Agrochemical compositions

Abstract

The disclosure relates to a composition, having a liquid continuous phase, a first agrochemical active ingredient in the liquid continuous phase, a capsule containing a second agrochemical active ingredient, the capsule dispersed within the liquid continuous phase and configured to create a physical barrier between the first agrochemical active ingredient and the second agrochemical active ingredient, and a buffer configured to maintain a pH below 9, and where the solubility of the first agrochemical active ingredient in the second agrochemical active ingredient is between 1% and 10% w / w at room temperature. The disclosure further provides methods of making and using such compositions.

Description

Agrochemical CompositionsCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of US Provisional Patent Application Ser. No. 63 / 649,550, filed May 20, 2024, the contents of which are incorporated by reference herein.TECHNICAL FIELD

[0002] The present invention relates to compositions comprising a combination of crop protection compounds, and a method of preparing and the use of such a composition.BACKGROUND

[0003] By 2050, the global population is expected to reach 9.7 billion people. Such an increase would require a 60% increase in food production compared with 2005-2007 levels. To this end, agrochemical compositions are used to facilitate the growth and health of crops thereby improving yields.

[0004] However, one challenge is distributing agrochemical to a farmer, or group thereof. This is because the growing of crops is usually coordinated regionally. As a result, e.g., all plantings occur around the same window. Failure to plant within an acceptable window can result in crop loss and unprofitability.

[0005] To help meet demand, agrochemical compositions need to be sufficiently storage stable so that the agrochemical compositions can be stockpiled until sold or held over to the next year avoiding waste.

[0006] One common challenge for agrochemical compositions is preventing crystallization of agrochemicals within the composition. Crystallization of agrochemicals within a composition can create issues in application by clogging equipment or uneven application. Furthermore, crystallization can lead to settling of the agrochemical, thereby impacting overall physical stability.

[0007] Accordingly, there remains a need for agrochemical compositions which mitigate crystallization of the agrochemicals within.Summary

[0008] The disclosure relates to a composition, having a liquid continuous phase, a first agrochemical active ingredient in the liquid continuous phase, a capsule containing a second agrochemical active ingredient, the capsule dispersed within the liquid continuous phase and configured to create a physical barrier between the firstagrochemical active ingredient and the second agrochemical active ingredient, and a buffer configured to maintain a pH below 9, and where the solubility of the first agrochemical active ingredient in the second agrochemical active ingredient is between 1% and 10% w / w at room temperature. The disclosure further provides methods of making and using such compositions.DETAILED DESCRIPTION

[0001] Before certain embodiments are described in greater detail, it is to be understood that this disclosure is not limited to certain embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing certain embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.

[0002] Described herein are several definitions. Such definitions are meant to encompass grammatical equivalents.

[0003] The use of “or” means “and / or” unless stated otherwise. Furthermore, the use of the terms “comprising,” “having,” “including,” as well as other forms, such as “includes” and “included,” are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0004] As used herein, the term “about” when referring to a measurable value such as an amount, a temporal duration, and the like, is meant to encompass variations. Such variations, however, are dependent on the specific component referred to and the context as understood by a person of ordinary skill in the art.

[0005] Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure.

[0006] Unless defined otherwise, 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 disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, representative illustrative methods, and materials are now described.24905-5705-2229.1

[0007] Each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order which is logically possible.

[0008] Embodiments of the disclosure can be practiced without any component not specifically mentioned in this disclosure.

[0009] Embodiments described herein may comprise, consist essentially of, or consist of the elements therein.

[0010] In specific embodiments, the total amount of encapsulation material (e.g., a polymer) can be less than 20% w / w of the total composition, less than 15% w / w of the total composition, less than 10% w / w of the total composition, or less than 5% w / w of the total composition.

[0011] In certain embodiments, the amount of encapsulation material can be defined relative to the amount of material being encapsulated. For example, the w / w ratio of encapsulating material to the material being encapsulated can be 1 :5 to 1 :25, 1 :8 to 1 : 18, 1 : 10 to 1 : 15, or about 1 : 12.Compositions

[0012] The compositions described herein are preferably ‘ZC’ formulations. ZCs comprise a stable suspension of capsules (CS) and active ingredient(s) in fluid (SC).Agrochemicals

[0013] The term agrochemical active ingredient includes compounds or ingredients registered as being biologically active against an agricultural pest. In general, agrochemical active ingredients include compounds listed in: The Pesticide Manual, 12th edition, 2001, British Crop Protection Council. Agrochemicals include, but are not limited to herbicides, fungicides, insecticides, bactericides, insect growth regulators, plant growth regulators, nematicides, molluscicides or mixtures of several of these preparations. The total amount of active ingredients is generally in the range of from about 1-60% w / w, preferably 5% to 55% w / w, in specific embodiments, the composition is at least 30% w / w agrochemical active ingredient. In specific embodiments, the amount of each active ingredient is between about 2-40% w / w, preferably about 5-35% w / w, more preferably about 10-30% w / w. In alternative embodiments, for example in diluted formulations, the total amount of the34905-5705-2229.1agrochemicals in the composition is from 0.002% to 5% w / w, preferably 0.01% to 3% w / w, and most preferably 0.02% to 1.75% w / w.

[0014] Three particular agrochemicals are S-metolachlor (S-MOC), tebuthiuron, and hexazinone. S-MOC is part of the chloroacetanilide family of herbicides, used to control grasses and broad-leafed weeds, often in maize. Acetamide herbicides are a group of structurally related herbicides that include acetanilide herbicides (e.g., chloroacetanilide herbicides) and other amide-containing herbicides.

[0015] Tebuthiuron is an herbicide that acts by inhibiting photosynthesis by disrupting photosystem II. Tebuthiuron is defined as a group 7, urea chemical class, by the Weed Science Society of America (WSSA): WSSA Group 7 or “Group 7 herbicide.” WSSA group 7 includes the following chemical classes: amides and ureas. Urea Group 7 herbicides include, for example, diuron, fluometuron, linuron, and tebuthiuron.

[0016] Hexazinone also acts by inhibiting photosynthesis by disrupting photosystem II, however, at a different binding site. Hexazinone is a Group 5 herbicide, as defined by the WSSA. Group 5 chemical classes include phenylcarbamates, pyridazinones, triazines, triazinones, and uracils. Hexazinone is triazinone. Other triazinones include metribuzin.

[0017] The structures and properties of these components are shown in Table 1.Table 144905-5705-2229.1* = E-pesticide manual, Sept. 2021

[0018] In some embodiments, the S-metolachlor may be present in an amount of from 15 to 55% by weight, such as from 20 to 50% by weight, preferably from 25 to 45% by weight, or even from about 30 to 40% by weight.

[0019] In some embodiments, the tebuthiuron may be present in an amount of from 1 to 30% by weight, such as from 3 to 25% by weight, preferably, from 10 to 25% by weight, or even from 15 to 20% by weight, or about 18% by weight.

[0020] In some embodiments, the hexazinone is present in amount of from 0.01 to 10% by weight, such as from 0.1 to 5% by weight, preferably from 0.5 to 5% by weight, such as from 2 to 4% by weight or even about 3% by weight.

[0021] In one embodiment, the composition comprises, from 200 to 400 g / L S- metolachlor, from 120 to 240 g / L tebuthiuron, and from 25 to 50 g / L hexazinone. In a specific embodiment, the composition comprises about 300 g / L S-metolachlor, about 180 g / L tebuthiuron, and about 36 g / L hexazinone.

[0022] The compositions preferably comprise one or more dispersing agents, more preferably the dispersing agent is selected from 2-[methyl-(l-oxo-9-octadecenyl)- amino]-ethanesulfonic acid and / or lignins; or salts thereof. In preferred embodiments, the dispersant is sodium lignosulfonate.

[0023] The composition can include one or more surfactants as wetting agents and / or emulsifiers and / or dispersants. The one or more surfactants is / are present in an amount of from 1 to 15% by weight, such as from 1 to 14% by weight, or from 1 to 12% by weight. In some embodiments, there are no additional wetting agents and / or emulsifiers, and only dispersants. In some embodiments, a dispersant is present at about 1.5% by weight.54905-5705-2229.1

[0024] Suitable ionic surfactants are the alkali, alkaline earth and ammonium salts of aromatic sulphonic acids, for example of lignosulphonic acid, phenolsulphonic acid, naphthal enesulphonic acid, dibutylnaphthal enesulphonic acid or of fatty acids, alkyland alkylaryl sulfonates, alkyl sulphates, lauryl ether sulphates and fatty alcohol sulphates, and salts of sulphated hexa-, hepta- and octa-decanols, and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulphonic acids with phenol and formaldehyde, polycarboxylates or phosphate esters of alkoxylated alcohols.

[0025] Suitable nonionic surfactants are polyoxyethylene octyl phenol ethers, alkoxylated alcohols such as ethoxylated isooctyl-, octyl- or nonyl-phenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors and also proteins, denatured proteins, polysaccharides (for example methylcellulose), hydrophobically modified starches, polyvinyl alcohols (for example Mowiol®), polyalkoxylates, polyvinylamines, polyethyleneimines, polyvinylpyrrolidones and their copolymers or block polymers.

[0026] Stabilizing agents, such as ammonium nitrate, can be present in the composition from, e.g., 0.1 to 2% w / w or about 1% w / w. The stabilizing agent can be used in an amount to improve dilution performance.

[0027] The compositions can comprise an ethoxylated alcohol as an emulsifier. Preferably the ethoxylated alcohol has an alkyl chain of from C2 to C30, such as from C5 to C20, from C10 to Cis, or even from C12 to C15. The ethoxylated alcohol may have from 5 to 30, such as from 10 to 25, preferably 20 ethoxylate monomers.

[0028] The compositions may comprise an anti-foam agent, preferably polydimethylsiloxane. Advantageously, the anti-foam agent is present in an amount of from 0.001 to 0.1% by weight, such as from 0.005 to 0.015% by weight.

[0029] The compositions may contain an anti-freeze agent, preferably a glycol, such as propane- 1,2-diol. The anti-freeze agent can be present in an amount of from 0.01 to 5% by weight or from 0.1 to 5% by weight, such as from 0.5 to 2% by weight.64905-5705-2229.1

[0030] The composition may contain a thickener or rheological modifier, such as xanthan gum. The thickener can be present in an amount of from 0.0001 to 5% by weight.

[0031] The composition may contain a preservative agent or an anti-bacterial agent, such as 2-bromo-2-nitropropan-l,3-diol, 5-chloro-2-methyl-4-isothiazolin-3-one and / or 2-methyl-4-isothiazolin-3-one. The anti-bacterial agent can be present in amount of from 0.0001 to 1% by weight, such as from 0.05 to 0.15% by weight.

[0032] The compositions may include other ingredients such as a colourant and a perfume, which are well known to the man skilled in the art.

[0033] The compositions can include adjuvants. Examples are surfactants (e.g. nonionic, anionic, cationic or amphoteric), wetting agents, spreading agents, sticking agents, humectants and penetration agents. Further examples of suitable adjuvants are mineral oils, vegetable oils, fatty acid esters, esters of aliphatic or aromatic dicarboxylic acids, alcohol ethoxylates, alkylphenol ethoxylates, alkylamine ethoxylates, ethoxylates of triglycerides, ethoxylates of fatty acids, ethoxylates of fatty acid esters, ethoxylates of sorbitan fatty acid esters, alkyl polyglycosides and silicone-based adjuvants. Preferred suitable adjuvants are surfactants which provide improved wetting or improved spray retention properties.

[0034] The composition herein can relate to compositions produced in a farmer’ s spray tank of water when a concentrate is mixed with water in the spray tank. A composition of the present invention may be in the form of a pre-mix formulation, packaged within a single vessel and ready to use directly after dilution. Thus, there is provided the use of the composition wherein such use comprises a dilution step prior to application.

[0035] The composition can be combined with at least one further active ingredient, typically another agrochemical active ingredient. This further agrochemical active ingredient may be in any form, such as EC, SE (suspo-emulsion concentrate) or an SL (soluble liquid).

[0036] In the formulation of the present disclosure a component is encapsulated and provided as a microcapsule suspension in the aqueous phase. By encapsulated it is meant that the second agrochemical or solvent droplets are contained within a discrete barrier of polyurea which acts as a diffusion barrier. This polyurea wall is an asymmetrical membrane formed through in situ polymerization in which the second agrochemical or solvent is able to diffuse through when applied in the field. This membrane is highly cross-linked by the ratio of the monomers used to form it as well74905-5705-2229.1as the temperature of reaction used. This is to control the diffusion of the solvent or second agrochemical across it. The polyurea wall provides physical stability as well as a chemical balance of the components in the formulation.

[0037] Methods for encapsulating agrochemicals in such a manner are reported in the art— see for example U.S. Pat. Nos 4,285,720, 4,280,833, 4,417,916, 4,534,783, 4,563,212 and 4,640,709.

[0038] In one embodiment, the formation of capsules is based on the Stauffer process. In such a process, isocyanates are provided which react with water to form carbamic acid. The carbamic acid decomposes into an amine and CO2, and this amine then reacts with the remaining isocyanate to form polyurea on heating.

[0039] Chloroacetamide microcapsules can be produced in the following manner. An aqueous solution comprising appropriate emulsifiers and an optional polyamine is provided in a suitable vessel and stirred at a low speed. Preferred emulsifiers are lignosulfonate salts, especially sodium lignosulfonate. In a separate vessel the organic phase is prepared — which comprises combining the chloroacetanilide herbicide and an appropriate polyisocyanate. Preferred isocyanates are blend of toluene diisocyanate (TDI) and diphenylmethane-4,4'-diisocyanate (MDI) — wherein the mixture of MDETDI is approximately 3: 1. The organic phase is then combined with the aqueous phase with continuous mixing. The particle size of the emulsion formed by mixing the aqueous and organic phase can range from about 1 micron to up to about 100 microns in diameter. A particle size range from about 7 to about 12 is preferred. A high shear blade can be used to achieve the desired particle size. Once the desired particle size is obtained the microcapsules are formed by appropriate heating of the mixture for an appropriate time. Typically, heating the mixture to 65-75°C for approximately 3 hours will suffice. It should be appreciated that the ratio of diisocyanates and the polymerisation temperature should be selected so as to increase the polymer cross linking in order to form a tight capsule around the chloroacetamide and thus minimise the interaction of the chloroacetamide with the hexazinone or tebuthiuron in the final formulation.

[0040] Unless otherwise stated are percentages are given as percentages by total weight and all embodiments and preferred features may be combined in any combination.Examples

[0041] Compositions of S-moc (300 g / L), hexazinone (36 g / L), and tebuthiuron (180 g / L) were prepared as a suspension emulsion (SE), oil dispersion (OD), emulsion84905-5705-2229.1concentrate (EC), a ZC. The SE and OD compositions failed due to tebuthiuron crystal growth. The EC compositions had mixed results under an accelerated storage stability test where certain batches showed active ingredient degradation. In sum the SE, OD and EC formulations each failed on at least one key property. The ZC was able to avoid crystal growth, but had other issues, such as, at high temperatures (>50C), wet sieve residue increased (from 0.01% to 0.5% in a 325MESH sieve 4 weeks at 50°C). Nevertheless, the ZC formulation was selected for further development.

[0042] In attempts to mitigate issues related to tebuthiuron, the following dispersants were screened Reax® 105M, Reax® 88, Reax® 825, Reax® 910, Reax® 1425E, Kraftsperse® 8828, Ultrazine® Na, Ufoxane® 3A, Morwet® D425, Atlox® 4913, and Polyfon® H. Table 2 provides a description of each dispersant.Table 294905-5705-2229.1

[0043] It was determined that the degree of sulphonation provided a large impact on the behaviour and stability of the composition, and Polyfon® H, low degree of sulphonation, provided the best results.

[0044] Challenges observed in the ZC formulation development included sedimentation, serum formation, particle size increase, and high wet sieve residue when tested at 50°C for 12 weeks. Furthermore, when the maximum concentrations of active ingredients were used (at a pH of 9) the formulations failed at high temperature storage (54°C / 2weeks, 50°C / 4weeks, and 50°C / 12weeks).

[0045] Based on the above work, Composition 1, as described in Table 3 below, was prepared. After various efforts, Composition 2, as described in Table 3, was prepared. Surprisingly, lowering the amount of sodium lignosulfonate from 18.6 g / L to 14.8 g / L provided a more robust formulation.Table 3Al = Active Ingredient104905-5705-2229.1

[0046] Storage stability results for Composition 2 are provided in Tables 4A and 4B.

[0047] As illustrated by the results, Composition 2 failed after storage at 54°C for 2 weeks and at 50°C for 4 weeks.

[0048] Various mitigation efforts were performed in an attempt to reach an acceptable formulation. Surprisingly, it was found that control of the pH improved the formulation. The pH of the composition was varied between 4 and 9. While compositions which had a pH of 4 and 9 failed, composition with a pH between 6 and 8 were found acceptable, giving Composition 3, described in Table 5114905-5705-2229.1

[0049] Storage stability results for Composition 3 are provided in Tables 6 A and 6B.

[0050] As illustrated by the results above, Composition 3 advantageously exhibits adequate viscosity, lower particle size, and reduced wet sieve residue in all tested conditions.

[0051] The many features and advantages of the disclosure are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of the disclosure which fall within the true spirit and scope of the disclosure. Further, since numerous modifications and variations will readily occur to those skilled in the art, it is not desired to limit the disclosure to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the disclosure.124905-5705-2229.1

Claims

Claims1. A composition, comprising: a liquid continuous phase; a first agrochemical active ingredient in the liquid continuous phase; a capsule comprising: a second agrochemical active ingredient, the capsule dispersed within the liquid continuous phase and configured to create a physical barrier between the first agrochemical active ingredient and the second agrochemical active ingredient; and a buffer configured to maintain a pH below 9; wherein the solubility of the first agrochemical active ingredient in the second agrochemical active ingredient is between 1% and 10% w / w at room temperature.

2. The composition of claim 1, wherein the buffer is configured to maintain a pH above 6.

3. The composition of claim 1, wherein the buffer is configured to maintain a pH between 6 and 8.

4. The composition of any one of the preceding claims, wherein the buffer is H3PO4.

5. The composition of any one of the preceding claims, wherein the first agrochemical active ingredient is a urea class herbicide.

6. The composition of any one of the preceding claims, wherein the first agrochemical is a photosystem II inhibitor, preferably a Weed Science Society of America (WSSA) group 7 herbicide.

7. The composition of any one of the preceding claims, wherein the first agrochemical is diuron, fluometuron, linuron, or tebuthiuron, preferably tebuthiuron.

8. The composition of any one of the preceding claims, wherein the second agrochemical active ingredient is an acetamide herbicide.134905-5705-2229.

19. The composition of any one of the preceding claims, wherein the second agrochemical active ingredient is a chloroacetanilide herbicide.

10. The composition of any one of the preceding claims, wherein the second agrochemical active ingredient is metolachlor, preferably S-metolachlor.

11. The composition of any one of the preceding claims, further comprising a third agrochemical active ingredient in the liquid continuous phase.

12. The composition of claim 11, wherein the third agrochemical active ingredient is an herbicide.

13. The composition of claim 11 or 12, wherein the third agrochemical active ingredient is a triazinone.

14. The composition of any one of claims 11 to 13, wherein the third agrochemical active ingredient is hexazinone or metribuzin, preferably hexazinone.

15. The composition of any one of the preceding claims, wherein the continuous phase comprises water.

16. The composition of any one of the preceding claims, wherein: the first agrochemical active ingredient is tebuthiuron; the second agrochemical active ingredient is S-metolachlor; and the third agrochemical active ingredient is hexazinone.

17. The composition of any one of the preceding claims, wherein the capsule has a volumebased particle size (Dv50) of from 3 to 40 microns, and preferably wherein the w / w ratio of capsule material to the second agrochemical active ingredient is 1 :5 to 1 :25, 1 :8 to 1 : 18, 1 : 10 to 1 : 15, or about 1 : 12.

18. The composition of any one of the preceding claims, further comprising: one or more surfactants as wetting agents and / or emulsifiers and / or dispersants in an amount of from 0.5 to 15% w / w;144905-5705-2229.1one or more thickeners in a range of 0.01 to 5% w / w; one or more anti-freeze agents in a range of 0.01 to 7% w / w; and less than 1% w / w a biocide.

19. The composition of any one of the preceding claims, wherein the first agrochemical active ingredient is tebuthiuron and the continuous phase comprises sodium lignosulfonate, preferably with a low degree of sulphonation, and more preferably with a low molecular weight.

20. The composition of claim 19, wherein the w / w ratio of tebuthiuron to sodium lignosulfonate is greater than about 10: 1, and preferably about 12:1.

21. The composition of any one of the preceding claims, wherein the first agrochemical active ingredient does not crystalize after 2-weeks at 54°C.

22. The composition of any one of the preceding claims, wherein the first agrochemical active ingredient does not crystalize after 4-weeks at 50°C.

23. The composition of any one of the preceding claims, the formulation contains w / w equal or lower than 2.5: 1 of the second agrochemical active ingredient and first agrochemical active ingredient.

24. The composition of any one of the preceding claims, the total amount of active ingredient in the composition is higher than 300 g / L.

25. The composition of any one of the preceding claims, wherein the solubility of the first agrochemical active ingredient in water is lower than 5 g / L.

26. The composition of any one of the preceding claims, wherein the solubility of the first agrochemical active ingredient as a melting point above 60°C.

27. A method of weed control, comprising: diluting the composition of any one of the preceding claims; and applying an effective amount of the composition to a crop or the locus of the crop.154905-5705-2229.

128. The method of claim 27, wherein the applying is soil-applied or early post-emergent in crops.

29. A method, comprising: encapsulating the second agrochemical active ingredient in a capsule to form a first composition; combining the first composition with the first agrochemical active ingredient to form a composition as defined in any one of the preceding claims.164905-5705-2229.1

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