Agricultural adjuvant oil dispersions

Abstract

The present disclosure is generally directed to stable oil dispersion compositions used in agriculture that comprise high concentrations of particulate agrochemical solids such as ammonium sulfate. The oil dispersion composition is useful as an additive or water conditioning adjuvant in agricultural tank mix applications to improve performance of agrochemicals negatively impacted by the mineral content of water used to dilute agrochemical application mixtures as well as provide other beneficial effects.

Description

AGRICULTURAL ADJUVANT OIL DISPERSIONSCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 542,258, filed October 3, 2023, the contents of which are incorporated by reference herein in their entirety.FIELD OF INVENTION

[0002] The present disclosure provides stable oil dispersion compositions used in agriculture that comprise high concentrations of a particulate agrochemical solid such as ammonium sulfate (AMS) in combination with one or more desirable agricultural adjuvant ingredients.BACKGROUND OF INVENTION

[0003] AMS (ammonium sulfate) is one of the most widely used fertilizers in agriculture, and it is a source of sulfur and nitrogen for plants. It is also used extensively as a water conditioning adjuvant in agricultural tank mix applications to improve performance of herbicides and other agrochemicals that might be negatively impacted by the mineral content of water used to dilute agrochemical application mixtures. When used as a water conditioner, AMS associates with hard water calcium and magnesium ions and provides ammonium ions for improved uptake. However, dried AMS and concentrated aqueous solutions of AMS are difficult to handle and the former presents health hazards associated with airborne particulates.

[0004] To address these problems, oil dispersion (OD) compositions are known and used to form pourable, concentrate formulations of particulate agrochemical solids such as AMS dispersed or suspended in an oily liquid carrier, such as a vegetable oil alkyl ester (e.g., methylated seed oil or MSO). However, oil dispersions often suffer from instability in that the suspended solid can partition and separate from the oil carrier and settle at the bottom of the container in which they are stored. Such settling causes inconsistent and ineffective dosing of the agrochemical solid when poured, mixed and diluted with water prior to application.

[0005] In addition to AMS and other water conditioners, there are a wide variety of other adjuvants commonly used to improve the efficacy of pesticides or impart other beneficial effects either as part of agricultural active formulations or as a separate tankmix additive. Although beneficial, tank mixing such agricultural adjuvants with herbicides or other agricultural actives is often cumbersome for the end user.

[0006] Accordingly, there remains a need for oil dispersion compositions containing high concentrations of agrochemical solids such as AMS that remain stable for extended periods of time at both high and low temperatures and that provide a useful vehicle for inclusion of other desirable adjuvant ingredients that can be readily delivered as part of an emulsion application mixture formed upon dilution with water.SUMMARY OF INVENTION

[0007] In various aspects, the present invention relates to a non-aqueous, agrochemical solid in oil dispersion composition. The composition comprises an agricultural oil carrier, a particulate agrochemical solid dispersed in the oil carrier, an emulsifier component, a water-insoluble, nonionic polymeric dispersant and a rheology additive. One or more of the ingredients are preferably agricultural adjuvants selected to improve the efficacy of pesticides with which the composition is mixed or to impart other beneficial effects as part of a tank mix, while also providing a stable dispersion at high and low temperatures.

[0008] In one embodiment, the non-aqueous, agrochemical solid in oil dispersion comprises from about 20 wt.% to about 40 wt.% of an agricultural oil carrier; from about 30 wt.% to about 50 wt.% of a particulate agrochemical solid component dispersed in the oil carrier; from about 10 wt.% to about 30 wt.% of an emulsifier component comprising nonionic emulsifier and an anionic emulsifying surfactant; from about 0.5 wt.% to about 3 wt.% of a water-insoluble, nonionic polymeric dispersant having an HLB no greater than about 10; and from about 0.1 wt.% to about 5 wt.% of a rheology additive comprising an organic derivative of a bentonite clay, fumed silica or combination thereof.

[0009] The present invention also relates to a water-conditioning agricultural adjuvant composition in the form of a non-aqueous, agrochemical solid in oil dispersion. The adjuvant composition comprises from about 26 wt.% to about 36 wt.% of an agricultural oil carrier selected from the group consisting of hydrotreated heavy paraffinic petroleum distillate, non-esterified vegetable oil, methylated seed oil, tall oil and combinations thereof; from about 30 wt.% to about 50 wt.% of a water-conditioning agent selected from the group consisting of ammonium sulfate, citric acid, sodium citrate, potassium citrate and combinations thereof; from about 12 wt.% to about 28wt.% of an emulsifier component comprising an ethoxylated soybean oil adjuvant and a phosphate ester of polyoxyethylene nonylphenol; from about 1 wt.% to about 2 wt.% of a water-insoluble, nonionic co-polymeric dispersant comprising a random copolymer based on an alkyd-polyethylene glycol resin comprising a polyisobutylene succinic anhydride oil soluble graft; and from about 0.5 wt.% to about 5 wt.% of a rheology additive comprising a fumed silica.

[0010] The present invention also relates to a method for preparing an agricultural tank mix application mixture. The method comprises mixing an agrochemical formulation comprising an agrochemical with an oil dispersion composition of the present invention and dilution water to form the agricultural tank mix application mixture.

[0011] The details of one or more embodiments of the invention are set forth in the accompanying description below.

[0012] Other features, objects, and advantages of the invention will be apparent from the description, and from the claims.DETAILED DESCRIPTION OF INVENTION

[0013] In general, the present invention relates to oil dispersion (OD) compositions comprising a particulate agrochemical solid suspended or dispersed in an agricultural oil carrier in combination with one or more desirable agricultural adjuvants. In accordance with the invention, particular dispersants, emulsifiers and rheology additives have been identified that allow the formulation of oil dispersion compositions containing high concentrations of the agrochemical solid suspended in the oil carrier that remain stable over prolonged periods of storage at low and high temperatures. The oil dispersion composition is non-aqueous in that water is not necessary and is not intentionally added to the composition. The oil dispersion composition is formulated and the particulate agrochemical solid and other ingredients are selected such that composition forms an emulsion or microemulsion and the solids dissolve rapidly upon dilution of the oil dispersion composition in water (e.g., in an agricultural spray mixture or tank mix). Further, the selected ingredients include one or more agricultural adjuvants that enhance efficacy or provide other beneficial effects when the oil dispersion composition is tank mixed with an herbicide or other agricultural active ingredient. The oil dispersant composition provides an easy to use agricultural adjuvant package.

[0014] The agrochemical suspended in the oil dispersion composition may include any solid particles that are insoluble in the oil carrier and suitable for dispersion therein. In one embodiment, the particles comprise an agricultural adjuvant solid and are free of any pesticide (e.g., herbicide, insecticide, etc.) active ingredients. For example, the particulate agrochemical solid may include at least one of water conditioners, fertilizers and combinations thereof.

[0015] In one embodiment, the particulate solid includes at least one water conditioner. Water conditioners are used with hard water in agricultural applications to reduce negative interactions between dissolved minerals and agricultural active ingredients such as herbicides that decrease efficacy. In one embodiment, the at least one water conditioner includes ammonium sulfate (AMS). As previously discussed, AMS is one of the most widely used fertilizers in agriculture, and it is a source of sulfur and nitrogen for plants. Further, AMS may help with uptake of certain agricultural active ingredients into a plant. The particulate solid may also include other water conditioners, such as citric acid and sodium or potassium citrate, instead of or in combination with AMS.

[0016] In accordance with the present invention, stable oil dispersion compositions are provided wherein the concentration of the particulate agrochemical solid is quite high. For example, the concentration of the particulate solid may be at least about 20 wt.%, at least about 25 wt.%, at least about 30 wt.%, at least about 35 wt.%, at least about 40 wt.% or higher. In one embodiment, the concentration of the particulate solid is from about 30 wt.% to about 50 wt.%.

[0017] In order to facilitate dispersion of the particulate agrochemical solid in the oil carrier and maintain composition stability, the particle size of the solid may be reduced by grinding or milling either before or after being combined with the other ingredients of the dispersion composition. Suitable dry grinding processes include hammer milling, pin milling, media milling (e.g., ball mill) or media-less milling (e.g., a jet mill). Suitable wet grinding processes include wet media milling or wet medialess milling (e.g., a homogenizer or a high shear mill). In accordance with one embodiment, the agrochemical solid is pre-milled to reduce the average particle size prior to combination with the other ingredients and thereby avoid wet-milling operations. For example, the particle size distribution of the particulate agrochemical solid component may be reduced such that it exhibits a D90 particle size of about 20 pm or about 10 pm. In other embodiments, the agrochemical solid may be unmilled orcoarsely milled prior to being combined with the other ingredients of the dispersion composition.

[0018] The agricultural oil carrier may suitably comprise vegetable oils such as com oil, soybean oil, linseed oil, cotton seed oil, canola oil and similar oils, tall oils derived from wood pulp manufacture as well as petroleum distillates.

[0019] The vegetable oil may be non-esterified and comprise a mixture of triglycerides. In another embodiment, the vegetable oil is esterified such as methylated seed oil (MSO). Methylated seed oil and similar esterified vegetable oils are often used (and sometimes recommended or required) as an oil-based surfactant adjuvant in combination with post-emergent herbicides to improve penetration into the leaf.

[0020] Petroleum distillates from the heavy distillate fraction of crude petroleum such as mineral oils or white oils may also be used as the agricultural oil carrier. They are typically refined to remove the unsaturated hydrocarbons and improve oxidation stability. Prima 100 is a hydrotreated heavy paraffinic petroleum distillate that is useful as an agricultural oil carrier.

[0021] Although a large variety of dispersants, emulsifiers and rheology additives or structuring aids such as modified silicas have been disclosed in the art for enhancing the stability of and inhibiting settling in non-aqueous, oil dispersion compositions, none have proved suitable for reliably formulating oil dispersions containing high concentrations of dispersed solids. In accordance with the present invention, high concentrations of the particulate agrochemical solid are stably maintained in dispersion in the oil carrier by proper selection of one or more dispersants in combination with a rheology additive and an emulsifier component.

[0022] The dispersants useful in stabilizing the particulate agrochemical solid suspended in the oil carrier of the non-aqueous composition generally include waterinsoluble, nonionic, polymeric dispersants having an HLB no greater than about 10, and more typically no greater than about 8. In one particular embodiment, the dispersant comprises a random co-polymer based on an alkyd-polyethylene glycol resin comprising a polyisobutylene succinic anhydride oil soluble graft, such as that sold under the tradename ATLOX 4914, commercially available from Croda Europe Ltd. (East Yorkshire, England). In another particular embodiment, the dispersant comprises an A-B-A block co-polymer based on 12-polyhydroxystearic acid (12 pHSA) and polyethylene glycol, such as that sold under the tradename ATLOX 4912, commercially available from Croda Europe Ltd. (East Yorkshire, England). Low HLB, water-insoluble, nonionic, polymeric dispersants can be used singularly or in combination and are surprisingly effective at relatively low concentrations. The concentration of the dispersant is typically from about 0.5 wt.% to about 3 wt.%, and more typically from about 1 wt.% to about 2 wt.%.

[0023] The oil dispersion composition further includes a rheology additive or structuring aid comprising bentonite clay, fumed silica or combinations thereof. In one embodiment, the rheology additive is based on bentonite clay. For example, in one particular embodiment, the rheology additive comprises an organic derivative of a bentonite clay such as that sold under the tradename BENTONE 1000, commercially available from Elementis Specialties, Inc. (East Windsor, New Jersey). This highly efficient and cost-effective rheological additive is designed for low- to intermediate polarity organic systems and when combined with the dispersants described herein, is highly effective in stabilizing the oil dispersion composition at lower concentrations. In another embodiment, the rheology additive comprises a fumed silica such as that sold under the tradename AEROSIL 200 or AEROSIL 300, commercially available from Evonik Corporation (Parsippany, New Jersey). In one particular embodiment, the rheology additive comprises a fumed silica surface-treated with polydimethylsiloxane such as that sold under the tradename AEROSIL R 202, also commercially available from Evonik Corporation (Parsippany, New Jersey). The rheology additives identified herein are compatible with various agricultural oil carriers. However, AEROSIL R 202 and similar materials have been found to be particularly flexible as a rheology additive in oil dispersion compositions containing either paraffinic petroleum distillates or vegetable oils as the agricultural oil carrier.

[0024] The concentration of the rheology additive is generally from about 0.1 wt.% to about 5 wt.%. In the case an organic derivative of a bentonite clay such as BENTONE 1000, the concentration is typically from about 0.1 wt.% to about 2 wt.%, and more typically, from about 0.5 wt.% to about 0.75 wt.%. When using a fumed silica rheology additive, the concentration is somewhat higher. For example, the concentration of a fumed silica rheology additive is typically from about 0.5 wt.% to about 5 wt.%, and more typically, from about 2 wt.% to about 4 wt.%.

[0025] In order to effectively form an emulsion or microemulsion upon dilution and mixture with water, the oil dispersion composition further comprises an emulsifier component. In accordance with the present invention, the emulsifier component comprises a combination of a nonionic emulsifier and an anionic emulsifyingsurfactant. In accordance with one embodiment, the emulsifier component comprises a nonionic emulsifier adjuvant such as an alkoxylated vegetable oil adjuvant and an anionic emulsifying surfactant such as a phosphate ester surfactant (e.g., an alkoxylated alkyl phosphate ester) or a blend of anionic emulsifying surfactants.

[0026] Suitable alkoxylated vegetable oil adjuvants include ethoxylated soybean oil such as that sold under the tradename AGNIQUE SBO-10, commercially available from BASF Corporation North America, which can be classified as a nonionic surfactant. In addition to its function as an emulsifier, ethoxylated soybean oil is often used to enhance the efficacy or potentiate various herbicides and other agricultural active ingredients. Other nonionic emulsifiers can be suitably employed. In one embodiment, the nonionic emulsifier is selected to have an HLB no greater than about 10, and more typically no greater than about 8.

[0027] Suitable anionic surfactants include calcium dodecylbenzene sulfonate (CDDBS) and phosphate ester surfactants. In one embodiment, the anionic emulsifying surfactant includes a phosphate ester surfactant (e.g., an alkoxylated alkyl phosphate ester) or a blend of phosphate ester surfactants. Suitable examples of alkoxylated alkyl phosphate esters include a polyoxyethylene nonylphenol phosphate ester such as that sold under the tradename NP 9 PE, polyoxyethylene isotridecyl ether phosphate such as that sold under the tradename PE-TDA 6, both commercially available from BASF Corporation North America, as well as combinations thereof. These anionic phosphate ester surfactants assist with emulsifying the oil carrier when mixed with water. In addition to this primary function, the anionic phosphate ester surfactants also aid in dispersing the particulate agrochemical solid in the oil dispersion to ensure composition stability. Further, such phosphate esters can act as an adjuvant in improving the efficacy of certain pesticidal application mixtures.

[0028] Typically, the concentration of the emulsifier component is from about 10 wt.% to about 30 wt.%, or from about 15 wt.% to about 30 wt.% and typically contains an excess of the nonionic emulsifier over the anionic surfactant(s) such that the weight ratio of the nonionic emulsifier to the anionic surfactant is greater than 1:1. In one embodiment, the concentration of the emulsifier component is from about 20 wt.% to about 28 wt.% and the weight ratio of the nonionic emulsifier to the anionic surfactant(s) is greater than 1:1, at least about 2:1, at least about 3:1 or at least about 4:1. In another embodiment, the concentration of the emulsifier component is from about 12 wt.% to about 28 wt.% or from about 12 wt.% to about 20 wt.% and the weightratio of the nonionic emulsifier to the anionic surfactant(s) is greater than 1:1, and typically from about 2:1 to about 3:1.

[0029] The oil dispersion composition can optionally contain a variety of other ingredients, including anti-foam agents, anti-drift agents as well as other useful adjuvants. In one embodiment, the oil dispersion composition contains an anti-drift agent such as the polyterpene resin described in U.S. Patent No. 9,578,874 B2 (Crosby et al.) and sold under the tradename PICCOLYTE A 25, commercially available from Pinova, Inc. (Brunswick, GA) or SYLVARES TRA 25, commercially available from Kraton Corporation (Houston, TX).

[0030] The oil dispersion compositions described herein can be prepared using techniques and equipment well known in the art. Although the order of addition is not critical, typically, the liquid ingredients are combined and mixed first followed by addition of the particulate agrochemical solid(s). As noted above, the oil dispersion composition is non-aqueous in that water is not necessary and is not intentionally added to the composition. Accordingly, the mixing equipment is dried prior to use and water is intentionally excluded from the composition including minimizing any extraneous water content in the ingredients to be mixed. In this manner, the oil dispersion compositions are substantially free of water and typically have a water content of 0.1 wt.% or less. The solids are advantageously pre-milled to the desired particle size as described above to reduce later batch milling requirements. The ingredients can be suitably combined and mixed in an overhead mixer equipped with a Cowles dispersion blade impeller. The batch can then be milled in a vertical ball mill while monitoring the viscosity and temperature of the batch. Alternatively, a homogenizer can be used in place of a ball mill to further reduce the particle size of the dispersed agrochemical solids. High shear milling can assist with activation of a bentonite clay rheology additive as well as other ingredients such as polymeric alkyd-polyethylene glycol resin dispersants (e.g., ATLOX 4914). Generally, the temperature of the batch is maintained below about 120°F (49°C) and the batch is milled until a viscosity of at least about 700 cP, at least about 1000 cP, at least about 1500 cP, at least about 2000 cP, or at least about 2500 cP is achieved. Compositions having a viscosity of at least about 1000 cP are generally associated with better stability and resistance to settling, while viscosities in excess of about 3000 cP may present the end user farmer with handling difficulties. Accordingly, in one embodiment, the batch oil dispersion compositions are milled until the viscosity is from about 1000 to about 3000 cP or from about 1500 to about 3000 cP.

[0031] As noted, the oil dispersion composition is intended as an additive or water conditioning adjuvant in agricultural tank mix applications to improve performance of herbicides and other agrochemicals that might be negatively impacted by the mineral content of water used to dilute agrochemical application mixtures as well as provide other beneficial effects.

[0032] The agrochemicals with which the oil dispersion composition may be advantageously mixed include pesticides (e.g., herbicides, insecticides, fungicides, etc.) as well as fertilizers. The agrochemicals mixed with the oil dispersion composition may be of any conventional formulation type, including without limitation, solids and various conventional liquid formulations such as solution concentrates containing water-soluble agrochemical salts, emulsion concentrates, microemulsion concentrates and suspension concentrates.

[0033] Representative and non-limiting examples of herbicides include acetyl CoA carboxylase (ACCase) inhibitors, acetolactate synthase (ATS) inhibitors, acetohydroxy acid synthase (AHAS) inhibitors, photosystem II inhibitors, photosystem I inhibitors, protoporphyrinogen oxidase (PPO or Protox) inhibitors, carotenoid biosynthesis inhibitors, enolpyruvyl shikimate-3-phosphate (EPSP) synthase inhibitor, glutamine synthetase inhibitor, dihydropteroate synthetase inhibitor, mitosis inhibitors, nucleic acid inhibitors; and auxins herbicides; salts and esters thereof; racemic mixtures and resolved isomers thereof; and combinations thereof.

[0034] Representative examples of ACCase inhibitors include clethodim, clodinafop, fenoxaprop-P, fluazifop-P, quizalofop-P, and sethoxydim.

[0035] Representative examples of ALS or AHAS inhibitors include flumetsulam, imazamethabenz-m, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, metsulfuron, prosulfuron, and sulfosulfuron.

[0036] Representative examples of photosystem I inhibitors include diquat and paraquat.

[0037] Representative examples of photosystem II inhibitors include atrazine, cyanazine, diuron, and metibuzin.

[0038] Representative examples of PPO inhibitors include acifluorofen, butafenacil, carfentrazone-ethyl, flufenpyr-ethyl, fluthiacet, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorofen, and sulfentrazone.

[0039] Representative examples of carotenoid biosynthesis inhibitors include aclonifen, amitrole, diflufenican, mesotrione, and sulcotrione.

[0040] A representative example of an EPSP inhibitor is N-phosphonomethyl glycine (glyphosate). Commercially available sources of glyphosate, and its agriculturally acceptable salts, include those products sold under the trade names DURANGO® DMA®, HONCHO PLUS®, ROUNDUP POWERMAX®, ROUNDUP WEATHERMAX®, TRAXION®, and TOUCHDOWN®.

[0041] A representative example of a glutamine synthetase inhibitor is glufosinate.

[0042] A representative example of a dihydropteroate synthetase inhibitor is asulam.

[0043] Representative examples of mitosis inhibitors include acetochlor, alachlor, dithiopyr, S-metolachlor, and thiazopyr.

[0044] Representative examples of nucleic acid inhibitors include difenzoquat, fosamine, metham, and pelargonic acid.

[0045] Representative examples of auxin herbicides include dicamba (3,6- dichloro-2-methoxybenzoic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid).

[0046] In accordance with one embodiment, the oil dispersion compositions of the present invention are suitable as an additive or water conditioning adjuvant in agricultural tank mix applications for herbicides selected from the group consisting of glyphosate, glufosinate, clethodim, 2,4-D, dicamba, mesotrione, topramezone, tembotrione, fomesafen, bromoxanil, bicyclopryone, gramoxone and mixtures thereof.

[0047] The quantity of the oil dispersion composition mixed with the agrochemical is not narrowly critical and will depend on various factors including the agrochemical(s) present in the tank mix, mineral content of the dilution water and spray conditions. The concentration of the oil dispersion composition in the tank upon dilution on a volume basis is typically at least about 0.01%, at least about 0.02%, at least about 0.04%, at least about 0.08%, or at least about 0.1% and up to about 10%, up to about 8% or up to about 5%. Typically, for water conditioning applications, wherein the particulate solid comprises AMS and / or other water conditioners, such as citric acid and sodium or potassium citrate, the concentration of the oil dispersion composition in the tank upon dilution on a volume basis is at least about 0.5%, at least about 1%, at least about 1.5%, at least about 2%, at least about 2.5%, at least about 3%, at least about 3.5%, or at least about 4%. For example, the concentration of the oil dispersion composition in the tank upon dilution on a volume basis may range from about 0.5% to about 10%, from about 1% to about 5% or from about 2% to about 4%.

[0048] As is known in the art, AMS present in the oil dispersion composition can be used to potentiate or improve the effectiveness of certain herbicides such as glutamine synthetase inhibitors (e.g., glufosinate) and mesotrione. Typically, in such applications, the oil dispersion composition is included in the tank mix in an amount so as to provide an AMS application rate of at least about 0.5 Ib / acre (0.56 kg / ha), at least about 0.75 Ib / acre (0.84 kg / ha), at least about 1 Ib / acre (1.12 kg / ha), at least about 1.25 Ib / acre (1.40 kg / ha), at least about 1.5 Ib / acre (1.68 kg / ha) or higher and according to the herbicide manufacturer's recommendation.

[0049] The following non-limiting examples are provided to further illustrate the present invention.EXAMPLESEXAMPLE 1: FORMULATIONS AND PROPERTIES

[0050] The exemplary oil dispersion compositions in accordance with the present invention set forth in Tables 1-29, 11 A, 14B, 15B, and 16B were prepared. Tables 14A and 15A describe formulations used in scale up batches. Tables 1A-8A, 11B, 14C, 15C, and 16C provide stability and other measured properties of the oil dispersion compositions.

[0051] The following ingredients were used in these compositions.

[0052] An overhead mixer equipped with a Cowles dispersion blade impeller was used to mix all of the liquid ingredients first followed by the particulate agrochemical solids, which were pre-milled to the desired particle size in order to reduce later batch milling requirements. Then the entire batch was milled with a vertical ball mill while monitoring the viscosity and temperature of the batch until a viscosity of from about 2,000-3,000 cP was achieved. The temperature was maintained below 120°F (49°C). Alternatively, a homogenizer can be used in place of a ball mill to activate the bentonite clay rheology additive and further reduce the particle size of the dispersed agrochemical solids.

[0053] The results reported in Table 1 A were determined with respect to the oil dispersion in Table 1 as prepared without aging. The results in Table 2A to 8A include both initial properties as well as properties determined after aging at varyingtemperatures. The results reported in Tables 1 IB, 14C, 15C, and 16C were determined with respect to the corresponding oil dispersions in Tables 11A, 14B, 15B, and 16B as prepared without aging. Top Separation refers to the percentage of the oil dispersion composition that separates as a liquid at the top of the composition. The pH was measured as a 1% by volume dilution of the oil dispersion composition in distilled water. The Draves Wetting (@3%) was determined in accordance with a procedure similar to that described in ASTM El 116-98. The freeze-thaw testing of the oil dispersion composition was conducted at -15°C for 24 hours followed by thawing at room temperature for 24 hours (1 cycle). Viscosities were measured using a Brookfield LV spindle 2 at 20 rpm. Emulsion testing was carried out using World Health Organization Standard Hard Water at 34 ppm, 342 ppm and 1000 ppm and 3% by volume dilution. The diluted 100 ml sample mixture was inverted 10 times at room temperature and allowed to set for approximately two hours before observation. The observation "no cream" means there was no separation of cream of oil from the resulting emulsion, while the observation "x ml top" means x ml of cream was observed at the top of the sample separated from the resulting emulsion.Table 1: AMS / MSO ODTable 1A: AMS / MSO OD Measured PropertiesTable 2: AMS / Prima 100 ODTable 2A: AMS / Prima 100 OD Measured Properties*ND = Not DeterminedTable 3: AMS / Citric Acid + MSOTable 3A: AMS / Citric Acid + MSO Measured Properties*ND = Not DeterminedTable 4: AMS / Citric Acid + Crop Oil Concentrate (COC) ODTable 4A: AMS / Citric Acid + COC OD Measured Properties*ND = Not DeterminecTable 5: AMS / Citric Acid + MSO + ResinTable 5A: AMS / Citric Acid + MSO + Resin Measured Properties*ND = Not DeterminedTable 6: AMS / Citric Acid + COC + ResinTable 6A: AMS / Citric Acid + COC + Resin Measured Properties*ND = Not DeterminedTable 7: AMS + MSO + ResinTable 7A: AMS + MSO + Resin Measured Properties*ND = Not DeterminedTable 8: AMS + COC + Resin + WettingTable 8A: AMS + COC + Resin + Wetting Measured Properties*ND = Not DeterminedTable 9: AMS + MSO + SilicaTable 10: AMS / MSO (Pre-milled AMS)Table 11 : AMS + NIS OD plus wettingTable 11 A: AMS + NIS OD plus wetting*Table 11A describes a slightly different, but chemically similar variation of the composition of Table 11.Table UB: AMS + NIS OD plus wetting Measured Properties (for the composition ofTable HA)*2@20 indicates spindle type and speed used on the viscometer.Table 12: AMS / Citric Acid + MSO (37% AMS, 7% citric, 10% MSO)Table 13: AMS / Citric Acid + COC OD Plus WettingTable 14: AMS / Citric Acid + NIS + Resin (44% AMS, 3% Citric, 4% Piccolyte +Wetting)Table 14A: AMS / Citric Acid + COC + Resin (44% COC, 3% Citric, 2% Piccolyte +Wetting) Scale Up Batch*Approximate specific gravity = 1.179 g / ml - 1.179 g / L; Lb / gal = 9.84 Ibs / gal.**Table 14A describes a slightly different, but chemically similar variation of the composition of Table 14.Table 14B: AMS / Citric Acid + NIS + Resin (44% AMS, 3% Citric, 4% Piccolyte +Wetting)Table 14C: AMS / Citric Acid + NIS + Resin (44% AMS, 3% Citric, 4% Piccolyte +Wetting) Measured Properties (for the composition of Table 14B)*3 @5 indicates spindle type and speed used on the viscometer.Table 15: AMS / Citric Acid + MSO + Resin (44% AMS, 3% Citric, 2% Piccolyte)Table 15A: AMS / Citric Acid + MSO + Resin (44% AMS, 3% Citric, 2% Piccolyte)Scale Up BatchTable 15B: AMS / Citric Acid + MSO + Resin (44% AMS, 3% Citric, 2% Piccolyte)Table 15C: AMS / Citric Acid + MSO + Resin (44% AMS, 3% Citric, 2% Piccolyte)Measured Properties (for composition of Table 15B)*2@20 indicates spindle type and speed used on the viscometer.Table 16Table 16BTable 16C: Measured Properties (for composition of Table 16B)*2@20 indicates spindle type and speed used on the viscometer.Table 17: AMS + COC + Resin + Wetting (37% AMS, 10% MSO, 2% Piccolyte)Table 18: AMS / Prima 100 OD*Failed to form emulsion at 342 ppm and 3% by volume dilution after 1 hour at room temperature.Table 19: AMS / Prima 100 OD* Failed to form emulsion at 342 ppm and 3% by volume dilution after 1 hour at room temperature.Table 20: AMS / MSO OD* Failed to form emulsion at 342 ppm and 3% by volume dilution after 1 hour at room temperature.Table 21: AMS / MSO OD (increased MSO content)Table 22: AMS / MSO OD (rheology adjustment)Table 23: AMS / MSO OD (rheology adjustment)Table 24: AMS / MSO OD (rheology adjustment)Table 25: AMS / MSO OD (rheology adjustment)Table 26: AMS / MSO OD* Failed to form emulsion at 342 ppm and 3% by volume dilution after 1 hour at room temperature.Table 27: AMS / MSO ODEXAMPLE 2: FIELD TESTING

[0054] Field plots consisting of various weed species, including Amaranthus palmeri (Palmer pigweed - AMAPA), Ipomoea hederacea (Ivyleaf momingglory - IPOHE), Abutilon theophrastii (Velvetleaf - ABUTH), Setaria viridis (green foxtail - SETV1) and Kochia scoparia (Kochia - KOSC) were grown and established. Field plots for all weed species except Kochia were established at Agricenter International (Memphis, TN, USA). The soil is a Memphis silt loam, (19.7% sand, 74.8% silt, 5.4% clay, 1.6% organic matter) managed with conventional tillage. The Kochia plot was a natural population found growing in Kansas, USA. Plot size was 6.3 feet wide and 20 feet long. The experimental design was a randomized complete block with 3 replications. Plots were sprayed with 15 gallons per acre spray solution through AIXR 8002 nozzles (Spraying Solutions Inc.).

[0055] Herbicide spray mixes including glufosinate, glufosinate in combination with 2,4-D choline salt, and glyphosate in combination with mesotrione along with various conventional adjuvants or an oil dispersion (OD) composition of the present invention were prepared as detailed below and applied at the 6-8 inch height of plant growth.

[0056] Results for observed plant control are reported in Tables 28 to 31 below.Table 28: Adjuvant effect on % weed control of 4 weed species 14 days after treatmentTable 29: Adjuvant effect on % weed control of 3 weed species 14 days after treatment DAT) with glufosinate 280 SL herbicide plus 2,4-D choline saltTable 30: Adjuvant effect on % weed control of Kochia 14 days after treatment (DAT) with glyphosate and mesotrione herbicidesTable 31: Adjuvant effect on % weed control of Palmer Amaranth 14 days after treatment (DAT) with glufosinate herbicide

[0057] The results reported in Tables 28 to 31 demonstrate that the oil dispersion compositions of the present invention provided comparable and sometimes superior weed control as compared with herbicides mixed with conventional adjuvants. Accordingly, the oil dispersion compositions of the present invention provide the end user with an effective tank mix adjuvant combined with greater ease of use.

[0058] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although methods and materials similar or equivalent to those described herein can be used to practice the invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0059] When introducing elements of the present invention or the preferred embodiments(s) thereof, including the appended claims, the singular articles "a", "an", "the" and "said" are intended to mean that there are one or more of the elements. The terms "comprising", "including" and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0060] In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.

[0061] It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the preceding description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims.

Claims

WHAT IS CLAIMED IS:

1. A non-aqueous, agrochemical solid in oil dispersion composition, the composition comprising: from about 20 wt.% to about 40 wt.% of an agricultural oil carrier; from about 30 wt.% to about 50 wt.% of a particulate agrochemical solid component dispersed in the oil carrier; from about 10 wt.% to about 30 wt.% of an emulsifier component comprising a nonionic emulsifier and an anionic emulsifying surfactant; from about 0.5 wt.% to about 3 wt.% of a water-insoluble, nonionic polymeric dispersant having an HLB no greater than about 10; and from about 0.1 wt.% to about 5 wt.% of a rheology additive selected from the group consisting of an organic derivative of a bentonite clay, fumed silica and combinations thereof.

2. The dispersion composition of claim 1, wherein the agricultural oil carrier is selected from the group consisting of hydrotreated heavy paraffinic petroleum distillate, non-esterified vegetable oil, methylated seed oil, tall oil and combinations thereof.

3. The dispersion composition of claim 1, wherein the agricultural oil carrier comprises methylated seed oil.

4. The dispersion composition of claim 1, wherein the agricultural oil carrier comprises a hydrotreated heavy paraffinic petroleum distillate.

5. The dispersion composition of claim 1, wherein the particulate agrochemical solid component comprises a water-conditioning agent.

6. The dispersion composition of claim 5, wherein the water-conditioning agent is selected from the group consisting of ammonium sulfate, citric acid and combinations thereof.

7. The dispersion composition of any one of claims 1 to 6 wherein the particulate agrochemical solid component comprises ammonium sulfate.

8. The dispersion composition of any one of claims 1 to 6, wherein the particulate agrochemical solid component is pre-milled.

9. The dispersion composition of any one of claims 1 to 6, wherein the particulate agrochemical solid component has a D90 particle size of about 20 pm or about 10 pm.

10. The dispersion composition of any one of claims 1 to 6, wherein the co- polymeric dispersant comprises a random co-polymer based on an alkyd-polyethylene glycol resin comprising a polyisobutylene succinic anhydride oil soluble graft.

11. The dispersion composition of any one of claims 1 to 6, wherein the co- polymeric dispersant comprises an A-B-A block co-polymer based on 12- polyhydroxystearic acid and polyethylene glycol.

12. The dispersant composition of any one of claims 1 to 6, wherein the nonionic emulsifier of the emulsifier component is selected to have an HLB no greater than about 10, or no greater than about 8.

13. The dispersion composition of any one of claims 1 to 6, wherein the nonionic emulsifier of the emulsifier component comprises an alkoxylated nonionic emulsifier.

14. The dispersion composition of any one of claims 1 to 6, wherein the nonionic emulsifier of the emulsifier component comprises an alkoxylated vegetable oil adjuvant.

15. The dispersion composition of any one of claims 1 to 6, wherein the anionic emulsifying surfactant of the emulsifier component comprises calcium dodecylbenzene sulfonate.

16. The dispersion composition of any one of claims 1 to 6, wherein the anionic emulsifying surfactant of the emulsifier component comprises an alkoxylated alkyl phosphate ester selected from the group consisting of a polyoxyethylene nonylphenol phosphate ester, polyoxyethylene isotridecyl ether phosphate and combinations thereof.

17. The dispersion composition of any one of claims 1 to 6, wherein the concentration of the emulsifier component is from about 10 wt.% to about 30 wt.%, from about 15 wt.% to about 30 wt.%, from about 20 wt.% to about 28 wt.%, from about 12 wt.% to about 28 wt.%, or from about 12 wt.% to about 20 wt.%.

18. The dispersion composition of any one of claims 1 to 6, wherein the weight ratio of the nonionic emulsifier to the anionic emulsifying surfactant(s) is greater than 1:1, at least about 2:1, at least about 3:1 or at least about 4:1.

19. The dispersion composition of any one of claim 1 to 6, wherein the concentration of the agricultural oil carrier is from about 26 wt.% to about 36 wt.%.

20. The dispersion composition of any one of claims 1 to 6, wherein the concentration of the water-insoluble, nonionic co-polymeric dispersant is from about 1 wt.% to about 2 wt.%.

21. The dispersion composition of any one of claims 1 to 6, wherein the rheology additive comprises an organic derivative of a bentonite clay and the concentration of the rheology additive is from about 0.1 wt.% to about 2 wt.%, or from about 0.5 wt.% to about 0.75 wt.%.

22. The dispersion composition of any one of claims 1 to 6, wherein the rheology additive comprises a fumed silica and the concentration of the rheology additive is from about 0.5 wt.% to about 5 wt.%, or from about 2 wt.% to about 4 wt.%.

23. The dispersion composition of any one of claims 1 to 6, further comprising at least one of a spray drift control agent and an antifoam component.

24. A non-aqueous, agrochemical solid in oil dispersion composition, the composition comprising: from about 26 wt.% to about 36 wt.% of an agricultural oil carrier selected from the group consisting of hydrotreated heavy paraffinic petroleum distillate, non- esterified vegetable oil, methylated seed oil, tall oil and combinations thereof; from about 30 wt.% to about 50 wt.% of a water-conditioning agent selected from the group consisting of ammonium sulfate, citric acid, sodium citrate, potassium citrate and combinations thereof; from about 12 wt.% to about 28 wt.% of an emulsifier component comprising an ethoxylated soybean oil adjuvant and a phosphate ester of polyoxyethylene nonylphenol; from about 1 wt.% to about 2 wt.% of a water-insoluble, nonionic co- polymeric dispersant comprising a random co-polymer based on an alkydpolyethylene glycol resin comprising a polyisobutylene succinic anhydride oil soluble graft; and from about 0.5 wt.% to about 5 wt.% of a rheology additive comprising a fumed silica.

25. A method for preparing an agricultural tank mix application mixture, comprising: mixing an agrochemical formulation comprising an agrochemical with an oil dispersion composition of any one of claims 1 to 6 or 24 and dilution water to form the agricultural tank mix application mixture.

26. The method of claim 25, wherein the agrochemical is selected from the group consisting of pesticides and fertilizers.

27. The method of claim 26, wherein the agrochemical is a pesticide selected from the group consisting of herbicides, insecticides, fungicides and combinations thereof.

28. The method of claim 25, wherein the agrochemical formulation is in the form of a solid, solution concentrate, emulsion concentrate, microemulsion concentrate or suspension concentrate.

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