RU2575746C2 - Pesticide compositions of meso-size particles with reinforced action - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: pesticide composition comprises meso-sized particles consisting of slightly water-soluble agricultural active ingredient, with an average diameter of 30 nm to 500 nm, an auxiliary substance selected from the group of the oil concentrate of crop and nonylphenol ethoxylate.

EFFECT: proposed composition of meso-particles, containing such auxiliary substances, provides increased efficiency in disinfestation, control of plant diseases and weeds.

22 cl, 14 dwg

Description

Link to related applications

This application claims the priority of provisional US Patent Application Serial No. 61/370838, registered Aug. 5, 2010, which is expressly incorporated herein by reference.

Field of Invention

Various aspects are described relating to pesticidal compositions with enhanced action, consisting of meso-sized particles combined with excipients, impregnating excipients, oils or mixtures thereof, and methods for their preparation and use.

State of the art

Modern agricultural pesticidal active ingredients, including fungicides, insecticides, mayticides, herbicides and antidotes, as well as growth regulators and nutrients, typically formulate in liquid or solid formulations. These compositions are formulated so that they are conveniently used by a farmer or end user, and so that their own biological activity of the active ingredient is manifested accordingly. The purpose of the various aspects and embodiments disclosed herein is to further increase the efficacy and effect of the delivery and biological activity of the active ingredients used in agriculture and agricultural pest control.

SUMMARY OF THE INVENTION

The term "agricultural active ingredient (AI)", as used herein, refers to a chemical used in agriculture, horticulture and agricultural pest control to protect crops, plants, buildings, animals and people from unwanted organisms such as fungal and bacterial plant pathogens, weeds, insects, ticks, algae, nematodes and the like. In particular, the active ingredients used for this purpose include fungicides, bactericides, herbicides, insecticides, mayticides, algaecides, nematicides and fumigants. The term "agricultural active ingredient" also includes repellents and attractants and pheromones, modifiers of physiology or plant structure, attractants for zoospores and herbicidal antidotes.

The term “meso”, as used herein, describes particles, capsules or droplets that have a volume average diameter between about 30 nanometers (nm) and about 500 nm. The term "mesoparticle", as used in the present description, describes capsules, particles with a core-shell structure, homogeneous particles or matrix particles having a volume average diameter between about 30 nm and about 500 nm.

The term “core-shell particle,” as used herein, describes a particle with a liquid or solid core containing an agricultural active ingredient, and an outer shell that partially or fully encapsulates or covers the core.

The term “capsule”, as used herein, describes a particle with a core-shell structure with a liquid core containing an agricultural active ingredient and an outer shell that partially or fully encapsulates or covers the core.

The term "matrix particle", as used herein, describes a particle consisting of an agricultural active ingredient dispersed within a solid polymer matrix, such as, for example, a synthetic latex polymer.

The term "homogeneous particle", as used in the present description, describes a particle in which the agricultural active ingredient is from about 80% to about 99%.

The term "approximately" means a range from plus to minus 10%, for example, approximately 1 includes values from 0.9 to 1.1.

The term "sparingly soluble in water," as used herein, refers to agricultural active ingredients with a solubility in water of less than about 1000 ppm. (ppm). Preferably, the water-poorly soluble active ingredient has a solubility in water of less than 100 ppm, more preferably less than 10 ppm.

The term “water immiscible solvent” as used herein, means a solvent or mixture of solvents with a solubility in water of about 10 g / 100 ml or less.

The term “substantial absence of a surfactant,” as used herein, means a concentration of a surfactant of less than 1 wt.% With respect to the oil phase and, more preferably, less than 0.5 wt.% Of a surfactant with respect to to the oil phase.

The term “surfactant”, as used herein, refers to a substance used to create and / or stabilize an emulsion. Surfactants include nonionic, anionic, cationogenic, or combinations of nonionic and anionic or nonionic and cationogenic. Examples of suitable surfactants include alkali metal lauryl sulfates such as sodium dodecyl sulfate, alkali metal salts of fatty acids such as sodium oleate and sodium stearate, alkali metal alkyl benzenesulfonates such as sodium dodecyl benzene sulfonates, non-ionic polyoxyethylene derivatives and surfactants based on polyoxyethylene quaternary ammonium. Sources of standard substances from which a technician can select suitable surfactants, without limiting the above classes, include Handbook of Industrial Surfactants, Fourth Edition (2005), published by Synapse Information Resources Inc., and McCutcheon's Emulsifiers and Detergents, North American and International Edition (2008) published by MC Publishing Company.

The term "adjuvant", as used in the present description, refers to substances that can increase the biological activity of the active ingredient, but in themselves have no significant biological activity. Auxiliary agents contribute to the effectiveness of the active ingredients, thus, for example, by improving the delivery and uptake of the herbicide by the target weed, leading to improved biological control. Aids in the form of solid particles or liquids can be included directly in the agricultural active ingredient composition, or they can be added to the aqueous dilution of the agricultural active ingredient formulated in the composition to provide improved product performance upon use. Typically, auxiliary agents used may include, for example, surfactants, dispersants, impregnating agents, oils derived from oil and plants, and solvents and wetting agents. Examples of commonly used adjuvants include, but are not limited to, paraffin oil, garden spray oils (e.g. summer oil), methyl rapeseed oil, methylated soybean oil, highly refined vegetable oil and the like, fatty acid esters of polyhydric alcohol, polyethoxylated esters, ethoxylated alcohols, ethoxylated phenols such as nonyl phenol ethoxylates, alkyl polysaccharides and mixtures, amine ethoxylates such as Ethomeen T / 25 ™ and Armoblend AB600 ™ (Akzo-Nobel), these fatty acid and sorbitan ester illates, polyethylene glycol esters such as PEG (Huntsman) and Polyglycol 26-2 ™ (Dow Chemical Co), organosilicon surfactants such as Boost ™ (Dow AgroSciences, LLC), acetic ester terpolymers ethylene vinyl alcohol, ethoxylated alkylaryl phosphoric acid esters such as Lubrol 17A17 ™ and Atlox MBA 13/10 ™ (Uniqema) and Rhodafac RS610 ™ (Rhodia) and the like. These and other aids are described in Compendium of Herbicide Adjuvants, 9th Edition, edited by Bryan Young, Dept. of Plant, Soil and Agricultural Systems, Southern Illinois University MC-4415, 1205 Lincoln Drive, Carbondale, Illinois 62901, which is available for viewing on the Internet at http://www.herbicide-adjuvants.com/. In addition, the Handbook of Industrial Surfactants and McCutcheon 'Emulsifiers and Detergents, as described herein, are two additional sources of some of the types of adjuvants described herein.

The term “impregnating agent”, as used herein, refers to materials that enhance the ability of an agricultural active ingredient to penetrate into or through a plant surface. Typical impregnating agents are paraffin oils, crop oils, seed oils, or methylated seed oils that can dissolve or penetrate wax layers on leaves. Impregnating agents also include these types of oils, mixed with 0.5 to about 40% emulsifiers or surfactants to further increase their usefulness and effectiveness. Examples of impregnating agents include, but are not limited to: petroleum oil concentrates such as Agri-dex ™ (Helena Chemical Co), crop oil concentrate (Helena Chemical Co. and others), Herbimax ™ (Loveland Products Inc.), Penetrator ™ (Helena Chemical Co) and Uptake ™ Oil (Dow AgroSciences, LLC). Leaded or methylated vegetable oils such as Hasten ™, (Wilbur Ellis Company) Tronic ™ (Kalo, Inc.) Renegade ™ (Wilbur-Ellis Company) and modified vegetable oil and vegetable oil concentrates such as Amigo ™ (Loveland Products Inc. ) and Peerless ™ (Customer Chemicides).

The term “integral adjuvant”, as used herein, refers to one or more adjuvants added to a particular composition, such as a granular or liquid composition, at the stage of production of the product, and not at the place of application of the product, for example, to a solution for spatter. The use of integral aids simplifies the use of agrochemical products for the end user by reducing the number of ingredients that need to be measured and applied individually.

The term "interfacial condensation", as used in the present description, refers to the reaction between two contacting, organic intermediate products, which takes place on the interface between two immiscible liquids, where one immiscible liquid is dispersed in another immiscible liquid. An example of an interfacial condensation reaction is given in US Pat. No. 3,577,515, which is expressly incorporated herein by reference. A “core-shell” capsule is a capsule created by an interfacial condensation reaction that takes place between two immiscible phases, where the first immiscible phase is a dispersed phase and the second immiscible phase is a dispersion phase; and the dispersed phase or core is encapsulated by a shell formed by the reaction of two contacting organic intermediates that form a shell, and a capsule with a core-shell structure is dispersed in the dispersion phase.

The term “crosslinker”, as used herein, means a substance that initiates and promotes the reaction between the polymer precursors to form a particle with a core-shell structure. The crosslinker may or may not become part of the structure of the polymer constituting a particle with a core-shell structure. Examples of crosslinkers as used herein include water, water soluble diamines, water soluble polyamines, water soluble polyamino acids, water soluble dihydric alcohols, water soluble polyhydric alcohols and mixtures thereof.

The present disclosure relates to new pesticidal compositions consisting of meso-sized particles containing AIs and specific auxiliary agents, such as integral auxiliary agents, which are added directly to the composition or to aqueous dilution of the composition, such as auxiliary means for tank mixtures, for ensuring increased effectiveness in pest control. Mesoparticle compositions containing such adjuvants have been found to provide enhanced biological efficacy compared to mesoparticle compositions not containing such adjuvants or as compared to conventional compositions. We have found that the addition of specific auxiliary agents, especially impregnating auxiliary agents, to mesoparticle compositions provides even greater efficacy than mesoparticle compositions not containing auxiliary agents. These compositions provide increased effectiveness compared to conventional compositions of the same active ingredient. Meso-sized particles have a size in the range of 30-500 nm and can have a variety of morphologies, including, but not limited to, meso-homogeneous particles consisting of substantially pure (> 80%) active ingredient, mesocapsules containing the active ingredient, and meso -matrix particles containing the active ingredient. The present disclosure relates to mesoparticle compositions containing specific integral aids, and diluted mesoparticle compositions mixed with specific auxiliaries prior to being brought into contact with plants, and bringing into contact a plant at risk of attack by an insect or disease, or an agricultural weed plant with these compositions to effectively control these pests.

One embodiment of the present invention includes a composition for delivering an agricultural active ingredient, comprising an adjuvant combined with a mesocapsule, where the mesocapsule has a polymer shell, and a poorly soluble agricultural active ingredient, where the active ingredient is at least partially included in the polymer shell, mesocapsules with a volume average particle diameter between about 30 nm and about 500 nm. The adjuvant is an integral adjuvant comprising from 1 to about 90% of the composition, or it may be in the form of a tank mix, comprising from 0.05 to about 5% of a diluted solution for spraying.

Another embodiment of the present invention includes a composition for delivering an agricultural active ingredient, combined with meso-homogeneous particles, where from about 80 to about 99% of the meso-homogeneous particles is a poorly soluble agricultural active ingredient in the water, where the meso-homogeneous particles have a volume average diameter between approximately 30 nm and approximately 500 nm. The adjuvant is an integral adjuvant, comprising from 1 to about 90% of the composition, or it may be in the form of a tank mixture, comprising from 0.05 to about 5% of a diluted solution for spraying.

Another embodiment of the present invention includes a composition for delivering an agricultural active ingredient comprising meso matrix particles combined with an adjuvant, where the meso matrix particle consists of a poorly water soluble agricultural active ingredient, where the active ingredient is distributed throughout the polymer matrix, meso matrix particles have a volume average diameter of between about 30 nm and about 500 nm. The adjuvant is an integral adjuvant comprising from 1 to about 90% of the composition, or it may be in the form of a tank mix, comprising from 0.05 to about 5% of a diluted solution for spraying.

The present invention also provides a method of treating or preventing a fungal disease in plants using fungicides formulated in the form of mesoparticles and combined with integral aids or aids in the form of a tank mixture, where the method consists of bringing the plant, plant tissue into contact, plant cells or seed with an agriculturally effective amount of the above compositions using application methods or sprinkling Ivanov, known to those skilled in the art.

The present invention also provides a method for treating or preventing infection by insects and ticks in plants using insecticides and mayticides formulated in the form of mesoparticles and combined with integral auxiliary means or auxiliary means in the form of a tank mixture, where the method consists of bringing an insect into contact , tick, plant, plant tissue, plant cells or seed with an agriculturally effective amount of the above compositions Applying or spraying application methods known to those skilled in the art.

The present invention also provides a method for treating or preventing weeds from overgrowing crops with herbicides formulated in the form of mesoparticles and combined with integral auxiliaries or aids in the form of a tank mixture, where the method consists of bringing plants, plant tissue into contact , plant cells or seed with an agriculturally effective amount of the above compositions using the method applying or spraying known to one skilled in the art.

As used in the present description, the terms "plant" and "crop" will mean any commercially available plant, either obtained by traditional cultivation of plants, vegetative propagation or by applying technology of genetic modification.

Brief Description of the Drawings

FIG. 1. In FIG. 1 shows the components of the mother liquors of glycine and lysine, which were obtained and used for the synthesis of the typical mesocapsules disclosed in the present description.

FIG. 2. In FIG. Figure 2 shows the compounds that were combined to synthesize the typical mesocapsules disclosed herein.

FIG. 3. In FIG. Figure 3 shows the compounds that were combined to synthesize mesocapsules containing 328255-92-1, as disclosed herein.

FIG. 4. In FIG. 4 shows compounds that were combined to synthesize the typical meso-matrix latex particles disclosed herein.

FIG. 5. In FIG. Figure 5 shows the compounds that were combined to synthesize the typical meso-homogeneous particles disclosed herein.

FIG. 6. FIG. 6 includes a list of typical fungicide compositions tested for their effectiveness as fungicides; the table lists the composition and the estimated content in weight% of the agricultural active ingredient (AI) in each composition.

FIG. 7. In FIG. 7 shows the test results of various compositions identified in FIG. 6 by their ability to treat and prevent leaf spot disease in wheat plants caused by Septoria tritici in 2-day treatment or 4-day protective tests, respectively.

FIG. 8. In FIG. 8 is a relationship showing an increase in the ability of various compositions identified in FIG. 6, with and without an adjuvant, treat and prevent the leaf spot disease in wheat plants caused by Septoria tritici in 2-day treatment or 4-day protective tests, respectively.

FIG. 9. In FIG. 9 shows the results of testing the mesocapsule compositions identified in FIG. 6 in their ability to prevent brown rust in wheat plants caused by Puccinia recondita f. Tritici species in 4-day defensive tests.

FIG. 10. In FIG. 10 shows the results of testing the meso-homogeneous compositions identified in FIG. 6 in their ability to prevent brown rust in wheat plants caused by Puccinia recondita f. Tritici species in 4-day defensive tests.

FIG. 11. In FIG. 11 shows the results of testing the mesoparticle compositions identified in FIG. 6 in their ability to treat and prevent brown rust in wheat plants caused by Puccinia recondita f. Tritici species in a 2-day treatment test.

FIG. 12. In FIG. 12 shows the test results of various compositions identified in FIG. 6 in their ability to prevent leaf spot disease in wheat plants caused by Septoria tritici in a 3-day protective test.

FIG. 13. In FIG. 13 shows the test results of various compositions identified in FIG. 6 by their ability to treat leaf spot disease in wheat plants caused by Septoria tritici in a 3-day treatment test.

FIG. 14. FIG. 14 shows the test results of various compositions identified in FIG. 6 by their ability to combat various species of weeds in tests with spray at the post-emergence stage.

DESCRIPTION

In order to improve understanding of the principles of the new technology, links will now be given to preferred options for its implementation, and a specific language will be used to describe it. Despite this, it must be understood that this does not mean any limitation of the volume of new technology, such as changes, modifications and additional applications of the principles of new technology, considered, as a rule, by a specialist in the field of technology to which the new technology relates.

The discovery, development and production of effective and economical agricultural active ingredients (AI), such as fungicides, insecticides, herbicides, physiological modifiers or plant structures and the like, are only part of the challenge facing the chemical industry for agriculture. It is also important to develop effective compositions of these types of compounds to enable them to be used efficiently and economically. The mere considerations in favor of lowering trading costs dictate the ever-growing need for new compositions and methods for creating and using AIov. This need is especially acute when the effectiveness of AIs is limited or when they are difficult to handle and the desired application desired due to problems such as low solubility in aqueous solutions, low bioavailability in and on plants and insects, or low penetration through the plant surface.

One of the most effective ways to improve the action of AIs is to increase the penetration of AIs into the plant either through the root system or through the stem and leaf surface. Often this includes compiling AIs in the composition in a water-soluble form. However, many effective AIs are not very soluble in water. Accordingly, a composition that increases the penetration of water-insoluble AIs into and through plants has the potential to improve the overall effectiveness of a wide variety of AIs, including, for example, AIs that are not very soluble in water.

Some aspects disclosed herein increase the bioavailability of an agricultural active ingredient by providing AI in the form of a very small particle, for example a mesoparticle having a volume average diameter of about 500 nm or less; in some aspects, the diameter of the mesoparticles is of the order of 300 nm or less. Some of these mesoparticles have a surface substituted with biocompatible hydrophilic functional groups, such as carboxyl groups. In many applications, AIs in the form of mesoparticles penetrate plants more efficiently and are more efficiently transported inside the plant and plant than AIs that are larger than mesoparticles.

This invention consists of adjuvant and mesoparticle compositions that include meso-sized particles with a core-shell structure, such as capsules, matrix particles, and homogeneous particles. Mesoparticles of the present invention can be obtained by the methods described in the present description.

Mesocapsules can be synthesized using the step of providing an oil phase, an oil phase comprising at least one agricultural active ingredient and one or more polymer precursors, such as polyisocyanate, capable of forming a shell reaction, providing an aqueous phase, where the aqueous phase, includes water and at least one crosslinker, adding a surfactant to at least one of the aqueous or oil phases, mixing the oil and water phases at a shear rate intramural to form an emulsion comprising meso-sized droplets with a mean diameter of about 500 nm or less, and a polymer precursor reaction with the crosslinker to form mezokapsuly.

Surfactant-free mesocapsules can be synthesized using the steps of providing an oil phase, an oil phase comprising at least one agricultural active ingredient and at least one polyisocyanate, providing an aqueous phase, wherein the aqueous phase includes at least one component, where the component includes at least one functional fragment, which is either a primary or secondary amine, or a primary or secondary amino group, and additionally, by at least one hydrophilic functional group, mixing the oil and water phases to form an emulsion and the reaction of the polyisocyanate with a crosslinker to form a mesocapsule.

Mesocapsules with a core-shell structure can be prepared in many ways, including interfacial polymerization on the surface of a droplet or particle or polymerization in a dispersed phase. A preferred polymer for capsulation is polyurea, including formed by the reaction of a polyisocyanate with a polyamine, polyamino acid or water. Other preferred capsule polymers include those formed from melamine-formaldehyde or urea-formaldehyde condensates, as well as similar types of amino plastics. Capsules in which the wall of the shell consists of polyurethane, polyamide, polyolefin, polysaccharide, protein, silicon dioxide, lipid, modified cellulose, resins, polyacrylate, polyphosphate, polystyrene and polyesters or combinations of these substances can also be used to form mesocapsules with a structure core-shell.

Suitable polymers for use in the preparation of the mesocapsules of the present invention include amine-based prepolymers such as urea, melamine, benzoguanamine and glyceryl formaldehyde resins and prepolymers such as dimethyl dihydroxyethylene urea. These prepolymers can be used as mixtures and cross-linkers with polyvinyl alcohol, polyvinyl amines, acrylates (acid functionality is preferred), amines, polysaccharides, polyureas / urethanes, polyamino acids and proteins. Other suitable polymers include polyesters, including biodegradable polyesters, polyamides, polyacrylates and polyacrylamides, polyvinyl polymer and copolymers with polyacrylates, polyurethanes, polyethers, polyureas, polycarbonates, naturally occurring polymers such as polyanhydrides, polyphosphazines, polyphosphazines, polyphosphazines curable polyolefins.

A poorly water-soluble agricultural active ingredient is encapsulated inside a particle with a very small core-shell structure, for example, about 500 nm or less, more preferably 300 nm or less. AIs encapsulated in these mesocapsules can exhibit increased penetration into plants, plant cells, and even plant pathogens compared to AIs that are not associated with mesocapsules and are combined with an tank aid mixture or an integral aid.

Mesocapsules may include hydrophilic functional groups embedded in the polyurea shell and at least partially extending to the surface of the mesocapsules. A partial listing of certain functional group substances that can be used to form these particles can be found in the following publication WO 2001/94001, which is incorporated herein by reference in its entirety. Hydrophilic functional groups include carboxylate, salt carboxylate, phosphonate, salt phosphonate, phosphate, salt phosphate, sulfonate, salt sulfonate, quaternary ammonium, betaine, oxyethylene or oxyethylene-containing polymer. Preferably, the hydrophilic group is a carboxylate or salt carboxylate.

Some AIs are solid at room temperature and must be dissolved in a solvent before they can be encapsulated in polyurea mesocapsules. In one example, water-insoluble AI is dissolved in a solvent that readily dissolves the AI before the oil phase is added. Suitable solvents may be one or a mixture of organic solvents that have low solubility in water, i.e. approximately 10 g / 100 ml or less, which include, but are not limited to, petroleum distillates or hydrocarbons such as mineral oil, aromatic solvents, xylene, toluene, paraffin oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; esters of monoalcohols or dibasic, tribasic or other lower polyhydric alcohols (containing 4-6 hydroxyl groups), such as 2-ethylhexyl stearate, ethylhexyl benzoate, isopropyl benzoate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, dioctyl diacetyl diacetyl diacetate triethyl phosphate and the like; esters of mono, di and polybasic carboxylic acids such as benzyl acetate, ethyl acetate and the like; ketones such as cyclohexanone, acetophenone, 2-heptanone, gamma-butyrolactone, isophorone, N-ethylpyrrolidone, N-octylpyrrolidone and the like; alkyldimethylamides such as C8 and C10 dimethylamide, dimethylacetamide and the like; low water solubility alcohols (i.e., approximately 10 g / 100 ml or less) such as benzyl alcohol, cresols, terpineols, tetrahydrofurfuryl alcohol, 2-isopropylphenol, cyclohexanol, n-hexanol and the like. In some cases, an ultra-hydrophobic substance is added to the oil phase, supposedly to maintain the stability of the emulsion, which will be later obtained in the method by mixing the oil phase with the aqueous phase. This additive is a very poorly soluble substance in water, which 1) has an insignificant diffusion coefficient and insignificant solubility in the aqueous dispersion phase and 2) has an affinity for the dispersed phase. Examples of ultra-hydrophobic substances include long chain paraffins such as hexadecane, polymers such as polyisobutene, polystyrene, polymethyl methacrylate, natural oils such as vegetable seed oils and organosilicon substances such as silicone oil or dimethicone. Preferably, the additive is used in an amount of not more than 10 wt.% Based on the weight of the dispersed phase.

The polymer precursor in the oil phase of the emulsion is a polyisocyanate. The polyisocyanate reacts with a crosslinker or with water to form a polyurea shell. Examples of polyisocyanates include, but are not limited to, toluene diisocyanate (TDI), diisocyanato-diphenylmethane (MDI), derivative compounds such as polyethylene polyphenyl isocyanate that contains MDI, an example of which is PAPI ™ 27 polymer MDI (Dow Chemical Company), isophorone diisocyanate isophorone, , 4-diisocyanatobutane, phenylenediisocyanate, hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) benzene, 1,8-diisocyanato-octane, 4,4'-methylenebis (phenylisocyanate) and 4,4'-methylenebis (cyclohexyl isocyanate). In another example, suitable dispersed oil phase polymer precursors may also include, but are not limited to, dibasic acid chlorides, polyacid chlorides, sulfonyl chlorides, chloroformates and the like.

The oily and aqueous phases are combined in the presence of a surfactant, which helps to create and / or stabilize mesoscale droplets with a diameter of less than 500 nm, but preferably less than 300 nm. A surfactant can be added either to the oil phase, or to the aqueous phase, or to the oil or water phases. Surfactants include nonionic, anionic, cationogenic, or combinations of nonionic and anionic or nonionic and cationogenic. Examples of suitable surfactants include alkali metal lauryl sulfates, such as sodium dodecyl sulfate, fatty acid and metal alkyl salts, such as oleates and stearates, alkaline methylalkylbenzenesulfonates, such as sodium dodecylbenzenesulfonate, non-ionic polyoxyethylene derivatives and tetra-based ammonium surfactants . Sources of standard substances from which a technician can select suitable surfactants without limiting the above classes include Handbook of Industrial Surfactants, fourth edition (2005), published by Synapse Information Resources Inc, and McCutcheon's Emulsifiers and Detergents, North American and International Edition (2008) published by MC Publishing Company.

An emulsion can be prepared in a variety of ways, including batch and continuous methods known in the art. In a preferred method, the emulsion is prepared using an ultra-fast shear device, such as an ultrasonic device or a high pressure homogenizer, to create mesoscale droplets with a diameter of less than 500 nm, preferably less than 300 nm. Ultrasonic devices include standard ultrasonic processing equipment containing an ultrasonic probe that is inserted into the composition to create meso-sized droplets, one representative example is the Sonicator 400 from Misonix Sonicators. High pressure homogenizers use very high pressure, 500-20000 psi, to force the liquid to pass through a small hole and create meso-sized droplets. Examples of such devices include, but are not limited to, EmulsiFlex ™ devices (Avestin, Inc.) and Microfluidizer ™ devices (Microfluidics).

In one approach, the polyisocyanate reacts with hydroxyl-containing or amine-containing molecules in a dispersion medium (i.e., water), such as water-soluble diamines, water-soluble polyamines, water-soluble polyamino acids, water-soluble dihydric alcohols, soluble in polyhydric alcohols and mixtures thereof, by interfacial polycondensation with the formation of a polymer shell. Examples of these reactive intermediates in an aqueous dispersion medium may include, but are not limited to, water-soluble diamines, such as ethylenediamine, and the like; water soluble polyamines such as diethylene triamine, triethylenetetramine, tetraethylene pentamine, pentaethylene hexamine and the like; water-soluble amino acids containing more than one functional group capable of reacting with an isocyanate, such as 1-lysine, arginine, histidine, serine, threonine, polymers or oligomers of these amino acids and the like; water soluble dihydric alcohols or water soluble polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene oxide dihydric alcohol, water soluble amino alcohols such as 2-aminoethanols, and the like. In one embodiment of the present invention, the water-soluble phase comprises a polyamine containing carboxylate functional groups (such as 1-lysine), which reacts to form a polyurea shell that includes carboxylate functional groups on the surface of the mesocapsule. These carboxylate functional groups can be neutralized, or they can be partially or completely neutralized to form a carboxylate salt.

In another approach, diamine or polyamines or their equivalents included in the above typical aqueous phase are excluded from the reaction mixture. In this approach, the polyisocyanate reacts with water to form a polyurea shell.

Various factors can be adjusted to increase or decrease the rate of interfacial condensation reaction. These factors include, for example, temperature, pH, mixing speed, duration of the reaction, osmotic pressure and, of course, changes in the levels and types of emulsifiers, polymer components, solvents, addition of catalysts and the like. For further discussion of the effect of temperature, catalysts, pH, and the like on these types of reactions, see, for example, US Pat. No. 4,285,750, which is incorporated herein by reference in its entirety. Additional information on the effect of salts and salt content on these types of reactions can be found in WO 2006/092409, which is incorporated herein by reference in its entirety.

Some embodiments of the present invention can be carried out by varying the content of certain reagents in the reaction mixture, where the reaction mixture consists of a dispersed oil phase and a dispersed aqueous phase, which are used to form mesocapsules that include at least one AI. In some embodiments, implementation of the present invention they include at least one AI, expressed in weight percent (wt.%) From the oil phase, in the range from about 1.0 wt.% To about 90 wt.%, More preferably, from about 1.0 wt.% to about 80 wt.%; optionally, a solvent suitable for dissolving the AI in the range of from about 1 wt.% to about 90 wt.%, more preferably from about 20 wt.% to about 80 wt.%; optionally an ultra-hydrophobic substance present in the range of from about 0.5 wt.% to about 10 wt.%, more preferably from about 1.0 wt.% to about 5.0 wt.%; at least one polyisocyanate present in the range of from about 1 wt.% to about 30 wt.%, more preferably from about 5 wt.% to about 20 wt.%; optionally an emulsifier present in the range from 0.1 wt.% to about 20 wt.%, more preferably from about 1 wt.% to about 10 wt.% of the oil phase, where the oil phase is on the order of from about 1% to approximately 60% of the total emulsion.

The aqueous phase of the reaction mixture is from about 40 wt.% To about 99 wt.% The total emulsion and contains from about 60 wt.% To about 90 wt.% Water, from about 1 wt.% To about 30 wt.% One or more crosslinkers and, if desired, from about 0.1 wt.% to about 20 wt.% one or more water-soluble surfactants.

Some ingredients used in some typical compositions are optional. For example, mesocapsules can be synthesized in some cases without the addition of a solvent and / or ultra-hydrophobic substance. Adding these types of additional components to the reaction mixture is especially useful when the AI is in a solid state.

As described herein, one method used to encapsulate water-insoluble substances is to create a polyurea shell by interfacial condensation of a polyisocyanate in an oil phase that reacts with at least one of water and a water-soluble polyamine in a dispersion medium. To stabilize microcapsules against agglomeration and to control the size of microcapsules before the reaction, it is often desirable to add one or more surfactants or colloidal stabilizers to the reaction mixture. A surfactant may be useful if the purpose of the reaction is to create a mesocapsule less than 500 nm in size. However, the presence of a surfactant can be harmful in many end user applications. For example, when agricultural active ingredients are delivered to a plant, a surfactant found in polyurea mesocapsules may be toxic to the plant. In other applications, the surfactant may also cause unwanted foaming in the final product. Accordingly, it may be useful to develop a method for the efficient synthesis of micro- and mesocapsules, which require less or no surfactant, compared with the methods discussed previously.

One aspect of the method of producing mesocapsules, in which a compound is added that includes at least one functional fragment, which is either a primary or secondary amino group and, optionally, at least one hydrophilic functional group, and in which the addition of this component allows an emulsion that is substantially free of a surfactant. In one variation of this method, the component is glycine, a glycine salt, or a mixture of glycine and glycine salts. These methods of preparing micro- or mesocapsules include adding glycine, a glycine salt or a mixture of glycine and a glycine salt to the aqueous phase of the reaction mixture before creating the final emulsion, and, if desired, before starting the crosslinking reaction between components, such as polyisocyanate, to create a polyurea shell mesocapsules. Additional molecules that can be used in addition to or instead of glycine include other molecules that contain either a primary or secondary amine group at one end of the molecule and a hydrophilic group, such as carboxylate or trimethylamine, at the other end of the molecule. It may not be necessary to neutralize all charged fragments to obtain a product formed by the methods disclosed herein. It may be that the addition of both glycine, a glycine salt, and glycine-like substances before the formation of the final emulsion allows glycine to react with a small part of the di- or polyisocyanate to form a molecule similar to a surfactant, which helps to create and / or stabilize the emulsion and helps to regulate droplet size in the final emulsion. Then, after creating the final emulsion, during the interfacial condensation reaction, a surfactant-like molecule formed by the glycine reaction reacts when it is included in the polyurea shell and no longer acts as a free surfactant. The hydrophilic functional group of glycine or glycine-like molecules is located on the surface of the shell, helping to stabilize the shell. A partial list of some of these types of molecules can be found in US patent No. 4757105, which is fully incorporated into this description by reference.

Polyurea mesocapsules can be made without a surfactant using colloidal stabilizers such as polyvinyl alcohol, but it is difficult to control the particle size. Some AIs compositions are made using surfactants that do not exhibit certain properties that must be avoided by using less phytotoxic surfactants or surfactants that exhibit less foaming.

Adding a glycine salt or similar molecule, which includes either primary or secondary amine groups and either a carboxylate group or trimethylamine, to the aqueous phase before creating the final emulsion reduces or eliminates the need to add a surfactant to the reaction mixture. Addition of a substance that is not a surfactant such as glycine and which reacts with a di- or polyisocyanate to form a molecule that promotes emulsification and stabilization of the organic phase and which further reacts with a polyurea shell as soon as the di or polyisocyanate forms mesocapsules, which do not contain or substantially do not contain surfactants. In some embodiments, “substantially free” implies that the oil phase contains less than about 1.0 wt.% And, more preferably, less than 0.5 wt.% Of a surfactant.

The ability to formulate mesocapsules that do not contain or contain a very small residual amount of surfactant has advantages in many applications where the presence of a free surfactant in the composition has a harmful or undesirable effect. There may also be a potential cost advantage in the event that the amount of expensive surfactant can be reduced.

A typical method for the formation of mesocapsules involves the reaction of interfacial polycondensation between AI in the oil phase and either water or a water-soluble crosslinker in the aqueous phase. To obtain mesocapsules, especially mesocapsules with an average diameter of about 500 nm or less, or mesocapsules with an average diameter of about 300 nm or less, either a surfactant such as sodium dodecyl sulfate can be added to the reaction mixture, or a molecule can be added to the aqueous phase , such as glycine, before creating the final emulsion and / or the beginning of the crosslinking reaction. In one variation, the oil and water phases are mixed at a high shear rate to form an emulsion that includes mesoscale droplets that are converted to polyurea mesocapsules, as described herein. Emulsion processing devices for promoting the formation of mesocapsules include ultrasonic processing devices and / or high pressure homogenizers. Ultrasonic processing devices include standard ultrasonic processing equipment containing an ultrasonic probe that is inserted into the system to create meso-sized droplets, one representative example is the Sonicator 400 from Misonix Sonicators. High pressure homogenizers use very high pressure, 500-20000 psi, to force the liquid to pass through a small hole and create meso-sized droplets. Examples of such devices include EmulsiFlex ™ devices (Avestin, Inc.) and Microfluidizer ™ devices (Microfluidics).

In another variation, AIs with low solubility in water are optionally dissolved in a solvent such as benzyl acetate. Optionally, an ultra-hydrophobic substance such as hexadecane can be added to help maintain the stability of the emulsion, which forms as soon as the oil and water phases are combined. To the oil phase, for example, PAPI ™ 27 polymeric MDI polyisocyanate (Dow Chemical Company) is added. To facilitate the formation of mesoscale droplets, which are the precursors of the resulting mesocapsules, a surfactant, such as sodium dodecyl sulfate (SDS), can be added to any or both of the oily and aqueous phases. Alternatively, glycine or any other molecule with an amine or with an amine fragment at one end of the molecule and a hydrophilic group at the other end of the molecule is added to the aqueous phase before forming the resulting emulsion or initiating the crosslinking reaction. The amount of glycine or a similar molecule can be increased as necessary to replace all or at least part of the surfactant. The oil and water phases are mixed and optionally treated with an ultra-high shear device, such as a Microfluidizer (Microfluidics) device, to create the desired small droplets that are converted to polyurea mesocapsules as described herein.

Meso-matrix particles can be obtained by applying the stages of providing the oil phase, where the oil phase includes at least one agricultural active ingredient, initiator, monomer, comonomer, additional coloring monomer and ultra-hydrophobic substance, providing an aqueous phase, where the aqueous phase includes water and a surfactant, mixing the oil and water phases at a shear rate sufficient to form a pre-emulsion, and subsequent ultrasonic treatment of the pre-emulsion to obtain Nia meso-sized droplets with a mean diameter of about 500 nm or less, and finally polymerizing the monomers within the droplets by heating the emulsion to form a polymeric matrix containing the AI, which is of the meso-matrix particles. In General, the methods used to obtain the emulsion of mesoscale droplets may be similar to those for the preparation of mesocapsules, as described above, which will be obvious to experts in the field of technology. The AI content of the meso matrix particle can be from about 1 to about 80% by weight based on the dry weight of the meso matrix particle.

Suitable initiators (including growth control systems with free radical initiation), ultra-hydrophobic substances, dispersing agents and surfactants, speed-dispersion dispersion procedures and equipment, polymerization conditions and monomers and comonomers for use in the preparation of the meso-matrix particles of the present invention are described, for example, US Pat. No. 2006/0052529 A1 (March 9, 2006), US Pat. No. 5,686,518 (November 11, 1997) and US Pat. No. 6,710,128 B1 (March 23, 2004), US Pat. No. 7,317,050 B2 (January 8, 2008), US Pat. No. 2002/0032242 A1 (May 16, 2001) and n tent US 2006/0223936 A1 (20 December 2002), but are not limited to. General methods for producing meso-sized emulsions and polymerization of these emulsions are described, for example, by M. Antonietti and K. Landfester in "Polyreactions in miniemulsions", Progress in Polymer Science, vol. 27 (4), pp. 689-757 (2002), and M.S. E1-aasser, C.D. Lack, Y.T. Choi, T.I. Min, J.W. Vanderhoff and F.M. Fowkes in "Interfacial aspects of miniemulsions and miniemulsion polymers", Colloids and Surfaces, vol. 12, p. 79 (1984).

Meso-homogeneous particles can be obtained by applying the stages of providing the aqueous phase, where the aqueous phase includes at least one agricultural active ingredient, a surfactant, a wetting agent and water, and grinding the aqueous phase in a ball mill to form meso-homogeneous particles with a volume average diameter of approximately 500 nm or less using suitable equipment and conditions that are known to those skilled in the art.

In one embodiment of the present invention, the agricultural active ingredient is at least one agricultural chemical selected from the group consisting of fungicides, bactericides, herbicides, insecticides, maycides, algaecides, nematicides, attractants and pheromones of insects, modifiers of physiology or plant structure, zoospore attractants and herbicidal antidotes.

In one embodiment, the mesoparticle containing the agricultural active ingredient has a water solubility of about 1000 ppm or less, preferably 100 ppm or less, and more preferably 10 ppm or less.

Many classes and types of insecticides are useful in agriculture. Examples include insecticides such as antibiotic insecticides such as allosamidine and thuringenzine, macrocyclic lactone insecticides such as spinosad, spinetorams and 21-butenylspinosins; avermectin insecticides such as abamectin, doramectin, emamectin, eprinomectin, ivermectin and selamectin; milbemycin insecticides such as lepimectin, milbemectin, milbemycinoxime and moxidectin; botanical insecticides such as anabazine, azadirachtin, d-limonene, nicotine, pyrethrins, cinerins, cinerin I, cinerin II, jasmoline I, jasmolin II, pyrethrin I, pyrethrin II, quassia, rotenone, riania and sabadilla; carbamate insecticides such as bendiocarb and carbaryl; benzofuranyl methyl carbamate insecticides such as benfuracarb, carbofuran, carbosulfan, decarbofuran and fluratiocarb; dimitanedimethylcarbamate insecticides, dimethylan, gikvinkarb and pyrimikarb; hydroxycarbamate insecticides such as alanicarb, aldicarb, aldoxycarb, butocarboxim, butoxycarboxim, metomil, nitrile carb, oxamyl, tazimcarb, thiocarboxim, thiodicarb and thiofanox; phenylmethylcarbamate insecticides such as allixicarb, aminocarb, bufencarb, butacarb, carbanolate, cloethocarb, dicresyl, dioxacarb, EMPC, etiofencarb, phenethacarb, phenobucarb, isoprocarb, methiocarbacarbacarb, methacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarbacarb dinitrophenol insecticides such as dinex, dinoprop, dinos and dinitro-o-cresol; fluoride insecticides such as barium hexafluorosilicate, cryolite, sodium fluoride, sodium hexafluorosilicate and sulfluramide; formamidine insecticides such as amitraz, chlordimeform, formanate and formparanate; fumigant insecticides such as acrylonitrile, carbon disulfide, carbon tetrachloride, chloroform, chloropicrin, paradichlorobenzene, 1,2-dichloropropane, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, hydrogen cyanide, iodomethane, methylchlorofluoromethane, methylchlorofluoride, methylene chloroform ; inorganic insecticides such as borax, calcium polysulfide, copper oleate, mercury chloride, potassium thiocyanate and sodium thiocyanate; chitin synthesis inhibitors such as bistrifluuron, buprofesin, chlorofluazuron, ciromazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluuron, teflubenuron and three; juvenile hormone mimetics such as epofenonan, phenoxycarb, hydroprene, kinoprene, metoprene, pyriproxifen and triprene; juvenile hormones such as juvenile hormone I, juvenile hormone II and juvenile hormone III; shedding hormonal contestants such as chlomafenoside, halofenoside, methoxyphenoside and tebufenoside; antagonists of the hormone fox, such as ecdysone and ecdysterone; molt inhibitors such as diophenolan; Precenes such as Precenes I, Precenes II and Precenes III; unclassified insect growth regulators, such as dicyclanil; nereistoxin-like insecticides such as bensultap, cartap, thiocyclam and thiosultap; nicotinoid insecticides such as flonicamide; nitroguanidine insecticides such as clothianidin, dinotefuran, imidacloprid and thiamethoxam; nitromethylene insecticides such as nitenpyram and nithiazine; pyridylmethylamine insecticides such as acetamipride, imidacloprid, nitenpyram and thiacloprid; organochlorine insecticides such as bromo-DDT, camfechlor, DDT, pp'-DDT, ethyl DDD, HCH, gamma-HCH, gamma-hexachlorocyclohexane, methoxychloride, pentachlorophenol and TDE; cyclodiene insecticides such as aldrin, bromocyclin, chlorobicyclene, chlordane, chlordecone, dieldrin, dealers, endosulfan, endrin, HEOD, heptachlor, HHDN, isobenzene, isodrine, kelevan and mirex; organophosphorus insecticides such as bromfenvinphos, chlorfenvinphos, crotoxiphos, dichlorvos, dicrotophos, dimethylvinphos, phosphirate, heptenophos, metocrotophos, mevinphos, monocrotophos, iced, naphthalophos, phosphamidofone, propamidofin, tetramidone, propamidofin, tetramidone, propamidofin, tetramidone, phosphamidone, propamidofin; organothiophosphate insecticides such as diohabenzophos, phosphomethylan and fentoate; aliphatic organothiophosphate insecticides such as acetone, amiton, cadusafos, chloroethoxyphos, chlormefos, demefion, demefion-O, demefion, demethone, demethone-O, demethones, demethone-methyl, demethone-O-methyl, demethone-S-methyl, demethone-demethone O-methylsulfone, disulfotone, ethion, etoprofos, IPSP, isothioate, malathion, metacryphos, oxydemetone-methyl, oxydeprofos, oxydisulfotone, forate, sulfotep, terbufos and thiometon; aliphatic amide organothiophosphate insecticides such as amidithion, cyantoate, dimethoate, etoate-methyl, formotion, mekarbam, omethoate, protoate, sofamide and vamidothione; oxyorganorganothiophosphate insecticides such as chlorfoxime, foxime and foxime methyl; heterocyclic organothiophosphate insecticides such as azamethiophos, coumaphos, kumitoate, dioxathion, endotion, menazone, morfotion, fosalon, pyraclofos, pyridafenthion and quinothione; benzothiopyran organothiophosphate insecticides such as dithicrophos and ticrophos; benzotriazine organothiophosphate insecticides such as azinphos-ethyl and azinphos-methyl; isoindole organothiophosphate insecticides such as dialiphos and phosphate; isoxazole organothiophosphate insecticides such as isoxathion and zolaprofos; pyrazolopyrimidine organothiophosphate insecticides such as chlorprazophos and pyrazophos; pyridine organothiophosphate insecticides such as chlorpyrifos and chlorpyrifos methyl; pyrimidine organothiophosphate insecticides such as butathiophos, diazinon, etrimphos, lyrimphos, pyrimifos-ethyl, pyrimifos-methyl, pyrimidophos, pyrimitate and tebupirimfos; quinoxaline organothiophosphate insecticides such as quinalphos and quinalphos-methyl; thiadiazole organothiophosphate insecticides such as atidation, lithidation, methidation and protidation; triazole organothiophosphate insecticides such as isazophos and triazophos; phenyl organothiophosphate insecticides, such as nitrogen, bromophos, bromophos-ethyl, carbofenotion, chlorothiophos, cyanophos, cythioate, dicapton, dichlorofention, ethaphos, famfur, phenflorofenfenfentofenfentofenfenfentofenfenfenfenfentofenfenfenfentonfenfenfenfentonfenfenfenfentonfenfenfenton parathion-methyl, fencapton, fosnichlor, profenofos, prothiophos, sulfophos, temefos, trichloromethaphos-3 and triphenophos; phosphonate insecticides such as butonate and trichlorfon; phosphonothioate insecticides, such as imitsiaphos and mekafon; phenyl ethylphosphonothioate insecticides such as phonophos and trichloronate; phenyl phenylphosphonothioate insecticides such as cyanphenphos, EPN and leptophos; phosphoramidate insecticides such as krufomat, fenamiphos, fostetane, mefospholan, phospholan and pyrimethaphos; phosphoramidothioate insecticides such as acephate, isocarbophos, isofenphos, metamidophos and propetamphos; phosphorodiamide insecticides such as dimefox, mazidox, mipafox and shradan; oxadiazine insecticides such as indoxacarb; phthalimide insecticides such as dialiphos, phosphate and tetramethrin; pyrazole insecticides such as acetoprol, etiprol, fipronil, pyrafluprol, pyriprol, tebufenpyrad, tolfenpyrad and vanilliprol; pyrethroid ester insecticides such as acrinatrin, allethrin, bioallertrin, bartnin, bifentrin, bioethanometrin, cyclotrin, cycloprotrin, cyfluthrin, beta-cyfluthrin, cygalotrin, gamma-cygalotrin, lambda-cygalotrin, cypermethrin-cypermethrin, cypermethrin, cypermethrin, cypermethrin, cypermethrin, cypermethrin, cypermetrin , theta cypermethrin, zeta cypermethrin, cifenotrin, deltamethrin, dimeflutrin, dimethrin, empentrine, fenfluthrin, fenpyrithrin, fenpropatrin, fenvalerate, esfenvalerate, flucytrinate, fluvalinate, tau-fluvalinperin, fimerulinfinperin, birufinurinmetrin, birufinurinmetrin, birufinurinmetrin, birufinurinmetrin, birufinurinetrin, bimetrinperinurinet, bimerinurinpert, ranspermetrin, phenothrin, prallethrin, proflutrin, piresmetrin, resmethrin, bioresmethrin, tsismetrin, tefluthrin, terallethrin, tetramethrin, tralomethrin and transfluthrin; pyrethroid ether insecticides such as etofenprox, flufenprox, galfenprox, protrifenbut and silafluofen; pyrimidinamine insecticides such as flufenerim and pyrimidiphene; pyrrole insecticides such as chlorfenapyr; ryanodine receptor insecticides such as flubendiamide, chlorantraniliprol (rinaxipyr) and cyanthranilipole; tetronic acid insecticides such as spirodiclofen, spiromesifen and spiro tetramate; thiourea insecticides such as diafentyuron; urea insecticides such as flucofuron and sulcofuron; sulfoximine insecticides such as sulfoxaflor and unclassified insecticides such as closantel, crotameton, EXD, phenazaflor, phenazaquin, phenoxacrim, phenpyroximet, flubendiamide, hydramethylnone, isoprothiolidifenidridione, metaflufridinidisonedone, triazamate. The present disclosure involves the selection of insecticides from this list with a water solubility of approximately 1000 ppm. or less and composing them into a composition in the form of mesoparticles with an integral auxiliary agent or auxiliary agent in the form of a tank mixture. Preferred insecticides are those which have a water solubility of about 100 ppm. or less. More preferred insecticides are those having a water solubility of 10 ppm. or less. Insecticides can be selected based on water solubility values published in handbooks such as the fourteenth edition of The Pesticide Manual (ISBN 1-901396-14-2), which is incorporated herein by reference in its entirety. The following editions of The Pesticide Manual will also be useful in selecting insecticides for inclusion in mesoparticles.

Many classes and types of fungicides are useful in agriculture. Examples include ametoktradin, amisulbrom 2- (tiotsianatometiltio) -benzotiazol, 2-phenylphenol, 8-gidroksihinolinsulfat, antimycin, azaconazole, azoxystrobin, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzilaminobenzol-sulfonate (BABS) salt, bicarbonates, biphenyl, bismertiazol, bitertanol , bixafen, blasticidin-S, borax, Bordeaux liquid, boscalide, bromukonazole, bupirimat, BYF 1047, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamide, carvone, chloroneb, chlorothalonil, chlorosolinate oxo copper, chlorosolinate oxo copper, hydrochloride, copper hydroxide d copper, copper sulfate, copper sulfate (tribasic), copper oxide, cyazofamide, cyflufenamide, cymoxanil, ciproconazole, cyprodinil, coumarin, dazomet, debacarb, diammonium ethylene bis (dithiocarbamate), dichlorofluanide, dichloro dichloro dichloro dichloro dichloro dichloro dichlorofen dichlorofen dichlorofen diphenoconazole, diphenosquat ion, diflumetorim, dimetomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, dinocap meptyl, diphenylamine, dithianon, dodemorph, ethynodoxine, ethynodoxine, ethynodoxine, ethynodoxine, ethynodioxin N, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpirazamin, fentin acetate, fentin, fentin hydroxide, ferbam, ferimzone, fluzinam, fludioxonil, flumorph, fluopikolid, fluopiram, fluoroimid, fluoxastrobin, fluquinconazole, fluzilazole, fluusulfamide, flutolanil, flutriafol, fluxapirade, folpet, formaldehyde, fosetil, fosetil-aluminum, fuberidazole, furalaxyl, furametpir, guazatin azolazole, azazole gazolazole gazolazole l, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, tris (albesilate) iminoctadine, ipconazole, iprobenfos, iprodion, iprovalicarb, isoprothiolan, isopyrazide, cresamycamycidroben, casugamycidicam, casugamycidicam, creme chamocycamycidicam, casugamycidicum, cresugamycidicam, hydroxycocycamycidicamide, creme chamocycamycidicam, casugamycidicam, cacougamycidicam, hydroxycocycamycidicam, mepanipyrim, mepronil, meptyldinocap, mercury chloride, mercury oxide, mercury chloride, metalaxyl, mefenoxam, metalaxyl-M, metam, metam ammonium, metam potassium, metam sodium, metconazole, metasulfocarb, methyl iodide, methyl isomithiocyan, metrafenone, mildiomycin, miklobutanil, nabam, nitrotal-isopropyl, nuarimol, octilinon, ofuras, oleic acid (fatty acids), oryzastrobin, oxadixyl, oxin-copper, oxococonazole fumarate, oxycarboxin, penflufenfenzofenzofenzofenzofenzofenzofenzofenzofenzofenzofenzofenzofenzofenzofenzofenzofenzofenzofent, , pentiopyrad, phenylmercurium acetate, phosphinic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochlorase, procymidone, propamocarb, propamonazarbum hydrochloride, ol, propineb, proquinazide, prothioconazole, pyraclostrobin, pyraxostrobin, pyrazofos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyromethostrobin, pyroquilone, quinoclamine, quinoxifen ecofenolamine, quintoxyn sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z071, SYP-048, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazine, tetraconazole, thiabendazole, tiflusamide, thiofanate-methyl, thiram, thiadosyl, tol-vinyl tolylfluanide, triadimefo n, triadimenol, triazolopyrimidine, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumisole, triforin, triticonazole, validamycin, valifenal, valifenate, vinclozolin, cineb, ciram, zoxamide, (RS) -N- (3,5) dichloro (methoxymethyl) succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate, 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane, 2- ( 2-heptadecyl-2-imidazolin-1-yl) ethanol, 2,3-dihydro-5-phenyl-1,4-dithi-in-1,1,4,4-tetraoxide, 2-methoxyethyl mercuric acetate, 2- chloride methoxyethyl mercury, 2-methoxyethyl mercury silicate, 3- (4-chlorophenyl) -5-methylrodany 4- (2-nitropropyl-1-enyl) phenyl thiocyanate: ampropilfos, anilazine, azitiram, barium polysulfide, Bayer 32394, benodanil, benkvinoks, bentaluron, benzamakril; benzamacryl-isobutyl, benzamorph, binapacryl, butiobate, zinc-copper-calcium-cadmium-chromate-sulfate, carbamorph, CECA, chlobentiazone, chloroaniformomethane, chlorphenazole, chlorquinox, climbazole, copper bis (3-phenyl salicylate), copper-zinc kufraneb, copper hydrazinium sulfate, cuprobam, cyclofuramide, cipendazole, ciprofuram, decafentin, dichlon, dichlorozoline, diclobutrazole, dimethyrimol, dinocton, dinosulfone, dinoterbone, dipyrithione, ethylene dosinone, dimesin etraz, efinosone, dimesin etraz, erazinone, drazin etraz, erazinone, drazin etraz fenapanil, fenitropan, fluotrimazole, furcarbanil, fu rconazole, furconazole-cis, furmecyclox, furofanate, gliodin, griseofulvin, galacrinate, Hercules 3944, hexylthiophos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzide, metazoxolone, metfuroxam, methyldosulfuric acid, mimerdisulfide, mimerdisulfide, dimer 3,5-dichlorophenyl-succinimide, N-3-nitrophenylacitonimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, nickel bis (dimethyldithiocarbamate), OCH, phenylmercurium dimethyldithiocarbamate, fosdiphene, prothiocarb; prothiocarb hydrochloride, pyracarbolide, pyridinitrile, pyroxychlor, pyroxyfur, quinacetol; quinacetol sulfate, quinazamide, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thiophene, thiochlorphenfim, thiofanate, thioquinox, thioximide, triamiphos, triarimol, UK-triamide, such as (3S, 6S, 7R, 8R) -8-benzyl-3- (3- (isobutyryloxymethoxy) -4-methoxypicolinamido) -6-methyl-4,9-dioxo-1,5-dioxonan-7- sludge isobutyrate, which has a registration number CAS 328255-92-1 and will be indicated in the present description as 328255-92-1, urbatzid, XRD-563, zarylamide, IK-1140 and propargylamides. The present disclosure involves the selection of fungicides from this list with a water solubility of approximately 1000 ppm. or less and composing them into a composition in the form of mesoparticles with an integral auxiliary agent or auxiliary agent in the form of a tank mixture. Preferred fungicides are those which have a water solubility of about 100 ppm. or less. More preferred fungicides are those having a water solubility of 10 ppm. or less. Fungicides can be selected based on water solubilities published in references, such as the fourteenth edition of The Pesticide Manual, (ISBN 1-901396-14-2), which is incorporated herein by reference in its entirety. The following editions of The Pesticide Manual will also be useful in selecting insecticides for inclusion in mesoparticles.

Many classes and types of herbicides are useful in agriculture. Examples include amide herbicides such as allidochlor, beflubutamid, benzadoks, benzipram, brombutid, cafenstrole, CDEA, chlorthiamid, tsiprazol, dimethenamid, dimethenamid-P, diphenamid, epronaz, etnipromid, fentrazamid, flupoxam, fomesafen, halosafen, isocarbamid, isoxaben, napropamide naphthalam, petoxamide, propisamide, quinonamide and tebutam; anilide herbicides such as chloranocryl, cisanilide, clomeprop, cypromide, diflufenican, etobenzanide, phenasulam, flufenacet, flufenican, mefenacet, mefluidide, metamifop, monalide, naproanilide, pentanochlor, and picolina; arylalanine herbicides such as benzoylprop, flamprop and flamprop-M; chloroacetanilide herbicides such as acetochlor, alachlor, butachlor, butenachlor, delachlor, diethyl, dimethachlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, prichachlor, terbuchlor, tenylchlor and xylachlor; sulfonanilide herbicides such as benzofluoride, perfluidone, pyrimisulfan and profluazole; sulfamide herbicides such as asulam, carbasulam, fenasulam and oryzaline; antibiotic herbicides such as bilanafos; benzoic acid herbicides such as chloramben, dicamba, 2,3,6-TBA and tricamba; pyrimidinyloxybenzoic acid herbicides such as bispiribac and pyriminobac; pyrimidinylthiobenzoic acid herbicides such as pyrithiobac; phthalic acid herbicides such as chlortal; picolinic acid herbicides such as aminopyralid, clopyralid and picloram; quinoline carboxylic acid herbicides such as quinclorac and quinmerac; arsenic-based herbicides such as cacodilic acid, CMA, DSMA, hexaflurate, MAA, MAMA, MSMA, potassium arsenite and sodium arsenite; benzoylcyclohexanedione herbicides such as mesotrione, sulcotrione, tefuryltrione and tembotrione; benzofuranyl alkyl sulfonate herbicides such as benfuresate and etofumezate; carbamate herbicides such as asulam, chloroprocarb carboxazole, dichlormat, phenasulam, carbutylate and terbucarb; carbanilate herbicides such as barbane, BCPC, carbasulam, carbetamide, CEPC, chlorbufam, chlorprofam, CPPC, desmedifam, phenizofam, fenmedifam, ethyl phenmedifam, prof and swap; cyclohexene oxime herbicides such as alloxydim, butroxydim, celodime, cloproxidime, cycloxydime, occupational oxime, sentoxydim, thermal oxime and thralkoxydim; cyclopropylisoxazole herbicides such as isoxachlortol and isoxaflutol; dicarboximide herbicides such as benzfendizone, cinidone-ethyl, flumezin, flumiclorac, flumioxazine and flumipropine; dinitroaniline herbicides such as benfluralin, butralin, dinitramine, etalfluralin, fluchloralin, isopropalin, metalpropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin and trifluralin; dinitrophenol herbicides such as dinophenate, dinoprop, dinosam, dinoseb, dinoterb, DNOC, ethinophen and medinoterb; diphenyl ether herbicides such as ethoxyphene; nitrophenyl ether herbicides such as acifluorfen, aclonifen, biphenox, chlomethoxifen, chloronitrophene, ethnipromide, fluorodifen, fluoroglycophene, fluoronitrophene, fomesafen, furyloxifene, halosafen, lactofenfenfluorofenfitrofenorfitrofenorfitrofenorfitrofenorfitrofluorofenfitrofenorfenrofenorfitrofluorofenorfitrofenorfenrofenorfitrofenorfenrofit dithiocarbamate herbicides such as dazomet and metam; halogenated aliphatic herbicides such as alorak, chloropon, dalapon, flupropanate, hexachloroacetone, iodomethane, methyl bromide, monochloracetic acid, SMA and TCA; imidazolinone herbicides such as imazametabenz, imazamox, imazapik, imazapir, imazakvin and imazetapir; inorganic herbicides such as ammonium sulfamate, borax, calcium chlorate, copper sulfate, iron sulfate, potassium azide, potassium cyanate, sodium azide, sodium chlorate and sulfuric acid; nitrile herbicides such as bromobonil, bromoxynil, chloroxinyl, dichlobenyl, iodobonyl, ioxinyl and pyraclonyl; organophosphorus herbicides such as amiprofos-methyl, anilophos, bensulide, bilanafos, butamifos, 2,4-DEF, DMPA, EBEP, fosamine, glufosinate, glyphosate and piperophos; phenoxy herbicides such as bromofenoxime, clomeprop, 2,4-DEB, 2,4-DEP, diphenopentene, disul, erbone, ethnipromide, phentoracol and trifopsime; phenoxyacetic herbicides such as 4-CPA, 2,4-D, 3,4-DA, MCPA, MCPA-thioethyl and 2,4,5-T; phenoxybased herbicides such as 4-CPB, 2,4-DB, 3,4-DB, MCPB and 2,4,5-TB; phenoxypropionic herbicides such as cloprop, 4-CPP, dichloroprop, dichloroprop-P, 3,4-DP, phenoprop, mecoprop and mecoprop-P; aryloxyphenoxypropionic herbicides such as chlorazifop, clodinafop, clofop, cyhalofop, diclofop, fenoxaprop, fenoxaprop-P, fentiaprop, fluazifop, fluazifop-P, haloxyfop, haloxyfop-P, izoksapirifop, metamifop, propaquizafop, quizalofop, quizalofop-P and trifop; phenylenediamine herbicides such as dinitramine and prodiamine; pyrazolyl herbicides such as benzofenap, pyrazolinate, pyrasulfotol, pyrazoxifene, pyroxasulfone and topramezon; pyrazolylphenyl herbicides such as fluazolate and piraflufen; pyridazine herbicides such as credazine, pyridafol and pyridate; pyridazinone herbicides such as bromopyrazone, chloridazone, dimidazone, flufenpir, metflurazone, norflurazone, oxapirazone and pidanone; pyridine herbicides such as aminopyralide, cliodinate, clopyralid, dithiopyr, fluroxypyr, fluroxypyr-meptyl, galoxidine, picloram, picolinafen, pyriclor, thiazopyr and triclopyr; pyrimidinediamine herbicides such as iprimidam and thioclorim; quaternary ammonium based herbicides such as cyperquat, diethquat, diphenzoquat, diquat, morphamquat and paraquat; thiocarbamate herbicides such as butylate, cycloate, di-allate, EPTC, esprocarb, etiolate, isopolinate, methiobencarb, molinate, orbencarb, pebulate, prosulfocarb, pyributicarb, sulfallate, thiobencarb, thiocarbazyl, triocarbyl azole; thiocarbonate herbicides such as dimexano, EXD and proxane; thiourea herbicides such as methiuron; triazine herbicides such as dipropetrin, triaziflam and trihydroxytriazine; chlorotriazine herbicides such as atrazine, chlorazine, cyanisine, ciprazine, eglinazine, ipazine, mesoprazine, procyazine, proglazine, propazine, sebutylazine, simazine, terbutylazine and trietazine; methoxytriazine herbicides such as atratone, methometon, prometon, secbumeton, simeton and terbumeton; methylthiotriazine herbicides such as ametrine, aziprotrin, cyanatrin, desmetrine, dimetamethrin, metoprotrin, promethrin, simethrin and terbutrin; triazinone herbicides such as ametridion, amibuzin, hexazinone, isomethiosine, metamitron and metribuzin; triazole herbicides such as amitrol, kafenstrol, epronase and flupoxam; triazolone herbicides such as amicarbazone, bencarbazone, carfentrazone, flucarbazone, propoxycarbazone, sulfentrazone and thiencarbazone methyl; triazolopyrimidine herbicides, such as cloransulam, diclosulam, florasulam, flumetsulam, metosulam, penoxulam and pyroxulam; uracil herbicides such as butafenacil, bromacil, flupropacil, isocyl, lenacil and terbacil; 3-phenyluracils; urea herbicides such as benzthiazuron, cumiluron, cycluron, dichloralurea, diflufenzopyr, isonoruron, isouron, metabenzothiazuron, monisouron and noruron; phenylurea herbicides such as anisuron, buturon, chlorobromuron, chloroeturon, chlortoluron, chloroxuron, daimuron, diphenoxuron, dimefuron, diuron, phenuron, fluomethuron, fluotiuron, neuronuronuronuronuronuron, monuronuronuronurononuronuronuronuronuronuronuronuronuronurinuronuronurinuronurinurinurinurinurinononuronurinurinurinurinurinurinurinonononurinonin oncline , parafluron, phenobenzuron, siduron, tetrafluron and thidiazuron; pirimidinilsulfonilmochevinnye herbicides such as amidosulfuron, azimsulfuron, bensulfuron, chlorimuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flutsetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, mesosulfuron, nicosulfuron, ortosulfamuron, oxasulfuron, primisulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron and trifloxysulfuron; triazinylsulfonylurea herbicides such as chlorosulfuron, cinosulfuron, etametsulfuron, iodosulfuron, metsulfuron, prosulfuron, tifensulfuron, triasulfuron, tribenuron, triflusulfuron and tritosulfuron; thiadiazolylurea herbicides such as butyuron, ethidimuron, tebutiuron, thiazafluron and thidiazuron; and unclassified herbicides, such as acrolein, allyl alcohol, azaphenidine, benazoline, bentazone, benzobicyclone, butidazole, calcium cyanamide, cambendichlor, chlorfenac, chlorfenprop, chlorflurazole, chlorofluurenol, cinmethylin, orlomolezol, clomolezol, clomazole, clomazole, clomazole, clomazole, clomazole, clomazole, clomazole, clomazole fluoromidine, fluridone, flurochloride, flurtamon, flutiacet, indanophan, metazol, methyl isothiocyanate, nipiraclofen, OCH, oxadiargyl, oxadiazone, oxaziclomefon, pentachlorophenol, pentoxazone, phenylmerceniriphenephenadicene acetate, phenylmerceniriphenephenadicene acetate thalide, quinoclamine, rodetanil, sulglycapine, thidiazimine, tridifan, trimethuron, tripropindan and tritak. The present disclosure involves the selection of herbicides from this list with a water solubility of approximately 1000 ppm. or less and composing them in a composition in the form of mesoparticles with an integral auxiliary tool or auxiliary tool in the form of a tank mixture. Preferred herbicides are those which have a water solubility of about 100 ppm. or less. More preferred herbicides are those having a water solubility of 10 ppm. or less. Herbicides may be selected based on water solubilities published in handbooks such as the fourteenth edition of The Pesticide Manual, ISBN 1-901396-14-2, which is incorporated herein by reference in its entirety. The following editions of The Pesticide Manual will also be useful in selecting herbicides for inclusion in mesoparticles.

Many classes and types of modifiers of physiology or plant structure are useful in agriculture. Examples include ancymidol, aminoetoksietoksivinilglitsin, 6-benzylaminopurine, carvone, hlorflurenol-methyl, chlormequat chloride, kloksifonak, 4-CPA, tsiklanilid, cytokinins, daminozide, dikegulak, ethephon, flurenol, flurprimidol, forchlorfenuron, gibberellic acid, gibberellins, inabenfide, indole 3-acetic acid, 4-indol-3-ylbutyric acid, maleic hydrazide, mepiquat chloride, 1-methylcyclopropene, 2- (1-naphthyl) acetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenolates, paclobutrazyl acid, prohexa calcium ion, n-propyl dihydrojasmonate, thidiazuron, tribufos, trineksepak-ethyl and uniconazole. The present disclosure involves the selection of modifiers from this list with a water solubility of approximately 1000 ppm. or less and composing them into a composition in the form of mesoparticles with an integral auxiliary agent or auxiliary agent in the form of a tank mixture. Preferred modifiers are those which have a water solubility of about 100 ppm. or less. More preferred modifiers are those which have a water solubility of 10 ppm. or less. Modifiers can be selected based on water solubilities published in references, such as the fourteenth edition of The Pesticide Manual, ISBN 1-901396-14-2, which is incorporated herein by reference in its entirety. The following editions of The Pesticide Manual will also be useful in selecting modifiers of physiology or plant structure for inclusion in mesoparticles.

Mesoparticle herbicidal compositions in accordance with various embodiments of the present invention can be used in combination with a wide variety of herbicidal antidotes, including antidotes such as benoxacor, bentiocarb, brassinolide, clocvintocet (mexyl), cyometrinyl, cyprosulfamide, daimuron, dichloride, dichloride dimepiperate, disulfhoton, fenchlorazole-ethyl, fenclorim, flurazole, fluxophenim, furylazole, isoxadifen-ethyl, mefenpyr-diethyl, MG 191, MON 4660, naphthoic anhydride (HA), oxabetrinyl, R29148 and N-amides onylbenzoic acid. The level of active ingredient in the mesoparticle used to obtain these compositions can vary from about 0.001 wt.% To about 99 wt.%. It is understood that the mesoparticle herbicidal compositions may be combined with integral adjuvants or adjuvants in the form of a tank mixture and herbicidal antidotes. It is further understood that the herbicidal antidotes themselves can be formulated in the form of mesoparticles, both in the form of particles of a traditional size, and even directly soluble in the composition containing the herbicidal mesoparticles and integral adjuvants.

It is understood that the mesoparticles and adjuvants of the present invention can be used with many conventional ingredients for formulation, such as an aqueous or non-aqueous solvent medium or solvents in which the mesoparticles are suspended or slurry is obtained at a concentration of the agricultural active ingredient relative to the composition, from about 0.1% to about 95% and, more traditionally, in the range of from about 5 to about 50%. An adjuvant may be included in these conventional mesoparticle compositions in a concentration relative to the composition from about 0.1% to about 90% and, more traditionally, in the range of about 5 to about 50%. Ordinary inactive or inert ingredients such as dispersants, thickeners, binders, film-forming agents, buffers, emulsifiers, antifreezes, paints, stabilizers, solid carriers and the like can also be included in these compositions containing mesoparticles and auxiliary agents.

It is understood that agricultural AI compositions contained in mesoparticles combined with integral auxiliary agents or auxiliary agents in the form of tank mixtures, in particular impregnating auxiliary agents, can be used to control insects, ticks, plant diseases or weeds by providing and using an agriculturally effective amount of a mesoparticle composition to at least one of the following: plant, foliage tenii, flowers, stems, fruits, the area adjacent to the plant, soil, seeds, germinating seeds, roots, liquid and solid media for growing and hydroponic solutions for growing. The mesoparticle composition combined with integral auxiliary agents or auxiliary mixtures in the form of tank mixtures can be diluted in a suitable agricultural diluent, such as water, and applied in any conventional manner, including, but not limited to: 1) application as foliar spraying, preferably in sufficient volume to moisten the foliage, 2) application in the form of soil impregnation, 3) application to seeds, 4) application of drip irrigation and 5) application by injection into the soil or guide Opon growth medium. It is further contemplated that mesoparticle compositions may be used in admixture with conventional agricultural AI compositions, nutritional elements, and growth regulators. Typical agricultural AIU compositions include solutions, such as oil-in-water or water-in-oil dispersions, emulsifiable concentrates, AIU solutions in water, sprayable AIow concentrates in the form of suspended particles with an average volume diameter of about 1 micron or more, AIs in the form of wettable powders with an average volume diameter about 1 micron or more; and AIs in the form of granules with a volume average diameter of about 10 microns or more.

EXAMPLES

Particle size measurements

Particle size can be determined, in particular, by a known method of quasi-elastic light scattering. One device that can be used for this determination is the Brookhaven 90Plus Nanoparticle Size Analyzer. This instrument measures average diameter by laser correlation spectroscopy (or PCS). In addition, the Malvern MasterSizer 2000 can also be used to measure particle sizes. Alternatively, particle size can be measured by other known methods, including centrifugation or electron microscopy.

Mesoparticle Synthesis

Obtaining mother solutions of amino acids used for the synthesis of mesocapsules.

Before starting the various reactions used to synthesize the typical mesocapsules disclosed in the present description, mother solutions of glycine and lysine were prepared in the ratios listed in FIG. one.

General methods used to obtain polyurea mesocapsules disclosed in the present description.

Below is formulated a typical method used for the synthesis of a representative composition of polyurea mesoparticles using the ingredients and amounts listed in FIG. 2. Briefly, fenbuconazole, benzyl acetate, hexadecane and PAPI ™ 27 polymer MDI (Dow Chemical Co.) were added to a 60 ml flask and mixed until homogeneous. Surfactant, water and glycine solutions were added to the flask and mixed using a Biohomogenizer portable mixer for approximately 10 seconds to create a pre-emulsion. The flask was placed in an ice bath, and the pre-emulsion was sonicated for 5 minutes using a Branson 184V ultra-ultrasonic apparatus at 40% power to create a final emulsion that turned into polyurea mesocapsules with a crosslinker. The volumetric mean particle diameter of mesocapsules in each sample was measured using a Brookhaven 90Plus Nanoparticle Size Analyzer. The mesocapsule compositions listed in FIG. 2 were obtained using this method. As indicated in FIG. 2, the compositions of the reacting mixtures were modified to create the compositions disclosed herein. Compositions referenced in FIG. 6, tested on plants to determine their medicinal and protective properties in the fight against plant diseases.

The following method was used with the ingredients and amounts listed in FIG. 3, to create suspensions of epoxiconazole mesocapsules (sample 15), fluroxypyr-meptyl (sample 16B) and 328255-92-1 (sample 14). The oil phase and the aqueous phase were obtained separately. The active ingredient 328255-92-1 was dissolved in a solvent mixture to create a 77% oil phase, followed by 3% hydrophobic substance and 20% isocyanate (1st monomer) to provide a complete oil phase. Proxel ™ GXL (Arch UK Biocides, Ltd .; 0.1% of the total composition) and sodium lauryl sulfate (3% of the oil phase) were added to the aqueous phase. The aqueous phase was combined with the oil phase, and the mixture was stirred with a magnetic stirrer for 2 minutes to create a pre-emulsion, which was then sonicated for 4-5 minutes using Vibra Cell ™ (Sonics & Matrials, Inc.) at 750 W and amplitude 24-25% in an ice / water bath to create a stable mesoscale oil-in-water emulsion. With stirring, a polyamine (2nd monomer) was added to react with the isocyanate to form a polyurea shell. Samples of compositions 14, 15 and 16B shown in FIG. 6, tested on plants to determine their pest control properties.

The general method used to prepare the latex meso-matrix particles disclosed herein.

A typical method used to synthesize a representative composition of latex meso-matrix particles is formulated below. The aqueous and oil phases were obtained separately. To obtain the aqueous phase, you need to add the desired amount of surfactant to DI water in an 8 oz laboratory glass beaker. To obtain the oil phase, fenbuconazole, initiator, monomer, comonomer, dye monomer and ultra-hydrophobic substance must be measured. After both solutions became transparent, the oil phase was added to the aqueous phase with stirring with a magnetic stirrer. This mixture was pre-emulsified in an ice water bath while stirring with a magnetic stirrer for 30 minutes. The above emulsion was sonicated (450 watts, 100 ml, 6-8 minutes) in an ice water bath to obtain a stable miniemulsion of oil in water. 50 ml of the resulting miniemulsion was added to a 250 ml round glass reactor flask, and the flask was degassed 3-4 times under vacuum / with N ₂ purge. The miniemulsion was polymerized at 75 ° C in a nitrogen atmosphere for 1-2 hours. In FIG. 4 shows specific amounts of each reagent. The polymerized compositions were used unchanged or diluted to achieve the desired level of active ingredient and tested on plants to determine their healing and protective properties in the fight against plant diseases.

The general method used to produce the meso-homogeneous particles disclosed herein.

A typical method used to obtain a representative composition of meso-homogeneous particles is formulated below. Using the ingredients and amounts shown in FIG. 5, an aqueous phase was obtained containing 328255-92-1, Pluronic ™ P105 (BASF Corporation), Morwet ™ D425 (AkzoNobel), Dow Corning ™ Antifoam B (Dow Corning Corporation) and water. The aqueous phase was placed in a plastic cup with 50 grams of 1/8 inch diameter stainless steel balls and tightly closed. The sample was shaken on a horizontal reciprocating shaker with a high frequency for 24-72 hours, depending on the nature of the AI crystals. AI particle size was periodically monitored using a Malvern MasterSizer 2000 until it reached a target volumetric average diameter of less than about 300 nm. An aqueous suspension of meso-homogeneous particles was separated from the grinding balls and transferred to a clean vessel using a needle-tip pipette, and used in the efficacy test unchanged or diluted to achieve the desired level of active ingredient.

Biological evaluation of mesoparticle compositions

Turning now to FIG. 6, the table includes a listing of the tested compositions. The fenbuconazole mesoparticle compositions listed in FIG. 6 were tested to measure their therapeutic and protective effect on spot leaf disease caused by Septoria Tritici. Latex meso-matrix particles and fenbuconazole particle compositions in the form of polyurea mesocapsules were tested for their therapeutic and protective effect on leaf spot disease in wheat on separate sets of wheat plants (cultivar Yuma). Each composition was diluted with water and tested at application rates of 125, 41.4, 13.8, 4.6 and 1.4 g of active substance / ha. Each of these four meso formulations was tested with and without Uptake Oil ™ (Dow AgroSciences, LLC) at a rate of 0.5% v / v in the final spray solution. Uptake Oil ™ is an impregnating adjuvant consisting of 582 g / L paraffin oil, 7.5 g / L oleic acid, 145 g / L Polyglycol 26-2 surfactant (Dow Chemical Company), 95 g / L Teric emulsifier ™ 12-A3 (Huntsman Corporation) and 42.5 g / l Aromatic 150. With respect to FIG. 6, the mesocapsule composition 328255-92-1 was tested with and without Uptake ™ or Trycol 5941; the mesocapsule epoxiconazole composition was tested with and without Uptake ™; and the meso-homogeneous epoxyconazole composition was tested with and without Emery Emgard. Each composition was diluted with water and tested at application rates of 62.5, 20.8, 6.9, 2.3, and 0.8 g of active substance / ha. The experimental units for these tests consisted of 8-10 wheat plants grown in 5 cm × 5 cm pots with a growing medium consisting of half MetroMix and half heavy loam soil. Each treatment was repeated four times, and the treatments were randomized after applying chemicals.

Plants for the test for therapeutic effect were inoculated at the stage of growth of 2 leaves two or three days before the use of the compositions, depending on the test. For the protective effect test, the compositions were applied at the second leaf growth stage, and the plants were inoculated three or four days later, depending on the test. Treatments were performed using a Gen III Research Sprayer spray machine (DeVries Mfg., Hollandale MN) calibrated to deliver 100 l / ha and equipped with a TeeJet Spraying Systems 8002E spray nozzle.

A deciduous pathogen inoculum, Septoria tritici, was obtained by collecting conidia from newly emerged and mature pycnids. An aqueous conidia suspension was obtained by counting several samples in a hemocytometer, followed by reducing the concentration in the suspension to 1,000,000 conidia / ml. Plants were inoculated by spraying fine mist with a low pressure compressed air sprayer in a volume of approximately 200 ml per 80 pots of wheat. After inoculation, the plants were incubated in a dark, humid room (22 ° C) at a relative humidity of 99-100% for 24 hours, then they were transferred to an illuminated moist room (20 ° C) at a relative humidity of 99-100% for another 48 hours and then placed in a greenhouse at 20 ° C and a 14-hour photoperiod until the end of the test. Plant growth was maintained by the regular use of a dilute liquid fertilizer solution.

The disease in wheat seedlings was evaluated approximately 21 days after inoculation. The percentage of disease was assessed by visually assessing the percentage of leaves exhibiting symptoms of the disease. Plants that were first inoculated and then treated with a chemical two days later showed signs of a therapeutic effect. Plants that were first treated and then inoculated four days later showed signs of a protective effect. The disease level on untreated control plants in the treatment test was 82%. The disease level on untreated control plants in the protective test was 95%.

The percentage of disease was converted to the percentage of disease in relation to the control using the following formula:

(Average% disease in the untreated control - average% disease in the treatment) / (Average% disease in the untreated control) × 100%. The percentage of disease control in each series of meso compositions used with the adjuvant was compared with the actual and expected levels of control for the same episodes applied without the adjuvant according to Colby's equation.

Turning now to FIG. 7 and 8, the following are the results of various tests. In the therapeutic and protective tests (Fig. 7), the addition of Uptake Oil ™ led to an increase in the therapeutic and protective effect of all fenbuconazole meso compositions on leaf spotting. FIG. 8 shows a comparison of potency ratios for these 4 meso compositions with respect to potency for fenbuconazole as 75% WP. The gain ratio is calculated by dividing the average level of the disease control factor among different application rates without oil by the average level of the factor between the application rates with Uptake Oil ™. The calculations show that, no matter what indications of the data of the medical or protective test, the level of amplification of meso-sized compositions is much higher than the amplification by 75 WP.

The protective or therapeutic effect of various fungicidal compositions of mesoparticles was tested on brown rust in wheat. The protective effect of the composition of polyurea mesocapsules 328255-92-1 (sample 14) and the composition of meso homogeneous particles 328255-92-1 (sample 68B) was tested on brown rust in wheat caused by the fungus, Puccinia recondita f. Species Tritici. The test was carried out on wheat plants (cultivar Yuma). Each composition was diluted with water and tested at application rates of 62.5, 20.8, and 6.9 g of active substance / ha. The meso composition was tested with and without Uptake Oil ™ at a rate of application of 0.5% v / v in the final spray solution. Each experimental unit consisted of 8-10 wheat plants grown in pots measuring 5 cm by 5 cm with a growing medium consisting of half MetroMix and half heavy loam soil. Each treatment was performed four times, and the treatments were randomized after applying chemicals.

Plants for the test for therapeutic effect were inoculated at the stage of growth of 2 leaves two days before the application of the composition. For the protective effect test, the compositions were used at the stage of growth of the second leaf, and four days later, the plants were inoculated with a fungus that causes brown rust. With reference to FIG. 6, the therapeutic effect of various mesoparticle compositions was tested on brown rust in wheat. The mesocapsule composition 328255-92-1 was tested with and without Uptake ™ or Trycol®5941; the epoxiconazole mesocapsule composition was tested with and without Uptake ™ oil; and the epoxiconazole meso-homogeneous composition was tested with and without Emery Emgard. Each composition was diluted with water and tested at application rates of 62.5, 20.8, 6.9, 2.3, and 0.8 g of active substance / ha. Treatments were performed using a Gen III Research Sprayer spray machine (DeVries Mfg., Hollandale MN) equipped with a Spraying Systems 8002E TeeJet spray nozzle calibrated to deliver 100 l / ha.

Inoculum of deciduous pathogen, Puccinia recondita f.sp. tritici, obtained by collecting uredospores from newly emerged and ripened pustules. The resulting aqueous suspension of uredospores was prepared using the following ratios, 0.1 g of uredospores was added to three drops of Tween 20 and then mixed to a paste state. To the paste was added 100 ml of distilled water. Approximately 1,000,000 uredospores / ml were in suspension. Plants were inoculated by applying fine mist in a volume of approximately 300 ml per 80 pots of wheat using a sprinkler under low pressure compressed air. After inoculation, the plants were incubated in a dark humid room (22 ° C) at a relative humidity of 99-100% for 24 hours and then transferred to a greenhouse with a temperature of 24 ° C and a 14-hour photoperiod until the test was completed. Plant growth was supported by the regular use of a dilute liquid fertilizer solution.

The disease in wheat seedlings was evaluated approximately 7-8 days after inoculation. The percentage of disease was evaluated by visually assessing the percentage of disease of the first leaf.

Turning now to FIG. 9, the test results indicate that the addition of Uptake Oil ™ (Dow AgroSciences, LLC) leads to enhanced protective effect of brown rust on mesocapsule composition 328255-92-1.

Turning now to FIG. 10, the test results indicate that the addition of Uptake Oil ™ (Dow AgroSciences, LLC) enhances the protective effect of the meso-homogeneous composition 328255-92-1 against brown rust.

Turning now to FIG. 11, the test results indicate that the addition of Uptake ™ (Dow AgroSciences, LLC) or Trycol®5941 (Cognis Corporation) increases the therapeutic effect of brown rust on mesocapsule composition 328255-92-1. Further, test results indicate that the addition of Uptake ™ (Dow AgroSciences, LLC) or Trycol ^® 5941 leads to increased efficiency of the therapeutic effect of the composition mezokapsul 328255-92-1 on brown rust. Additionally, the test results indicate that the addition of Uptake ™ (Dow AgroSciences, LLC) leads to an increase in the therapeutic effect of the epoxyconazole mesocapsule composition on brown rust and that the addition of Emery Emgard (85:15 wt.% ME Agnique 181-u mixture ( formerly known as Emery 2301; Cognis Corporation) and Emgard 2033 (Cognis Corporation)), enhances the therapeutic effect of the meso-homogeneous epoxyconazole composition on brown rust.

Turning now to FIG. 12, test results indicate that the addition of Uptake ™ (Dow AgroSciences, LLC) or Trycol®5941 (Cognis Corporation) enhances the protective effect of the mesocapsule composition 328255-92-1 against leaf spotting. Additionally, test results indicate that the addition of Uptake ™ (Dow AgroSciences, LLC) enhances the protective effect of epoxyconazole mesocapsule formulations against leaf spotting.

Turning now to FIG. 13, test results indicate that the addition of Uptake ™ (Dow AgroSciences, LLC) or Trycol®5941 enhances the therapeutic effect of leaf spot mesocapsule composition 328255-92-1. Additionally, test results indicate that the addition of Uptake ™ (Dow AgroSciences, LLC) leads to increased efficacy of the therapeutic effect of epoxyconazole mesocapsules on leaf spotting and that the addition of Emery Emgard (85:15 wt.% ME Agnique 181-u (formerly known as Emery 2301; Cognis Corporation) and Emgard 2033 (Cognis Corporation)), enhances the therapeutic effect of the meso-homogeneous epoxiconazole composition on leaf spotting.

Turning now to FIG. 6, the table includes a listing of tested compositions containing the atrazine, fluroxypyr-meptyl and pyroxulam herbicidal active ingredients. Polyurea mesocapsules and meso-homogeneous particle compositions prepared in accordance with various embodiments disclosed herein were compared with and without the addition of 0.25% v / v Agral 90 (Norac Concepts Inc.) or 2.0% v / v crop oil concentrate (COC, Agri-dex; Helena Chemical Co.). The composition of the polyurea mesocapsules of fluroxypyr meptyl and the composition of the meso-homogeneous particles of atrazine and pyroxulam listed in FIG. 6, were tested to measure their herbicidal action at the post-emergence stage for various species of dicotyledonous and monocotyledonous weeds using the methods described in the present description.

For this test, peat potted soil, Metro-mix 360, was used as the soil medium. Metro-mix is a growing medium consisting of 35-45% of specially treated coconut coir fibers, 10-20% of garden vermiculite, 15-25% of processed bark ash, 20-30% of Canadian peat sphagnum moss to choose from and patented nutrients and other ingredients. Several seeds of each species were sown in 10 cm square pots and watered on top twice a day. Highlander, Polygonum convolvulus (POLCO), rodent, Abutilon theophrasti (ABUTH), wild oats, Avena fatua (AVEFA), mouse-tailed foxtail, Alopecurus myosuroides (ALOMY), spiked gooseberry, Amaranthus retroflexus ampharia (Amaranthus retroflexewola EPHHL), middle starlet, Stellaria media (STEME), field violet, Viola arvensis (VIOAR) and white gauze, Chenopodium album (CHEAL) were germinated in a greenhouse at a constant temperature of 26-28 ° C and a relative humidity of 50-60%. Natural light was provided by metal-halide ceiling lamps with a power of 1000 watts with an average illumination of 500 μE m ^-2 s ^-1 photosynthetically active radiation (PAR). The photoperiod was 16 hours. Before processing, plant material was watered from above and, after treatment, they were irrigated subsoil.

The atrazine meso composition was used at a rate of 560 g of active ingredient / ha. The meso-composition of fluroxypyr-meptyl was tested at rates of application of 100, 50, 25 and 12.5 g of acid equivalent / ha, and the meso-composition of pyroxulam was tested at rates of application of 1.17, 2.34 and 4.7 g of active ingredient / ha. All three compositions were diluted with tap water and used alone, together with Agral 90 (Norac Concepts Inc.) in an amount of 0.25% v / v or with an agricultural oil concentrate (COC, Agri-dex; Helena Chemical Co.) in an amount 2% volume / volume. The treatments were carried out using a spray machine manufactured by Allen Machine Works. The sprayer had a spray nozzle 8002E, a spray pressure of 262 kPa and a speed of 1.8 mph to deliver 187 l / ha. The height of the nozzle was 46 cm above the leaf cover. The stage of growth of various species of weeds varied from 2 to 4 leaves. The treatment was repeated 1, 2 or 3 times depending on the availability of plant material. Plants were returned to the greenhouse after treatment and were irrigated subsoil throughout the experiment. The plant material was fertilized twice a week with a Hoagland fertilizer solution. Visual estimates of the percentage of control were carried out on a scale of 0 to 100% compared with untreated control plants (where 0 corresponds to the absence of signs of control, and 100 corresponds to complete destruction).

Turning now to FIG. 14, the results of the herbicide test at the post-emergence stage indicate that the use of a composition of meso-homogeneous particles of atrazine with both Agral 90 at a content of 0.25% v / v and with an agricultural oil concentrate (COC, Agri-dex; Helena Chemical Co.), at a content of 2% v / v, generally leads to higher levels of control compared to the use of a composition of meso-homogeneous atrazine particles alone. The use of the composition of fluroxypyr-meptyl mesocapsules with both Agral 90 (Norac Concepts Inc.) at a content of 0.25% vol / vol, and with a crop oil concentrate (COC, Agri-dex; Helena Chemical Co.) at a content of 2% vol / volume leads, in general, to higher levels of control compared with the composition of the fluroxypyr meptyl mesocapsules individually. The use of a composition of meso-homogeneous particles of pyroxulam with both Agral 90 at a content of 0.25% volume / volume and with a concentrate of agricultural oil (COC, Agri-dex; Helena Chemical Co.) at a content of 2% volume / volume results in in general, to higher levels of control compared to the use of a composition of meso-homogeneous particles of pyroxulam separately.

Claims (22)

1. A composition comprising:
a) a mesoparticle consisting of a poorly soluble agricultural active ingredient in water, with a volume average diameter in the range of from about 30 nm to about 500 nm; and
b) an adjuvant selected from the group consisting of an oil concentrate from crops and nonyl phenol ethoxylate. 2. The composition of claim 1, further comprising inert ingredients and solvents. 3. The composition according to claim 1, in which the mesoparticle is at least one of the mesocapsule, meso-matrix particles and meso-homogeneous particles. 4. The composition according to p. 3, in which the agricultural active ingredient in the oil phase of the mesocapsule is from about 1 to about 90 wt.%. 5. The composition according to p. 3, in which the agricultural active ingredient in the meso-matrix particle is from about 1 to about 90 wt.%. 6. The composition according to p. 3, in which the agricultural active ingredient in the meso-homogeneous particle is from about 80 to about 99 wt.%. 7. The composition of claim 1, wherein the agricultural active ingredient has a water solubility of less than about 1000 ppm. 8. The composition according to p. 1, in which the auxiliary means is one of the integral auxiliary means and auxiliary means in the form of a tank mixture. 9. The composition according to p. 1, in which the adjuvant is a concentrate of oil from crops. 10. The composition according to claim 1, in which the auxiliary agent is a tank mixture and comprises from about 0.05 to about 5 vol.% Diluted solution for spraying. 11. The composition of claim 1, wherein the adjuvant is integral and comprises from about 1 to about 90 wt.% An aqueous or non-aqueous concentrate of the composition. 12. The composition of claim 11, wherein the adjuvant is nonylphenol ethoxylate. 13. The composition of claim 1, further comprising an agricultural active ingredient formulated in a conventional manner. 14. A method for controlling insects, ticks, plant diseases or weeds, comprising the steps of:
compiling a composition comprising the composition according to claim 1, and
applying an agriculturally effective amount of the composition to at least one of the following: plant, foliage, flowers, stems, fruits, territory adjacent to the plant, soil, seeds, germinating seeds, roots, liquid and solid medium for growing and hydroponic growing solutions. 15. A method of controlling insects, plant diseases or weeds, comprising the steps of:
compiling a composition comprising the composition according to claim 1, and
applying an agriculturally effective amount of the composition in admixture with one or more ordinary agricultural active ingredient or nutrient compositions to at least one of the following: plant, plant foliage, flowers, stems, fruits, territory adjacent to the plant, soil, seeds, germinating seeds, roots, liquid and solid growing media, and hydroponic growing solutions. 16. The composition according to p. 1, in which the agricultural active ingredient is selected from the group consisting of fungicides, insecticides, maycicides, herbicides, herbicidal antidotes and modifiers of plant physiology or structure. 17. The composition according to p. 16, in which the fungicide is a triazole fungicide. 18. The composition of claim. 17 wherein the triazole fungicide is selected from the group consisting of cyproconazole, difenokolazola, epoxiconazole, fenbuconazole, fluquinconazole, flutriafol, ipconazole, metconazole, myclobutanil, propiconazole, prothioconazole, tebuconazole, tetraconazole, triadimefon, triadimenol and triticonazole. 19. The composition of claim 16, wherein the fungicide is (3S, 6S, 7R, 8R) -8-benzyl-3- (3- (isobutyryloxymethoxy) -4-methoxypicolinamido) -6-methyl-4,9-dioxo 1,5-dioxolane-7-isobutyrate. 20. The composition according to p. 16, in which the herbicide is atrazine. 21. The composition according to p. 16, in which the herbicide is a pyridine herbicide selected from the group consisting of aminopyralide, clopyralid, fluroxypyr, picloram and triclopyr. 22. The composition of claim 16, wherein the herbicide is a triazolopyrimidine herbicide selected from the group consisting of cloransulam, diclosulam, florosulam, flumetsulam, metosulam, penoxulam and pyroxulam.

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