TW201315380A - Formulations for paddy rice fields - Google Patents

Abstract

The present invention relates to microcapsules, formulations comprising such microcapsules and to methods of combating phytopathogenic pests in paddy rice fields based on such microcapsules.

Description

Formulated for rice fields

The present invention relates to a microcapsule, a formulation comprising the microcapsules, and a method for controlling phytopathogenic pests in rice fields based on the microcapsules, wherein (i) the capsule has a core-shell structure; and (ii) at least 80 % of the pesticide is dissolved in the organic solvent in the core at 25 ° C; and (iii) the capsule shell is based on a polyurethane comprising a polyfunctional isocyanate and a polyamine in a polymerized form; and (iv) a capsule The ratio of the weight of the outer shell to the weight of the capsule is from 1 to 20% by weight.

One of the primary targets of rice insecticidal treatment is to achieve targeted release of the pesticide of the applied formulation while allowing it to adhere quickly to individual plants, thereby avoiding undesired release of the pesticide into the environment. The latter can pose a major problem because of the environmental safety issues on the one hand and the loss of protection against insecticides and insects that are resistant to soil transmission, leading to an urgent need in the industry to provide specialized formulations that meet these objectives.

Accordingly, it is an object of the present invention to provide formulations for treating rice fields that provide rapid activity of the pesticide on the plants to be protected, thereby preventing significant release into the environment (water or soil).

This is especially important in the fact that many pesticides can have undesirable side effects on aquatic organisms if certain concentrations of pesticide material in water are exceeded. Therefore, when the insecticide contacts the plant and the individual pests (such as harmful fungi, harmful insects) need to establish sufficient concentration to enable effective control At the same time, reducing the parallel release of the pesticide in the water will have significant environmental benefits.

Another potential object of the present invention is to obtain a formulation of an improved plant, which is generally and hereinafter referred to as "plant health", in particular with respect to rice plants.

The term plant health includes various modifications to plants that are not related to pest control. For example, advantageous properties that may be mentioned include improved crop characteristics: emergence, crop yield, protein content, oil content, starch content, enhanced roots (modified root growth), improved stress tolerance (eg for drought, Heat, salt, UV, water, cold resistance), reduce ethylene (reduce production and / or inhibit acceptance), increase tillering, increase plant height, larger leaves, less dead basal leaves, strong lychee, green color , pigment content, photosynthetic activity, less required input (eg fertilizer or water), less seed required, higher productivity, early flowering, early grain ripening, lower plant jointing (falling), increased shoot growth, enhancement Plant vigor, increase plant stand and early and better germination.

This object is solved by providing microcapsules, wherein (i) the capsule has a core-shell structure; and (ii) at least 80% of the pesticide is dissolved in the organic solvent in the core at 25 ° C; and (iii) the capsule The outer shell is based on a polyurethane comprising a polyfunctional isocyanate and a polyamine in a polymerized form; and (iv) the ratio of the weight of the capsule shell to the weight of the capsule is from 1 to 20% by weight.

Preferably, the ratio of the weight of the insecticide to the total weight of the capsule is from 5 to 50% by weight, preferably from 8 to 45% by weight, more preferably from 25 to 35% by weight.

As mentioned above, at least 80% by weight, preferably at least 90% by weight of the pesticide in the core is soluble in the organic solvent at 25 °C.

The term "insecticide" means at least one insecticide selected from the group of fungicides and insecticides. Mixtures of two or more insecticides from the above categories may also be used. Experts are familiar with such insecticides, and other insecticides are described in particular in the Pesticide Manual, 14th Edition (2006), The British Crop Protection Council, London or e-Pesticide Manual V5.1, ISBN 978 1 901396 84 3.

Suitable fungicides are: A) Respiratory Inhibitors - Inhibitors of Complex III at the Q _o site: strobilurines, azoxystrobin, coumethoxystrobin, Coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin (fluoxastrobin), kresoxim-methy, metominostrobin, oressastrobin, picoxystrobin, baikemin (baikemin), pyrazolamide ( Pyrametostrobin), pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid Ester and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylaminooxymethyl)-phenyl)-2-methoxyimino -N-methyl-acetamide; and pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone; - Q _i locus Inhibitor of complex III Cyazofamid, amisulbrom, 2-methylpropionic acid [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-) Oxy-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], 2-methylpropionic acid [(3S,6S,7R,8R)-8-benzyl -3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl-amino]-6-methyl-4,9-di-oxy-1,5-di Oxacyclodec-7-yl]ester, 2-methylpropionic acid [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-benzo)diox Cyclopentene-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-di-oxy-1,5-dioxole Cycloalkyl-7-yl] ester; - inhibitor of complex II (eg, formazan): benodanil, bixafen, boscalid, carboxin , fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazol Amine (isopyrazam), mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, cyanofluoride 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-carbonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole- 4-methanamine; - other respiratory inhibitors (eg complex I, uncoupling agent): diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[ 2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl derivative: binapacryl, large dislocation ( Dinobuton), dinocap, fluazinam; ferimzone; organometallic compounds: ametoctradin; and silthiofam; B) steroid biosynthesis Inhibitor (SBI fungicide) - C14 demethylase inhibitor (DMI fungicide): triazole: oxaconazole (azacona) Zole), bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, yip Epoxiconazole), fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, Metaconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, carbazole (simeconazole), tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole; imidazole: imazalil , pefurazoate, prochloraz, triflumizol; pyrimidine, pyridine and hexahydropyrazine: fenarimol, nuarimol, pyrifenox , triforine; - δ14-reductase inhibition Agents: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin ), piperalin, spiroxamine; - 3-ketoreductase inhibitor: fenhexamid; C) nucleic acid synthesis inhibitor - phenylguanamine or decylamine Base fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M Mefenoxam, ofurace, oxadixyl; - others: hymexazole, octhilinone, oxolinic acid, Bupirimate, 5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidine-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidine -4-amine; D) Inhibitors of cell division and cytoskeleton - Tubulin inhibitors, such as benzimidazole, thiophanate: benomyl, carbendazim, wheat ears Fuberidazole, thiabendazole, methyl Thiophanate-methyl; triazolopyrimidine: 5-chloro-7-(4-methylhexahydropyridin-1-yl)-6-(2,4,6-trifluorophenyl)-[1 , 2,4]triazolo[1,5-a]pyrimidine - other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide , zoxamide, metrafenone, pyrolifenone; E) amino acid and inhibitor of protein synthesis - methionine synthesis inhibitor (anilino-pyrimidine): match Cyprodinil, mepanipyrim, pyrimethanil; - protein synthesis inhibitors: blasticidin-S, kasugamycin, gibberellin hydrochloride Compound (kasugamycin hydrochloride-hydrate), mildiomycin, streptomycin, oxytetracyclin, polyoxine, and validamycin A; Signal transduction inhibitors - MAP / histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil ) Fludioxonil; - G protein inhibitor: quinoxyfen; G) lipid and membrane synthesis inhibitors - phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, white pine ( Pyrazophos), isoprothiolane;- lipid peroxidation peroxidation inhibitor: dicloran, quintozene, tecnazene, tolclofos- Methyl), biphenyl, chloroneb, etridiazole; phospholipid biosynthesis and cell wall deposition inhibitors: dimethomorph, flumorph, man Mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1-(1-(4-cyano) -Phenyl) ethanesulfonyl)butan-2-yl)carbamic acid-(4-fluorophenyl) ester;- Compounds that affect cell membrane permeability and fatty acids: propamocarb, prok (propamocarb-hydrochlorid) H) Inhibitors with multiple sites - Inorganic active substances: -- Organochlorine compounds (eg o-phthalazinium) , sulfonamide, chloronitrile): anilazine, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorphenole and its salts, Phthalide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide; Others: guanidine, dodine, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, Ignitine-tris (albesilate); I) cell wall synthesis inhibitors - inhibitors of glucan synthesis: vesinomycin, polyoxin B Melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil; J) plant defense inducer - S- Acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonic acid :K) Unknown mode of action - chinomethionat, cyflufenamid, cymoxanil, debacarb, diclomezine, difenzoquat, grass Difenzoquat-methylsulfate, fenpyrazamine, flumetover, fluthiophene, flutianil, methasulfocarb, nitrapyrin, sputum Nitrothal-isopropyl, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3- Propyl Ace-4-one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenylacetamidine Amine, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methylformamidine, 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]-hexa Hydropyridin-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-hexahydropyridyl]-2-[5-methyl-3 -(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinoline-4- Base ester, N-methyl-2-{1-[(5-methyl-3-trifluoro) -1H-pyrazol-1-yl)-ethenyl]-hexahydropyridin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]- 4-thiazolylamide, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazol-3-yl]-pyridine, 3-[5-(4-chloro -phenyl)-2,3-dimethyl-isoxazol-3-yl]-pyridine (pyrisoxazole), N-(6-methoxy-pyridin-3-yl) ring Propane meglumine, 5-chloro-1-(4,6-dimethoxy-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); suitable insecticide The agents are - organic (thio) phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, gram Chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, pentoxon Fenitrothion), fenthion, isoxathion, malathion, methamidophos, methidathion, Methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate ), phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos , prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;-carbamate: cotton boll Alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenno Fenoxycarb, furathiocarb, metiocarb, methodylyl, oxamyl, pirimicarb, propoxur, sulfur enemy Thiodicarb), triazamate;- pyrethroids: allethrin, bifenthrin, cyfluthrin ), cyhalothrin, cyphenothrin, cypermethrin, α-赛灭宁, β-赛灭宁, ζ-赛灭宁, 灭灭宁(deltamethrin),益化Esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, imiprothrin, λ-cylonine, permethrin, prallethrin , pyrethrin (I and II), resmethrin, silafluofen, tau-fluvalinate, tefluthrin, and chlorpyrifos Tetramethrin), tralmethrin, transfluthrin, profluthrin, dimefluthrin, flucythirnate;- insect growth regulator: a) Chitin synthesis inhibitors: benzamidines: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflu (hexaflumuron), lufenuron, novaluron, teflubenzuron, triflumuron; bufenfen (bu Profezin), diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonist: hafenofozide, methoxyfenozide , tebufenozide, azadirachtin; c) juveniles: pyriproxyfen, metoprene, fenoxycarb; d) lipid biosynthesis inhibition Agent: spirodiclofen, spiromesifen, spirotetramat; - nicotinic receptor agonist/antagonist compound: clothianidin, dinotefuran , imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chloro-thiazol-5-yl 2-nitroimido-3,5-dimethyl-[1,3,5]triazolidine;- GABA antagonist compound: endosulfan, ethiprole, fen Fipronil, vaniliprole, pyrafluprole, pyriprol, 5-amino-1-(2,6-dichloro-4-methyl- Phenyl)-4-amine sulfinyl-1H- Pyrazole-3-methylthioguanamine; - macrolide insecticide: abamectin, emamectin, milbemectin, lepimectin, sino Spinosad, spinetoram;- mitochondrial electron transfer inhibitor (METI) I acaricide: fenazaquin, pyridaben, tebufenpyrad, defenfen (tolfenpyrad), flufenerim; - METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon; - uncoupling agent: kefanpai Chlorfenapyr);- oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite;- suede interfering compound: cyromazine )-- Mixed-function oxidase inhibitor: piperonyl butoxide; - sodium channel blocker: indoxacarb, metaflumizone; - others: benclothiaz, bifenfen ( Bifenazate), cartap, flonicamid, pyridalyl, pymetrozine, sulphur, Thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen, flupyrazofos, Cyflumetofen, amidoflumet, imicyafos, bistrifluron and pyrifluquinazon.

The encapsulated insecticide comprises at least one of the above-mentioned insecticides, which is one or more fungicides and/or one or more insecticides or one or more fungicides and/or one or more insecticides. mixture.

Preferred insecticides are pyrethroids, preferably propylene pyrethrum, bifenin, savonon, cylonine, cyprofen, α-saiding, β-saiding, ξ-赛Ningning, Diming, Yihuali, Fenpanning, Fenhuali, Epnin, Λ-赛洛宁,百灭宁, 普亚列宁, pyrethrin I and II, fenfenyl ester, τ-fuhuali, heptamethrin, Zhiningning, Tainingning, Baifuling, Fenfluthrin, tetrafluthrin and chloramphenicol; preferably pyrethroids are protected.

Equally preferred insecticides are nicotinic receptor agonist/antagonist compounds, of which edetamine, arbutin, celecoxib, nitenpyram, konidine, acesulfame and dadnam are preferred.

Equally preferred insecticides are insect growth regulators, of which Fufulong, Defulong, Kefulong, Flufenoxalam, Hexafluronium, Chlortetracycline, Lufenron are preferred, and Fulong and Flufenide Long is better.

Equally preferred insecticides are macrolide insecticides, of which amphetamine, emamectin benzoate, abatatin, methiophene are preferred.

Another equally preferred insecticide is kefanpai.

Another equally preferred insecticide is the Fluoride.

Another equally preferred insecticide is Fenpney.

Another equally preferred insecticide is rynaxypyr (chloranthraniliprole).

More preferred insecticides are nicotinic receptor agonist/antagonist compounds, of which edetamine, arbutin, celecoxib, nitenpyram, konidine, acesulfame and dadnam are preferred.

Equally better insecticides are insect growth regulators, of which Fufulong, Defulong, Kefulong, Flufenolone, Hexaproron, Chlortetracycline, Lufenron are preferred, and Fulong and Flufen Long is better.

An equally preferred insecticide is a macrolide insecticide, wherein the amphetamine, the indomethacin, the abatatin, and the methiophene are preferred.

Another equally better insecticide is the Kaffi.

Another equally better insecticide is the Fluoride.

Another equally better insecticide is Fenpney.

Another equally better insecticide is chlorantamine (closperm).

In a preferred embodiment, the encapsulated pesticide comprises one or more fungicides.

Preferably, the encapsulated insecticide comprises one or more insecticides selected from the group consisting of echinocanthin fungicides, such as atoreno, mephate, syringic acid, norepine, Enoxacin, phenalamine, schizobin, flubenzolbine/fluoxetine, fluoxastrobin, kexinxin, phenoxystrobin, acesulfame, pyridoxine, dexamethasone, pyrazolamide Bacteriocin, pyraclostrobin, trifluoro-sensitive, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-methyl acrylate and 2-(2) -(3-(2,6-dichlorophenyl)-1-methyl-allylaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl- Acetamine; a group of methotrexate fungicides selected from the group consisting of: wheat rust, chlorfenapyr, leucoside, wiltonin, metoprofen, flupirtine, butonine, fluoride得得,福拉比, isopyrazolamide, chlorfenapyr, jiabaoxin, flufenac, pirfenium, ciprofloxacin, chlorhexidine, cyprofen, N-(4'-trifluoro Methylthiobiphenyl-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-carboxamidine , N-[9-(Dichloromethylene)-1,2,3,4-tetrahydro-1,4-carbonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl -1H-pyrazole-4-carboxamide; a group of terpenoids, such as oxycyclazole, more than Nong, Broken, Ring, Kleine, Dakli, Dakli-M, Epp, Fink, Froquinazole, Hydrazine, Difen, Fickley, Easy Amine, Oxazole , 灭座, 麦克尼, cyanosin, bucksin, pingke, pugli, propofol, flurazepam, derkeley, quaternary chlorpyrifos, triptyron, saponin, sterilized azole, uniconazole ; and a group of various active substances, such as triptothecin, acetonide and gupamine.

In a more preferred embodiment, the encapsulated insecticide comprises a muscarinic fungicide, wherein the azotomin, the carbaryl ester, the syringic acid ester, the oxystrobin, the enestrobin, the phenamine宾, 芬 咢 卓 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / Baikemin, pyridoxybacter, fluoxastrobin is better and the best is 100 grams.

In another more preferred embodiment, the encapsulated insecticide comprises an anthraquinone fungicide wherein oxacyclazole, biconic, bluron, cyclist, holly, darke, darke-m, Puzuo, Fenke, fluoroquinazole, Hydrazine, Difen, Fickley, Easy Amine, Oxazole, Gator, McKee, Cyansulfazole, Bacchus, Pink, Puckley, Prothioconazole, flurazepam, derkele, tetraclimate, trimethoate, saponin, sterilized azole, and ureconazole are preferred, espresso, prothioconazole, sylvain and pugli are better, yup Block, prothioconazole, tonic, and Puckley are the best and the best.

In another more preferred embodiment, the encapsulated insecticide comprises a methotrexate fungicide, wherein the bactericidal phenol, the pirfenide, the isopyrazolamide, the flufenium, the pirfenium, the pirimipen Insectamine, 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 and N-[9-(dichloromethylene)-1,2,3,4 -tetrahydro-1,4-methanol naphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide is preferred, chlorfenapyr, chlorpyrifos Isopyrazole, flufenac, penthiopyramine and ciprofloxacin are better and the ratio of fluorine is best.

In another more preferred embodiment, the encapsulated insecticide comprises trimethoxazole, sulforaphane, fentonyl, bicyclovirin, carnitamicin or gupamine, more preferably trioxazole or samarium .

The best encapsulated insecticide is Baikemin or Fluoride, and Baikemin is the best.

As mentioned above, a mixture of insecticides can also be encapsulated. Preferably, it is a mixture of at least one of baikemin and the above-mentioned insecticide.

The best mixture is the following binary mixture as set forth in Table 1.

The mixture of Table 1 generally comprises the active substance in a weight ratio of the following compound I to component II: from 500:1 to 1:500, preferably from 100:1 to 1:100, more preferably from 50:1 to 1:50. Even more preferably from 20:1 to 1:20, particularly preferably from 10:1 to 1:10, in particular from 5:1 to 1:5.

In a preferred embodiment, the encapsulated insecticide is a dexamethasone, a chlorpyrifos and a mixture of M-1, M-2, M3 and M4, wherein in this subgroup, a mixture of hexagram and fluororesin is obtained. M-1 and M-2 are preferred, and the keke-sensitive and fluoro-compounds are better than the mixture M-1 and the keke is the best.

The encapsulated insecticide comprises from 1% to 40%, preferably from 2% to 25%, even more preferably from 8% to 15% of the formulation. If the formulation contains a mixture of the encapsulated active ingredient and other non-encapsulated active ingredients, the formulation contains from 1% to 30% encapsulated active ingredient and from 1% to 30% non-encapsulated active ingredient, preferably 2% to 15% encapsulates the active ingredient and 2% to 25% of the non-encapsulated active ingredient and even more preferably 5% to 15% of the encapsulated active ingredient and 5% to 20% of the non-encapsulated active ingredient.

The average particle diameter of the capsule (z-average obtained by light scattering; preferably the average value of D[4,3]) is from 0.5 μm to 50 μm, preferably from 0.5 μm to 10 μm, more preferably from 2 μm to 10 μm and especially 5 μm to 10 μm, preferably 6 μm to 10 μm.

The particle size of the microcapsule dispersion was determined according to the standard measurement method described in the literature using a Malvern Particle Size Analyzer Model 3600E or a Malvern Mastersizer 2000. The D[v, 0.1] value means that the particle size of 10% of the particles (according to the average volume) reaches this value. Accordingly, D[v, 0.5] means that the particle diameter of 50% of the particles (according to the average volume) is less than/equal to this value, and D[v, 0.9] means the particle diameter of 90% of the particles (according to the average volume) Less than / equal to this value. The span value is derived from the quotient of the difference D[v,0.9]-D[v,0.1] and D[v,0.5]. The D[4.3] value is the weight average.

The solvent of the capsule core includes at least one non-polar solvent (by definition, this means one or more non-polar solvents), one or more non-polar solvents and polar a mixture of solvents. The polar solvent is a solvent having a solubility in water of at least 5% by weight at 25 °C. The non-polar solvent is a solvent having a solubility in water of less than 5% by weight at 25 °C.

Suitable non-polar solvents are C ₈ -C ₁₁ aromatic petroleum derivatives (aromatic hydrocarbons) having a solubility in water <0.1% (w/w) at room temperature and a distillation range of 130 ° C to 300 ° C (with the following trademarks) The name is from ExxonMobil or BP: Solvesso® 100, Solvesso® 150, Solvesso® 200, 30 Solvesso® 150ND, Solvesso® 200ND, Aromat® 150, Aromat® 200, Hydrosol® A 200, Hydrosol® A 230/270, Caromax® 20, Caromax® 28, Aromat® K 150, Aromat® K200, Shellsol® A 150, Shellsol® A 100, Fin® FAS-TX 150, Fin® FAS-TX 200); vegetable oils such as coconut oil, palm kernel oil, Palm oil, soybean oil, rapeseed oil, corn oil and methyl or ethyl ester of the above oil; hydrocarbons such as flash point between 40 ° C and 250 ° C and distillation range between 150 ° C and 450 ° C Aromatic depleted hydrocarbons, linear paraffin hydrocarbons, isoparaffins, paraffin hydrocarbons; esters such as decyl esters (eg isodecyl acetate), benzyl acetate, benzyl benzoate, butyl benzoate Ester, 2-ethoxypropyl acetate, methyl proxitol acetate; tributyl phosphate And a guanamine such as N,N-dialkylalkylguanamine, preferably a fatty acid dimethyl decylamine, more preferably N,N-dimethyloctylamine and/or N,N-dimethyl The base amine (mixture is available from Hallcomide® M 8-10 from PCHall, Agnique® KE3658 from Cognis, Genagen® 4166 from Clariant) and n-octyl-2-pyrrolidone (NOP).

Examples of polar solvents are anisole; anthraquinones such as dimethyl hydrazine (DMSO); and lactones such as γ-butyrolactone (GBLO); N-ethyl-2-pyrrolidone (NEP); and N-dodecylpyrrolidone; ketones such as 2-heptanone , cyclohexanone, acetophenone and acetophenone derivatives (for example 4-methoxyacetophenone); and alcohols such as cyclohexanol, benzyl alcohol, diacetone alcohol (eg 4-hydroxy-4-methyl) Mixyl-2-pentanone), n-octanol, 2-ethylhexanol; and diesters such as dimethyl glutarate and dimethyl succinate and dimethyl adipate (purchased Rhodiasolv® RPDE from Rhodia or a mixture of diisobutyl glutarate and diisobutyl succinate and diisobutyl adipate; and diols and derivatives such as propylene glycol monomethyl ether Acid ester, dipropylene glycol monomethyl ether, propylene glycol monophenyl ether; and alkyl carbonate, such as propylene carbonate, butylene carbonate; and pyrrolidone, derivatives such as N-ethylpyrrolidone And lactate, such as n-propyl lactate, methyl lactate, ethyl lactate, isopropyl lactate, butyl lactate, under the trade names PURASOLV® NPL, PURASOLV® ML, PURASOLV® EL, PURASOLV® IPL, PURASOLV® BL purchase Or, selected from a mixture of at least two of the above solvents.

Preferably, the solvent of the capsule core comprises one or more non-polar solvents.

Preferred non-polar solvents are as follows: a non-polar solvent: a C ₈ -C ₁₁ aromatic petroleum derivative having a solubility in water of <0.1% (w/w) at room temperature and a distillation range of 130 ° C to 300 ° C. a hydrocarbon, such as coconut oil, palm kernel oil, palm oil, soybean oil, rapeseed oil, corn oil, and a methyl or ethyl ester of the above oil; hydrocarbons such as flash points between 40 ° C and 250 ° C And an aromatic spent hydrocarbon, linear paraffin, isoparaffin, cycloparaffin; and amidoxime, such as N,N-dialkylalkylguanamine, between 150 ° C and 450 ° C; The preferred fatty acid dimethyl decylamine is more preferably N,N-dimethyloctylamine and/or N,N-dimethyl decylamine. Other preferred non-polar solvents are esters of phthalic acid, such as isodecyl acetate.

More preferably, the non-polar solvent is a C ₈ -C ₁₁ aromatic petroleum derivative (aromatic hydrocarbon) having a solubility in water of <0.1% (w/w) at room temperature and a distillation range of from 130 ° C to 300 ° C; For example, aromatic spent hydrocarbons, linear paraffins, isoparaffins, cycloparaffins having a flash point between 40 ° C and 250 ° C and a distillation range between 150 ° C and 450 ° C; and guanamines such as N, The N-dialkylalkylguanamine is preferably a fatty acid dimethyl decylamine, more preferably N,N-dimethyloctylamine and/or N,N-dimethyl decylamine.

The amount of solvent required will depend on the nature of the solvent selected and the solubility of one or more of the active ingredients that are intended to be encapsulated. For example, a suitable amount is from 0,1% w/w to 40% w/w, more preferably from 5% w/w to 25% w/w and even more preferably from 8% w/w to 15% w/w. All concentrations of solvent refer to the final formulation, ie, a mixture with other crystalline active ingredients.

The ratio of the weight of the capsule shell to the total weight of the capsule is from 1 to 25% by weight, preferably from 5 to 25% by weight, more preferably from 5 to 20% by weight, most preferably from 10 to 20% by weight.

The given ratio of the weight of the capsule shell to the total weight of the capsule corresponds to the wall thickness and the wall thickness is preferably from 0.07 μm to 0.5 μm, more preferably from 0.1 μm to 0.4 μm and even more preferably from 0.13 μm to 0.35 μm.

The capsule shell is based on a polyurethane comprising a polyfunctional isocyanate and a polyamine in a polymerized form.

Capsules having encapsulating materials comprising such polyurethanes have been well received It is known and can be made in a manner similar to the prior art. It is preferably prepared by an interfacial polymerization process suitable for polymer wall forming materials. Interfacial polymerization is typically carried out in an aqueous water-in-oil emulsion or suspension of a core material comprising at least a portion of the polymeric wall forming material dissolved therein. During polymerization, the polymer separates from the core material to the boundary surface between the core material and water, thereby forming a microcapsule wall. An aqueous suspension of the microcapsule material is thus obtained. Suitable methods for the preparation of interfacial polymerization processes for the preparation of microcapsules containing insecticidal compounds are disclosed in the prior art, for example, in US 3,577,515, US 4,280,833, US 5,049,182, US 5,229,122, US 5,310,721, US 5,705,174, US 5,910,314, WO 95/ 13698, WO 00/10392, WO 01/68234, WO 03/099005, EP 619,073 or EP 1,109,450, all of which are incorporated herein by reference.

Suitable wall forming materials for the polyurethane capsules of the present invention include polyfunctional isocyanates (also known as polyisocyanates) and polyamines in polymerized form.

It is also known that isocyanate groups can react with water to form hydroxy formate groups so that carbon dioxide can be removed to ultimately produce amine groups.

Thus, in another embodiment, a 2-component system polyfunctional isocyanate/polyamine can be prepared by reacting a polyfunctional isocyanate with water.

In general, polyurethanes are formed by the combination of polyisocyanates having at least two isocyanate groups and polyamines having at least two primary amine groups in the presence of polyfunctional ruthenium chloride, as appropriate. The reaction is to form a polyurea wall material. The polyisocyanates may be used singly or in the form of a mixture of two or more polyisocyanates. Suitable polyisocyanates include diisocyanates and triisocyanates in which isocyanate groups and aliphatic or cycloaliphatic moieties (Aliphatic isocyanate) or attached to an aromatic moiety (aromatic isocyanate).

Examples of suitable aliphatic diisocyanates include tetramethylene diisocyanate, pentamethylene diisocyanate and hexamethylene diisocyanate, and cycloaliphatic isocyanates such as isophorone diisocyanate. , 1,4-bisisocyanatocyclohexane and bis-(4-isocyanatocyclohexyl)methane.

Suitable aromatic isocyanates comprise toluene diisocyanate (TDI: a mixture of 2,4-isomer and 2,6-isomer), diphenylmethane-4,4'-diisocyanate (MDI), poly-methylene Quitophenyl isocyanate, 2,4,4'-diphenyl ether triisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, diisocyanate 3,3' -dimethoxy-4,4'-diphenyl acid ester, 1,5-anthranyl diisocyanate and 4,4',4"-triphenylmethane triisocyanate. Also suitable for the above Higher carbon number oligomers of diisocyanates, such as the isocyanurates and biurethes of the above diisocyanates and mixtures thereof with the above diisocyanates.

In another embodiment, the polyisocyanate is an oligomeric isocyanate. The oligomeric isocyanates may comprise the above aliphatic diisocyanates and/or aromatic isocyanates in oligomeric form. The average functionality of the oligomeric isocyanate is in the range of from 2.0 to 4.0, preferably from 2.1 to 3.2, more preferably from 2.3 to 3.0. Typically, the viscosity of the oligomeric isocyanates (determined according to DIN 53018) is in the range from 20 mPas to 1000 mPas, more preferably from 80 mPas to 500 mPas and especially from 150 mPas to 320 mPas. Such oligomeric isocyanates may, for example, be sold under the tradename Lupranat® M10, Lupranat® M20, Lupranat® M50, Lupranat® M70, Lupranat® M200, Lupranat® MM103 or (aliphatic isocyanate) Basonat® A270 or Basonat HI 100 from BASF SE purchased.

Also suitable are adducts of diisocyanates with polyols such as ethylene glycol, glycerol and trimethylolpropane, which are obtained by reacting each mole polyol with a hydroxyl group corresponding to the respective alcohol A number of moles of diisocyanate and a mixture of the diisocyanate and the above diisocyanate are added to obtain. Thereby, some diisocyanate molecules are linked to the polyol via a urethane group to form a high molecular weight polyisocyanate. Particularly suitable such products DESMODUR® L (Bayer, Pittsburgh) can be prepared by reacting 3 moles of toluene diisocyanate with 1 mole of 2-ethyl glycerol (1,1-bismethylolpropane). Other suitable products are obtained by adding hexamethylene diisocyanate or isophorone diisocyanate to ethylene glycol or glycerin.

Preferred are polyisocyanate isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate, toluene diisocyanate. In another embodiment, a polyisocyanate oligomeric isocyanate is preferred.

Suitable polyamines within the scope of the invention are understood to generally mean compounds in which two or more amine groups are present in the molecule, the amine group being attachable to the aliphatic or aromatic moiety.

An example of a suitable aliphatic polyamine is a polyethyleneimine of the formula H ₂ N-(CH ₂ -CH ₂ -NH) _n -H, wherein n is an integer from 2 to 5. Representative examples of such polyethyleneimines are di-ethyltriamine, tri-extension ethyltetramine, tetra-extended ethylpentamine, and penta-ethylhexamine.

Examples of suitable aromatic polyamines are 1,3,5-triaminobenzene, 2,4,6-triaminotoluene, 1,3,6-triaminonaphthalene, 2,4,4'-triamine Diphenyl ether, 3,4,5-triamino-1,2,4-trimethyl and 1,4,5,8-tetraaminopurine. The polyamines which are insoluble or insoluble in water can be used in the form of their hydrochlorides.

Polyamines (such as those mentioned above) may be used individually or as a mixture of two or more polyamines.

Suitable diamines within the scope of the invention are understood to mean generally the compounds containing two amine groups in the molecule, the amine groups being attachable to the aliphatic or aromatic moiety.

An example of a suitable aliphatic diamine is an alpha, omega-diamine of the formula H ₂ N-(CH ₂ ) _n -NH ₂ wherein n is an integer from 2 to 6.

Examples of suitable aromatic diamines are 1,3-phenylenediamine, 2,4- and 2,6-toluenediamine, 4,4'-diaminodiphenylmethane, 1,5-diamine. Keina. The polyamines which are insoluble or insoluble in water can be used in the form of their hydrochlorides.

Diamines (such as those mentioned above) may be used individually or as a mixture of two or more diamines.

Preferred diamines are aliphatic diamines as defined above, wherein the formula H ₂ N-(CH ₂ ) _n —NH ₂ (where n is an integer from 2 to 6) is preferably α,ω-diamine, B. The diamine, propyl-1,3-diamine, tetramethylenediamine, pentamethylenediamine and hexamethylenediamine are more preferred, and hexamethylenediamine is most preferred.

Preferred are aliphatic polyamines of the formula H ₂ N-(CH ₂ -CH ₂ -NH) _n -H (wherein n is an integer of from 2 to 5), preferably di-ethyltriamine, tris. The base tetraamine, the tetra-extension ethyl pentamine and the penta-ethylhexamine are the most preferred.

The relative amount of each complementary wall forming component will vary with the equivalent weight of the polyamine. In general, a stoichiometric amount is preferred, and a component may also be used in excess, especially in an excess of polyisocyanate. The total amount of wall forming components corresponds approximately to the total amount of polymeric wall forming material.

The microcapsule of the present invention may additionally comprise a surfactant which is dissolved in the capsule core In the solvent.

The ratio of the weight of the surfactant to the total weight of the capsule is from 1 to 60% by weight, preferably from 1 to 50% by weight, more preferably from 15 to 40% by weight, most preferably from 25 to 40% by weight.

Suitable surfactants are nonionic surfactants. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Examples of suitable nonionic surfactants are alkoxylates, alkoxylated N-substituted fatty acid guanamines, amine oxides, esters, sugar-based surfactants, polymers, block polymers, eucalyptus oils, and mixtures thereof. Examples of alkoxylates are, for example, compounds which have been alkoxylated to have an alkoxy equivalent of from 1 to 50: alcohols, alkylphenols, amines, decylamines, arylphenols, fatty acids or fatty acid esters. Alkoxylation can be carried out using ethylene oxide and/or propylene oxide, preferably ethylene oxide. 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 polymers are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate. Examples of eucalyptus oils are polydimethyl methoxy olefins and alkoxylated polydimethyl methoxy olefin derivatives such as the Breakthru product from Evonik or the Silwet product from O-Si Chemical. Examples of block polymers are block polymerizations of type AB or ABA (including blocks of polyethylene oxide and polypropylene oxide) or ABC types (including alkanols, polyethylene oxides, and polypropylene oxides). Things.

Preferred nonionic surfactants are alkoxylates and block polymers.

The microcapsules of the invention can be further converted into an agrochemical formulation.

The microcapsules are prepared in a known manner by interfacial polymerization, for example, by preparing an organic phase and an aqueous phase, wherein the organic phase is the active ingredient in a suitable solvent and a solution of the desired amount of isocyanate and emulsifier. The solution is emulsified into an aqueous phase using a high shear mixing apparatus (e.g., a colloid mill) at a temperature of 5 ° C to 30 ° C, preferably 15 ° C to 25 ° C, optimally 18 ° C to 25 ° C. Depending on the selected emulsifier and the given rate at the selected rate, the shear input of the colloid mill will determine the emulsion droplet size, which is in a narrow range and is received after the capsule formation process is completed. The capsules are the same size. In view of the specific solution, the emulsion droplet size distribution and thus the capsule size distribution can be adjusted to a certain range by presetting the rotational speed of the colloid mill, which is equivalent to the different shear forces in the colloid mill. It depends on the chosen program). The obtained emulsion was gently stirred while slowly adding a weighed amount of the amine or amine solution. After the addition is completed, the mixture is heated to a temperature between 40-80 ° C for 2-24 hours, and then the curing reaction is completed. The preferred temperature is 50-70 ° C, and even more preferably 55-65 ° C. Optimally, infrared spectroscopy can be used to determine the completion of the reaction. In IR, a strong band between 2300 cm-1 and 2250 cm-1 indicates the presence of unreacted isocyanate. As the band completely disappeared, the reaction was complete and the capsule suspension was cooled to 20-30 °C.

In a particularly preferred embodiment, the resulting composition comprising microcapsules comprises from 10 to 500 g/l, preferably from 30 to 300 g/l, more preferably from 50 to 250 g/l of encapsulated insecticide, by weight. Agent, 10 g-450 g/l, preferably 50 g-300 g/l, more preferably 80 g-200 g/l organic solvent, 1-200 g/l surfactant (nonionic surfactant), 35-80 g/l polyisocyanate and 0,5-15 g/l polyamine and water (to one liter).

The ratio of the sum of the weight of the organic solvent encapsulated in the capsule, the dissolved active ingredient, the optional surfactant, and the capsule wall polyurea (formed by the reaction of the isocyanate and the amine) relative to the total weight per liter is sometimes referred to as Solid content. This solids content may range from 10% w/w to 60% w/w, more preferably from 15% w/w to 45% w/w, even more preferably from 20% w/w to 35% w/w.

Agrochemical formulations can be prepared by adding suitable auxiliaries to the resulting microcapsules and, optionally, another insecticide (described below) to ultimately achieve the desired active ingredient loading. The final formulation contains 2-55% w/w, preferably 5-50% w/w, even more preferably 15-50% w/w capsules.

Examples of suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants (eg dispersants, emulsifiers, wetting agents, solubilizers, penetration enhancers, protective colloids, adhesives, adjuvants) ), thickeners, humectants, insect repellents, attractants, compatibilizers, bactericides, antifreezes, defoamers, colorants, tackifiers, buffers and adhesives.

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

The amount of other surfactants (such as dispersants, emulsifiers, wetting agents, solubilizers, penetration enhancers, protective colloids, adhesives) used in the final capsule suspension is 5-25% w/w, Good land 5-20% w/w, more preferably 7-15% w/w.

Suitable anionic surfactants are sulfonates, sulfates, phosphates, alkali metal, alkaline earth metal or ammonium salts of carboxylates and mixtures thereof. Examples of sulfonates are alkyl aryl sulfonates, diphenyl sulfonates, alpha olefin sulfonates, lignosulfonates, fatty acid and oil sulfonates, ethoxylated alkyl phenols. Sulfate, alkoxylated aryl sulfonate, condensed naphthalene sulfonate, dodecyl- and tridecylbenzene sulfonate, naphthalene and alkylnaphthalene sulfonate, sulfo group Succinate or sulfosuccinamide. Examples of sulphates are fatty acids and oils, ethoxylated alkyl phenols, alcohols, ethoxylated alcohols or sulfates of fatty acid esters. An example of a phosphate is a phosphate. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid guanamines, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are, for example, compounds which have been alkoxylated to have an alkoxy equivalent of from 1 to 50: alcohols, alkylphenols, amines, decylamines, arylphenols, fatty acids or fatty acid esters. Alkoxylation can be carried out using ethylene oxide and/or propylene oxide and/or butylene oxide, preferably ethylene oxide. Examples of N-substituted fatty acid decylamines are also fatty acid glucosides or fatty acid alkanolamines. Examples of esters are fatty acid esters, glycerides or glycerol ester. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinyl pyrrolidone, vinyl alcohol or vinyl acetate.

Suitable cationic surfactants are fourth-grade 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 examples of block polymers are blocks of type AB or ABA (including blocks of polyethylene oxide and polypropylene oxide) or blocks of ABC type (including alkanols, polyethylene oxides and polypropylene oxides). polymer. Suitable polyelectrolyte polybasic acids or polybasic bases. Examples of polybasic acids are polyacrylic acid base salts or polybasic acid comb polymers. Examples of polybasic bases are polyvinylamines or polyethylenediamines.

Suitable adjuvant systems inherently have compounds which neglect pesticidal activity or even no insecticidal activity and which improve the biological properties of the insecticide for the target. Examples are surfactants, mineral or vegetable oils and other auxiliaries. Other examples are listed in Knowles, Adjuvants and others, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5. Preferred surfactants useful as adjuvants are, for example, nonionic surfactants such as alkoxylates, N-substituted fatty acid guanamines, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof Examples of alkoxylates are, for example, compounds which have been alkoxylated to have an alkoxy equivalent of from 1 to 50: alcohols, alkylphenols, amines, decylamines, arylphenols, fatty acids or fatty acid esters. The alkoxylation can be carried out using ethylene oxide and/or propylene oxide and/or butylene oxide, preferably ethylene oxide and/or propylene oxide. An example of an N-substituted fatty acid guanamine Fatty acid glucosamine or fatty acid alkanolamine. 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 homopolymers or copolymers of vinyl pyrrolidone, vinyl alcohol or vinyl acetate. If an adjuvant is present in the formulation, the adjuvant will be in the formulation in an amount of from 3 to 40% w/w, preferably from 5 to 20% w/w, even more preferably from 8 to 15% w/w.

Suitable bactericidal agents are bronopol and isothiazolinone derivatives (for example alkylisothiazolinones and benzisothiazolinones).

If a bactericide is present in the formulation, the amount of biocide in the final formulation ranges from 0.1 to 1% w/w, preferably from 0.1 to 0.5% w/w, and even more preferably from 0,1 0,3% w/w.

Suitable thickeners are polysaccharides (eg xanthan gum, carboxymethylcellulose), organic clays (organic modified or unmodified), polycarboxylates and citrates.

If a thickener is present in the formulation, the amount of thickener in the final formulation will range from 0, 1-1, 5% w/w, preferably 0, 1-1, 0% w/w, Even better, 0, 2-0, 5%.

Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin. In a preferred embodiment, the formulation includes an antifreeze. The amount of antifreeze in the final formulation ranges from 2 to 15% w/w, preferably from 4 to 10% w/w, and even more preferably from 5 to 10%.

Suitable antifoaming agents are polyoxo, long chain alcohols, and fatty acid salts.

If an antifoaming agent is present in the formulation, the amount of defoaming agent in the final formulation ranges from 0 to 5% w/w, preferably from 0, 1-1% w/w, and even more preferably 0. 1- 0,5% w/w.

Suitable buffering agents are phosphate buffers, citric acid based buffers, acetic acid based buffers and other buffer systems based on weak organic or inorganic acids known to those skilled in the art. Please describe the weight ratio of the neutralizer (buffer) to be used in the CS Formulation.

If a buffer is present in the formulation, the amount of buffer in the final formulation will range from 0, 1-10% w/w, preferably 0, 1-3% w/w, or even more preferably 0. 1-2%.

If other additives (such as humectants, insect repellents, attractants, compatibilizers, colorants, tackifiers, and binders) are present in the final formulation, the amount of such adjuvants is 0.1% w/w to 20% w/w.

Formulations as defined above may also optionally include other non-encapsulated insecticides.

The other insecticide may be selected from the above insecticides. The non-encapsulated other insecticide may be present in dissolved, suspended and/or emulsified form. Preferably, the non-encapsulated other insecticide is present in a dispersed form, preferably in a form suspended in a solid. In practice, the insecticide may be added as a ground solid particle during post-treatment with a suitable surfactant or in a suitable formulation (for example in a conventional suspension concentrate, an emulsifiable organic solution or a dissolved form). Other non-encapsulated insecticides may include fungicides or insecticides.

Preferred non-encapsulated fungicides are steroidal fungicides, of which oxycyclazole, biconics, bromo, cycloure, holly, dyckley, dyckle-M, yup, fenque, Fluoroquinazole, Hydrazine, Difen, Fickley, Easy Amine Block, inocastazole, chlorpyrifos, miconi, cyanoxazole, bucksin, pingke, pugli, prothioconazole, guanidazole, dextran, quaternary chlorpyrifos, triptyron, taitailong, sterilized azole It is better to use uniconazole, Ipodil, prothioconazole, PK and Pkley, Epp, Prothioconazole, P. Klein, and Puckley are the best and Epson is the best.

In another more preferred embodiment, the non-encapsulated insecticide comprises a methotrexate fungicide, wherein the bactericidal phenol, the chlorpyrifos, the isopyrazolamide, the flufenium, the pirfenium, the cyano Pyraclostrobin, 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 and N-[9-( Dichloromethylene)-1,2,3,4-tetrahydro-1,4-carbonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4 -Metformin is preferred, and the phenol, fluphene, isopyrazolamide, flufenac, pirimipenem and ciprofloxacin are preferred and the fluocyanide ratio is optimal.

In another more preferred embodiment, the non-encapsulated insecticide comprises trimethoxazole, sulforaphane, thiabicide, isotianil or gupamine, more preferably trimethoprim.

In another more preferred embodiment, the non-encapsulated insecticide comprises carnitamicin, phlegm or dicyandiamide. Examples of suitable combinations are set forth in Table 2, where R-1 to R- are combined:

The CS formulation typically comprises from 20 g to 400 g/l, preferably from 30 g to 250 g/l, more preferably from 40 g to 200 g/l, and most preferably from 50 g to 150 g/l. Insecticides.

The invention also relates to a method of increasing the health of a plant, in particular a rice plant, in a rice field, which comprises using a formulation as defined above Reason.

The invention further relates to a method of controlling a phytopathogenic pest in a rice field, which comprises treating with a formulation as defined above.

The term "pest" refers to a phytopathogenic fungus or a phytopathogenic insect by the presence of an active substance or a non-encapsulated insecticide present in the core of the capsule.

Examples of phytopathogenic fungi in rice

Alternaria spp., Bipolaris (such as Bipolaris oryzae ), and Drechslera species on rice, Cercospora cerevisiae ( Cercospora oryzae ), Cochliobolus miyabeanus , Curvularia lunata , Sarocladium oryzae , S attenuatum , Entyloma oryzae , Fusarium spp (such as Fusarium semitectum ) and/or moniliforme Gibberella fujikuroi (malignant seedlings), grain dyeing complex (various pathogens) and/or rot spp, Helminthosporium (Helminthosporium .spp) (e.g. rice Helminthosporium (Helminthosporium oryzae)), Aspergillus fungus Microdochium (Microdochium oryzae), rice blast fungus (Pyricularia grisea) (synonyms (Pythium ssp.): rice thermal pathogen (Pyricularia oryzae)), Rhizoctonia (Rhizoctonia species) (e.g. Rhizoctonia solani (Rhizoctonia solani) (synonym: Rhizoctonia solani of rice grains (Pellicularia sasakii))) Rice sheath Hyun f bacteria (Corticium sasakii) and green rice solani (Ustilaginoidea virens).

Examples of phytopathogenic insects in rice are rice water weevil ( Lissorhoptrus oryzaphilus ), rice aphid ( Chilo suppresalis ), rice leaf curler , rice leaf worm, rice latent Leaf worm (Agromyca oryzae), spider mites ( Nephotettix spp .; especially small brown leafhopper, green rice leafhopper), planthopper ( Delphacidae ) In particular, it is white-backed planthopper, brown rice planthopper, and bed bug.

In a preferred embodiment, the method of controlling a phytopathogenic pest in a rice field comprises treating with a CS formulation as defined above, wherein the encapsulated insecticide is a cytotoxic and phytopathogenic pest of Magnaporthe oryzae ( Synonym: rice fever pathogen and/or Rhizoctonia (specifically, Rhizoctonia solani (synonym: rice sheath blight in rice)).

In another preferred embodiment, the method of controlling a phytopathogenic pest in a rice field comprises treating with a CS formulation as defined above, wherein the encapsulated insecticide is a cytotoxic and chlorpyrifos and phytopathogenic The pest is a rice blast fungus (synonym: rice fever) and/or a genus Rhizoctonia (specifically, Rhizoctonia solani (synonym: rice sheath blight in rice)).

In another preferred embodiment, the method of controlling a phytopathogenic pest in a rice field comprises treating with a CS formulation as defined above, wherein the encapsulated insecticide is a kekemin and the non-encapsulated insecticide system Fluoride, and the plant pathogenic pest is Magnaporthe oryzae and/or Rhizoctonia (specifically, Rhizoctonia solani (synonym: Rhizoctonia solani) .

In another preferred embodiment, the method of controlling a phytopathogenic pest in a rice field comprises treating with a CS formulation as defined above, wherein the encapsulated insecticide is a kekemin and the non-encapsulated insecticide system Trimethoxazole, and plant pathogenicity The pest is a rice blast fungus (synonym: rice fever) and/or a genus Rhizoctonia (specifically, Rhizoctonia solani (synonym: rice sheath blight in rice)).

In the above mentioned methods, the amount of the pesticide is usually between 10 and 500 g/ha.

For example, for baikemin, a preferred ratio is 10-150 g/ha.

For example, for fluridazole, a preferred ratio is 10-120 g/ha

The invention is further illustrated by the following examples without limitation.

Instance Example 1 - Preparation of microcapsules

Solvesso® 200: aromatic hydrocarbon solvent with a distillation range of 238-278 ° C (purchased from Exxon)

Puccini® P 29: Highly refined mineral oil (purchased from Q8)

Plurafac® LF 1300: alkoxylated stearyl alcohol (available from BASF SE)

Emulsogen® 3510: butanediol, polyoxyethylene, polyoxypropylene block copolymer (purchased from Clariant)

Tersperse® 2500: 33 wt% methyl methacrylate graft polymer (reaction product of methyl methacrylate, methacrylic acid and methoxy PEG methacrylate), propylene glycol and water (purchased from Huntsman)

Mowiol® 18-88: Polyvinyl alcohol from partially hydrolyzed polyvinyl acetate (purchased from Kuraray)

Borresperse® Na: sodium lignosulfonate (purchased from Borregaard Lignotech)

Lupranat® M 20 S: Solvent-free polyisocyanate based on 4,4'-diphenylmethane dicyanate (MDI) with an average functionality of 2,7; NCO content approx. 32 g/100 g (available from BASF Elastogran)

Basonat® HI 100: hexamethylene-1,6-diisocyanate (available from BASF SE)

DETA: diethylene ethylamine (available from BASF SE)

HMDA: hexamethylene-1,6-diamine (available from BASF SE), 10% aqueous solution

Atlox® 4912: Polyethylene glycol esterified polyhydroxamic acid (available from Croda)

Acticide® MBS: an aqueous solution of methylisothiazolinone (MIT) and benzisothiazolinone (BIT) used as a biocide (purchased from Thor)

Silicon SRE-PFL: used as a defoamer on cerium oxide particles Polydimethyloxane emulsion (purchased from Wacker)

Plurafac LF 711: alcohol alkoxylate (available from BASF SE)

Plurafac LF 801: C8-C10 alcohol alkoxylate (available from BASF SE)

Lutensol® ON 60: Alcohol ethoxylate (6 EO) (available from BASF SE)

Genapol® C 100: Coconut Oil Ethoxylate (10 EO) (purchased from Clariant)

Lutensit® A-BO: a solution of sodium dioctylsulfosuccinate in water/propylene glycol (purchased from BASF SE)

Tween® 20: sorbitan monooleate ethoxylate (available from Croda)

Empilan® KR 6: C9/11 alcohol ethoxylate (6 EO) (purchased from Huntsman)

Synergen® GL 5: Polyglycerol esterified with phthalic acid and coconut oil fatty acid (purchased from Clariant)

Plurafac LF 900: alcohol alkoxylate (available from BASF SE)

Sipernat 22: Amorphous precipitated cerium oxide (available from Evonik Industries)

A suspension of PU capsules in Tables 1 A-D) and Table 2) was prepared using the concentrations [g/l; referred to as the concentration of the total suspension] as summarized in Table I.

The composition of the comparative example [Table 2, No. 1] is a composition of WO 10/105971.

The aqueous phase was prepared by dissolving Borresperse Na in water at ambient temperature. In a separate vessel, prepare a 100 grams of sensitive solution in a solvent and heat slightly to a maximum of 60 °C as needed. After the solution becomes clear, it is cooled to 20 ° C, and if the capsule core contains other surfactants, the other surfactant is added and subsequently dissolved and finally added with an amount of isocyanate (as given by the formulation).

This solution is then pre-emulsified by pouring the organic solution into an aqueous solution using a simple wing agitator in a suitable large vessel. After stirring for 5-15 seconds, the entire contents were introduced into the reaction vessel through a rotor-stator mill at a preset energy input level (in %) of 100% (Cavitron CD 1000), which was equipped with a slow Stir the agitator, dropping funnel and heat exchange jacket. After the transfer was completed, the stirrer was started at 200 rpm and the diluted amine solution (usually 10% w/w) was added over a period of 15 minutes.

After the amine addition was completed, the heating was turned on and the temperature inside the encapsulating vessel was increased to 60 ° C for 4 hours (the end scheme and the amount and type of isocyanate used therein). Finally, if foaming occurs during the curing reaction, add one Part of the defoamer.

After completion of the reaction, which can be monitored by the disappearance of the isocyanate band in the IR spectrum, the mixture is cooled and added with antifreeze, biocide, residual defoamer, tackifier, other optional adjuvants and water. Post-treatment is carried out by adjusting the target active ingredient loading.

The final capsule suspension of baikemin may be further mixed with a suspension concentrate of other active ingredients (e.g., Epp), or the surfactant/oil mixture may be emulsified into a capsule suspension or may be incorporated into other surfactants.

The amount of non-encapsulated 100-gram ("free 100 grams") was determined as follows:

The smaller sample of the formulation was diluted in two steps. First, a 1:100 dilution was performed and the sample was allowed to stand at 22 ° C for 2 hours without being disturbed. Next, an aliquot of this sample was diluted 1:5000 and allowed to stand again at 22 ° C for 2 hours.

After the second rest time, the sample was centrifuged at 4000 rpm for 15 minutes and the probe of the clarified supernatant was subjected to HPLC to analyze the free cytosentic content.

Example 2

The rice was sown in the field in small plots, each plot was about 1 sqm and repeated 4 times. When the first signs of natural infection occurred, they were treated with a given ratio as specified in Table 1/2 at about 5001 water/ha.

In addition, plants are inoculated with an inoculum suspension of M. thermophilus spores produced by washing infected leaf material from aged plants after the first application. Apply 3 times at 7 day intervals. From the 21st day after the first equivalent application to the 8th day after the last application, the infection rate was visually evaluated in the form of the percentage of damaged leaf area and the Abbott efficacy was calculated based thereon.

The Abbot-type performance (E) is calculated as follows: E = (1-α/β). 100 α corresponds to fungal infection of treated plants (expressed in %) and β corresponds to fungal infection of untreated (control) plants (expressed in %)

Potency 0 means that the degree of infection of the treated plant corresponds to the degree of infection of the untreated control plant; efficacy 100 means that the treated plant is not infected.

It demonstrates that although the release rates in water under rice field conditions are very similar, the formulations exhibited by the present invention are far superior to the prior art formulations from the comparative examples (Table 2, No. 1).

Claims (15)

a microcapsule wherein (v) the capsule has a core-shell structure; and (vi) at least 80% of the pesticide is dissolved in an organic solvent in the core at 25 ° C; and (vii) the capsule shell is based on A polyfunctional isocyanate and a polyamine polyurethane in a polymeric form are included; and (viii) the ratio of the weight of the capsule shell to the weight of the capsule is from 1% to 20% by weight. The microcapsule of claim 1, wherein the capsules have an average particle diameter of from 0.5 μm to 8 μm. The microcapsule of claim 1 or 2, wherein the solvent comprises at least one non-polar solvent. The microcapsule of claim 1 or 2 additionally comprising a surfactant in the core. The microcapsule of claim 1 or 2, wherein the at least one encapsulated insecticide is selected from the group consisting of a strobilurine fungicide or a methotrexate fungicide. The microcapsule of claim 5, wherein the tropin is a pyraclostrobin. The microcapsule of claim 5, wherein the encapsulated methotrexate fungicide is fluxapyroxad. The microcapsule of claim 5, wherein the encapsulated fungicide is a mixture of hexamidine and hexagram. A formulation comprising the microcapsules of any of claims 1 to 7 and other formulation auxiliaries. The formulation of claim 8 further comprising other non-encapsulated insecticides. The formulation of claim 10, wherein the encapsulated insecticide is baikemin and the other non-encapsulated insecticide is selected from the group consisting of bixafen, pirimidol, isopyrazam , penflufen, penthiopyrad, sedaxane, tricyclazole, isoprothiolane, carpropamid, Epp Epoxiconazole, prothioconazole, difenoconazole, propiconazole, isotianil, kasugamycin, gupamine, probenazole, and bis Ciclocymet. A method of controlling a phytopathogenic pest in a rice field, which comprises treating with a formulation as claimed in claim 9 or 10. A method of increasing the health of a rice plant in a rice field, which comprises treating with a formulation as claimed in claim 9 or 10. The method of claim 12, wherein the pests are phytopathogenic fungi. The method of claim 12, wherein the pests are plant pathogenic insects.