HK1173043B - Meso-sized capsules useful for the delivery of agricultural chemicals - Google Patents

Description

Medium size capsules for delivery of agrochemicals

Cross Reference to Related Applications

This application claims the benefit of U.S. provisional patent application 61/232,044 filed on 8/7/2009, which is incorporated herein by reference in its entirety.

Technical Field

Aspects of the present invention relate to materials and methods for preparing medium-sized capsules and methods of using them to deliver active ingredients such as fungicides, insecticides, acaricides, herbicides, safeners, and modifiers of plant physiology or structure to plants.

Background

Modern pesticide active ingredients (including fungicides, insecticides, acaricides, herbicides and safeners and also modifiers of plant physiology and structure and nutrients) are typically formulated as liquid or solid formulations. These formulations are designed so that they are convenient for the grower or end user to use and so that the intrinsic biological activity of the active ingredient is properly expressed. It is an object of various aspects and embodiments disclosed herein to further improve the delivery efficacy and efficiency and biological activity of active ingredients used in agriculture and pest management in general.

Definition of

The term "agriculturally Active Ingredient (AI)" as used herein refers to chemicals used in agriculture, horticulture, and pest treatment for protecting crops, plants, structures, humans, and animals from harmful organisms (plant pathogens such as fungi and bacteria, weeds, insects, mites, algae, nematodes, and the like). Specifically, active ingredients used for these purposes include fungicides, bactericides, herbicides, insecticides, acaricides, algicides, nematicides and fumigants.

The term "agriculturally active ingredient" also includes insect attractants, repellents and pheromones, modifiers of plant physiology or structure, and herbicide safeners. The term "meso" as used herein describes particles, capsules or droplets (droplets) having a volume-average diameter of between about 30nm and about 500 nm. The term "mesocapsule (mesocapsule)" as used herein describes a capsule or core-shell particle having a volume-average diameter between about 30nm and about 500 nm.

The term "about" means a range of ± 10%, e.g. about 1 includes values of 0.9 to 1.1.

The term "sparingly water soluble" as used herein means that the active ingredient has a solubility in water of less than about 1000 ppm. Preferably, the poorly water soluble active ingredient has a solubility in water of less than 100ppm, more preferably less than 10 ppm.

The term "water-immiscible solvent" as used herein means that the solubility of the solvent or solvent mixture in water is about 10g/100ml or less.

The term "substantially free of surfactant" as used herein means a surfactant concentration of less than 1 wt.% (with respect to the oil phase) and more preferably a surfactant concentration of less than 0.5 wt.% (with respect to the oil phase).

The term "surfactant" as used herein means a material used to create and/or stabilize an emulsion. The surfactant includes a nonionic surfactant, an anionic surfactant, a cationic surfactant or a combination of a nonionic surfactant and an anionic surfactant or a combination of a nonionic surfactant and a cationic surfactant. Examples of suitable surfactants include alkali metal dodecyl sulfates such as sodium dodecyl sulfate, alkali metal fatty acid salts such as sodium oleate and sodium stearate, alkali metal alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, polyoxyethylene nonionic surfactants, and quaternary ammonium surfactants. Those skilled in the art can select suitable surfactants from standard reference sources, including Handbook of industrial surfactants, Fourth Edition (2005) published by synergistic Information resources Inc, and McCutcheon's Emulsifiers and Detergents, North American and national Editions Edition (2008) published by MC Publishing Company, without limitation to the above-mentioned species.

The term "interfacial condensation" as used herein means a reaction between two complementary organic intermediates that occurs at the interface between two immiscible liquids, one of which is dispersed in the other. An example of an interfacial condensation reaction is given in U.S. Pat. No. 3,577,515, which is incorporated herein by reference in its entirety. "core-shell" capsules are produced by an interfacial condensation reaction between two immiscible phases, the first of which is the dispersed phase and the second of which is the continuous phase; and the dispersed phase or core is encapsulated within a shell formed by the reaction of two complementary organic intermediates forming the shell, and the core-shell capsules are dispersed within the continuous phase.

The term "crosslinking agent" as used herein means a substance that causes and facilitates the reaction of polymer precursors to form core-shell particles. The crosslinking agent forms part of a polymeric structure comprising core shell particles. Examples of the crosslinking agent used herein include water, water-soluble diamines, water-soluble polyamines, water-soluble polyamino acids, water-soluble diols, water-soluble polyols, and mixtures thereof.

Disclosure of Invention

One embodiment of the present invention includes a composition for delivering an agriculturally active ingredient, comprising a mesocapsule having a polymeric shell, wherein the active ingredient is at least partially contained within the polymeric shell, and a poorly water soluble agriculturally active ingredient, the mesocapsule having a volume-average particle diameter between about 30nm and about 500 nm.

Another embodiment of the present invention includes a method for synthesizing a mesocapsule comprising the steps of: providing an oil phase comprising at least one agriculturally active ingredient and one or more polymer precursors capable of reacting to form a shell; providing an aqueous phase comprising water and at least one cross-linking agent; adding a surfactant to at least one of the aqueous phase and the oil phase; mixing the oil phase and the aqueous phase under shear conditions sufficient to form an emulsion having medium-sized droplets having a volume-average diameter of about 500nm or less; and reacting the polymer precursor with the crosslinking agent to form the mesocapsule.

Another embodiment of the present invention includes a method for synthesizing surfactant-free mesocapsules comprising the steps of: providing an oil phase comprising at least one agriculturally active ingredient and at least one polyisocyanate; providing an aqueous phase, wherein the aqueous phase comprises at least one component, wherein the component comprises at least one functional moiety that is a primary or secondary amine or a primary or secondary amino group, and additionally comprises at least one hydrophilic functional group; mixing the oil phase and the aqueous phase to form an emulsion; and reacting the polyisocyanate with the crosslinking agent to form mesocapsules.

Drawings

Fig. 1. fig. 1 summarizes the components of a stock solution of glycine and lysine prepared for synthesizing exemplary medium-sized capsules disclosed in the present application.

Fig. 2. fig. 2 summarizes such ingredients, which are combined for use in synthesizing an exemplary mesocapsule of fenbuconazole (fenbuconazole) as disclosed in the present application.

Fig. 3. fig. 3 summarizes such ingredients, which are combined to synthesize an exemplary mesocapsule of herbicide, fungicide, and insecticide as disclosed in the present application.

FIG. 4 includes a listing of exemplary formulations tested for effectiveness as insecticides; the table lists the formulations and provides an assessment of the wt.% of agriculturally Active Ingredient (AI) in each formulation.

FIG. 5 summarizes the results of testing the respective formulations identified in FIG. 4 for their ability to cure fungal infections caused by the fungus Sphingobium tritici (Septoria tritici) on plants.

FIG. 6. FIG. 6 summarizes the results of testing the respective formulations identified in FIG. 4 for their ability to prevent fungal infection caused by Ralstonia tritici on plants.

Figure 7 summarizes the results of testing the ability of each of the formulations identified in figure 4 to prevent fungal infection caused by puccinia tritici on plants.

Figure 8 summarizes the results of testing the ability of each atrazine (atrazine) formulation identified in figure 4 to control weeds. Data are percent weed control.

FIG. 9. FIG. 9 summarizes the results of testing the ability of each fluroxypyr 1-methylheptyl formulation identified in FIG. 4 to control weeds. Data are percent weed control.

FIG. 10. FIG. 10 summarizes the results of testing the ability of each indoxacarb (indoxacarb) preparation identified in FIG. 4 to reduce leaf feeding by Diamondback moth (Diamondback moth).

FIG. 11. FIG. 11 summarizes the results of testing the ability of each indoxacarb preparation identified in FIG. 4 to cause diamondback moth death.

Figure 12 summarizes the results of testing the ability of each indoxacarb formulation identified in figure 4 to cause death of German cockroaches (German cockroach) when administered by injection.

Figure 13. figure 13 summarizes the results of testing the ability of each indoxacarb formulation identified in figure 4 to cause death of german cockroaches when given by topical application.

Figure 14 summarizes the results for testing the ability of each indoxacarb formulation identified in figure 4 to cause a german cockroach to stop feeding when administered via bait ingestion.

Detailed Description

For the purposes of promoting an understanding of the principles of the new technology, reference will now be made to the preferred embodiments and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the novel technology is thereby intended, such alterations, modifications, and further applications of the principles of the novel technology being contemplated as would normally occur to one skilled in the art to which the novel technology relates.

The discovery, development and production of effective and economical varieties of agriculturally Active Ingredients (AIs), such as fungicides, insecticides, herbicides, safeners, modifiers of plant physiology or structure, and the like, is only part of the challenges facing the agrochemical industry. It is also important to develop effective formulations of these types of compounds to enable their effective and economical use. There is a continuing need for new formulations and new methods for making and using AIs for cost considerations only. The above needs are particularly acute when the effectiveness of AIs is limited or they are difficult to effectively control and apply as expected due to problems such as low solubility in aqueous solutions or poor bioavailability in plants and insects.

The terms 'plant' and 'crop' as used herein shall mean any commercially fertile plant, whether produced by conventional plant breeding, vegetative propagation or by the use of genetically modified techniques.

One of the most effective ways to improve the effectiveness of AI is to increase the permeability of AI to plants via the root system or stem and leaf surface or to insects via the gut or exoskeleton. Typically this approach involves formulating the AI into a water soluble form. However, many other effective AIs are not very soluble in water. Thus, compounds or formulations that increase the penetration of poorly water soluble AIs into and through plants and insects have the potential to improve the overall effectiveness of a variety of AIs, including for example AIs that are not very soluble in water.

Some aspects and embodiments disclosed herein increase the bioavailability of an agriculturally active ingredient by: encapsulating the AI in polyurea core-shell particles having a small size, such as mesocapsules having a volume-average particle diameter of about 500nm or less; in some embodiments, the mesocapsule has a diameter similar to 300nm or less. Some of these mesocapsules contain surfaces functionalized with biocompatible hydrophilic functional groups such as carboxylic acid groups. In many applications, an AI that is at least partially encapsulated in a mesocapsule more effectively penetrates plants and insects and is more effectively transported within and through plants than an unencapsulated AI.

In addition to the utility for formulating and delivering pesticidal active ingredients, many of the mesocapsules and methods for preparing the mesosized encapsulated formulations disclosed herein have utility when used in combination with other active ingredients such as biocides, inks, opacifiers, flavoring ingredients, fragrances, cosmetics, pharmaceutical formulations, and the like. The mesocapsules and methods of making the capsules disclosed herein can also be used to deliver nucleic acid polymers such as double or single stranded DNA or RNA and/or protein molecules. These formulations have a wide range of applications including genetic engineering, diagnostics and therapeutics, such as vaccination and the like.

Core-shell mesocapsules can be prepared by a variety of methods, including interfacial polymerization at the surface of a droplet or particle. Preferred encapsulating polymers are polyureas, including those formed by reacting polyisocyanates with polyamines, polyamino acids, or water. Other preferred encapsulating polymers include those formed from melamine-formaldehyde or urea-formaldehyde condensates, as well as those formed from similar types of aminoplasts. Capsules having shell walls composed of polyurethanes, polyamides, polyolefins, polysaccharides, proteins, silicas, lipids (lipids), modified celluloses, gums (gum), polyacrylates, polyphosphates, polystyrenes, and polyesters (polyesters), or combinations of these substances, may also be used to form core-shell mesocapsules.

Suitable polymers for forming the mesocapsules of the present invention include amino-based prepolymers such as urea-, melamine-, benzoguanamine-and glycoluril-formaldehyde resins and dimethylol dihydroxyethylene urea-type prepolymers. These prepolymers can be used as blends and crosslinkers with: polyvinyl alcohols, polyvinylamines, acrylates (preferred acid functional groups), amines, polysaccharides, polyureas/polyurethanes, polyaminoacids and proteins. Other suitable polymers include polyesters including biodegradable polyesters, polyamides, polyacrylates and polyacrylamides, polyethylene polymers and copolymers with polyacrylates, polyurethanes, polyethers, polyureas, polycarbonates, naturally occurring polymers such as polyanhydrides, polyphosphazenes, polyoxazolines, and UV-cured polyolefins.

In one embodiment, the poorly water soluble agriculturally active ingredient is encapsulated within core-shell particles having a very small size (e.g., about 500nm or less, more preferably 300nm or less). The AI encapsulated in these mesocapsules may show increased penetration into insects and plants, plant tissues, plant cells, and even plant pathogens compared to AI not bound to the mesocapsule.

In one embodiment, the mesocapsule comprises hydrophilic functional groups built into the polyurea shell and at least partially exposed on the mesocapsule surface. A partial list of some functional materials that can be used to form these particles can be found in the following publication WO2001/94001, the entire contents of which are incorporated herein by reference. Hydrophilic functional groups include carboxylate groups, phosphonate groups, phosphate groups, sulfonate groups, quaternary ammonium groups, betaine groups, ethylene oxide groups, or polymer groups containing ethylene oxide. Preferably, the hydrophilic group is a carboxylate group or a carboxylate group.

In one embodiment, the agriculturally active ingredient is at least one agrochemical selected from the group consisting of: fungicides, insecticides, acaricides, herbicides, safeners and modifiers of plant physiology or structure.

In one embodiment, the solubility of the agriculturally active ingredient in water is on the order of about 1,000ppm (parts per million) or less, preferably on the order of 100ppm or less and more preferably 10ppm or less.

In one embodiment, the invention is a method for synthesizing a mesocapsule comprising the steps of: providing an oil phase comprising at least one active ingredient and at least one polyisocyanate; providing an aqueous phase, and adding an emulsifier; and mixing the oil phase and the aqueous phase under shear conditions sufficient to form an emulsion having medium-sized droplets having a volume-average diameter of about 500nm or less, and preferably less than 300 nm; and reacting a polyisocyanate with at least one crosslinker or water to form the mesocapsule.

Some AIs are solid at room temperature and must be dissolved in a solvent before they can be encapsulated in polyurea mesocapsules. In one embodiment, the sparingly water-soluble AI is dissolved in a solvent that readily solubilizes the AI prior to addition to the oil phase. Suitable solvents may be one or a mixture of organic solvents that have low water solubility (i.e., about 10g/100ml or less), including but not limited to petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, xylene, toluene, paraffin-based oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil (tung oil), and the like; esters of the above vegetable oils; esters of monohydric or dihydric, trihydric or other lower polyhydric alcohols (containing 4 to 6 hydroxyl groups) such as 2-ethylhexyl stearate, ethylhexyl benzoate, isopropyl benzoate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, dioctyl succinate, dibutyl adipate, dioctyl phthalate, acetyl tributyl citrate, triethyl phosphate, etc.; esters of monocarboxylic, dicarboxylic and polycarboxylic acids such as benzyl acetate, ethyl acetate, and the like; ketones such as cyclohexanone, acetophenone, 2-heptanone, γ -butyrolactone, isophorone, N-ethylpyrrolidone, N-octylpyrrolidone, and the like; alkyl dimethyl amides such as C8 and C10 dimethyl amide, dimethyl acetamide, and the like; alcohols having low water solubility (i.e., about 10g/100ml or less) such as benzyl alcohol, cresol, terpineol, tetrahydrofuryl alcohol, 2-isopropylphenol, cyclohexanol, n-hexanol, and the like. In some cases, an ultrahydrophobe (ultrahydrophobe) is added to the oil phase to superficially maintain the stability of the emulsion that is generated late in the operation when the oil and water phases are mixed. The additive is a highly water-insoluble substance that 1) has a negligible diffusion coefficient and negligible solubility in the continuous aqueous phase, and 2) is compatible with the dispersed phase. Examples of ultrahydrophobes include long chain paraffin oils such as hexadecane; polymers, such as polyisobutenes, e.g. Indopol^TMH15(INESO oligomer), polystyrene, polymethyl methacrylate; natural petroleum oils, such as seed oils; and silicones, such as silicone oilsOr dimethicone. Preferably, the additive is used in an amount of no greater than 10 wt.% (based on the weight of the dispersed phase).

In one embodiment, the polymer precursor in the dispersed phase is a polyisocyanate or a mixture of polyisocyanates. The polyisocyanate reacts with the crosslinker or water to form a polyurea shell. Examples of polyisocyanates include, but are not limited to, Toluene Diisocyanate (TDI), diisocyanato-diphenylmethane (MDI), derivatives of MDI, such as MDI containing polymethylene polyphenylcyanates, an example of which is PAPI27^TMPolymeric MDI (the Dow Chemical company), isophorone diisocyanate, 1, 4-diisocyanatobutane, phenylene diisocyanate, hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) benzene, 1, 8-diisocyanatooctane, 4 '-methylene bis (phenyl isocyanate), 4' -methylene bis (cyclohexyl isocyanate), and mixtures thereof. In further embodiments, the polymer precursors in the dispersed phase may also include, but are not limited to, diacid chlorides, polyacyl chlorides (polyacyl chlorides), sulfonyl chlorides, chloroformates, and the like, and mixtures thereof.

The oil phase and the aqueous phase are mixed in the presence of a surfactant which helps to create and/or stabilise medium sized droplets of less than 500nm, preferably less than 300 nm. The surfactant may be added to the oil phase or the aqueous phase or both the oil and aqueous phases. The surfactant includes a nonionic surfactant, an anionic surfactant, a cationic surfactant or a combination of a nonionic surfactant and an anionic surfactant or a combination of a nonionic surfactant and a cationic surfactant. Examples of suitable surfactants include alkali metal dodecyl sulfates such as sodium dodecyl sulfate, alkali metal fatty acid salts such as sodium oleate and sodium stearate, alkali metal alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, polyoxyethylene nonionic surfactants, and quaternary ammonium surfactants. Those skilled in the art can select suitable Surfactants from standard reference sources, including Handbook of Industrial Surfactants, Fourth Edition (2005) public synthetic Information Resources Inc, and McCutcheon's Emulsifiers and Detergens, North American and International Editions (2008) public by MCpublishing Company, without limitation to the types mentioned above.

The emulsions can be prepared by a variety of methods, including batch and continuous methods known in the art. In a preferred method, the emulsion is prepared using an ultra-high shear device such as an ultrasonic treatment device or a high pressure homogenizer to produce medium sized droplets of less than 500nm, preferably less than 300 nm. The sonication device includes a standard sonication apparatus containing a sonication probe that is inserted into the formulation to create medium sized droplets, a representative example of which is a sonifier 400 from Misonix sonifiers. High-pressure homogenizers (high-pressure homogenizers) use very high pressures of 500 to 20,000psi to pass the fluid through small openings and produce medium-sized droplets. Examples of such devices include, but are not limited to, Emulsiflex^TM(Avestin, Inc.) device and Microfluidizer^TM(Microfluidics) device.

In one embodiment, the polyisocyanate or mixture of polyisocyanates is reacted with a hydroxyl-or amino-containing molecule (such as a water-soluble diamine, a water-soluble polyamine, a water-soluble polyamino acid, a water-soluble diol, a water-soluble polyol, and mixtures thereof) in the continuous phase (i.e., water) via interfacial polycondensation to form a polymeric shell. Examples of such chain extenders or crosslinkers in the continuous aqueous phase may include, but are not limited to, at least one water soluble diamine such as ethylene diamine and the like; water-soluble polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like; water-soluble amino acids having more than one isocyanate-reactive functional group such as L-lysine, arginine, histidine, serine, threonine, polymers or oligomers of these amino acids, and the like; water-soluble diols or polyols such as ethylene glycol, propylene glycol, polyoxyethylene glycol, resorcinol, water-soluble amino alcohols such as 2-aminoethanol, and the like; and guanidines, guanidine compounds, polyamidines and derivatives, and mixtures thereof. In one embodiment, the water-soluble phase includes a diamine having a carboxylate functional group (such as L-lysine) that reacts to form a polyurea shell comprising carboxylate functional groups on the surface of the mesocapsule. The carboxylate functionality may be unneutralized or may be partially or fully neutralized to form a carboxylate salt.

In a further embodiment, the di-or polyamines or their equivalents contained in the aforementioned exemplary aqueous phase leak out of the reaction mixture. In this embodiment, the polyisocyanate reacts with water to form a polyurea shell.

Each factor may be adjusted to increase or decrease the interfacial condensation process reaction rate. These factors include, for example, temperature, pH, mixing rate, reaction time, osmotic pressure, and the requisite changes in the level and type of emulsifiers, polymer components, solvents, and the addition of catalysts, among others. Additional discussion of the effects of temperature, catalyst, pH, etc. on these types of reactions is found, for example, in U.S. patent No. 4,285,750, which is incorporated herein by reference in its entirety. Additional information on the effect of salts and salt levels on these types of reactions can be found in publication WO2006/092409, which is incorporated herein by reference in its entirety.

Some embodiments of the invention may be achieved by varying the levels of some of the reactants in a reaction mixture consisting of a dispersed oil phase and a continuous aqueous phase for forming mesocapsules comprising at least one AI. In some embodiments, the reaction mixtures comprise at least one AI given in terms of wt.% (wt.%) of the oil phase, which ranges 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 a range of about 1 wt.% to about 90 wt.%, more preferably about 20 wt.% to about 80 wt.%; optionally, ultrahydrophobes present in the following ranges: about 0.5 wt.% to about 10 wt.%, more preferably about 1.0 wt.% to about 5.0 wt.%; at least one polyisocyanate present in the following ranges: about 1 wt.% to about 30 wt.%, more preferably about 5 wt.% to about 20 wt.%; optionally, an emulsifier present in the following ranges: 0.1 wt.% to about 20 wt.%, more preferably about 1 wt.% to about 10 wt.%, wherein the oil phase constitutes similarly about 1% to about 60% of the total amount of the emulsion.

The aqueous phase of the reaction mixture consists of about 40 wt.% to about 99 wt.% of the overall emulsion and contains about 60 wt.% to about 90 wt.% water, about 1 wt.% to about 30 wt.% of one or more crosslinking agents, and optionally about 0.1 wt.% to about 20 wt.% of one or more water-soluble surfactants.

Similarly, some of the ingredients used in some exemplary formulations are optional. For example, it is possible in some embodiments to synthesize effective mesocapsules without the addition of solvents and/or ultrahydrophobes. These types of optional ingredients are particularly effective when the AI is a solid, when added to the reaction mixture.

As described herein, one method for encapsulating poorly water soluble substances is to produce a polyurea core-shell by the interfacial condensation reaction of a polyisocyanate or a mixture of polyisocyanates in a dispersed oil phase with at least one water and a water soluble polyamine in a continuous phase. In order to stabilize the microcapsules against agglomeration and to control the size of the microcapsules prior to reaction, it is often desirable to add one or more surfactants or colloidal stabilizers to the reaction mixture. The surfactant may be effective if the purpose of the reaction is to produce mesocapsules of less than 500 nm. However, the presence of surfactants in many end-use applications is detrimental. For example, in the delivery of agriculturally active ingredients to plants, the surfactants present in capsules such as polyurea are detrimental to the plant. In other applications, the surfactant may also cause unwanted foaming of the final product. Accordingly, it would be beneficial to develop a process for the efficient synthesis of microcapsules and mesocapsules that requires less or no surfactant than the previously discussed processes.

One aspect of the invention is a process for producing microcapsules or mesocapsules, wherein a compound comprising at least one functional moiety which is a primary or secondary amine or a primary or secondary amino group, and additionally comprising at least one hydrophilic functional group, is added, and wherein the component is added such that it is substantially free of surfactant to prepare an emulsion. In one embodiment of the invention, the component is glycine, a salt of glycine, or a mixture of glycine and a salt of glycine. These methods for producing microcapsules or mesocapsules include adding glycine, a salt of glycine, or a mixture of glycine and a salt of glycine to the aqueous phase of the reaction mixture prior to producing the final emulsion and, if desired, prior to initiating the crosslinking reaction between components such as polyisocyanates to produce the polyurea mesocapsule shell. Additional molecules that may be used in addition to or in place of glycine include other molecules having a primary or secondary amine at one end of the molecule and a hydrophilic group such as carboxylate or triethylamine at the other end of the molecule. It may not be necessary to neutralize all charged moieties to obtain the product formed by the process disclosed herein. A partial list of some of these types of molecules can be found in us patent 4,757,105, which is incorporated herein by reference in its entirety.

Without wishing to be bound by any single theory or explanation, glycine, glycinate salts, or glycine-like substances may be added prior to forming the final emulsion to allow glycine to react with a small portion of the diisocyanate or polyisocyanate to produce surfactant-like molecules that help create and/or stabilize the emulsion and help control the droplet size in the final emulsion. Next, after the final emulsion is produced, during the interfacial condensation reaction, the surfactant-like molecules formed by the glycine reaction are reacted to become contained in the polyurea shell and no longer serve as free surfactant. The hydrophilic functional group of glycine or glycine-like molecules is present at the surface of the shell to help stabilize the shell.

The present disclosure includes methods for encapsulating sparingly water-soluble AI within polyurea core-shell particles using reduced levels of surfactants or colloidal stabilizers, or no surfactants or colloidal stabilizers and still maintaining dispersion stability and particle size control. The disclosure has application in the delivery of agriculturally active ingredients, where excess surfactant may have a phytocidal effect on plants and other delivery or controlled release applications where the presence of surfactant is detrimental in the end application.

Polyurea meso-capsules can be prepared using colloidal stabilizers such as polyvinyl alcohol without the use of surfactants, but it is difficult to control particle size. Some formulations of AI are prepared using surfactants that do not exhibit some properties that need to be avoided, such as using surfactants that are weaker to kill plants or surfactants that exhibit less foaming.

Adding a glycinate salt or similar molecule comprising a primary or secondary amino group and a carboxylate group or triethylamine to the aqueous phase prior to producing the final emulsion reduces or eliminates all the need to add a surfactant to the reaction mixture. Such materials are added to enable the production of medium capsules free or substantially free of surfactants: the material is not a surfactant such as glycine and reacts with the diisocyanate or polyisocyanate to produce molecules that help emulsify and stabilize the organic phase and further reacts the diisocyanate or polyisocyanate once within the polyurea shell. In some embodiments, substantially free means that the oil phase comprises less than about 1.0 wt.% and more preferably less than 0.5 wt.% surfactant.

Being able to formulate a moderate capsule that contains no or very little residual surfactant has advantages in many applications where the presence of free surfactant in the formulation has a deleterious or undesirable effect. There may also be potential cost advantages where the amount of expensive surfactant can be reduced.

One embodiment of the present invention is a mesocapsule comprising at least one AI, such as the fungicide fenbuconazole. Exemplary methods of forming these mesocapsules include interfacial polycondensation reactions between compounds in the oil phase and water in the water phase or between compounds in the oil phase and water-soluble crosslinkers in the water phase. To produce a medium capsuleEither mesocapsules having an average diameter of about 500nm or less or mesocapsules having an average diameter of about 300nm or less, a surfactant such as sodium lauryl sulfate may be added to the reaction mixture, or a molecule such as glycine may be added to the aqueous phase, prior to creating the final emulsion and/or initiating the crosslinking reaction. In one embodiment, the oil phase and the aqueous phase are mixed under high shear to form an emulsion comprising medium sized microdroplets that are converted into polyurea mesocapsules as described herein. The means for processing the emulsion to assist in the formation of the mesocapsule include sonication means and/or a high pressure homogenizer. The sonication device includes a standard sonication instrument containing a sonication probe that is inserted into the system to create medium-sized droplets, a representative example of which is a Sonicator 400 from misonix sonicators. High pressure homogenizers use very high pressures of 500 to 20,000psi to pass the fluid through small openings and produce medium sized droplets. Examples of such devices include, but are not limited to, Emulsiflex^TM(Avestin, Inc.) device and Microfluidizer^TM(Microfluidics) device.

In one embodiment, the poorly water soluble AI is optionally dissolved in a solvent such as benzyl acetate. Optionally, an ultrahydrophobe such as hexadecane may be added to help maintain the stability of the emulsion, which is formed once the oil and water phases are combined. Reacting polyisocyanates such as PAPI^TM27 polymeric MDI (the Dow chemical company) was added to the oil phase. To assist in forming medium sized droplets as a precursor for forming medium capsules, a surfactant such as Sodium Dodecyl Sulfate (SDS) may be added to the oil phase or the water phase or both. Alternatively, glycine or any other molecule having an amine or amino moiety at one end of the molecule and a hydrophilic group at the other end of the molecule is added to the aqueous phase prior to forming the final emulsion or initiating the crosslinking reaction. The amount of glycine or similar molecule may be increased as desired to replace all or at least some of the surfactant. Next, the oil phase and the aqueous phase are mixed and optionally with an ultra-high shear device such as a Microfluidizer^TM(Microfluidics) device processing to produceThe small droplets required, which are converted to the medium size polyurea capsules described herein.

Many types and types of pesticides are used in agriculture and pest management. Examples include insecticides such as antibiotic insecticides such as aloamicin (allosamidin) and thiringensin, macrolide insecticides such as spinosad, spinetoram and 21-butenyl spinosyn; pesticides such as abamectin (abamectin), doramectin (doramectin), emamectin (emamectin), eprinomectin (eprinomectin), ivermectin (ivermectin) and selamectin (selamectin); milbemycin insecticides such as lepimectin, milbemectin (milbemectin), milbemycin oxime (milbemycin oxime), and moxidectin (moxidectin); plant insecticides such as neonicotinoid (anabasene), azadirachtin (azadirachtin), d-limonene (d-limonene), nicotine (nicotinoid), guar (pyrethrins), guar (cinerin I), guar (cinerin II), jasmin I (jasmolin I), jasmin II (jasmolin II), pyrethrin I (pyrethrin I), pyrethrin II (pyrethrin II), quassia (quassia), rotenone (rotenone), muddy fish (ryana), and sabai (badillala); carbamate insecticides such as bendiocarb (bendiocarb) and carbaryl (carbaryl); benzofuranylmethyl carbamate insecticides such as benfuracarb, carbofuran, carbosulfan, carbofuran and furacarb; dimethyl carbamate insecticides such as dimitan, dichlorcasean (dimetilan), quinocarb (hyquincarb), and pirimicarb (pirimicarb); oxime carbamate insecticides such as cotton boll-carbofuran (alanycarb), aldicarb (aldicarb), sulfocarb (aldoxycarb), buticarb (butocarbxim), oxybutyrocarb (butoxycarbxim), methomyl (methomyl), nitrilocarb (nitrilacarb), carbamyl (oxamyl), thiodicarb (tazimcarb), carbofuran (thiocarbome), thiodicarb (thiodicarb) and tetramethonium (thiofanox); phenylmethylcarbamate insecticides such as propoxycarb, methomyl (amicarb), carbofuran (bufencarb), bendiocarb (butacarb), carbofuran (carbacamate), cycloxycarb (carbonilate), cycloxycarb (cloethocarb), methyl N- (3-methylphenyl) carbamate (dicreyl), dioxacarb (dioxacarb), methomyl (EMPC), bendiocarb (ethiofencarb), fenoxycarb (fentebucarb), fenoxycarb (fenobucarb), isoprocarb (isoprocarb), methiocarb (methiocarb), metolcarb (metolcarb), carbofuran (methocarb), carbofuran (methiocarb), methiocarb (xmixocarb), promacyl (promecarb), propoxur (proxporur), mixed pesticide (trichocarb), dimetocarb (xmpropoxycarb), and methocarb (xmixocarb); dinitrophenol insecticides such as dicofol (dinex), nitrophenol (dinoprop), dinetol (dinosam), and Dinitrocresol (DNOC); fluorine pesticides such as barium hexafluorosilicate (barium hexafluorosilicate), sodium fluoroaluminate (cryolite), sodium fluoride (sodium fluoride), sodium hexafluorosilicate (sodium hexafluorosilicate), and sulfluramide (sulfluramide); formamidine insecticides such as chlorfenamidine (amitraz), chlorfenamidine (chlormideform), varroamidine (formanate), and carboximate (formanate); fumigant insecticides such as acrylonitrile (acrylonitrite), carbon disulfide (carbandisulide), carbon tetrachloride (carbon tetrachloride), chloroform (chloroform), chloropicrin (chloropicrin), p-dichlorobenzene (para dichlorobenzene), 1, 2-dichloropropane (dichloropropane), ethyl formate (ethyl formate), 1, 2-dibromoethane (ethylene bromide), 1, 2-dichloroethane (ethylene dichloride), ethylene oxide (ethylene oxide), hydrogen cyanide (hydrogen cyanide), iodomethane (iodomethane), methyl bromide (methyl bromide), trichloroethane (methylene chloride), methylene chloride (methylene chloride), naphthalene (naphthalene), phosphine (phosphine), sulfuryl fluoride (fluoride), and tetrachloroethane (tetrachloroethane); inorganic insecticides such as borax (borax), lime sulphur (lime polysulphide), ketooleate (copper oleate), mercurous chloride (mercurous chloride), potassium thiocyanate (potassium thiocyanate) and sodium thiocyanate; chitin synthesis inhibitors such as diflubenzuron (bistrifluron), buprofezin (buprofezin), chlorfluazuron, cyromazine (cyromazine), diflubenzuron (diflubenzuron), flucycloxuron (flucycloxuron), flufenoxuron (flufenoxuron), hexaflumuron (hexaflumuron), fluoropropoxide urea (lufenuron), noviflumuron (novaluron), noviflumuron (fluxuron), tefluxuron (tefluxuron), and chlorbenzuron (triflumuron); juvenile hormone mimics, such as juvenil ether (eponenane), fenoxycarb (fenoxycarb), methoprene (hydroprene), heptamenephrine (kinerene), methoprene (pyriproxyfen), pyriproxyfen (pyriproxyfen), and thioacrylate (triprene); juvenile hormones such as juvenile hormone i (juvenile hormone i), juvenile hormone ii (juvenile hormone ii) and juvenile hormone iii (juvenile hormone iii); ecdysone agonists such as chromafenozide (chromafenozide), halofenozide (halofenozide), methoxyfenozide (methoxyfenozide), and diphenylhydrazide (tebufenozide); ecdysones such as alpha-ecdysone (alpha ecdysone) and ecdysterone (ecdysterone); molting inhibitors such as dioxolane (diofenolan); precoxins such as precocene i (precocene i), precocene II and precocene III; unclassified insect growth regulators such as dicyclanil (dicyclanil); nereistoxin analog insecticides such as bensultap, cartap, thiocyclam and thiosultap; nicotinic insecticides, such as flonicamid (flonicamid); nitroguanidine insecticides such as clothianidin (clothianidin), dinotefuran, imidacloprid (imidacloprid) and thiamethoxam (thiamethoxam); nitromethylene insecticides such as nitenpyram and nithiazine; pyridylmethylamines such as acetamiprid, imidacloprid, nitenpyram and thiacloprid; organochlorine insecticides such as bromoddt, toxaphene (camphechlorir), dichlorodiphenyl trichloroethane (DDT), pp' -DDT, ethyldiphenyl trichloroethane (ethyl DDD), hexachlorodiphenyl trichloroethane (HCH), gamma-hexachlorodiphenyl trichloroethane (gamma HCH), lindane (lindane), methoxydiphenyl trichloroethane (methoxychlor), pentachlorophenol (pentachlorophenol), and dichlorodiphenyl Trichloroethane (TDE); cyclopentadiene-type insecticides such as aldrin (aldrin), bromeneide (bromocylene), borneolum (chlorocylene), chlordane (chloredane), galbanum (chloredione), dieldrin (dieldrin), dilor (endosulfan), endrin (endrin), endrin (endin), dieldrin (HEOD), heptachlor (heptachlor), aldrin (HHDN), chloroneb (isobenzan), isoaldrin (isoldrin), keleyan (keleyan), and mirex (mirex); organophosphate insecticides such as bromophenol (bromofenvinfos), chlorfenphos (chlorofenvinphos), crotofos (crotoxyphos), dichlorvos (dichlorvos), chlormephos (dicrotophos), methylcrotophos (dimethylvinphos), chlorpyrifos (fospirate), heptenophos (heptanophos), crotonophos (methylcrotophos), mephos (mevinphos), monocrotophos (monocrotophos), dibromophos (naled), naphthylenephos (naftalos), phosphamidon (phosphamidon), propaphos (propaphos), TEPP (TEPP), and chlorfenphos (tetrachloris); organic thiophosphate or salt insecticides such as pinoxaden (dioxabenzofos), fenthion (fosmethialan) and phenthoate (phenthoate); aliphatic organic thiophosphate or salt insecticides such as housefly phosphorus (acetofos), amifostine phosphorus (amifoston), cadusafos (cadusafos), phosphorous oxychloride (chlorophenoxyfos), phosphorous oxychloride (chlorophenoxy), phosphorous farmate phosphorus (demeton), phosphorous O (demeton O), phosphorous demeton S (demeton S), phosphorous methyldemeton (demeton O methyl), phosphorous demeton S-methyl (demeton S methyl), phosphorous disulfoton (disulfoton), ethion (ethion), thion (ethoprophos), thion (propylthion), phosphorous (thion), phosphorous (demeton p), thion (isoprofos), thion (isoprothion), thion (isoprofos), thion (isoprofos), isoprofos (isoprothion), isoprothion (isoprofos), isoprofos (isoprothion) and isoprothion (isoprofos) S (isoprothion), isoprothion (, Thiotep (sulfotep), terbufos (terbufos) and fosetyl methyl (thiometon); aliphatic amide organic thiophosphate or salt insecticides such as methiocard (amidition), methoate (cyantate), dimethoate (dimethoate), motherwort (ethomat), formoterol (formothion), triazophos (mecarbam), omethoate (omethoate), pomace (prothioate), perilla fruit (sophamide) and aphidicol (vamidothion); oxime organic thiophosphate or salt insecticides such as chloronitrile oxime (chlorphoxim), oxime sulfur (phos), and methyl oxime sulfur (phos methyl); heterocyclic organic thiophosphate or salt insecticides such as azamethiphos, coumaphos, fosthien, dioxathion, indofos, menazon, morphos, phosmet, pyraclofos, pyrithion and quincuflon; thiochromane organic thiophosphate or salt insecticides such as thiopyrane (dithofos) and thiochlorophm (thiocofos); benzotriazine organic thiophosphate or salt insecticides such as azophos (azinphos ethyl) and bazinpho (azinphos methyl); isoindoline organic thiophosphate or salt insecticides such as chlorophosphine (dialifos) and phosmet (phosmet); isoxazole organic thiophosphate or salt insecticides such as oxazaphosphorine (isoxathion) and zolaprofos; pyrazolopyrimidine organic phosphorothioate or salt insecticides such as chloropyrazolophos (chloropyrazophos) and pyrazophos (pyrazophos); pyridine organic thiophosphate or salt insecticides such as chlorpyrifos (chlorpyrifos) and chlorpyrifos-methyl (chlorpyrifos methyl); pyrimidine organic thiophosphate or salt insecticides, such as temephos (butathiofos), diazinon (diazinon), etrimfos (etrimfos), pyrifenofos (lirimfos), tebufenpyrad (pirimiphos ethyl), methamphos methyl, pyriminostrobin (primidophos), pyriminophos (pyrimitate), and pyrimiphos (tebutirimfos); quinoxaline organothiophosphate or salt pesticides, such as quinoxaline (quinalphos) and methyl quinoxaline (quinalphos methyl); thiadiazole organic thiophosphate or salt insecticides such as dithianon (athiathiathiathion), fosthiazate (lythidathion), methidathion (methidathion), and ethidium (ethidathion); triazole organic thiophosphate or salt insecticides, such as chlorzofos and triazophos; phenyl organic thiophosphate or salt insecticides such as azophos (azothoate), bromophos (bromophos), ethyl bromophos (bromophos-ethyl), thiophosphor (carbophenothion), chlorthiophos (chlorthiophos), pyrazofos (cyanophos), methidathion (cythion), isochlorothiophos (dicapthon), dichlofenthion (dichlofenthion), ethophos (famshur), pyraclofos (fenchlophos), fenitrothion (fenthion), fenthion (fenthion), ethyl fenthion (fenthion), fenthion (thiophos), iodophos (jofenthion), thiophos (methyl thiophos), thion (thiophosphorum), thion (chlorphos), chlorphos (s (3-ethyl thiophos), chlorphos) and chlorphos (chlorphos) and; phosphonate insecticides such as butyl phosphate (butonate) and trichlorfon (trichlorfon); thiophosphonate insecticides, such as neonicotinoids (imicyafos) and methidathion (mecarphon); phenyl ethyl thiophosphonate insecticides, such as dinofos and loafos (trichloronat); phenylphenyl thiophosphonate insecticides, such as cyanophos (cyanofenophos), thiophenyl (EPN) and bromophenyl (leprophos); phosphoramidate insecticides such as fosthienate (crufomate), fenamiphos (fenamiphos), fenaminodan (fosthiolan), dithiafos (mephosphan), gossypos (phosfolan), and methamidophos (pirimophos); thiophosphoryl amide insecticides such as acephate (acephate), isocarbophos (isocarbophos), profenofos (isofenphos), methamidophos (methamidophos), and methoprene (propetamphos); phosphorodiamidate insecticides such as phosphorus methofluoride (dimefox), phosphorus azide (mazidox), phosphorus alaninate (mipafox), and phosphorus octate (schrad); oxadiazine insecticides such as indoxacarb; phthalimide insecticides such as phosphorous oxychloride (dialifos), phosmet (phosmet), and tetramethrin (tetramethrin); pyrazole insecticides such as acetoprole, ethiprole (ethiprole), fipronil (fipronil), pyricarb (pyriproxle), pyridinol (pyriproxle), tebufenpyrad (tebufenpyrad), tolfenpyrad (tolfenpyrad), and flupyrad (vaniprole); pyrethroid insecticides such as bifenthrin (acrinathrin), allethrin (allethrin), trans-allethrin (bioallethrin), chrysanthemums (barthrin), bifenthrin (bifenthrin), bioethanemethrin, cyclopentene (cyclopentenin), cycloprothrin (cycloprothrin), cyfluthrin (cyfluthrin), beta-cyfluthrin (betacyfluthrin), cyhalothrin (cyhalothrin), gamma-cyhalothrin (gamma cyhalothrin), lambda-cyhalothrin (lambda cyhalothrin), cypermethrin (cypermthrin), alpha-cypermethrin (alpha cypermthrin), beta-cypermethrin (beta cypermthrin), theta-cypermethrin (theta cyhalothrin), zeta-cypermethrin (cyhalothrin), beta-cypermethrin (beta cyhalothrin), theta-cypermethrin (theta-cyhalothrin), cyhalothrin (beta-cyhalothrin), beta-cyhalothrin (beta-cyhalothrin), cyhalothrin (fluthrin), cyhalothrin (fluthrin, Fenpropathrin, fenvalerate, esfenvalerate, flucythrinate, fluvalinate, tau-fluvalinate, furaldehyde pyrethrin, imidacloprid, metobifenthrin, permethrin, bioperfluthrin, permethrin, phenothrin, prallethrin, profluthrin, resmethrin, tefluthrin, and tefluthrin; pyrethroid ether insecticides such as etofenprox (etofenprox), fluprophenyl ether (flufenprox), haloethrin (halofenprox), protifenbute and silate (silafluofen); pyrimidineamine insecticides such as flufenerim and pyriminophen (pyrimidifen); pyrrole insecticides such as chlorfenapyr (chlorfenapyr); ryanodine receptor insecticides, such as flubendiamide (flubendiamide), chlorantraniliprole (rynaxypyr), and cyantraniliprole (cyantraniliprole); tetronic insecticides such as spirodiclofen (spirodiclofen), spiromesifen (spiromesifen) and spirotetramat (spirotetramat); thiourea insecticides such as diafenthiuron (diafenthiuron); urea insecticides such as flucloxuron and sulfophenyl ether (sulcofuron); sulfoximine insecticides such as sulfoxaflor; and unclassified insecticides such as closantel (closantel), crotamiton (crotamiton), fenpyrad (EXD), antimite (fenzaflor), fenazaquin (fenazaquin), fenoxacrim, fenpyroximate (fenpyroximate), flubendiamide (flubendiamide), hydramethylnon (hydramethylnon), isoprothiolane (isoprothiolane), benalazil (malononitrile), metaflumizone (metaflumizone), methoxazone (methoxadone), fluformin (nifuride), pyridaben (pyridaben), pyridalyl (pyridalyl), pyrifluquinazon, iodoetheramide (rafoxanide), triathiabendane (triathapyrarthene), and triasulfuron (triazasulfuron). The present invention contemplates selecting from the above list insecticides having a water solubility of about 1000ppm or less and formulating them as core-shell polyurea meso-capsules. Preferred insecticides are those having a water solubility of about 100ppm or less. More preferred insecticides are those having a water solubility of 10ppm or less. The Pesticide may be selected based on The water solubility disclosed in The summary, such as The Pesticide Manual fountain Edition, (ISBN1-901396-14-2), The entire contents of which are incorporated herein by reference. The additional version of The Pesticide Manual was also used to select insecticides for inclusion in The core-shell polyurea meso-capsule.

Many types and types of fungicides are used in agriculture. Examples include ametoctradin (ametoctradin), amisulbrom (amisulbactam) (2- (thiocyanomethylthio) -benzothiazole), 2-phenylphenol, 8-hydroxyquinoline sulfate, antimycin, azaconazole (azaconazole), azoxystrobin (azoxystrobin), benalaxyl (benalaxyl), benomyl (benomyl), isopropylbenthiavalicarb (benthiavalicarb-isoproxyl), benzylaminophenyl-sulfonate (BABS) salt, bicarbonate, biphenyl, biscumazol (bismerhiazol), bitertanol (bitertanol), bixafen, blasticidin-S (blasticidin-S), borax (borax), Bordeaux mixture, boscalid (boscalid), furonazole (bruconazole), ethirimol (buprimate), bypriptamide (bypripta7, thiamethoxam (fenpyrad), propiconazole (fenpyraclostrobin), propiconazole (carbapenem), propiconazole (pyraclostrobin (carbapenem), propiconazole (carbapenem), benomyl (benomyl), benomyl (, Carvone (carvone), anisole (chloroneb), chlorothalonil (chlorothalonil), dichlozoline (chlorozolite), copper hydroxide, copper octanoate, copper oxychloride, copper sulphate (tribasic), cuprous oxide, cyazofamid (cyazofamid), cyflufenamid (cyflufenamid), cymoxanil (cymoxanil), cyproconazole (cyproconazole), cyprodinil (cyprodinin), coumarin, dazomet (dazomet), prochloraz (debacarb), 1, 2-diethyicarbamyl disulfate diammonium, dichlofluanid (dichlorfluanid), dichlorophen (dichlorphen), diclocyme (diclocymet), diclocymen (diclomezine), dicloanil (diclofen), diethofencb (diclofen), difenoconazole (diclofenpropidin), dichlorphenazine (diclofen), dinotefuran (diclofen), dinone (diclofen), fenap, Diphenyldiamine, dithianon (dithianon), moroxydine (dodemorph), moroxydine acetate, dodine (dodine), dodine free base, edifenphos (edifenphos), enestrobin (enostrobin), epoxiconazole (epoxyconazole), clonidine (ethaboxam), ethoxyquinoline (ethoyquin), hymexazol (etridiazole), famoxadone (famoxadone), fenamidone (fenamidone), fenarimol (fenarimol), fenbuconazole, flufuramide (fenfuram), fenhexamid (fenhexamid), fenpyrad (fenoxanil), fenpropathrin (fenpropathrin), fenpropathrin (fenpropinil), fenpiclonil (fenpropathrin), fenpropidium hydroxide (fenpiclonil), fenpropidin (fenpropidin), fenpropimorph (fenpropih), fenpyrazamide (fenpyrazamide), fenthizone (fenthidiazuron), fenthiflufen (fenpyrazone), fenpyrazone (fenpyrazone), fenpyraclostrobin (flufen), fenflurazone (fenflurazone), fenflurazone (fenflurazone, fen, Flusilazole (flusilazole), flusulfamide (fluusufamide), flutopalanine (flutolanil), flutriafol (flutriafol), fluopicolide (fluxapyroxad), folpet (folpet), formaldehyde, triethylenephosphonic acid (foseyl), fosetyl-aluminum, fuberidazole (fureridazole), furalaxyl (furalaxyl), furalaxyl (furametpyr), biguanide salt (guazatine), biguanide acetate, GY-81, hexachlorobenzene (hexachlorobenezene), hexaconazole (hexaconazole), hymexazol (hymexazol), imazalil (imazalil), imazalil nitrate, imibenconazole (imazazol), iminoctadine (iminoctadine), iminoctadine triacetate, iminoctadine (fenpropinebenzamide), isopenidine (iprodione), iprodione (iprodione), pyrimethanazole (iprodione), pyrimethanil hydrochloride (iprodione), pyricularia (iprodione), pyrimethanil (iprodione (pyrimethanil), pyrimethanil (iprodione), pyrimethanil (pyrimethanil), pyrimethanil (iprodione (pyrimethanil), pyrimethanil (pyrimethanil), pyrimethanil (ipronifen-sodium (ipronifen, Mancozeb (mancozeb), mandipropamid (mandipopamid), maneb (maneb), mepanipyrim (mepanipyrim), mefenoxam (mepronil), meptyldinocap (meptyldinocap), mercuric chloride, mercurous chloride, metalaxyl (metalaxyl), mefenoxam (metalaxyl-M), meta-am, meta-ammonium, meta-potassium, meta-sodium, metconazole (metconazol), sulfocarb (metsualfarb), methyliodide, methyl isothiocyanate, metiram, metominostrobin (metominostrobin), metrafenone (metrafenone), alemycin (dimycin), myclobutanil (myclobutanil), sodium metsul (metsulosin), fenflurazone (fenflurazone), thiofenamate (difenoconazole), difenoconazole (difenoconazole), thiofenacet (difenoconazole), thifluzone (8-oxozoline (octoxycarb), thiuracil (octopine), thiuracil (octopamil), thiuracil (ester-amide), thiuracil-amide (ester), thiuracil-, Penflufen (penflufen), pefurazoate (pefurazoate), penconazole (penconazole), pencycuron (pencycuron), pentachlorophenol, pentachlorophenyl laurate, penthiopyrad (penthiopyrad), mercuric phenylacetate, phosphoric acid, phthalide (phthalide), picoxystrobin (picoxystrobin), polyoxin B, polyoxin (polyoxins), dactinomycin (polyoxin), potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole (probenazole), prochloraz (prochlororaz), trifluraline (procymidone), propamocarb (pamocarb), propamocarb hydrochloride, propiconazole (propiconazole), propineb (propineb), proquinazine (proquinazine), prothioconazole (propiconazole), pyriproxyfen (pyraclostrobin), pyriproxyfen (pyriproxyfen), pyrimethanil (flufenozide), pyrimethanil (pyribenzofenapyr), pyrimethanil (flufenozide), pyriproxyfen (pyriproxyfen), pyriproxyfen (pyriproxyfen), pyriproxyfen (pyrimethanil), pyriproxyfen (pyri, Quinoxyfen (quinoxyfen), quintozene (quintozene), Polygonum cuspidatum (Reynoutria sachalinensis) extract, sedaxane (sedaxane), silthiopham (silthiofam), simeconazole (simeconazole), sodium 2-phenylphenol, sodium bicarbonate, sodium pentachlorophenate (sodium pentachlorophenoxide), spiroxamine (spiroxamine), sulfur (sulfur), SYP-Z071, SYP-048, SYP-Z048, tar, tebuconazole (tebuconazole), isobutoxyquinoline (tebufloquin), tetrachloronitrobenzene (tecnazole), tetraconazole (tetraconazole), thiabendazole (tebuconazole), thifluzamide (thifluzamide), thiophanate-methyl thiophanate (thiophanate-triazole), thifluzamide (thifluzamide), thifluzamide (trimethoprim (trifloxystrobine (trifloxystrobin), thiflutriafol (trifloxystrobin), thifluzone (trifloxystrobin), thifluzone (trifloxystrobin), thiuracil (thiuracil), thiuracil (thiuracil, Triflumizole (triflumizole), fluazinam (triforine), triticonazole (triticonazole), validamycin (validamycin), valiprenal, valifenate, vinclozolin (vinclozolin), zineb (zineb), ziram (ziram), zoxamide (zoxamide), (RS) -N- (3, 5-dichlorophenyl) -2- (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-dithiane 1, 1, 4, 4-tetraoxide, 2- (heptadecyl) -2-imidazolin-1-yl) ethanol, 2, 3-dihydro-5-phenyl-1, 4-dithiane 1, 1, 4, 4-tetraoxide, 2-methoxyethyl mercuric acetate, 2-methoxyethyl mercuric chloride, 2-methoxyethyl mercuric silicate, 3- (4-chlorophenyl) -5-methylthioxoic acid, 4- (2-nitroprop-1-enyl) phenyl thiocyanate: 1-aminopropyl phosphoric acid (amprophylfos), dichlofluanid (anilazine), thiram (azithiram), barium polysulfide (barium polysulfide), Bayer 32394, benorine (benodanil), quinoxime hydrazone (benzoquinone), bentaluron, benzamace-isobutryl, benzamorf, binapacryl (binapacryl), buthionine (buthiobate), witherate (cadium chloride sulfate), carbapenem (carbamorph), CECA, chlozoazole (chlobenzothiazone), chloranile (chlozolinate), chlorazol (chlazone), tetrachloroquinoxaline (chlorquinox), chlorfenazole (climbazole), 3-phenylbenzoate (salicylic acid), copper salicylate (fenpropinebrodenazole), fenpropidium chloride (fenpropidium chloride), fenpropidium chloride (fenpyr), fenpyr (fenpyr), fenpyrenoid (fenpyrachloride), fenpyrrochlorate (fenphos), fenpyrenoate (fenpyr), fenpyrenoate (fenpyrenozide), fenpropidium chloride (fenpyr-methyl chloride), fenpyr (fenpyr-methyl), fenpyr-methyl benzoate (fenpyr-methyl benzoate), fenpyr-ethyl (fenpropidium chloride (fenpropiolate), fenpropidium chloride (fenpropineb), fenpropidium chloride (fenpropiolate), fenpropineb (fenpropineb), fen, Nitrobutyl (dinoterbon), pyrithione (dipyrithione), sterile phosphorus (dithimafos), doxycycline (dodiscin), fenaminosulf (drazoxolon), EBP, ESBP, epoxiconazole (etaconazole), ethametem (etem), ethirimol (ethirim), fenaminosulf (fenaminosulf), fenapanil (fenapanil), fentrazone (fentroban), triflumizole (flutrimazole), nitrozole (furaranil), furametpyr (furconazol-cis), furametpyr (furazolidone-cis), furametpyr (furametporan-ates), furametpyr (furametporan), furametporan (fenpropineb), furametporan (fenamidone, furametporan (acide), furametporan (fumagiline), furamethod (fumagiline), fenpropiomulinamide (fenpropiconazole, fenpropiomuofenamide (fenpropiconazole), fenpropiconazole (fenpropiconazole, fen, N-3-nitrophenyl itaconimide, natamycin (natamycin), N-ethylmercurous-4-toluenesulfonamide, nickel bis (dimethyldithiocarbamate), OCH, phenylmercuric dimethyldithiocarbamate, phosophosphate (phosdiphen), prochloraz (prothiocarb), prochloraz (pyracarbolid), cyanophenyl (pyridinitril), pyridalyl (pyroxychloride), pyrazoxyfen (pyroxyfurol), quinocetone (quinoxyfuran), quinophthalone (quinazone), pyrazolazole (rabenzazole), salicylanilide (salicylanilide), SSF-109, penylsulfone (sultropen), thiram (thiophanate), fluthiabendamide (thiadiflorfon), thiocyanamide (thiocyanide), thiophanate (trichlorocyanamide), thiophanate (triazoxide), triazophos (thiophanate), triazophos (thiophosphoryl), triazophos (fenamide (triazophos (fenac), triazophos (fenacils (fenac), triazophos (fenac), triazophos (fenacils), triazophos (fenacils (fenac), triazophos (fenac (fenacils (fenac), triazophos (fenac), triazopho, Salicylamide (trichlamide), UK-2A, UK-2A derivatives such as (3S, 6S, 7R, 8R) -isobutyric acid 8-benzyl-3- (3- (isobutyryloxymethoxy) -4-methoxypyridinamido) -6-methyl-4, 9-dioxo-1, 5-dioxazinedione-7-ester (which has CAS registry number 328255-92-1 and is referred to herein as 328255-92-1), foscarnet (urbacid), XRD-563 and cyanamide (zarilamid), IK-1140 and propargylamide. The present invention contemplates selecting fungicides from the above list that have a water solubility of about 1000ppm or less and formulating them into core-shell polyurea meso-capsules. Preferred fungicides are those having a water solubility of about 100ppm or less. More preferred fungicides are those having a water solubility of 10ppm or less. Fungicides can be selected based on The water solubility disclosed in The summary, such as The Pesticide Manual watering Edition, (ISBN1-901396-14-2), which is incorporated herein by reference in its entirety. The additional version of The Pesticide Manual was also used to select fungicides for inclusion in core-shell polyurea iso-capsules.

Many classes and types of herbicides are used in agriculture. Examples include amide herbicides such as dicloxacillin (alidochlor), beflubutamid (beflubutamide), benzadox (benzadox), benfluramine (benzzipam), bemobutyramide (bromobutyride), cafenstrole (cafenstrole), CDEA, chlorazole (chlorethamide), cyprodinil (cyprazole), dimethenamid (dimethenamid-P), molinate (diphenamid), metamifop (eponaz), ethofenprox (etnipromide), tebuconazole (fentrazamide), flutriamid (flupropafen), fomesafen (mesalamine), flunifamide (halosafen), cimetimide (isarobamide), isoxabenoxanilide (isabenamide), propyzamide (fenamide), propyzamide (fenazamide), propyzamide (fenamide), fenaminosulfenamide (fenamide), propyzamide (fenamide), fenaminosulfenamide (fenamide), fenamide (fenaminosulfenamide (fenamide), fenamide (fenamide), fenaminosulfenamide (fenamide (fena; aniline herbicides such as butachlor (chlorocarpyl), fluazifop (cisanilide), cockspur-grass (clomeprop), cyprodinil (cypramide), diflufenican (diflufenican), ethoxybenfop (etobenzanid), bensulam (fenasulam), flufenacet (flufenacet), flufenapyr (flufenacin), mefenacet (mefenacet), fluorosulfonamide (meflunidide), metamifop (metam), heptanoamide (monatide), napropamide (naproxide), mechlorethamine (pentachlor), picolinafen (picolinafen) and propanil (panproil); aryl alanine herbicides such as neodelphine (benzolprop), fluazinam (flamprop), and norfluazinam (flamprop-M); chloroacetanilide herbicides, such as mowing amines (acet)ochlor), alachlor (alachlor), butachlor (butachlor), butachlor (butenachlor), dichlormate (delachlor), anta (diethyl), butachlor (dimethachlor), metazachlor (metazachlor), metolachlor (metolachlor), S-metolachlor (S-metolachlor), pretilachlor (propalachlor), propachlor (propachlor), propisochlor (propiochlor), guanacol (prynachlor), mermaid (terbuchlor), thifennel (thelylchlor) and xylalin (xylachlor); sulfonanilide herbicides such as fomesafen (benzofluor), fomesafen (perfluodine), pyrimisulfan and flumetsulam (profluazol); sulfonamide herbicides such as asulam (asulam), carbaryl (carbasulam), carbosulfan (fenasulam) and oryzalin (oryzalin); antibiotic herbicides such as bialaphos (bilanafos); benzoic acid herbicides such as chloramben (chloramben), dicamba (dicamba), 2, 3, 6-TBA and dicamba (tricamba); pyrimidinyloxybenzoic acid herbicides such as bispyribacic acid (bispyribacc) and pyribenzoxim (pyriminobac); pyrimidinyl thiobenzoic acid herbicides such as pyrithiobac (pyrithiobac); phthalic acid herbicides such as chlorophthalic acid (chlorophthal); picolinic acid herbicides such as aminopyralid (aminopyralid), clopyralid (clopyralid), and picloram (picloram); quinoline carboxylic acid herbicides such as quinclorac and quinclorac; arsenical herbicides such as cacodylic acid (cacodylic acid), Calcium Methylarsenate (CMA), sodium methylarsenate (DSMA), hexafluoroarsonate (hexaflurate), methylarsenic acid (MAA), monoammonium methylarsenate (MAMA), monosodium methylarsenate (MSMA), potassium arsenite (potassium arsenite), and sodium arsenite (sodium arsenite); benzoylcyclohexanedione herbicides such as mesotrione (mesotrione), sulcotrione (sulcotrione), tefuryltrione and tembotrione; benzofuranone alkylsulfonates herbicides such as benfuresate and ethofumesate; carbamate herbicides such as asulam (asulam), fenoxacarb (carboxazole), methiocarb (chlorocarb), benazolin (dichlormate), bensulam (fenasulam), terbinafine (karbutilate) and terbufarb (terbutrab); carbanilate herbicides, such as barban, BCPC, carbaryl (carbasu)lam), carbendazim (carbendazim), diclofop (CEPC), clodinafam (chlorofam), chlorpropham (CPPC), desmedipham (desmedipham), phenisopham (phenisopham), phenmedipham (phenmedipham-ethyl), phenmedipham (propham) and swep (sweep); cyclohexenoxime herbicides such as dicumyl (alloxydim), butroxydim, clethodim (clethodim), cycloxydim (cycloproxydim), cycloxydim (cycloxydim), cycloxydim (profoxdim), sethoxydim (sethoxydim), tepraloxydim (teproxydim), and tralkoxydim (tralkoxydim); cyclopropyl isoxazole herbicides such as isoxachlorotole (isoxacachlortholite) and isoxaflutole (isoxaflutole); dicarboximide herbicides such as benfenacet (benzfendizone), cinidon-ethyl (cinidon-ethyl), trifluorooxazine (flumezin), fluoroelenic acid (flumiclorac), flumioxazin (flumioxazin), and flumetsulam (flumipropyn); dinitroaniline herbicides such as flumioxazin (benzfluralin), dimethomorph (butralin), dinoamine (dinitramine), ethalfluralin (ethalfluralin), flufenozide (fluchlalin), isoprotulin (isoproxalin), primeverin (methamphalin), metribulin (nitralin), oryzalin (oryzalin), pendimethalin (pendimethalin), prodiamine (prodiamine), cyhalofop-butyl (profluralin) and trifluralin (trifluralin); dinitrophenol herbicides such as dinotefuran, dinoropl, dinoprom, dinoseb, dinotefuran, and dinotefuran; diphenyl ether herbicides such as fluroxypyr (ethoxyfen); nitrophenyl ether herbicides such as acifluorfen (aclflurfen), aclonifen (aclonifen), bifenox (bifenox), nictrofen (chloronifen), cumylether (chlorornitrofen), pyrimethan (etniprodil), pyraflufen (fluoroodifen), fluoroglycofen (fluoroglycofen), fluorofen (fluoronitrofen), fomesafen (fomesafen), fluroxypyr (furyloxyfen), nitrolosamide (halosafen), lactofen (lactofen), aclonifen (nitrofen), trifolifen (nitrofen) and oxyfluorfen (oxyfluorfen); dithiocarbamate herbicides such as dazomet (dazomet) and metam (metam); halogenatedAliphatic herbicides such as pentachlorophenonoic acid (alorac), trichloropropionic acid (chlorophon), dalapon (dalapon), tetrafluoropropionic acid (flupopanate), hexachloroacetone, iodohexane, methyl bromide, monochloroacetic acid, chloroacetic acid (SMA), and trichloroacetic acid (TCA); imidazolinone herbicides such as imazamethabenz (imazamethabenz), imazamox (imazamox), imazapyr (imazapic), imazapyr (imazapyr), imazaquin (imazaquin), and imazethapyr (imazethapyr); inorganic herbicides such as ammonium sulfamate, borax (borax), calcium chlorate (calcium chloride), copper sulfate (copper sulfate), ferrous sulfate (ferrous sulfate), potassium azide, potassium cyanate, sodium azide, sodium chlorate, and sulfuric acid; nitrile herbicides such as furfuryl cyanide (bromoonil), bromoxynil (bromoxynil), hydroxyfenapyr (chloroxynil), dichlobenil (dichlobenil), iodoxynil (iodobonil), ioxynil (ioxynil), and pyraclonil (pyraclonil); organophosphorus herbicides such as methylaminophos (amiprofos-methyl), anilofos (anilofos), bensulide (bensulide), bialaphos (bialaphos), butafosinate (butamfos), fenfluros (2, 4-DEP), glufosinate (DMPA), EBEP, phosphinothricin (fosamine), glufosinate (glufosinate), glyphosate (glyphosate), and piperaphos (piperophos); phenoxy herbicides such as bromofenoxam (bromofloxyme), barnyard grass amine (clomeprop), seirsin (2, 4-DEB), varespos (2, 4-DEP), flubenopentenic acid (difenopentene), 2, 4-d sodium sulfate (disul), bixafen (erbon), pyrimethabenz ether (etnipromid), chlorophenoxyethanol (fenteracol), and trifolium oxime (trifopsimide); phenoxyacetic acid herbicides such as propham (4-CPA), 2, 4-D, 3, 4-D, 2-methyl-4-chloro (MCPA), MCPA-thioethyl and 2, 4, 5-T-nasal discharge (2, 4, 5-T); phenoxy butanoic acid herbicides such as chlorophenoxybutyric acid (4-CPB), 2, 4-d-butyric acid (2, 4-DB), 3, 4-d-butyric acid (3, 4-DB), 2-methyl-4-chlorobutyric acid (MCPB), and 2, 4, 5-rhinorrhea butyric acid (2, 4, 5-TB); phenoxypropionic acid herbicides such as clorprop, clorproprop (4-CPP), 2, 4-dichlorprop (dichlorprop-P), 3, 4-dichlorprop (3, 4-DP), 2, 4, 5-rhinoprop (fenoprop), 2-methyl-4-chloropropionic acid (mecoprop) and refined 2-methyl-4-chloropropionic acid (mecoprop-P); herbicides of aryloxy phenoxy propionic acids, e.g. clodinafop-propargyl (chlor)azifop), clodinafop (clodinafop), chlorobutyl (clofap), cyhalofop-butyl (cyhalofop), chlorothalofop (diclofop), fenoxaprop (fenoxaprop-P), thiazofenoxaprop (fenthiaprop), fluazifop-P (fluazifop-P), haloxyfop (haloxyfop), fluazifop-P (haloxyfop-P), oxadixyl (isoxapyrfop), metamifop (metamifop), propaquizafop (propaquizafop), quizalofop (quizalofop-P), and fenoxypropionic acid (trip); phenylenediamine herbicides such as dinoamine (dinitramine) and prodiamine (prodiamine); pyrazolyl herbicides such as tralkoxydim (benzofenap), pyrazoxan (pyrazolinate), pyrasulfotole, pyrazoxyfen (pyrazoxyfen), pyroxasulfone, and topramezone; pyrazolyl phenyl herbicides such as pyraflufen-ethyl (fluazolate) and pyraflufen-ethyl (pyraflufen); pyridazine herbicides such as pyriminostrobin (credazine), pyridafol and pyridate (pyridate); pyridazinone herbicides such as ametryn (bromopyrazone), chloranil (chloridazon), dimidazon (dimidazone), flupyridazinyl (flufenpyr), flurazon (metflurazon), norflurazon (norflurazon), oxadizin (oxapyrazon), and biadenon (pydanon); pyridine herbicides such as aminopyralid (aminopyralid), iodochlodinate (clodinate), clopyralid (clopyralid), dithiopyr (dithiopyr), fluroxypyr (fluroxypyr), fluroxypyr 1-methylheptyl ester, haloxydine (haloxydine), picloram (picloram), picolinafen (picolinafen), triclopyr, thiazopyr (thiazopyr), and triclopyr; pyrimidinediamine herbicides such as propadix (iprymidam) and pyrimethanil (tioclorim); quaternary ammonium herbicides such as diquat (cyperquat), diethambus (diethamquat), dichlormate (difenzoquat), diquat (diquat), varez (morfamquat) and paraquat (paraquat); thiocarbamate herbicides, such as butyrates, cycotates, dichloram (di-allate), promethazine (EPTC), esprocarb (esprocarb), fenoxycarb (ethiolate), azoteGrass (isopolinate), methiocarb (methiobencarb), sodaMolinate, prosulfocarb (orbicular), pefurazon (pebulate), prosulfocarb (propufocarb), pyributicarb (pyributicarb), chlorambucil (sulfofate), prosulfocarb (thiobencarb), carbofuran (tiocarbazil), triallate (triallate) and vernolate (Vernollate); thiocarbonate herbicides such as dimethomono (dimexano), nebivolol (EXD) and prometryn (proxan); thiourea herbicides such as metoxuron; triazine herbicides such as dimethomorph (dipropetryn), triaziflam (triaziflam), and trihydroxytriazine (trihydroxytriazine); chlorotriazine herbicides such as atrazine, clonazine, cyanazine, cypress, liquirizine, metribuzine, mesotrazine, cycloprozine, propaquizazine, promazine, terbuthylazine, simazine, terbuthylazine and metrizine; methoxytriazine herbicides such as atraton (atraton), ethameteton (methometon), prometon (prometon), metolachlor (secbumeton), simaton (simeton) and metoxyfen (terbumeton); methylthiotriazine herbicides such as ametryn, azinpryne, cyanazine, desmetryn, tefrazizine, metribuzin, fentrazine, prometryn, simetryn, and terbutryn; triazinone herbicides such as metribuzin (ametridione), amethozine (amibuzin), hexazinone (hexazinone), butazinone (isomethizin), metamitron (metamitron), and metribuzin (metribuzin); triazole herbicides such as imazapyr (amitrole), cafenstrole (cafenstrole), pyraflufen (epronaz) and flufenoxam (flupoxam); triazolone herbicides such as amicarbazone (amicarbazone), bencarbazone, carfentrazone (carfentrazone), flucarbazone (flucarbazone), propoxycarbazone (propyzamide), sulfentrazone (sulfentrazone) and thiencarbazone-methyl; triazolopyrimidine herbicides such as flumetsulam (cloransulam), flumetsulam (diclosulam), florasulam (florasulam), flumetsulam (flumetsulam), metosulam (metosulam), penoxsulam (penoxsulam) and pyroxsulam (pyroxsulam); uracil herbicides, a plurality ofSuch as butafenacil (butafenacil), bromacil (brofenail), flupropacil (brofenacil), isocmedil (isocil), lenacil (lenacil) and terfenadine (terbacil); 3-phenyluracil; urea herbicides such as thidiazuron (benzthiazuron), prosulfuron (cumyluron), cyclouron (cyclouron), chlorotoluron (dichloralurea), diflufenzopyr (diflufenzopyr), isoprocuron (isonororon), isolocuron (isouron), thiabendazole (methabenzthiazuron), tebuconazole (moniron), and cayraron (noruron); phenylurea herbicides such as white grass (anisuron), clodinafuron (buturon), chlorobromoron (chlorobromoron), chlororturon (chlorobiuron), chlortoluron (chlorotoluron), withered grass (chloroxuron), cymarone (daimuron), withered grass (difenoxuron), oxazolon (dimefuron), diuron (diuron), fenuron (fenuron), fluometuron (fluometuron), fluometuron (fluazuron), isoproturon (isoproturon), linuron (linuron), chlorbenzuron (methlyron), cymarone (methydyron), chromancon (metobenuron), bromouron (metoloburon), metoxuron (metoxuron), chloruron (monuron), monuron (monuron), fenflurron (fenoxuron), para-fluoxauron (para-fluoxauron), fluometuron (fluxuron), and cycuron (flurron); pyrimidylsulfonylurea herbicides such as sulfamuron (amidosulfuron), sulfosulfuron (azimsulfuron), bensulfuron (bensululfuron), chlorimuron (chlorimuron), cyclosulfamuron (cyclosulfamuron), ethoxysulfuron (ethosulfuron), flazasulfuron (flazasulfuron), flucetosulfuron (flucetosulfuron), flonicasulfuron (flupyrsulfuron), foramsulfuron (formamsulfuron), picosulfuron (halosulfuron), imazasulfuron (imazosulfuron), mesosulfuron (mesosulfuron), nicosulfuron (nicosulfuron), orthiosulfuron, cyclosulfaron (oxypsulfuron), cyclosulfamuron (oxasulfuron), primisulfuron (priron), pyrazosulfuron (pyrazosulfuron), pyrisulfuron (pyrazosulfuron), sulfosulfuron (sulfosulfuron), and sulfosulfuron (sulfosulfuron); triazinylsulfonylurea herbicides such as chlorsulfuron (chlorsulfuron), cinosulfuron (cinosulfuron), ethametsulfuron (ethametsulfuron), iodosulfuron (iodosulfuron), metsulfuron (metsulfuron), prosulfuron (prosulfuron), thifensulfuron (thifensulfuron), ethersulphonyl ureaTribenuron-methyl (triasulfuron), tribenuron-methyl (tribenuron), triflusulfuron-methyl (triflusulfuron), and triflusulfuron-methyl (tritosulfuron); thiadiazolyl urea herbicides such as buthiuron (buthiuron), thiadiazolyl (ethidimuron), tebuthiuron (tebuthiuron), thizafluron (thiafluuron) and thidiazuron (thiazuron); and unclassified herbicides such as acrolein (acrolein), allyl alcohol (allyl alcohol), pyraclonidine (azafenidin), benazolin (benazolin), bentazone (bentazone), benzobicyclon (benzobicyclon), tebuthiazole (buthiazole), calcium cyanamide (calcium cyanamide), cloxachlor (camfenchler), varek (chlorifenac), oat ester (chlorifenanprop), flurazone (chloriflufenazole), chlorfenapyr (chloriflufenanol), cinmethyliminon (cinmethyliclin), isoxazone (clofenane), Chlorambucil (CPMF), cresol (cresol), orthodichlorobenzene, dimercan (dipiperidate), metamifop (fenflurazone), fenthiflufen), fentrazone (fenflurazone), isoflurazone (clofenflurazone), cloflufenadine (clofenapyr), clofenadine (clofenadine), cloflufenapyr (clofenadine), clofenadine (clofenadine), clofenapyr (clofenadine), clofenadine (clofenapyr (clofenadine), clofenapyr (clofenapyr), clofenapyr (clofenac), clofenapyr (, Pentachlorophenol (pentachlorophenol), penconazole (pentoxazone), mercuric phenylacetate (phenylmercuric acetate), pinoxaden (pinoxaden), pinoxaden (prosulalin), pyriminostrobin (pyribenzoxim), pyriminostrobin (pyriftalid), imazaquin (quinoxaline), thiocyanobenzylamine (rhodethanil), azaheptafosinate (sulglycocalyxin), thiadiazolidine (thiazimin), imazapyr, trimetron (trimeturon), indanthrone (propindan), and indacak (tritac). The present invention contemplates selecting from the above list herbicides having a water solubility of about 1000ppm or less and formulating them as core-shell polyurea meso-capsules. Preferred herbicides are those having a water solubility of about 100ppm or less. More preferred herbicides are those having a water solubility of 10ppm or less. Herbicides can be selected based on the water solubility disclosed in the summary, such as the pesticide Manual watering Edition, (ISBN1-901396-14-2), the entire contents of which are incorporated herein by reference. The pesticideAdditional versions of e Manual are also used to select herbicides for inclusion in core-shell polyurea meso-capsules.

Many types and types of modifiers of plant physiology and structure are used in agriculture. Examples include cyprodinil (aminocyclopyramid), aminoethoxyvinylglycine, 6-benzylaminopurine, carvone (carvone), chlordane-methyl (chloroflurenol-methyl), chlormequat chloride (chloromequat chloride), asiatic acid (cloxyfonac), nootropic (4-CPA), cyclanilide (cyclanilide), cytokinin (cyclinins), daminozide (daminozide), diuron (dikegulac), ethephon (ethephon), fluorenol methyl ester (flurenol), flurprimidol (flurprimidol), forchlorfenuron (formolongiron), gibberellic acid (gibberellacids), gibberellin (gibberelins), trinin (ababenafide), indol-3-ylacetic acid, 4-indol-3-yl butyric acid, maleic anhydride (maleinimide), naphthylacetic acid (1- (naphthylacetic acid, 2-naphthylacetic acid, naphthylmethyl-1-naphthylacetic acid, naphthylacetic acid (naphthylmethyl-1-naphthylacetic acid), naphthylacetic acid (naphthylacetic acid-2-naphthylacetic acid, naphthylacetic acid-2-naphthylacetic acid (naphthylacetic acid, naphthylacetic acid-methyl-1-naphthylacetic acid, 2-naphthylacetic acid, 2-methyl-2-naphthylacetic acid, methylester, nitrophenolate, paclobutrazol (paclobutrazol), N-phenylphthalamic acid, prohexadione calcium, N-propyl dihydrojasmonate, thidiazuron, defoliation (tribufos), trinexapac-ethyl (trinexapac-ethyl), and uniconazole (uniconazol). The present invention contemplates selecting from the above list growth regulators having a water solubility of about 1000ppm or less and formulating them as core-shell polyurea meso-capsules. Preferred modifiers of plant physiology and structure are those having a water solubility of about 100ppm or less. More preferred modifiers of plant physiology and structure are those having a water solubility of 10ppm or less. Modifiers of plant physiology and structure can be selected based on The water solubility disclosed in The summary, such as The Pesticide Manual four analysis, (ISBN1-901396-14-2), which is incorporated herein by reference in its entirety. The additional version of The pesticide manual was also used to select modifiers for plant physiology and structure contained in core-shell polyurea meso-capsules.

The mesocapsule formulation of herbicides according to various embodiments may be used in combination with various herbicide safeners such as benoxacor (benoxacor), benfuresate (benthiocarb), brassinolide (brassinolide), cloquintocet (mexyl), chloranil (cyclotrinil), cyprosulfamide (cyclopropanamide), difenon (daimuron), dichlorpropenyl (dichlormid), dicyclonon (dicyclonon), proparathion (dimepiperate), ethoprophos (disulfoton), fenchlorazole (fenchlorazole-ethyl), fenclorim (fenclorim), sulfentrazone (fluxofenamide), fluxofenacet (flufenpyroximal), furazol (isoxafen-ethyl), fenclorim (fenpropiconazole), fentrazone (fluxoxime), fenpyrazone (MG-191), fenpyrazone (benzoxazole), fenpyrazone-ethyl, fenpyrazone-60, fenpyrazone (benzoxazide, fenpyrazone-ethyl-60, fenpyrazone (benzoxazide, fenpropidium-ethyl-60), and phenyl-ethyl-N-phenyl-ethyl-N, sulphonamide (29148). The level of active ingredient in the oil phase used to synthesize these formulations may range from about 0.001 wt.% to about 99 wt.%. The safeners can be encapsulated in the core-shell mesocapsule alone or in combination with a suitable herbicide or they can be added to the formulation medium outside the mesocapsule.

It is believed that the intermediate particles of the present invention may be used with many conventional formulation ingredients, such as aqueous or non-aqueous solvent media or diluents, which are suspended or slurried in the ingredient at concentrations of agriculturally active ingredient (for the formulation) of about 0.1% to about 30%. Conventional inactive or inert ingredients such as dispersants, thickeners, stickers, film formers, buffers, emulsifiers, antifreeze, dyes, stabilizers, solid carriers, and the like may also be included in the medium particle-containing formulation.

The formulation of the agricultural AI contained in the mesocapsule is considered to be useful for controlling insects, mites, plant diseases or weeds by providing and applying an agriculturally effective amount of the formulation to at least one of the following and the pests themselves: plants, plant leaves (plant foliage), flowers, stems, fruits, areas adjacent to plants, soil, seeds, germinating seeds (germinating seeds), roots, liquid and solid growth media, hydroponic growth solutions (hydroponic growth solutions) and surfaces to be treated. The mesocapsule formulation may be diluted in a suitable agricultural diluent such as water and applied by conventional methods including, but not limited to: 1) as a foliar spray application, preferably a volume sufficient to wet the foliage or treat the surface, 2) as a drench application to the soil, 3) application to the seed, 4) application by injection to the soil or a hydroponic growth medium, and 5) direct application to the pest. It is further contemplated that the mesocapsule formulation may be applied in admixture with conventional formulations of agricultural AI, plant nutrients, and modifiers of plant physiology and structure. Conventional formulations of agricultural AIs include solutions such as oil-in-water or water-in-oil emulsified stock solutions and dispersions, solutions of AIs in water, spray stock solutions of AIs as suspended particles having a volume average diameter of about 1 micron or more, wettable powder-form AIs having a volume average diameter of about 1 micron or more, and particle-form AIs having a volume average diameter of about 10 microns or more.

Examples

Particle size measurement

The particle size can be determined in particular by the known method of quasi-elastic light scattering (quasi-elastic light scattering). One device that can be used for this determination is a Brookhaven90Plus Nanoparticle SizeAnalyzer. The device provides a measure of the mean diameter by photon correlation spectroscopy (or PCS). Furthermore, a Malvern MasterSizer 2000 can also be used for particle size measurement. Alternatively, particle size may be measured by other known techniques including centrifugation or electron microscopy.

Synthesis of mesocapsules

Preparation of stock solutions of amino acids for the synthesis of mesocapsules

Stock solutions of glycine and lysine were prepared in the proportions listed in figure 1 prior to starting the individual reactions for synthesizing the exemplary mesocapsules disclosed in this application.

General Process for preparing some polyurea mesocapsules disclosed herein

The ingredients and amounts listed in FIG. 2 were used, as set forth belowTypical methods for synthesizing representative polyurea mesocapsule formulations. Briefly, fenbuconazole, benzyl acetate, hexadecane and PAPI^TM27 polymeric MDI (The Dow Chemical Co.) was added to a 60ml jar and mixed until homogeneous. The surfactant, water, and glycine solution were added to the jar and mixed for about 10 seconds with a hand-held biohomogen mixer (bioptic Products, Inc.) to produce a pre-emulsion (pre-emulsion). The jar was placed in an ice bath and the pre-emulsion was sonicated using a Branson 184V sonicator at 40% power for 5 minutes to produce the final emulsion. A crosslinker is added to the final emulsion to react with the polymeric MDI to produce the final product, except that the polymeric MDI is reacted with water in sample 4 for a period of time to produce the final product. The particle volume-average diameter of the meso-capsules in each sample was measured using a Brookhaven90Plus nanoparticle analyzer. Each of the mesocapsule formulations listed in figure 2 was prepared using these methods. As shown in fig. 2, the combination of the reaction mixtures was varied to produce different formulations disclosed herein. The formulations cited in fig. 4 were tested in plants to determine their cure and plant disease control properties.

Polyurea mesocapsule formulations containing fenbuconazole were prepared using the ingredients described herein in percent (wt%) relative to the overall formulation. The oil and water phases are prepared separately. In the oil phase, 5.07 wt% fenbuconazole, 14.33 wt% cyclohexanone, and 14.08 wt% aromatic 200 solvent were mixed to provide an initial solution. To this initial solution was added 1.31 wt% of Indopol^TMH15(INEOSOLigomers), 6.54% by weight of isophorone diisocyanate and 2.18% by weight of PAPI^TM27(the Dow Chemical Company). In the aqueous phase, 42.56 wt% of water, 0.10 wt% of Proxel^TMGXL (Arch UK biochides, Ltd.) was mixed with 0.44 wt% sodium lauryl sulfate. The aqueous phase was mixed with the oil phase while mixing with a Silverson L4RT High Shear Mixer/Emulsifier at 6000rpm for 2 minutes to prepare a pre-emulsion which was cooled in an ice/water bath. Then pass through(Avestin, Inc., 600-1000 bar) the pre-emulsion was uniformly processed at high pressure with ice/water cooling to prepare a stable medium-sized oil-in-water emulsion. While stirring, 0.87 wt% solid sodium lauryl sulfate was added followed by 1.31 wt% of a 44.4 wt% solution of L-lysine (dry weight basis) in water to react with the PAPI^TM27 and a 25 wt% solution of 2.20 wt% diethylenetriamine in diethylene glycol-water (0.76: 0.24, wt%/wt%) was added over 1 hour to react with isophorone diisocyanate. The mixture was stirred at room temperature for 4 hours to complete the formation of a polyurea shell. The formulation contains a fenbuconazole mesocapsule with particles having a volume average diameter of 313 nm.

The following procedure was used to prepare a medium capsule suspension of 328255-92-1, epoxiconazole, atrazine, fluroxypyr 1-methylheptyl, spinosad and indoxacarb. The oil and water phases were prepared separately using the ingredients and amounts shown in figure 3. The active ingredient was dissolved in a solvent/solvent mixture to make a 77% oil phase, followed by the addition of 3% ultrahydrophobe and 20% isocyanate (monomer 1). Adding Proxel to the aqueous phase^TMGXL (Arch UK Boicides, Ltd.; 0.1% total formulation) and sodium lauryl sulfate (3% oil phase). The aqueous and oil phases were combined and the mixture was magnetically stirred for 2 minutes to prepare a pre-emulsion, followed by the use of VibraCell^TM(Sonics &Materials, Inc.) sonicator sonicated at 750W and 24-25% amplitude in an ice/water bath (4-5 minutes) to prepare stable medium-sized oil-in-water emulsions. After stirring, polyamine (monomer 2) is added to react with isocyanate to form a polyurea shell. Each of the mesocapsule formulations listed in figure 3 was prepared using these methods. The formulations cited in figure 4 were tested in plants to determine their pest control properties.

Aqueous suspension concentrate formulations of 328255-92-1, epoxiconazole and indoxacarb were prepared by conventional methods using standard surfactants, wetting agents and milling equipment to provide samples 7, 9 and 13 shown in figure 4. These samples each had a volume mean diameter of about 2.5 μm.

Now it isReferring to fig. 4, the table includes a list of some of the formulations tested on wheat leaf blisters. The polyurea mesocapsules of fenbuconazole listed in figure 4 were tested to measure their healing and protective effects against wheat leaf blister disease caused by the fungus, i.e. triticum aestivum. Measurements were performed in an isolated group of wheat (cultivar Yuma) plants. Polyurea meso-capsules and Indar prepared according to various embodiments disclosed herein^TM75WP (a commercially available preparation of fenbuconazole) was compared. Each fenbuconazole formulation was diluted in water and tested at a ratio of 62.5, 20.8, 6.9, 2.3 and 0.77g active ingredient/Ha. Each test unit consisted of 8 to 10 wheat plants grown in 5cm x 5cm growth medium consisting of half of MetroMix and half of clay loam soil. Each treatment was repeated three times and treatments were randomized after chemical administration.

In the cure test, plants were inoculated for two days at the two-leaf stage of growth, after which the test and control formulations were applied to the plants. For the protection test, the test and control formulations were applied to the plants at the two-leaf stage of growth and inoculated with the fungus causing the leaf blister disease four days later. The treatment was applied using a Gen III Research Sprayer (tracksprayer) equipped with Spraying Systems8002E TeeJet nozzles and labeled to deliver 100L/Ha.

An inoculum of leaf pathogens, i.e. Leptosphaeria tritici, was prepared by harvesting conidia from freshly cracked and mature conidia vessels. Aqueous suspensions of conidia were prepared by counting several samples in a hemocytometer and then conditioning the suspension to contain about 1,000,000 conidia/ml. Inoculation was performed by applying a fine spray with a low pressure compressed air sprayer in a volume of about 200ml per 80 wheat. After inoculation, plants were inoculated for 24 hours in a dark humid room (22 ℃) of 99-100% relative humidity, then moved to a light humid room (20 ℃) of 99-100% relative humidity for an additional 48 hours, and then placed in a greenhouse set to 20 ℃ and 14 hour photoperiod for the remainder of the test. Plant growth was maintained by conventional application of dilute liquid fertilizer solutions.

Approximately 21 days after inoculation, wheat seedlings were evaluated for disease. The percent disease was assessed by visually estimating the percentage of leaves showing symptoms of disease. Plants inoculated first and then treated with chemicals two days later showed signs of healing. Plants treated first and then inoculated four days later showed signs of protection. The disease level measured on untreated plants in the cure test was about 82%. The disease level measured on untreated plants in the protection test was about 95%.

Referring now to fig. 5 and 6, the results of the various tests are as follows. In the cure test (fig. 5), all of the medium capsule formulations of fenbuconazole generally produced lower levels of disease when compared to the standard wettable powder formulation of fenbuconazole. Similarly, in the protection test (fig. 6), the medium capsule formulation of fenbuconazole produced lower levels of disease at one or more of the tested ratios when compared to the standard wettable powder formulation.

Referring now to fig. 4, the table includes a list of some of the formulations tested on wheat leaf rust. The polyurea mesocapsule formulations of 328255-92-1 and epoxiconazole listed in figure 4 were tested to measure their protective effect against wheat diseases known as leaf rust caused by the fungus Puccinia recondita f.sp.tritici. Measurements were performed in wheat (cultivar Yuma) plants. Polyurea meso-capsules prepared according to various embodiments disclosed herein were compared to conventional water-based granular formulations. Each formulation was diluted in water and tested at a ratio of 62.5, 20.8, 6.9, 2.3 and 0.77g active ingredient/Ha. Each test unit consisted of 8 to 10 wheat plants grown in 5cm x 5cm growth medium consisting of half of MetroMix and half of clay loam soil. Each treatment was repeated four times and treatments were randomized after chemical administration.

The test and control formulations were applied to the plants at the two-leaf stage of growth and inoculated with the leaf rust fungus four days later. The treatment was applied using a Gen III Research Sprayer (tracksprayer) equipped with Spraying Systems8002E TeeJet nozzles and labeled to deliver 100L/Ha.

An inoculum of leaf pathogens, i.e. Puccinia graminis, was prepared by harvesting of uredosporites from freshly cracked and mature pustules. The final aqueous suspension of the sporozoites was prepared using the following procedure. 0.1g of uredospore was added to three drops of Tween 20 and then mixed as a paste. To the paste was added 100ml of distilled water. The suspension yielded about 1,000,000 summer spores/ml. Inoculation was performed by applying a fine spray with a low pressure compressed air sprayer in a volume of about 300ml per 80 wheat. After inoculation, plants were inoculated in a dark humid room (22 ℃) of 99-100% relative humidity for 24 hours and then moved to a greenhouse set to 24 ℃ and 14 hour photoperiod for the remainder of the test. Plant growth was maintained by conventional application of dilute liquid fertilizer solutions.

Wheat seedlings were evaluated for disease approximately 7-8 days after inoculation. The percent disease was assessed by visual assessment of the percent disease of primary leaves. The results were averaged across each class. The tests were performed twice and the results of the individual tests were combined.

Referring now to fig. 7, the combined results of the two protection tests against leaf rust show that the medium capsule formulation of 328255-92-1 and epoxiconazole generally gives lower levels of disease when compared to the standard sprayable concentrate formulation.

Referring now to figure 4, the table includes a list of formulations tested against the herbicidal active ingredients atrazine and fluroxypyr 1-methylheptyl ester. Polyurea intermediate formulations prepared according to various embodiments disclosed herein were compared to conventional water-based granular formulations. The polyurea medium capsule formulations of atrazine and fluroxypyr 1-methylheptyl esters listed in figure 4 were tested using the methods described herein to measure their post-emergence herbicidal effect against a variety of dicot and monocot weed species.

A peat-based potting soil, Metro-mix 360, was used as the soil medium for this test. Metro-mix is a growth medium consisting of the following components: 35 to 45% specially processed coir pith of coconut husk (cocout coir pith), 10 to 20% horticulture grade vermiculite, 15 to 25% processed ash bark, 20 to 30% selected Canadian Sphagnum Peat Moss and proprietary nutrients and other ingredients. Several seeds of each species were planted in 10cm square pots and watered from the top twice daily. Cassia obtusifolia (Casia obtusifolia, CASOB), Abutilon theophrasti (ABUTH), Sida acuta (Sidsp), Setaria viridis (Setaria faberi, SETFA), Digitaria sativa (DIGSA), Kochia scoparia (KCHSC), Stellaria media (STEME), Polygonum convolvulus (POLCO), Chenopodium quinoa (Chenopodium album, CHEAL) and Ambrosia Artemisiifolia (AMBEL) were propagated in a greenhouse at a constant temperature of 26 to 28 ℃ and a relative humidity of 50 to 60%. Natural light was supplemented with 1000W metal halide overhead lamps with an average illumination of 500uE m-2s-1 Photosynthetically Active Radiation (PAR). The photoperiod was 16 hours. Plant material was watered at the top before treatment and sub-irrigate was irrigated after treatment.

A medium capsule formulation of atrazine was combined with a standard water dispersible granule commercially available as AAtrexnine-0^TM(Syngenta) for comparison. The two atrazine formulations were diluted in deionized water and applied at a ratio of 2240, 1120, 460 and 280g active ingredient/Ha. A medium capsule formulation of fluroxypyr 1-methylheptyl ester was combined with a standard commercially available fluroxypyr 1-methylheptyl ester formulation, Casino^TM25WP (Dow Agrosciences, LLC) for comparison. Two fluroxypyr 1-methylheptyl ester formulations were diluted in deionized water and applied at rates of 200, 100, 50, 25 and 12.5g active per Ha. The treatment was applied using a route nebulizer from Allen Machine Works. The nebulizer used an 8002E nozzle, a spray pressure of 262kPa and a speed of 1.5mph to deliver 187L/Ha. The height of the nozzle is 46cm higher than the plant canopy. The growth stage of each weed species ranges from 2 to 4 leaf stages. The treatment was repeated 3 times. After treatment the plants were returned to the greenhouse and proceeded throughout the experimentAnd (5) watering underground. Plant material was fertilized twice weekly with Hoagland's fertilizer solution. Visual assessment of the percent control was performed on a scale of 0 to 100% compared to untreated control plants (where 0 equals no control and 100 equals full control).

Referring now to figure 8, the post-emergent herbicide test results show that the medium capsule formulation of atrazine gave a higher level of control when compared to the standard water dispersible granule formulation.

Referring now to fig. 9, post-emergent herbicide test results show that intermediate capsule formulations of fluroxypyr 1-methylheptyl ester generally give higher levels of control when compared to standard wettable powder formulations.

Referring now to fig. 4, the table includes a list of formulations tested for the insecticidal active ingredient indoxacarb. The indoxacarb polyurea mesocapsule formulation listed in FIG. 4 (sample 12) was tested to measure separately against second instar diamondback moth larvae (diamondback moth: (diamondback moth) ((sample 12)Plutella xylostella) And male adult German cockroach (German cockroach) ((Blatella germanica) ) death and leaf disc or bait consumption. The indoxacarb polyurea mesocapsule formulation prepared according to the various embodiments disclosed herein was compared to an aqueous-based suspension concentrate formulation of indoxacarb (sample 13).

Each indoxacarb formulation was diluted in water for testing. The rates tested for death of diamondback moth and consumption of treated leaf discs were 0.15, 0.62, 2.5, 10, 20, 40, 80 and 160 ppm. The ratio tested for death of german cockroaches and treated water-based baits was 0.0001%, 0.001%, 0.01%, 0.1% and 1%, depending on the type of test (i.e., injection, topical application or ingestion of water-based baits).

For the diamondback moth test, cabbage plants were grown in the greenhouse and trimmed to 2 leaves per plant. The formulation was diluted with deionized water and 0.025% Silwet L-77 surfactant was added. The test ratios were 0.15, 0.62, 2.5, 10, 20, 40, 80 and 160 ppm. Cabbage plants were sprayed using a path sprayer delivering a spray volume of about 200 liters/hectare. After the treated cabbage plants were dried, leaf discs were taken from each sprayed plant and 1 leaf disc was placed in each well of a 32-well bioassay tray containing a thin layer of agar at the bottom of the well. Three second instar diamondback moth larvae were placed in the center of each leaf disc and the discs were covered with a plastic lid. Data were collected on mortality and% leaf disc consumption at various time intervals (1-4 days).

Referring now to fig. 10 and 11, the diamondback moth test results are as follows. Differences in favor of medium capsule formulations in polyurea were noted at the ratios of 2.5 and 10 ppm.

At the 2.5ppm rate, the polyurea medium capsule formulation treatment reduced the leaf disc consumption of the treatment by 28-46% compared to the water-based suspension concentrate formulation treatment at 3 and 4 days after treatment, respectively. At the 10ppm rate, the polyurea medium capsule formulation treatment reduced leaf disc consumption of the treatment by 18-37% compared to the water-based suspension concentrate formulation treatment at 3 and 4 days after treatment, respectively. The reduction in leaf disc consumption for this treatment indicates that the mid-capsule formulation of indoxacarb polyurea is better able to protect the treated cabbage plants from feeding by diamondback moth larvae than the aqueous-based suspension concentrate formulation of indoxacarb.

At a rate of 10ppm 4 days after treatment, the polyurea mesocapsule formulation treatment increased the amount of diamondback moth larvae mortality by 19% compared to the water-based suspension concentrate formulation treatment. This increased mortality rate indicates that the indoxacarb polyurea intermediate formulation is able to better enhance the toxic activity at the 10ppm rate compared to the water-based suspension concentrate formulation of indoxacarb.

Three types of tests were performed on german cockroaches, namely injection, topical application and ingestion bioassay. For the injection test, 10 male adult german cockroaches from each treatment group were injected with 1 μ l of each treatment solution. The treatment solution was prepared by diluting the indoxacarb formulation in Milli-Q purified water to yield indoxacarb concentrations of 0.001%, 0.01%, 0.1% and 1%. Injected cockroaches were fixed in 100x25mm petri dishes containing food and water and placed in a laboratory controlled climate chamber at 26 ℃ and 60% relative humidity. Injected cockroaches were checked daily for 7 days and the number of deaths recorded. The food and water are refreshed as required.

Referring now to fig. 12, the results of the german cockroach injection test for percent mortality are as follows, where differences in favor of a medium formulation in polyurea are noted. Differences between the tested formulations were noted at a rate of 0.01%.

The polyurea mesocapsule formulation treatment increased the amount of german cockroach mortality by 20-30% compared to the water-based suspension concentrate formulation treatment at an indoxacarb concentration of 0.01% 2-7 days after treatment. This increased mortality rate indicates that indoxacarb in the polyurea medium capsule formulation had better efficacy at a rate of 0.01% compared to the suspension concentrate formulation of indoxacarb.

In a topical bioassay, the formulations were tested for mortality expression when diluted water-based formulations were applied directly to german cockroaches. For the topical test, 10 adult male german cockroaches from each treatment group received 1ul of each treatment solution applied topically to the forebreast back plate via syringe. Before and after treatment cockroaches were treated with CO₂And (6) anaesthetizing. The formulations were tested in Milli-Q-purified water dilutions (giving indoxacarb concentrations of 0.001%, 0.01%, 0.1% and 1%). Treated cockroaches were fixed in 60x15mm petri dishes (one cockroach/dish) containing food and water and placed in a laboratory controlled climate chamber. Treated cockroaches were checked daily for 7 days and the number of deaths recorded. The food and water are refreshed as required.

Referring now to fig. 13, the results of the german cockroach topical test for percent mortality are as follows, where differences in favor of a medium formulation in polyurea are noted. Differences between the tested formulations were noted only at the rate of 0.1%.

The polyurea mesocapsule formulation treatment increased the amount of german cockroach mortality by 20-40% compared to the water-based suspension concentrate formulation treatment at a rate of 0.1% for 1-7 days after treatment. This increased mortality rate indicates that the indoxacarb polyurea mesocapsule formulation is better able to enhance the toxic activity at a rate of 0.1% compared to the indoxacarb suspension concentrate formulation. In addition, the polyurea mesocapsule formulation treatment also increased the mortality rate compared to the aqueous-based suspension concentrate formulation of indoxacarb.

When the water-based dilution was ingested by a german cockroach, the ingestion bioassay was used to test the mortality expression of the formulation. For feeding tests, 10 adult male German cockroaches treated every 5 replicates were placed in a place with a small cardboard house (cardboard) and a single Purina^TMDog food in 100x25mm petri dishes. Cockroaches were rendered water impermeable for 3 days before exposure to water-based treated bait. Exposure to bait for water-based treatment was a no-selection exposure, with 30 minutes of exposure on days 1-3, with 200ul bait provided on the first day and 150ul bait provided on the second and third days. The water bait provided on the first day was removed and replaced with new water bait on days 2 and 3. After 3 days exposure to the water bait, the cockroaches were provided with untreated water and food for the next 11 days. The formulations were diluted in deionized water to give indoxacarb concentrations of 0.0001%, 0.001%, 0.01% and 0.1%. Treated cockroaches were checked daily for 15 days and the number of deaths recorded. The consumption of water bait was recorded 3 days after this exposure occurred.

There was no difference between the formulations tested for percent mortality, with the polyurea medium formulation being better than the aqueous-based suspension concentrate formulation of indoxacarb. However, at the 0.1% ratio, differences in bait consumption data were noted. Referring now to fig. 14, the german cockroach ingestion test results are as follows: mg consumption at a rate of 0.1%.

The polyurea medium capsule formulation bait treatment reduced bait consumption of 86mg of german cockroach at a rate of 0.1% 1 day after treatment compared to the water-based suspension concentrate formulation bait treatment. At an indoxacarb concentration of 0.1% in the polyurea mesocapsule formulation, this reduced consumption of indoxacarb bait indicates a faster reduction/termination of feeding on day 1 compared to the aqueous-based suspension concentrate formulation of indoxacarb.

While the novel technology has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character, it being understood that only the preferred embodiments have been shown and described and that all changes and modifications that come within the spirit of the novel technology are desired to be protected. Also, while the novel techniques are illustrated using specific embodiments, theoretical demonstrations, explanations and examples, these illustrations and the accompanying discussion should in no way be construed as limiting the technique. The contents of all patents, patent applications, and textual references, scientific papers, publications, and the like, cited in this application are hereby incorporated by reference.

Claims (22)

1. A composition for delivering an agriculturally active ingredient, comprising:

a mesocapsule having a polymeric shell with a hydrophilic outer surface, wherein the polymeric shell is comprised of polyurea; and

a poorly water soluble agriculturally active ingredient having a solubility in water of less than 1000ppm, wherein the poorly water soluble agriculturally active ingredient is at least partially contained in the polymeric shell, the mesocapsule having a volume-average particle diameter between 30nm and 500 nm;

wherein the shell comprises hydrophilic functional groups and at least some of the hydrophilic functional groups are in contact with water, wherein the hydrophilic functional groups on the surface of the shell are carboxylate groups.

2. The composition of claim 1, wherein the polyurea is a reaction product of at least one polyisocyanate and at least one polyamine.

3. The composition of claim 1, wherein the mesocapsule has a volume average diameter in the range of 50nm to 300 nm.

4. The composition of claim 1, wherein the active ingredient has a solubility in water of 1,000 parts per million or less.

5. A method of controlling insects, mites, plant diseases or weeds comprising the steps of:

providing a formulation comprising the composition of claim 1, and

applying an agriculturally effective amount of the formulation to at least one of: plants, plant leaves, flowers, stems, fruits, areas adjacent to plants, soil, seeds, germinated seeds, roots, liquid and solid growth media, hydroponic growth solutions, treated surfaces; as well as to the pests themselves.

6. A method of controlling insects, plant diseases or weeds comprising the steps of:

providing a formulation comprising the composition of claim 1, and

applying an agriculturally effective amount of the formulation mixed with a conventional formulation of one or more agriculturally active ingredients or nutrients to at least one of: plants, plant leaves, flowers, stems, fruits, areas adjacent to plants, soil, seeds, germinated seeds, roots, liquid and solid growth media, hydroponic growth solutions, treated surfaces; as well as to the pests themselves.

7. A method of synthesizing the composition of claim 1, comprising the steps of:

providing an oil phase comprising at least one agriculturally active ingredient and one or more polymer precursors capable of reacting to form a shell, the agriculturally active ingredient having a solubility in water of less than 1000 ppm;

providing an aqueous phase comprising water and at least one cross-linking agent;

adding a surfactant to at least one of the aqueous phase and the oil phase;

mixing the oil phase and the aqueous phase under shear conditions sufficient to form an emulsion, wherein the emulsion comprises less than 1 wt% surfactant relative to the oil phase; and

reacting with the cross-linking agent to form a polymeric shell that at least partially encapsulates the agriculturally active ingredient in mesocapsules having a volume-average diameter between 30nm and 500 nm.

8. The method of claim 7, wherein the polymer precursor comprises a polyisocyanate or a siloxane.

9. The method of claim 7, wherein the crosslinking agent is selected from the group consisting of water, amino acids, resorcinol, melamine, formaldehyde, urea, guanidine compounds, diamines, polyamines, polyamidines, and mixtures thereof.

10. The method of claim 7, wherein the polymer precursor comprises at least one polyisocyanate.

11. The method of claim 7, wherein the surfactant is sodium lauryl sulfate.

12. The method of claim 7, wherein the shearing sufficient to form an emulsion is achieved by sonication or high pressure homogenization.

13. The method of claim 9, wherein the crosslinking agent is selected from the group consisting of water, ethylene diamine, diethylene triamine, triethylene tetramine, and L-lysine.

14. The method of claim 7, wherein the oil phase further comprises between 1 wt.% to 90 wt.% of a solvent that substantially dissolves the agriculturally active ingredient.

15. The method of claim 14, wherein the solvent is benzyl acetate, cyclohexanone, aromatic solvents, acetophenone, seed oil, esters of seed oil, paraffinic oils, and mixtures thereof.

16. The method of claim 7, wherein the oil phase further comprises between 0.5 wt.% to 10 wt.% of an ultrahydrophobe.

17. The method of claim 16 wherein the superhydrophobic is hexadecane or polyisobutylene.

18. The method of claim 7, wherein the agriculturally active ingredient is selected from the group consisting of fungicides, insecticides, miticides, herbicides, safeners and modifiers of plant physiology or structure.

19. The method of claim 7, wherein the oil phase of the mesocapsule comprises 1 to 90 wt.% agriculturally active ingredient.

20. A method of synthesizing the composition of claim 1, comprising the steps of:

providing an oil phase comprising at least one agriculturally active ingredient and at least one polyisocyanate, the agriculturally active ingredient having a solubility in water of less than 1000 ppm;

providing an aqueous phase, wherein the aqueous phase comprises water and an amino acid having at least one hydrophilic functional group;

mixing the oil phase and the aqueous phase to form an emulsion, wherein the emulsion comprises less than 1% by weight of surfactant relative to the oil phase; and

reacting a polyisocyanate with a cross-linking agent selected from ethylenediamine, diethylenetriamine, triethylenetetramine and L-lysine to form a polyurea shell at least partially encapsulating an herbicide, insecticide or fungicide in a surfactant-free mesocapsule having a volume average diameter between 30nm and 500 nm.

21. The method of claim 20, wherein the hydrophilic functional group is a carboxylate group.

22. The method of claim 20, wherein said amino acid is selected from the group consisting of lysine and glycine.