anionic surfactant, and (c) extruding the paste resulting from step (b). The invention further relates to emulsifiable granules containing a water-insoluble solvent, a pesticide, which is dissolved in the water-insoluble solvent, a water-soluble polycarboxylate, and a water-soluble anionic surfactant.

Description

Emulsified granules obtained by mixing a pesticide emulsion with a solid dispersant and extruding the resulting paste

The present invention relates to a process for preparing emulsified granules comprising the steps of: a) emulsifying a solution of water and a water-insoluble solvent containing a pesticide, b) allowing the emulsion produced in the step a) to be dissolved with a water-soluble polycarboxylate and water. The solid dispersant of the anionic surfactant is contacted, and c) the paste produced from step b) is extruded. The present invention further relates to an emulsified granule comprising: a water-insoluble solvent, a pesticide dissolved in the water-insoluble solvent, a water-soluble polycarboxylate, and a water-soluble anionic surfactant. It must be understood that the preferred embodiments of the invention mentioned below are preferably independent of one another or combined with each other.

The crop protection agent is formulated into a solid or liquid composition, usually in the form of a concentrate for disposal and transportation, which is diluted by the user with water prior to application. Liquid formulations in the form of emulsified concentrates contain a very high proportion of organic solvents (typically up to 80%) which are of increasing interest due to their environmental impact; emulsion concentrates have a higher water content but still contain Organic solvents. Suspension concentrates are another form of water-based liquid which is generally viscous, causing disposal problems and loss of active ingredient due to retention in the package. Solid formulations can also have disadvantages; in particular, more commonly, particles and powders can be difficult to measure, but more importantly, they can cause dust and cause an aspiration hazard to the formulator and the user. Tablets have not been widely used due to their generally slow dissolution. In addition, solid formulations have been found to generally have lower biological activity than liquid formulations. Moreover, due to the place of use The use of simple mixing techniques (usually in farmland), so that the tendency of the solid form to not be emulsified immediately can not only cause the undispersed formulation to clog the spray equipment, but also render the active ingredient insufficiently applied to the crop to be treated. Accordingly, there is a need in the industry for a fast-emulsified solid crop protection formulation that has superior handling properties and enhanced biological activity over conventional forms to meet environmental concerns and to provide farmers with efficient products for easy use in the field. The object of the present invention is to overcome the above problems.

Emulsified granules and methods for their preparation are known: WO 2006/029718 discloses the preparation of emulsified granules by granulating a pesticide-containing emulsion in a fluid bed dryer. WO 1997/39626 discloses the preparation of emulsified granules by spray drying a pesticide-containing emulsion. GB 2230700 discloses the preparation of emulsified granules by spray drying a pesticide-containing emulsion.

The object is solved by a method for preparing emulsified granules comprising the steps of: a) emulsifying a solution of water with a pesticide-insoluble water-insoluble solvent, b) bringing the emulsion produced from step a) with a water-soluble polycarboxylic acid The salt is contacted with a solid dispersant of a water-soluble anionic surfactant, and c) is extruded from the paste produced in step b).

This object is also solved by the following emulsified particles: a water-insoluble solvent, a pesticide dissolved in a water-insoluble solvent, a water-soluble polycarboxylate, and a water-soluble anionic surfactant.

The emulsified granules form an emulsion (e.g., an oil-in-water emulsion) when diluted with an excess (e.g., 10 times the amount) of water at 20 °C.

The particles may have an extrudate shape based on the extrusion process. In the case of a round hole in the extruder, the spaghetti-shaped extrudate can be cut into a cylindrical shape. In the case of a polygonal hole such as a triangle or a rectangle, the extrudate can be cut into a corresponding shape. The resulting agglomerates can be broken into shorter particles. Preferably, the resulting particles have a cylindrical shape with a length of 0.2 mm to 10 mm and a diameter of 0.2 mm to 10 mm. In another preferred implementation In the example, the particles produced have a shape having a length of 0.2 mm to 10 mm at the farthest point and a diameter of 0.2 mm to 10 mm at the widest diameter.

The solubility of the water insoluble solvent in water may be up to 20 g/l, preferably up to 4 g/l and in particular up to 1.5 g/l, each at 25 °C.

The water insoluble solvent may have a boiling point of at least 110 ° C, preferably at least 140 ° C and specifically at least 170 ° C.

The flash point of the water insoluble solvent can be at least 60 ° C, preferably at least 80 ° C and specifically at least 100 ° C.

A suitable example of a water-insoluble solvent is - NC ₄ -C ₁₂ -alkylpyrrolidone, preferably NC ₆ -C ₁₀ -alkylpyrrolidone, for example N-octylpyrrolidone; - N,N-dimethyl a C ₆ -C ₁₄ alkanoguanamine, preferably N,N-dimethyl C ₈ -C ₁₂ alkanoguanamine; - a C ₅ -C ₁₂ -alkyl lactate, preferably a C ₆ -C ₁₀ -alkane lactic acid a base ester such as 2-ethylhexyl lactate; - an aliphatic and/or aromatic hydrocarbon having a boiling point of at least 140 ° C, preferably an aromatic hydrocarbon having a boiling point of at least 180 ° C; - C ₁ -C ₁₂ alkylphenol, Preferred is a C ₂ -C ₁₀ alkyl phenol such as 2-(1-methylpropyl) phenol; a C ₄ -C ₂₂ alkyl benzoate or a C ₆ -C ₂₂ aryl benzoate, preferably benzene C ₆ -C ₁₂ aryl formate, such as benzyl benzoate; and - di-C ₄ -C ₂₂ alkyl phthalate, preferably di-C ₆ -C ₁₄ alkyl phthalate For example, diisononyl phthalate.

Mixtures of water insoluble solvents are also suitable.

The water-insoluble solvent may contain a small amount of a water-soluble solvent, for example up to 30% by weight, preferably up to 10% by weight and specifically up to 3% by weight. A water-soluble solvent is an organic solvent, which is in water The solubility in the medium may be at least 10 g/l, preferably at least 50 g/l and in particular at least 100 g/l.

The water-insoluble or water-soluble solvent may be selected from the following list of examples according to its solubility in water: mineral oil fractions of medium to high boiling point, such as kerosene, diesel; oils of vegetable or animal origin; aliphatic, cyclic and aromatic Hydrocarbons such as toluene, paraffin, tetrahydronaphthalene, alkylated naphthalene; alcohols such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones such as cyclohexanone; esters, for example Lactic acid ester, carbonate, fatty acid ester, γ-butyrolactone; fatty acid; phosphonate; amine; guanamine, such as N-methylpyrrolidone, fatty acid dimethyl decylamine; and mixtures thereof.

The solid dispersant contains a water-soluble polycarboxylate and a water-soluble anionic surfactant and, optionally, other solid adjuvants. The solid dispersant may be present in the form of a powder or dust. It is typically a solid at 25 ° C or a melting point of at least 30 ° C, preferably at least 50 ° C.

The water-soluble polycarboxylate is soluble in water, for example at least 50 g/l, preferably at least 100 g/l, each at 20 °C. The melting point of the water-soluble polycarboxylate may be higher than 30 ° C, preferably higher than 60 ° C and specifically higher than 100 ° C. A polycarboxylate-based polymer which may comprise a carboxylic acid group in the form of a free acid and/or a salt. More specifically, the polycarboxylate is a copolymer of an ethylenically unsaturated carboxylic acid and/or an acid anhydride.

Preferably, the water-soluble polycarboxylate is a copolymer of at least one ethylenically unsaturated carboxylic acid and/or anhydride and at least one ethylenically unsaturated nonionic monomer. More preferably, the polycarboxylate is an ethylenically unsaturated linear or branched aliphatic, cycloaliphatic or aromatic monocarboxylic or polycarboxylic acid or anhydride and an alpha-monoolefin having from 2 to 20 carbon atoms. Copolymer.

Suitable acid or anhydride monomers containing their lines 3-10 carbon atoms, for their preferred system having the formula ^{(R 1) (R 2)} C = C (R 3) COOH those, wherein R ^1, R ² And R ^{3 are the} same or different and independently represent a hydrogen atom, a hydrocarbyl group having 1 to 4 carbon atoms (preferably a methyl group), a -COOH functional group, a group -R-COOH, wherein R represents A hydrocarbyl residue of 1 to 4 carbon atoms, preferably an alkyl residue of 1 or 2 carbon atoms, most specifically a methylene group. Mixtures of such monomers are also suitable.

At least one of the groups R ¹ and R ² is preferably hydrogen. Specifically, the acid or anhydride monomer system selected from acrylic acid, methacrylic acid, crotonic acid (crotonic acid), maleic acid, fumaric acid, citraconic acid (citraconic acid) or itaconic acid (itaconic acid) or acid anhydride Among them, maleic acid and/or its anhydride are the best.

Suitable ethylenically unsaturated nonionic mono-system alpha-monoolefin monomers, such as ethylene, propylene, 1-butene, isobutylene, n- pentene, 2-methyl-1-butene, positive-1 -hexene, 2-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, diisobutylene (or 2,4,4-trimethyl-1- Pentene) and 2-methyl-3,3-dimethyl-1-pentene. Mixtures of such monomers are also suitable.

The molar ratio between the ethylenically unsaturated nonionic monomer and the acid or anhydride monomer may range from 20/80 to 80/20, preferably from 30/70 to 70/30 and specifically from 40/60 to 60/. Within the range of 40. The polycarboxylate may have a molecular weight of from 1 kDa to 40 kDa, preferably from 2 kDa to 20 kDa and specifically from 3 kDa to 14 kDa.

The water-soluble anionic surfactant is soluble in water, for example at least 50 g/l, preferably at least 100 g/l, each at 20 °C. The water-soluble anionic surfactant may have a melting point above 100 ° C, preferably above 150 ° C and specifically above 200 ° C. Suitable water-soluble anionic surfactants are sulfonates, sulfates, phosphates, alkali metal salts of ammonium carboxylates, alkaline earth metal salts or ammonium salts, and mixtures thereof. Examples of sulfonates are sulfonated phenol-formaldehyde condensation products, sulfonated cresol-formaldehyde condensation products, alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignosulfonates , sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, dodecylbenzenes and tridecyl a benzene sulfonate, a naphthalene and an alkylnaphthalene sulfonate, a sulfosuccinate or a sulfosuccinamide. Examples of sulphates are sulphates of fatty acids and oils, sulphates of ethoxylated alkyl phenols, sulphates of alcohols, sulphates of ethoxylated alcohols or sulphates of fatty acid esters. An example of a phosphate is a phosphate ester. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.

Preferred water-soluble anionic surfactants are alkali metal, alkaline earth or ammonium salts of sulfonates or sulfates, such as sulfonated and/or sulfated phenol-formaldehyde condensation products, sulfonated and/or sulfated An alkali metal salt of a phenol-formaldehyde condensation product (e.g., CAS 115535-44-9). Typically, the sulfate or sulfonate has a molecular weight of from 200 g/mol to 2000 g/mol, preferably from 250 g/mol to 1000 g/mol.

The term pesticide refers to at least one active substance selected from the group consisting of fungicides, insecticides, nematicides, herbicides, safeners and/or growth regulators. Preferred pesticides are fungicides, insecticides and herbicides. Mixtures of two or more pesticides in the above categories may also be used. Those skilled in the art are familiar with such pesticides, see, for example, the Pesticide Manual, 15th Edition (2009), The British Crop Protection Council, London. Examples of pesticides may be selected from the following list (Group A) to L) fungicides): A) Respiratory inhibitors - inhibitors of complex III at the Q _o site (eg strobilurin) ): azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fluorobacteria Ester (fenoxystrobin/flufenoxystrobin), fluoxastrobin, kresoxim-methyl, metominostrobin, oressastrobin, picoxystrobin, baikemin (pyracostrobin), pyramatetostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl] 3-methoxyethyl methacrylate and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylaminooxymethyl)-phenyl) -2-methoxyimino-N-methylacetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone ); - _i complex at the site Q Inhibitor of substance III: cyazofamid, amisulbrom, 2-methylpropionic acid [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy) 4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-di- oxy-1,5-dioxan-7-yl] ester 2-methylpropionic acid [(3S,6S,7R,8R)-8-benzyl-3-[[3-(ethyloxymethoxy)-4-methoxy-pyridine-2-carbonyl Amino]-6-methyl-4,9-di-oxy-1,5-dioxan-7-yl]ester, 2-methylpropionic acid [(3S,6S,7R,8R) )-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-di-oxyl -1,5-dioxacyclo-7-yl]ester, 2-methylpropionic acid [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3- Benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-di- oxy-1,5 -dioxacyclo-7-yl]ester; (3S,6S,7R,8R)-2-methylpropionic acid 3-[[(3-hydroxy-4-methoxy-2-pyridyl)carbonyl Inhibitor of amino]-6-methyl-4,9-di-oxy-8-(phenylmethyl)-1,5-dioxan-7-yl ester-complex II For example, carboxyguanamine): benodanil, bixafen, white cl (bo Scalid), carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, Isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam , thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N-[ 9-(Dichloromethylene)-1,2,3,4-tetrahydro-1,4-methylnaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H- Pyrazole-4-carboxamide, 3-(difluoromethyl)-1-methyl-N-(1,1,3 trimethylindan-4-yl)pyrazole-4-carboxamide , 3-(trifluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1,3-dimethyl --N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1,5-dimethyl-N- (1,1,3-Trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1,5-dimethyl-N-(1,1 , 3-trimethyldihydroindol-4-yl)pyrazole-4-carboxamide, 1,3,5-trimethyl-N-(1,1,3-trimethylindoline-4- Pyrazol-4-carboxamide;- other respiratory inhibitors (eg complex I, non-coupling agent): diflumetorim, (5,8-difluoroquinazolin-4-yl) -{2-[2-Fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl derivative: binapacryl , dinobuton, dinocap, fluazinam; ferimzone; organometallic compounds: fentin salts, such as triphenyltin acetate, triphenyl chloride Tin or triphenylhydroxytin; amytoctradin; and silthiofam; B) sterol biosynthesis inhibitor (SBI fungicide) - C14 demethylase inhibitor (DMI kill Fungicides: triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, right dc (diniconazole-M), epoxiconazole, fenbuconazole, fluquinconazole, flusilazole Flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole ), penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, Triadimenol, triticonazole, uniconazole, 1-[ rel -(2 S ;3 R )-3-(2-chlorophenyl)-2-(2,4-di Fluorophenyl)-oxiranylmethyl]-5-thiocyanato-1H-[1,2,4]triazole, 2-[ rel -(2 S ;3 R )-3-(2- Chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1,2,4]triazole-3-thiol; imidazole: thiophene Imazalil), pefurazoate, prochloraz, triflumizol; pyrimidine, pyridine and hexahydropyrazine: fenarimol, nuarimol, bifenofol ( Pyrifenox), triforine; - δ 14-reductase inhibitor: aldimorph, morphine (dodemor Ph), carbendazim acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine; 3-keto group reduction Inhibitor of the enzyme: fenhexamid; C) inhibitor of nucleic acid synthesis - phenylguanamine or guanylamino acid fungicide: benalaxyl, benalaxyl-M , kiralaxyl, metalaxyl, metalaxyl-M, mefenoxam, ofurace, oxadixyl; other : hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy) Pyrimidine-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidine-4-amine; D) cell division and cytoskeletal inhibitors - tubulin inhibitors, such as benzimidazole , thiophanate: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl; triazolopyrimidine: 5 -chloro-7-(4-methylhexahydropyridine-1- - 6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine - other cell division inhibitors: diethofencarb, thiazole Ethoboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone; E) amino acid and protein synthesis Inhibitors - methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil, mepanipyrim, pyrimethanil; - protein synthesis inhibitors: baminamycin Blasticidin-S), kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, Polyoxine, validamycin A; F) signal transduction inhibitors - MAP / histidine kinase inhibitors: fluoroimid, iprodione, chlorpheniramine (procymidone), vinclozolin, fenpiclonil, fludioxonil; - G protein inhibitor: quinoxyfen; G) lipid and membrane synthesis - phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane; - lipid peroxidation: dicloran, pentachloro Nitrobenzene (quintozene), tetrachloronitrobenzene (tecnazene), tolclofos-methyl, biphenyl, chloroneb, etridiazole; - phospholipid biosynthesis and cell wall deposition: Dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate And N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-butan-2-yl)carbamic acid-(4-fluorophenyl) ester;- affecting cell membrane permeability Compounds and fatty acids: propamocarb, propamocarb-hydrochlorid - fatty acid guanamine hydrolase inhibitor: 1-[4-[4-[5-(2,6-difluoro) Phenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-hexahydropyridyl]-2-[5-methyl-3-(trifluoromethyl)- 1H-pyrazol-1-yl]ethanone H) Multi-site inhibitors - Inorganic active substances: Bohr Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulphate, sulphur; - thio- and dithiocarbamate: ferbate, zinc-manganese ( Mancozeb), manne, manam, metiram, propineb, thiram, zineb, ziram ;- Organochlorine compounds (eg phthalimide, sulfonamide, chloronitrile): anilazine, chlorothalonil, captafol, captan , volcano (folpet), dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorophenol and its salts, phthalide, methyl valproate ( Tolylfluanid), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;- 胍 and others: 胍, 多果定(dodine), 多果Free base, biguanide salt, biguanide acetate, iminoctadine, gram-heat triacetate, gram-net oxime (alkylbenzene sulfonate), dithianon, 2,6- Dimethyl-1H,5H-[1,4]dithieno[dithiino][2,3 -c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone; I) cell wall synthesis inhibitor - glucan synthesis inhibitor: Jinggangmycin, Pleurotus ostreatus B; melanin synthesis inhibitor: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil; J) plant defense inducer - Acibenzolar-s-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phosphine Acid salt: fosetyl, fossil aluminum, phosphorous acid and its salts; K) unknown mode of action - bronopol, chinomethionat, cyflufenamid, gram Cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, wild swallow-methylsulfate, diphenylamine, penicillin ( Fenpyrazamine), flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, Faster (ox In-copper), proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propyl Benzopyran-4-one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-benzene Ethylamine, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl脒, N'-(4-(4-Fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methylformamidine, N '-(2-Methyl-5-trifluoromethyl-4-(3-trimethyldecyl-propoxy)-phenyl)-N-ethyl-N-methylformamidine, N'- (5-Difluoromethyl-2-methyl-4-(3-trimethyldecyl-propoxy)-phenyl)-N-ethyl-N-methylformamidine, 2-{1- [2-(5-Methyl-3-trifluoromethyl-pyrazol-1-yl)-ethinyl]-hexahydropyridin-4-yl}-thiazole-4-carboxylic acid methyl-(1,2 ,3,4-tetrahydro-naphthalen-1-yl)-decylamine, 2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-ethenyl ]-Hexahydropyridin-4-yl}-thiazole-4-carboxylic acid methyl-(R)-1,2,3,4-tetrahydro-naphthalen-1-yl-decylamine, 1-[4-[4 -[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-hexahydropyridinyl]- 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, methoxy-acetic acid 6-t-butyl-8-fluoro-2,3-di Methyl-quinolin-4-yl ester, N -methyl-2-{1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-ethenyl]- Hexahydropyridin-4-yl} -N -[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolylcarbamide, 3-[5-(4-methyl Phenyl)-2,3-dimethyl-isoxazodin-3-yl]-pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazole 3-yl]-pyridine (pyrisoxazole), N-(6-methoxy-pyridin-3-yl)cyclopropanecarboxylic acid decylamine, 5-chloro-1-(4,6-di Methoxy-pyrimidin-2-yl)-2-methyl-1H-benzimidazole, 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl) -isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide; L) antifungal biological control agent, plant bioactive agent: white powder parasite ( Ampelomyces quisqualis , for example from Intrachem Bio AQ 10 ^{® from} GmbH & Co. KG, Germany, Aspergillus flavus (for example, AFLAGUARD ^® from Syngenta, CH), Aureobasidium pullulans (for example, BOTECTOR ^® from bio-ferm GmbH, Germany) , short Bacillus (Bacillus pumilus, for example, registration number NRRL B-30087, from AgraQuest Company, USA and the SONATA ^® BALLAD ^® Plus), Bacillus subtilis (Bacillus subtilis, for example, isolate NRRL-Nr.B-21661, from AgraQuest Company, USA's RHAPSODY ^® , SERENADE ^® MAX and SERENADE ^® ASO), Bacillus subtilis FZB24 (eg TAEGRO ^® from Novozyme Biologicals, USA), Candida oleophila I-82 (eg from Ecogen, USA) ASPIRE ^® ), Candida saitoana ( eg , from Micro Flo, USA (BASF SE) and Arysta's BIOCURE ^® (in the form of a mixture with lysozyme) and BIOCOAT ^® ), polyglucosamine (Chitosan, for example From BotriZen Co., Ltd., NZ's ARMOUR-ZEN), Clonostachys rosea f. catenulata , also known as Gliocladium catenulatum , such as the isolate J1446 from Verdera, Finland: PRESTOP ^® ), Coniothyrium minitans ( such as CONTANS ^® from Prophyta, Germany), Cryphonectria parasitica (eg from CNIC) M, France's Endothia parasitica , Cryptococcus albidus (eg, YIELD PLUS ^® from Anchor Bio-Technologies, South Africa), Fusarium oxysporum ( eg from SIAPA, Italy) BIOFOX ^®, from Natural Plant Protection, France's FUSACLEAN ^®), United States and Australia type Metschnikowia (Metschnikowia fructicola, for example from Agrogreen, Israel's SHEMER ^®), (Microdochium dimerum twin micro-nodular bacteria, for example from Agrauxine, France's ANTIBOT ^® ), Phlebiopsis gigantea ( eg ROTSOP ^® from Verdera, Finland), Pseudozyma flocculosa (eg SPORODEX ^® from Plant Products Ltd., Canada), Pythium oligandrum DV74, for example, from Remeslo SSRO, Biopreparaty, Czech Rep. of POLYVERSUM ^®), large knotweed (Reynoutria sachlinensis, for example, from Marrone BioInnovations, USA's REGALIA ^®), yellow and blue like bacteria V117b (Talaromyces flavus V117b, for example from Prophyta, Germany's PROTUS ^® ), Trichoderma sp. SKT-1 ( Trichoderma asperellum SKT-1, for example from Kumiai Chemical Industry Co., Ltd., Japan's ECO-HOPE ^®), black and green Trichoderma LC52 (T.atroviride LC52, e.g. from Agrimm Technologies Limited, NZ the SENTINEL ^®), Trichoderma harzianum T- 22 ( T.harzianum T-22, for example, plant SHIELD ^® from Firma Bio Works, USA), Trichoderma harzianum TH 35 (eg from Mycontrol Ltd., ROOT PRO ^® from Israel), Trichoderma harzian T-39 (eg From Mycontrol Co., Ltd., Israel and Makhteshim Co., Ltd., Israel's TRICHODEX ^® and TRICHODERMA 2000 ^® ), T. harzianum and T. viride (eg TRICHOPEL from Agrimm Technologies Ltd., NZ), Trichoderma harzian ICC012 And Trichoderma viride ICC080 ( T.viride ) (eg REMEDIER ^® WP from Isagro Ricerca, Italy), T. polysporum and Trichoderma harzian (eg BINAB ^® from BINAB Bio-Innovation AB, Sweden) Trichoderma ( T. stromaticum ( eg from TRICOVAB ^® from CEPLAC, Brazil), Trichoderma GL-21 ( T.virens GL-21, eg soil GARD ^® from Certis LLC, USA), Trichoderma viride ( E.g Since Ecosense Labs. (India) Pvt. Ltd., Indien of TRIECO ^®, from T.Stanes & Co. Ltd., Indien of BIO-CURE ^® F), viride TV1 (eg from Agribiotec srl, Italy's green wood Mildew TV1), Ulocladium oudemansii HRU3 (eg BOTRY-ZEN ^® from Botry-Zen Ltd., NZ); M) growth regulator abscisic acid, amidochlor , ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat, choline chloride, cyproteril Amine (cyclanilide), daminozide, dikegulac, dimethipin, 2,6-lutidine, ethephon, flumetralin, Flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, bismuth maleate, Mefluidide, strong cotton (mepiquat, strong cotton chloride), naphthaleneacetic acid, N-6-benzyl adenine, bar , cyclohexanoic acid (calcium cyclate), propyl jasmonate (prohydrojasmon), thidiazuron, triapenthenol, tributyltrithiophosphate, 2,3,5-three -iodobenzoic acid, trinexapac-ethyl and monoclonal; N) herbicides - acetochlor: acetochlor, alachlor, butachlor, Dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, nectar Napropamide), naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor; - amino acid derivatives: bianafos, Glyphosate, glufosinate, sulfosate; - aryloxyphenoxypropionate: clodinafop, cyhalofop-butyl, cacao Fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalof Op), quizalofop-P-tefuryl;-bipyridyls: diquat, paraquat; -(thio)urethane:sulfaline (asulam) , butylate, carbeamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, and rice , orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate; - cyclohexanedione: butyl Butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim ;-Dinitroaniline: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; - Diphenyl ethers: acifluorfen, aclofenf, bifenox, diclofop, ethoxyfen, flufenazone (fome Safen), lactofen, oxyfluorfen; - hydroxybenzonitrile: bomoxynil, dichlobenil, ioxynil; - imidazolinone Class: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imimathapyr; - phenoxyacetic acid : Clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, A Chloropropionate; - pyrazines: chloridazone, flufenpyr-ethyl, flufenazone, norflurazone, pyridate; - Pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, poison Picloram, picolinafen, thiazopyr; - sulfonylureas: amidosulfuron, azimusulfuron, bensulfuron ), chlorsulfuron (c Hlorimuron-ethyl), chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, fluridine Flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, diether chloropyridin Metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, Pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron ), trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chloro-6-propylimidazo[1,2-b]哒Azin-3-yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea;-triazines: ametryn, grass removal (at Razine), cyanazine, dimethametryn, ethiozin, hexazinone, metaamitron, metribuzin, chlorpyrifos Prometryn, simazine, terbuthylazine, terbutryn, triaziflam; - urea: chlorotoluron, daimuron ), diuron, fluometuron, isoproturon, linuron, methabenzthiazuron, tebuthiuron; - other acetamidine lactide Enzyme inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, Flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz -propyl), pyribenzoxim, pyrifalid, pyriminobac-methyl, pyrimidine Lfan), pyrithiobac, pyroxasulfone, pyroxullam; - others: amicarbazone, aminotriazole, samarium phosphate Anilofos), beflubutamid, benazolin, bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclic Benzobicyclon, bicyclopyrone, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, azole Carfentrazone, cinidon-ethyl, chlorthal, cinmethylin, clomazone, cumyluron, ciprofloxacin Cyprosulfamide, dicamba, wild swallow, diflufenzopyr, Drechslera monoceras , endothal, ethofumesate, Etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pent Yl), flomioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, iso Isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinramac, mesotrione (mesotrione), methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, cyclopentazone ( Pentoxazone), pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazoolynate , quinocalamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, cyclosulfone (tembotrione), thiencarbazone, topramezone, (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-di-oxy-4) -trifluoromethyl-3,6- Hydrogen-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid Methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro- Phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic acid Base ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester; O) insecticide - Organic (thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, clofenac (chlorfenvinphos), dizizon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion , fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, ya Monocrotophos, methotrex ( Oxydemeton-methyl), paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, blessing Phosphon, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, tofusone (terbufos), triazophos, trichlorfon; - urethanes: alanycarb, aldicarb, bendiocarb, benfuracarb ), carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, metiocarb, methodyl ), oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; - pyrethroids: arylene (allethrin), bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin , alpha-cypermethrin, β-赛内宁, ζ-赛灭宁, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fen Fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, liningen (resmethrin), silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralmethrin, transfluthrin, propofol Profluthrin, dimefluthrin; - insect growth regulator: a) chitin synthesis inhibitor: benzammonium: chlorfluazuron, cyramazin , diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, Triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole , clefentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenile hormone mimics Juvenoids: pyriproxyfen, methoprene, fennox; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirulina Spirotetramat;- nicotinic receptor agonist/antagonist compound: clothianidin, dinotefuran, flupyradifurone, imidacloprid, 赛速安(thiamethoxam), nitenpyram, acetamiprid, thiacloprid, 1-2-chloro-thiazol-5-ylmethyl)-2-niminoimido-3, 5-Dimethyl-[1,3,5]triazine;- GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, Pyrafluprole, pyriprol, 5-amino-1-(2,6-dichloro-4-methyl-phenyl)-4-amine sulfinyl-1H-pyrazole -3-thioformic acid decylamine;- macrolide lactone Insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram; - mitochondrial electrons Mitochondrial electron transport inhibitor (METI) I acaricide: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim ;- METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon; - non-coupling agent: chlorfenapyr; - oxidative phosphorylation inhibitor: tin Cyhexatin, diafenthiuron, fenbutatin oxide, propargite;-peeling interfering compound: cryomazine;-mixed functional oxidase inhibitor: piperonyl Piperonyl butoxide; - sodium channel blocker: indoxacarb, metaflumizon; - other: benzimidazole (benclothiaz), bifenazate, petal (cartap ), flonicamid, pyridalyl, pyrym Ozine), sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyanpyyryramine (HGW86), cyenopyrafen, pyridinium Flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron and pyrifluquinazon.

In another preferred embodiment, the pesticide is selected from the group consisting of Pyripyropene pesticides of Formula I or Formula II.

The ratio of the ratio of the ratio of the compound of the formula (I) to WO 2009/081851 (example, compound 4) is in the category of the ratio of the derivative of the ratio. Billi Biluo A (Bibibilol pesticide of Formula II) can be illustrated, for example, in the Journal of Society of Synthetic Organic Chemistry, Japan (1998), Vol. 56, No. 6, 478-488 The method of page or WO 94/09417 is produced.

In another preferred embodiment, the pesticide is selected from any of the pesticides other than the pirimizone pesticides of Formula I and Formula II.

The pesticide is preferably insoluble in water. For example, the solubility of the pesticide in water at 20 ° C is at most 10 g/l, preferably at most 2 g/l, and in particular at most 0.5 g/l.

The pesticide is preferably soluble in a water insoluble solvent (for example N-octylpyrrolidone), for example at least 10 g/l, preferably at least 50 g/l and in particular at least 100 g/l, each at 25 ° C under.

The emulsified granules contain at least one pesticide which is usually dissolved in a water-insoluble solvent at 20 °C. A small amount of the pesticide may be present in solid form, for example, up to 40% by weight, preferably up to 10% by weight, and specifically up to 3% by weight, based on the total amount of the pesticide.

The emulsified granules may contain other pesticides which are insoluble in the water-insoluble solvent, but are stored in the granules, for example, in a solid state. Suitable other pesticides are, for example, at least 10 g/l, preferably at least 50 g/l of water-soluble pesticide at 20 °C.

The emulsified granules may comprise a formulation auxiliaries. Suitable formulation auxiliary is solid carrier or filler, surfactant, dispersant, emulsifier, wetting agent, adjuvant, solubilizer, penetration enhancer, protective colloid, adhesive, thickener, moisturizer, Repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreezes, antifoaming agents, colorants, tackifiers, foaming agents and adhesives.

Suitable solid carrier or filler fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; sugars, such as monosaccharides or disaccharides, monosaccharides or disaccharides, oligosaccharides; homopolymers of vinylpyrrolidone, A copolymer of vinylpyrrolidone comprising at least 80 mole % of vinyl pyrrolidone (based on the total amount of monomers in the copolymer), or a mixture thereof. The solid carrier can be a solid at 25 °C. Preferably, the solid carrier is water soluble, and its solubility in water at 20 ° C can be at least 3 wt%, preferably at least 7 wt%, and specifically at least 10 wt%.

In a preferred form, the emulsified particles comprise a polyvinylpyrrolidone, such as a homopolymer of vinylpyrrolidone, a copolymer of vinylpyrrolidone, comprising at least 80 mole % of vinylpyrrolidone (based on the copolymer) The total amount of monomers), or a mixture thereof. Suitable for polyvinylpyrrole The ketone (e.g., a homopolymer of vinylpyrrolidone) has a solubility in water of at least 3 wt%, preferably at least 7 wt%, and specifically at least 10 wt% at 20 °C.

In another preferred form, the solid carrier is a monosaccharide or a disaccharide, especially a monosaccharide such as lactose.

In another preferred form, the solid carrier is a monosaccharide or a homopolymer of a disaccharide or vinylpyrrolidone, or a mixture thereof. More preferred solid carriers are monosaccharides (e.g., lactose), homopolymers of vinylpyrrolidone, or mixtures thereof.

Suitable blowing agents are combinations of bicarbonate and organic acids, such as a combination of citric acid and potassium bicarbonate. Examples of the hydrogencarbonate include sodium hydrogencarbonate, potassium hydrogencarbonate, and ammonium hydrogencarbonate. Examples of the organic acid include citric acid, succinic acid, malic acid, lactic acid, tartaric acid, fumaric acid, and maleic acid. The organic acid is preferably used in an amount of from 0.5% by weight to 20% by weight and especially from 1% by weight to 10% by weight, based on the total weight. The organic acid may be used singly or as a mixture of two or more thereof. The hydrogencarbonate is preferably used in an amount of from 0.25 to 2 times the amount of the organic acid in terms of a molar ratio.

Suitable surfactants are surface-active compounds such as anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants; polyelectrolytes and mixtures thereof. These surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids or adjuvants. Examples of surfactants are listed in McCutcheon, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International or North American Edition).

In addition to the water-soluble anionic surfactant, other anionic surfactants may be added. Typically, other anionic surfactants are selected from anionic surfactants other than water soluble anionic surfactants. Suitable other anionic surfactants are the sulfonates, sulfates, phosphates, alkali metal salts of the carboxylates, alkaline earth metal or ammonium salts, and mixtures thereof. Examples of sulfonates are alkyl aryl sulfonates, diphenyl sulfonates, Α-olefin sulfonate, lignosulfonate, sulfonate of fatty acid and oil, sulfonate of ethoxylated alkylphenol, sulfonate of alkoxylated arylphenol, sulfonic acid of condensed naphthalene Salt, sulfonate of dodecylbenzene and tridecylbenzene, sulfonate of naphthalene and alkylnaphthalene, sulfosuccinate or sulfosuccinamide. Examples of sulphates are sulphates of fatty acids and oils, sulphates of ethoxylated alkyl phenols, sulphates of alcohols, sulphates of ethoxylated alcohols or sulphates of fatty acid esters. An example of a phosphate is a phosphate ester. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.

Suitable nonionic surfactants based alkoxylates, N- substituted acyl of a fatty acid, amine oxides, esters, sugar-based surfactants, polymeric surfactants and mixtures thereof. Examples of the alkoxylate are compounds having 1 to 50 equivalents of an alkoxy group such as an alcohol, an alkylphenol, an amine, a guanamine, an aryl phenol, a fatty acid or a fatty acid ester. Ethylene oxide and/or propylene oxide may be employed, preferably ethylene oxide for alkoxylation. Examples of N-substituted fatty acid guanamines are fatty acid glucosamine or fatty acid alkanolamines. Examples of esters are fatty acid esters, glycerides or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are vinyl alcohol or vinyl acetate.

Suitable cationic surfactants are quaternary ammonium surfactants (for example quaternary ammonium compounds having one or two hydrophobic groups) or long chain primary amine salts. Suitable amphoteric surfactants are alkyl betaines and imidazolines.

Suitable adjuvant systems inherently have compounds which negligible or even no pesticide activity and which improve the biological properties of Compound I against the target. Examples are surfactants, mineral or vegetable oils and other auxiliaries. Other examples are listed by Knowles, Adjuvants and others, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5.

Suitable thickeners are polysaccharides (eg xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylate thickeners and decanoates.

Suitable bactericidal agents are bronopol and isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazolinones.

Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable antifoaming agents are salts of polyoxyl, long chain alcohols and fatty acids.

The emulsified particles may contain at least 2%, preferably at least 4% by weight and in particular at least 7% by weight of a water-insoluble solvent. The emulsified particles may contain from 3 wt% to 60 wt%, preferably from 5 wt% to 50 wt% and specifically from 8 wt% to 40 wt% of a water-insoluble solvent, such as NC ₄ -C ₁₂ -alkylpyrrolidone, N,N-dimethyl C ₈ -C ₁₂ alkanoguanamine, C ₅ -C ₁₂ -alkyl lactate, aliphatic and/or aromatic hydrocarbons having a boiling point of at least 140 ° C, or mixtures thereof.

The emulsified granules may contain at least 1%, preferably at least 2.5 wt% and in particular at least 4 wt% of the pesticide. The emulsified particles may contain from 0.1 wt% to 35 wt%, preferably from 1 wt% to 25 wt% and specifically from 2.5 wt% to 17 wt% of a pesticide such as a water-insoluble pesticide.

The emulsified particles may contain at least 5%, preferably at least 12% by weight and in particular at least 20% by weight of a water-soluble polycarboxylate. The emulsified particles may contain from 10% to 80% by weight, preferably from 15% to 70% by weight and in particular from 22% to 60% by weight, of a water-soluble polycarboxylate such as an ethylenically unsaturated, linear or A copolymer of a branched aliphatic, cycloaliphatic or aromatic monocarboxylic or polycarboxylic acid or anhydride and an alpha-monoolefin having from 2 to 20 carbon atoms.

The emulsified particles may contain at least 0.5%, preferably at least 2% by weight and in particular at least 3% by weight of a water-soluble anionic surfactant. The emulsified particles may contain from 0.2 wt% to 50 wt%, preferably from 1 wt% to 30 wt% and specifically from 2 wt% to 15 wt% of a water-soluble anionic surfactant such as a sulfonate.

The emulsified particles may contain at least 0.5%, preferably at least 2% by weight and in particular at least 3% by weight of a water-soluble solid carrier. The emulsified granules may contain up to 65%, preferably up to 55% by weight and in particular up to 45% by weight of a water-soluble solid carrier. The emulsified particles may contain from 0 to 65 wt%, preferably from 1 wt% to 55 wt% and specifically from 3 wt% to 45 wt% of a water-soluble solid carrier, such as a monosaccharide or a disaccharide or a vinylpyrrolidone. Polymer or a mixture thereof.

Preferably, the emulsified particles may contain 5 wt% to 50 wt% water-insoluble solvent, 1 wt% to 25 wt% pesticide, 15 wt% to 70 wt% water-soluble polycarboxylate, 1 wt% to 30 wt% water-soluble anionic surface The active agent, and optionally a formulation adjuvant (e.g., a water soluble solid carrier), is added to 100 wt%.

More preferably, the emulsified particles may contain from 8 wt% to 40 wt% of a water-insoluble solvent, from 3 wt% to 20 wt% of the pesticide, from 20 wt% to 60 wt% of the water-soluble polycarboxylate, and from 2 wt% to 15 A wt% water-soluble anionic surfactant, and optionally a formulation adjuvant (e.g., a water-soluble solid carrier), supplemented to 100 wt%.

The weight ratio of the water-soluble polycarboxylate to the water-soluble anionic surfactant may range from 30:1 to 1:3, preferably from 20:1 to 1:1 and specifically from 15:1 to 2:1.

The weight ratio of the water-soluble polycarboxylate to the water-insoluble solvent may range from 15:1 to 1:2, preferably from 8:1 to 1:2 and specifically from 4:1 to 1:1.5.

The weight ratio of the sum of the water-soluble polycarboxylate to the water-soluble anionic surfactant to the water-insoluble solvent may be from 20:1 to 1:3, preferably from 8:1 to 1:2 and specifically from 5:1 to Within the range of 1.2:1.

The weight ratio of the water-soluble polycarboxylate, the water-soluble anionic surfactant and the water-soluble solid carrier to the water-insoluble solvent may be from 20:1 to 1:3, preferably from 10:1 to 1:1.5 and specific For the range of 7:1 to 1.1:1.

The method for preparing the emulsified granules may comprise the steps of: a) emulsifying a solution of water and a water-insoluble solvent containing a pesticide, b) allowing the emulsion produced from the step a) to contain a water-soluble polycarboxylate and a water-soluble anionic surface. Contacting the solid dispersant of the active agent, c) extruding the paste produced from step b), and d) drying the extrudate produced in step c) as appropriate.

The emulsified particles are preferably obtainable by the process of the invention (in particular by the process of the invention). Steps a) through d) are usually carried out in the specified order.

The emulsification step of the solution of water and the pesticide-containing water-insoluble solvent can be achieved by any conventional emulsification method. Usually, the pesticide is first dissolved in a water-insoluble solvent, followed by the addition of water, and then emulsified by, for example, stirring or applying a high shear force. Step a) typically produces an oil-in-water emulsion . Step a) can be carried out at a temperature of from 3 ° C to 95 ° C, preferably from 10 ° C to 40 ° C. Other formulation auxiliaries may have been added to the water or water insoluble solvent. For example, a water soluble formulation adjuvant can be added to the water. The droplet size of the emulsified droplets may range from 0.1 μm to 10 μm, preferably from 0.5 μm to 3 μm.

When used in plant protection, the amount of pesticide (also known as active substance) applied depends on the type of effect desired, from 0.001 kg/ha to 2 kg/ha, preferably from 0.005 kg/ha to 2 kg/ Ha, more preferably 0.05 kg/ha to 0.9 kg/ha and specifically 0.1 kg/ha to 0.75 kg/ha. When treating plant propagation material (eg, seeds) by, for example, dusting, coating, or soaking seeds, typically from 0.1 g to 1000 g, preferably from 1 g to 1000, per 100 kg of plant propagation material (preferred seed) g, more preferably from 1 g to 100 g and most preferably from 5 g to 100 g. When used to protect or store a product, the amount of active applied depends on the type of application area and the desired effect. The usual application amount in the case of protecting the material is 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active material per cubic meter of the treated material.

When the user applies the solid composition, it is typically applied from a predetermined dose device, a knapsack sprayer, a spray can, a spray aircraft, or an irrigation system after making an aqueous tank mix. Typically, the agrochemical composition is formulated with water, buffer, and/or other adjuvants to the desired applied concentration, and thereby obtaining a ready-to-use spray or agrochemical composition of the present invention. Typically, 20 to 2,000 liters, preferably 50 liters to 400 liters of ready-to-use spray fluid is applied per hectare of agriculturally effective area.

Contacting the emulsion produced in step a) with a solid dispersant comprising a water soluble polycarboxylate and a water soluble anionic surfactant typically results in a paste which may be a squeezable paste. The liquid content of the extrudable paste (e.g., water content) produces an extrudate that retains its shape for at least 1 h at 20 °C. Preferably, the paste produced from step b) contains less than 30 wt% water, more preferably less than 20 wt%, and specifically less than 17 wt%, based on the total weight of the paste. Preferably, the paste produced from step b) contains less than 50 wt% (more preferably less than 40 wt%, specifically less than 35 wt%) of a water-insoluble solvent based on the total weight of the paste. The paste produced from step b) may contain at least 30 wt%, more preferably at least 35 wt% and specifically at least 40 wt% of water-soluble polycarboxylate and water-soluble anionic surfactant, based on the total weight of the paste. The sum of them. The paste produced from step b) may contain at least 35 wt%, more preferably at least 42 wt% and specifically at least 46 wt% of water-soluble polycarboxylate, water-soluble anionic surfactant, based on the total weight of the paste. The sum of the water-soluble solid carrier.

Extruding from step b) the step of generating the paste c) generally produce extrudate. Extrusion can be carried out on conventional extrusion equipment. The extrusion in step c) can be carried out at a temperature below 60 ° C, preferably below 45 ° C and in particular below 35 ° C. This temperature refers to the paste during extrusion. If necessary, the temperature is maintained at a desired value by cooling.

The expert will adjust the water content of the extrudable paste to achieve the squeezable texture of the paste. Extruders are well known in the industry. For example, a single or twin screw extruder can be used. An extruder for producing pasta can also be used. Typically, the extrusion is done at a pressure of from 1 bar to 80 bar, preferably from 1 bar to 60 bar and more preferably from 1 bar to 40 bar, usually obtained just prior to entering the extrusion grid. An extruded grid of holes of any shape, preferably circular, can be used. Usually, the diameter of the holes is from 0.2 mm to 5.0 mm, preferably from 0.5 mm to 3 mm, more preferably from 0.5 mm to 2.0 mm.

The rod-shaped extrudate can be cut into shorter rods before or after drying, preferably prior to drying, using, for example, a rotary knife. In the case of a round hole, the pasta extrusion can be cut into Cylindrical. In the case of a polygonal hole such as a triangle or a rectangle, the extrudate can be cut into a corresponding shape. The resulting agglomerates can be broken into shorter particles before or after drying, preferably after drying.

Optionally, in step d) the extrudate produced in step c) can be dried by conventional drying means (for example heated air or vacuum). The drying method can be carried out by applying a high temperature (for example, hot air) from 30 ° C to 150 ° C, preferably from 50 ° C to 80 ° C. The heating time depends on the temperature, the size of the extrudate and the desired amount of water in the final product. The drying process can produce emulsified granules containing up to 10% by weight, preferably up to 5% by weight and in particular up to 2% by weight of water.

The invention further relates to sprayable emulsions (e.g., large tank mixtures) obtainable by contacting water with the emulsified granules of the invention or the granules obtained by the process of the invention. The sprayable emulsion may contain from 0.02 wt% to 2 wt%, preferably from 0.05 wt% to 0.5 wt% of emulsified particles. The term sprayable means that the emulsion can be sprayed by conventional spray agrochemicals. The droplet size of the emulsified droplets may range from 0.1 μm to 10 μm, preferably from 0.5 μm to 3 μm.

The invention further relates to a method for controlling the growth of phytopathogenic fungi and/or undesired plants and/or undesired insects or mites and/or modulating plant growth, wherein the emulsified granules of the invention are obtained or obtained by the method of the invention The emulsified particles act on a particular pest, its living environment or plants, soils and/or acts that are intended to protect against unwanted pests and/or act on undesirable plants and/or useful plants and/or their living environment.

When used to protect plants, the amount of pesticide (also known as active substance) applied depends on the type of effect desired, from 0.001 kg/ha to 2 kg/ha, preferably from 0.005 kg/ha to 2 kg/ha. More preferably, it is 0.05 kg/ha to 0.9 kg/ha and specifically 0.1 kg/ha to 0.75 kg/ha. When treating plant propagation material (eg, seeds) by, for example, dusting, coating, or soaking seeds, typically from 0.1 g to 1000 g, preferably from 1 g to 1000, per 100 kg of plant propagation material (preferred seed) g, more preferably from 1 g to 100 g and most preferably from 5 g to 100 g. When used to protect or store a product, the amount of active applied depends on the type of application area and the desired effect. The usual application amount of the protective material is 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active substance per cubic meter of treated material.

When the user applies the emulsified granules, it is typically applied from a predetermined dosage device, a back sprayer, a spray can, a spray aircraft or an irrigation system after making a large aqueous mixture (e.g., a sprayable emulsion). Typically, the agrochemical composition is formulated with water, buffer, and/or other adjuvants to the desired application concentration, and thereby obtaining a ready-to-use spray or agrochemical composition of the present invention. Typically, 20 to 2,000 liters, preferably 50 liters to 400 liters of ready-to-use spray fluid is applied per hectare of agriculturally effective area.

The present invention provides various advantages : the emulsified particles are rapidly emulsified when mixed with water; they require almost no baking; they are easy to flow; they have only a low organic solvent content; they have high bioavailability, and optionally do not require other adjuvants; Reduce the amount of expensive polymers (such as expensive polyvinylpyrrolidone or polyvinyl alcohol). The method of the present invention can use low temperature extrusion; this method is extremely mild, so even temperature sensitive pesticides can be formulated. In particular, the process is extremely sustainable compared to spray drying or fluidized bed technology: it requires less energy, less water, produces less waste, or the machine is easier to clean.

Instance

S1: N-octylpyrrolidone

S2: a mixture of 50-65 wt% N,N-dimethyloctylamine and 37-50 wt% N,N-dimethyldecylamine.

S3: (S)-2-ethylhexyl lactate

S4: A technical mixture of aromatic hydrocarbons having a boiling point above 210 ° C and a freezing point below -8 ° C.

A1: an aqueous solution (25 wt%) of a water-soluble sodium salt of a copolymer (molecular weight of about 4-8 kDa) prepared from maleic anhydride and diisobutylene (mole ratio about 1/1).

A2: Lactose

A3: poly(vinylpyrrolidone), a water-soluble powder having a K value of 26-34 in water and a melting point higher than 130 °C.

A4: C ₁₆ -C ₁₈ alcohol ethoxylate propoxylate.

A5: Defoamer based on hydrazine.

A6: an ethoxylated short chain fatty alcohol having a molecular weight of about 430 g/mol and being soluble in water (>10 wt%).

A7: an anionic dispersant, a calcium dodecylbenzenesulfonate (70 wt%) in isobutanol.

D1: a water-soluble anionic dispersant, a powdery sodium salt of a reaction product of sulfurous acid and a cresol-formaldehyde-nonylphenol polymer, having a pH of 7-8 in water at a concentration of 5 wt%, and a molecular weight of 300-900 g/mol.

D2: a water-soluble anionic dispersant, a powdery copolymer of maleic anhydride and diisobutylene (sodium salt; monomer molar ratio of 7/3 to 3/7).

Example 1 - Preparation of 100 grams of emulsified granules

1) Preparation of emulsion

The kekemin ("active") is dissolved in a solvent or solvent mixture (S1, S2, S3). Water, a portion of dispersant D2 and, optionally, water soluble additive A1 were added and the mixture was emulsified at 1800 rpm for about 4 minutes at room temperature.

2) Preparation of extrudable paste

The solid dispersants D1 and D2 and optionally other solid adjuvants (for example A2, A3, A4) or liquid additives (for example A5 or A6) are mixed. The emulsion of step 1) is sprayed onto the mixture and kneaded to produce a paste.

3) Squeeze

The paste of step 2) was extruded at room temperature. The extrudate was dried in an air stream at 50 °C. The final granules have an average cross section of about 1 mm and a length of about 2-4 mm.

Five different samples A to E were prepared. The amounts of each component are summarized in Table 1, wherein all components except water are up to 100%. The water is removed by a drying step such that the final water content in the granules is about 1 wt%.

Example 2 - Preparation of emulsified granules

By the method described in Example 1 of Laid-off seat emulsified particles prepared, and the ingredients are summarized in Table 2 below.

Example 3 - Preparation of yamidine emulsified granules

The sub-imident emulsified granules were prepared by the method described in Example 1, and the components are summarized in Table 3.

Example 4 - Preparation of Billy Bilobol Emulsion Particles

The emulsified granules of the ratio of pirimizone of formula I were prepared by the method set forth in Example 1, and the components are summarized in Table 4.

Claims (17)

A method for preparing emulsified granules comprising the steps of: a) emulsifying a solution of water and a water-insoluble solvent containing a pesticide, b) allowing the emulsion produced from the step a) to contain a water-soluble polycarboxylate and a water-soluble anion The solid dispersant of the surfactant is contacted, and c) the paste produced from step b) is extruded. The method of claim 1, wherein the extrusion in step c) is carried out at a temperature below 60 °C. The method of claim 1 or 2, wherein the paste produced from step b) contains less than 20% by weight of water based on the total weight of the paste. The method of any one of claims 1 to 3, wherein the paste produced from step b) contains less than 40% by weight of a water-insoluble solvent based on the total weight of the paste. The method of any one of claims 1 to 4, wherein the paste produced from the step b), based on the total weight of the paste, the total of the water-soluble polycarboxylate and the water-soluble anionic surfactant The content is at least 35 wt%. The method of any one of claims 1 to 5, wherein the particles have a cylindrical shape with a length of 0.2 mm to 10 mm and a diameter of 0.2 mm to 10 mm. An emulsified granule comprising: a water-insoluble solvent, a pesticide, dissolved in the water-insoluble solvent, a water-soluble polycarboxylate, and a water-soluble anionic surfactant. The granule of claim 7, which can be obtained by the method as defined in claims 1 to 6. The granule of claim 7 or 8, which contains 5 wt% to 50 wt% of the water-insoluble solvent, 1 wt% to 25 wt% of the pesticide, 15 wt% to 70 wt% of the water-soluble polycarboxylate, 1 wt% to 30 wt% of the water-soluble anionic surfactant, and optionally formulated Additives, which are added to 100 wt%. The granule according to any one of claims 7 to 9, wherein the water-soluble anionic salt has a weight ratio of the water-soluble anionic surfactant of from 20:1 to 1:1. The granule according to any one of claims 7 to 10, wherein a weight ratio of the water-soluble polycarboxylate to the water-insoluble surfactant to the water-insoluble solvent is from 10:1 to 1:2. The granule according to any one of claims 7 to 11, further comprising a water-soluble solid carrier selected from the group consisting of a monosaccharide or a disaccharide, a homopolymer of vinylpyrrolidone, a copolymer of vinylpyrrolidone, Containing at least 80 mole % of vinyl pyrrolidone (based on the total amount of monomers in the copolymer), or a mixture thereof. The granule of claim 12, wherein the solid carrier is selected from the group consisting of monosaccharides or disaccharides, homopolymers of vinylpyrrolidone, and mixtures thereof. The granule of claim 12 or 13 which contains from 1 wt% to 55 wt% of the water-soluble solid carrier. The granule according to any one of claims 12 to 14, wherein the water-soluble polycarboxylate, the sum of the water-soluble anionic surfactant and the water-soluble solid carrier, the weight ratio of the water-insoluble solvent to the water-insoluble solvent is 10 :1 to 1:1.5 range. A sprayable emulsion prepared by contacting the emulsified particles as defined in any one of claims 7 to 15 with the emulsified particles as defined in any one of claims 1 to 6 or by the method as defined in any one of claims 1 to 6. . A method of controlling phytopathogenic fungi and/or undesirable plant growth and/or undesirable insect or cockroach invasion and/or modulating plant growth, wherein the emulsified particles as defined in claims 7 to 15 are made or by request The methods defined in items 1 to 6 obtain such The emulsified particles act on a particular pest, its living environment or such plants, soils and/or acts that are intended to protect against the particular pest and/or act on undesirable plants and/or useful plants and/or their living environment.