New pesticidal formulations

Abstract

Formulation comprising microparticles, where said microparticles are dispersed in an aqueous solvent, where said aqueous solvent comprises xanthan gum, and where said microparticles are microcapsules having a core and a shell, and where said microparticles comprise a. a water insoluble active ingredient, said active ingredient being comprised in the core of said micro-capsule b. a shell, c. a protective colloid comprising polyvinyl alcohol; wherein the pH of said aqueous solvent is 5 or less.

Description

New pesticidal formulationsThe present invention is directed to formulations comprising microparticles, where said microparticles are dispersed in an aqueous solvent, where said aqueous solvent comprises xanthan gum, and where said microparticles are microcapsules having a core and a shell, and where said microparticles comprise a. a water insoluble active ingredient, said active ingredient being comprised in the core of said microcapsule, b. a shell, c. a protective colloid comprising polyvinyl alcohol; wherein the pH of said aqueous solvent is 5 or less.It is further directed to processes for making such formulations and to methods of controlling pests using such formulations.The encapsulation of active substances has been known for a long time. It offers several advantages over nonencapsulated formulations. For example, it is possible to control the release profile of the active substance.However, microencapsulation of actives like pesticides poses many challenges. Inter alia, it is very difficult to prepare such microcapsules in a way that the desired release profile is achieved and that the formulations so prepared are stable, especially during storage. One important parameter for microencapsulation is the control of the capsule size and their stability over time.It has now been surprisingly found that the stability of microcapsule formulations can be increased by formulations comprising microparticles, where said microparticles are dispersed in an aqueous solvent, where said aqueous solvent comprises xanthan gum, and where said microparticles are microcapsules having a core and a shell, and where said microparticles comprise a. A water insoluble active ingredient, said active ingredient being comprised in the core of said microcapsule b. A shell, c. A protective colloid comprising polyvinyl alcohol; wherein the pH of said aqueous solvent is 5 or less.Microcapsules are a form of microparticles. Herein, these terms are used synonymously.In formulations of the invention, microcapsules are dispersed in an aqueous solvent.“Aqueous” as used herein shall mean that such formulations comprise a solvent or a solvent mixture and that saidsolvent mixture comprises at least 50 wt% more preferably at least 70 wt% of water. Any water immiscible solvent comprised in the capsule core shall not be considered part of this solvent mixture. In one preferred embodiment, the aqueous solvent comprises at least 95 wt% or at least 99 wt% of water.Typically, formulations of the invention comprise microcapsules having a core shell structure. This means that such capsules comprise a core, in which an active ingredient is comprised, and a shell.Said shell typically comprises a polymeric material. In one embodiment, said shell comprises polyurea.Polyurea is also a known shell material for microcapsules. They are preferably prepared by an interfacial polymerization process of a suitable polymer wall forming material, such as a polyisocyanate and a polyamine. Interfacial polymerization is usually performed in an aqueous oil-in-water emulsion of the core material containing dissolved therein at least one part of the polymer wall forming material. During the polymerization, the polymer segregates from the core material to the boundary surface between the core material and water thereby forming the wall of the microcapsule. Thereby an aqueous suspension of the microcapsule material is obtained.In general, polyurea is formed by reacting a polyisocyanate having at least two isocyanate groups with a polyamine having at least two primary amino groups to form a polyurea wall material. In one embodiment, the polyisocyanate or the polyamine or both have more than two reactive - NCO- or NH-groups, respectively. In a further embodiment, the polyurea may be formed by contacting polyisocyanate with water. In one embodiment, the polyurea results from a reaction of polyisocyanate with both polyamine and water. Preferably, the polyurea shell contains a polyisocyanate and a polyamine in polycondensed form. Suitable polyisocyanates are known, e.g. from US 2010 / 0248963 A1, paragraphs

[0135] to

[0158] , to which full reference is made. Suitable polyamines are known, e.g. from US 2010 / 0248963 A1, paragraphs

[0159] to

[0169] , to which full reference is made.Polyisocyanates may be used individually or as mixtures of two or more polyisocyanates. Suitable polyisocyanates are for example aliphatic isocyanates or aromatic isocyanates. These isocyanates may be present as monomeric or oligomeric isocyanates The NCO content may be determined according to ASTM D 5155-96 A.Examples of suitable aliphatic diisocyanates include tetramethylene diisocyanate, pentamethylene diisocyanate and hexamethylene diisocyanate as well as cycloaliphatic isocyanates such as isophorone diisocyanate, 1 ,4- bisisocyanatocyclohexane and bis-(4-isocyanatocyclohexyl)methane.Suitable aromatic isocyanates include toluene diisocyanates (TDI: a mixture of the 2,4- and 2,6-isomers), diphenyl- methene-4, 4' -diisocyanate (MDI), polymethylene polyphenyl isocyanate, 2,4,4'-diphenyl ether triisocyanate, 3,3'- dimethyl-4, 4' -diphenyl diisocyanate, 3,3’-dimethoxy-4,4’-diphenyl diisocyanate, 1 ,5-naphthylene diisocyanate and 4, 4', 4" -triphenylmethane triisocyanate. Also suitable are higher oligomers of the aforementioned diisocyanates such as the isocyanurates and biurets of the aforementioned diisocyanates and mixtures thereof with the aforementioned diisocyanates.In another preferred embodiment, the polyisocyanate is an oligomeric isocyanate, preferably an aromatic or aliphatic, oligomeric isocyanate. Such oligomeric isocyanates may comprise above mentioned aliphatic diisocyanates and / or aromatic isocyanates in oligomerized form. Preferred aliphatic oligomeric isocyanates include isocyanurates, biurets or allophanates of 1,6-hexymethylenediisocyanate or isophoronediisocynate, preferred are isocyanurates of 1 ,6.- hexamethylenediisocyanate. Such oligomeric isocyanates, especially of hexamethylenediisocyanate, can optionally be functionalized with functional groups to improve the water dispersibility of such oligomers, such functional groups including polyethylene glycol chains or ionic groups such as sulfonate groups. The oligomeric isocyanates typically have an average functionality in the range of 2.0 to 4.0, preferably 2.1 to 3.2, and more preferably 2.3 to 3.0. Typically, these oligomeric isocyanates have a viscosity (determined according to DIN 53018) in the range from 20 to 1000 mPas, more preferably from 80 to 500 mPas and especially from 150 to 320 mPas. Such oligomeric isocyanates are commercially available, for example from BASF SE under the tradenames Lupranat® M10, Lupranat® M20, Lupran- at® M50, Lupranat® M70, Lupranat® M200, Lupranat® MM103, Basonat®.Also suitable are adducts of diisocyanates with polyhydric alcohols, such as ethylene glycol, glycerol and trimethylolpropane, obtained by addition, per mole of polyhydric alcohol, of a number of moles of diisocyanate corresponding to the number of hydroxyl groups of the respective alcohol and mixtures thereof with the aforementioned diisocyanates. In this way, several molecules of diisocyanate are linked through urethane groups to the polyhydric alcohol to form high molecular weight polyisocyanates. A particularly suitable product of this kind can be prepared by reacting three moles of toluene diisocyanate with one mole of 2-ethylglycerol (1,1 -bismethylolpropane). Further suitable products are obtained by addition of hexamethylene diisocyanate or isophorone diisocyanate with ethylene glycol or glycerol.Preferred polyisocyanates are isophorone diisocyanate, diphenylmethane-4, 4’ -diisocyanate, toluene diisocyanates, and oligomeric isocyanates, whereas oligomeric isocyanates are in particular preferredSuitable polyamines within the scope of this invention will be understood as meaning in general those compounds that contain two and more primary amino groups in the molecule, which amino groups may be linked to aliphatic or aromatic moieties.Examples of suitable aliphatic polyamines are diamines of the formula H2N-(CH2)P-N H2, wherein p is an integer from 2 to 6. Exemplary of such diamines are ethylene diamine, propylene-1,3-diamine, tetramethylene diamine, pentamethylene diamine and hexamethylene diamine. A preferred diamine is hexamethylene diamine. Further suitable aliphatic polyamines are polyethyleneimines of the formula H2N-(CH2-CH2-NH)q-H, wherein q is an integer from 2 to 20, preferably 3 to 5. Representative examples of such polyethyleneimines are diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine. Further suitable aliphatic polyamines are dioxaalkanediamines, such as 4,9-dioxadodecane-1,12-diamine of the formula H2N-(CH2)3O-(CH2)4O-(CH2)3-NH2.Examples of suitable aromatic polyamines are 1,3-phenylene diamine, 2,4- and 2,6-toluene diamine, 4, 4' -diaminodiphenyl methane, 1 ,5-diaminonaphthalene, 1,3,5-triaminobenzene, 2,4,6-triaminotoluene, 1,3,6-triaminonaphthalene, 2,4,4’-triaminodiphenyl ether, 3,4,5- triamino-1 ,2,4-triazole and 1,4,5,8-tetraaminoanthraquinone. Polyamines that are insoluble or insufficiently soluble in water may be used as their hydrochloride salts.Polyamines, such as those mentioned above may be used individually or as mixtures of two or more polyamines. Preferred polyamine is a polyethyleneimine, such as tetraethylene pentamine.The relative amounts of each complementary wall-forming component will vary with their equivalent weights. In general, approximately stoichiometric amounts are preferred, while an excess of one component may also be employed, especially an excess of polyisocyanate. The total amount of wall-forming components approximately corresponds to the total amount of polymeric wall-forming materials.The microcapsules contain up to 30 wt%, preferably up to 25 wt% and in particular up to 20 wt% of shell (e.g. based on the total amount of pesticide, all solvents in the core, shell material (especially polyisocyanate and polyamine) and not taking into account any protective colloid. The microcapsules contain usually at least 0.5 wt%, preferably at least 1.5 wt% shell. In another form the microcapsules contain up to 25 wt%, preferably up to 20 wt% and in particular up to 18 wt% of shell (e.g. based on the total amount pesticide, especially pyraclostrobin, all solvents in the core, shell material (especially polyisocyanate and polyamine).According to the invention, such microcapsules comprise an active ingredient in the core of such microcapsules.According to the invention, active substances contained in the microparticles of the invention are insoluble in water.“Insoluble in water” in this context shall mean that such active substances have a solubility in water of less than 10 g / l at 21 °C, preferably less than 1 g / l at 21 °C In one embodiment, water immiscible active substances have a solubility in water of less than 0.1 g / l at 21 °C.Typically, said active ingredient is a pesticide P.The term pesticides refers to at least one active substance selected from the group of the fungicides, insecticides, nematicides, herbicides, pheromones, safeners and / or growth regulators.Suitable pesticides P can in principle be any kind of pesticide that is insoluble in water.Preferred pesticides P are fungicides, insecticides, herbicides and growth regulators. In one embodiment, pesticides P are insecticides. In one embodiment, pesticides are fungicides. In one embodiment, pesticides P are herbicides. In one embodiment, pesticides are pheromones. Mixtures of pesticides from two or more of the abovementioned clas-ses may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, LondonThe composition may comprise one or more pesticides.Suitable pesticides include the following:The following lists of pesticides that are suitable for use in formulations of the invention, is intended to illustrate the possible combinations but does not limit them:A) Respiration inhibitors inhibitors of complex III at Qosite: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestro- burin, fenaminstrobin, fenoxystrobin / flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metom- inostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, pyriben- carb, triclopyricarb / chlorodincarb, famoxadone, fenamidone, pyriminostrobin, bifujunzhi, metyltetraprole;- inhibitors of complex III at Qi site: cyazofamid, amisulbrom, fenpicoxamid, florylpicoxamid, metarylpicoxamid;- inhibitors of complex II: benodanil, benzovindiflupyr, bixafen, boscal id, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetamid, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, pyd- iflumetofen, pyraziflumid, sedaxane, tecloftalam, thifluzamide, inpyrfluxam, pyrapropoyne, fluindapyr, isoflu- cypram, cyclobutrifluram;- other respiration inhibitors: diflumetorim; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, mep- tyldinocap; ferimzone; organometal compounds: fentin salts, e.g. fentin-acetate, fentin chloride or fentin hydroxide; silthiofam;- quinone outside inhibitor stigmatellin binding type: ametoctradin;B) Sterol biosynthesis inhibitors (SBI fungicides)- C14 demethylase inhibitors: triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, pro- piconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole , fluoxytioconazole, ipfentrifluconazole, mefentrifluconazole; imidazoles: imazalil, pefurazoate, pro- chloraz, triflumizol; pyrimidines, pyridines, piperazines: fenarimol, pyrifenox, triforine;Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;- Inhibitors of 3-keto reductase: fenhexamid, fenpyrazamine;- other Sterol biosynthesis inhibitors: chlorphenomizole;C) Nucleic acid synthesis inhibitors- RNA polymerase I inhibitors: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M, ofurace, oxadixyl;- other nucleic acid synthesis inhibitors: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, ipflufenoquin, quinofumelin;D) Inhibitors of cell division and cytoskeletontubulin polymerization inhibitors: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl, pyr- idachlometyl;- other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyrio- fenone, phenamacril, fluopimomide;E) Inhibitors of amino acid and protein synthesis methionine synthesis inhibitors: cyprodinil, mepanipyrim, pyrimethanil;- protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin;F) Signal transduction inhibitorsMAP I histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fludioxonil;- mechanism unknown: quinoxyfen, proquinazid;G) Lipid and membrane synthesis inhibitors- Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane;- lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;- compounds affecting cell membrane permeability and fatty acides: propamocarb;- inhibitors of oxysterol binding protein: oxathiapiprolin, fluoxapiprolin;H) Inhibitors with Multi Site Action- inorganic active substances: Bordeaux mixture, copper, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;- organochlorine compounds: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid;- guanidines and others: guanidine, dodine, dodine free bas, guazatine, guazatine-acetate, iminoctadine, iminoc- tadine-triacetate, iminoctadine-tris(albesilate), dithianon, fluoroimide, methasulfocarb, chinomethionat;I) Cell wall synthesis inhibitors inhibitors of glucan synthesis: validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil, tolprocarb; cellulose synthase inhibitors: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate;J) Plant defense inducers- acibenzolar-S-methyl, probenazol, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl- aluminum, phosphorous acid and its salts, calcium phosphonate, potassium phosphonate, potassium or sodium bicarbonate, dichlobentiazox;K) Unknown mode of action- bronopol, cyflufenamid, cymoxanil, dazomet, debacarb, diclocymet, diclomezine, difenzoquat, difenzoquat- methylsulfate, diphenylamin, fenitropan, fenpyrazamine, flumetover, flumetylsulforim, flusulfamide, flutianil, harpin, nitrapyrin, nitrothal-isopropyl, oxin-copper, seboctylamine, tebufloquin, tecloftalam, triazoxide, pyrisoxa- zole, , benziothiazolinone, bromothalonil, aminopyrifen, flufenoxadiazam;L) BiopesticidesL1) Microbial pesticides with fungicidal, bactericidal, viricidal and / or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. amyloliq- uefaciens ssp. plantarum (also referred to as B. velezensis), B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, B. velezensis, Candida oleo- phila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus epiphyticus, P. polymyxa, Pantoea vagans, Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp. , Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and / or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract;L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and / or nematicidal activity: Agrobacterium radio- bacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B. brongniartii, Burkholderia spp., Chromobacterium subtsugae, Cydia pomonella granulovirus, Cryptophlebia leucotreta granulovirus, Flavobac- terium spp., Helicoverpa armigera nucleopolyhedrovirus, Helicoverpa zea nucleopolyhedrovirus, Helicoverpa zea single capsid nucleopolyhedrovirus, Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopliae, M. anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria spp., P. nishi- zawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus, Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces galbus, S. microflavus,'L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and / or nematicidal activity: L- carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,11 , 13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2- methyl 1-butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadien- 1 -ol acetate, (E,Z)-3,13-octadecadien-1-ol, (R)-1-octen-3-ol, pentatermanone, (E,Z,Z)-3, 8, 11 -tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1-yl acetate, (Z)-7-tetradecen-2-one, (Z)-9-tetradecen-1-yl acetate, (Z)-11- tetradecenal, (Z)-11-tetradecen-1-ol, extract of Chenopodium ambrosiodes, Neem oil, Quillay extract;L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and / or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Brady- rhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sino-rhizobium meliloti;0) Insecticides from classes 0.1 to 0.290.1 Acetylcholine esterase (AChE) inhibitors: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isopro- carb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl 0- (methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thi- ometon, triazophos, trichlorfon, vamidothion;0.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; ethiprole, fipronil, flufiprole, pyrafluprole, py riprole;0.3 Sodium channel modulators: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa- bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, the- ta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, me- perfluthrin, metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluthrin, tetramethylfluthrin, tetramethrin, tralo- methrin, transfluthrin; DDT, methoxychlor;0.4 Nicotinic acetylcholine receptor (nAChR) agonists: acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; nicotine; sulfoxaflor, flupyradifurone, triflumezopyrim, fenmezoditiaz, flupyrimin;0.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, spinetoram;0.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin;0.7 Juvenile hormone mimics: hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen;0.8 miscellaneous non-specific (multi-site) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;0.9 Chordotonal organ TRPV channel modulators: afidopyropen, pymetrozine, pyrifluquinazon;0.10 Mite growth inhibitors: clofentezine, hexythiazox, diflovidazin; etoxazole;0.11 Microbial disruptors of insect midgut membranes: Bacillus thuringiensis, B. sphaericus and the insecticdal proteins they produce: Bacillus thuringiensis subsp. israelensis, B. sphaericus, B. thuringiensis subsp. aizawai, B. thuringiensis subsp. kurstaki, B. thuringiensis subsp. tenebrionis, the Bt crop proteins: Cry1 Ab, CrylAc, Cry1 Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1;0.12 Inhibitors of mitochondrial ATP synthase: diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon;0.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient: chlorfenapyr, DNOC, sulfluramid;0.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap, cartap hydrochloride, thiocyclam, thio- sultap sodium;0.15 Inhibitors of the chitin biosynthesis type 0: bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;0.16 Inhibitors of the chitin biosynthesis type 1 : buprofezin;0.17 Moulting disruptors: cyromazine;0.18 Ecdyson receptor agonists: methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide;0.19 Octopamin receptor agonists: amitraz;0.20 Mitochondrial complex III electron transport inhibitors: hydramethylnon, acequinocyl, fluacrypyrim, bifenazate;0.21 Mitochondrial complex I electron transport inhibitors: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone;0.22 Voltage-dependent sodium channel blockers: indoxacarb, metafl umizone;0.23 Inhibitors of the of acetyl CoA carboxylase: spirodiclofen, spiromesifen, spirotetramat, spiropidion, spirobudifen, spidoxamat;0.24 Mitochondrial complex IV electron transport inhibitors: aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide;0.25 Mitochondrial complex II electron transport inhibitors: cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide;0.28 Ryanodine receptor-modulators: chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, fluchlod- iniliprole; tetrachlorantraniliprole; tetraniliprole; tiorantraniliprole; cyhalodiamide;0.29 Chordotonal organ modulators: flonicamid;0.30 GABA-gated chloride channel allosteric modulators: broflanilide, fluxametamide, isocycloseram;0.33 Calcium-activated potassium channel modulators: acynonapyr;0.34 Mitochondrial complex III electron transport inhibitors at Qi site: flometoquin;O.UN Insecticidal compounds of unknown or uncertain mode of action: afoxolaner, azadirachtin, amidoflumet, ben- zoximate, bromopropylate, chinomethionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufen- erim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonyl butox- ide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, actives on basis of Bacillus firmus (Votivo); fluazaindoliz- ine; tyclopyrazoflor; sarolaner, lotilaner; benzpyrimoxan; tigolaner; oxazosulfyl; cyproflanilide, nicofluprole; inda- zapyroxamet; flupentiofenox; cyclobutrifluram.P) Herbicides from the classes P1 to P15P1) lipid biosynthesis inhibitors:- ACC-herbicides: alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cy- cloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, halox-yfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim;- non-ACC herbicides: benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;P2) ALS inhibitors: sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlo- rimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysul- furon, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron- sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasul- furon, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron; imidazolinones: imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, ima- zaquin and imazethapyr; triazolopyrimidine herbicides and sulfonanilides: cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam; pyrimidinylbenzoates: bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyrimi- nobac-methyl, pyrithiobac, pyrithiobac-sodium; sulfonylaminocarbonyl-triazolinone herbicides: flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl; and triafamone;P3) photosynthesis inhibitors: amicarbazone, inhibitors of the photosystem II, triazine herbicides, including of chlorotriazine, triazinones, triazindi- ones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, desmetryn, di- methametryn, hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, ter- buthylazin, terbutryn and trietazin, aryl urea such as chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinu- ron, neburon, siduron, tebuthiuron and thiadiazuron, phenyl carbamates such as desmedipham, karbutilat, phen- medipham, phenmedipham-ethyl, nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters, uraciles such as bromacil, lenacil and terbacil, and bentazon and bentazon-sodium, pyridate, pyridafol, pentanochlor and propanil and inhibitors of the photosystem I such as diquat, diquat-dibromide, paraquat, paraquat-dichloride and paraquat-dimetilsulfate;P4) protoporphyrinogen-IX oxidase inhibitors: acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, car- fentrazone-ethyl, chlomethoxyfen, chlorphthalim, cinidon-ethyl, cyclopyranil, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl,fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, trifludimoxazin, epyrifenacil;P5) bleacher herbicides:- PDS inhibitors: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, rimisoxafen;- HPPD inhibitors: benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquinotrione, isoxaflutole, mesotrione, oxotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, toprame- zone, bipyrazone, fenpyrazone, cypyrafluone, tripyrasulfone, benquitrione, dioxopyritrione;- bleacher, unknown target: aclonifen, amitrole flumeturon, bixlozone;P6) EPSP synthase inhibitors: glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate-trimesium (sulfosate);P7) glutamine synthase inhibitors: bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate-ammonium;P8) DHP synthase inhibitors: asulam;P9) mitosis inhibitors: group K1 : dinitroanilines: benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin; phosphoramidates: amiprophos, amiprophos-methyl, and butamiphos; benzoic acid herbicides: chlorthal, chlorthal-dimethyl; pyridines: dithiopyr and thiazopyr; benzamides: propyza- mide and tebutam; group K2: carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M- isopropyl, flamprop-M-methyl and propham;P10) VLCFA inhibitors:- chloroacetamides: acetochlor, alachlor, amidochlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor,- oxyacetanilides: flufenacet and mefenacet;- acetanilides: diphenamid, naproanilide, napropamide and napropamide-M;- tetrazolinones: fentrazamide;- other herbicides: anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone, dimesulfazet and isoxazoline;P11) cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam;P12) decoupler herbicides: dinoseb, dinoterb and DNOC and its salts;P13) auxinic herbicides:2,4-D and its salts and esters such as clacyfos, 2,4-DB and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as aminopyralid-dimethylammonium, aminopyralid-tris(2- hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop- P and its salts and esters, flopyrauxifen, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, halauxifen and its saltsand esters; MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, florpyrauxifen, florpyrauxifen-benzyl and 4-amino-3- chloro-5-f luoro-6-(7-fl uoro-1 H-\ ndol-6-yl)picolinic acid;P14) auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium;P15) other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate and its salts and esters, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methiozolin, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, tetflupyrolimet, tridiphane.Q) Safeners(quinolin-8-oxy)acetic acids, 1 -phenyl-5-haloalkyl-1 H-1 ,2,4-triazol-3-carboxylic acids, 1 -phenyl-4,5-dihydro-5-alkyl- 1 H-pyrazol-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazol carboxylic acids, dichloroacetamides, alpha- oximinophenylacetonitriles, acetophenonoximes, 4,6-dihalo-2-phenylpyrimidines, N-[[4- (aminocarbonyl)phenyl]sulfonyl]-2-benzoic amides, 1 ,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazol carboxylic acids, phosphorthiolates and N-alkyl-O-phenylcarbamates and their agriculturally acceptable salts and their agriculturally acceptable derivatives such amides, esters, and thioesters, provided they have an acid group.In one embodiment, pesticide P comprises metyltetraprole, mefentrifluconazole, fluxapyroxad, Inpyrfluxam, Kresoxim methyl, Pyraclostrobin, Fluopyram, saflufenacil, broflanilide, dimpropyridaz, fenmezoditiaz, Cinnamaldehyde, Prothi- oconazole, Trifloxystrobin, Fluxapyroxad, Spiroxamine, afidopyropen, alpha-cypermethrin, fipronil, cyflumetofen, boscalid, epoxiconazole, metconazole, metrafenone, prothioconazole, bentazone, dimethenamide, tembotrione, trifludimoxazin, Mefenpyr-Diethyl, azoxystrobin, picoxystrobin, fluoxastrobin, oryzastrobin, dimoxystrobin, indiflin or mixtures thereof. Preferably, pesticide P comprises metyltetraprole, mefentrifluconazole, fluxapyroxad, Inpyrfluxam, Kresoxim methyl, Pyraclostrobin, Fluopyram, saflufenacil, broflanilide, dimpropyridaz, fenmezoditiaz, pendimethalin, Cinnamaldehyde, Prothioconazole, Trifloxystrobin, Fluxapyroxad, Spiroxamine, afidopyropen, alpha-cypermethrin, fipronil, cyflumetofen, boscalid, epoxiconazole, metconazole, metrafenone, prothioconazole, bentazone, dimethenamide, tembotrione, trifludimoxazin, Mefenpyr-Diethyl or mixtures thereof.More preferably, pesticide P comprises metyltetraprole, mefentrifluconazol, fluxapyroxad, Inpyrfluxam, Kresoxim methyl, Pyraclostrobin, Fluopyram, alpha-cypermethrin, Cinnamaldehyde, Prothioconazole, Trifloxystrobin, Pendimethalin, Fluxapyroxad, Spiroxamine, Mefenpyr-Diethyl, indiflin or mixtures thereof.In one embodiment, pesticide P comprises a strobilurin pesticide. Examples of strobilurin pesticides include azoxystrobin, kresoxim methyl, picoxystrobin, fluoxastrobin, oryzastrobin, dimoxystrobin, pyraclostrobin, trifloxystrobin and metyltetraprole.In one embodiment, pesticide P comprises alpha cypermethrin, pyraclostrobin or mixtures thereof.In one embodiment, pesticide P comprises alpha cypermethrin.In one embodiment, pesticide P is liquid at 20 °C and is comprised in the core of such microcapsules as a pure compound.In one embodiment, pesticide P is comprised in the core of such microcapsules as a solution in a water immiscible solvent S.Water immiscible solvents S have a solubility in water of 1 wt% or less at 20 °C, preferably of 0.1 wt% or less at 20°C.Examples of Solvents S include: mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and C8 to C11 aromatic petroleum derivatives (aromatic hydrocarbons) with a boiling point range from 130°C to 300°C; vegetable oils such as coco oil, palm kern oil, palm oil, soya oil, rapeseed oil, corn oil and the methyl or ethyl esters of the afore-mentioned oils, hydrocarbons such as aromatic depleted, linear paraffinic, isoparaffinic, cycloparaffinic having a flash point between 40°C and 250°C and a distillation range between 150°C and 450°C; ketones, e.g. acetophenone; carbonates, e.g. dibutyl carbonate; esters, e.g. benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl lactate, 2- phenoxyethyl propionate; lactates, e.g. 2-ethylhexyl lactate; fatty acid esters, fatty acids; phosphonates; fatty acid amines; pyrrolidones, such as N-butyl pyrrolidone, N-octylpyrrolidone, N-ethyl pyrrolidone, N-docedyl pyrrolidone, hydroxy ethyl pyrrolidone; fatty acid amides, e.g. N,N-dimethyloctanamide, N,N-dimethylnonaneamide, N,N-dimethyldecanamide, N,N-Dimethyl 9-decenamide, lauryl N, N-dimethylamide, lauryl N,N-dimethylamide, and mixtures thereof.Herein, “C8 dimethylamide'' and “N, N-dimethyl octaneamide" shall be understood to mean ”C8 fatty acid N,N- dimethylamide” (analogously for other chain lengths).“Fatty acid” herein shall denote a linear or branched carboxylic acid with a saturated or unsaturated aliphatic chain.In one embodiment, solvent S is selected from benzyl benzoate, C8-fatty acid N, N-dimethylamide, C10 fatty acid N, N-dimethylamide, dibutyl adipate, ethyl hexyl lactic acid, propylene glycol dibenzoate, tris-ethyl hexyl phosphate, solvesso, benzyl acetate, methyl oleate, or mixtures thereof.Typically, formulations of the invention comprise 0.01 to 50 wt% of the active ingredient, preferably 0.1 to 45 wt%, more preferably 0.5 to 40 wt%.Microparticles used in the present invention typically have an average diameter d50 of 0.1 to 20 m, preferably 0.5 to 10 pm, even more preferably 0.5 to 5 pm. All particle sizes given herein are determined by statistic laser scattering using a Malvern Mastersizer 2000 according to European norm ISO 13320 EN.According to the invention, such microcapsules comprise a protective colloid that comprises a polyvinyl alcohol (PVA). PVA as used herein shall include polymer prepared from homopolymers of polyvinyl acetate as well as polyvinyl alcohol copolymers.Herein, the term "polyvinyl alcohol copolymer" means a polymer of vinyl alcohol / vinyl acetate with comonomers.Typically, polyvinyl alcohol is produced by hydrolysis (deacetylation) of polyvinyl acetate, whereby the ester groups of polyvinyl acetate are hydrolyzed into hydroxyl groups, thus forming polyvinyl alcohol.The degree of hydrolysis is a parameter of how many groups are converted into hydroxyl groups. The term "polyvinyl alcohol" in connection with a given degree of hydrolysis means therefore, in fact, a vinyl polymer containing ester and hydroxyl groups.In one embodiment of the invention, polyvinyl alcohol copolymers with degrees of hydrolysis from 85 to 99 9%, especially between 85 to 95% are used. In another form polyvinyl alcohol copolymers with degrees of hydrolysis from 60 to 99.9%, preferably from 70 to 98%, more preferably from 75 to 97 %, and in particular from 85 to 96 % are used.The degree of hydrolysis of polyvinyl alcohol may be determined according to DIN 53401 .The polyvinyl alcohol polymers according to the invention may contain additional comonomers, i.e. other comonomers are polymerized together with vinyl ester in a first step, followed by the hydrolysis of the ester groups to form the copolymer of polyvinyl alcohol in a second step.Typically, copolymers of polyvinyl alcohol are prepared by a radical polymerization reaction between the vinyl acetate and comonomers.In one embodiment of the invention polyvinyl alcohol copolymers contain unsaturated hydrocarbons as comonomers. These unsaturated hydrocarbons are optionally modified with functional non-charged and / or charged groups.In particular the following comonomers are suitable: unsaturated hydrocarbons having anionic groups like carboxyl- and / or sulfonic acid groups. In another form the polyvinyl alcohol copolymer contains comonomers with anionic groups selected from carboxyl- and / or sulfonic acid groups. In another form the polyvinyl alcohol copolymer contains 0.1 to 30 mol% (preferably 0.3 to 20 mol%, more preferably 0.5 to 10 mol%) of the comonomers with anionic groups.In one embodiment of the invention copolymers of polyvinyl alcohol with hydrolysis degrees from 85 to 99.9, preferred 85 % to 95% and containing 0.1 to 30 mol% (preferably 0.3 to 20 mol%, more preferably 0.5 to 10 mol%) comonomers with anionic groups like carboxyl- and / or sulfonic acid groups are used, wherein mol% is based on polymerization mixture vinyl acetate / comonomer.In another form copolymers of polyvinyl alcohol with hydrolysis degrees from 60 to 99.9, preferred 70 % to 98%, and containing 0.1 to 30 mol% (preferably 0.3 to 20 mol%, more preferably 0.5 to 10 mol%) comonomers with anionic groups like carboxyl- and / or sulfonic acid groups are used, wherein mol% is based on polymerization mixture vinyl acetate / comonomer.The polyvinyl alcohol copolymers typically have a viscosity from 1 to 100 mPas, preferably from 1 .5 to 70 mPas, more preferably from 2 to 50 mPas. The viscosity may be determined according to Brookfield at 4% in water at 20 °C.The following protective colloids are examples of suitable PVAs for the production of microcapsules according to the invention: Anionic polyvinyl alcohol copolymers with the hydrolysis degree > 80% - preferably 85.0%-99.5% and the viscosity 2 mPas-70 mPas (DP 100-6000). In another form anionic polyvinyl alcohol copolymers with the hydrolysis degree from 60 to 99.9 %, preferably from 85.0%-99.5%, and the viscosity from 2 mPas to 70 mPas (DP 100-6000). Examples of such type of colloids are: K-Polymer 25-88KL from Kuraray (viscosity 20-30 mPas, hydrolysis 85.0- 90.0%), Poval 18-88 from Kuraray (viscosity 16.5 - 19 5 mPas, hydrolysis 86 7-88.7 %), Gohsenal T-350 from Nippon Gohsei (viscosity 27-33 mPas, hydrolysis 93.0-95.0%), Gohseran L-3266 from Nippon Gohsei (viscosity 2.3-2.7 mPas, hydrolysis 86.5-89.0%)In general, the protective colloids (e.g. the polyvinyl alcohol copolymer) are used with amounts from 0.1 to 10% by weight, but preferably in the range from 0.2 to 5% by weight and in particular from 0.3 to 2% by weight, based on the weight of the microcapsules. The weight of the microcapsules is usually based on the total sum of the shell and the core materials, e.g. all isocyanates, all bifunctional amines, all water-insoluble materials, and the polyvinyl alcohol copolymer.Combinations of two or more different protective colloids may also be used.Formulations of the invention further comprise xanthan gum as a thickener.Typically, formulations of the invention comprise 0.01 to 1 wt% of xanthan gum, based on the formulation. In one embodiment, formulations of the invention comprise 0.1 to 0.8 wt% of xanthan gum, based on the formulation.According to the invention, the pH of the aqueous solvent in the formulation is below 5. In one embodiment, the pH of the aqueous solvent in the formulation is from 1 to 5, preferably 4.0 to 4.9, more preferably from 4.5 to 4.85.Another aspect of the present invention are processes for preparing formulations comprising microparticles comprising the following steps: i. Providing an oil phase comprising a water immiscible solvent, in which a water insoluble active ingredient is dissolved or a water insoluble active ingredient that is liquid at 20 °C, ii. Providing an aqueous phase, that comprises polyvinyl alcohol, ill. emulsifying the oil phase in the aqueous phase, iv. preparing the shell of the microcapsule, v. adding xanthan gum to the aqueous phase, vi. adjusting the pH of the aqueous phase to a value of 5 or less, preferably of 3 to 5, more preferably of 4 to 4.9.In one embodiment, said oil phase comprises a polyisocyanate, said shell comprises polyurea and said polyurea is prepared by adding a polyamine in step iv..Thus, in one embodiment, processes for making formulations comprising microparticles comprise the following steps:I. Providing an oil phase comprising a water immiscible solvent, in which an active ingredient is dissolved or an active ingredient that is liquid at 20 °C; as well as a polyisocyanate, ii. Providing an aqueous phase, that comprises polyvinyl alcohol, ill. emulsifying the oil phase in the aqueous phase, iv. adding a polyamine to prepare polyurea in an interfacial reaction, v. adding xanthan gum to the aqueous phase, vi. adjusting the pH of the aqueous phase to a value of 5 or less, preferably of 3 to 5, more preferably of 4 to 4.9.The nature of the acid in step vi. is not relevant for the process as long it does not undergo any side reactions with any of the other components of the formulation under the reaction conditions. Thus, the acid is not limited to any particular acids. Examples of suitable acids include acetic acid, phosphoric acid, hydrochloric acid, citric acid.Typically, processes of the invention are carried out at a temperature from 10 °C to 70 °C, preferably 15 to 50 °C. In one embodiment, processes of the invention are carried out without applying cooling or heating to the reaction vessel.The user applies such formulations usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, a drone, an unmanned aerial vehicle or an irrigation system. Usually, the agrochemical formulation is made up with water, buffer, and / or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical formulation according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.According to one embodiment, individual components of the formulation of the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.In a further embodiment, either individual components of the formulation according to the invention or partially premixed components, e. g. components comprising the pesticide and the adjuvant, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate. In a further embodiment, either individual components of the formulation according to the invention or partially premixed components, e. g. components comprising the pesticide and / or the adjuvant can be applied jointly (e.g. after tank mix) or consecutively.The present invention furthermore relates to methods for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired attack by insects or mites and regulating the growth of plants, where formulations of the invention or formulations prepared according to processes of the invention are allowed to act on the particular pests, their habitat or the plants to be protected from the particular pest, such as crop plants, the soil and / or on undesired plants and / or the useful plants and / or their habitat.Examples of suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins / squash, cucumbers or melons; fiber crops, for example cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tangerines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, pumpkin / squash or capsicums; plants of the laurel family, for example avocados, cinnamon or camphor; energy crops and industrial feedstock crops, for example maize, soybeans, wheat, oilseed rape, sugar cane or oil palm; maize; tobacco; nuts; coffee; tea; bananas; wine (dessert grapes and grapes for vinification); hops; grass, for example turf; sweetleaf (Stevia rebaudania)', rubber plants and forest plants, for example flowers, shrubs, deciduous trees and coniferous trees, and propagation material, for example seeds, and harvested produce of these plants.The term crop plants also includes those plants which have been modified by breeding, mutagenesis or recombinant methods, including the biotechnological agricultural products which are on the market or in the process of being developed. Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by hybridizing, mutations or natural recombination (i e. recombination of the genetic material). Here, one or more genes will, as a rule, be integrated into the genetic material of the plant in order to improve the plant's properties. Such recombinant modifications also comprise posttranslational modifications of proteins, oligo- or polypeptides, for example by means of glycosylation or binding polymers such as, for example, prenylated, acetylated or farnesylated residues or PEG residues.The present invention also relates to seeds (such as seeds or other plant propagation materials) comprising the formulation according to the invention. Plant propagation materials can be treated preventively with the formulation according to the invention at the point of or even before sowing or at the point of or even before transplanting. The formulations of the invention can be applied to the propagation materials, in particular seed, in undiluted form or, preferably, in diluted form. Here, the formulation in question can be diluted 2- to 10-fold, so that from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, of active substance is present in the formulations used for the seed dressing. The application may be effected before or during sowing. The treatment of plant propagation material, in particular the treatment of seed, is known to the skilled worker and carried out by dusting, coating, pelleting, dipping or soaking the plant propagation material, the treatment preferably being carried out by pelleting, coating and dusting or by in-furrow treatment so that, for example, untimely early germination of the seed is prevented. It is preferred to use suspensions for the treatment of seed. Usually, such formulations comprise from 1 to 800 g / l of active substance, from 1 to 200 g / l of surfactants, from 0 to 200 g / l of antifreeze agents, from 0 to 400 g / l of binders, from 0 to 200 g / l of colorants and solvent, preferably water.Formulations of the invention and processes of the invention offer the following advantages: They are easy and economical to make.The have a high biological activity.They have excellent storage stabilities. In particular, the particle size of the microparticles remains stable upon storage.The examples which follow illustrate the invention without imposing any limitation.ExamplesUsed MaterialsSolvent A: Solvesso 200 NDProtective Colloid A Polyvinyl acetate having a viscosity of 16.5 - 19.5 mPas and a degree of hydrolysis of 86.7-88.7 % (Kuraray Poval 18-88)Polyisocyanate A polymeric MDI with a functionality of approximately 2.7, NCO content 31.5 wt%Antifoam A Aqueous emulsion of PolyorganosiloxanesSurfactant A C9-C11 alcohol, ethoxylated (6 EO)Surfactant B ethoxylated / -C13 oxo alcohol (10 EO)Thickener A Xanthan GumPreservative A combination of bronopol and isothiazolinoneExample 1 : Comparative Example with pH above 5.0A capsule suspension formulation having the following composition was prepared:The aqueous phase was prepared by mixing Protective colloid A, of antifoam A, and a third of the Preservative A into a portion of the water. The organic oil phase was prepared by dissolving alpha-cypermethrin into the Solvent A and 2-Heptanone. Once the active was dissolved, Polyisocyanate A was added to the organic oil phase. Next, the oil-in-water emulsion was prepared by slowly pouring the organic oil phase into the aqueous phase and high shearing until the aim particle size was achieved. Once the target particle size (d(50) 1.5 - 2.0 micron) was achieved, the mixing was switched to low shear and the tetraethylene pentaamine was added as a 25% dilution in water The mixture was mixed under low shear until the pH reached a value of 9 0 to 9.5, indicating completion of the interfacial polymerization. Immediately after the encapsulation process, the d(50) of the capsule was approximately 2.5 urn and the d(90) was less than 15 urn.After the encapsulation process was complete, the 1.5% Xanthan Gum mixture comprising of Xanthan Gum, a portion of Preservative A, and water was added to the capsules and allowed to mix for one hour. Then the Surfactant A, Surfactant B, the remaining Preservative A, Propylene Glycol, and a portion of the water was added to thecapsules and allowed to mix for 30 minutes Lastly, the CS formulation so obtained was pH adjusted with a 50% Dilution of monohydrate citric acid and any remaining water to the desired pH and allowed to mix for up to 4 hours to deagglomerate and the final particle size measurement was taken.The final D(50) and D(90) particle size was measured by a Malvern Mastersizer 3000 of several samples at various pHs (> 5.0) after final sample was mixed for 2 hours are summarized below.It turned out that at formulation pH greater than 5.0, formulations are physically unstable.Example 2: Inventive Example with pH below 5.0Capsule suspensions with the same recipe were prepared as stated in Example 1 . Only the pH was targeted to be below 5.0The final D(50) and D(90) particle size was measured by a Malvern Mastersizer 3000 of several samples at various pHs (< 5.0) after the final sample was mixed for 2 hours are summarized below.The results show no significant agglomeration when the pH was adjusted below 5.

Claims

Claims1 Formulation comprising microparticles, where said microparticles are dispersed in an aqueous solvent, where said aqueous solvent comprises xanthan gum, and where said microparticles are microcapsules having a core and a shell, and where said microparticles comprise a a water insoluble active ingredient, said active ingredient being comprised in the core of said microcapsule b. a shell, c. a protective colloid comprising polyvinyl alcohol; wherein the pH of said aqueous solvent is 5 or less.

2. Formulation according to claim 1 , where said active ingredient is a pesticide P.

3. Formulation according to any of claims 1 to 2, where said microparticles are microcapsules having a core and a shell, where said shell comprises polyurea.

4. Formulation according to any of claims 1 to 3, where said microparticles have an average diameter d50 of 0.5 to 20 pm.

5. Formulation according to any of claims 1 to 4, where said pH has a value from 3 to 5, preferably 4 to 4.9.

6. Formulation according to any of claims 1 to 5, where said formulation comprises 0.01 to 50 wt% of the active ingredient.7 Formulation according to any of claims 1 to 6, where said formulation comprises 0.01% to 1 wt% of xanthan gum.8 Formulation according to any of claims 1 to 7, where said formulation comprises 0.1 to 2 wt% of polyvinyl alcohol.

9. Process for preparing formulations comprising microparticles comprising the following steps: i. Providing an oil phase comprising a water immiscible solvent, in which a water insoluble active ingredient is dissolved or a water insoluble active ingredient that is liquid at 20 °C, ii. Providing an aqueous phase that comprises polyvinyl alcohol, ill. emulsifying the oil phase in the aqueous phase, iv. preparing the shell of the microcapsules, v. adding xanthan gum to the aqueous phase,vi. adjusting the pH of the aqueous phase to a value of 5 or less, preferably of 1 to 5, more preferably of 4 to 4 9.

10. Process according to claim 9, wherein said oil phase provided in step i. comprises a polyisocyanate, said shell prepared in step iv. comprises polyurea and said polyurea is prepared by adding a polyamine in step iv..

11. A non-therapeutic method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired attack by insects or mites and regulating the growth of plants, where formulations according to any of claims 1 to 8 or formulations prepared according any of claims 9 to 10 is allowed to act on the particular pests, their habitat or the plants to be protected from the particular pest, such as crop plants, the soil and / or on undesired plants and / or the useful plants and / or their habitat.

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