AU2007338045B2

AU2007338045B2 - Phytosanitary formulation generating nanoparticles, method for preparing nanoparticles and use thereof

Info

Publication number: AU2007338045B2
Application number: AU2007338045A
Authority: AU
Inventors: Marc Balastre
Original assignee: Rhodia Operations SAS
Current assignee: Rhodia Operations SAS
Priority date: 2006-12-22
Filing date: 2007-12-21
Publication date: 2012-02-02
Anticipated expiration: 2027-12-21
Also published as: AU2007338045A1; FR2910239A1; EP2099306A1; FR2910239B1; WO2008077921A1

Abstract

The present invention relates to a phytosanitary formulation capable of generating nanoparticles. The formulation includes a solvent having a low water miscibility, an active ingredient and at least one amphiphilic compound. The formulation is concentrated and is intended to be diluted in water by a farmer. The present invention also relates to a method for preparing nanoparticles of a phytosanitary active ingredient using the formulation of the invention.

Description

Phytosanitary formulation generating nanoparticles, method for preparing nanoparticles and use thereof The present invention relates to a crop protection 5 formulation which is capable of generating nanoparticles. The formulation comprises a solvent of low miscibility in water, an active ingredient, and at least one amphiphilic compound. It is a concentrated formulation intended for dilution in water by the farmer. The present invention also 10 relates to a process for preparing nanoparticles of an active crop protection ingredient, using the formulation of the invention. Any discussion of the prior art throughout the 15 specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field. Numerous active compounds are used in agriculture, such as 20 fertilizers or pesticides, examples being insecticides, herbicides or fungicides. They are referred to as crop protection products. These active compounds or crop protection products are generally produced in a pure or highly concentrated form. On farms they must be used at low 25 concentrations. For this purpose, the active compounds are generally formulated with other ingredients in order to allow easy weight dilution by the farmer. These formulations are referred to as crop protection formulations. The dilution carried out by the farmer is 30 generally accomplished by mixing the crop protection formulation with water. Hence crop protection formulations must allow easy weight dilution by the farmer, so as to produce a product in which 35 the crop protection product is properly dispersed, in the form, for example, of a solution, emulsion, suspension or - la suspoemulsion. Crop-protection formulations thus permit the transport of a crop protection product in a relatively concentrated form, and permit easy packaging and/or easy handling for the end user. Various types of crop protection 5 - 2 formulations may be used, according to the different crop protection products. Examples include emulsifiable concentrates (EC), dispersible concentrates (DC), suspension concentrations (SC), wettable powders (WP), 5 and water-dispersible granules (WDG). The formulations it is possible to use depend on the physical form of the crop protection product (for example, solid or liquid), and on its physicochemical properties in the presence of other compounds such as water or the 10 solvents. Following weight or volume dilution by the farmer, by mixing with water, for example, the crop protection product may be in a variety of physical forms: 15 solution, dispersion of solid particles, dispersion of droplets of the product, droplets of solvent in which the product is dissolved, etc. The crop protection formulations generally comprise compounds which allow these physical forms to be obtained. These compounds 20 may be, for example, surfactants, solvents, mineral supports, or dispersants. Very often these compounds do not have an active character but instead have an intermediary character for aiding formulation. It is thus quite often desired to limit the amount of these 25 compounds in order to limit the costs and/or any environmental unfriendliness. The crop protection formulations may especially be in a liquid form, or in a solid form, in the form, for example, of powder or granules. 30 For practical reasons, preference may be given to using crop protection formulations in liquid form. Formulations of this kind have the advantage, especially, of not generating dust and therefore of not 35 raising questions of the effect on health when there are particles present in the air that is breathed. Document EP 1023832 describes a process for preparing suspension concentrates (SC) in water of solid -3 particles of an active crop protection ingredient. The suspensions comprise water, the active ingredient, an adjuvent able to reduce the surface tension on spraying, which does not promote growth of the 5 particles, and at least one nonionic or anionic surfactant. The suspensions are prepared by grinding processes, and the particles are micron-sized. Document EP 1087658 describes processes for preparing 10 microdispersions of solid particles of a solid active crop protection ingredient. In one process the active ingredient is melted, an emulsion is made of the active ingredient in melted form, and then this emulsion is cooled, to give solid particles dispersed in water. In 15 another process, the active ingredient is dissolved in a water-immiscible solvent, the solution is emulsified in water, and then the solvent is removed, to give particles of the active ingredient dispersed in water. In one process the active ingredient is melted in the 20 presence of a surfactant and optionally in the presence of a cosurfactant, an emulsion is made of the active ingredient in melted form, and then this emulsion is cooled, to give solid particles dispersed in water. The cosurfactants which may be employed are heptyl acetate 25 (water-immiscible), NMP (total miscibility in water), butyrolactone (total miscibility in water), or octyl pyrrolidone (miscibility in water of not more than 0.1%). The preparation process described comprises numerous steps and is not practical to implement. 30 Moreover, the compositions obtained have a relatively high water content (of the order of 50% by weight), which is undesirable for reasons of transport cost. A need exhibits for simpler processes, and for simpler compositions. 35 Nanoparticles of active crop protection ingredients have also been described. Document WO 02/082900 indicates that the nanoparticles may have increased biological activity in comparison with emulsified droplets, or with micron-sized particles. Document WO 02/082900 describes more specifically a process of forming nanoparticles of active crop 5 protection ingredients by mixing water and a composition comprising the water-insoluble active crop protection ingredient, a water-miscible solvent such as methanol (totally miscible with water), and an amphiphilic compound, for example, a block copolymer 10 deriving from unsaturated monomers. Document WO 03/039249 describes solid formulations of primarily amorphous nanoparticles of active crop protection ingredients, and their dispersions in water. 15 The formulations comprise a particular random free radical copolymer. In one process ("precipitation route") the particles may be obtained by very vigorous mixing of an aqueous solution of the copolymer with a solution of the active ingredient in a water-miscible 20 solvent, followed by solidification by removal of the water and the solvents, by means, for example, of spray drying, freeze drying or drying in a fluidized bed. The solvents have a miscibility of at least 10%. The examples employ completely water-miscible solvents. The 25 particles following the dispersion in water have a hydrodynamic diameter of 10 to 500 nm. Document WO 2005/087002 describes a process for preparing a dispersion of crop protection particles 30 which are said to be nanometric, by mixing with water a solution of the active ingredient in a water-miscible solvent, in the presence, where appropriate, of a surfactant. Numerous solvents are cited: NMP (complete water miscibility), DMSO (complete water miscibility), 35 sulfolane (complete water miscibility), acetone (complete water solubility), ethanol (complete water miscibility), DMF (complete water miscibility), acetophenone (0.55% miscibility in water), methanol, (complete miscibility in water), butyrolactone -5 (complete miscibility in water), cyclohexanone (2.4% miscibility in water), dimethylacetamide (complete miscibility in water), and C1-C4 alkyl esters of lactates (miscibility in water ranging from 4.5% to 5 100% depending on the length of the alkyl chain) . The examples employ solvents of complete miscibility in water: novaluron in solution in DMSO (completely water miscible), or tebuconazole in solution in ethyl lactate (completely water miscible) . The particle size is not 10 given in the examples. Document WO 2006/002984 describes concentrated formulations of pesticides that comprise a pesticide, at least one amphiphilic compound (poly(ethylene 15 oxide)-poly(propylene or other oxide) block copolymer), and a solvent with a miscibility in water of greater than 1%, preferably at least 5%, in particular at least 10%. The formulations are said to form particles, by mixing with water, with a size of less than 500 nm. In 20 the examples, solvents of high miscibility are used. The document, especially a study of example 10 and comparative example A (pages 42 and 43), shows that, for the solvents of complete miscibility that are used, the use of the block copolymers makes it possible, 25 after dilution, to stabilize the change in particle size over time; the initial formation of the particles on dilution, probably switching in water of the miscible solvent, remains obtained irrespective of the amphiphilic system (block copolymer or amphiphilic 30 compound). There is a need for other solutions for forming nanoparticles, allowing the active ingredients employed and the solvents employed to be varied. There exists, furthermore, a continual need for 35 different formulation systems that allow variation in the active crop protection ingredients, the forms in which they are used (especially liquid forms), their efficacy (especially an absence of crystallization or a low level of crystallization, since crystallization may -6 be detrimental to the biological efficacy), while managing constraints of practical use (good stability, good sprayability, absence of crystallization or low level of crystallization, absence of nozzle clogging, etc.). 5 It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative. 10 The invention provides a liquid crop protection formulation capable of forming, by mixing with water, solid nanoparticles whose average diameter as measured by light scattering is between 10 and 500 nm, of a water-insoluble active crop protection ingredient, and comprising: 15 a) a water-insoluble organic active crop protection ingredient, b) a partially water-miscible solvent system whose miscibility in water is between 0.001% and 10%, and c) an amphiphilic system, 20 with the proviso that, if the amphiphilic system is composed only of a block copolymer of ethylene oxide and

C

3

-C

1 0 alkylene oxide, then the solvent system has a miscibility in water of less than 1%; and wherein the formulation comprises less than 20% by 25 weight of water. The invention provides the formulation according to the first aspect wherein the miscibility in water of the solvent system is between 0.001% and 1%. 30 The invention provides the formulation according to the first aspect or the second aspect wherein the amphiphilic system comprises a surfactant. 35 The formulation of the invention may be dubbed a "nano dispersible concentrate" (NDC).

-6a It has been found, surprisingly, that it is possible to form nanoparticles of active crop protection ingredients using solvents that are partially water-miscible that have 5 - 7 a very low miscibility in water. The invention may especially allow formulations and nanoparticles to be produced of a large variety of active 5 ingredients (especially by virtue of the use of solvents having a high solvency). The invention may especially make it possible to maximize the active ingredient contents in the formulations (especially by virtue of the use of solvents having a higher solvency) . This has an advantage 10 in terms of cost of transport, of storage and/or of handling. The formulations and the nanoparticles generated from them may especially have a high efficacy. The high efficacy 15 makes it possible for greater effects to be obtained and/or for equal effects to be obtained using less active compounds, which is beneficial, and/or is at least perceived as being beneficial, for the environment, and which is advantageous in terms of cost. 20 The invention also relates to a process for preparing a dispersion of solid nanoparticles of an organic active crop protection ingredient, comprising a step of mixing with water a formulation of any of the preceding aspects. 25 The invention also relates to a process for preparing the formulation. The invention also relates to a process for preparing a dispersion of nanoparticles of the organic active crop protection ingredient by mixing the formulation 30 with water. The invention in particular relates to a process for preparing a dispersion of solid or liquid nanoparticles of an organic active crop protection ingredient, comprising a step of mixing with water a formulation of the present invention. The invention also 35 relates to the use of the formulation to prepare nanoparticles of an organic active crop protection ingredient. The operation of mixing with water is - 7a advantageously carried out by the farmer. Consequently the formulation may be referred to as a tank-mix formulation. The invention also relates to the use of the formulation and/or of the dispersion for treatment of plants. 5 Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive 10 sense; that is to say, in the sense of "including, but not limited to". The operation of mixing with water and of forming nanoparticles can be particularly simple, and may not 15 necessitate substantial stirring. Stirring may even be superfluous. This simplicity has advantages in terms of handling time and/or reproducibility for the farming user. Lastly, the formulation and/or the dispersion of 20 nanoparticles have original optical properties which are appreciated by the user and may enable him or her to distinguish the liquids with ease. The formulation is generally single-phase, homogeneous, and often clear, while the nanoparticle dispersion is generally clear with a 25 slight color, and iridescent color, for - 8 example, which may be pinkish or bluish. Definitions 5 In the present application a "water-insoluble active ingredient" is a compound whose solubility in water is less than or equal to 0.5 g/l, preferably to 0.2 g/l, but which may be soluble in the solvent system. Without constituting a preference, it is mentioned that there 10 is no intention to exclude the possibility of the active ingredient being dissolved in water at levels less than or equal to 0.01 g/l. In the present application, the miscibility of a 15 solvent in water is expressed in % (by weight). In the present application, nanoparticles are particles with a size of less than 1000 nm. With regard to the size, it is the hydrodynamic radius of the particles, 20 obtained by light scattering measurement, carried out, for example, on a Malvern ALV CGS-3. The diameters may be measured, for example, at 900 (D 90 ) and 135 D 135 ) angle. The autocorrelation function allows two values to be obtained: the average hydrodynamic diameter 25 weighted by the scattered intensity, and a polydispersity index (dimensionless, labeled Ip), which is close to zero for a monodisperse sample. The particle size is the hydrodynamic diameter. It may be considered as being the smallest of the two values 30 indicated for 900 and for 135'. Formulation and process for preparing the formulation The formulation of the invention is liquid. The liquid 35 character may be evaluated at the temperature of use, for example, at 20 0 C. The formulation may be prepared by simple, more or less vigorous, mixing of its constituent ingredients. The ingredients may be introduced for mixing separately, or in the form of -9 premixes of some of them. It is mentioned that, since the formulation is liquid, the process of preparing this liquid formulation, which can be used directly, will typically not include a step of drying, 5 evaporation, concentration, extrusion and/or granulation. The implementation of a drying operation or partial evaporation is not, however excluded, for the purpose, for example, of adjusting the concentration of active ingredient. In that case, 10 preference would be given to not removing more than 50%, preferably not more than 25%, by weight of liquids. Preferably, not more than 50%, preferably not more than 25%, by weight of the solvent is removed. It is stated that the formulation may sometimes be 15 converted in the course of a subsequent step into a solid formulation, for example, by extrusion, granulation, atomization or impregnation of a powder, granules or an extrudate. 20 The formulation of the invention typically comprises little water or comprises no water. If the formulation comprises water, the amount of water relative to the amount of solvent system is typically such that the water/solvent system mixture is miscible. In other 25 words, the amount of water is less than the maximum of water that can be introduced into the solvent system without phase separation. In other words, the amount of water is less than the miscibility limit of water in the solvent system. 30 The formulation may, for example, contain less than 23% by weight of water, preferably less than 20%, preferably less than 15%, preferably less than 10% by weight, preferably less than 1% by weight. In one 35 advantageous embodiment, if the formulation comprises water, it comprises only the water that may be present in the ingredients: advantageously, there will be no additional introduction of water.

- 10 The formulation is capable of forming nanoparticles by mixing with water. Typically, the formulation of the invention will be able to be such that: - it is single-phase, and 5 - it forms an oil-in-water emulsion, by mixing with water, having at least a proportion of water relative to the solvent of DEmuls, DEmuls being preferably between 5/95 and 95/5, preferably between 50/50 and 95/5, - it forms a nanoparticle dispersion, by mixing with 10 water, having at least a proportion of water relative to the solvent, DNano, of greater than DEmuls, DNano being preferably between 5/95 and 99.999/0.001, preferably between 95/5 and 99.999/0.001, preferably between 99/1 and 99.995/0.005, and preferably between 15 99.5/0.5 and 99.95/0.05. The formulation as it is is therefore typically single phase, which means that it presents no phase separation visible to the eye. It may be clear, especially if it 20 comprises little water or contains no water at all. By clear is meant that characters with a height of 2 mm can be read through a thickness of 2 cm of the formulation. It is mentioned that the formulation may alternatively be single-phase and opaque. By opaque is 25 meant that characters with a height of 2 mm cannot be read through a thickness of 2 cm of formulation. Following mixing with water, the formulation may form an oil-in-water emulsion, at least at a proportion of 30 water relative to the solvent of DEmuls. The emulsion may for example be characterized by a turbid, nonclear character (characters 2 mm in height cannot be read through a thickness of 2 cm of formulation). The emulsion phase may especially exist over a range of 35 proportions, for example, over a range of proportions of at least 25% of the ranges mentioned earlier on above. The emulsion may especially be off-white. The diameter of the droplets of the emulsion, dispersed in water, may especially be greater than 1 pm, or even ~ 11 2 pm. Beyond the proportion DEmuls, the formulation may form a dispersion of nanoparticles, with a proportion of water 5 relative to the solvent of DNano which is greater than DEmuls. At this proportion, the dilute formulation may especially become clear again, with a color, where appropriate, which has a pinkish or bluish iridescence. The nanoparticles may be present over wide ranges of 10 proportions in water, for example, over at least 25%, preferably at least 50%, and even 100% of the ranges mentioned earlier on above. Without wishing to be tied to any one theory, it is 15 thought that the existence of an intermediate state in emulsion form at modest dilutions may contribute to the formation of nanoparticles at greater dilutions. It is thought that the emulsion becomes emptied in the course of the subsequent dilution, before then, finally, 20 forming nanoparticles. Phenomena of this kind cannot be observed with highly water-miscible solvents, for which the mechanisms of formation are likely very different. It is thought that the formation of nanoparticles is due to physicochemical phenomena which are quite 25 different from encapsulation techniques. The formulation is preferably free from beads or capsules of polymers or from inorganic capsules. During the preparation of the formulation of the invention, it is preferred not to use beads of polymers or of polymer 30 crosslinking systems to form bead or capsule walls. The nanoparticles may be solid or liquid nanoparticles whose average diameter is measured by light scattering is between 10 and 1000 nm, preferably between 20 and 35 500 nm, preferably between 50 and 400 nm, for example, between 100 and 300 nm. The nanoparticles advantageously have an amorphous character. A morphology of this kind may be beneficial to the efficacy. The morphology may be evaluated by optical - 12 microscopy under crossed polarizers: an absence of birefringence indicates an amorphous character. The formulation may especially comprise: 5 - from 1% to 89.9% by weight of the organic active crop protection ingredient, - from 10% to 80% by weight of the partially water miscible solvent system, and - from 0.1% to 35% by weight, preferably from 1% to 10 30%, of the amphiphilic system. In one particular embodiment the formulation contains from 7% to 30% by weight of the amphiphilic system, preferably from 10% to 25% by weight. 15 In one particular embodiment the weight ratio between the organic active crop protection ingredient and the amphiphilic system is between 0.5 and 5, preferably between 1 and 3. 20 In one particular embodiment the weight ratio between the organic active crop protection ingredient and the solvent system is between 0.05 and 5, preferably between 0.2 and 2. 25 Active ingredient Nonlimiting examples of active ingredients that may form part of the formulation include, among others, 30 ametryne, diuron, linuron, novaluron, chlortoluron, isoproturon, nicosulfuron, metamitron, diazinon, aclonifen, atrazine, chlorothalonil, bromoxynil, bromoxynil heptanoate, bromoxynil octanoate, mancozeb, maneb, zineb, phenmedipham, propanyl, the phenoxy 35 phenoxy series, the heteroaryloxyphenoxy series, CMPP, MCPA, 2,4-D, simazine, the active products of the imidazolinone series, the class of the organo phosphorous compounds, including especially azinphos ethyl, azinphos-methyl, alachlor, chlorpyriphos, - 13 diclofop-methyl, fenoxaprop-p-ethyl, methoxychlor, cypermethrin, alpha-cypermethrin, phenmedipham, propanil, oxyfluorfen, dimethoate, imidacloprid, propoxur, benomyl, deltametrin, fenvalerate, abamectin, 5 amicarbazone, bifenthrin, carbosulfan, cyfluthrin, difenconazole, ethofenprox, fenoxaprop-ethyl, flu azifop-p-butyl, flufenoxuron, hexazinone, lambda cyhalothrin, permethrin, prochloraz, methomyl, fenoxy carb, cymoxanil, chlorothalonyl, the neonicotinoid 10 insecticides, the class of triazole fungicides such as azaconazole, bromuconazole, cyproconazole, difeno conazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, myclobutanil, tebuconazole, triadimefon, triadimenol, strobilurins such as pyraclostrobin, 15 picoxystrobin, azoxystrobin, famoxadone, kresoxim methyl and trifloxystrobin, sulfonylureas, such as bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, metsulfuron-methyl, nicosulfuron, sulfomethuron-methyl, triasulfuron, and tribenuron-methyl. 20 A mixture of active ingredients may be contemplated in the formulation. The water-insoluble organic active ingredients that are 25 of particular interest are especially tebuconazole, cyproconazole, propiconazile, chlorothalonil, fipronil, cypermethrin, cymoxanil, nicosulfuron, isoproturon, linuron, oxasulfuron, bensulfuron-methyl, thidiazuron, sulfosulfuron, triasulfuron, chlorbromuron, chloro 30 methiuron, triadimefon, beta-cypermethrin, carbendazim, haloxyfop, profenofos, prometryn, thiobencarb, and chlorfenprop. It is possible especially to employ an azole, 35 preferably tebuconazole. It is possible especially to employ dinitroanilines, such as pendimethalin or trifuralin.

- 14 Solvent system The solvent system may comprise a single solvent, or a combination or mixture of two or more solvents. Where a 5 combination of two or more solvents is involved, the miscibility of the solvent system is included in the miscibility of the mixture of solvents of the solvent system. Often the miscibility of a mixture is close to the average of the miscibilities, weighted by the 10 relative weight proportions of each solvent. Still in this case, it is mentioned that the various solvents may be introduced into the formulation separately, or in the form of a mixture prepared beforehand (in which case reference may be made to a solvent composition). 15 It is noted that the solvent system may comprise solvents of complete miscibility in water or relatively high miscibility in water (greater than 10%) , and/or water-immiscible solvents, which in that case are in combination or in a mixture with solvents of partial 20 miscibility (less than or equal to 10%, preferably to 1%). The solvent system may thus comprise, for example, at least 33% by weight, preferably at least 50%, preferably at least 90%, or even 100% of solvents said to have partial miscibility. 25 The solvent system especially may comprise at least 33% by weight, preferably at least 50%, preferably at least 90%, of a solvent selected from the following solvents: - N,N-dialkyl amides of a carboxylic acid, preferably 30 an N,N-dimethyl amide of a C 6

-C

18 carboxylic acid - ketones - alkylpyrrolidones in which the alkyl group is C 3

-C

1 8 , preferably

C

6

-C

12 - aldehydes 35 - monoesters, dieters or oxalates - ethers - halogenated solvents - alcohols - phosphate, phosphonate, phosphinate, phosphine, or - 15 phosphine oxide solvents - nitriles - amines, preferably alkylamines, dialkylamines, trialkylamines, or heterocyclic amines, in which the 5 alkyl groups are Ci-C 18 - lactones - carbonates - mixtures or combinations thereof, said solvents, mixtures or combinations having a 10 miscibility in water of between 0.001% and 10%, preferably between 0.001% and 1%. Solvents which can be used include especially the solvents of the following type: 15 - The class of the amides, alkyl amides, and dialkyl aides, with especially the AlkylDiMethylAmides (ADMA) where the alkyl is, for example, C 2

-C

2 0 , more particularly N,N-dimethyldecanamide (miscibility 0.034%) and N,N-dimethyloctanamide (miscibility 20 0.43%), or mixtures with different sizes of alkyls. Mention is made especially of the compounds sold by Rhodia, Rhodiasolv@ ADMA810 and Rhodiasolv@ ADMA10, and of the compounds sold by Clariant under the Genegen@ name. 25 - Ketones such as cyclohexanone (miscibility 2.3%), acetophenone (miscibility 0.55%), isophorone (miscibility 1.2%), and methyl isobutyl ketone (miscibility 1.7%). - Alkyl lactams, especially alkylpyrrolidones such as 30 N-octylpyrrolidone (miscibility 0.1%). - The class of monoesters, diesters or oxalates, for example, butyraldehyde (miscibility 7.1%), benzaldehyde (miscibility 0.3%), styrallyl acetate, benzyl acetate (miscibility 0.001%), butyl acetate 35 (miscibility 2.9%), propyl acetate (miscibility 2.3%), ethyl acetate (miscibility 8%), N-pentyl acetate (miscibility 1%), isoamyl acetate (miscibility 2%), isobutyl acetate (miscibility 0.67), isopropyl acetate (miscibility 2.9%), isobutyl - 16 isobutyrate (miscibility 0.5%), diethyl phthalate (miscibility 0.1%), dimethyl phthalate (miscibility 1.84%), methyl salicylate (miscibility 0.074%), benzyl salicylate (miscibility 0.005%), methyl 5 salicylate (miscibility 0.07%), ethyl salicylate, isoamyl salicylate, diethyl malonate (miscibility 3.31%), dimethyl oxalate (miscibility 5%), dimethyl adipate (miscibility 2.5%), dimethyl oxalate, and also mixtures of diesters such as the product 10 Rhodiasolv@ RPDE sold by Rhodia (miscibility 5.3%). - The class of ester alcohols or their derivatives, such as (S)-2-hydroxybutyl propionate (Purasolv@ BL), (S)-n-butyl lactate (miscibility 4.5%); propanoic acid, 2-hydroxy-2-ethylhexyi ester (Purasolv@ EHL), 15 ethylhexyl S-lactate (miscibility 0.03%), and diethylene glycol n-butyl ether (miscibility 6.5%). - The class of ethers such as anisole (miscibility 1.04%), dimethoxymethane (miscibility 2.4%), epichlorohydrin (miscibility 6.58%), and diphenyl 20 ether (miscibility 0.002%). - The class of halogenated solvents such as 1,1 dichloroethane (miscibility 5.03%) and dichloro methane (miscibility 1.3%). - The class of alcohols such as benzyl alcohol 25 (miscibility 0.08%), 2-ethylbutanol (miscibility 0.63%), 2-ethylhexanol (miscibility 0.07%), 2-ethyl 1,3-hexanediol (miscibility 0.6%), 2-heptanol (miscibility 0.35%), and decanol (miscibility 0.02%). - The class of aldehydes, such as benzaldehyde 30 (miscibility 0.3%) and furfuraldehyde (miscibility 8.3%). - The class of phosphates, such as tributyl phosphate (miscibility 0.04%), tributoxyethyl phosphate (miscibility 0.11%), and tris(2-ethylhexyl) phosphate 35 (miscibility 0.1%). - The class of phosphonates, such as dibutyl butylphosphonate. - The class of nitriles, such as acrylonitrile (miscibility 7.35%), butyronitrile (miscibility - 17 3.3%), and benzonitrile (miscibility 0.2%). - The class of amines, alkylamines, dialkylamines, trialkylamines, and heterocyclic amines, such as, for example, quinoline (miscibility 0.61%) and 5 dodecylamine. - The class of lactones such as hexalactone. - The class of carbonates, such as ethylene carbonate and propylene carbonate. - The mixtures and combinations of these classes and 10 solvents. It is possible especially to contemplate mixtures or combinations with solvents having higher miscibilities, such as DMSO, NMP, butyrolactone, acetone, and ethanol. 15 In one particular embodiment the formulation is free of NMP. Among the partially miscible solvents, preference may be given to those which have a relatively polar group 20 and a comparatively hydrophobic group. Solvents of this kind may be beneficial to the mechanism of formation described above. Amphiphilic system 25 The amphiphilic system may comprise a single amphiphilic compound, or a combination or a mixture of two or more amphiphilic compounds. The skilled worker knows of amphiphilic compounds, and it may especially 30 involve surfactants or polymers, often block polymers. The amphiphilicity is often characterized by the HLB, which is a parameter known to the skilled worker. It is often tabulated. It may be evaluated in a known way. 35 If the system in question is a combination of two or more amphiphilic compounds, the HLB of the amphiphilic system is understood as the HLB of the mixture of compounds of the amphiphilic system. Often the HLB of a mixture is close to the average of the HLBs, weighted - 18 by the relative weight proportions of each amphiphilic compound. Still in this case, it is stated that the various amphiphilic compounds may be introduced into the formulation separately, or in the form of a mixture 5 prepared beforehand (in which case reference may be made to an amphiphilic composition). The amphiphilic system may comprise a surfactant. Surfactants are known compounds which have a molar mass 10 which is generally relatively low, for example, less than 1000 g/mol. The surfactant may be an anionic surfactant in salified or acid form, a nonionic surfactant, preferably polyalkoxylated, a cationic surfactant, an amphoteric surfactant (a term which also 15 includes zwitterionic surfactants), or a mixture of these surfactants. It is noted that the formulation may comprise: - at least one amphiphilic compound with a molar mass 20 of less than 1000 g/mol, which may especially be a surfactant, and - at least one amphiphilic compound with a molar mass of greater than or equal to 1000 g/mol. 25 An amphiphilic compound with a molar mass of greater than or equal to 1000 g/mol may especially be a polymeric compound. By way of examples of anionic surfactants, mention may 30 be made, without wishing to be limited thereto, of: - alkylsulfonic acids or arylsulfonic acids, optionally substituted with one or more hydrocarbon-based groups, and the acid function of which is partially or totally salified, such as C 8 -C5o, more particularly 35 CB-C 30 , preferably C10-C 2 2 alkylsulfonic acids, benzenesulfonic acids or naphthalenesulfonic acids substituted with one to three c-C30, preferably C4-C16, alkyl and/or C2-C30, preferably C4-C16, alkenyl groups; - 19 - alkylsulfosuccinic acid monoesters or diesters, the linear or branched alkyl part of which is optionally substituted with one or more hydroxylated and/or linear or branched C2-C4 alkoxylated (preferably 5 ethoxylated, propoxylated or ethopropoxylated) groups; - phosphate esters selected more particularly from those comprising at least one linear or branched, saturated, unsaturated or aromatic hydrocarbon-based 10 group containing 8 to 40 and preferably 10 to 30 carbon atoms, optionally substituted with at least one alkoxylated (ethoxylated, propoxylated or ethopropoxylated) group. In addition, they comprise at least one monoesterified or diesterified phosphate 15 ester group such that one or two free or partially or totally salified acid groups may be present. The preferred phosphate esters are of the type such as monoesters and diesters of phosphoric acid and of alkoxylated (ethoxylated and/or propoxylated) mono-, 20 di- or tristyrylphenol, or of alkoxylated (ethoxylated and/or propoxylated) mono-, di- or trialkylphenol, optionally substituted with one to four alkyl groups; of phosphoric acid and of an alkoxylated (ethoxylated or ethopropoxylated) C-C30, 25 and preferably C10-C22, alcohol; of phosphoric acid and of a nonalkoxylated C8-C22, and preferably C10-C22, alcohol; - sulfate esters obtained from saturated or aromatic alcohols, optionally substituted with one or more 30 alkoxylated (ethoxylated, propoxylated or ethopropoxylated) groups, and for which the sulfate functions are in free or partially or totally neutralized acid form. By way of example, mention may be made of the sulfate esters obtained more 35 particularly from saturated or unsaturated C8-C20 alcohols, which may comprise 1 to 8 alkoxylated (ethoxylated, propoxylated or ethopropoxylated) units; the sulfate esters obtained from polyalkoxylated phenol, substituted with 1 to 3 - 20 saturated or unsaturated C2-C30 hydroxycarbon-based groups, and in which the number of alkoxylated units is between 2 and 40; the sulfate esters obtained from polyalkoxylated mono-, di- or tristyrylphenol in 5 which the number of alkoxylated units ranges from 2 to 40. The anionic surfactants may be in acid form (they are potentially anionic) or in a partially or totally 10 salified form, with a counterion. The counterion may be an alkali metal, such as sodium or potassium, an alkaline earth metal, such as calcium, or an ammonium ion of formula N(R) 4 ' in which R, which may be identical or different, represent a hydrogen atom or a Ci-C4 alkyl 15 radical optionally substituted with an oxygen atom. By way of examples of nonionic surfactants, mention may be made, without wishing to be limited thereto, of: - polyalkoxylated (ethoxylated, propoxylated or 20 ethopropoxylated) phenols substituted with at least one C4-C20 and preferably C4-C12 alkyl radical, or substituted with at least one alkylaryl radical, the alkyl part of which is C1-C6. More particularly, the total number of alkoxylated units is between 2 and 25 100. By way of example, mention may be made of polyalkoxylated mono-, di- or tri(phenylethyl) phenols, or polyalkoxylated nonylphenols. Among the ethoxylated and/or propoxylated, sulfated and/or phosphated di- or tristyrylphenols, mention may be 30 made of ethoxylated bis(l-phenylethyl)phenol, containing 10 oxyethylenated units, ethoxylated bis (1-phenylethyl) phenol, containing 7 oxyethylenated units, ethoxylated sulfated bis (1-phenylethyl)phenol, containing 7 oxyethylenated units, ethoxylated 35 tris(l-phenylethyl)phenol, containing 8 oxyethyl enated units, ethoxylated tris (1-phenylethyl)phenol, containing 16 oxyethylenated units, ethoxylated sulfated tris(l-phenylethyl)phenol, containing 16 oxyethylenated units, ethoxylated tris(1- - 21 phenylethyl)phenol, containing 20 oxyethylenated units, and ethoxylated phosphated tris(1 phenylethyl)phenol, containing 16 oxyethylenated units; 5 - optionally polyalkoxylated (ethoxylated, propoxylated or ethopropoxylated) C 6

-C

2 2 fatty alcohols or fatty acids. When they are present, the number of alkoxylated units is between 1 and 60. The term "ethoxylated fatty acid" includes both the products 10 obtained by ethoxylation of a fatty acid with ethylene oxide and those obtained by esterification of a fatty acid with a polyethylene glycol; - polyalkoxylated (ethoxylated, propoxylated or ethopropoxylated) triglycerides of plant or animal 15 origin. Triglycerides derived from lard, tallow, groundnut oil, butter oil, cottonseed oil, linseed oil, olive oil, palm oil, grapeseed oil, fish oil, soybean oil, castor oil, rapeseed oil, copra oil or coconut oil, and comprising a total number of 20 alkoxylated units of between 1 and 60, are thus suitable for use. The term "ethoxylated triglyceride" is directed both to the products obtained by ethoxylation of a triglyceride with ethylene oxide and to those obtained by transesterification of a 25 triglyceride with a polyethylene glycol; - polyalkoxylated (ethoxylated, propoxylated or ethopropoxylated) sorbitan esters, more particularly cyclized sorbitol esters of Ci to C 2 0 fatty acids, for instance lauric acid, stearic acid or oleic acid, and 30 comprising a total number of alkoxylated units of between 2 and 50. The polyalkoxylated, preferably polyethoxylated and/or polypropoxylated, surfactants may be particularly 35 preferred in the context of dried emulsions. The amphiphilic system may comprise a block copolymer, comprising a hydrophilic block containing hydrophilic units deriving from hydrophilic monomers, and the - 22 hydrophobic block containing hydrophilic units deriving from hydrophobic monomers. The compound in question may be, for example, a polymeric compound selected from: - block copolymers of ethylene oxide and C3-Cio alkylene 5 oxide, - amphiphilic block copolymers, preferably linear, comprising at least one block, preferably at least two blocks, comprising units deriving from ethylenically unsaturated monomers. 10 The block copolymer is for example a diblock copolymer. Preferably at least one block, preferably two or at least two, derive from mono-alpha-ethylenically unsaturated monomers. Examples of block copolymers 15 suitable for this embodiment are described in document WO 02/082900. Some of these block copolymers deriving from mono-alpha-ethylenically unsaturated monomers may have an effect, additionally, of inhibiting crystal lization. 20 It will often be possible for the amphiphilic system to comprise at least one of the amphiphilic compounds selected from the following compounds: - ethoxylated and/or propoxylated fatty alcohols, 25 - ethoxylated and/or propoxylated fatty acids, - unalkoxylated fatty acids, - block copolymers of poly(ethylene oxide) and poly(propylene oxide), - ethoxylated and/or propoxylated di- and/or tri 30 styrylphenols, optionally phosphated or sulfated, or - alkyl sulfates or alkylsulfonates in which the alkyl is C6-C30, - mixtures or combinations thereof. 35 Especially forming part of the amphiphilic system, alone or in mixtures or combinations, may be the following: - Nonionic surfactants of fatty acid or ester type, such as, for example, esters, glycol esters, glycerol - 23 esters, PEG esters, sorbitol esters, ethoxylated sorbitol esters, ethoxylated or ethoxy-propoxylated acids, esters and triglycerides (class of the Alkamuls@ from RHODIA, examples being ethoxylated 5 castor oils, Alkamuls@ OR 36 (HLB=13.1), Alkamuls@ RC (HLB 10.5), Alkamuls® R81 (HLB=9.2), Alkamuls@ 696 (HLB 8.2). - Nonionic surfactants of ethoxylated or ethoxy propoxylated alcohol type, or polyalkylene glycol 10 type, such as (the class of the Rhodasurf@ from RHODIA, examples being Rhodasurf@ LA/30 (HLB=8), Rhodasurf@ ID5 (HLB=10.5), Rhodasurf@ 860P (HLB=12.4)). - Ethoxylated or ethoxy propoxylated aromatic nonionic 15 surfactants, an example being the class of the Igepal@ from RHODIA. - Ethoxylated or ethoxy propoxylated block copolymers, for example the class of the Antarox® from RHODIA, such as Antarox@ B848 (HLB=13.1), Antarox@ PLG 254 20 (HLB=10), Antarox@ PL 122 (HLB=5). - Anionic surfactants, such as sulfonates, aliphatic sulfonates, sulfonates carrying ester or amide groups such as isethionates (sulfo esters), taurates (sulfoamides), sulfosuccinates, sulfosuccinamates, or 25 else sulfonates containing no amide or ester groups, such as alkyldiphenyl oxide disulfonates, alkyl naphthalenesulfonates, naphthalene/formaldehyde sulfonates, including, for example, dodecyl benzenesulfonates (Rhodacal@ class from RHODIA, such 30 as, for example, Rhodacal@ 60 BE (HLB=8.3)). - Phosphate esters, for example, the class of the Rhodafac® from RHODIA such as Rhodafac@ PA 17 (HLB=ll.7), Rhodafac@ MB (HLB=9.2). - Styrylphenol-based compounds such as distyrylphenols 35 and tristyrylphenols, which may be ethoxylated or ethoxypropoxylated, phosphated and/or sulfated, for example, the class of the Soprophors® from RHODIA such as Soprophor@ DSS7, Soprophor@ BSU (HLB=12.6), Soprophor 3D33 (HLB=16), Soprophor 4D384 (HLB=16), - 24 Soprophor@ 796P (HLB=13.7). - Surfactants derived from terpenes, for example, the class of the Rhodoclean@ from RHODIA. - Ethoxylated fatty amines, for example, the class of 5 the Rhodameen@ from RHODIA. The amphiphilic system may especially have an HLB of greater than or equal to 6, preferably to 8, preferably between 9 and 18, preferably between 9 and 15, 10 preferably between 10 and 13. Without wishing to be tied to any one theory, it is thought that the selection of an amphiphilic system within these ranges may be beneficial to the formulation of the nanoparticles. 15 In one preferred embodiment the amphiphilic system comprises: - at least one amphiphilic compound with an HLB of less than 10, and 20 at least one amphiphilic compound with an HLB of greater than or equal to 10. For example, the amphiphilic system may comprise: - at least one amphiphilic compound with an HLB of less 25 than 9, preferably less than or equal to 8, and/or - at least one amphiphilic compound of an HLB of greater than or equal to 11, preferably greater than or equal to 12. 30 The formulation may especially comprise at least two amphiphilic compounds having a difference in HLB of greater than or equal to 2, preferably greater than or equal to 3, preferably greater than or equal to 4. 35 Without wishing to be tied to any one theory, it is thought that the use of at least two amphiphilic compounds with different HLBs may be beneficial to the mechanism of formation of the nanoparticles, perhaps by emulsification and exhaustion of the droplets as - 25 described above. Such a combination may thus be particularly favorable for the formation of nanoparticles from a low-miscibility formulation based on a solvent system of partial miscibility or low 5 miscibility. Other ingredients The formulation may further comprise additives such as 10 adjuvants, humectants, wetting agents, antifoams, thickeners, anticaking agents, crystalline growth inhibitors such as, for example, polyvinylpyrrolidone, dyes, chemical stabilizers, inert fillers, preservatives, antifreeze agents, nanoparticle size 15 stabilizers or nanoparticle growth inhibitors, penetrants, examples being the compounds sold by Rhodia under the brand name Geronol@, etc. Humectants include, for example, agents such as the 20 polyethylene glycols ("PEG"), for example, PEG-200, PEG-400, PEG-2000, and PEG-4000. The PEG may also act as crystallization inhibitors. Suitable wetting agents, without limitation thereto, 25 include N-methyl-N-oleoyl taurates; alkylarylsulfonate salts, such as alkylbenzenesulfonate salts, alkyl diphenyl ether sulfonate salts, alkylnaphthalene sulfonate salts; mono-alkyl sulfosuccinates, di-alkyl sulfosuccinates; and ethoxylated alkylphenols. These 30 wetting agents may be used alone or in a mixture. As wetting surfactants mention may be made, for example, of Geropon® SDS, Geropon@ T/77, Supragil@ NC/85, Rhodacal® DS/10, Supragil® WP, sold by Rhodia. The amount of wetting agent may be between 0.5% and 10% by 35 weight, relative to the total weight of the solid formulation, preferably between 1% and 5% by weight, relative to the same reference. Without wishing to be tied to any one theory, it is - 26 thought that the wetting agents may help to make the organic or inorganic substrate compatible with the water which may be employed when the solid formulation is prepared, especially in the preparation of wettable 5 powders and water-dispersible granules. They may also aid the dispersion in water of the solid formulation. Chemical stabilizers include, without limitation thereto, alkaline earth metal or transition metal 10 sulfates, sodium hexametaphosphate, calcium chloride, boric anhydride, etc. Agents for stabilizing the size of the nanoparticles or agents which inhibit nanoparticle growth include 15 polyvinylpyrrolidone (PVP), dicarboxylic diesters, for example, diisobutyl adipate, glutarate, and succinates or mixtures thereof, an example being the product Rhodiasolv@ DIB (Rhodia). 20 It is specified that it is possible for one ingredient to fulfill two or more functions in the solid formulation. Process for preparing nanoparticles - Use of the 25 formulation The formulation of the invention can be used to prepare a dispersion of solid or liquid nanoparticles by mixing with water. Everything said above in relation to the 30 nanoparticles which can be formed from the formulation, and the dispersions, is applicable to the process for preparing the nanoparticles. It is mentioned, however, that, in practice, mixing with water can be done in a single operation, without necessarily carrying out 35 intermediate dilution before an emulsion is formed. In other words, it is possible for an emulsion to be formed at a certain moment, without this being observed by the user and/or without the user carrying out specific operations to make such an observation.

- 27 Dilution with water is preferably carried out at a temperature of less than 400C, preferably less than 35*C, preferably preferably less than 300C, preferably 5 less than 250C. Ambient temperature is typically employed. Contacting of the active ingredient and the solvent may be carried out especially at a temperature of less than 400C, preferably less than 35 0 C, preferably preferably less than 300C, preferably less 10 than 25 0 C. Ambient temperature is typically employed. Thus, as indicated above, the nanoparticles obtained by the process may have an average diameter as measured by light scattering of between 10 and 1000 nm, preferably 15 between 20 and 500 nm, preferably between 50 and 400 nm, for example, between 100 and 300 nm. The nanoparticles obtained by the process may be amorphous. Mixing with water may at least be carried out at a 20 proportion of water relative to the solvent, DNano, Of greater than DEmuls, where DNano and DEmuls are as described above. In practice, the mixing with water may be such as to 25 produce a dilution (of the formulation according to the invention) by a factor F of greater than or equal to 50/(miscibility in % of the solvent system), preferably F > 100, preferably F < 5000, preferably F < 1000. 30 Moreover, mixing with water may be carried out at least at a proportion of water relative to the solvent of between 5/95 and 99.999/0.001, preferably between 95/5 and 99.999/0.001, preferably between 99/1 and 99.995/0.005, and preferably between 99.5/0.5 and 35 99.95/0.05. Dilution with water is preferably carried out on the site of agricultural exploitation, in a tank from which the nanoparticle dispersion will be applied (a - 28 procedure known as tank mixing). The liquid crop protection formulation capable of forming the nanoparticles may thus be transported and/or stored before dilution is carried out. The level of active 5 ingredient is therefore considered to be relatively important. This kind of method allows the costs of transport, storage, and handling to be optimized. The water content of the formulation capable of forming the nanoparticles, in this embodiment, is generally low, 10 for example, typically less than 23% by weight. According to another embodiment it is possible to carry out preliminary dilution at the production site of a crop protection formulation, to give the nanoparticles, 15 and then to carry out redilution in a tank from which the nanoparticle dispersion will be applied. The prediluted product may thus be transported and/or stored before dilution is carried out. The water content is then considered to be relatively important. 20 The water content of the formulation capable of forming the nanoparticles may in this embodiment be relatively high, for example, typically greater than 23% by weight, and indeed often greater than 50% by weight or 75% by weight. 25 The formulation and the process may therefore be used to prepare nanoparticles of an active organic crop protection ingredient and for treatment of plants. 30 The dilute formulation comprising the nanoparticles is subsequently applied to the fields or crops, by means of suitable apparatus, such as sprayers or aircraft such as airplanes, which broadcast the dilute formulation. The formulation may have a limited 35 stability before crystallization, of less than 2 days, for example, or even less than 1 day, or even less than 10 hours. Its stability is generally greater than 2 hours, and usually greater than 3 hours. It is preferred that the dilute formulation comprising the - 29 nanoparticles is applied during the stability period. The preferred formulations are those which allow, in the diluted state, at the application rate, the production of nanoparticles with a stability of at 5 least 3 hours, preferably of at least 5 hours. Other details or advantages of the invention may emerge in light of the examples which follow, without limitative character. 10 EXAMPLES Ingredients used The amounts used are indicated in amounts as they are. 15 The ingredients used do not substantially comprise water. The amounts are therefore substantially close to amounts of active ingredient or solids. Characterizations 20 Size of the particles obtained after dilution: This is the hydrodynamic radius of the particles, obtained by light scattering measurement carried out on a Malvern ALV CGS-3 (the concentrations used are those indicated in the examples). The diameter measurements are made at 25 900 (D 90 ) and 1350 (D 135 ) angle. The autocorrelation function provides two values: the average hydrodynamic diameter weighted by the scattered intensity, and a polydispersity index (dimensionless, referred to as Ip), which is close to zero for a monodisperse sample. The 30 size is evaluated at 250C, 30 minutes after preparation of the formulation. The dilution range studied in examples 1 to 43 (typically 0.1% to 0.5% of the Nanoparticle Dispersible 35 Concentrate (NDC)) corresponds typically to a possible range of concentration for field application. The range studied in the following examples corresponds to optimized dilutions. All of the dispersions are stable for at least 3 hours.

- 30 Example 1 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are 5 dissolved in 5.58 g (57.5% by weight) of Genagen 4166 (Clariant). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.9 g (9.3% by weight) of Alkamuls OR/36 (Rhodia) and 0.6 g (6.2% by weight) of Antarox B/848 (Rhodia). The system is stirred until a 10 clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 110 nm with an I = 0.11, D135 = 105 nm with an I, = 0.13. 15 Example 2 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Genagen 4166 20 (Clariant). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.3 g (3.1% by weight) of Alkamuls OR/36 (Rhodia) and 1.2 g (12.4% by weight) of Antarox B/848 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. 25 Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D90 = 396 nm with an Ip = 0.50, D 135 = 375 nm with an Ip = 0.46. 30 Example 3 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Genagen 4166 (Clariant). This mixture is admixed with 1.5 g (15.5%) 35 of surfactants, made up of 1.2 g (12.4% by weight) of Alkamuls OR/36 (Rhodia) and 0.3 g (3.1% by weight) of Antarox B/848 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, - 31 after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 116 nm with an IP = 0.10, D 135 = 114 nm with an Ip = 0.14. 5 Example 4 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27.8% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (59.2% by weight) of Genagen 4166 (Clariant) . This mixture is admixed with 10 1.22 g (13%) of surfactants, made up of 0.73 g (7.8% by weight) of Alkamuls OR/36 (Rhodia) and 0.49 g (5.2% by weight) of Antarox B/848 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml 15 of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 151 nm with an Ip = 0.13, D 1 3 5 = 144 nm with an Ip = 0.12. Example 5 - Nanoparticles based on tebuconazole 20 In a test tube, using a stirrer, 2.62 g (28.6% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (60.8% by weight) of Genagen 4166 (Clariant). This mixture is admixed with 0.97 g (10.6%) of surfactants, made up of 0.58 g (6.3% 25 by weight) of Alkamuls OR/36 (Rhodia) and 0.39 g (4.3% by weight) of Antarox B/848 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, 30 nanoparticles with diameters measured at D 90 = 186 nm with an Ip = 0.15, D 135 = 170 nm with an Ip = 0.15. Example 6 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (29.3% by 35 weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (62.5% by weight) of Genagen 4166 (Clariant) . This mixture is admixed with 0.73 g (8.2%) of surfactants, made up of 0.44 g (4.9% by weight) of Alkamuls OR/36 (Rhodia) and 0.29 g (3.3% - 32 by weight) of Antarox B/848 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, 5 nanoparticles with diameters measured at D 90 = 217 nm with an Ip= 0.21, D 135 = 197 nm with an Ip = 0.18. Example 7 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (30.2% by 10 weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (64.3% by weight) of Genagen 4166 (Clariant). This mixture is admixed with 0.48 g (5.5%) of surfactants, made up of 0.29 g (3.3% by weight) of Alkamuls OR/36 (Rhodia) and 0.19 g (2.2% 15 by weight) of Antarox B/848 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 402 nm 20 with an Ip = 0.42, D 135 = 312 nm with an Ip = 0.43. Example 8 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are 25 dissolved in 5.58 g (57.5% by weight) of Genagen 4166 (Clariant) . This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.84 g (8.7% by weight) of Alkamuls OR/36 (Rhodia) and 0.66 g (6.8% by weight) of Antarox PLG/254 (Rhodia). The system is stirred until a 30 clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 764 nm with an Ip = 0.46, D 1 3 5 = 631 nm with an Ip = 0.52. 35 Example 9 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (29.3% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (62.5% by weight) of - 33 Genagen 4166 (Clariant) . This mixture is admixed with 0.73 g (8.2%) of surfactants, made up of 0.41 g (4.6% by weight) of Alkamuls OR/36 (Rhodia) and 0.32 g (3.6% by weight) of Antarox PLG/254 (Rhodia) . The system is 5 stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 600 nm with an Ip= 1.18, D 135 = 920 nm with an Ip = 0.40. 10 Example 10 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Genagen 4166 15 (Clariant). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 1.25 g (12.9% by weight) of Alkamuls OR/36 (Rhodia) and 0.25 g (2.6% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. 20 Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 97 nm with an Ip = 0.16, D 135 = 92 nm with an Ip = 0.10. 25 Example 11 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (29.3% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (62.5% by weight) of Genagen 4166 (Clariant) . This mixture is admixed with 30 0.73 g (8.2%) of surfactants, made up of 0.61 g (6.8% by weight) of Alkamuls OR/36 (Rhodia) and 0.12 g (1.4% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml 35 of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 317 nm with an Ip = 0.18, D 135 = 298 nm with an Ip = 0.26. Example 12 - Nanoparticles based on tebuconazole - 34 In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Genagen 4166 (Clariant). This mixture is admixed with 1.5 g (15.5%) 5 of surfactants, made up of 0.45 g (4.6% by weight) of Antarox B/848 (Rhodia) and 1.05 g (10.9% by weight) of Soprophor BSU (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, 10 after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 100 nm with an Ip = 0.10, D 135 = 95 nm with an Ip = 0.10. Example 13 - Nanoparticles based on tebuconazole 15 In a test tube, using a stirrer, 2.62 g (29.3% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (62.5% by weight) of Genagen 4166 (Clariant) . This mixture is admixed with 0.73 g (8.2%) of surfactants, made up of 0.22 g (2.5% 20 by weight) of Antarox B/848 (Rhodia) and 0.51 g (5.7% by weight) of Soprophor BSU (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, 25 nanoparticles with diameters measured at D 90 = 220 nm with an Ip = 0.05, D 135 = 208 nm with an Ip = 0.06. Example 14 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) 30 of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Genagen 4166 (Clariant) . This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.58 g (6% by weight) of Antarox PL/122 (Rhodia) and 0.92 g (9.5% by weight) of 35 Soprophor 3D33 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 96 nm with an - 35 Ip = 0.21, D135 = 93 nm with an Ip = 0.15. Example 15 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (29.3% by 5 weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (62.5% by weight) of Genagen 4166 (Clariant). This mixture is admixed with 0.73 g (8.2%) of surfactants, made up of 0.28 g (3.2% by weight) of Antarox PL/122 (Rhodia) and 0.45 g (5% by 10 weight) of Soprophor 3D33 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 230 nm 15 with an Ip = 0.16, D 13 = 206 nm with an Ip = 0.19. Example 16 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are 20 dissolved in 5.58 g (57.5% by weight) of Genagen 4166 (Clariant). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.38 g (3.9% by weight) of Alkalmuls R/81 (Rhodia) and 1.12 g (11.6% by weight) of Soprophor BSU (Rhodia). The system is stirred until a 25 clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 204 nm with an Ip = 0.09, D 1 3 5 = 178 nm with an Ip = 0.23. 30 Example 17 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (29.3% by weight) of tebuconazole in' solid form (Makhteshim Orius) are dissolved in 5.58 g (62.5% by weight) of 35 Genagen 4166 (Clariant). This mixture is admixed with 0.73 g (8.2%) of surfactants, made up of 0.18 g (2.1% by weight) of Alkamuls R/81 (Rhodia) and 0.55 g (6.1% by weight) of Soprophor BSU (Rhodia). The system is stirred until a clear solution is obtained which is - 36 called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 199 nm with an Ip = 0.13, D 135 = 185 nm with an Ip = 0.09. 5 Example 18 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Genagen 4166 10 (Clariant). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.88 g (9.1% by weight) of Alkalmuls RC (Rhodia) and 0.62 g (6.4% by weight) of Antarox B/500 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. 15 Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 395 nm with an I, = 0.17, D 135 = 348 nm with an Ip = 0.33. 20 Example 19 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (29.3% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (62.5% by weight) of Genagen 4166 (Clariant). This mixture is admixed with 25 0.73 g (8.2%) of surfactants, made up of 0.43 g (4.8% by weight) of Alkamuls RC (Rhodia) and 0.30 g (3.4% by weight) of Antarox B/500 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml 30 of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 646 nm with an Ip = 0.19, D 135 = 571 nm with an Ip = 0.21. Example 20 - Nanoparticles based on tebuconazole 35 In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Genagen 4166 (Clariant). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 1.08 g (11.1% by weight) of - 37 Alkalmuls OR/36 (Rhodia) and 0.42 g (4.4% by weight) of Rhodacal 60/BE (Rhodia) . The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, 5 after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 211 nm with an Ip = 0.15, D 135 = 192 nm with an Ip = 0.22. Example 21 - Nanoparticles based on tebuconazole 10 In a test tube, using a stirrer, 2.62 g (29.3% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (62.5% by weight) of Genagen 4166 (Clariant) . This mixture is admixed with 0.73 g (8.2%) of surfactants, made up of 0.52 g (5.9% 15 by weight) of Alkamuls OR/36 (Rhodia) and 0.21 g (2.3% by weight) of Rhodacal 60/BE (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, 20 nanoparticles with diameters measured at D 9 0 = 401 nm with an Ip= 0.40, D 135 = 341 nm with an Ip = 0.54. Example 22 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) 25 of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 10 (Rhodia) . This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.79 g (8.10% by weight) of Soprophor 3D33 (Rhodia) and 0.72 g (7.40% by 30 weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles 35 with diameters measured at D 90 = 109 nm with an Ip = 0.07, D 135 = 111 nm with an Ip = 0.08. Dilution of 0.5 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 101 nm with an - 38 I, = 0.19, D 135 = 112 nm with an Ip = 0.09. Example 23 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) 5 of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 10. This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.82 g (8.45% by weight) of Soprophor 3D33 (Rhodia) and 0.68 g (7.05% by weight) of 10 Antarox PL/122 (Rhodia). The system is stirred until a clear solution NDC is obtained. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 101 nm with an 15 Ip = 0.11, D 135 = 101 nm with an Ip = 0.09. Dilution of 0.5 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 97 nm with an Ip = 0.18, D 135 = 105 nm with an I, = 0.15. 20 Example 24 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ 25 ADMA 10 (Rhodia) . This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.89 g (9.16% by weight) of Soprophor 3D33 (Rhodia) and 0.62 g (6.34% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is 30 called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 9 e = 109 nm with an Ip = 0.12, D 135 = 108 nm with an Ip = 0.10. 35 Dilution of 0.5 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 98 nm with an Ip = 0.19, D 135 = 103 nm with an Ip = 0.12.

- 39 Example 25 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ 5 ADMA 10 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.92 g (9.5% by weight) of Soprophor 3D33 (Rhodia) and 0.58 g (6% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is 10 called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 98 nm with an Ip = 0.06, Di35 = 101 nm with an Ip = 0.04. 15 Dilution of 0.5 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D90 = 93 nm with an Ip = 0.12, D 135 = 100 nm with an Ip = 0.08. 20 Example 26 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 10 (Rhodia) . This mixture is admixed with 1.5 g 25 (15.5%) of surfactants, made up of 0.96 g (9.86% by weight) of Soprophor 3D33 (Rhodia) and 0.55 g (5.64% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. 30 Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D9o = 99 nm with an Ip = 0.07, D 135 = 100 nm with an Ip = 0.06. Dilution of 0.5 g of this NDC in 100 ml of water gives, 35 after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 90 nm with an Ip = 0.13, D 135 = 97 nm with an Ip = 0.09. Example 27 - Nanoparticles based on tebuconazole - 40 In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This mixture is admixed with 1.5 g 5 (15.5%) of surfactants, made up of 1.03 g (10.57% by weight) of Soprophor 3D33 (Rhodia) and 0.48 g (4.93% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. 10 Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D90 = 88 nm with an Ip = 0.03, Di35 = 88 nm with an Ip = 0.04. Dilution of 0.5 g of this NDC in 100 ml of water gives, 15 after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 88 nm with an Ip = 0.09, Di35 = 92 nm with an Ip = 0.06. Example 28 - Nanoparticles based on tebuconazole 20 In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 10 (Rhodia) . This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 1.06 g (10.92% by 25 weight) of Soprophor 3D33 (Rhodia) and 0.44 g (4.58% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, 30 after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 88 nm with an Ip = 0.04, D135 = 88 nm with an Ip = 0.04. Dilution of 0.5 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles 35 with diameters measured at D 90 = 88 nm with an Ip = 0.14, D 135 = 93 nm with an Ip = 0.1. Example 29 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) - 41 of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 1.09 g (11.27% by 5 weight) of Soprophor 3D33 (Rhodia) and 0.41 g (4.23% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, 10 after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 82 nm with an Ip = 0.06, D 135 = 82 nm with an Ip = 0.08. Dilution of 0.5 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles 15 with diameters measured at D 90 = 84 nm with an = 0.12, Dias = 89 nm with an I = 0.1. Example 30 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) 20 of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 1.16 g (11.98% by weight) of Soprophor 3D33 (Rhodia) and 0.34 g (3.52% by 25 weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles 30 with diameters measured at D 90 = 86 nm with an Ip = 0.01, D 135 = 84 nm with an Ip = 0.09. Dilution of 0.5 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 78 nm with an 35 Ip = 0.09, D 1 3 5 = 80 nm with an Ip = 0.09. Example 31 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are - 42 dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 1.23 g (12.68% by weight) of Soprophor 3D33 (Rhodia) and 0.27 g (2.82% by 5 weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles 10 with diameters measured at D 90 = 101 nm with an Ip = 0.07, D 135 = 99 nm with an Ip = 0.04. Dilution of 0.5 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 79 nm with an 15 Ip = 0.15, D 135 = 82 nm with an I, = 0.08. Example 32 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are 20 dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 1.30 g (13.39% by weight) of Soprophor 3D33 (Rhodia) and 0.21 g (2.11% by weight) of Antarox PL/122 (Rhodia). The system is 25 stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 94 nm with an 30 I, = 0.02, D 135 = 95 nm with an I, = 0.07. Dilution of 0.5 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 107 nm with an Ip = 0.42, D 135 = 138 nm with an Ip = 0.34. 35 Example 33 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ - 43 ADMA 810 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.62 g (6.34% by weight) of Soprophor 3D33 (Rhodia) and 0.89 g (9.16% by weight) of Antarox PL/122 (Rhodia). The system is 5 stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 76 nm with an 10 Ip = 0.06, D 135 = 80 nm with an Ip = 0.01. Dilution of 0.5 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 82 nm with an Ip = 0.08, D 135 = 90 nm with an Ip = 0.05. 15 Example 34 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ 20 ADMA 810 (Rhodia) . This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.68 g (7.05% by weight) of Soprophor 3D33 (Rhodia) and 0.82 g (8.45% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is 25 called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 218 nm with an Ip = 0.23, D 135 = 174 nm with an Ip = 0.26. 30 Dilution of 0.5 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 252 nm with an Ip = 0.41, D 135 = 40 nm with an Ip = 0.41. 35 Example 35 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 810 (Rhodia). This mixture is admixed with 1.5 g - 44 (15.5%) of surfactants, made up of 0.75 g (7.75% by weight) of Soprophor 3D33 (Rhodia) and 0.75 g (7.75% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is 5 called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 9 0 = 67 nm with an Ip = 0.04, D 135 = 67 nm with an Ip = 0.06. 10 Example 36 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ 15 ADMA 810 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.79 g (8.10% by weight) of Soprophor 3D33 (Rhodia) and 0.72 g (7.40% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is 20 called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 71 nm with an I, = 0.08, D 135 = 73 nm with an Ip = 0.03. 25 Example 37 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ 30 ADMA 810 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.82 g (8.45% by weight) of Soprophor 3D33 (Rhodia) and 0.68 g (7.05% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is 35 called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 74 nm with an Ip = 0.04, D 135 = 74 nm with an I, = 0.08.

- 45 Example 38 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are 5 dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 810 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.89 g (9.16% by weight) of Soprophor 3D33 (Rhodia) and 0.62 g (6.34% by weight) of Antarox PL/122 (Rhodia). The system is 10 stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 76 nm with an 15 Ip = 0.09, D 135 = 74 nm with an Ip = 0.08. Example 39 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are 20 dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 810 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.92 g (9.5% by weight) of Soprophor 3D33 (Rhodia) and 0.58 g (6% by weight) of Antarox PL/122 (Rhodia). The system is 25 stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 86 nm with an 30 Ip = 0.08, D 135 = 87 nm with an Ip = 0.08. Example 40 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are 35 dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 810 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 0.96 g (9.86% by weight) of Soprophor 3D33 (Rhodia) and 0.55 g (5.64% by weight) of Antarox PL/122 (Rhodia). The system is - 46 stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles 5 with diameters measured at D 90 = 77 nm with an Ip = 0.1,

D

1 3 5 = 77 nm with an Ip = 0.06. Example 41 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) 10 of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 810 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 1.03 g (10.57% by weight) of Soprophor 3D33 (Rhodia) and 0.48 g (4.93% by 15 weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles 20 with diameters measured at D 90 = 78 nm with an Ip = 0.07, D 135 = 77 nm with an Ip = 0.1. Example 42 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) 25 of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 810 (Rhodia). This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 1.06 g (10.92% by weight) of Soprophor 3D33 (Rhodia) and 0.44 g (4.58% by 30 weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles 35 with diameters measured at D 90 = 88 nm with an Ip = 0.14, D 135 = 86 nm with an I, = 0.14. Example 43 - Nanoparticles based on tebuconazole In a test tube, using a stirrer, 2.62 g (27% by weight) - 47 of tebuconazole in solid form (Makhteshim Orius) are dissolved in 5.58 g (57.5% by weight) of Rhodiasolv@ ADMA 810 (Rhodia) . This mixture is admixed with 1.5 g (15.5%) of surfactants, made up of 1.30 g (13.39% by 5 weight) of Soprophor 3D33 (Rhodia) and 0.21 g (2.11% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.1 g of this NDC in 100 ml of water gives, 10 after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 139 nm with an Ip = 0.18, D 135 = 121 nm with an Ip = 0.22. Example 44 - Nanoparticles based on tebuconazole 15 In a 250 ml pyrex flask, with stirring with a magnetized bar, 54.0 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in a mixture containing 31 g (15.5% by weight) of surfactants, made up of 21 g (10.5% by weight) of 20 Soprophor 3D33 (Rhodia) and 10 g (5% by weight) of Antarox PL122 (Rhodia) and 115 g (57.5% by weight) of Rhodiasolv@ ADMA 10. The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 62.5 pl of this NDC in 100 ml of water 25 (i.e., 0.156 g/1 of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 97 nm with an Ip = 0.24,

D

135 = 97 nm with an Ip = 0.14. Dilution of 43.7 pl of this NDC in 100 ml of water 30 (i.e., 0.109 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 104 nm with an Ip = 0.19,

D

135 = 98 nm with an Ip = 0.17. Dilution of 25.0 pl of this NDC in 100 ml of water 35 (i.e., 0.062 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 109 nm with an Ip = 0.23, Di35 = 101 nm with an Ip = 0.09.

- 48 Storage of this NDC for 7 days at 0*C (CIPAC test MT 39) does not change the appearance of the NDC (no crystals appear). Dilution of 62.5 pl of this NDC stored at 0*C in 100 ml 5 of water (i.e., 0.156 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 90 nm with an Ip = 0.15,

D

135 = 96 nm with an Ip = 0.13. Dilution of 43.7 pl of this NDC stored at 00C in 100 ml 10 of water (i.e., 0.109 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 92 nm with an Ip = 0.09,

D

135 = 93 nm with an Ip = 0.08. Dilution of 25.0 pl of this NDC stored at 0*C in 100 ml 15 of water (i.e., 0.062 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 93 nm with an Ip = 0.09,

D

135 = 91 nm with an Ip = 0.06. 20 Storage of this NDC for 14 days at 540C (CIPAC test MT 46) does not change the appearance of the NDC (no crystals appear). Dilution of 62.5 pl of this NDC stored at 540C in 100 ml of water (i.e., 0.156 g/1 of active ingredient) 25 gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 97 nm with an I, = 0.23, D 1 35 = 96 nm with an Ip = 0.11. Dilution of 43.7 pl of this NDC stored at 540C in 100 ml of water (i.e., 0.109 g/l of active ingredient) 30 gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 99 nm with an Ip = 0.21, D 135 = 97 nm with an Ip = 0.14. Dilution of 25.0 pl of this NDC stored at 540C in 100 ml of water (i.e., 0.062 g/l of active ingredient) 35 gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 106 nm with an Ip = 0.21, Di35 = 97 nm with an Ip = 0.14.

- 49 Example 45 - Nanoparticles based on tebuconazole In a 250 ml pyrex flask, with stirring with a magnetized bar, 54.0 g (27% by weight) of tebuconazole in solid form (Makhteshim Orius) are dissolved in a 5 mixture containing 31 g (15.5% by weight) of surfactants, made up of. 28.7 g (14.35% by weight) of Alkamuls OR 36 (Rhodia) and 2.3 g (1.15% by weight) of Antarox PL122 (Rhodia) and 115 g (57.5% by weight) of Rhodiasolv@ ADMA 10. The system is stirred until a 10 clear solution is obtained which is called an NDC. Dilution of 62.5 pl of this NDC in 100 ml of water (i.e., 0.156 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 128 nm with an Ip = 0.24, 15 D 135 = 136 nm with an Ip = 0.14. Dilution of 43.7 pl of this NDC in 100 ml of water (i.e., 0.109 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 146 nm with an Ip = 0.23, 20 D 135 = 141 nm with an Ip = 0.11. Dilution of 25.0 pl of this NDC in 100 ml of water (i.e., 0.062 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 159 nm with an I, = 0.24, 25 D 135 = 142 nm with an Ip = 0.14. Storage of this NDC for 7 days at 0 0 C (CIPAC test MT 39) does not change the appearance of the NDC (no crystals appear). 30 Dilution of 62.5 pl of this NDC stored at 0*C in 100 ml of water (i.e., 0.156 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 127 nm with an Ip = 0.24,

D

135 = 136 nm with an Ip = 0.16. 35 Dilution of 43.7 pl of this NDC stored at 0*C in 100 ml of water (i.e., 0.109 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 140 nm with an Ip = 0.22, Di35 = 139 nm with an Ip = 0.09.

- 50 Dilution of 25.0 pl of this NDC stored at 00C in 100 ml of water (i.e., 0.062 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 141 nm with an Ip = 0.15, 5 D 135 = 132 nm with an Ip = 0.15. Storage of this NDC for 14 days at 540C (CIPAC test MT 46) does not change the appearance of the NDC (no crystals appear). 10 Dilution of 62.5 pl of this NDC stored at 540C in 100 ml of water (i.e., 0.156 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D9o = 134 nm with an Ip = 0.30, D 135 = 145 nm with an Ip = 0.26. 15 Dilution of 43.7 pl of this NDC stored at 540C in 100 ml of water (i.e., 0.109 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 150 nm with an Ip = 0.23, D 135 = 152 nm with an Ip = 0.212. 20 Dilution of 25.0 pl of this NDC stored at 540C in 100 ml of water (i.e., 0.062 g/l of active ingredient) gives, after 3 inversions of the test tube, nanoparticles with diameters measured at D 90 = 149 nm with an Ip= 0.18, D 135 = 139 nm with an Ip = 0.13. 25 Example 46 - Nanoparticles based on fipronil In a test tube, using a stirrer, 1.4 g (28% by weight) of fipronil in solid form are dissolved in 2.6 g (52% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This 30 mixture is admixed with 1 g (20%) of surfactants, made up of 0.182 g (3.64% by weight) of Soprophor 3D33 (Rhodia) and 0.818 g (16.36% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. 35 Dilution of 0.357 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 213 nm with an Ip = 0.262; D 1 35 = 208 nm with an Ip = 0.176. 40 - 51 Example 47 - Nanoparticles based on fipronil In a test tube, using a stirrer, 1.4 g (28% by weight) of fipronil in solid form are dissolved in 2.6 g (52% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This 5 mixture is admixed with 1 g (20%) of surfactants, made up of 0.273 g (5.45% by weight) of Soprophor 3D33 (Rhodia) and 0.727 g (14.55% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. 10 Dilution of 0.357 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 158 nm with an Ip = 0.344; D 135 = 137 nm with an Ip = 0.26. Dilution of 0.357 g of this NDC in 100 ml of CIPAC D 15 water (342 ppm) gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D9= 116 nm with an Ip = 0.253; D 135 = 112 nm with an Ip= 0.172. Dilution of 0.357 g of this NDC in 100 ml of 1000 ppm 20 water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 118 nm with an Ip = 0.232; D 135 = 112 nm with an Ip = 0.169. Example 48 - Nanoparticles based on fipronil 25 In a test tube, using a stirrer, 1.4 g (28% by weight) of fipronil in solid form are dissolved in 2.6 g (52% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This mixture is admixed with 1 g (20%) of surfactants, made up of 0.364 g (7.27% by weight) of Soprophor 3D33 30 (Rhodia) and 0.636 g (12.73% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.357 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, 35 nanoparticles with diameters measured at D 90 = 206 nm with an Ip = 0.179; D 135 = 182 nm with an Ip = 0.31. Example 49 - Nanoparticles based on fipronil In a test tube, using a stirrer, 1.4 g (28% by weight) - 52 of fipronil in solid form are dissolved in 2.6 g (52% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This mixture is admixed with 1 g (20%) of surfactants, made up of 0.455 g (9.09% by weight) of Soprophor 3D33 5 (Rhodia) and 0.545 g (10.91% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.357 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, 10 nanoparticles with diameters measured at D 90 = 202 nm with an Ip = 0.734; D 135 = 212 nm with an Ip = 0.25. Example 50 - Nanoparticles based on fipronil In a test tube, using a stirrer, 1.4 g (28% by weight) 15 of fipronil in solid form are dissolved in 2.6 g (52% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This mixture is admixed with 1 g (20%) of surfactants, made up of 0.545 g (10.91% by weight) of Soprophor 3D33 (Rhodia) and 0.455 g (9.09% by weight) of Antarox 20 PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.357 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 224 nm 25 with an Ip = 1.17; D 135 = 231 nm with an Ip = 0.219. Example 51 - Nanoparticles based on fipronil In a test tube, using a stirrer, 1.4 g (28% by weight) of fipronil in solid form are dissolved in 2.6 g (52% 30 by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This mixture is admixed with 1 g (20%) of surfactants, made up of 0.636 g (12.73% by weight) of Soprophor 3D33 (Rhodia) and 0.364 g (7.27% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear 35 solution is obtained which is called an NDC. Dilution of 0.357 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 193 nm with an Ip = 1.54; D 135 = 225 nm with an Ip = 0.134.

- 53 Example 52 - Nanoparticles based on fipronil In a test tube, using a stirrer, 1.4 g (28% by weight) of fipronil in solid form are dissolved in 2.6 g (52% 5 by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This mixture is admixed with 1 g (20%) of surfactants, made up of 0.727 g (14.55% by weight) of Soprophor 3D33 (Rhodia) and 0.273 g (5.45% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear 10 solution is obtained which is called an NDC. Dilution of 0.357 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 187 nm with an Ip= 0.56; D 135 = 215 nm with an Ip = 0.206. 15 Example 53 - Nanoparticles based on fipronil In a test tube, using a stirrer, 1.4 g (28% by weight) of fipronil in solid form are dissolved in 2.6 g (52% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This 20 mixture is admixed with 1 g (20%) of surfactants, made up of 0.818 g (16.36% by weight) of Soprophor 3D33 (Rhodia) and 0.182 g (3.64% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. 25 Dilution of 0.357 g of this NDC in 100 ml of water gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 170 nm with an Ip = 1.41; D 135 = 235 nm with an Ip = 0.0958. 30 Example 54 - Nanoparticles based on fipronil In a test tube, using a stirrer, 1.4 g (28% by weight) of fipronil in solid form are dissolved in 2.6 g (52% by weight) of Rhodiasolv@ ADMA 10 (Rhodia). This mixture is admixed with 1 g (20%) of surfactants, made 35 up of 0.909 g (18.18% by weight) of Soprophor 3D33 (Rhodia) and 0.091 g (1.82% by weight) of Antarox PL/122 (Rhodia). The system is stirred until a clear solution is obtained which is called an NDC. Dilution of 0.357 g of this NDC in 100 ml of water - 54 gives, after 30 inversions of the test tube, nanoparticles with diameters measured at D 90 = 171 nm with an Ip= 1.13; D 135 = 238 nm with an Ip = 0.156. 5 Example 55 - Nanoparticles based on pendimethalin In a glass tablet bottle, 2.5 g of Soprophor 3D33 (5% by weight) (Rhodia) are dissolved in 35.0 g (70% by weight) of Rhodiasolv ADMA 10 (Rhodia) . The mixture is admixed with 12.5 g (25% by weight) of pendimethalin 10 (BASF). The system is heated (to facilitate the dissolution of the active ingredient) at 540C and stirred until a clear solution is obtained, which is referred to as an NDC. Dilution of 0.05 g of this NDC in 100 ml of water 15 gives, after 30 inversions of the test tube, nanoparticles' with diameters measured as D 90 = 206 nm with an Ip = 0.136, D 135 = 194 nm with an Ip = 0.126. This nanometer-size dispersion is stable for 24 hours at ambient temperature. 20 Example 56 - Nanoparticles based on pendimethalin In a glass tablet bottle, 1.5 g of Alkamuls 14 /R (15% by weight) (Rhodia) are dissolved in 6.0 g (60% by weight) of Rhodiasolv ADMA 10 (Rhodia). The mixture is 25 admixed with 2.5 g (25% by weight) of pendimethalin (BASF). The system is heated at 540C (to facilitate the dissolution of the active ingredient) and stirred until a clear solution is obtained, which is referred to as an NDC. 30 Dilution of 0.5 g of this NDC in 100 ml of water gives, after 10 inversions of the test tube, nanoparticles with diameters measured as D 90 = 125 nm with an Ip = 0.24, D 135 = 136 nm with an Ip = 0.179. After 24 hours at 300C the diameters measured are 35 D 90 = 111 nm with an Ip = 0.453, D 135 = 150 nm with an Ip= 0.338. Example 57 - Nanoparticles based on pendimethalin In a glass tablet bottle, 1.5 g of Soprophor 3D33 (15% - 55 by weight) (Rhodia) are dissolved in 6.0 g (60% by weight) of Rhodiasolv ADMA 810 (Rhodia). The mixture is admixed with 2.5 g (25% by weight) of pendimethalin (BASF). The system is heated at 500C (to facilitate the 5 dissolution of the active ingredient) and stirred until a clear solution is obtained, which is referred to as an NDC. Dilution of 0.5 g of this NDC in 100 ml of water gives, after 10 inversions of the test tube, nanoparticles 10 with diameters measured as D 90 = 41 nm with an Ip = 0.062, D 135 = 41 nm with an Ip = 0.068. After 24 hours at 30'C the diameters measured are D90= 68 nm with an I, = 0.159, D 135 = 70 nm with an Ip= 0.1; the solution which was completely clear to 15 start with has undergone slight opacification. Dilution of 0.5 g of this NDC in 100 ml of water gives, after 10 inversions of the test tube, nanoparticles with diameters measured 6 hours after dilution as

D

90 = 56 nm with an Ip = 0.214, D 135 = 52 nm with an 20 Ip = 0.167. Dilution of 1.0 g of this NDC in 100 ml of water gives, after 10 inversions of the test tube, nanoparticles with diameters measured 6 hours after dilution as D9= 99 nm with an Ip = 0.421, D 135 = 75 nm with an 25 Ip = 0.378. Dilution of 0.5 g of this NDC, after accelerated aging in an oven (CIPAC MT 46), in 100 ml of water gives, after 10 inversions of the test tube, nanoparticles. 30 After 1 month at 450C, the diameters measured 6 hours after dilution are D 90 = 57 nm with an Ip = 0.236,

D

135 = 55 nm with an I, = 0.155. After 15 days at 54 C, the diameters measured 6 hours 35 after dilution are D 90 = 57 nm with an Ip = 0.231,

D

135 = 55 nm with an Ip = 0.149. After 1 month in a -5/+45*C cycle, the diameters measured 6 hours after dilution are D 90 = 57 nm with an - 56 Ip = 0.238, D 135 = 55 nm with an Ip = 0.155. Example 58 - Nanoparticles based on pendimethalin In a glass tablet bottle, 1.5 g of Alkamuls 14 /R (15% 5 by weight) (Rhodia) are dissolved in 6.0 g (60% by weight) of Rhodiasolv ADMA 810 (Rhodia). The mixture is admixed with 2.5 g (25% by weight) of pendimethalin (BASF). The system is heated at 50 0 C (to facilitate the dissolution of the active ingredient) and stirred until 10 a clear solution is obtained, which is referred to as an NDC. Dilution of 0.5 g of this NDC in 100 ml of water gives, after 10 inversions of the test tube, nanoparticles with diameters measured as D 90 = 267 nm with an 15 Ip = 0.475, D 135 = 225 nm with an Ip = 0.413. After 24 hours at 30'C the diameters measured are

D

90 = 183 nm with an Ip = 0.471, D 135 = 195 nm with an Ip= 0.365.

Claims

1. A liquid crop protection formulation capable of forming, by mixing with water, solid nanoparticles whose 5 average diameter as measured by light scattering is between 10 and 500 nm, of a water-insoluble active crop protection ingredient, and comprising: a) a water-insoluble organic active crop protection ingredient, 10 b) a partially water-miscible solvent system whose miscibility in water is between 0.001% and 10%, and c) an amphiphilic system, with the proviso that, if the amphiphilic system is composed only of a block copolymer of ethylene oxide and 15 C 3 -C 10 alkylene oxide, then the solvent system has a miscibility in water of less than 1%; and wherein the formulation comprises less than 20% by weight of water. 20

2. The formulation according to claim 1 wherein the miscibility in water of the solvent system is between 0.001% and 1%.

3. The formulation according to claim 1 or claim 2 25 wherein the amphiphilic system comprises a surfactant.

4. The formulation of any one of the preceding claims wherein the formulation comprises less than 23% by weight of water. 30

5. The formulation of claim 1 wherein the formulation comprises less than 10% by weight of water.

6. The formulation of claim 5 wherein the formulation 35 comprises less than 1% by weight of water.

7. The formulation of any one of the preceding claims wherein: -58 - it is single-phase, and - it forms an oil-in-water emulsion, by mixing with water, having at least a proportion of water relative to the solvent of DEmuls, DEmuis being between 5/95 and 95/5, 5 - it forms a nanoparticle dispersion, by mixing with water, having at least a proportion of water relative to the solvent, DNano, of greater than DEmuls, DNano being between 5/95 and 99.999/0.001. 10

8. The formulation of claim 7 wherein: the proportion of water relative to the solvent of DEmuls, DEmuls is between 50/50 and 95/5.

9. The formulation of claim 7 or claim 8 wherein: 15 DNano is between 95/5 and 99.999/0.001.

10. The formulation of claim 9 wherein: DNano is between 99/1 and 99.995/0.005. 20

11. The formulation of claim 10 wherein: DNano is between 99.5/0.5 and 99.95/0.05.

12. The formulation of any one of the preceding claims, wherein the solvent system comprises at least 33% by 25 weight, of a solvent selected from the following solvents: - N,N-dialkyl amides of a carboxylic acid, - ketones - alkylpyrrolidones in which the alkyl group is C 3 -C 18 - aldehydes 30 - monoesters, diesters or oxalates - ethers - halogenated solvents - alcohols - phosphate, phosphonate, phosphinate, phosphine, or 35 phosphine oxide solvents - nitriles - amines, - lactones -59 - carbonates - mixtures or combinations thereof, said solvents, mixtures or combinations having a miscibility in water of between 0.001% and 10%. 5

13. The formulation of claim 12, wherein the solvent system comprises at least 50% by weight, of the solvent.

14. The formulation of claim 13 wherein the solvent system 10 comprises at least 90% by weight of the solvent.

15. The formulation of any one of claims 12 to 14 wherein N,N-dialkyl amide of a carboxylic acid, is an N,N-dimethyl amide of a C 6 -Ci 8 carboxylic acid. 15

16. The formulation of any one of claims 12 to 15 wherein the alkyl group of the alkylpyrrolidones is C 6 -C 12 .

17. The formulation of any one of claims 12 to 16 wherein 20 the amines are alkylamines, dialkylamines, trialkylamines, or heterocyclic amines, in which the alkyl groups are Ci C 18 .

18. The formulation of any one of claims 12 to 17 wherein 25 the solvents, mixtures or combinations have a miscibility in water of between 0.001% and 1%.

19. The formulation of any one of the preceding claims, wherein the active crop protection ingredient is an azole. 30

20. The formulation of claim 19 wherein the azole is a tebuconazole.

21. The formulation of any one of the preceding claims, 35 wherein the amphiphilic system has an HLB of greater than or equal to 6.

22. The formulation of claim 21 wherein the HLB is between -60 9 and 18.

23. The formulation of any one of the preceding claims, wherein the amphiphilic system comprises: 5 - at least one amphiphilic compound with an HLB of less than 10, and - at least one amphiphilic compound with an HLB of greater than or equal to 10. 10

24. The formulation of claim 23, wherein the amphiphilic system comprises: - at least one amphiphilic compound with an HLB of less than 9, and/or - at least one amphiphilic compound of an HLB of 15 greater than or equal to 11.

25. The formulation of claim 24 wherein the at least one amphiphilic compound has an HLB less than or equal to 8. 20

26. The formulation of claim 24 wherein the at least one amphiphilic compound has an HLB greater than or equal to 12.

27. The formulation of any one of claims 23 to 26, wherein 25 it comprises at least two amphiphilic compounds having a difference in HLB of greater than or equal to 2.

28. The formulation according to Claim 27 wherein the difference in HLB is greater than or equal to 3. 30

29. The formulation according to Claim 27 wherein the difference in HLB is greater than or equal to 4.

30. The formulation of any one of the preceding claims, 35 comprising: - at least one amphiphilic compound with a molar mass of less than 1000 g/mol, and - at least one amphiphilic compound with a molar mass -61 of greater than or equal to 1000 g/mol.

31. The formulation of claim 30, wherein the amphiphilic compound with a molar mass of greater than or equal to 5 1000 g/mol is a polymeric compound.

32. The formulation of claim 31, wherein the polymeric compound is selected from: - block copolymers of ethylene oxide and C 3 -Cio 10 alkylene oxide, - amphiphilic block copolymers, comprising at least one block, comprising units deriving from ethylenically unsaturated monomers. 15

33. The formulation of claim 32 wherein the amphiphilic block copolymers is linear.

34. The formulation of claim 32 wherein the amphiphilic block comprises at least two blocks. 20

35. The formulation of any one of the preceding claims, wherein the amphiphilic system comprises at least one of the amphiphilic compounds selected from the following compounds: 25 - ethoxylated and/or propoxylated fatty alcohols, - ethoxylated and/or propoxylated fatty acids, - unalkoxylated fatty acids, - block copolymers of poly(ethylene oxide) and poly(propylene oxide), 30 - ethoxylated and/or propoxylated di- and/or tri styrylphenols, optionally phosphated or sulfated, or - alkyl sulfates or alkylsulfonates in which the alkyl is C 6 -C 3 0 , - mixtures or combinations thereof. 35

36. The formulation of any one of the preceding claims, comprising: - from 1% to 89.9% by weight of the organic active -62 crop protection ingredient, - from 10% to 80% by weight of the partially water miscible solvent system, and - from 0.1% to 35% by weight of the amphiphilic 5 system.

37. The formulation of claim 36 comprising from 1% to 30%, of the amphiphilic system. 10

38. The formulation of any one of the preceding claims, comprising from 7% to 30% by weight of the amphiphilic system.

39. The formulation of any one of the preceding claims, 15 comprising from 10% to 25% by weight of the amphiphilic system.

40. The formulation of any one of the preceding claims, wherein the weight ratio between the organic active crop 20 protection ingredient and the amphiphilic system is between 0.5 and 5.

41. The formulation of claim 40 wherein the weight ratio between the organic active crop protection ingredient and 25 the amphiphilic system is between 1 and 3.

42. The formulation of any one of the preceding claims, wherein the weight ratio between the organic active crop protection ingredient and the solvent system is between 30 0.05 and 5.

43. The formulation of claim 42 wherein the weight ratio between the organic active crop protection ingredient and the solvent system is between 0.2 and 2. 35

44. The formulation of any one of the preceding claims, wherein it forms, by mixing with water, solid nanoparticles whose average diameter as measured by light scattering is -63 between 20 and 500 nm.

45. The formulation of claim 44 wherein the average diameter as measured by light scattering is between 50 and 5 400 nm.

46. The formulation of claim 45 wherein the average diameter as measured by light scattering is between 100 and 300 nm. 10

47. The formulation of any one of the preceding claims, forming by mixing with water, amorphous nanoparticles.

48. A process for preparing a dispersion of solid 15 nanoparticles of an organic active crop protection ingredient, comprising a step of mixing with water a formulation of any one of the preceding claims.

49. The process of claim 48, wherein the nanoparticles 20 have an average diameter as measured by light scattering of between 10 and 500 nm.

50. The process of claim 49 wherein the average diameter as measured by light scattering is between 50 and 400 nm. 25

51. The process of claim 50 wherein the average diameter as measured by light scattering is between 100 and 300 nm. 30

52. The process of any one of claims 48 to 51, wherein the nanoparticles are amorphous.

53. The process of any of claims 48 to 52, wherein the mixing with water is at least at a proportion of water 35 relative to the solvent, DNano, of greater than DEmuls, where DNano and DEmuls are as defined in claim 7.

54. The process of any of claims 48 to 53, wherein the -64 mixing with water produces a dilution with a factor F of greater than or equal to 50/(miscibility in % of the solvent system). 5

55. The process of claim 52 wherein F > 100.

56. The process of claim 53 wherein F < 5000.

57. The process of claim 54 wherein F < 1000. 10

58. The process of any of claims 48 to 57, wherein the mixing with water is at least at a proportion of water relative to the solvent of between 5/95 and 99.999/0.001, 15

59. The process of any of claims 48 to 57 wherein the proportion of water relative to the solvent is between 95/5 and 99.999/0.001.

60. The process of any of claims 48 to 57 wherein the 20 proportion of water relative to the solvent is between 99/1 and 99.995/0.005.

61. The process of any of claims 48 to 57 wherein the proportion of water relative to the solvent is between 25 99.5/0.5 and 99.95/0.05.

62. The use of the formulation according to any of claims 1 to 47 for preparing nanoparticles of an organic active crop protection ingredient and for treatment of plants. 30

63. A liquid crop protection formulation; a process for preparing a dispersion of solid nanoparticles of an organic active crop protection ingredient or the use of the formulation according to any of claims 1 to 47 35 substantially as herein described in the accompanying examples but excluding comparative examples, if any.