JP2023510868A - Non-Toxic Coating Concentrate for Agricultural Applications - Google Patents

Abstract

The present invention encompasses non-toxic agricultural formulations of concentrated liquid suspensions comprising drying oil and suspended particulate material, and also encompasses aqueous formulations comprising concentrated liquid suspensions and agricultural treatments. The invention further includes methods of treating agricultural targets.

Description

RELATED APPLICATIONS This application claims the benefit of Provisional Application No. 62/961,055, filed January 14, 2020. The entire contents of each of the above applications are hereby incorporated by reference.

FIELD OF THE APPLICATION The present application relates to coating formulations for agricultural applications.

BACKGROUND Agrochemicals used as fertilizers, pesticides, herbicides, etc. are susceptible to erosion and leaching from treated soils and plants. For example, fertilizers applied to fields can suffer surface runoff or loss caused by rapid watering, rain or other water exposure. As another example, chemicals applied to the surface of leaves tend to disappear from treated plants due to decay. As yet another example, previously appearing agents (i.e. those agents applied to the soil prior to plant or weed germination) need to stay where they are applied for a certain amount of time, whereas the plant and/or Or weeds are sprouting. Loss of previously-appearing drug by microbial activity, photodegradation, chemical degradation, surface runoff due to water exposure, etc. is undesirable during the germination period, keeping drug in the top 1 or 2 inches of soil during this period. is advantageous. These problems arise from agents that need to act over an extended period of time to achieve their desired effect, as opposed to agents that exert their effect immediately, such as contact-killing pesticides. It is especially important for optimizing properties. Without improved retention properties, agrochemicals can be washed away by rain or wiped off very easily.

As an example, pre-harvest fruit/nut/vegetable protection is of utmost importance. Fruits or vegetables that grow on trees and vines and shrubs are susceptible to pest infestation and their soft skins are susceptible to sunburn, reducing the overall yield of these products. In new farming practices, there are efforts to reduce or eliminate the amount of synthetic pesticides used, especially on fruits or vegetables whose skins are edible. To help overcome pest problems, these fruits or vegetables are often sprayed with particles that can form a barrier layer to prevent pest infestation and prevent sunburn. In some other fruits such as cherries and tomatoes, even the accumulation of water in the fruit stem leads to water uptake, to osmotic imbalances inside the fruit, and to unsightly cracking of the fruit skin. . To prevent this, there is a need for breathable, harmless, rainfast barrier coatings. There remains a need in the art for non-toxic alternatives to the use of pesticides to protect agricultural materials from insects, fungi, animals, drought conditions, air pollution damage and sun damage. Additionally, to improve herbicide performance by (1) enhanced retention of the active ingredient in the topsoil, (2) prevention of leaching of the active ingredient (i.e., sustained release), and (3) protection of the herbicide against photodegradation. There is a need for Due to the high value of these crops and the demand for organic produce, there is a special need for pre-harvest fruit/nut/vegetable protection.

For successful pest management, conventional pesticides may be selected based on a variety of factors such as pest species and crop-specific management programs. Due to the biological and behavioral complexity of pest species, pre-harvest protection with a range of properties such that performance parameters can be tailored to control specific pests on specific crops should be provided. For example, for coatings applied to plant surfaces, it is advantageous to optimize the durability and flexibility of the coating for use with particular plant surfaces. Furthermore, although there are coatings that can be applied to plant surfaces, these coatings can be targeted to the feeding behavior, reproductive activity and life cycle of specific pests, e.g. There remains a need in the art to optimize for time. For a given pest species, an optimized coating regimen is tailored to the habits of the pest species and its interaction with its host. Therefore, a range of pest inhibition mechanisms, along with options for customization, may be desirable for coatings. For example, a coating can cover an agricultural surface and render it imperceptible to certain pests. As another example, coatings can alter the natural habits of pests toward their hosts by interfering with the pest's ingestion, reproduction or motility. As yet another example, if a pest can be induced to ingest a coating, the ingested coating material can interfere with its metabolism or digestion, thus compromising the pest's natural developmental or reproductive processes. Given the type of pest, the behavior of the pest to control and the host that harbors the pest, it is desirable to provide coating formulations with a variety of properties that can be selected given the particular pest-host interaction.

It is also desirable that the coating formulation be combinable with other treatment modalities, either through a single application of the formulation or through treatment protocols combined with multiple applications of the same or different formulations. A new generation of herbicides and other such agricultural treatments are of biological origin. For example, there are biological control agents that require delivery to agricultural targets, where retention and/or controlled release of these agents in the immediate vicinity of the agricultural target is desirable. As used herein, the term "agricultural target" refers to leaves, fruits, vegetables, seeds or pericarp, stems, post-harvest agricultural products, and soil, agricultural growth media, or other targets understood by those skilled in the art. selected from the group consisting of agricultural substances; Desirably, delivery formulations that provide improved retention properties are suitable for use with biological control agents.

Herbicides, insecticides, fungicides, plant growth regulators, insect pheromones, nutrients and other agricultural treatments are also advantageously used in direct spraying of fruits or vegetables and plants. For example, cocoa pods can suffer from "black pod" disease and can be treated by spraying the pods with both fungicides and insecticides. Black pod is a disease of plants caused by oomycetes of the genus Phytophthora, such as Phytophthora infestans, the pathogen that caused poor potato crops. Enhanced retention of therapeutic agents on targets (eg, cocoa pods) can improve their potency and improve the efficiency of treatment protocols. Naturally derived coatings on cocoa pods could create a physical barrier (ie, a barrier coating composition formed, for example, as a film) to deter pests and reduce or eliminate the need for additional treatments.

Agricultural treatments (pesticides, fertilizers, plant growth regulators, etc.) are expensive and can cause environmental damage if misused. There is a need for materials and methods to improve the efficiency and costs associated with the use of agricultural treatments, or to reduce or eliminate the need for agricultural treatments.

SUMMARY In an aspect, disclosed herein is a non-toxic agricultural formulation of a concentrated liquid suspension comprising an organic phase and suspended particulate material. In embodiments, the formulation forms a cured coating on the agricultural target. In embodiments, the cure is water resistant, resistant to rubbing or rain resistant. In embodiments, the cured coating retains suspended particulate matter on the agricultural target when subjected to adverse conditions, where the adverse conditions include rainfall, friction, wind, water exposure and secondary agricultural use. It can be conditions such as treatment. In embodiments, the formulation is stable against phase separation. In embodiments, the formulations contain food grade ingredients, or contain organically produced ingredients, or contain ingredients that are generally recognized as safe. In embodiments, the formulation consists essentially of organically produced ingredients or consists essentially of ingredients generally recognized as safe. In embodiments, a concentrated liquid suspension contains only non-aqueous liquids. The organic phase of the formulation can be about 40-99% by weight of the formulation. The organic phase may comprise drying oils, which include linseed oil, raw linseed oil, boiled linseed oil, castor oil, castor oil glycidyl ether, tung oil, poppy seed oil, grape seed oil, safflower oil, linoleic acid, linolenic. It may be selected from the group consisting of acid, oleic acid, salicornia oil, sunflower oil, evening primrose oil, perilla oil, soybean oil, corn/corn oil, canola/rapeseed oil and walnut oil. In embodiments, the drying oil comprises alpha-linolenic acid, linoleic acid, or a combination thereof.

In embodiments, the drying oil is a naturally occurring mixture of one or more acylglycerols that can undergo spontaneous conversion from a liquid to a solid state upon exposure to oxygen; Contains two or more different acylglycerols. In embodiments, spontaneous conversion is characterized by the occurrence of crosslinks between double bonds on one or more acylglycerols; in embodiments, spontaneous conversion results in formation of a polymer network.

In embodiments, the organic phase of the formulation comprises a first oil and a second oil mixed together to form a mixture, wherein at least one of the first oil and the second oil is a drying oil. and the formulation may have one or more physical properties that are different from those of the first oil and the second oil, the physical properties being the glass transition temperature of the cured film, the curing solubility of small molecules in the cured film, permeability of the cured film to small molecules, film stiffness, film viscosity, film dry time and durability. In embodiments, the formulation may have improved pest control properties when compared to the pest control properties of a control formulation whose organic phase comprises a single drying oil, wherein the pest control properties are measured in terms of pest survival time. reduction of pest fertility, deterrence of pest food intake, deterrence of pest reproduction and reduction of plant damage. In embodiments, the organic phase of the formulation comprises alpha-linolenic acid or linoleic acid. In embodiments, the first oil and the second oil are both drying oils and the first oil and the second oil can have different degrees of unsaturation. In embodiments, the mixture comprises at least one additional oil; the at least one additional oil may be a drying oil, the at least one oil being linseed oil, raw linseed oil, boiled linseed oil, castor oil, castor oil glycidyl. Ether, tung oil, poppy seed oil, grape seed oil, safflower oil, linoleic acid, linolenic acid, oleic acid, poppy seed oil, sunflower oil, evening primrose oil, perilla oil, soybean oil, corn/corn oil, canola/rapeseed oil and walnut oil. can be selected from the group consisting of In embodiments, the mixture further comprises a diluent, which may be selected from the group consisting of mineral oil, petroleum distillates, alcohols, terpenes and glycols.

In embodiments, the suspended particulate is about 0.5-50% of the formulation. Suspended particulates can be permanently suspended in the organic phase or readily resuspended in the organic phase. In embodiments, the suspended particulate matter is selected from the group consisting of clay minerals and organically modified minerals. Clay minerals may be selected from the group consisting of kaolin clays, smectite clays, illite clays, chlorite clays, meerschaum and attapulgite. In embodiments, the clay mineral can be bentonite clay. In embodiments, the organically modified mineral is a clay mineral, and the organically modified mineral is fatty acids, fatty amines, fatty amides, fatty esters, fatty amine quats, quaternary amine surfactants. , cetyltrimethylammonium bromide, fatty alcohols, decyl alcohol, dodecyl alcohol, linseed oil, alkenyl succinic anhydrides, styrene maleic anhydride copolymers, colophony, rosin, chitosan and castor oil derivatives. can be modified by In embodiments, the formulation further comprises pesticides, herbicides, beneficial bacteria, beneficial fungi, plant growth regulators, pheromones, sunscreens, biopesticides or nutrients. In embodiments, the formulation further comprises a botanical extract or botanical oil. In embodiments, the formulation further comprises additional particulate material. In embodiments, the additional particulate material is talc, calcium carbonate, gypsum, magnesium silicate, calcium silicate, corn starch, cellulose fibers, psyllium fibers, ethylene bisstearamide, microcrystalline cellulose, stearic acid, oleic acid, waxes, It may be selected from the group consisting of carnauba wax and beeswax, or the particulate material may be kaolin or titanium dioxide. In embodiments, the formulation further comprises a surfactant. Surfactants may be selected from the group consisting of anionic, cationic, nonionic, biodegradable, food grade and organic surfactants. In embodiments, the formulation further comprises an adjuvant selected from the group consisting of cellulose derivatives, polylactic acid, polyglycolic acid and polylactic-glycolic acid. In embodiments, the formulation further comprises a salt or curing additive.

In an aspect, further disclosed is an aqueous formulation comprising the concentrated liquid suspension described above and an agricultural treatment. Also disclosed in an aspect is a coated agricultural treatment comprising an agricultural treatment and the concentrated liquid suspension described above, wherein the concentrated liquid suspension is applied to the agricultural treatment as a coating. Also disclosed herein are aspects of plant products having surfaces treated with the formulations described above.

In an embodiment, an agricultural method comprising providing an agricultural formulation of a concentrated liquid suspension comprising an organic phase and suspended particulate matter, and applying the agricultural formulation to an agricultural target, thereby treating the agricultural target. Methods of treating targets are disclosed herein. In embodiments, the method protects agricultural targets from pests or from environmental damage. In embodiments, the treatment comprises non-lethally modifying the behavior of the pest. In embodiments, the agricultural target is a soil surface or an agricultural growing medium. In embodiments, the soil surface has a beneficial effect selected from the group consisting of erosion control, nutrient retention, agricultural treatment retention, dust control, delivery of beneficial microorganisms, delivery of biopesticides or enhanced growth of beneficial microorganisms. is processed to produce In embodiments, the agricultural target is a plant surface. The plant surface may be selected from the group consisting of leaves, fruits, seeds, berries, nuts, berries, stems and roots. The plant surface can be a harvested product surface for harvested products. In embodiments, the agricultural target is an agricultural growth medium. In embodiments, the agricultural formulation is applied to agricultural targets at a dosage rate of from about 1 to about 200 lb. of formulation per acre of crop. In embodiments, the agricultural formulation is diluted with a solvent prior to the step of applying the formulation.

Further disclosed herein is a method for reducing spore-based transmission of a fungal plant disease by treating a plant surface with a formulation as described above, wherein the fungal plant disease Caused by the causative fungal spores, contact with the formulation impairs the ability of the disease-causing fungal spores to become airborne, thereby reducing spore-based transmission of fungal plant diseases. Also disclosed herein is a method of reducing spore-based transmission of a fungal plant disease by applying a formulation as described above to a plant surface, wherein the fungal plant disease is caused by disease-causing fungal spores. Contact with the induced formulation impairs the ability of disease-causing fungal spores to germinate on plant surfaces, thereby reducing spore-based transmission of fungal plant diseases. Also disclosed herein are methods of treating plant infections by applying the formulations described above to the surfaces of plants in need of treatment of plant infections. Such treatment methods include preventing infection.

Brief description of the drawing
FIG. 1 is a graph showing rolling ball distance and alkene conversion as a function of time. FIG. 2 is a graph showing the force on the probe required to dislocate the film versus probe dislocation as measured on a cured linseed oil film. FIG. 3 is a graph showing the distance traveled in the rolling ball test as a function of curing time for mixtures of linseed and soybean oil. FIG. 4 is a graph showing elastic modulus for films as a function of % soybean oil in a mixture of linseed and soybean oil. FIG. 5 is a graph showing the distance traveled in the rolling ball test as a function of curing time for linseed oil and mixtures of different vegetable oils.

DETAILED DESCRIPTION The present disclosure relates to non-toxic agricultural formulations in the form of concentrated liquid suspensions, wherein the formulations are capable of forming hardened coatings on agricultural targets. Concentrated liquid suspensions of non-toxic agricultural formulations can be diluted in water to make solutions of the agricultural formulation for application by spraying, brushing, dipping, spraying or irrigating. Agricultural preparations can be applied to plant surfaces (leaves, fruits, seeds, berries, nuts, glumes, stems, roots, etc.), soil or agricultural growth media and harvested fruits, vegetables, seeds, glumes, stems, roots, etc. It can be applied to a variety of agricultural materials or targets, such as agricultural surfaces containing processed plant products. As used herein, a plant surface is the surface of a plant, whether pre-harvest or post-harvest; a plant product is a post-harvest agricultural product. Agricultural formulations and methods for treating agricultural substances and targets are disclosed herein.

A. Agricultural Formulations In embodiments, non-toxic agricultural formulations include vegetable oils containing fatty acid or fatty ester functional groups with at least one degree of unsaturation, such as monounsaturated and polyunsaturated fats. In embodiments, vegetable oils contain unsaturated fatty groups such as alpha-linolenic acid, linoleic acid and oleic acid, where these fatty groups are fatty acids, fatty acid salts, fatty esters, triglycerides, diglycerides, monoglycerides or fatty amides. can be in the form In embodiments, the non-toxic agricultural formulation is a free fatty acid or an ester, salt, or amide form of a fatty acid comprising an acyl chain with sufficient unsaturation to produce at least two carbon-carbon double bonds per molecule. Contains vegetable oils containing fatty acids. In embodiments, fatty acids include unsaturated fatty acids such as alpha-linolenic acid, linoleic acid and oleic acid.

In embodiments, the vegetable oil is a drying oil. As used herein, the term "drying oil" can refer to a self-crosslinked oil consisting of glycerol triesters of fatty acids or a vegetable oil as described herein. Alternatively, as used herein, the term "drying oil" refers to naturally occurring mixtures of glycerol esters of fatty acids (acylglycerols) in which the oil spontaneously converts from a liquid to a solid state upon exposure to oxygen. I get it. This transformation occurs through the generation of cross-links between double bonds on different acylglycerols, resulting in the formation of a polymer network. As such, drying oils are characterized by high concentrations of molecules with at least two degrees of unsaturation, such as polyunsaturated acylglycerols. By way of example, drying oils may be characterized by high levels of polyunsaturated fatty acids, particularly alpha-linolenic acid. Examples of drying oils include linseed oil (i.e. flax seed oils such as boiled linseed oil (BLO) and raw linseed oil (RLO)), tung oil, poppy seed oil, canola/rapeseed oil, sunflower oil, safflower oil. , soybean oil, fish oil, hemp oil, corn/corn oil, dehydrated castor oil, tall oil, perilla oil and walnut oil. When cross-linking occurs between the double bonds of adjacent chains in the presence of atmospheric oxygen, a polymer network is formed and the oil hardens or "dries out". Since drying oils themselves form tough hydrophobic films, they can be used to coat surfaces or particles to repel moisture. As disclosed herein, the drying oil may also be used so that the particulate material does not separate from the drying oil (a "durable" suspension) or the particulate material is easily separated from the drying oil if it is first completely separated. The particulate material can be suspended in any of them so that it is resuspended in a liquid. In one aspect, acylglycerols include linolein. As an example, linseed (or linseed) oil is a drying oil that is derived from the dried, ripe seeds of linseed. It contains three important fatty acids, linoleic acid, linolenic acid and oleic acid, which are preferentially formed as glycerides (particularly triglycerides). Flaxseed oil contains a significant amount of triglyceridelinolein formed as acylglycerols by three molecules of linoleic acid. Small amounts of palmitic acid and arachidonic acid are also found in linseed oil as free fatty acids.

In embodiments, the oil phase of the concentrated liquid suspension is dried oil, wax, cellulose derivative, linseed oil, boiled linseed oil, castor oil, castor oil glycidyl ether, magnesium stearate, linseed oil, tung oil, poppy seed oil, grape Seed oil, safflower oil, linoleic acid, linolenic acid, oleic acid, capsicum oil, sunflower oil, corn oil, hemp oil, wheat germ oil, cottonseed oil, soybean oil, sesame oil, canola oil, evening primrose oil, perilla oil, walnut oil, etc. include. In embodiments, the oil phase of the concentrated liquid suspension contains mineral oil, petroleum distillates, alcohols, terpenes or glycols such as glycerin or to improve fluid handling properties or to improve dry film flexibility. Contains diluents such as propylene glycol. Preferably, the oil phase comprises alpha-linolenic acid, linoleic acid or a combination thereof.

In embodiments, two or more drying oils with different degrees of unsaturation can be mixed together to form an oil phase that develops different physical properties than those found in any one of the constituent oils. resulting in a film that By way of example, properties such as duration of wetting, drying profile, viscosity or film firmness can be adjusted by combining two or more drying oils. Other properties, such as the glass transition temperature of the cured film, the solubility of small molecules in the cured film, the permeability of the cured film to small molecules, etc., can be determined by combining two or more drying oils and mixing can be adjusted by curing to form a film. Without being bound by theory, it is understood that these properties of oil mixtures can be attributed to the chemical properties of unsaturated oils when exposed to ambient conditions: when exposed to light and/or oxygen , the unsaturated bonds in the oil can become reactive and subsequently form intermolecular bonds or crosslinks. This cross-linking behavior involving the oils in the oil mixture can affect the physical properties of the film that the mixture forms when the film dries or hardens on the plant surface. For example, oils with low concentrations of unsaturated bonds typically exhibit a weaker ability to form films; in contrast, oils with higher concentrations of unsaturated bonds have a higher affinity for forming films. indicates Thus, by using a formula chassis, different drying oils with different unsaturation profiles can be measured and mixed, resulting in a formulation with a range of desirable properties for pest control. By selecting oils for a given mixture and varying the amount of constituent oils in the mixture, tuning the physical properties of the mixture when it is used as the oil phase of a concentrated liquid suspension , adjusting and customizing mechanisms are provided. In embodiments, unsaturated oils used alone to form the oil phase of the concentrated liquid suspension may also be mixed together to form the oil phase. Two or more unsaturated oils can be used in proportions that take advantage of the properties of each. For example, linseed oil, boiled linseed oil, castor oil, castor oil glycidyl ether, tung oil, poppy seed oil, grape seed oil, safflower oil, linoleic acid, linolenic acid, oleic acid, poppy seed oil, sunflower oil, corn oil, hemp oil, Various drying oils can be used, such as wheat germ oil, cottonseed oil, soybean oil, sesame oil, canola oil, evening primrose oil, perilla oil, walnut oil, and the like. Preferably, the oil phase comprises alpha-linolenic acid, linoleic acid or a combination thereof. In one aspect, the first oil is linseed oil (such as boiled linseed oil) and the second oil is tung oil, poppy seed oil, grape seed oil, safflower oil, linoleic acid, linolenic acid, oleic acid, poppy seed oil. oil, sunflower oil, corn oil, hemp oil, wheat germ oil, cottonseed oil, soybean oil, sesame oil, canola oil, evening primrose oil, perilla oil, walnut oil. In a further aspect, the first oil is linseed oil and the second oil is tung oil, poppy seed oil, grape seed oil, safflower oil, poppy seed oil, evening primrose oil, perilla oil, walnut oil, soybean oil and canola oil. selected from the group consisting of In a still further aspect, the first oil is linseed oil and the second oil consists of tung oil, poppy seed oil, grape seed oil, safflower oil, poppy seed oil, evening primrose oil, perilla oil, walnut oil and soybean oil. Selected from the group.

In embodiments, non-drying oils may be used in addition to the drying oils described herein. In embodiments, the oil mixture comprises at least one drying oil and one additional oil, wherein the additional oil is miscible with the drying oil. Additional oils can be naturally occurring mixtures of such constituents such as monoacylglycerides, diacylglycerides, triacylglycerides, vegetable oils, or artificially prepared mixtures of these constituents.

It has been unexpectedly discovered that oil phases formed from oil mixtures have certain advantageous properties compared to oil phases formed from single mixtures. In embodiments, such properties include improved drying properties and improved impact on pest control (e.g., reduced pest survival, reduced pest fertility, pest food intake, etc.), as discussed in more detail below. deterrence, deterrence of pest reproduction, reduction of plant damage, etc.).

Concentrated liquid suspensions contain particulate materials suspended in an oily phase as described above. In embodiments, the particulate material may be a clay mineral. Clay minerals include, but are not limited to, _the following types of clays: (a) kaolin clays (minerals kaolinite, dickite, _halloysite and nacrite (polymorphs of _Al2Si2O5 (OH) ₄ ); (b) smectite clays, including dioctahedral smectites such as nontronite and montmorillonite, and trioctahedral smectites such as saponite; (c) illite clays, including clay-mica; (d) chlorite clays. and (e) other types of clay such as meerschaum and attapulgite. In embodiments, the clay mineral can be bentonite clay.

In embodiments, the particulate material can be an organically modified mineral such as an organoclay. For example, organoclays include fatty acids, fatty amines, fatty amides, fatty esters, fatty amine quats, quaternary amine surfactants, cetyltrimethylammonium bromide, fatty alcohols, decyl alcohol, dodecyl alcohol, linseed oil, alkenylsuccinic anhydride. bentonites, kaolins, zeolites, attapulgite or talc, modified with organic modifications such as styrene maleic anhydride (SMA) copolymers, colophony, rosin, chitosan or castor oil derivatives such as THIXCIN® of minerals.

In embodiments, the particulate material is talc, calcium carbonate, gypsum, magnesium silicate, calcium silicate, corn starch, cellulose fibers, psyllium fibers, ethylene bisstearamide, microcrystalline cellulose, stearic acid, paraffin wax, carnauba wax. or beeswax, the particulate materials used either individually or together as a mixture. In other embodiments, the particulate material can be specialized particles selected to form a barrier to moisture or pest infestation, for example. In embodiments, specialized particles may include planar high aspect ratio particles such as clays, mica, etc. that have the ability to form flat textured films when combined with a suitable binder. In some embodiments, the particulate material of the formulation can be non-clay minerals such as mica, talc, silica, titanium dioxide, gypsum, calcium carbonate, aluminum phosphate, and the like. In preferred embodiments, the particulate material of the formulation can be bentonite, exfoliated bentonite, organoclay, kaolin, gypsum, zeolite, plastered earth or diatomaceous earth.

In embodiments, clays for these applications are described in WO2013/123150 (PCT Application No. PCT/US13/2684, entitled "Processes for Clay Exfoliation and Uses Thereof"), the contents of which are incorporated herein by reference. It can be exfoliated by use of the method described. Incorporation of particles in barrier films provides the additional benefit of reflecting or absorbing light and thermal energy. Certain fruits and vegetables are susceptible to excessive sunlight, freezing or frost conditions, oxidative damage, microbial or fungal growth, osmotic swelling and cracking during wet conditions, heat stress, and low humidity or windy conditions. They are subject to crop loss or economic damage due to exposure to environmental stresses such as dry season. Incorporation of particles in barrier films of the disclosed formulations can reduce damage caused by these stresses. These particles are used to reduce heat absorption from sunlight, thereby providing a white or reflective surface that reduces sunburn-induced or heat-induced damage, such as titanium dioxide ( _TiO2 ). It may be combined with additional high brightness pigments. TiO ₂ can also enhance the ultraviolet (UV) light resistance of agricultural target surfaces by absorbing or reflecting most of the UV radiation incident on the agricultural target surface. Other sunscreen materials such as conjugated organic compounds may also be included.

Agricultural formulations are provided in the form of concentrated liquid suspensions comprising an oily continuous phase and suspended particulates. A concentrated suspension is a liquid having a viscosity of from about 10 cP to about 50,000 cP as measured by a Brookfield LVDV-III+ rheometer with a spindle LV-3 or LV-4 at 30 rpm; The product is a pasty liquid with a viscosity of about 50,000 cP to 500,000 cP when measured by the same instrument under the same conditions. In embodiments, the concentrated suspension is a liquid having a viscosity of about 50 cP to about 5000 cP. In embodiments, the concentrated suspension is stable to separation of particles from the oil-based continuous phase (ie, phase separation), and the suspension resists settling for at least 24 hours after mixing it. In embodiments, the suspension resists settling for at least 90 days after mixing it. In embodiments, the concentrated suspension comprises, by weight, more oil-based liquid than the suspended particulate. In embodiments, the mass ratio of particulate to oily liquid in the formulation ranges from 1 to 100 parts particulate per 100 parts oily liquid. In embodiments, the concentrated liquid suspension does not contain water.

In embodiments, the agricultural formulation is used to improve dispersibility of particulate minerals in the oil phase, provide surface stability of particulate minerals in the oil, and/or reduce wetting of diluted formulations on agricultural targets. Contains surfactants for enhancement. As is understood in the art, particulate minerals such as minerals can be hydrophilic in nature, so they are not readily suspended in oil. Thus, in embodiments, the formulation includes a surfactant or dispersant that can act as a wetting agent. In embodiments, agricultural formulations may contain additives such as ethoxylated alcohols, sorbitan fatty esters, alkyl polyglycosides, ethylene oxide/propylene oxide (EO/PO) copolymers, guar, xanthan, soy lecithin or ethoxylated sorbitan stearate. . In other embodiments, nonionic silicone polymeric surfactants such as Sylgard OFX-0309 (Dow) and Triton HW-1000 (Dow) can be used as wetting agents. As will be appreciated by those skilled in the art, various additives can act as wetting agents. It is understood that, in embodiments, the various additives also facilitate stable suspension of particulate minerals in the oil phase, thereby enabling a durable and stable concentrated liquid formulation.

In embodiments, the agricultural formulation improves dispersibility and dilution of the formulation in water, improves stability of the diluted formulation, and/or improves wetting of the diluted formulation on the agricultural target. including dispersing or suspending agents for In embodiments, the concentrated liquid suspension contains guar, xanthan, carboxymethylcellulose, carrageenan, alginate, gelatin, pectin, starch, hydroxypropyl guar, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxypropylethylcellulose, hydroxyethylcellulose and ethylcellulose, and the like. of dispersing or suspending agents. In embodiments, the dispersing or suspending agent is added to the agricultural formulation at about 0.01% to about 5% by weight. In embodiments, the dispersing or suspending agent is added to the agricultural formulation at about 0.1% to about 2% by weight. In embodiments, the dispersing or suspending agent is added to the agricultural formulation at about 0.1% to about 1% by weight.

In embodiments, the agricultural formulation comprises one or more stabilizing additives that can be added in amounts ranging from 0.1 wt% to 30 wt%, depending on the additive. Without being bound by theory, because the formulation comprises domains of high density material dispersed in continuous domains of low density material, gravity causes the high density material to settle to the bottom of the container forming a sediment. It is understood that Conversely, stabilizing additives can be used to increase the viscosity of the continuous phase and thereby reduce the settling velocity, but they make it difficult for the user to pour the formulation. Alternatively, additives can be selected that cause the continuous phase to exhibit pseudoplastic behavior, ie viscosity decreases with increasing shear rate. Since the shear rate characteristics of settling are much lower than those of pouring, mixing or other fluid transfer processes, formulations containing such additives exhibit reduced settling rates but can still be poured easily.

In embodiments, stabilizing additives can be selected that cause the continuous phase to form a brittle solid at low shear stress that converts to a liquid once a critical stress level is exceeded. The composition and concentration of such additives are chosen such that the critical stress is slightly higher than the shear stress associated with sedimentation. Formulations containing such excipients exhibit essentially no sedimentation, but are free-flowing once the friable solids are broken up by shaking, mixing or other forms of gentle agitation. In embodiments, stabilizing additives that produce this behavior comprise one or more macromolecules that contain weakly binding groups. Interactions between these weakly binding groups lead to the formation of network structures that extend throughout the formulation and are characterized by yield stress. Desirably, applied shear stress exceeding the yield stress disrupts these bonds, resulting in network collapse and macroscopic flow of the formulation.

In embodiments, additives particularly suitable for exhibiting these properties include nonionic triblock copolymers, such as a central hydrophobic chain (e.g., polyoxypropylene) between two hydrophilic chains (e.g., polyoxyethylene). ), such as those provided by PLURONIC® series of materials (BASF) and polyetheramines, such as polyether diamines in the JEFFAMINE® ED series (Huntsman). In other embodiments, useful stabilizing additives include castor oil derivatives such as trihydroxystearin and related rheological modifiers (THIXCIN® and THIXATROL® (Elementis Specialties)) or RHEOCIN ( ®) or RHEOCIN T® (BYK Additives and Instruments). Additives for these purposes may be added in doses ranging from 0.01 to 1 wt%, preferably from 0.05 to 0.3 wt%. In embodiments, the stabilizing additive can be added to the agricultural formulation at an elevated temperature compared to that of the formulation during high intensity mixing, for example at a temperature in the range of about 55 to about 65°C.

In embodiments, stabilizing additives include modified ureas, urea modified polyamides, urea modified polyurethanes, hydroxyl terminated polybutadiene resins (KRASOL® (Cray Valley)), glycol ethers (e.g. DOWANOL ^TM series (Dow Chemical)), Polyamides, polyesteramides, and the like may be mentioned. As an example, compounds such as the BYK® products: BYK 7411 ES, BYK 431, BYK 430 and BYK 425 (BYK Additives and Instruments) can be used. These additives can be incorporated into the system at concentrations ranging from about 0.1 to about 4 wt% and preferably from about 0.2 to about 2 wt%. In embodiments where glycol ethers (eg, DOWANOL ^™ series (Dow Chemical)) are used, the glycol ether selected preferably has high solubility in water. By way of example, Dowanol TPM can be used in doses ranging from about 3 to about 5 wt% and preferably about 4 wt%. In other embodiments, stabilizing additives can include surfactants derivatized from fatty acids such as fatty acid polydiethanolamides: examples of these are cocamide diethanolamine, lauramide diethanolamine, soybean oil fatty acid amide diethanolamide, etc. , representative versions of which can be found in Lubrizol's AMIDEX ^™ CE, KD, LSM products. In other embodiments, fatty acid-derived surfactants, such as polyglycerol esters of fatty acids, can be used as stabilizing additives. These fatty acid-derived additives may be added in doses ranging from about 1 to about 5 wt% and preferably about 3%.

In embodiments, the agricultural formulation comprises or consists essentially of biodegradable components. In embodiments, the agricultural formulation comprises organically produced or "organic" ingredients as defined in the United States Department of Agriculture (USDA) National Organic Program (NOP) ingredient list. In embodiments, the agricultural formulation comprises food grade ingredients as defined by US Food and Drug Administration (FDA) guidelines. In embodiments, the agricultural formulation contains inactive ingredients as defined in 40 CFR 180 paragraphs 910-960 US Environmental Protection Agency (EPA) Inert Ingredients List. In embodiments, the agricultural formulation comprises FIFRA least risk ingredients as defined in 40 CFR 152.25 under the United States Federal Insecticide Fungicide and Rodenticide Act (FIFRA). In embodiments, agricultural formulations are non-toxic, naturally occurring and/or organic, and the formulations can be used to prevent damage to crops from insects, animals, fungi, bacteria and environmental insults. In embodiments, the formulation ingredients are derived from food grade raw materials. In embodiments, the formulation components are generally recognized as safe (“GRAS”) by the U.S. Food and Drug Administration and are certified under the Federal Food, Drug, and Cosmetic Act (FDCA), Sections 201(s) and 409 under 21 CFR 170.3. and contain or consist essentially of materials generally recognized as safe.

This concentrated liquid suspension has several commercial advantages, such as a highly concentrated product form that minimizes the volume of product transported from the point of manufacture to the point of use. Storage capacity requirements are minimized by having a highly concentrated product form. This also has advantages over solid, granular or powdered formulations: ease of handling as a liquid product, compatibility with automated pumping equipment, greater safety for handling with reduced worker exposure and Provides lower dust formation. A minimal amount of water in the product can provide advantages in reduced viscosity, reduced propensity for mold and bacterial growth and a lower freezing or pour point of the product.

In certain embodiments, a concentrated liquid suspension may be diluted with water or other solvent at or near the point of use to form a diluted liquid suspension, which is then diluted with , spraying, misting, fogging, electrostatic spraying, dipping, brushing or dusting. Dilution can be accomplished by in-line or batch mixing to form a diluted suspension, which can be handled and applied using conventional spray equipment. Dilute suspensions can be formed as oil-in-water emulsions or suspensions, wherein the oil phase comprises a drying oil.

When applied to agricultural targets, the agricultural formulation forms a curable coating comprising the oil or oil mixture and particulate material. In embodiments, the curing mechanism is based on the behavior of the drying oil(s), where cross-linking occurs between the double bonds of adjacent fatty acid or triglyceride chains via atmospheric oxygen insertion to form a cured polymer. A network is formed. The rate of hardening can be enhanced through the use of hardening additives, ie, additives such as oxidizing agents or metal salts that increase the speed of hardening of the drying oil(s).

In embodiments, concentrated suspensions are made by mixing a surfactant, a drying oil and particulates, wherein the surfactant represents from about 0.1 to about 15% by weight of the suspension. In embodiments, the suspension does not contain water. In embodiments, the suspension contains less than about 20% water by weight. In embodiments, concentrated suspensions comprise from about 40% to about 98% by weight oil phase. In embodiments, concentrated suspensions contain from about 5% to about 90% by weight oil phase. In embodiments, concentrated suspensions contain from about 60% to about 80% oil phase by weight. In embodiments, the concentrated suspension comprises from about 1% to about 50% by weight suspended particulates. In embodiments, the concentrated suspension comprises from about 10% to about 40% by weight suspended particulates. In embodiments, the concentrated suspension comprises from about 20% to about 35% by weight suspended particulates.

In embodiments, a concentrated suspension is made by mixing a surfactant, a mixture of drying oils and particulates, wherein the particulate concentration ranges from about 0% to about 38% by weight of the suspension. with a surfactant concentration ranging from about 4% to about 10% by weight of the suspension, and a mixture of drying oils forming the balance of the suspension. In embodiments, the formulation is water-free; in other embodiments, water is present in an amount ranging from about 0% to about 5% by weight.

In embodiments, the agricultural formulations comprise or consist essentially of non-toxic ingredients, and they have low toxicity to plants or animals. Low toxicity can be defined as having an _LD50 >1000 mg/kg or preferably > ₅₀₀₀ mg/kg. Toxicity is classified according to the Hodge-Sterner classification based on the article "Tabulation of Toxicity Classes" by Harold Hodge and James Sterner, published in American Industrial Hygiene Association Quarterly Volume 10, Issue 4, 1949. In embodiments, the agricultural formulation may meet the Hodge-Sterner Classification 1, 2 or 3 description; in preferred embodiments, the formulation may meet the Hodge-Sterner Classification 1 description. In embodiments, the agricultural formulation comprises naturally derived ingredients such as vegetable oils, triglycerides and naturally occurring minerals.

In embodiments, agricultural formulations can be applied such that they are dried in the form of porous films, allowing transpiration by plants. In embodiments, porous films can be formed by incorporating or forming micropores in the form of gas voids or by incorporating porous minerals. In embodiments, the pores may be formed by dissolution or decomposition of the minor constituents of the coating, leaving behind a porous coating.

In embodiments, the agricultural formulations disclosed herein can be used as a vehicle or adjuvant to deliver agricultural treatments in fluid form to agricultural targets. As used herein, the term "treatment" means beneficially affecting the longevity, productivity or other biological or economic aspects of an agricultural target, and "agricultural treatment" refers to such Refers to any chemically or biologically active ingredient used to effect a treatment. The term "second agricultural treatment" refers to an agricultural treatment applied in addition to, before or after treatment with the agricultural formulations disclosed herein. Non-limiting examples of agricultural treatments include pesticides, herbicides, fungicides, sulfur, copper oxides, plant growth regulators, plant hormones, pheromones, insecticide soaps, insect pheromones, sunscreens, beneficial bacteria. , beneficial fungi, Trichoderma, Bacillus thuringiensis (Bt), Aspergillus, nematodes, RNAi; botanical extracts and neem, cloves, d-limonene, citrus extracts, pinene essential oils such as pine extract, capsaicin, camphor, geraniol; probiotics, beneficial bacteria or fungi, extracts of bacterial or fungal cultures, spinosyn A, spinosyn D, biopesticides, biofungicides, linen Insects, biological control agents and nutrients.

As used herein, the term "nutrient" or "nutrients" refers to those elements that are essential for plant growth. The term "nutrient" includes both macronutrients and micronutrients. In addition to the essential elements for growth (carbon, hydrogen, oxygen) provided by air and water, the three macronutrients (nitrogen, phosphorus, potassium) that plants need in large amounts and lesser and even trace amounts There are several secondary and micronutrients (calcium, magnesium, sulfur, boron, chlorine, copper, iron, manganese, molybdenum, zinc, etc.) required in the body. Micronutrients can perform particularly critical functions in the plant life cycle, such as enhancing glycosyltransferase, enhancing protein formation, increasing photosynthesis, improving root strength, enabling plant immunity, and the like.

Nutrient-containing foliar sprays can be used to provide essential nutrients to plants, for example, to correct nutritional deficiencies that limit plant growth or increase susceptibility to pests and pathogens. However, simple sprays in current use consist of one or more nutrients dissolved or dispersed in water; after application, these formulations are easily washed or brushed off the leaf surface. This susceptibility to washout or shedding reduces nutrient availability, which can add runoff of these chemicals to the local water supply. In embodiments, the formulations disclosed herein contain nutrients and form a nutrient-containing film that retains one or more nutrients in the leaves. This property minimizes nutrient washout or shedding, prolongs the time available for absorption by plants, and prolongs residual activity of nutrients. Examples of suitable nutrients include nitrogen, phosphorus, potassium, boron, copper, iron, manganese, molybdenum, zinc, chlorine, nickel, calcium, magnesium, sulfur and silicon. Nutrients can be supplied as salts, complexes, chelating agents or organic-inorganic compounds. Nutrients can be dissolved in the formulation, dispersed in the formulation, or absorbed into components of the formulation. In embodiments, for example, nutrients can be absorbed by clay present in the formulation. The dispersed nutrients may be in the form of particles having an average particle size of less than 100 microns, less than 10 microns or less than 1 micron.

In embodiments, non-toxic agricultural formulations can be combined with pheromones that affect mating behavior or cause mating disruption in insects. For example, pheromone-containing agricultural formulations can be used to deter successful insect reproduction or egg-laying, or to force insects to lay eggs in areas where born larvae do not survive.

Agricultural treatments can include agrochemicals that can be formulated as liquids, solutions, dispersions, pastes, gels or aerosols. Agricultural treatments can non-lethally alter the behavior of pests. For example, agricultural treatments can reduce the natural burden of agricultural pests by, for example, competing with agricultural pathogens for space or nutrients on agricultural targets, or by attenuating the growth of agricultural pathogens, thereby inducing resistance to agricultural pests. beneficial to agricultural targets through their biological activity by acting as an enemy of the It may contain efficacious biological control agents. As used herein, agricultural targets may include plant surfaces and seed surfaces (pre-harvest or post-harvest), plant products and soil or agricultural growth medium surfaces.

As used herein, the term "agrochemical" includes herbicides, pesticides, fungicides, fertilizers, insecticides, probiotics, nematicides, plant growth regulators, plant hormones, insect hormones, An active chemical ingredient used for agricultural purposes, such as a pheromone, pest repellent or nutrient. For example, the formulations can serve as protective coatings for plants, fruits, vegetables, leaves, berries, seeds, nuts, etc. while also delivering agrochemicals. In embodiments, agrochemicals can be herbicides such as dicamba, chloramben, nicosulfuron and glyphosate; they can be insecticides such as imidacloprid, neonicotinoids, pyrethroids, chlorantraniliprole or sulfoximine. . In embodiments, the agrochemical is azoxystrobin, calcium polysulfide, metalaxyl, chlorothalonil, fenarimol, copper salts, copper oxide, metal-dithiocarbamate complexes, farbum, mancozeb, mefenoxam, microbutanil, pyraclostrobin, Bactericides such as prothioconazole, propiconazole, sulfur, thiophanate-methyl, triadimefon and trifloxystrobin. In embodiments, the agrochemical can be an oil soluble chemical, a water soluble chemical or a dispersible solid material.

In embodiments, the agricultural treatment can be a physical agent such as a sunscreen or a moisturizing agent. In embodiments, agents such as caffeine, benzoic acid, para-aminobenzoic acid, avobenzone, zinc oxide and titanium dioxide can be used as sunscreen agents. In embodiments, wetting agents such as urea, glycerol, polyvinyl alcohol, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, calcium chloride and polyethylene glycol (PEG) can be used as humectants.

In embodiments, agricultural treatments can include biological agents such as Gram-positive bacteria, Gram-negative bacteria, motile microorganisms, non-motile microorganisms, nodule microorganisms, soil microorganisms, rhizosphere microorganisms, fungi, and the like.

In some embodiments, the biological agent comprises one or more beneficial microorganisms. As used herein, the term "microbe" is interchangeable with "microorganism" and refers to microscopic unicellular or multicellular organisms. Classes of microorganisms include, but are not limited to, organisms such as bacteria, fungi, algae, archaea, viruses and protozoa. The use of microorganisms as agricultural treatments has been shown to increase nitrogen fixation, control disease, protect against plant pathogens, induce disease resistance in plants, improve nutrient uptake, stimulate growth and productivity, and tolerate environmental stresses. It can provide agricultural benefits such as enhancement. For example, in embodiments, microorganisms used in agricultural treatments can provide direct protection to plants by infecting them with insect pests or phytopathogenic microorganisms that can attack the plants. As an example of this use, Beauveria bassiana, a fungus naturally occurring in soil, can be used as an entomological pathogen against insect pests. Or, for example, in other embodiments, microorganisms used in agricultural treatments compete with pathogenic species for nutrients, limit or eliminate nutrients required by pathogenic species or insect pests, or Indirect protection may be provided to plants by creating antimicrobial compounds that act detrimentally on sexual species. In still other embodiments, microorganisms used in agricultural treatments can increase the supply or bioavailability of nutrients to plants. In other embodiments, microorganisms used in agricultural treatments are e.g. stimulating leaf growth, stimulating root growth, stimulating immune responses, promoting tolerance to abiotic stresses, etc., can stimulate beneficial biological activities in plants.

In embodiments, the agricultural treatment is beneficial bacteria or fungi, such as fungi that have a mycorrhizal relationship with the roots of plants, entomopathogenic strains of fungi, Beauveria bassiana, Metarhizium, Isaria , Nomuraea, Tolypocladium, Lecanicillium, Entomophthora muscae, Beauveria bassiana, Pandora neoaphidis, Hirsutella thompsonii, Neosigites floridina ( Neozygites floridana), Paecilomyces fumosoroseus, Metarhizium anisopliae, Bacillus aspergillus, Bacillus thuringiensis (Bt) and nematodes. In embodiments, agricultural treatments can be biopesticides as defined by the US EPA (https://www.epa.gov/pesticides/biopesticides). In embodiments, agricultural treatments may be produced by bacteria, such as Spinosyn A and Spinosyn D produced by soil actinomycetes (Saccharopolyspora spinosa).

In embodiments, the formulation may contain beneficial microorganisms that are viable microorganisms. A viable microorganism can be a fertile microorganism, ie one that is a living organism capable of replication. Alternatively, beneficial microorganisms may be viable, but not fertile, and have beneficial properties that are independent of their replication. For these viable microorganisms, whether replicable or not, their specific beneficial properties may result from their ability to release beneficial substances that contribute to well-being (such as freedom from disease) in plants. or their specific beneficial properties may result from their ability to induce plant beneficial effects when consumed by another organism associated with such plants. For example, a viable beneficial microorganism, whether fertile or not, may have a detrimental effect on pests that may otherwise infect plants, e.g., when the pest consumes the microorganism; This detrimental effect on pests therefore has a beneficial effect on otherwise vulnerable plants.

In embodiments, the formulation may contain beneficial microorganisms that are non-viable microorganisms. Although such microorganisms are in some respects living organisms, they are no longer living in formulations and their beneficial properties do not depend on their viability. Non-viable microorganisms or substances derived from them, e.g. by providing beneficial substances that contribute to well-being in plants (such as freedom from disease), or when consumed by another organism associated with such plants can exert beneficial effects by inducing plant beneficial effects in For example, microorganisms such as B. thuringesis can damage the gut of insects that consume them, even though the microorganism itself is no longer alive.

Non-viable materials, such as viable or non-viable microbial compounds, may be included in the term "biopesticide". Such biopesticides may include material derived from live microorganisms (e.g. compounds, secretions, excretions, etc.); (derivatives derived from processing of

In embodiments, the concentrated liquid suspension comprises a cellulosic polymer, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, starch, thermoplastic starch, polyethylene glycol, polylactic acid, polyglycolic acid, polylactic-glycolic acid, propylene glycol. , block copolymers of ethylene oxide and propylene oxide, glycerin, osmotic agents such as calcium chloride, adjuvants such as terpenes and vegetable oils. In embodiments, the dry oil-based agricultural formulation contains cellulosic or cellulose-derived materials such as cellulose esters, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose fibers, cellulose microfibers. , cellulose nanofibers, cellulose ethers, ethylcellulose, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and the like. In embodiments, the cellulosic or cellulosic-derived material can be a cellulosic polymer having a drying oil covalently attached thereto, such as by esterification. In embodiments, cellulosic-derived materials can include the cellulosic materials described above combined with one or more functional groups that impart advantageous properties. In other embodiments, non-toxic barrier coating compositions for agricultural surfaces can be formed from biodegradable compositions comprising polyhydroxyalkanoates such as polyhydroxybutyrate.

B. Methods of Using Formulations The present disclosure also relates to methods of using non-toxic agricultural formulations in the form of concentrated liquid suspensions. Agricultural formulations can be applied to a variety of agronomic substances or targets, such as plant surfaces (leaves, fruits, seeds, berries, nuts, capsules, stems, roots, etc.), soil or agricultural growth media, and harvested plant production. It can be applied to objects such as fruits, vegetables, seeds, glumes, stems, roots and the like.

In embodiments, the soil surface is treated to produce a beneficial effect selected from the group consisting of erosion control, nutrient retention, agricultural treatment retention, dust control, delivery of beneficial microorganisms or enhanced growth of beneficial microorganisms. can be

In embodiments, the non-toxic agricultural formulation forms a seed coating to improve seed properties such as viability, productivity, growth rate, time of emergence, insect resistance, mold resistance, dust control, shedding of active pesticide ingredients. can be used to improve resistance to and humidity resistance. When used as a seed coating, the formulations may provide protection against Rhizoctonia and Fusarium and soybean rust and nematodes, aphids, maggots and helminths. Formulations may provide improved handling, safety, reduced surface dusting of seed coatings for environmental contamination, and avoidance of non-targeted applications. A seed coating can improve the dry flow and non-clumping of treated seeds; this produces less residue and requires less cleaning of equipment. Seed coatings may contain rooting compounds, hormones and plant growth regulators. In embodiments, the formulation can be diluted with water and applied to agricultural targets to form a cured coating.

In embodiments, non-toxic agricultural formulations can be applied to tropical crops such as cocoa, coffee, papaya, mango, pineapple, avocado, melon, watermelon and banana. In the example of cocoa, non-toxic agricultural formulations can deter cocoa pod borers (Conopomorpha cramerella) from damaging crops. Also for cocoa, non-toxic agricultural formulations are used, for example, by organisms of the Phytophsora species, such as P. palmivora, P. megakarya, P. capsici, P. citrofusora ( It can deter the invasion of black dwarf disease associated with P. citrophthora, P. megasperma, P. katsurae and others. Also, for cocoa, non-toxic agricultural preparations are used for frosty pods and witch's blooms associated with organisms such as the Basidiomycete fungi, Moniliophthora loreri, Moniliophthora perniciosa, and the like. It can deter disease (WBD) invasion. In coffee, non-toxic agricultural formulations can control insects, such as coffee nut borers, or plant diseases, such as coffee rust. In embodiments, non-toxic agricultural formulations may prevent or reduce the spread of fungal infestations by reducing the ability of spores to become airborne. In embodiments, non-toxic agricultural formulations may prevent or reduce the spread of fungal infestations by reducing the ability of airborne spores to germinate on plant surfaces. In embodiments, the non-toxic agricultural formulations contain or otherwise immobilize the fungi on the plant surface, preventing some or all of the microorganisms from gaining access to the interior of the plant, thereby reducing fungal invasion. Diffusion may be prevented or reduced.

In embodiments, the non-toxic agricultural formulation can be applied to vegetable crops such as squash, onions, celery, lettuce, spinach, pumpkin, tomato, eggplant, pepper, broccoli, cabbage, cucumber, and the like. In embodiments, the non-toxic agricultural formulation can be applied to root vegetables such as potatoes, beets, carrots, turnips, ginger and sweet potatoes. In embodiments, the non-toxic agricultural formulation can be applied to leguminous crops such as beans, soybeans and peanuts. In embodiments, the non-toxic agricultural formulation can be applied to the cereals of cereals such as corn, oats, wheat, sorghum, alfalfa, barley and rice. In embodiments, the non-toxic agricultural formulations can be used to control pests such as the larvae of the bollworm moth, the navel orangeworm and the pecan case borer. In embodiments, the non-toxic agricultural formulation may be applied to tree nut crops such as almonds, cashews, macadamia nuts, walnuts, pecans and pistachios. In embodiments, the non-toxic agricultural formulation may be applied to tree fruits such as apples, pears, peaches, plums, cherries, lemons, oranges, grapefruits, pomelos and limes. In embodiments, the non-toxic agricultural formulation may be applied to berry crops such as strawberries, raspberry berries, blue berries, cran berries, black berries and elderberry. In embodiments, the non-toxic agricultural formulation can be applied to table grapes, grapes for juice or wine production. In embodiments, non-toxic agricultural formulations can be applied to turf grass, lawn, golf courses and ornamental plants.

In embodiments, non-toxic agricultural formulations can be used to improve crop yield. Harvest yield is determined by many factors such as plant health, nutrient and water availability, pest pressure, heat stress, environmental conditions, sunlight and the microbiome around the plant. . When applied to crops, non-toxic agricultural formulations can affect some of these factors. In embodiments, non-toxic agricultural formulations can reduce crop water demand by reducing loss of water vapor through transpiration to the atmosphere.

In embodiments, non-toxic agricultural formulations can be used to protect plants and crops from diseases caused by microorganisms, including, but not limited to, potato X virus (PVX), potato Y virus (PVY ), blight, zebra chip, bacterial infection, phytoplasma, leaf spot, brown rot, scab, downy mildew, smut, apple rust, leaf curl, leaf spot , mosaic virus, oomycete, mistletoe, dwarf mistletoe, fungi causing diseases such as fleas, canker, anthracnose, and microorganisms such as molds, powdery mildew, bacteria and viruses. In embodiments, non-toxic agricultural formulations can be used to protect plants and crops from bacteria and viruses carried by insects. As used herein, the term "infection" refers to the pathological invasion of plants by microorganisms or the disease caused thereby. Infection can result from invasion of the plant by an exogenous source of microorganisms, where attachment of the plant to the microorganism or colonization by the microorganism is directed to a surface-directed activity, entry of the exogenous microorganism into the plant interior, or It is understood that any of the other pathogenic behaviors of microorganisms (eg, toxogenesis) result in plant pathology or disease. Infection is an endogenous supply of microorganisms that behave in a pathological fashion, either through surface-directed activity, entry of endogenous microorganisms into the plant interior, or other pathogenic behavior of microorganisms (e.g., toxin formation). It is also understood that it can happen because of the source. By way of example, infection can occur when a microorganism is initially present on the surface of a plant (whether the microorganism is exogenous or endogenous in nature) and some or all of this microorganism is present inside the plant. can occur when infestation into plants causes plant pathology. In certain embodiments, in preventing or ameliorating or eradicating an infection (collectively "treatment of infection"), the non-toxic agricultural preparation can trap or otherwise immobilize potentially pathogenic microorganisms on the plant surface. and thereby prevent some or all of the microorganisms from gaining access to the interior of the plant. In other embodiments, in the treatment of infections, non-toxic agricultural formulations can prevent the introduction of potentially pathological exogenous microorganisms onto plants. In yet other embodiments, in the treatment of infections, non-toxic agricultural formulations may interfere with or prevent surface-directed activity or other behavior of microorganisms, such as toxin formation.

In embodiments, the non-toxic agricultural formulation is effective against weevils, maggots, worms, slugs, flies, fruit flies, mites, ants, spiders, caterpillars, moths, grasshoppers, locusts, leafhoppers, leafhoppers, leaf worms, aphids, psyllids, ants, It can be used to protect plants and crops from insect and animal damage caused by beetles, bugs, thrips, rabbits, deer, rodents and the like. In embodiments, the non-toxic agricultural formulation is resistant to excessive sunlight, freezing or frost conditions, oxidative damage, microbial or fungal growth, osmotic swelling and cracking during moist conditions and low humidity or windy conditions. It can be used to protect plants and crops from environmental stresses such as drought.

After preparation, agricultural formulations can be delivered to the point of distribution or point of use. The formulation remains stable for an extended period of time, eg, 3-6 months or longer. For application to agricultural targets, the concentrated liquid suspension can be diluted with a diluent, such as water, and sprayed onto the plant surface. In embodiments, diluted liquid suspensions may contain from about 60 to about 99% water. In embodiments, the agricultural formulation may be applied to the agricultural target by spraying, brushing, misting, aerosolizing, fogging, back spraying, immersion or irrigating the agricultural target. The spray solution is further modified with a small amount of a flow aid such as a hydrophilic polymer, e.g. can be In some embodiments, the formulations are resistant to rubbing or scraping and/or they are water resistant. In other embodiments, water soluble polymers or waxes such as polyethylene glycol may be added to create fills that are easily removable after minor washing.

In some embodiments, formulations may be applied to agricultural targets such as plants, fruits, vegetables, and the like. For example, in embodiments the formulation is sprayed onto an agricultural target, such as a fruit or vegetable surface or plant surface (stem, foliage, leaves, branches, seeds, berries, nuts, roots, etc.) or soil or other agricultural growth medium. may be used, wherein the formulation may comprise an active ingredient. Oil droplets containing the active ingredient can coat agricultural target surfaces and form a crosslinked film upon drying. In embodiments, the non-toxic barrier coating is effective against weevils, maggots, worms, burrs, slugs, flies, fruit flies, moths, grasshoppers, locusts, leafhoppers, leafhoppers, leaf worms, aphids, ants, beetles, bugs, thrips, rabbits, deer. , can protect plants from pests such as rodents. In embodiments, non-toxic barrier coatings can protect plants and crops from damage caused by insect-transmitted diseases. In embodiments, the non-toxic barrier coating is effective against fungi, molds, powdery mildew, citrus greening, huanglongbing (HLB), leaf spot, brown rot, thorn, downy mildew, smut. , apple rust, leaf leaf spot, mosaic virus, fleas, canker and anthracnose.

In some embodiments, dry oil-based agricultural formulations can be used to form non-toxic barrier coating compositions when applied to agricultural targets such as plants, fruits, vegetables, and the like. For example, in embodiments, the formulation may be sprayed onto an agricultural target, such as a fruit or vegetable surface or a plant surface (trunk, foliage, leaves, seeds, berries, nuts, roots, branches, etc.), wherein the formulation is a pesticide. It does not contain toxic ingredients such as In embodiments, the non-toxic barrier coating composition can deter pest damage due to altered sensory perception of the plant surface; It can have energy, slipperiness, compatibility with the physiological structure of insect limbs, surface feel, odor profile, visual appearance and heat signature. This altered sensory presentation can change the behavior of insects and animals such that they do not decide to eat or otherwise damage the treated plants. In embodiments, the non-toxic barrier coating composition can induce pests to adopt grooming behavior and deter pests from damaging agricultural targets. In embodiments, the non-toxic barrier coating can immobilize pests that come into contact with the coating by adhering to the pests. The mechanical and rheological properties of non-toxic barrier coatings are such that once the coating adheres to the pest, the pest is unable to free itself from the coating or remove the coating from the agricultural target. can be selected to Such pests may be present on the agricultural target prior to formation of the non-toxic barrier coating, or the pests may reach the agricultural target after the coating is established. In embodiments, the non-toxic barrier coating can impede pest movement on the surface of the agricultural target, resulting in detrimental consequences for the pest, such as impairing the pest's ability to locate sites of food intake or reproduction. In embodiments, the non-toxic barrier coating can impair the odor profile associated with the pest or plant surface to harm the pest, such as selectively absorbing compounds released by the pest or plant surface or odor profiles. releases compounds that impair, block, perturb or otherwise alter the In embodiments, the non-toxic barrier coating composition can serve as protection of agricultural targets from insects, fungi, animals, drought conditions, air pollution damage, heat stress and sun damage. As used herein, the term "barrier coating" or "barrier coating composition" can be formed as a continuous or discontinuous film or otherwise applied at a desired thickness.

In embodiments, the non-toxic barrier coating formulation can be applied to agricultural targets at a dosage rate of from about 1 to about 200 lb. of formulation per acre of harvest (undiluted basis). In embodiments, the non-toxic barrier coating formulation may be applied to agricultural targets at a dosage rate of from about 3 to about 100 lb. of formulation per acre of crop. In embodiments, the non-toxic barrier coating formulation can be applied to agricultural targets at a dosage rate of from about 10 to about 75 lb. of formulation per acre of crop. In embodiments, concentrated formulations of non-toxic barrier coating formulations, such as the oil mixture formulations described herein, are applied to agricultural targets at dose rates of 0.2 kg/ha to 100 kg/ha. (undiluted basis). obtain. In other embodiments, concentrated formulations of non-toxic barrier coating formulations can be applied to agricultural targets at dosage rates of about 1-150 L/ha or about 5-50 L/ha.

Any of these beneficial effects described above are non-limiting examples of desired therapeutic effects. Agricultural treatments are intended to provide a desired treatment effect, i.e., any effect that enhances the production of pre-harvest agricultural products or enhances the appearance, taste, durability or other beneficial properties of post-harvest agricultural products. Intend. Materials used in agricultural treatments are agricultural treatments. For example, the desired treatment effect may be a protective effect (e.g., pests, fungi, sun damage, drought, ozone, acid rain, environmental toxins, etc.) or a nutrient effect (e.g., delivery of fertilizers, growth hormones, plant nutrients, etc.) or pre-harvest enhancement. effects (e.g., providing agents that enhance the natural properties of pre-harvest products, such as those by genetic modification) or post-harvest protective or enhancing effects (e.g., protecting the skin or surface of post-harvest fruit, vegetables or seeds). or to improve their appearance, taste or commercial appeal). Certain fruits and vegetables suffer from excessive sunlight, freezing or frost conditions, oxidative damage, microbial or fungal growth, osmotic swelling and cracking during moist conditions, and desiccation during low humidity or windy conditions, etc. are subject to crop loss or economic loss due to exposure to environmental stressors. Reduction of these crop losses and economic losses is another example of a desired therapeutic effect of a coating formulation. Other examples of desired therapeutic effects are well known to those of ordinary skill in the art. In order to achieve the desired therapeutic effect, the target can be treated with the formulation for an exposure time, which is the time assumed appropriate to achieve the desired therapeutic effect. Exposure times for various formulations and targets are well known to those of skill in the art. The exposure time can be preselected, or it can be determined after exposure based on the degree of achievement of the desired therapeutic effect or based on other parameters that can be observed or determined by one skilled in the art.

In embodiments, the agricultural formulations and methods disclosed herein can prolong the therapeutic effect of active agricultural ingredients such as biological agents or agrochemicals. For example, the disclosed formulations can act to protect active agricultural ingredients from dispersal or deactivation after contact with agricultural targets. Agricultural formulations disclosed herein can deliver agrochemicals to agricultural targets and retain them there; It may be protected from harmful conditions such as rain, friction, wind, water exposure and secondary agricultural treatments (eg subsequent spraying or subsequent application or use of agricultural treatments) which may be removed.

In embodiments, the agricultural formulations and methods disclosed herein are used to deliver biological agents and/or biological control agents, such as beneficial bacteria, beneficial fungi, to agricultural targets and/or biological can be used to retain biological control agents on agricultural targets. Biological control agents can include various life forms such as plants, insects and microorganisms such as bacteria, fungi and viruses. In embodiments, agricultural formulations may contain a biocontrol agent in an amount from about 0.001% to about 10%. In embodiments, the agricultural formulation may contain the biocontrol agent in an amount of about 0.01% to about 1%. In embodiments, the agricultural formulation may contain the biocontrol agent in an amount of about 0.05% to about 0.5%. In embodiments, the biological control agent comprises at least one strain of Bacillus thuringiensis (Bt) or endotoxin produced by Bt. The use of Bt is understood to be safe and effective for controlling insects, and delivery of Bt by the agricultural formulations and methods disclosed herein can improve or prolong effectiveness of insect control. Biological control may include importation of natural enemies of agricultural pests, conservation of natural enemies of agricultural pests or increase of natural enemies of agricultural pests. The formulations and methods disclosed herein provide barrier coatings or films that aid in the delivery of biological control agents in solid or liquid formulations to agricultural targets or other biological control efforts. may play a role in biological regulation. In embodiments, delivery of a biocontrol agent by the agricultural formulations and methods disclosed herein can enhance or prolong the effectiveness of the biocontrol agent by improving its resistance to rain. In embodiments, for example, the barrier coatings described above can include the biological control agent in particulate form so that the biological control agent is held in close proximity to the agricultural surface and/or it is allowed to grow at a predetermined rate. Released in a radioactive fashion.

In embodiments, the biological control agent can be formulated in liquid or solid form. For example, commercially available suspensions of spores, toxins, fungi, virus particles, etc. can be sprayed onto crops as well as conventional pesticides that act as biological control agents. A non-exhaustive list of exemplary biocontrol agent formulations is provided in Table 1:

The formulations and methods described above for making agricultural treatments containing solid or liquid agrochemicals can also be applied to agricultural treatments containing biological control agents formulated as solids or liquids. .

Example materials Boiled linseed oil, Cargill
・National Standard Bentonite 325, Bentonite Performance Minerals LLC
・Industrial corn starch, Casco
・Ecosense 919, DOW
- Raw linseed oil, Cargill
- Glycidyl ether of castor oil, CVC Specialty, Moorestown, NJ
・Pluronic L121, BASF, Florham Park, NJ
・Isopar M, Exxon Mobil Chemical
- Gum rosin, Sigma Aldrich, St. Louis, MO
・Arabic coffee plant, Amazon.com
・decyl glucoside, Dow Chemical Connection
- Flaxseed Oil, Sigma Aldrich, St. Louis, MO
- Triethylenetetramine (TETA), Sigma Aldrich, St. Louis, MO
・Span 85, Tokyo Chemical Industry (TCI)
・SugaNate 160, Colonial Chemical Co.
・Potassium Laurate, Viva Corporation
・Xanthan gum, Cargill
- Geraniol, Sigma Aldrich, St. Louis, MO
・d-Limonene, Florida Chemical Co.
- Magnesium stearate, Sigma Aldrich, St. Louis, MO
・Microcrystalline Cellulose, Sigma Aldrich, St. Louis, MO
- Castor oil, Sigma Aldrich, St. Louis, MO
・Bentonite, Sigma Aldrich, St. Louis, MO
・Titanium Dioxide, JT Baker, Phillipsburg, NJ
・Precipitated Calcium Carbonate, Specialty Minerals Inc., New York, NY
- other materials described in the examples below

Example 1: Preparation of linseed oil/rosin 1:1 mixture Rosin was added to linseed oil in a 1:1 weight ratio. The mixture was mixed and heated above 60° C. for 2 hours to dissolve the rosin in the linseed oil.

Example 2: Preparation of linseed oil/castor oil glycidyl ether/triethylenetetramine Flaxseed oil, castor oil glycidyl ether (GE35-H) and triethylenetetramine (TETA) were mixed in a ratio of 1:1:0.05. The mixture was mixed on a vortexer (VWR Scientific Products, Mini Vortexer 945800) for approximately 10 seconds.

Example 3: Preparation of linseed oil/castor oil glycidyl ether/magnesium stearate/triethylenetetramine Flaxseed oil, castor oil glycidyl ether (GE35-H), magnesium stearate and triethylenetetramine (TETA) 1:1:0.75 : 0.05 ratio. The mixture was mixed with a vortexer (VWR Scientific Products, Mini Vortexer 945800) for approximately 10 seconds.

Example 4 Method of Treating Agricultural Products The formulation of Example 5 (below) was applied to cocoa pods to reduce fruit damage for infestation by cocoa pod borers (Cocoa pods). can be applied to The formulations may be applied at various stages of pod development, preferably during the time frame when the skin of the fruit is green, preferably 2-4 weeks after the pods start growing on the plant. Application can be carried out using standard spray applicators such as a backpack sprayer. This method of application is particularly suitable for pre-harvest coating applications on large fruit growing trees such as cocoa, pineapple, apple and papaya, but conventional mechanical sprayers used in large fields for row plants, etc. Other application methods of may also be used. The formulation can remain on the cocoa pod skin for weeks at a time, protecting the fruit from cocoa pod borers. The coating is expected to be flexible and allow fruit growth, after which a second application may be required several weeks before harvest. After harvest, fruits with inedible skins (eg, cocoa pods) can be processed without post-harvest washing. However, other fruits and vegetables with edible skins, such as papaya, mangoes, apples, cherries, tomatoes, etc., may require a brief post-harvest washing with mild soap to remove the coating.

This applied coating is expected to result in high yields of fruit with clean, intact skin without the effects of pest infestation. The coated fruits and vegetables are expected to be appealing to consumers and safe for consumption with minimal washing steps commonly performed by consumers of these fruits and vegetables.

Example 5: Formulation for Treatment of Agricultural Targets A formulation was prepared by mixing the ingredients shown in Tables 2 and 3 below. Each formulation was a viscous but free flowing liquid.

Example 6: Formulations Containing Different Surfactants Several aqueous surfactant solutions were prepared for incorporation into formulations. Each solution was prepared at 20% by adding 2 grams of surfactant to 8 grams of tap water. A list of tested surfactants and their hydrophilic-lipophilic balance (HLB) values are listed in Table 4 below:

A 3.60 gram aliquot was taken from each of the 20% surfactant solutions in Table 4 and added to separate vials each containing 21.60 grams of raw linseed oil. The surfactant solution was vigorously stirred just prior to transfer to the linseed oil-containing vial. After mixing the surfactant solution and raw linseed oil, 10.80 grams of bentonite was added to each vial and vigorously stirred again. The final component percentages for each sample vial were 60% raw linseed oil, 30% bentonite, 8% water and 2% surfactant; these samples are listed in Table 5.

Stability was assessed by allowing the formulation to stand for 65 hours and then assessing how easily the precipitated bentonite could be redispersed. Each vial was gently inverted to determine how much bentonite settled to the bottom of the vial and how redispersible the settled bentonite was. Tumbled samples were rated with a bentonite packing number from 1 to 5, where 1 means "easy to redisperse" and 5 means "difficult to redisperse". We focused on samples with bentonite redispersed upon tipping by gravity alone. Each sample was then shaken vigorously by hand for about 5 seconds and again evaluated for redispersion of the precipitated bentonite. The results are listed in Table 5 below.

Example 7: Formulations with bentonite or corn starch granules The following formulations were prepared.
• Formulation #7a: 30% National Standard 325 Bentonite, 70% Raw Flaxseed Oil. Add 9g of National Standard 325 Bentonite to 21g of raw linseed oil. Mix until homogeneous.
• Formulation #7b: 30% National Standard 325 Bentonite, 10% Ecosense 919, 60% raw linseed oil. 18 g of raw linseed oil (RLO) and 3 g of Ecosense 919 (ES) were combined to make 9:1 raw linseed oil:Ecosense 919. Mix until homogeneous. Add 9 g of National Standard 325 bentonite to 21 g of 9:1 raw linseed oil:Ecosense 919 mixture. Mix until homogeneous.
• Formulation #7c: 30% industrial corn starch, 70% raw linseed oil. 9g of industrial corn starch was added to 21g of raw linseed oil. Mix until homogeneous.
• Formulation #7d: 30% industrial corn starch, 10% Ecosense 919, 60% raw linseed oil. 18g of raw linseed oil (RLO) and 3g of Ecosense 919 were combined to make 9:1 raw linseed oil: Ecosense 919. Mix until homogeneous. Add 9 g of industrial corn starch to 21 g of 9:1 raw linseed oil:Ecosense 919 mixture. Mix until homogeneous.

Samples of formulated 7a, 7b, 7c and 7d were allowed to stand for 2 hours and then observed for oil separation and any other precipitation observations. The sample was then inverted to determine the amount of effort required to resuspend the mixture. A water dispersibility test was performed on the resuspendable formulations. To conduct the water dispersibility test, 2 g of the concentrate was mixed with 31.3 g of tap water and the sample was vortexed. Observations are recorded in Table 6.

Example 8: Formulations with Different Surfactants The following formulations were prepared:
• Formulation #8a: 30% National Standard 325, 70% raw linseed oil. Add 9g of National Standard 325 to 21g of raw linseed oil. Mix until homogeneous.
• Formulation #8b: 30% National Standard 325, 5% Pluronic L121, 65% raw linseed oil. 19.95 g of raw linseed oil (RLO) and 1.05 g of Pluronic L121 were combined to make a 19:1 (Raw linseed oil: Pluronic L121) mixture. Pluronic L121 material is 100% active material without water. Mix until homogeneous. Add 9g of National Standard 325 Bentonite to 21g of oil/surfactant. Mix until homogeneous.
• Formulation #8c: 30% National Standard 325, 10% Ecosense 919, 60% raw linseed oil. 18.9 g of raw linseed oil (RLO) and 2.1 g of Ecosense 919 were combined to make 9:1 raw linseed oil:Ecosense 919. Mix until homogeneous Add 9g of National Standard 325 to 21g of oil/surfactant. Mix until homogeneous. Ecosense 919 surfactant is 50% actives and 50% water.
• Formulation #8d: 30% National Standard 325, 10% Decyl Glucoside, 60% Raw Flaxseed Oil. Combine 18.9 g of raw linseed oil (RLO) and 2.1 g of decyl glucoside to make a 9:1 mixture of (raw linseed oil:decyl glucoside). Mix until homogeneous Add 9g of National Standard 325 bentonite to 21g of oil/surfactant. Mix until homogeneous. Decyl glucoside surfactant is 50% active.

These formulations were tested according to the following protocol: samples are allowed to sit for 24 hours. Oil separation and any other precipitation observations are then measured. Then invert and determine the amount of effort required to resuspend the mixture. After these steps, a water dispersibility test was performed on the resuspendable formulation; 2 g of concentrate was mixed with 31.3 g of tap water and the sample was vortexed. The results of the test are recorded in Table 7.

Example 9: Formulations with Suspending Additives The following formulations were prepared:
• Formulation #9a: 30% National Standard 325, 10% Pluronic L121, 60% raw linseed oil. Mix 18g of raw linseed oil (RLO) with 3g of Pluronic L121. Mix until homogeneous. Add 9g of National Standard 325 to 21g of oil/surfactant. Mix until homogeneous.
• Formulation #9b: 30% National Standard 325, 10% Pluronic L121, 3% Magnesium Stearate, 57% Raw Flaxseed Oil. Mix 17.1g of raw linseed oil (RLO) with 3g of Pluronic L121. Mix until homogeneous. Then add 0.9 g of magnesium stearate. Add 9g of National Standard 325 to 21g of oil/surfactant. Mix until homogeneous.
• Formulation #9c: 30% National Standard 325, 10% Pluronic L121, 3% microcrystalline cellulose (MCC), 57% raw linseed oil. Mix 17.1g of raw linseed oil (RLO) with 3g of Pluronic L121. Mix until homogeneous. Then add 0.9 g of MCC. Add 9g of National Standard 325 Bentonite to 21g of oil/surfactant. Mix until homogeneous.

These formulations were tested according to the following protocol: samples were allowed to sit for 24 hours. Oil separation and any other precipitation observations are then measured. Then invert to determine the amount of effort required to resuspend the mixture. At the conclusion of these tests, the following results were observed: Magnesium stearate containing sample (#9b) had higher viscosity and no oil separation layer compared to sample #9a. Control sample 9a had an oil separation layer. The MCC containing sample (#9c) showed less oil separation and was easier to resuspend than the control sample 9a.

Example 10: Agricultural Formulation with Insecticide Soap A formulation suitable for agricultural application was prepared with the insecticide soap potassium laurate. An 18.88 g aliquot of raw linseed oil was added to a 40 mL glass vial followed by 1.60 g of SugaNate 160 and 1.60 g of 40% Span 85 dispersion in water. These materials were shaken together and vortexed. A 0.32 g sample of potassium laurate was then added to the vial and shaken and vortexed again. A 0.32 g sample of xanthan gum was added and the sample was shaken and vortexed once more. The final addition to the concentrated form was a 9.60 g sample of bentonite, which was added in thirds with shaking and vortexing between each addition. After all the bentonite was added, the vial was placed on a bottle roller for 30 minutes to disperse any remaining solid clumps. The finished product was a formulation suitable for agricultural applications containing an insecticidal soap. To prepare the solution for plant application, 1.0 g aliquots of the formulation were taken and added to 20 mL vials containing 15.65 g of tap water. Vials were shaken and vortexed and observed. After 1-2 minutes, the vial showed a stable dispersion in water with no signs of solid precipitation or oil separation for at least 30 minutes.

Example 11: Agricultural Formulation with Geraniol The essential oil geraniol, an insect repellent, was used to prepare formulations suitable for agricultural applications. An 18.24 g aliquot of raw linseed oil was added to a 40 mL glass vial followed by 1.60 g of SugaNate 160 and 1.60 g of 40% Span 85 dispersion in water. These materials were shaken together and vortexed to ensure a well-mixed product. A 0.64 g sample of geraniol was added to the vial and shaken and vortexed again. A 0.32 g sample of xanthan gum was then shaken and vortexed once more. The final addition to the formulation was a 9.60 g sample of bentonite, which was added in thirds with shaking and vortexing between each addition. After all the bentonite was added, the vial was placed on a bottle roller for 30 minutes to disperse any remaining clumps of solids. The finished product was a formulation suitable for agricultural applications containing an insect repellent essential oil. To prepare dilutions for plant application, 1.0 g aliquots of formulation were taken and added to 20 mL vials containing 15.65 g of tap water. The vial was shaken, vortexed and observed. After 30 minutes, the emulsion showed no signs of bentonite precipitation or oil separation.

Example 12: Agricultural Formulation with d-Limonene A formulation suitable for agricultural application was prepared with d-limonene, a vegetable oil pesticide. An 18.24 g aliquot of raw linseed oil was added to a 40 mL glass vial followed by 1.60 g of SugaNate 160 and 1.60 g of 40% Span 85 dispersion in water. These materials were shaken together and vortexed to ensure a well-mixed product. A 0.64 g sample of d-limonene was added to the vial and shaken and vortexed again. A 0.32 g sample of xanthan gum was then shaken and vortexed once more. The final addition to the concentrated form was a 9.60 g sample of bentonite, which was added in thirds with shaking and vortexing between each addition. After all the bentonite was added, the vial was placed on a bottle roller for 30 minutes to disperse any remaining clumps of solids. The finished product was a formulation suitable for agricultural applications containing d-limonene. To prepare dilutions for plant application, 1.0 g aliquots of the mixture were taken and added to 20 mL vials containing 15.65 g of tap water. The 20 mL vial was shaken, vortexed and observed. After 30 minutes, the emulsion showed no signs of bentonite precipitation or oil separation.

Example 13: Agricultural Formulation with Capsaicin The biopesticide capsaicin was used to prepare formulations suitable for agricultural applications. An 18.24 g aliquot of raw linseed oil was added to a 40 mL glass vial followed by 1.60 g of SugaNate 160 and 1.60 g of 40% Span 85 dispersion in water. These materials were shaken together and vortexed to ensure a well-mixed product. Tabasco Chipotle Pepper Sauce (McIlhenny Company) having a Scoville value of 1500-2500 thermal units for a 0.64 g sample was added to the vial followed by additional shaking and vortexing. The amount of capsaicin in the sauce is about 90-160 ppm based on conversion of the Scoville Units scale, where 16,000,000 Scoville Units equals pure capsaicin. A 0.32 g sample of xanthan gum was then shaken and vortexed once more. The final addition to the concentrated form was a 9.60 g sample of bentonite, which was added in thirds with shaking and vortexing between each addition. After all the bentonite was added, the vial was placed on a bottle roller for 30 minutes to disperse any remaining solid clumps. The finished product was a formulation suitable for agricultural applications containing capsaicin. To prepare dilutions for plant application, 1.0 g aliquots of the mixture were taken and added to 20 mL vials containing 15.65 g of tap water. The 20 mL vial was shaken, vortexed and observed. After 30 minutes, the emulsion showed no signs of bentonite precipitation or oil separation.

Example 14: Agricultural formulation with neem oil A formulation suitable for agricultural application was prepared using neem oil, a vegetable oil used as a pesticide in organic agriculture. A 15.68 g aliquot of raw linseed oil was added to a 40 mL glass vial followed by 1.60 g of SugaNate 160 and 1.60 g of 40% Span 85 dispersion in water. These materials were shaken together and vortexed to ensure a well-mixed product. A 3.20 g sample of neem oil (Blue Lily Organics) was added to the vial and shaken and vortexed again. A 0.32 g sample of xanthan gum was then shaken and vortexed once more. The final addition to the concentrated form was a 9.60 g sample of bentonite, which was added in thirds with shaking and vortexing between each addition. After all the bentonite was added, the vial was placed on a bottle roller for 30 minutes to disperse any remaining solid clumps. The finished product was a formulation suitable for agricultural applications containing neem oil. To prepare dilutions for plant application, 1.0 g aliquots of the mixture were taken and added to 20 mL vials containing 15.65 g of tap water. The 20 mL vials were shaken, vortexed and observed. After 30 minutes, the emulsion showed no signs of bentonite precipitation or oil separation.

Example 15: Rainfastness of agricultural formulations containing neem oil
The rain resistance of the agricultural formulation of Example 14 was tested as follows. A comparative neem oil formulation was prepared by adding 15.90 g of tap water, then 1.0 g of neem oil, 0.0175 g of potassium laurate and 0.1134 g of 1.0 M sodium hydroxide (Sigma Aldrich) to a 20 mL vial. bottom. This comparative mixture was vortexed and found to be sufficiently stable to nebulization. 3 g of the comparative neem oil formulation was sprayed onto the surface of a tared 5″×3″ acrylic sheet (Plaskolite brand) and then rolled up with an applicator roller. An acrylic sheet material was used as a model of the plant surface. Onto another tared 5″×3″ acrylic sheet, a 3.0 g aliquot of the diluted agricultural formulation of Example 14 with neem oil was sprayed and spread with an applicator roller. Both treated acrylic sheets were allowed to dry for 18 hours to cure the coatings, their weights were recorded and then the sheets were sprayed with water from a spray bottle for 15 seconds to simulate rainfall. After being sprayed with water, both sheets were placed in a forced convection air oven at 37C for 1.5 hours to dry and their weights were recorded again. Sheets treated with the agricultural formulation of Example 14 containing neem oil retained 68% of the applied coating after simulated rainfall, while the comparative formulation of neem oil, potassium laurate and sodium hydroxide did not retain the coating after simulated rainfall.

Example 16: Agricultural Formulation with Camphor Oil White camphor oil, an essential oil used as a pest repellent, was used to prepare a formulation suitable for agricultural applications. A 15.68 g aliquot of raw linseed oil was added to a 40 mL glass vial followed by 1.60 g of SugaNate 160 and 1.60 g of 40% Span 85 dispersion in water. These materials were shaken together and vortexed to ensure a well-mixed product. A 3.20 g sample of white camphor oil (Sigma Aldrich) was added to the vial and shaken and vortexed again. A 0.32 g sample of xanthan gum was then shaken and vortexed once more. The final addition to the concentrated form was a 9.60 g sample of bentonite, which was added in thirds with shaking and vortexing between each addition. After all the bentonite was added, the vial was placed on a bottle roller for 30 minutes to disperse any remaining solid clumps. The finished product was a formulation suitable for agricultural applications containing white camphor oil. To prepare dilutions for plant application, 1.0 g aliquots of the mixture were taken and added to 20 mL vials containing 15.65 g of tap water. The 20 mL vial was shaken, vortexed and observed. After 30 minutes, the emulsion showed no signs of bentonite precipitation or oil separation.

Example 17: Agricultural Formulations with Beneficial Fungi Beneficial fungi were used to prepare formulations suitable for agricultural applications. An 18.56 g aliquot of raw linseed oil was added to a 40 mL glass vial followed by a 1.60 g aliquot of the product SugaNate 160 and a 1.60 g aliquot of a 40% Span 85 dispersion in water. These materials were shaken together and vortexed to ensure a well-mixed product. A 0.32 g sample of the product "White Shark" (Plant Revolution Inc.) was added to the vial and shaken and vortexed again. White Shark is a beneficial fungal powder containing 187,875 CFU/g Trichoderma koningii and 125,250 CFU/g Trichoderma harzianum. A 0.32 g sample of xanthan gum was then added and the mixture was shaken and vortexed once more. A 9.60 g sample of bentonite was then added in thirds with shaking and vortexing between each addition. After all the bentonite was added, the vial was placed on a bottle roller for 30 minutes to disperse any remaining solid clumps. The finished product was a formulation suitable for agricultural applications containing beneficial fungi. To prepare dilutions for plant application, 1.0 g aliquots of the mixture were taken and added to 20 mL vials containing 15.65 g of tap water. The 20 mL vial was shaken, vortexed and observed. After 30 minutes, the emulsion showed no signs of bentonite or fungal spore powder precipitation or oil separation.

Example 18: Agricultural Formulations with Sulfur Formulations suitable for agricultural applications were prepared with elemental sulfur that can be used as a fungicide. An 18.56 g aliquot of raw linseed oil was added to a 40 mL glass vial followed by 1.60 g of SugaNate 160 and 1.60 g of 40% Span 85 dispersion in water. These materials were shaken together and vortexed to ensure a well-mixed product. A 0.32 g sample of elemental sulfur powder was added to the vial and shaken and vortexed again. A 0.32 g sample of xanthan gum was then added and the mixture was shaken and vortexed once more. A 9.60 g sample of bentonite was then added in thirds with shaking and vortexing between each addition. After all the bentonite was added, the vial was placed on a bottle roller for 30 minutes to disperse any remaining solid clumps. The finished product was a formulation suitable for agricultural applications containing beneficial fungi. To prepare dilutions for plant application, 1.0 g aliquots of the mixture were taken and added to 20 mL vials containing 15.65 g of tap water. The 20 mL vial was shaken, vortexed and observed. After 30 minutes, the emulsion showed no signs of bentonite precipitation or oil separation.

Example 19: Rain resistance of agricultural formulations with geraniol The rain resistance of the agricultural formulations of Example 11 was tested as follows. A comparative geraniol formulation was prepared by adding 15.90 g tap water, then 1.0 g geraniol, 0.0175 g potassium laurate and 0.1134 g 1.0 M sodium hydroxide (Sigma Aldrich) to a 20 mL vial. This comparative mixture was vortexed and found to be stable enough to be nebulized. 3 g of the comparative geraniol formulation was sprayed onto the surface of a tared 5″×3″ acrylic sheet (Plaskolite brand) and spread with an application roller. A separate tared 5" x 3" acrylic sheet was sprayed with a 3.0 g aliquot of the diluted agricultural formulation with geraniol of Example 11 and spread with an application roller. Both treated acrylic sheets were allowed to dry for 18 hours to cure the coatings, their weights were recorded and then the sheets were sprayed with water from a spray bottle for 15 seconds to simulate rainfall. After spraying with water, both sheets were dried in a forced convection air oven at 37°C for 1.5 hours and their weights were recorded again. Sheets treated with the Example 11 agricultural formulation containing geraniol retained 34.5% of the applied coating after simulated rainfall, while sheets treated with the comparative formulation of geraniol, potassium laurate and sodium hydroxide The coating did not retain after simulated rainfall.

Example 20: Rain resistance of agricultural formulations with d-limonene The rain resistance of the agricultural formulations of Example 12 was tested as follows. A comparative d-limonene formulation was prepared by adding 15.90 g tap water, then 1.0 g d-limonene, 0.0175 g potassium laurate and 0.1134 g 1.0 M sodium hydroxide (Sigma Aldrich) to a 20 mL vial. bottom. This comparative mixture was vortexed and found to be stable enough to be nebulized. 3 g of the comparative d-limonene formulation was sprayed onto the surface of a tared 5″×3″ acrylic sheet (Plaskolite brand) and then spread with an application roller. A 3.0 g aliquot of the agricultural formulation with diluted d-limonene of Example 12 was sprayed onto another tared 5" x 3" acrylic sheet and spread with an application roller. Both treated acrylic sheets were allowed to dry for 18 hours to cure the coatings, their weights were recorded, and then the sheets were sprayed with water from a spray bottle for 15 seconds to simulate rainfall. After spraying with water, both sheets were dried in a forced convection air oven at 37°C for 1.5 hours and their weights were recorded again. Sheets treated with the agricultural formulation of Example 12 containing d-limonene retained 53.9% of the applied coating after simulated rainfall, while the comparative Sheets treated with the formulation did not retain any of the coating after simulated rainfall.

Example 21: Agricultural Formulation A formulation suitable for agricultural application was prepared as follows. An 18.88 g aliquot of raw linseed oil was added to a 40 mL glass vial followed by 1.60 g of SugaNate 160 and 1.60 g of 40% Span 85 dispersion in water. These materials were shaken together and vortexed. A 0.32 g sample of xanthan gum was then added and the mixture was shaken and vortexed once more. A 9.60 g sample of bentonite was then added in thirds with shaking and vortexing between each addition. After all the bentonite was added, the vial was placed on a bottle roller for 30 minutes to disperse any remaining clumps of solids. The finished product was a formulation suitable for agricultural application in the form of a fluid suspension. To prepare dilutions for plant application, 1.0 g aliquots of the mixture were taken and added to 20 mL vials containing 15.65 g of tap water. The 20 mL vials were shaken, vortexed and observed. After 30 minutes, the emulsion showed no signs of solid precipitation or oil separation.

Example 22: Rain fastness of agricultural formulations with Trichoderma
The rain resistance of the agricultural formulation of Example 17 was tested as follows. A comparative Trichoderma formulation (Example 22a) was prepared by adding 14.85 g of tap water followed by 0.15 g of the product "White Shark" (Plant Revolution Inc.) to a 20 mL vial. This comparative mixture was vortexed and found to be stable enough to be nebulized. 3 g of this comparative Trichoderma formulation was then sprayed onto the surface of a 5″×3″ acrylic sheet (Plaskolite brand). On two separate 5″×3″ acrylic sheets, 3 g of the diluted agricultural formulation of Example 17 with Trichoderma (Samples a and b) was sprayed onto each surface. All treated acrylic sheets were placed in a non-convection oven at 37C for 1.5 hours to dry. Optical images of each sheet were taken using an optical microscope (Zeiss AxioImager.A1M). Each sheet was then exposed to simulated rainfall by spraying water from a spray bottle for 15 seconds. After spraying with water, the sheets were placed in a non-convection oven at 37C for 1.5 hours to dry. Images of each sheet were retaken using an optical microscope. ImageJ software (National Institutes of Health) was used to analyze the distribution of particles in each acrylic sheet and these results are summarized in Table 8. Sheets treated with the diluted agricultural formulation of Example 17 containing Trichoderma retained 81-86% of the applied particles after simulated rainfall, while sheets treated with the comparative formulation of Trichoderma retained 81-86% of the applied particles after simulated rainfall. Only 8% of the applied particles were retained afterward.

Example 23: Agroformulation Several surfactant products were evaluated by incorporating one of each into an agroformulation sample. Eight formulation samples were prepared using the ingredients listed in Table 9 below:

To prepare the samples, eight 40 mL vials were first filled with the amounts listed in Table 9 of raw linseed oil (Cargill). After adding the linseed oil, an aliquot of each surfactant product was added to the corresponding 40 mL vial listed in Table 9 so that 2% of the active surfactant component was in the final sample formulation. calculated to exist in A dispersion of 40% Span 85 (Millipore) was then shaken vigorously and then added to each individual vial in an amount of 1.60 grams. Each sample vial was then shaken and vortexed together to ensure a well-mixed product. After this, 0.32 grams of xanthan gum was added to each vial and each vial was shaken and vortexed. The final addition to each vial was a 9.60 gram sample of bentonite, which was added in thirds with shaking and vortexing between each addition. After all the bentonite was added, each vial was placed on rollers for 30 minutes to disperse any remaining solid clumps. After 30 minutes, each vial was removed and a 1.0 gram aliquot of each mixture was taken and added to a 20 mL vial containing 15.65 grams of tap water to form diluted samples. Diluted samples were vigorously shaken, vortexed and observed. Concentrated samples were left overnight.

A control was then prepared in the same manner using amounts of 18.72 grams raw linseed oil, 1.60 grams 40% Span 85 dispersion in water, 1.60 grams water, 0.48 grams xanthan gum and 9.60 grams bentonite. After 30 minutes on the roller, a 1.0 gram aliquot was taken and added to a 20 mL vial containing 15.65 grams of tap water to form a diluted sample. Diluted samples were vigorously shaken, vortexed and observed. Concentrated samples were left overnight.

The diluted samples were evaluated as to whether the bentonite remained dispersed or settled out completely, and whether the oil remained dispersed throughout the sample or separated at the top. A good result was a thorough and uniform dispersion of clay and oil in water. The results are listed in Table 10 below:

Stability was assessed by leaving the concentrated formulation untouched for 71 hours and then assessing how easily the precipitated bentonite could be redispersed. Each vial was gently tumbled to see how the bentonite was compacted at the bottom and how the bentonite was redispersible. The tumbled samples were graded with a "dispersibility" number from 1 to 5, where 1 means "easily dispersible" and 5 means "not dispersible." We focused on samples with bentonite that redispersed with only a simple tipping. Each sample was then shaken vigorously by hand for about 5 seconds and again evaluated for redispersion of the precipitated bentonite. Results are listed in Table 11 below:

Example 24: Seed coating with agricultural formulations
Burpee Pea Super Snappy seeds were coated with an aqueous mixture of 3%, 10% and 16% (w/w) of the agricultural formulation of Example 21 in water; the coated seeds were then allowed to air dry at 22°C. Seeds (6 replicates of each coating type) were planted in Conrad Fafard Organic Potting Mix and watered daily. After the different amounts of time shown in Table 12, the germination rate determined as % of planted seeds that germinated was recorded.

Example 25: Agricultural Formulations with Stabilizers Several different additives were evaluated for their ability to stabilize formulations when diluted with water. To prepare these formulations, 18.88 grams of raw linseed oil (Cargill) was added to each of 14 separate vials, followed by 1.60 gram aliquots of the product SugaNate 160 (Colonial Chemical Company) and 1.60 gram aliquots of water. Filled with 40% Span 85 (Millipore) dispersion. These materials were shaken together and vortexed to ensure a well-mixed product. A single 0.32 gram sample of each emulsion stabilizer (as listed in Table 13) was measured and added to each vial. After each vial received their respective emulsion stabilizer, the samples were shaken and vortexed again. A 9.60 gram sample of bentonite was then added in thirds with shaking and vortexing between each addition. After all the bentonite was added to the vial, it was placed on a roller for 30 minutes to disperse any remaining solid clumps. After 30 minutes, each vial was removed and a 1.0 gram aliquot of each mixture was taken and added to each 20 mL vial containing 15.65 grams of tap water to form diluted samples. Diluted samples were vigorously shaken, vortexed and observed.

The diluted samples were evaluated as to whether the bentonite remained dispersed or settled out completely, and whether the oil remained dispersed throughout the sample or separated at the top. A good result was a thorough and uniform dispersion of the clay and oil in the water. The results are listed in Table 13 below.

Example 26: Trichoderma spore germination in agricultural formulations The agricultural formulations of Example 17 were compared to a control formulation to assess the viability of the Trichoderma spores each contained. A control Trichoderma formulation was prepared as follows: 0.15 gm of the Trichoderma-containing product "White Shark" was added to 14.85 g of tap water in a 20 mL vial. This control mixture was vortexed and found to be stable enough to be nebulized. 1 g of this control Trichoderma formulation was then sprayed onto the surface of a 1″×3″ glass slide. On another 1″×3″ glass slide, 1 g of the diluted agricultural formulation of Example 17 was sprayed onto the surface. Both treated glass slides were then placed in a non-convection oven at 37C for 1.5 hours to dry. Following this drying, a 0.2 g aliquot of 0.02% Potato Dextrose Agar (“PDA”, Sigma Aldrich) in water was pipetted onto each previously coated glass slide. Each glass slide was then placed on top of another 200 mL container, each of which was then secured inside another 1 L container with glue. 60 g of tap water was placed inside each 1 L container to create a highly humid environment for Trichoderma spores to grow and slow the evaporation rate of the PDA medium. Both prepared 1 L containers were sealed with caps and incubated at 25C in a non-convection oven for 3 days. After 3 days, the slides were removed from the oven and examined for Trichoderma spore germination by colony formation using a Zeiss AxioImager.A1M microscope. Both control Trichoderma formulations and the formulation of Example 17 showed signs of Trichoderma germination, as indicated by the appearance of branched hyphae.

Example 27: Trichoderma spore germination in agricultural formulations after simulated rainfall The experiment of Example 26 was reproduced to test control and experimental samples for the presence of viable spores after exposure to simulated rainfall. A control Trichoderma formulation was prepared as described in Example 26. Test formulations were prepared as described in Example 17. Each formulation was applied to a glass slide and allowed to dry as described in Example 26. After this drying had taken place, each glass slide was then exposed to simulated rainfall by spraying water from a spray bottle for 15 seconds. After water spraying, both slides were placed in a non-convection oven at 37C for 1.5 hours to dry.

After drying, each slide received a 0.2 g aliquot of 0.02% potato dextrose agar in water and incubated as described in Example 26. After 3 days, samples were examined for spore germination as described in Example 26. Glass slides treated with the agricultural formulation of Example 17 containing Trichoderma showed germination (as indicated by the appearance of branched hyphae) even after simulated rainfall, whereas comparative formulations of Trichoderma showed germination. The treated glass slides did not show any Trichoderma germination after simulated rainfall.

Examples 28-32: Additional Materials:
Examples 28-32 used the following materials in addition to those previously described:
- Raw Flaxseed Oil (RLO), (CAS# 67746-08-1) (Cargill)
Bentonite (sodium bentonite clay) (CAS# 1302-78-9) (BPM / Halliburton)
Jarfactant 325N, an alkyl polyglycoside surfactant with an alkyl chain length of 9-11 carbon units (CAS#132778-08-6) (Jarchem)
・Span 85 (sorbitan trioleate) (CAS# 26266-58-0)
- Pluronic® F108 (PEG-PPG-PEG triblock copolymer and surfactant) (CAS#9003-11-6) (Sigma-Millipore)
Water (Cambridge MA tap water) (all water is tap unless specified)
Ammonium hydroxide: 30% solution of ammonia and water (CAS# 1336-21-6)
・Dowanol ^TM TPM (tripropylene glycol methyl ether) (Dow Chemicals)
- THIXCIN® R (non-hygroscopic castor oil derivative) (Elementis Specialties)
Break Thru SP133 (additive based on polyglycerol esters and fatty acid esters) (Evonik)
- HPMC-Hydroxypropyl methylcellulose (Methocel E15 LV, CAS#9004-54-3) (Dow Chemical Company)

Example 28: Formulation Preparation Agricultural formulations were prepared as concentrates in large and small batch sizes (small < 250g) using the amounts of reagents listed in Table 14:

To prepare the formulations described above, a polymer solution was first prepared. An appropriate amount of Pluronic® F108 was measured according to the amounts shown in Table 14. Appropriate amount of water was added to a mixing vessel (eg, a beaker for large solutions or a centrifuge tube for small solutions) so that an 18.2% solution of Pluronic® F108 could be made. The Pluronic® F108 was then slowly added and mixed into the water, taking care to ensure that the Pluronic® F108 was completely transferred to the water and not adhered to the walls of the container. If a centrifuge tube mixing container was used, it was then capped and placed on a laboratory roller at approximately 70% maximum speed. If a beaker size mixing vessel was used, this was mixed in a laboratory mixer using a fan blade mixing shaft sized appropriately for the mixing vessel. Pluronic® F108 was mixed into water until no solid polymer remained and only a little water and foam remained. If lumps started to form, a spatula was used to stir and separate further to ensure complete dissolution. After demonstrating no more solid polymer (usually after several hours of mixing), the mixing vessel is removed from the mixing apparatus and allowed to sit for a period of time to allow the foam above the solution to return to its full liquid form (relax back); this stationary phase required several hours, often overnight.

After preparing the Pluronic® F108 solution, the appropriate amount of bentonite was weighed into the designated solid container. The solid container was then shaken to break up any solid clumps. Appropriate amounts of RLO, Pluronic® F108 solution and Jarfactant 325N were then combined and appropriate amounts of NaOH solution were added. These liquids were briefly mixed to homogeneity using an overhead mixer with fan shaft blades. After combining the RLO and aqueous reagents, the appropriate amount of Span 85 was added to the stirred sample. All liquid reagents were thoroughly mixed and then such mixture was combined with the solids. Solid materials were added gradually and mixed thoroughly during the addition process.

Example 29: Sedimentation Stability Formulations prepared according to Example 28 were tested for sedimentation stability. To do so, a 1″ diameter clear plastic cylinder was packed with a 12″ column of freshly prepared formulation. Sedimentation of the aqueous phase in the concentrate resulted in the appearance of a clear fluid layer at the top of the column and the formation of a dense concentrate at the bottom of the column. The thickness of the transparent fluid layer was determined by eye. The thickness of the dense concentrate is determined by pouring the fluid out of the tube and noting the height of the column of unpoured material, or by lowering the weight into the column to stop the weight from penetrating the fluid. Determined by either looking at depth. Sedimentation measurements were taken periodically until the sum of the clear and dense layers reached approximately 100%; see Table 15 below.

Example 30: Stabilization of formulation against sedimentation with Dowanol ^™ TPM An agricultural formulation prepared according to Example 28 was used for the following experiments. 200g of agricultural formulation was added to the beaker. Then 8 g (4 wt%) of Dowanol TPM (Dow) was added while stirring at 300 rpm. Mixing was continued for 10 minutes. The resulting mixture was a pourable fluid with pseudoplastic properties. Yield stress at 0.1 rpm was measured using a Brookfield YR-1 rheometer. The yield stress obtained was 12.7Pa. The formulations were then tested for sedimentation stability according to Example 29. After 7 days, a clear layer was observed with a thickness equal to 3% of the original column height.

Example 31: Stabilization of formulations with THIXCIN® R (Elementis Specialties) An agricultural formulation prepared according to Example 28 was used for the following experiments. 200 g of agricultural formulation was added to each of three beakers. Sufficient THIXCIN® R (Elementis Specialties) was then added to each beaker to achieve a THIXCIN® R concentration of 0.05 wt%, 0.1 wt% or 0.3 wt% while stirring at 300 rpm. bottom. Mixing was continued for 10 minutes while heating at 60°C. Upon cooling to room temperature, the resulting mixture was a pourable fluid with pseudoplastic properties. All formulations were tested for sedimentation stability according to Example 29. After 7 days, no settling was observed in any of the formulations tested.

Example 32: Formulation Preparation An agricultural formulation was prepared as a concentrate in small batch sizes (small < 250g) using the amounts of reagents listed in Table 16:

To prepare the formulations described above, first, appropriate amounts of HPMC and bentonite were each weighed into a sealable container; the container was then sealed and shaken to promote homogeneity. Appropriate amounts of water and Jarfactant 325N were then combined in a beaker and stirred to facilitate dissolution of Jarfactant 325N. After stirring, the RLO was added and appropriate amounts of Break-Thru SP 133 and Span 85 were also added to the sample. All liquid reagents were then thoroughly mixed in a laboratory overhead mixer fitted with a small fan blade, after which such mixture was combined with the solids. While stirring the mixture, slowly add the solid ingredients with a spatula; once all the solids have been added, start a 10 minute timer and scrape the walls of the beaker (as well as the stirring shaft) with a spatula to remove any clay. Prevented arbitrary chunks from being left unmixed.

Examples 33-36: Additional Materials:
Examples 33-36 used the following materials in addition to those previously described: Methocel E15-LV (hydroxypropyl methylcellulose) (CAS 9004-65-3) (Dow)
- Soybean Oil (CAS 8001-22-7) (Sigma-Aldrich)

Example 33: Formulation Preparation Agricultural formulations were prepared as concentrates in small batch sizes (small < 250g) using the amounts of reagents described in Table 17 below:

Using the ingredients in Table 17, formulations were prepared using batch mixing with an overhead mixer. First, the solids (bentonite and methocel) were mixed in a sealed container by hand shaking for 10-20 seconds. In a separate vessel, the desired oil combination was mixed to prepare the oil phase of the formulation using an overhead mixer at very low speed (200-300 rpm) to prevent splashing. Aqueous reagents (Jarfactant 325N and distilled water) and non-aqueous reagents (Span 85 and Break Thru SP 133) were subsequently combined into the oil phase and mixed until homogeneity was achieved. The solids were added to the previous oil mixture under continuous mixing. During solids consolidation, the mixing speed was slowly increased to a speed that produced sufficient vortex (700-800 rpm) and maintained at that speed for 15 minutes to sufficiently wet the solids and form a homogeneous mixture. The formula was then further mixed under high shear using a homogenizer or a high speed disperser (5000-6000 rpm) for 25 minutes to fully develop the formula body. After mixing, the viscosity of the formulations was measured to determine differences between compositions as a measure of injectability.

Example 34: Methods Used to Evaluate Coating Properties The following observations and tests were used to evaluate the properties of various coatings formed according to the following examples.

(a) Air-drying Observation: The air-drying process of the coating can be determined under natural or artificial lighting. Artificial lighting was preferred as it provided control and continuous exposure. This provides the ability to accelerate development and testing. To correlate the intensity of artificial and natural illumination, radiance in the UVB range was measured. Unsaturated bonds in oil were the most sensitive to light in this region.

(b) Rolling ball tack test: The rolling ball tack test was used to measure changes in the coating upon exposure. The method was modified from industry standard measurements for pressure sensitive adhesion. In this method, a stainless steel ball was rolled across the coated surface at a predetermined initial velocity. Adhesive interactions between the ball and the surface caused the ball to lose kinetic energy to the coating and eventually come to rest. The total distance traveled by the ball was used as a measure of the strength of these interactions. Generally, two coating states were observed for the coated surfaces as a function of time. In the first state, the coating preferentially progressed from a viscous to a viscoelastic state. Chemically, this is the early stage of autoxidation, a process that can be monitored using infrared spectroscopy to follow the conversion of alkenes or unsaturated bonds when the oil is exposed to oxygen and light. Relating. It is understood that significant intermolecular cross-linking events follow the initial state of autoxidation. This resulted in an increase in the adhesion strength of the coating and reduced the distance traveled by the rolling ball. In the second state, the coating progressed from a viscoelastic to a preferentially elastic state when cross-linking continued. This reduced the bond strength and increased the distance traveled by the rolling ball. Eventually, the coating became non-tacky and dry to the touch, and the distance traveled by the rolling ball reached a maximum value set by the size of the coating specimen. The time to reach this maximum was termed the "dry time" for the coating. The initial reduction in rolling ball distance was shown to coincide with an increase in alkene conversion rate as shown in FIG.

(c) Testing for Film Stiffness: Flexibility or stiffness of self-supporting films was determined by force deflection measurements. The results obtained were analyzed to assess the Young's modulus (or elastic modulus) for the films. To make the measurements, a film of known thickness was attached to the stage using double-sided adhesive across a 1 inch diameter annular opening. A 1/2 inch diameter cylindrical probe was mounted on the translation stage, coupled to the force sensor, and positioned over the center of the film. A translation stage was used to bring the probe into contact with the center of the film, and the force required to deform the film was recorded as a function of distance traveled by the probe.

図2に示される測定値を式1に適合することで、26MPaおよび950Paそれぞれのフィルムのヤング率および残留応力についての推定値が生じる。 The force required to produce a given deflection for a pure linseed oil film (SB0), thickness 130 μm is shown in FIG. To estimate the Young's modulus and residual stress of the film, the stiffness data shown in Figure 2 were fitted to a model of a thin annular plate, clamped at the edges and subjected to uniform pressure over the annular area at the center of the plate. (Young, WC Roark's Formulas for Stress and Strain, 6th ed. 1989. McGraw-Hill Inc, New York, p477-478). For a film of thickness t, radius R, Young's modulus E, residual stress σ _R and a Poisson's ratio of 0.3 applied to a force F over a central region of radius a, the dislocations d at the center of the film are estimated to satisfy Was:

Fitting the measurements shown in FIG. 2 to Equation 1 yields estimates for the Young's modulus and residual stress of the films of 26 MPa and 950 Pa, respectively.

Example 35: Formulations with mixtures of soybean oil and linseed oil Soybean oil and linseed oil were mixed in different proportions and then tested to determine the properties of the different mixtures. The following formulations shown in Table 18 were tested:

In this example, soybean oil and linseed oil were mixed in different proportions and then tested to determine the effect of the oil mixture on the physical properties of the formulation. A rolling ball test determined that drying time increased with increasing concentration of soybean oil in the mixture (ie, from SB0 to SB75), as shown in FIG. As seen in Figure 4, the modulus decreased with increasing soybean oil content. Therefore, blends of different oils can be used to adjust the final rate of dry film.

Example 36: Formulations with a mixture of canola and linseed oils In this example, as shown in Table 19, formulations were prepared in which canola and linseed oils were mixed in a 50:50 ratio. The formulations were then tested to determine the effect of the oil mixture on the formulation's physical properties.

Dry time measurements made using the rolling ball tack test were significantly improved by including canola oil (CA50), which contains relatively low concentrations of polyunsaturated acylglycerols, in pure linseed oil (SB0) and linseed and soybean oil. (SB50) resulted in a significant increase in the drying time of the mixture; see FIG.

Example 37: Formulation Preparation For Example 37, the following materials can be used in addition to those described in previous examples:
・Polyethylene glycol dodecyl ether (Brij L4 (CAS 9002-92-0) (Croda))
・Low molecular weight nonionic silicone polyether surfactant (Sylgard OFX-0309 (CAS 125997-17-3, 75-85%) (Dow))

Agricultural formulations may be prepared as concentrates using the amounts of reagents listed in Table 20 below:

Formulations using the ingredients in Table 20 can be prepared using batch mixing with an overhead mixer. First, measure out the solid (bentonite). In a separate vessel, the oil combination may be mixed to prepare the oil phase of the formulation using an overhead mixer at low speed (200-300 rpm) to prevent splashing. Subsequently, the reagents (Brij L4 and Sylgard OFX-0309) can be incorporated into the oil phase and mixed until homogeneity is achieved. Solids may be added to the previous oil mixture under continuous mixing. During consolidation of the solids, the mixing speed can be slowly increased to a speed that produces a sufficient vortex (400-500 rpm) and maintained at that speed for 10 minutes to sufficiently wet the solids and produce a homogeneous mixture. can form. The formulation may then be further mixed under high shear using a high speed disperser (1800-2500 rpm) for 10 minutes to develop a formulation. After mixing, the viscosity of the formulation can be measured to determine differences between compositions as a measure of injectability. Properties of exemplary formulations are expected to be similar to those described above in Examples 35 and 36.

Equivalents While certain aspects of the present invention are disclosed herein, the foregoing specification is illustrative and not restrictive. Although the invention has been particularly shown and described with reference to preferred embodiments thereof, various changes in form and detail may be made without departing from the scope of the invention encompassed by the appended claims. Those skilled in the art will understand what can be done in the present invention. Many variations of the invention will become apparent to those skilled in the art upon review of this specification. Unless otherwise indicated, all numbers expressing reaction conditions, amounts of ingredients, etc. as used in the specification and claims are assumed to be modified in all instances by the term "about." understood. Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending on the desired properties sought to be obtained by the present invention.

Claims (65)

A non-toxic agricultural formulation of a concentrated liquid suspension comprising an organic phase and suspended particulate material, comprising:
i. the organic phase comprises a drying oil, the drying oil comprising one or more different acylglycerols; or
ii. the organic phase comprises a first oil and a second oil mixed together to form a mixture, wherein at least one of the first oil and the second oil is a drying oil;
Non-toxic agricultural formulation. 2. The formulation of claim 1, which forms a cured coating on an agricultural target. 3. The formulation of claim 2, wherein the cured coating is water resistant. 3. The formulation of claim 2, wherein the cured coating is abrasion resistant. 3. The formulation of claim 2, wherein the cured coating is rain resistant. 3. The formulation of claim 2, wherein the cured coating retains the particulate material suspended on the agricultural target when subjected to adverse conditions. 7. The formulation of claim 6, wherein the adverse conditions are selected from the group consisting of rainfall, friction, wind, water exposure and secondary agricultural treatments. 2. The formulation of claim 1, which is stable to phase separation. 2. The formulation of claim 1, comprising food grade ingredients. 2. The formulation of claim 1, comprising organically produced ingredients. 11. The formulation of claim 10, consisting essentially of organically produced ingredients. 2. The formulation of claim 1, comprising ingredients generally recognized as safe. 13. The formulation of claim 12, consisting essentially of ingredients generally recognized as safe. 2. The formulation of claim 1, wherein the concentrated liquid suspension contains only non-aqueous liquids. 2. The formulation of claim 1, wherein the organic phase is from about 40 to about 99% by weight of the formulation. Drying oils include linseed oil, raw linseed oil, boiled linseed oil, castor oil, castor oil glycidyl ether, tung oil, poppy seed oil, grape seed oil, safflower oil, linoleic acid, linolenic acid, oleic acid, poppy seed oil, sunflower 2. The formulation of claim 1 selected from the group consisting of oil, evening primrose oil, perilla oil, soybean oil, corn/corn oil, canola/rapeseed oil and walnut oil. 2. The formulation of Claim 1, wherein the drying oil comprises alpha-linolenic acid, linoleic acid, or a combination thereof. 2. The formulation of Claim 1, wherein the drying oil comprises one or more different acylglycerols. 19. The formulation of claim 18, wherein the drying oil is a naturally occurring mixture of one or more acylglycerols that can undergo spontaneous conversion from liquid to solid state upon exposure to oxygen. 20. A formulation according to claim 19, wherein spontaneous conversion is characterized by the occurrence of crosslinks between double bonds on one or more acylglycerols. 21. The formulation of claim 20, wherein spontaneous conversion results in the formation of a polymer network. 2. The formulation of claim 1, wherein the organic phase comprises a first oil and a second oil mixed together to form a mixture, at least one of the first oil and the second oil being a drying oil. 23. The formulation of claim 22, having one or more physical properties that are different from those of the first oil and the second oil. The one or more physical properties are glass transition temperature of the cured film, solubility of small molecules in the cured film, permeability of the cured film to small molecules, film stiffness, film viscosity, film drying. 24. The formulation of claim 23, selected from the group consisting of time and durability. 25. The formulation of claim 24, wherein the organic phase has improved pest control properties when compared to the pest control properties of a control formulation comprising a single drying oil. 26. The formulation of claim 25, wherein the pest control properties are selected from the group consisting of reduced pest survival time, reduced pest spawning capacity, inhibition of food intake by pests, inhibition of pest reproduction and reduced plant damage. 23. The formulation of claim 22, wherein both the first oil and the second oil are drying oils. 28. The formulation of Claim 27, wherein the first oil and the second oil have different degrees of unsaturation. 28. A formulation according to claim 27, wherein the mixture comprises at least one additional oil. 30. The formulation of Claim 29, wherein the at least one additional oil is an additional drying oil. 28. The formulation of Claim 27, wherein the mixture further comprises a diluent. 32. The formulation of Claim 31, wherein the diluent is selected from the group consisting of mineral oil, petroleum distillates, alcohols, terpenes and glycols. 2. The formulation of claim 1, wherein the suspended particulates are from about 0.5 to about 50% by weight of the formulation. 2. The formulation of claim 1, wherein the suspended particulate matter is permanently suspended in the organic phase. 2. The formulation of claim 1, wherein the suspended particulates are readily resuspended in the organic phase. 2. The formulation of claim 1, wherein the suspended particulate matter is selected from the group consisting of clay minerals and organically modified minerals. 37. The formulation of claim 36, wherein the clay mineral is selected from the group consisting of kaolin clay, smectite clay, illite clay, chlorite clay, meerschaum and attapulgite. 37. The formulation of claim 36, wherein the clay mineral is bentonite clay. 37. The formulation of Claim 36, wherein the organically modified mineral is a clay mineral. Organically modified minerals are fatty acids, fatty amines, fatty amides, fatty esters, fatty amine quats, quaternary amine surfactants, cetyltrimethylammonium bromide, fatty alcohols, decyl alcohol, dodecyl alcohol, linseed oil, alkenyl 37. The formulation of Claim 36 modified with an organic variant selected from the group consisting of succinic anhydride, styrene-maleic anhydride copolymer, colophony, rosin, chitosan and castor oil derivatives. 2. The formulation of claim 1, further comprising pesticides, herbicides, beneficial bacteria, beneficial fungi, plant growth regulators, pheromones, sunscreens, biopesticides or nutrients. 2. The formulation of Claim 1, further comprising a plant extract. 2. The formulation of claim 1, further comprising vegetable oil. 2. The formulation of claim 1, further comprising additional particulate material. Further particulate materials are talc, calcium carbonate, gypsum, magnesium silicate, calcium silicate, maize starch, cellulose fibres, psyllium fibres, ethylenebisstearamide, microcrystalline cellulose, stearic acid, paraffin wax, carnauba wax or beeswax. 45. The formulation of claim 44, selected from the group consisting of: 45. The formulation of Claim 44, wherein the additional particulate material is selected from the group consisting of kaolin and titanium dioxide. 2. The formulation of claim 1, further comprising a surfactant. 48. The formulation of Claim 47, wherein the surfactant is selected from the group consisting of anionic, cationic, nonionic, biodegradable, food grade and organic surfactants. 2. The formulation of claim 1, further comprising an adjuvant selected from the group consisting of cellulose derivatives, polylactic acid, polyglycolic acid and polylactic-glycolic acid. 2. The formulation of Claim 1, further comprising a salt. 2. The formulation of Claim 1, further comprising a curing additive. An aqueous formulation comprising a concentrated liquid suspension as defined in claim 1 and an agricultural treatment. A coated agricultural treatment comprising an agricultural treatment and a concentrated liquid suspension as defined in claim 1, wherein the concentrated liquid suspension is applied to the agricultural treatment as a coating. Agricultural treatment agent. A plant product having a surface treated with the formulation of claim 1. Treating an agricultural target comprising providing an agricultural formulation of a concentrated liquid suspension comprising an organic phase and suspended particulates, and applying the agricultural formulation to the agricultural target, thereby treating the agricultural target. Method. 56. The method of claim 55, wherein the method of treating agricultural targets protects the agricultural targets from pests, diseases or environmental damage. 56. The method of claim 55, wherein treating the agricultural target comprises non-lethally modifying pest behavior. 56. The method of claim 55, wherein the agricultural target is the soil surface. from the group wherein the soil surface comprises erosion control, nutrient delivery, nutrient retention, agricultural treatment delivery, agricultural treatment retention, dust control, delivery of beneficial microorganisms, delivery of biopesticides or enhanced growth of beneficial microorganisms 59. The method of claim 58, processed to produce a selected beneficial effect. 56. The method of claim 55, wherein the agricultural target is a plant surface. 61. The method of claim 60, wherein the plant surface is selected from the group consisting of leaves, fruits, seeds, berries, nuts, berries, stems and roots. 62. The method of claim 61, wherein the plant surface is a harvested product surface for harvested products. 56. The method of claim 55, wherein the agricultural target is an agricultural growing medium. 56. The method of claim 55, wherein the agricultural formulation is applied to the agricultural target at a dosage rate of from about 1 to about 200 lbs of formulation per acre of harvest. 56. The method of claim 55, wherein the agricultural formulation is diluted with a solvent prior to the step of applying the formulation.

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