New agrochemical formulations

Abstract

Microparticles comprising a core and a shell, where - the shell comprises silica - the core comprises a water insoluble liquid, said water insoluble liquid being a liquid agrochemical active ingredient or a water insoluble solvent comprising an agrochemical active ingredient in dissolved form, - the microcapsule comprises a protective colloid, e.g. polysaccharides (e.g. xanthan gum), polyvinyl alcohol or proteins, - the average diameter d90 of said microparticles is 1 to 50 µm.

Description

[0001] New agrochemical formulations

[0002] The present invention is directed to microparticles comprising a core and a shell, where the shell comprises silica the core comprises a water insoluble liquid, said water insoluble liquid being a liquid agrochemical active ingredient or a water insoluble solvent comprising an agrochemical active ingredient in dissolved form, the microcapsule comprises a protective colloid, e.g. polysaccharides (e.g. xanthan gum), polyvinyl alcohol or proteins, the average diameter d90 of said microparticles is 1 to 50 m.

[0003] The inventions is further directed to processes for making microparticles and their use in agrochemical applications.

[0004] The encapsulation of agrochemical active ingredients has been known for a long time. It offers several advantages over non-encapsulated formulations. For example, it is possible to control the release profile of the agrochemical active ingredient in the formulation.

[0005] Known encapsulation technologies involve for example the formation of polymer shells or polymer particles around an encapsulated active substance. Polymers often used for such encapsulation include acrylic polymers, polyurea or polyurethane polymers or aminoplast polymers.

[0006] It is a drawback of the abovementioned encapsulation technologies that the polymers are not always easily biodegradable and may lead to the formation of small polymer particles that may persist over extended periods of time. Such persistent polymer particles are sometime also referred to as microplastics. An alternative to polymeric capsules are silica capsules. While silica capsules are in principle known, there is a need for microparticles containing pesticides with high loadings and a well defined release profile.

[0007] It was therefore the objective of the present invention to provide microparticles agrochemical active ingredients that have excellent release profiles and form stable formulations, yet at the same time do not form microplastics.

[0008] This objective was achieved by microparticles, wherein said microparticles comprise a core and a shell, where the shell comprises silica the core comprises a water insoluble liquid, said water insoluble liquid being a liquid agrochemical active ingredient or a water insoluble solvent comprising an agrochemical active ingredient in dissolved form, the microcapsule comprises a protective colloid, e.g. polysaccharides (e.g. xanthan gum) or proteins (e.g. potatoes proteins), the average diameter d90 of said microparticles is 1 to 50. In one embodiment, this objective was achieved by microparticles, wherein said microparticles comprise a core and a shell, where the shell comprises silica the core comprises a water insoluble liquid, said water insoluble liquid being a liquid agrochemical active ingredient or a water insoluble solvent comprising an agrochemical active ingredient in dissolved form, the microcapsule comprises a protective colloid, e.g. polysaccharides (e.g. xanthan gum) or proteins (e.g. potatoes proteins), the average diameter d90 of said microparticles is 1 to 30.

[0009] Microparticles of the invention are typically microcapsules having a shell and a core.

[0010] The agrochemical active ingredient can be partly dissolved in the matrix material and partly present in a separate phase as droplets that are distributed in the matrix.

[0011] The microparticles of the invention contain in the core of the microcapsule one or more agrochemical active ingredients. Preferably, said agrochemical active ingredient is a pesticide, a repellant or a pheromone. It is also possible to include mixtures of more than one agrochemical active ingredients.

[0012] According to the invention, agrochemical active ingredients contained in the microparticles of the invention are immiscible with water.

[0013] "immiscible with water” in this context shall mean that such agrochemical active ingredients 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 agrochemical active ingredients have a solubility in water of less than 0.1 g / l at 21 °C.

[0014] In one embodiment, the agrochemical active ingredient is selected from pesticides.

[0015] In one embodiment, the agrochemical active ingredient is selected from a plant health agent.

[0016] In one embodiment, the agrochemical active ingredient is selected from insect repellants.

[0017] In one embodiment, the agrochemical active ingredient is selected from pheromones.

[0018] Pheromones are well known chemical compounds used for controlling undesired insects. For example, Metcalf, R.

[0019] L. Ullmann's Encyclopedia of Industrial Chemistry 2000, keyword "Insect Control”, lists in chapter 15.1 (Sex pheromone attractants) and chapter 15.2 (Aggregation pheromones” suitable examples, wherein the pheromones for Lepidoptera in Table 4 are highly suitable. Examples of pheromones include volatile alkanols and alkenols having from 5 to 18 carbon atoms, volatile alkanals and alkenals having from 5 to 18 carbon atoms, alkanones having from 6 to 18 carbon atoms, 1,7-dioxaspirononan and 3- or 4-hydroxy-1,7-dioxaspiroundecan, benzyl alcohol, Z-(9)-tricosene (muscalure), heneicosene, diacetyl, alcanoic acids having from 5 to 16 carbon atoms such as caprylic acid, laurylic acid, a-pinen, methyleugenol, ethyldodecanoate, tert-butyl 4-(or 5-)chloro-2-ethylcyclohexane-carboxylate, mycrenone, cucurbitacin, trimedlure (commercially available as Capilure®), and (E,E)-8, 10-dodecadien-1-ol (codlemone).

[0020] Further examples of known pheromones are: Z-5-Decenyl acetate, dodecanyl acetate, Z-7-dodecenyl acetate, E-7- dodecenyl acetate, Z-8-dodecenyl acetate, E-8-dodecenyl acetate, Z-9-dodecenyl acetate, E-9-dodecenyl acetate, E- 10-dodecenyl acetate, 11 -dodecenyl acetate, Z-9, 11 -dodecadienyl acetate, E-9, 11 -dodecadienyl acetate, Z-11- tridecenyl acetate, E-11 -tridecenyl acetate, tetradecenyl acetate, E-7-tetradecenyl acetate, Z-8-tetradecenyl acetate, E-8-tetradacenyl acetate, Z-9-tetradecenyl acetate, E-9-tetradecenyl acetate, Z-10-tetradecenyl acetate, E-10- tetradecenyl acetate, Z- 11 -tetradecenyl acetate, E-11 -tetradecenyl acetate, Z-12-pentadecenyl acetate, E-12- pentadecenyl acetate, hexadecanyl acetate, Z-7-hexadecenyl acetate, Z-11 -hexadecenyl acetate, E-11-hexadecenyl acetate, octadecanyl acetate, E,Z-7,9-dodecadienyl acetate, Z,E-7,9-dodecadienyl acetate, E,E-7,9-dodecadienyl acetate, Z,Z-7,9-dodecadienyl acetate, E,E-8, 10-dodecadienyl acetate, E,Z-9, 12-dodecadienyl acetate, E,Z-4,7-tri- decadienyl acetate, 4-methoxy-cinnamaldehyde, [beta]-ionone, estragol, eugenol, indole, 8-methyl-2-decyl propanoate, E, E-9, 11 -tetradecadienyl acetate, Z,Z-9,12-tetradecadienyl acetate, Z,Z-7, 11 -hexadecadienyl acetate, E,Z-7, 11 -hexadecadienyl acetate, Z,E-7, 11 -hexadecadienyl acetate, E,E-7, 11 -hexadecadienyl acetate, Z,E-3,13- octadecadienyl acetate, E,Z-3, 13-octadecadienyl acetate, E,E-3, 13-octadecadienyl acetate, hexanol, heptanol, octanol, decanol, Z-6-nonenol, E-6-nonenol, dodecanol, 11-dodecenol, Z-7-dodecenol, E-7-dodecenol, Z-8- dodecenol, E-8-dodecenol, E-9-dodecenol, Z-9-dodecenol, E-9, 11 -dodecadienol, Z-9, 11 -dodecadienol, Z.E-5,7- dodecadienol, E,E-5,7-dodecadienol, E,E-8, 10-dodecadienol, E,Z-8, 10-dodecadienol, Z,Z-8, 10-dodecadienol, Z,E-

[0021] 8.10-dodecadienol, E,Z-7,9-dodecadienol, Z,Z-7,9-dodecadienol, E-5-tetradecenol, Z-8-tetradecenol, Z-9- tetradecenol, E-9-tetradecenol, Z-10-tetradecenol, Z-11 -tetradecenol, E-11 -tetradecenol, Z-11 -hexadecenol, Z,E-

[0022] 9.11 -tetradecadienol, Z,E-9, 12-tetradecadienol, Z,Z-9, 12-tetradecadienol, Z.Z-10, 12-tetradecadienol, Z,Z-7,11- hexadecadienol, Z,E-7, 11 -hexadecadienol, (E)-14-methyl-8-hexadecen-1-ol, (Z)-14-methyl-8-hexadecen-1-ol, E,E- 10, 12-hexadecadienol, E.Z-10, 12-hexadecadienol, dodecanal, Z-9-dodecenal, tetradecanal, Z-7-tetradecenal, Z-9- tetradecenal, Z-11-tetradecenal, E-11-tetradecenal, E-11,13-tetradecadienal, E,E-8, 10-tetradecadienal, Z, E-9, 11- tetradecadienal, Z,E-9,12-tetradecadienal, hexadecanal, Z-8-hexadecenal, Z-9-hexadecenal, Z-10-hexadecenal, E- 10-hexadecenal, Z-11-hexadecenal, E-11-hexadecenal, Z-12-hexadecenal, Z-13-hexadecenal, (Z)-14-methyl-8- hexadecenal, (E)-14-methyl-8-hexadecenal, Z,Z-7, 11-hexadecadienal, Z,E-7, 11-hexadecadienal, Z, E-9, 11- hexadecadienal, E.E-10, 12-hexadecadienal, E.Z-10, 12-hexadecadienal, Z, E-10, 12-hexadecadienal, Z.Z-10, 12- hexadecadienal, Z,Z-11,13-hexadecadienal, octadecanal, Z-11-octadecenal, E-13-octadecenal, Z-13-octadecenal, Z- 5-decenyl-3-methyl butanoate disparlure: (+) cis-7,8-epoxy-2-methyloctadecane, seudenol: 3-methyl-2-cyclohexen-1- ol, sulcatol: 6-methyl-5-hepten-2-ol, ipsenol: 2-methyl-6-methylene-7-octen-4-ol, ipsdienol: 2-methyl-6-methylene-2,7- octadien-4-ol, grandlure I: cis-2-isopropenyl-1-methylcyclobutane-ethanol, grandlure II: Z-3,3-dimethyl-1- cyclohexane-ethanol, grandlure III: Z-3,3-dimethyl-1-cyclohexane-acetalde-hyde, grandlure IV: E-3,3-dimethyl-1- cyclohexane-acetaldehyde, cis-2-ver-benol: cis-4,6,6-trimethylbicyclo[3, 1 ,1]hept-3-en-2-ol cucurbitacin, 2-methyl-3- buten-2-ol, 4-methyl-3-heptanol, cucurbitacin, 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, [alpha]-pinene: 2,6,6- trimethylbicyclo[3, 1 ,1]hepten-2-ene, [alpha]-caryophyllene: 4,11,11-trimethyl-8-methylene-bicyclo[7,2,0]undecane, Z- 9-tricosene, ([alpha]-multistriatin, 2-(2-endo,4-endo)-5-ethyl-2,4-dimethyl-6,8-dioxabicyclo[3,2, 1]octane, methyleugenol: 1 ,2-dimethoxy-4-(2-propenyl)phenol, lineatin: 3,3,7-trimethyl-2,9-dioxatricyclo[3,3, 1 ,0]nonane, chalcogran: 2-ethyl-1 ,6-dioxaspiro[4,4]nonane, frontalin: 1 ,5-dimethyl-6,8-dioxabicyclo[3,2,1]octane, endo- brevicomin: endo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2, 1]octane, exo-brevicomin: exo-7-ethyl-5-methyl-6,8- dioxabicyclo[3,2, 1 ]octane, (Z)-5-(1-decenyl)dihydro-2-(3H)-furanone, farnesol: 3,7,11 -trimethyl-2, 6, 10-dodecatrien-1- ol, nerolidol 3,7-11-trimethyl-1,6,10-dodecatrien-3-ol, 3-methyl,6-(1-methylethenyl)-9-decen-1-ol acetate, (Z)-3- methyl-6-(1-methylethenyl)-3,9-decadien-1-ol acetate, (E)-3,9-methyl-6-(1-methyl-ethenyl)-5,8-decadien-1-ol acetate, 3-methylene-7-methyl-octen-1-ol propionate, (Z)-3,7-dimethyl-2,7-octadien-1 -ol propionate, (Z)-3,9-dimethyl-6-(1- methyl-ethenyl)-3,9-decadlien-1-ol propionate.

[0023] Preferred pheromones are Z-9-dodecenyl acetate (commercially available as RAK® 1 from BASF SE), (E7,Z9)- dodecadienyl acetate (commercially available as RAK® 2 from BASF SE), (E, E)-8, 10-dodecadien-1 -ol (commercially available as RAK® 3 from BASF SE) and Z-8-dodecenyl acetate.

[0024] Particularly preferred pheromones comprise (E, E)-8, 10-dodecadien-1 -ol, which is also known as codlemone or codlure, and commercially available (e.g. as CheckMate® CM-F from Suterra LLC, USA, lsomate®-C Plus from Pacific Biocontrol Corp. USA; RAK® 3 from BASF SE). Codlemone may be used in pure form, in technical quality or mixed with other pheromones.

[0025] When mixtures of different isomers or of different pheromones are used, these are typically used in a mass ratio of 1 : 100 to 100:1 , preferably 1 : 10 to 10: 1.

[0026] In case of ternary or higher mixtures such ratios shall apply with respect to each combination of the mixing partners.

[0027] Preferred insect repellants as agrochemical active ingredient are ethyl butylacetylaminopropionate, diethyltoluamide, picaridin, 2-undecanone.

[0028] In one embodiment, the agrochemical active ingredients are pesticides such as insecticides, fungicides, nematicides, rodenticides, molluscicides, growth regulators, herbicides or biocides.

[0029] In one embodiment, the agrochemical active ingredient are pesticides such as insecticides, fungicides, nematicides, rodenticides, molluscicides, growth regulators and herbicides.

[0030] Preferred pesticides are insecticides, fungicides and herbicides.

[0031] The term pesticide refers to at least one agrochemical active ingredient selected from the group of fungicides, insecticides, nematicides, herbicides, rodenticides, safeners and / or growth regulators. Mixtures of pesticides of two or more of the aforementioned classes can also be used. The person skilled in the art is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 14th ed. (2006), The British Crop Protection Council, London.

[0032] Pesticides:

[0033] The U.S Environmental Protection Agency (EPA) defines a pesticide as "any substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest". The skilled worker is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London. A pesticide may be a chemical substance or biological agent (such as a virus or bacteria) used against pests including insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms) and microbes that compete with humans for food, destroy property, spread disease or are a nuisance. In the following examples, pesticides suitable for the agrochemical compositions according to the present invention are given.

[0034] A pesticide is generally a chemical or biological agent (such as pesticidal active ingredient, compound, composition, virus, bacterium, antimicrobial, or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term "pesticide” includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.

[0035] The following lists of pesticides that are suitable for use in microcapsules and formulations of the invention, is intended to illustrate the possible combinations but does not limit them:

[0036] A) Respiration inhibitors inhibitors of complex III at Qosite: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin / flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, pyribencarb, triclopyricarb / chlorodincarb, famoxadone, fenamidone, pyriminostrobin, bifujunzhi, metyltetraprole;

[0037] - inhibitors of complex III at Qi site: cyazofamid, amisulbrom, fenpicoxamid, florylpicoxamid, metarylpicoxamid;

[0038] - inhibitors of complex II: benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetamid, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, pydiflumetofen, pyraziflumid, sedaxane, tecloftalam, thifluzamide, inpyrfluxam, pyrapropoyne, fluindapyr, isoflucypram, cyclobutrifluram;

[0039] - other respiration inhibitors: diflumetorim; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, meptyldinocap; ferimzone; organometal compounds: fentin salts, e.g. fentin-acetate, fentin chloride or fentin hydroxide; silthiofam; - quinone outside inhibitor stigmatellin binding type: ametoctradin;

[0040] B) Sterol biosynthesis inhibitors (SBI fungicides)

[0041] - 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, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole , fluoxytioconazole, ipfentrifluconazole, mefentrifluconazole; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines, piperazines: fenarimol, pyrifenox, triforine;

[0042] - Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;

[0043] Inhibitors of 3-keto reductase: fenhexamid, fenpyrazamine;

[0044] - other Sterol biosynthesis inhibitors: chlorphenomizole;

[0045] C) Nucleic acid synthesis inhibitors

[0046] - RNA polymerase I inhibitors: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M, ofurace, oxadixyl;

[0047] - other nucleic acid synthesis inhibitors: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, ipflufenoquin, quinofumelin;

[0048] D) Inhibitors of cell division and cytoskeleton

[0049] - tubulin polymerization inhibitors: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl, pyridachlometyl;

[0050] - other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone, phenamacril, fluopimomide;

[0051] E) Inhibitors of amino acid and protein synthesis

[0052] - methionine synthesis inhibitors: cyprodinil, mepanipyrim, pyrimethanil;

[0053] - protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin;

[0054] F) Signal transduction inhibitors

[0055] - MAP I histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fludioxonil;

[0056] - mechanism unknown: quinoxyfen, proquinazid;

[0057] G) Lipid and membrane synthesis inhibitors

[0058] - Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane;

[0059] - lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;

[0060] - compounds affecting cell membrane permeability and fatty acides: propamocarb;

[0061] - inhibitors of oxysterol binding protein: oxathiapiprolin, fluoxapiprolin;

[0062] H) Inhibitors with Multi Site Action

[0063] - inorganic active substances: Bordeaux mixture, copper, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;

[0064] - thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;

[0065] - organochlorine compounds: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid;

[0066] - guanidines and others: guanidine, dodine, dodine free bas, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, fluoroimide, methasulfocarb, chinomethionat;

[0067] I) Cell wall synthesis inhibitors

[0068] - inhibitors of glucan synthesis: validamycin, polyoxin B;

[0069] - melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil, tolprocarb;

[0070] - cellulose synthase inhibitors: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate;

[0071] J) Plant defense inducers

[0072] - 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;

[0073] K) Unknown mode of action

[0074] - bronopol, cyflufenamid, cymoxanil, dazomet, debacarb, diclocymet, diclomezine, difenzoquat, difenzoquat- methylsulfate, diphenylamin, fenitropan, fenpyrazamine, flumetover, flumetylsulforim, flusulfamide, flutianil, harpin, nitrapyrin, nitrothal-isopropyl, oxin-copper, seboctyl amine, tebufloquin, tecloftalam, triazoxide, pyrisoxazole, , benziothiazolinone, bromothalonil, aminopyrifen, flufenoxadiazam;

[0075] L) Biopesticides

[0076] L1) Microbial pesticides with fungicidal, bactericidal, viricidal and / or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. amyloliquefaciens 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 oleophila, 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);

[0077] L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and / or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract;

[0078] L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and / or nematicidal activity: Agrobacterium radiobacter, 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, Flavobacterium 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. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus, Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces galbus, S. microflavus,'

[0079] 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;

[0080] 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, Bradyrhizobium 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, Sinorhizobium melilotr,

[0081] 0) Insecticides from classes 0.1 to 0.29

[0082] 0.1 Acetylcholine esterase (AChE) inhibitors: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, 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 O-(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, thiometon, triazophos, trichlorfon, vamidothion;

[0083] 0.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; ethiprole, fipronil, flufiprole, pyrafluprole, pyri prole;

[0084] 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, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin, transfluthrin; DDT, methoxychlor;

[0085] 0.4 Nicotinic acetylcholine receptor (nAChR) agonists: acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; nicotine; sulfoxaflor, flupyradifurone, triflumezopyrim, fenmezoditiaz, flupyrimin;

[0086] 0.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, spinetoram;

[0087] 0.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin;

[0088] 0.7 Juvenile hormone mimics: hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen;

[0089] 0.8 miscellaneous non-specific (multi-site) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;

[0090] 0.9 Chordotonal organ TRPV channel modulators: afidopyropen, pymetrozine, pyrifluquinazon;

[0091] 0.10 Mite growth inhibitors: clofentezine, hexythiazox, diflovidazin; etoxazole;

[0092] 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: Cry 1 Ab, Cry 1 Ac, Cry 1 Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1;

[0093] 0.12 Inhibitors of mitochondrial ATP synthase: diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon;

[0094] 0.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient: chlorfenapyr, DNOC, sulfluramid;

[0095] 0.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium;

[0096] 0.15 Inhibitors of the chitin biosynthesis type 0: bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;

[0097] 0.16 Inhibitors of the chitin biosynthesis type 1: buprofezin;

[0098] 0.17 Moulting disruptors: cyromazine;

[0099] 0.18 Ecdyson receptor agonists: methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide;

[0100] 0.19 Octopamin receptor agonists: amitraz;

[0101] 0.20 Mitochondrial complex III electron transport inhibitors: hydramethylnon, acequinocyl, fluacrypyrim, bifenazate;

[0102] 0.21 Mitochondrial complex I electron transport inhibitors: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone;

[0103] 0.22 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone;

[0104] 0.23 Inhibitors of the of acetyl CoA carboxylase: spirodiclofen, spiromesifen, spirotetramat, spiropidion, spirobudifen, spidoxamat;

[0105] 0.24 Mitochondrial complex IV electron transport inhibitors: aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide;

[0106] 0.25 Mitochondrial complex II electron transport inhibitors: cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide; 0.28 Ryanodine receptor-modulators: chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, fluchlodiniliprole; tetrachlorantraniliprole; tetraniliprole; tiorantraniliprole; cyhalodiamide;

[0107] 0.29 Chordotonal organ modulators: flonicamid;

[0108] 0.30 GABA-gated chloride channel allosteric modulators: broflanilide, fluxametamide, isocycloseram;

[0109] 0.33 Calcium-activated potassium channel modulators: acynonapyr;

[0110] 0.34 Mitochondrial complex III electron transport inhibitors at Qi site: flometoquin;

[0111] O.UN Insecticidal compounds of unknown or uncertain mode of action: afoxolaner, azadirachtin, amidoflumet, benzoximate, bromopropylate, chinomethionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadi azone, piperonyl butoxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, actives on basis of Bacillus firmus (Votivo); fluazaindolizine; tyclopyrazoflor; sarolaner, lotilaner; benzpyrimoxan; tigolaner; oxazosulfyl; cyproflanilide, nicofluprole; indazapyroxamet; flupentiofenox; cyclobutrifluram.

[0112] P) Herbicides from the classes P1 to P15

[0113] P1) lipid biosynthesis inhibitors:

[0114] - ACC-herbicides: alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, 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, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim;

[0115] - non-ACC herbicides: benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;

[0116] P2) ALS inhibitors:

[0117] - sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, 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, oxasulfuron, 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;

[0118] - imidazolinones: imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr;

[0119] - triazolopyrimidine herbicides and sulfonanilides: cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam;

[0120] - pyrimidinylbenzoates: bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium; - sulfonylaminocarbonyl-triazolinone herbicides: flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl;

[0121] - and triafamone;

[0122] P3) photosynthesis inhibitors: amicarbazone, inhibitors of the photosystem II, triazine herbicides, including of chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn, hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn and trietazin, aryl urea such as chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron and thiadiazuron, phenyl carbamates such as desmedipham, karbutilat, phenmedipham, 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;

[0123] P4) protoporphyrinogen-IX oxidase inhibitors: acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-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;

[0124] P5) bleacher herbicides:

[0125] - PDS inhibitors: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, rimisoxafen;

[0126] - HPPD inhibitors: benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquinotrione, isoxaflutole, mesotrione, oxotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone, bipyrazone, fenpyrazone, cypyrafluone, tripyrasulfone, benquitrione, dioxopyritrione;

[0127] - bleacher, unknown target: aclonifen, amitrole flumeturon, bixlozone;

[0128] P6) EPSP synthase inhibitors: glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate-trimesium (sulfosate);

[0129] P7) glutamine synthase inhibitors: bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate-ammonium;

[0130] P8) DHP synthase inhibitors: asulam;

[0131] P9) mitosis inhibitors:

[0132] - 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: propyzamide and tebutam; group K2: carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl and propham;

[0133] P10) VLCFA inhibitors:

[0134] - chloroacetamides: acetochlor, alachlor, amidochlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor,

[0135] - oxyacetanilides: flufenacet and mefenacet;

[0136] - acetanilides: diphenamid, naproanilide, napropamide and napropamide-M;

[0137] - tetrazolinones: fentrazamide;

[0138] - other herbicides: anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone, dimesulfazet and isoxazoline;

[0139] P11) cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam;

[0140] P12) decoupler herbicides: dinoseb, dinoterb and DNOC and its salts;

[0141] P13) auxinic herbicides:

[0142] 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 salts and 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 I uoro-6-(7-f I uoro- 1 / 7-i ndol-6-y I )pi col in ic acid;

[0143] P14) auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium;

[0144] 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.

[0145] 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. Preferred pesticides are herbicides, insecticides and fungicides.

[0146] In one embodiment, the agrochemical active ingredient is a herbicide.

[0147] In one embodiment, the agrochemical active ingredient is a fungicide.

[0148] In one embodiment, the agrochemical active ingredient is an insecticide.

[0149] Especially preferred pesticides as the agrochemical active ingredient are tepraloxydim, flufenacet, napropamid, isoxaben, fluazifop-P-butyl, metamitron, propyzamide, phenmedipham, clethodim, chloridazon, dimethenamid-P, pendimethalin, Chlorpyrifos, dimethoate alpha-cypermethrin, cypermethrin, clothianidin, chlorfenapyr, fipronil, dimethenamid-P, clomazone, picolinafen, metazachlor, S-metalochlor, acetochlor, pendimethalin, saflufenacil, pyroxasulfone, bixlozone, pyraclostrobin, dimethenamide-P, fenpropimorph, saflufenacil, trifludimoxazin, trifloxystrobin and cinmethylin .

[0150] In one embodiment, the agrochemical active ingredient is a herbicide selected from dimethenamid-P, clomazone, picolinafen, metazachlor, S.metalochlor, acetochlor, pendimethalin, saflufenacil, pyroxasulfone, bixlozone, cinmethylin, fenpropimorph, trifloxystrobin or mixtures thereof.

[0151] Particularly preferred pesticides as the agrochemical active ingredient are cinmethylin, pyraclostrobin, fenpropimorph, trifloxystrobin and dimethenamide-P. In one embodiment, the agrochemical active ingredient is cinmethylin. In one embodiment, the agrochemical active ingredient is pyraclostrobin. In one embodiment, the agrochemical active ingredient is fenpropimorph. In one embodiment, the agrochemical active ingredient is trifloxystrobin. In one embodiment, the agrochemical active ingredient is dimethenamide-P.

[0152] In one embodiment, the agrochemical active ingredient is a pheromone selected from Z-11-Hexadecenal, Z-13- Octadecenal or Z-9-Hexadecenal.

[0153] In one embodiment, the agrochemical active ingredient is Z-11-Hexadecenal. In one embodiment, the agrochemical active ingredient Z-13-Octadecenal. In one embodiment, the agrochemical active ingredient is Z-9-Hexadecenal. The pesticide may be solid or liquid at 20 °C.

[0154] Suitable agrochemical active ingredients, especially pesticides or pheromones, typically have a water-solubility up to 10 g / l, preferably up to 5 g / l, and more preferably up to 1 g / l.

[0155] Typically, microparticles of the invention contain from 1 to 95 wt%, preferably 10 to 90 wt%, more preferably 30 to 85 wt% of said one or more agrochemical active ingredient, based on the microparticles.

[0156] In principle, agrochemical active ingredient may be a liquid or a solid at 21 °C, where the solid itself may also be present dissolved in a water immiscible solvent S. Solvent S is liquid at 21 °C. In one embodiment, the agrochemical active ingredient used in the capsule according to the invention is liquid at

[0157] 21 °C.

[0158] In one embodiment, the agrochemical active ingredient used in the capsule according to the invention is liquid at 21 °C and is contained in the microparticles of the invention without being dissolved in a solvent.

[0159] In one embodiment, the agrochemical active ingredient used in the capsule according to the invention is a liquid at 21 °C and is contained in the microparticles of the invention as a pure substance.

[0160] In one embodiment, the agrochemical active ingredient is comprised in microparticles of the invention as a solution in a water immiscible solvent S.

[0161] Sometimes, the agrochemical active ingredient can also act as a solvent, or a solvent can also act as an agrochemical active ingredient.

[0162] Water immiscible solvents S have a solubility in water of 1 wt% or less at 21 °C, preferably of 0.1 wt% or less at

[0163] 21 °C.

[0164] 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).

[0165] "Fatty acid” herein shall denote a linear or branched carboxylic acid with a saturated or unsaturated aliphatic chain.

[0166] In one embodiment, solvent S is an oil. The phrase "oil" in the context of the present invention encompasses all kinds of oil bodies or oil components, in particular vegetable oils like e.g. rape seed oil, sunflower oil, soy oil, olive oil and the like, modified vegetable oils e.g. alkoxylated sunflower or soy oil, synthetic (tri)glycerides like e.g. technical mixtures of mono, di and triglycerides of C6-C22 fatty acids, fatty acid alkyl esters e.g. methyl or ethyl esters of vegetable oils (Agnique® ME 18 RD-F, Agnique® ME 18 SD-F, Agnique® ME 12C-F, Agnique® ME1270, all products of BASF SE, Germany) fatty acid alkyl esters based on said C6-C22 fatty acids, mineral oils and their mixtures. In one form the oil comprises preferably mineral oils.

[0167] Examples illustrating the nature of suitable solvents S without limiting the invention to these examples are: Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched C6-C 13-carboxylic acids with linear or branched C6-C 22-fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are esters of linear C6-C22-fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C18-C38- alkyl hydroxy carboxylic acids with linear or branched C6-C 22-fatty alcohols, in particular Dioctyl Malate, esters of linear and / or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and / or Guerbet alcohols, triglycerides based on C6-C10-fatty acids, liquid mono- / di- / triglyceride mixtures based on C6-C18-fatty acids, esters of C6-C22-fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2- C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22-fatty alcohol carbonates, such as, for example, dicaprylyl carbonate (Cetiol® CC), Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and / or branched C6-C22-alcohols, linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicone methicone grades, etc.), aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes, and / or mineral oils. In one form the oil comprises preferably aliphatic or naphthenic hydrocarbons, and / or mineral oils.

[0168] Within the context of the present invention, preferred solvents S are, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched 06-013-carboxylic acids with linear or branched C6-C22-fatty alcohols, such as e.g. myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate.

[0169] Also preferred oils are esters of linear C6-C22-fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C18-C38-alkylhydroxycarboxylic acids with linear or branched C6-C22-fatty alcohols, linear or branched 06-022- fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as e.g. propylene glycol, dimerdiol or trimertriol) and / or Guerbet alcohols, triglycerides based on 06-010-fatty acids, liquid mono- / di- / triglyceride mixtures based on 06-018-fatty acids, esters of C6-C22-fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of 02-012-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22-fatty alcohol carbonates, such as e.g. dicaprylyl carbonate (Cetiol™ CO), Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and / or branched C6-C22-alcohols (e.g. Finsolv™ TN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as e.g. dicaprylyl ether (Cetiol™ OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicon methicone types etc.) and / or aliphatic or naphthenic hydrocarbons, such as e.g. squalane, squalene or dialkylcyclohexanes.

[0170] Furthermore, liquid linear and / or branched and / or saturated or unsaturated hydrocarbons or any desired mixtures thereof can be used as oils within the context of the present invention. These may be e.g. alkanes having 4 to 22, preferably 6 to 18, carbon atoms, or any desired mixtures thereof. Also of suitability are the unsaturated hydrocarbons having 4 to 22 carbon atoms, or unsaturated hydrocarbons of identical carbon number, and any desired mixtures of these hydrocarbons. Cyclic hydrocarbons and aromatics, e.g. toluene and mixtures thereof may also be oils within the context of the present invention. In another preferred form the oil comprises aromatics. Also suitable are silicone oils. Any desired mixtures of all of the specified core materials Particular preference is given to those sparingly water-soluble or water-insoluble organic agrochemical active ingredient which are soluble or suspendable in the water-insoluble or sparingly water-soluble sol-gel precursor which is used for constructing the shell of the capsule according to the invention.

[0171] Preferred solvents S, especially for pesticides as agrochemical active ingredient, are: 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; acetophenone; dibutyl carbonate; benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl lactate, 2-phenoxyethyl propionate; 2-Ethylhexyl lactate; fatty acid esters; fatty acids; C8-C12 fatty acid dimethyl amides; and mixtures thereof.

[0172] More preferred organic solvents S are: acetophenone; dibutyl carbonate; benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl lactate, 2-phenoxyethyl propionate; 2-Ethylhexyl lactate; fatty acid esters; fatty acids; C8-C12 fatty acid dimethyl amides; and mixtures thereof.

[0173] C8-C12 fatty acid dimethyl amides include and preferred C8-C12 fatty acid dimethyl amides are: C8 dimethyl amide (N,N-dimethyloctanamide), C8 / C10 dimethyl amide (mixture of N,N-dimethyloctanamide and N,N- dimethyldecanamide), C9 dimethyl amide (N,N-dimethylnonaneamide or N,N-Dimethyl iso-nonaneamide), C10 dimethyl amide (N-Dimethyldecanamide or N, N-Dimethyl 9-decenamide), C12 dimethyl amide (lauryl N,N- dimethylamide), 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.

[0174] Especially preferred organic solvents S are 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, benzyl acetate, methylbenzoate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbons or their mixtures.

[0175] Particularly preferred organic solvents S are aromatic hydrocarbons, adipates (e.g. dibutyladipate), 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 aforementioned oils or their mixtures. Besides the one or more agrochemical active ingredient and optionally solvent S, the core of the microcapsules according to the invention, can also comprise auxiliaries which are usually used in the respective fields of application

[0176] Microparticles according to the invention contain a shell that surrounds the core. Said shell comprises silica. Said shell comprises a continuous layer comprising silica, meaning that silica is not present as individual silica particles, but as part of a continuous layer.

[0177] According to the invention, said shell does not comprise any material that may form microplastics. In particular, said shell does not contain any organic polymers that do not degrade easily. For example, such shell does not comprise polyacrylate, polyurethane or polyurea polymers.

[0178] Typically, said silica containing shell has an average thickness of 40 to 200 nm. The thickness of the shell can be determined by microscopic methods, e.g. by electron microscopy.

[0179] In one embodiment, the silica containing shell is prepared by hydrolysis of alkoxy silanes. Suitable alkoxysilanes include tetraethoxy silane, methyldiethoxysilane, ethoxytrimethylsilane, methoxytrimethylsilane, triethoxy (ethyl)silane, trimethoxymethylsilane, diethoxydimethylsilane, dimethoxymethylvinylsilane, dimethoydimethylsilane, vinyltrimethoxysilane, triethoxyvinylsilane, 1 ,2-Bis(trimethoxysilyl)ethane and 1 ,2-Bis(triethoxysilyl)ethane.

[0180] Microcapsules of the invention comprise a protective colloid.

[0181] Examples of suitable protective colloids include polysaccharides (e.g. xanthan gum), polyvinyl alcohol (PVA) or proteins (e.g. potatoes proteins) or mixtures thereof. In one embodiment, the protective colloid is a polysaccharide. In one embodiment, the protective colloid is a polyvinyl alcohol. In one embodiment, the protective colloid is a protein. Examples of proteins suitable as protective colloids include animal based proteins (e.g. gelatine or caseines like sodium caseinate) or plant based proteins, such as pea proteins, rice proteins, wheat proteins, sunflower proteins, soy proteins or potato proteins.

[0182] Examples of polysaccharides suitable as protective colloids include xanthan gum, calcium alginate, calcium pectinate, pectin, modified pectins, agar agar, modified starch, tara gum, konjac gum, locus bean gum, cassia gum, gum Arabic, guar gum, and carrageenan.

[0183] PVA as used herein includes polymers prepared from homopolymers of polyvinyl acetate as well as polyvinyl alcohol copolymers.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] Typically, copolymers of polyvinyl alcohol are prepared by a radical polymerization reaction between the vinyl acetate and comonomers.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] 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.

[0193] Combinations of two or more different protective colloids may also be used.

[0194] Typically, the protective colloid is prepared by adding an aqueous solution of the protective colloid to the dispersed microcapsules after the completion of the formation of the silica containing shell. Typically, microcapsules of the invention contain protective colloids in an amount of 0.1 to 5 g / l, preferably 0.2 to 2 g / l, based on the formulation. Microparticles of the invention typically have an average diameter d90 of 1 to 50 micrometer. In one embodiment, microparticles of the invention typically have an average diameter d90 of 1 to 30 micrometer. All particle sizes given herein are determined by statistic laser scattering using a Malvern Mastersizer 2000 according to European norm ISO 13320 EN.

[0195] Microparticles of the invention can have high loadings of agrochemical active ingredients.

[0196] In one embodiment microparticles of the invention comprise less than 50 wt% of silica based on the weight of the microparticle. In one embodiment microparticles of the invention comprise less than 25 wt% of silica based on the weight of the microparticle. In one embodiment microparticles of the invention comprise less than 10 wt% of silica based on the weight of the microparticle. In one embodiment microparticles of the invention comprise less than 5 wt% of silica based on the weight of the microparticle.

[0197] It was a very surprising result that it was possible to prepare microcapsules with a silica containing shell with narrow particle size distribution, small average particle sizes and a high loading of agrochemical active ingredient, especially pesticides or pheromones.

[0198] Another aspect of the present invention are processes for making microcapsules comprising the following steps: a. Providing a water insoluble liquid, said water insoluble liquid being a liquid agrochemical active ingredient or a water insoluble solvent comprising in dissolved form an agrochemical active ingredient, said water insoluble liquid comprising an alkoxy silane compound, b. Providing an aqueous phase comprising one or more surfactants, c. Emulsifying the water insoluble liquid obtained in step a. in the aqueous phase obtained in step b, d. adjusting the pH in the aqueous phase obtained in step c. to a basic value (between 9 and 13), e. Adding an alkoxy silane compound to the aqueous phase, f. adjusting the pH in the aqueous phase to an acidic value (between 2 and 6), g. Addition of a protective colloid after the completion of step e. and f. (e.g. comprising Polysaccharides (e.g. xanthan gum) or proteins (e.g. potatoes proteins)).

[0199] Preferably, said alkoxysilane is selected from tetraethoxy silane, methyldiethoxysilane, ethoxytrimethylsilane, methoxytrimethylsilane, triethoxy(ethyl)silane, trimethoxymethylsilane, diethoxydimethylsilane, dimethoxymethylvinylsilane, dimethoydimethylsilane, vinyltrimethoxysilane, triethoxyvinylsilane, 1,2- Bis(trimethoxysilyl)ethane or 1 ,2-Bis(triethoxysilyl)ethane.

[0200] In one embodiment, said water insoluble liquid in step a. comprises 10 to 100 g / l tetraalkoxy silane, preferably 10 to 70 g / l or 30 to 70 g / l. In one embodiment, steps e. and f. are carried out simultaneously. In one embodiment, steps e. and f. are carried out consecutively. In one embodiment, step f. is carried out after step e. In one embodiment, step e. is carried out after step f.

[0201] Typically, the aqueous phase in step b. comprises one or more surfactants. Said surfactants help emulsifying the water insoluble liquid in the aqueous phase.

[0202] In one embodiment, the surfactant comprised in the aqueous phase in step b. is selected from zwitterionic surfactants, preferably aminoxide, or lecithin.

[0203] The emulsification of the insoluble liquid in the aqueous phase is typically supported by stirring or ultrasound. When reference is made herein that an emulsification is supported by "stirring”, this shall be understood to include all customary mechanical means for supporting emulsification, such as stirring, application of ultrasound, shaking or the like. In one embodiment, a rotor-stator is used.

[0204] In one embodiment, the addition of the silane in step e. is carried out at a pH between 9 and 13, preferably between 9.5 and 12.

[0205] When the addition of the silane is completed, the pH of the system is adjusted to an acidic value. Typically, the pH is adjusted to a value of 2 to 6. In one embodiment, the pH is adjusted to 3 to 5.

[0206] For the pH adjustment it is in principle possible to use any acid. In one embodiment, hydrochloric acid, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid or succinic acid are used. In one embodiment hydrochloric acid, acetic acid or citric acid is used as an acid.

[0207] The adjustment of the pH to an acidic value is typically done in directly after or up to 10 hours after the finalization of the addition of the alkoxy silane. In one embodiment, the adjustment of the pH to an acidic value is done 20 minutes to 3 hours after the finalization of the addition of the alkoxy silane. The speed of the addition of the acid may inter alia depend on the size of the reaction vessel and the temperature.

[0208] In one embodiment, the process of the invention is carried out at a temperature between 10 °C and 50 °C.

[0209] With the adjustment of the pH to an acidic value, the formation of the microcapsules is completed. Thereafter, a protective colloid is added. The protective colloid is typically a polymeric material providing a sterical stabilization of the microcapsules.

[0210] Examples of suitable protective colloids are described above and include Polysaccharides (e.g. xanthan gum, calcium alginate, calcium pectinate, pectin, modified pectins, agar agar, modified starch, tara gum, konjac gum, locus bean gum, cassia gum, gum Arabic, guar gum, and carrageenan), PVA or proteins of plants (e.g. potato, pea, wheat, corn) or animal origins (e.g. gelatin, sodium caseinate).

[0211] The protective colloid is typically added as an aqueous solution. In one embodiment, the addition of the protective colloid is completed 48 hours after the completion of the pH adjustment to an acidic value.

[0212] In one embodiment, the addition of the protective colloid is not started immediately after the completion of the pH adjustment to an acidic value but is for example started 4 hours thereafter.

[0213] In one embodiment, the addition of the protective colloid is carried out 4 to 48 hours after step e.

[0214] In one embodiment, the so prepared microcapsules are isolated by removing the water immiscible solvent and the water.

[0215] Another aspect of the present invention are formulations comprising the inventive microcapsules. "Inventive microcapsules'' as used herein shall mean microcapsules of the invention or microcapsules prepared according to processes of the invention.

[0216] Microparticles of the invention or microparticles prepared according to processes of the invention can be converted into customary types of agrochemical compositions suspensions, pastes, granules, pressings or mixtures thereof.

[0217] In one embodiment, the inventive microcapsules are dispersed in a liquid medium, preferably an aqueous medium.

[0218] In one embodiment, formulations of the invention have a loading with the agrochemical active ingredient comprised in the core of the microcapsules of at least 10 g / l, based on the liquid formulation. In one embodiment, formulations of the invention have a loading with the agrochemical active ingredient comprised in the core of the microcapsules of at least 20 g / l, 30 g / l or 50 g / l. In one embodiment, formulations of the invention have a loading with the agrochemical active ingredient comprised in the core of the microcapsules of at least 100 g / l. In one embodiment, formulations of the invention have a loading with a pheromone comprised in the core of the microcapsules of at least 10 g / l. In one embodiment, formulations of the invention have a loading with a pesticide different from a pheromone comprised in the core of the microcapsules of at least 50 g / l. In one embodiment, formulations of the invention have a loading with a pesticide different from a pheromone comprised in the core of the microcapsules of at least 100 g / l. In one embodiment, formulations of the invention have a loading of at least 10 g / l with a pheromone comprised in the core of the microcapsules, or a loading of at least 50 g / l with a pesticides different from a pheromone comprised in the core of the microcapsules. In one embodiment, formulations of the invention have a loading with a pheromone comprised in the core of the microcapsules of at least 100 g / l. In one embodiment, formulations of the invention have a loading of at least 10 g / l with a pheromone comprised in the core of the microcapsules, or a loading of at least 100 g / l with a pesticides different from a pheromone comprised in the core of the microcapsules.

[0219] The term "aqueous medium" stands for the liquid phase of the composition and comprises an aqueous solvent and optionally compounds dissolved therein, e.g. surfactants as mentioned above, and if present, conventional one or more conventional formulation additives, such as thickeners or biocides. The aqueous solvent of the aqueous suspension is either water or a mixture thereof with a water-miscible organic solvent, such as C1-C4-alkanols, e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, or tert, butanol, C2-C5-alkanediols and C3-C8- alkanetriols, preferably from the group consisting of ethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, glycerol and 1 ,4-butanediol. Generally, the amount of water in the aqueous solvent is at least 50% by weight, in particular at least 80% by weight or at least 90 % by weight, based on the aqueous solvent. The aqueous solvent may consist mainly of water, i.e. water makes up at least 95% by weight of the total amount of solvent present in the suspension. The aqueous solvent may also be a mixture of the aforementioned water-miscible organic solvent and water. In the latter case, the weight ratio of water to water-miscible organic solvent in the aqueous solvent preferably is in the range of from 99: 1 to 1 : 1 ; more preferably in the range of from 50:1 to 3: 1; and most preferably in the range of from 20:1 to 4: 1. Expressed differently the amount of organic solvent may be from 1 to 50% by weight, more preferably from 2 to 25% by weight, and most preferably from 5 to 20% by weight, based on the total weight of the aqueous solvent.

[0220] Formulations of the invention may comprise one or more further agrochemical active ingredients outside the microparticles. Such further agrochemical active ingredients can for example be dissolved in the solvent medium, preferably the aqueous phase, or may be present as solid particles that are dispersed in the solvent medium, preferably the aqueous phase.

[0221] If present, the concentration of surfactants in the aqueous suspension will frequently be in the range from 0.01 to 10% by weight, in particular from 0.05 to 5% by weight, based on the total weight of the aqueous suspension of the microparticles.

[0222] The aqueous compositions according to the invention may also comprise customary formulation auxiliaries. Examples of auxiliaries include such as viscosity-modifying additives (thickeners), antifoam agents, preservatives, buffers, inorganic dispersants, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders etc., which are usually employed in aqueous formulations of agrochemical active ingredient.

[0223] The amount of auxiliaries will typically not exceed 10% by weight, in particular 5% by weight of the total weight of the formulation.

[0224] Such auxiliaries may be incorporated into the aqueous suspension during or after the formation of the microparticles as described herein has been carried out. The amount of additives will generally not exceed 10% by weight, in particular 5% by weight of the total weight of the formulation.

[0225] Suitable thickeners are compounds which affect the flow behavior of the suspension concentrate and may assist in stabilizing the aqueous suspension of the microparticles against caking. Mention may be made, in this connection, for example, of commercial thickeners based on polysaccharides, such as methylcellulose, carboxymethylcellulose, hydroxypropyl cellulose (Klucel® grades), Xanthan Gum (commercially available e.g. as Kelzan® grades from Kelco or Rhodopol® grades from Rhodia), synthetic polymers, such as acrylic acid polymers (Carbopol® grades), polyvinyl alcohol (e.g. Mowiol® and Poval® grades from Kuraray) or polyvinyl pyrrolones, silicic acid or phyllosilicates, such as montmorillonite and bentonites, which may be hydrophobized, (commercially available as Attaclay® grades and Attaflow® grades from BASF SE; or as Veegum® grades and Van Gel® grades from R.T. Vanderbilt). In the context of the present invention, Xanthan Gum is a preferred thickener. The concentration of thickeners in the aqueous suspension will generally not exceed 2% by weight, based on the total weight of the aqueous suspension, and is preferably in the range from 0.01 to 2% by weight, in particular from 0.02 to 1 .5% by weight and especially from 0.1 to 1 % by weight, based on the total weight of the aqueous suspension or the final formulation, respectively. In one embodiment, suitable thickeners include polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

[0226] According to one embodiment, the thickener is selected from the group consisting of natural gums, in particular xanthan gum, tara gum, konjac gum, locus bean gum, cassia gum, gum Arabic, guar gum, and carrageenan; silicates, in particular magnesium aluminum silicates; modified cellulose, in particular hydroxypropyl cellulose, carboxymethyl cellulose and microcrystalline cellulose; modified starches, in particular hydroxypropyl starch phosphate; fatty alcohols, in particular cetyl alcohol, cetearyl alcohol, stearyl alcohol, behenyl alcohol; fatty acids, in particular stearic acid, palmitic acid; fatty acid esters, in particular myristyl stearate, pentaerythrityl distearate, cetyl palmitate, tribehenin, dextrin, palmitate; waxes, in particular beeswax, carnauba wax, microcrystalline wax, ceresin, ozocerite, Oryza Sativa bran wax, sunflower was; hydrogenated vegetable oil, in particular hydrogenated castor oil, hydrogenated vegetable glycerides; hydrogenated castor oil / sebacic acid copolymer; polyamides; silica compounds, in particular silica, and silica dimethyl silylate; calcium alginate, calcium pectinate, pectin, modified pectins, agar agar, acrylic polymers, and mixtures thereof. According to one embodiment of the invention, the thickener is selected from xanthan gum.

[0227] Antifoam agents suitable for the compositions according to the invention are, for example, silicone emulsions (such as, for example, Silicone SRE-PFL from Wacker or Rhodorsil® from Bluestar Silicones), polysiloxanes and modified polysiloxanes including polysiloxane blockpolymers such as FoamStar® SI and FoamStar® ST products of BASF SE, long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.

[0228] Suitable preservatives to prevent microbial spoiling of the compositions of the invention include formaldehyde, alkyl esters of p-hydroxybenzoic acid, sodium benzoate, 2-bromo-2-nitropropane-1 ,3-diol, o-phenylphenol, thiazolinones, such as benzisothiazolinone, 5-chloro-2-methyl-4-isothiazolinone, pentachlorophenol, 2,4-dichlorobenzyl alcohol and mixtures thereof. Commercially available preservatives that are based on isothiazolinones are for example marketed under the trademarks Proxel® (Arch Chemical), Acticide® MBS (Thor Chemie) and Kathon® MK (Rohm & Haas).

[0229] In addition, the formulations according to the invention, in particular the aqueous suspensions, can be formulated with conventional binders, for example aqueous polymer dispersions, water-soluble resins, for example water-soluble alkyd resins, or waxes. The formulations of the invention may also contain one or more adjuvants. Suitable adjuvants are known to skilled persons and include surfactants, crop oil concentrates, spreader-stickers, wetting agents, and penetrants. In other particular groups of embodiments, the microparticle composition is in the form of solid composition. Such a solid composition contains the microparticles of the invention, optionally one or more surfactants, , and optionally an inert solid carrier material.

[0230] The solid compositions may e.g. be redispersible powders, water-dispersible granules wettable powders and the like.

[0231] Solid carriers include e.g. mineral earths, such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.

[0232] Suitable surfactants include surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. 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.).

[0233] Suitable anionic surfactants include alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

[0234] Suitable nonionic surfactants include alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar- based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate. Suitable cationic surfactants include quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

[0235] Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

[0236] Suitable bactericides include bronopol, phenoxyethanol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.

[0237] Suitable anti-freezing agents include ethylene glycol, propylene glycol, urea and glycerin.

[0238] Suitable anti-foaming agents include silicones, long chain alcohols, and salts of fatty acids.

[0239] Suitable colorants (e.g. in red, blue, or green) include pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

[0240] Suitable tackifiers or binders include polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

[0241] In one embodiment, formulations of the invention are solid formulations. Solid formulations according to the invention may also comprise customary formulation auxiliaries, such as antifoam agents, preservatives, buffers, inorganic dispersants, etc., which are usually employed in solid formulations of agrochemical active ingredient. Such auxiliaries may be incorporated into the solid formulation at any conventional stage of their preparation process. The amount of additives will generally not exceed 10% by weight, in particular 5% by weight of the total weight of the solid composition.

[0242] The inventive microparticles and formulations are particularly useful in the control of a multitude of phytopathogenic fungi, undesired vegetation of insects or nematodes on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (Table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broadleaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.

[0243] Preferred crops are Arachis hypogaea, Beta vulgaris spec, altissima, Brassica napus var. napus, Brassica oleracea, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cynodon dactylon, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hordeum vulgare, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Medicago sativa, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa , Phaseolus lunatus, Phaseolus vulgaris, Pistacia vera, Pisum sativum, Prunus dulcis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Triticale, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays

[0244] Especially preferred crops are crops of cereals, corn, soybeans, rice, oilseed rape, cotton, potatoes, peanuts or permanent crops.

[0245] In one embodiment microparticles or formulations according to the invention or microparticles prepared according to processes of the invention are used in non-crop applications like home and garden, turf and amenity.

[0246] In one embodiment microparticles or formulations according to the invention or microparticles prepared according to processes of the invention are used in seed treatment.

[0247] Another aspect of the present invention is a method of controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite attack and / or for regulating the growth of plants, wherein the inventive microcapsules or inventive formulations are allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and / or on undesired plants and / or on the crop plants and / or on their environment.

[0248] Another aspect of the present invention are seeds containing microparticles of the invention or prepared according to the invention, especially containing one or more pesticides as agrochemical active ingredients.

[0249] Another aspect of the present invention are seeds containing a coating containing microparticles of the invention or prepared according to the invention, especially containing one or more pesticides as agrochemical active ingredients.

[0250] Microparticles according to the invention or prepared according to processes of the invention formulations according to the invention, in each case containing one or more pesticides as an agrochemical active ingredient are in one embodiment used for treatment of treatment of plant propagation materials, particularly seeds, as part of Suspoemulsions (SE), flowable concentrates (FS), and gels (GF) The formulations in question give, after two-to- tenfold dilution, agrochemical active ingredient concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying microparticles on plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.

[0251] When employed in plant protection, the amounts of agrochemical active ingredients applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.

[0252] In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of agrochemical active ingredient of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.

[0253] When used in the protection of materials or stored products, the amount of agrochemical active ingredient applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of agrochemical active ingredient per cubic meter of treated material.

[0254] Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the microparticles or the formulations comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1, preferably 1:10 to 10:1.

[0255] The user usually applies the composition according to the invention containing one or more pesticides as agrochemical active ingredient in crop protection applications from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition 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 composition 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.

[0256] According to one embodiment, individual components of the composition according to 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.

[0257] The present invention offers the following advantages. Typically, the identified advantages apply to the inventive microparticles as well as to the inventive formulations:

[0258] Microparticles of the invention are environmentally friendly.

[0259] Microparticles of the invention do not form any microplastic.

[0260] Microparticles of the invention have a favorable EHS profile and are easy to produce.

[0261] Microparticles and formulations of the invention can have a high loading of the agrochemical active ingredient.

[0262] Microparticles of the invention allow for a controlled release of agrochemical active ingredient. The release profile can be adjusted to the requirements of the application. It is possible to provide capsules with very easy release of the agrochemical active ingredients. It is possible to provide capsules with very slow release of the agrochemical active ingredients. In particular, it is possible to provide formulations with a slow initial release (e.g. almost no release until 10 minutes after the application), but a complete release after two days. It is possible to provide capsules with good volatility profiles. It is possible to provide capsules with low volatility of the agrochemical active ingredient. Microcapsules of the invention have smooth surface.

[0263] Microcapsules of the invention have a porous shell.

[0264] Microparticles of the invention can be used in a broad range of agrochemical applications (e.g. crop protection, agricultural non-crop applications, seed treatment).

[0265] Microparticles of the invention comprising one or more pesticides show a high efficacy for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired attack by insects or mites and / or for regulating the growth of plants.

[0266] Microparticles of the invention comprising one or more pheromones show a high efficacy for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired attack by insects or mites and / or for regulating the growth of plants.

[0267] Microparticles of the invention are easy and economical to make. They do not require complicated equipment. They can be formed at room temperature and do not requiring cooling during their preparation. They can be prepared in high amounts and processes for their manufacture can be scaled up.

[0268] Microparticles and formulations of the invention are storage stable.

[0269] Microparticles and formulations of the invention are compatible with a broad range of other agrochemical active ingredient and can be formulated with a broad range of other agrochemical active ingredient.

[0270] Examples

[0271] Surfactant A: polyethylene oxide-polypropylene oxide co-polymer of the structure PEO-PPO-PEO comprising 50 wt% EO and with the PPO block having an average molar mass of 3250 Da

[0272] Example 1 a) 100g of pyraclostrobin and 25g tetraethoxy silane were dissolved in 150g of naphthalene-depleted Solvesso, b) This oil phase was then added to a water phase containing 5g of lauramine oxide and 611g of distillated water. The emulsifying step took place in an open vessel, to allow evaporation of ethanol resulting from the reaction, at 15000 rpm for 10 minutes with a rotor stator homogenizer. After completion of the emulsification step, the rotor stator was replaced by a dissolver stirrer. The following steps took place at 25°C, c) pH of the emulsion was brought to 10.5-10.7 by slow addition of sodium hydroxide (1 N). Concomitantly, 25g of tetraethoxy silane were slowly added to the emulsion, d) After stirring the emulsion at 25°C during one hour, HCI (1 N) was slowly added to the emulsion to reach a pH of 4, e) The resulting emulsion was left under stirring at 25°C overnight. f) Subsequently, 150g of xanthan gum (1% ww. Solution) and 1g of surfactant A (10% in solution) was further added under stirring to stabilize the suspension.

[0273] Example 2

[0274] The experiment was proceeded exactly as described in example 1 (steps a to e) but in step f, 1 ,5g of soluble potato proteins (0.15%) was added to the suspension instead of polyethylene oxide-polypropylene oxide.

[0275] Example 3

[0276] The experiment was proceeded exactly as described in example 1 (steps a and b) but after stirring the emulsion at 25°C during one hour, HCI (1 N) was slowly added to the emulsion to reach a pH of 4. Subsequently, the experiment was conducted identically to what is described in example 1 (step d to f).

[0277] Example 4

[0278] The experiment was proceeded exactly as described in example 1 (steps a to c) except that HCI was not added to the emulsion which stayed at pH10.5. Subsequently, the experiment was conducted identically to what is described in example 1 (step e to f).

[0279] Example 5

[0280] The experiment was proceeded exactly as described in example 1 (steps a to c), except that in step c, the pH of the emulsion was brought to 6.5 (instead of 10.5) by slow addition of sodium hydroxide (1N). Subsequently, the experiment was run identically to what is described in example 1 (step d to f).

[0281] Example 6

[0282] The experiment was proceeded exactly as described in example 1 (steps a to e). The step f was omitted.

[0283] The resulting particles size distribution was in a good range after synthesis but shows clear agglomeration after several (12) weeks of storage at 20°C. This phenomenon was not observed for the samples containing xanthan gum or potatoes proteins. Example 7

[0284] The experiment was proceeded exactly as described in example 1 (steps a to f), except that the addition of tetraethoxy silane was omitted in step c.

[0285] Example 8

[0286] 71.5g of pyraclostrobin and 25g tetraethoxy silane were dissolved in 178.5g of dibutyladipate instead of the Solvesso. The rest of the experiment was proceeded exactly as described in example 1 (steps b to f).

[0287] Example 9

[0288] A) A water phase was prepared with 616g distilled water and 5g of lauramine oxide.

[0289] B) An oil phase was prepared with 250g of cinmethylin and 25g of tetraethylorthosilicat.

[0290] C) The oil phase was then added to the water phase and emulsified at 15 000 rpm for 120 seconds with a rotor stator homogenizer at 20°C. After completion of the emulsification step, the rotor stator was replaced by a dissolver stirrer. The following steps took place at 25°C.

[0291] D) 10g NaOH (1 N) was slowly added at first. After stirring the emulsion at 25°C during one hour 25g of tetraethylorthosilicate were added concomitantly with 40g NaOH (1 N).

[0292] E) Now 48,55ml methanesulfonic acid (1 N) was slowly added to the emulsion to reach a pH of 4.

[0293] F) The resulting emulsion was left under stirring at 25°C overnight.

[0294] G) Xanthan gum and surfactant A were added and the suspension completed to 1 L with distilled water.

[0295] Example 10

[0296] The experiment was proceed as described in example 9, except that cinmethylin was replaced by fenpropimorph and that 30g of tetraethylorthosilicate were used in core (step B) and 30g in shell (step D). In the step G distilled water only was added to complete the suspension to 1L.

[0297] Example 11 :

[0298] A) A water phase was prepared with 600g distilled water and 5g of lauramine oxide.

[0299] B) An oil phase was prepared with 100g of Z-11-Hexadecenal, 150g of coconut oil and 30g of tetraethylorthosilicate at 25°C.

[0300] C) The oil phase was then added to the water phase and emulsified at 17 500rpm for 120 seconds with a rotor stator homogenizer at 20°C. After completion of the emulsification step, the rotor stator was replaced by a dissolver stirrer. The following steps took place at 25°C.

[0301] D) 10g NaOH (1 N) was slowly added at first. After stirring the emulsion at 25°C during one hour, 30 g of tetraethylorthosilicate were added concomitantly with 40g NaOH (1 N) and stirred during 2h.

[0302] E) Then 47.44mL methanesulfonic acid (1 N) was slowly added to the emulsion to reach a pH of 4. F) After overnight stirring, xanthan gum was added (final concentration in the suspension 1 ,5g / L) and the suspension completed to 1L with distilled water.

[0303] Example 12:

[0304] A) A water phase was prepared with 615g distilled water and 5g of lauramine oxide.

[0305] B) 62.5g of trifloxystrobin and 25g tetraethylorthosilicate silane were dissolved in 187.5g of naphthalene-depleted Solvesso,

[0306] C) The oil phase was then added to the water phase and emulsified at 13 OOOrpm for 120 seconds with a rotor stator homogenizer at 19°C. After completion of the emulsification step, the rotor stator was replaced by a dissolver stirrer. The following steps took place at 25°C.

[0307] D) 10g NaOH (1 N) was slowly added at first. Then 25g of tetraethylorthosilicate were added concomitantly with 40g NaOH (1 N).

[0308] E) After stirring the emulsion at 25°C during one hour, 48.43mL methanesulfonic acid (1 N) was slowly added to the emulsion to reach a pH of 4.

[0309] F) The resulting emulsion was left under stirring at 25°C overnight.

[0310] G) Xanthan gum and surfactant A were added and the suspension completed to 1 L with distilled water.

[0311] Example 13 Particle size distribution in volume, (measured according to ISO 13320 EN)

[0312] For formulations obtained in examples 1 to 12, the average size (d50) of the microcapsules was determined by laser diffraction according to ISO 13320, Particle Size Analysis - Laser Diffraction Methods, December 1st, 2009.

[0313] Table 1 : Particles size distribution of Sol-Gel particles after preparation Light microscopy picture of capsules of example 1 is shown in figure 1 .

[0314] Scanning electron microscopy picture of capsules of example 1 are shown in figure 2.

[0315] Picture 2: Scanning electron microscopy picture of capsules of example 1

[0316] It was observed that the capsules were small (1 -50pm), in a spherical shape with smooth and thin capsules walls. It was possible to observe rests of organic colloid covering the surface.

[0317] Example 14: Release rate test

[0318] Furthermore, the formulations obtained in examples 1 to 10 and 12 were subjected to a release test according to the following procedure ("Pluronic Test”):

[0319] In a glass beaker, equipped with a magnetic stirrer, 100 ml of a 10% solution of Surfactant A in demineralized water was placed. To this solution 50 pl of the formulation were added and after 10 min an aliquot was taken for analysis of free active ingredient. For this analysis, the aliquot was firstly filtered through a 22 pm syringe filter, then injected into an HPLC equipment for quantitative analysis of active ingredient. The value obtained represents the released active ingredient in a 10% surfactant solution after the time given below at room temperature (21 ° C).

[0320] Table 2: Release rate of pyraclostrobin from Sol-Gel Capsules from examples 1 to 8

[0321] Table 3: Release rate of cinmethylin, fenpropimorph und trifloxystrobin from Sol-Gel Capsules from examples 9, 10 and 12. Example 15: Release rate test of Z-11-Hexadecenal in dry conditions

[0322] The sample obtained in example 11 was diluted at a ratio of 1 :300 in water. Then 10 droplets of 1 pl each were applied onto a clean glass slide. The latter was stored at 20°C in a climate chamber. The quantification of the active ingredient was performed by extraction in methanol using UHPLC-MS / MS at different time points. The first point was after dilution before drying, then directly after drying and afterwards after 24h, 48h and 72h.

[0323] Table 4: Release rate of Z-11-Hexadecenal from Sol-Gel Capsules from example 11

Claims

Claims1. Microparticles comprising a core and a shell, where the shell comprises silica the core comprises a water insoluble liquid, said water insoluble liquid being a liquid agrochemical active ingredient or a water insoluble solvent comprising an agrochemical active ingredient in dissolved form, the microcapsule comprises a protective colloid, the average diameter d90 of said microparticles is 1 to 50 m.

2. Microcapsule according to claim 1, wherein said agrochemical active ingredient is selected from fungicides, herbicides, insecticides, pheromones.

3. Microcapsule according to any of claims 1 to 2, wherein the shell of said capsules has an average thickness of 40 to 200 nm.

4. Microcapsule according to any of claims 1 to 3, wherein said protective colloid is selected from polysaccharides, polyvinyl alcohol or proteins.

5. Process for making microcapsules comprising the following steps: a. Providing a water insoluble liquid, said water insoluble liquid being a liquid agrochemical active ingredient or a water insoluble solvent comprising in dissolved form an agrochemical active ingredient, said water insoluble liquid comprising an alkoxy silane compound, b. Providing an aqueous phase comprising one or more surfactants, c. Emulsifying the water insoluble liquid obtained in step a. in the aqueous phase obtained in step b, d. adjusting the pH in the aqueous phase obtained in step c. to a basic value, e.g. between 9 and 13, e. Adding an alkoxy silane compound to the aqueous phase, f. adjusting the pH in the aqueous phase to an acidic value, e.g. between 2 and 6, g. Addition of a protective colloid after completion of steps e. and f„6. Process according to claim 5, where said alkoxysilane is selected from tetraethoxy silane, methyldiethoxysilane, ethoxytrimethylsilane, methoxytrimethylsilane, triethoxy (ethyl)silane, trimethoxymethylsilane, diethoxydimethylsilane, dimethoxymethylvinylsilane, dimethoydimethylsilane, vinyltrimethoxysilane, triethoxyvinylsilane, 1 , 2-Bis(tri methoxysily l)eth ane, 1 , 2-Bis(triethoxy si ly l)eth ane .

7. Process according to any of claims 5 to 6, where the addition of the silane in step d. is carried out at a pH between 9 and 13, preferably between 9.5 and 12.

8. Process according to any of claims 5 to 7, where said process is carried out at a temperature between 10 °C and 50 °C.

9. Process according to any of claims 5 to 8, where the surfactant comprised in the aqueous phase in step b. is selected from zwitterionic surfactants, preferably aminoxide or lecithin.

10. Process according to any of claims 5 to 9, where the adjustment of the pH in step f is done directly after or up to 10 hours after, or 10 minutes to 3 hours after the finalization of the addition of the alkoxy silane in step e.11 . Process according to any of claims 5 to 10, where step g (addition of the protective colloid), is done 4 to 48 hours after step e.

12. Formulation comprising microcapsules according to any of claims 1 to 4 or prepared according to any of claims 5 to 11, where said microcapsules are dispersed in a liquid medium, preferably an aqueous medium.

13. Formulation according to claim 12, where the loading with the agrochemical active ingredient comprised in the core of the microcapsules is at least 10 g / l, based on the formulation.

14. Method of controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite attack and / or for regulating the growth of plants, wherein the microcapsules according to any of claims 1 to 4 or microcapsules prepared according to claims 5 to 11 or formulations according to claims 12 to 13 or are allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and / or on undesired plants and / or on the crop plants and / or on their environment.

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