Stable oil dispersions

Abstract

The present application relates to an agrochemical oil dispersion formulation comprising:-more than 30 wt.%, relative to the total weight of the formulation, of a first agrochemical active ingredient that is liquid at room temperature and insoluble in water; between 0.5 and 30 wt.%, relative to the total weight of the formulation, of a second agrochemical active ingredient insoluble in the first agrochemical active ingredient and solid at room temperature; -between 0.1 and 10 wt.%, relative to the total weight of the formulation, of a first surfactant, which is a sulfonate salt; and-between 1 and 30 wt.%, relative to the total weight of the formulation, of a second surfactant selected from the group consisting of arylalkylarylalkoxylates.

Description

Technical Field

[0001] The present invention belongs to the field of agrochemistry. The present invention relates to stable oil dispersions for agricultural applications, their preparation processes, and methods for controlling weeds, diseases, and pests in plants. Background Art

[0002] The preparation of oil dispersions containing a high loading of active ingredients poses significant challenges to formulating chemists. These challenges increase with the number and complexity of the components, and formulating chemists must avoid many potential problems such as sedimentation of solids, recrystallization of solid components, or chemical degradation of the ingredients.

[0003] The challenge for formulating chemists is to select the appropriate dispersants and emulsifiers in appropriate proportions to produce a stable system. Selecting the appropriate components in appropriate proportions can be challenging, especially if the goal is to find a specific combination of surfactants / emulsifiers that is applicable to a wide range of active ingredient combinations.

[0004] WO 01 / 17346 discloses the preparation of an oil dispersion mainly containing acetochlor and glyphosate, which contains a complex mixture of surfactants including ethoxylated tallow amine, sulfonic acid, ethoxylated alcohol, ethoxylated sorbitol fatty acid ester, and EO / PO copolymer. Summary of the Invention

[0005] The inventors have developed an oil dispersion formulation that is stable even when incorporated with a high loading of active ingredients.

[0006] Thus, a first aspect is an agrochemical oil dispersion formulation comprising:

[0007] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water and exceeds 30 wt.% relative to the total weight of the formulation;

[0008] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature and is between 0.5 and 30 wt.% relative to the total weight of the formulation;

[0009] - A first surfactant that is selected from sulfonates and is between 0.1 and 10 wt.% relative to the total weight of the formulation; and

[0010] - A second surfactant that is selected from arylalkylaryloxides and is between 1 and 30 wt.% relative to the total weight of the formulation.

[0011] The inventors have found that a specific combination of sulfonates and arylalkylaryloxyides provides unexpectedly stable oil dispersions even at very high loadings of active ingredients.

[0012] Another aspect disclosed herein relates to a method for preparing the above oil dispersions, the method comprising mixing the components.

[0013] A further object of the invention is a tank mixture comprising the oil dispersions disclosed herein and agrochemically acceptable adjuvants.

[0014] Another aspect of the invention is a method for controlling unwanted plants, pests or diseases, which comprises bringing an effective amount of a formulation as disclosed herein into contact with the locus of the unwanted plants, pests or diseases. Detailed Description

[0015] Definitions

[0016] Before elaborating on the subject matter of the present invention, it may be helpful to provide definitions of certain terms to be used herein. 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 subject matter pertains.

[0017] As used herein, the term "stable", when used in connection with physical stabilization or when used in connection with a composition, means that no significant thickening is observed after storage at a temperature of at least 54 °C for at least 2 weeks. That is, after storage at a temperature of at least 54 °C for at least 2 weeks, the stability of the oil dispersion according to CIPAC MT 180 does not change significantly.

[0018] As used herein, the term "effective amount", when used in connection with an agrochemical active ingredient, refers to the amount of agrochemical active ingredient that is sufficient to achieve good control or an active level against pests, diseases and / or unwanted plants when ingested, contacted or sensed.

[0019] "Agrochemical active ingredient" is a substance capable of controlling unwanted plants, plant pests or plant diseases and does not cause significant damage to the crop plants being treated. In the present application, the agrochemical active ingredient is preferably a herbicide.

[0020] As used herein, the term "plant" or "crop" or "crop plant" includes reference to an entire plant, plant organs (such as leaves, stems, twigs, roots, trunks, branches, buds, fruits, etc.), plant cells, or plant seeds having industrial significance, including grasslands and pastures, such as plants for human consumption, animal consumption, or other industrial uses. The term also encompasses crops such as fruits. The term "plant" may also include its propagation material, which may include all reproductive parts of the plant (such as seeds) and vegetative plant material (such as cuttings and tubers) that can be used to propagate the plant. The term may also include spores, bulbs, corms, rhizomes, sprouts, basal branches, stolons, and flower buds, as well as other parts of the plant, including seedlings and young plants, which will be transplanted after germination or after emergence from the soil. As used herein, the term "crop" includes plants that have been modified by breeding, mutagenesis, or genetic engineering. Genetically modified plants are plants whose genetic material has been modified using recombinant DNA technology. Typically, one or more genes have been integrated into the genetic material of such plants in order to improve certain characteristics of the plant.

[0021] As used herein, the term "site" includes habitats, breeding areas, plants, propagation materials, soil, regions, materials, or environments in which unwanted plants, pests, or diseases grow or can grow.

[0022] As used herein, the terms "control" or "controlling" or "combatting" mean preventing the growth of diseases, pests, or unwanted plants, protecting plants from diseases or pests, delaying the onset of diseases, or reducing the harmful effects of diseases or pests, or killing or reducing the growth of unwanted plants, pests, or microorganisms.

[0023] As used herein, the phrase "block copolymer" means a polymer comprising at least two different polymers covalently bonded together. Each block is typically a homopolymer, but can also be a copolymer having specific unique physical / chemical or functional characteristics (e.g., having one block that is soluble in water and another block that is not soluble in water at all).

[0024] "Alkyl" as used in this document means a straight-chain or branched hydrocarbon chain group composed of carbon and hydrogen atoms, containing no unsaturation, having the number of carbon atoms indicated in each case (e.g., 1 to 16 carbon atoms), and attached to the remainder of the molecule by a single bond. In embodiments of the present invention, the alkyl contains 1 to 8 carbon atoms. In additional embodiments, it contains 1 to 4 carbon atoms. Exemplary alkyls can be methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, or n-pentyl.

[0025] "Aryl" as used herein means an aromatic hydrocarbon group having the indicated number of carbon atoms in each case, such as phenyl or naphthyl. The aryl may optionally be substituted by one, two or three groups selected from the group consisting of halogen, alkyl and haloalkyl.

[0026] The oil dispersions of the present invention may additionally contain agriculturally acceptable inert additives. They are defined herein as any substance that is not itself an agrochemical active ingredient but is added to the composition to improve its physical and / or chemical properties (e.g., stability, bioavailability of the active ingredient, viscosity, pH, etc.).

[0027] The oil dispersions disclosed herein may be mixed with tank mix adjuvants prior to their application in the field to improve physical properties and efficacy. Some substances may be used as agriculturally acceptable inert additives (built-in adjuvants) in the oil dispersions disclosed herein, or may be mixed with the oil dispersions disclosed herein as tank mix additives (adjuvants) immediately prior to application in the field. The tank mixtures obtained by mixing the oil dispersions disclosed herein with one or more tank mix adjuvants are also an aspect of the present invention.

[0028] Non-limiting examples of additional agriculturally acceptable inert additives and tank mix adjuvants are additional surfactants, or wetting agents (or spreading agents), sticker agents, emulsifying agents, dispersing agents, suspending agents, plant penetrants (or translocators), antifreeze agents, preservatives, binders, fertilizers, thickening agents, antioxidants, drift retardants, buffering agents, inverting agents, soil penetrants, UV absorbers, protective agent binders, defoaming agents or wetting agents.

[0029] Unless otherwise specifically stated, the term "a / an" as used herein includes the singular and the plural. Thus, the terms "a / an" or "at least one" may be used interchangeably in this application.

[0030] For the purpose of better understanding the teachings herein and without in any way limiting the scope of these teachings, unless otherwise indicated, all numerical values representing amounts, percentages or proportions, as well as other numerical values used in the specification and claims, should be understood to be modified in all instances by the term "about". Thus, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. In this regard, the term "about" as used herein specifically includes ±10% of the indicated value within the range. Additionally, all endpoints of all ranges involving the same component or property herein include the endpoints, are combinable independently, and include all intermediate points and ranges.

[0031] Unless otherwise indicated, weight percentages (“wt. %”) are expressed relative to the total amount of the components. For example, if a particular component of a formulation of the present invention is mentioned as 5 wt. %, it must be understood as 5 wt. % relative to the total weight of the formulation of the present invention.

[0032] Oil dispersion

[0033] Oil dispersions are typically prepared by combining the components, where the order of addition has no particular relevance.

[0034] For the purposes of this document, it should be understood that an oil dispersion contains a solid active ingredient dispersed in an oil. In an oil dispersion, the oil can be an organic solvent that is typically substantially insoluble in water and is agrichemically acceptable, a liquid active ingredient (a first agrochemical active ingredient), or a mixture of both. The solvent is selected such that it is at least partially miscible in the first agrochemical active ingredient and such that a second agrochemical active ingredient is substantially insoluble and remains as a suspended solid at the same time.

[0035] The oil disclosed herein can contain an organic solvent, although it is not necessary, and stable formulations can also be obtained without a solvent (see formulation H in the examples). The organic solvent is typically a vegetable oil. Vegetable oils are mixtures of triacylglycerols and small amounts of diacylglycerols and monoacylglycerols. The acyl groups are saturated or unsaturated fatty acids having 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms. For example, the vegetable oil can be an unepoxidized or epoxidized vegetable oil. For example, the vegetable oil is made from unsaturated fatty acids having 12 to 22 carbon atoms. The solvent can also be an esterified alkyl ester derived from a vegetable oil, such as a methyl ester of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms. The solvent can be selected from the group consisting of: rapeseed oil, almond oil, jojoba oil, apricot kernel oil, avocado oil, babassu kernel oil, borage oil, Brazil nut oil, carrot root extract, ozokerite oil, dog rose fruit oil, emu oil, evening primrose oil, grape seed oil, hemp seed oil, macadamia oil, macadamia nut oil, mango seed oil, olive oil, pine oil, peanut oil NF, rice bran oil, safflower oil, sesame oil, soybean oil, sunflower oil, sweet almond oil, wheat germ oil, and mixtures thereof, or it can be a methyl ester of the corresponding fatty acid. The solvent can also be other organic solvents that are insoluble in water, such as ethyl acetate, mineral oil, toluene, xylene, etc.

[0036] The concentration of the organic solvent can be between 0.1 and 50 wt.%, for example, between 1 and 40 wt.%, or between 1 and 30 wt.%, or between 1 and 20 wt.%, or between 1 and 15 wt.%, or between 1 and 10 wt.%, or between 2 and 40 wt.%, or between 3 and 20 wt.%, or between 3 and 18 wt.%, or between 3 and 8 wt.%, or between 15 and 35 wt.%, relative to the total weight of the formulation.

[0037] The inventors have found that the combination of two types of surfactants is crucial in providing the desired stability: sulfonates and arylalkylaryloxyalkylates. More specifically, the inventors have found that sulfonate surfactants provide a surprisingly stabilizing effect on solids dispersed in liquid AI, such as [α]-chloroacetamides (e.g., acetochlor, alachlor, butachlor, butenachlor, isobutachlor, diethatyl-ethyl, dimethachlor, dimethenamid, metazachlor, pethoxamid, pretilachlor, propachlor, propisochlor, prynachlor, metolachlor, and thenylchlor).

[0038] The formulations disclosed herein can contain sulfonate surfactants in an amount between 0.1 and 9 wt.%, relative to the total weight of the composition. These concentrations have been found to provide stable oil suspensions. For example, the amount of sulfonate surfactant is between 0.2 and 8.5 wt.%, or between 0.5 and 8 wt.%, relative to the total weight of the composition, for example, between 1 and 7 wt.%, preferably between 1.5 and 6 wt.%, preferably between 1.7 and 5.5 wt.%, for example between 1.8 and 5 wt.%, preferably between 2 and 4.5 wt.%.

[0039] On the other hand, the formulations disclosed herein typically contain arylalkylaryloxyalkylates in an amount between 2 and 30 wt.%, relative to the total weight of the composition, for example between 3 and 29 wt.%, or between 3 and 28 wt.%, or between 3 and 25 wt.%, or between 4 and 25 wt.%, or between 5 and 25 wt.%, or between 5 and 24 wt.%, or between 5 and 23 wt.%, for example between 3 and 15 wt.%, for example between 3 and 10 wt.%, or between 5 and 12 wt.%, or between 7 and 12 wt.%.

[0040] The weight ratio of the arylalkylaryloxyide surfactant to the sulfonate surfactant is typically between 1:5 and 20:1, such as between 1:2 and 15:1, or between 1:2 and 12:1, or between 1:2 and 10:1, or between 1:2 and 8:1, or between 1:2 and 6:1, or between 1:1 and 5:1, or between 1:1 and 4:1, or between 1:1 and 3:1.

[0041] Sulfonate surfactants generally refer to salts of organic sulfonic acids, such as those having the formula R-SO 3 - M + wherein R is an organic residue (i.e., mainly comprising carbon and hydrogen atoms, which may also have other heteroatoms such as oxygen and nitrogen), and M + is a cation, and M is, for example, a metal (e.g., an alkali metal or an alkaline earth metal such as sodium, potassium or calcium) or an organic residue such as ammonium (e.g., NH 4 + or R n N(H) 4-n + ).

[0042] Examples of sulfonate surfactants are arylsulfonates, alkylsulfonates, alkylarylsulfonates (e.g., sulfonates of dodecylbenzene or tridecylbenzene), dialkylsulfosuccinates, naphthalenesulfonates, alkylnaphthalenesulfonates (e.g., sodium alkylnaphthalenesulfonate), diphenylsulfonates or α-olefinsulfonates. Examples of commercially available sulfonate surfactants include sodium dodecyl sulfate (Na-DS, SDS), MORWET D-425 (sodium salt of an alkylnaphthalenesulfonate condensate, available from Akzo Nobel), MORWET D-500 (sodium salt of an alkylnaphthalenesulfonate condensate and a block copolymer, available from Akzo Nobel), sodium dodecylbenzenesulfonate (Na-DDBS), diphenyl ether disulfonate, naphthaldehyde condensate, DOWFAX (available from Dow), Nansa EVM70 or ATLOX 4838B (calcium salt of an alkylarylsulfonate in 2-ethylhexanol), dihexyl sulfosuccinate or dioctyl sulfosuccinate, or combinations thereof.

[0043] Preferred arylalkylaryloxides are selected from the group consisting of alcohols, phosphates, and sulfates. Typically, the arylalkylaryloxide will be an arylalkylphenol alkoxide, such as triphenylvinylphenol ethoxide, triphenylvinylphenol ethoxide phosphate ether (also known as triphenylvinylphenol phosphate), or triphenylvinylphenol ethoxide sulfate ether (also known as triphenylvinylphenol sulfate). Triphenylvinylphenol ethoxide contains a polymer distribution having an average of 3 styrenes and a defined number of ethylene oxide units, depending on the grade. They may also contain propoxide units, either in a random or block copolymer distribution. Examples of triphenylvinylphenol alkoxides include triphenylvinylphenol PEO(10); triphenylvinylphenol PEO(16); triphenylvinylphenol PEO(20); triphenylvinylphenol PEO(25); triphenylvinylphenol PEO(40); triphenylvinylphenol PEO(54); diphenylvinylphenol PEO(8); diphenylvinylphenol PEO(13); diphenylvinylphenol PEO(17); triphenylvinylphenol PEO-PPO; polyaryl phosphate PEO(16); the amine salt of polyaryl phosphate PEO(16); or the potassium salt of polyaryl phosphate PEO(16), where PEO represents polyethylene oxide, PPO represents polypropylene oxide, and the numbers in parentheses indicate the average number of polyalkylene units.

[0044] The first agrochemical active ingredient is an ingredient that is liquid at room temperature and substantially insoluble in water, preferably a herbicide. In one embodiment, the formulations disclosed herein contain from 30 to 90 wt.% of the first agrochemical active ingredient, relative to the total weight of the formulation. For example, the formulation may contain from 30 to 85 wt.%, such as from 30 to 80 wt.%, such as from 30 to 75 wt.%, such as from 30 to 70 wt.%, such as from 30 to 65 wt.%, such as from 30 to 60 wt.%, such as from 30 to 55 wt.%, such as from 30 to 50 wt.%, such as from 30 to 45 wt.%, such as from 30 to 40 wt.%, such as from 35 to 90 wt.%, such as from 40 to 90 wt.%, such as from 45 to 90 wt.%, such as from 50 to 90 wt.%, such as from 65 to 90 wt.%, such as from 70 to 90 wt.%, such as from 75 to 90 wt.%, such as from 80 to 90 wt.%, such as from 40 to 85 wt.%, such as from 50 to 80 wt.%, such as from 55 to 80 wt.% of the first agrochemical active ingredient, relative to the total weight of the formulation.

[0045] Typically, the weight ratio of the first agricultural chemical component to the sulfonate surfactant is between 2:1 and 30:1, such as between 3:1 and 28:1, or between 3:1 and 25:1, or between 5:1 and 24:1, or between 8:1 and 23:1.

[0046] The oil dispersions disclosed herein typically contain a second agrichemically active ingredient in an amount between 0.5 and 28 wt.% relative to the total weight of the formulation. For example, between 0.5 and 25 wt.% relative to the total weight of the formulation, such as between 0.5 and 23 wt.%, such as between 0.5 and 20 wt.%, such as between 0.5 and 15 wt.%, such as between 0.5 and 12 wt.%, such as between 0.5 and 10 wt.%, such as between 0.5 and 8 wt.%, such as between 0.5 and 5 wt.%, such as between 1.0 and 25 wt.%, such as between 2.0 and 25 wt.%, such as between 3.0 and 25 wt.%, such as between 4.0 and 25 wt.%, such as between 5.0 and 25 wt.%, such as between 8 and 25 wt.%, such as between 10 and 25 wt.%, such as between 12 and 25 wt.%, such as between 12 and 22 wt.% of the second agrichemically active ingredient.

[0047] Alternatively, the oil dispersion contains a second agrichemically active ingredient in an amount between 1.0 and 8 wt.% relative to the total weight of the formulation, such as between 1.0 and 7 wt.%, such as between 1.0 and 6 wt.%, such as between 1.0 and 5 wt.%, such as between 2.0 and 8 wt.%, such as between 2.0 and 7 wt.%, such as between 2.0 and 6 wt.%, such as between 2.0 and 7 wt.%.

[0048] The first agrichemically active ingredient is typically [α]-chloroacetamide. For example, [α]-chloroacetamides selected from the group consisting of: acetochlor, alachlor, butachlor, butenachlor, isobutachlor, acetochlor-methyl, dimethachlor, dimethenamid, pyzotolamid, pretilachlor, propachlor, propanil, metolachlor, pendimethalin and thenylchlor. Preferably, the first agrichemically active ingredient is [α]-chloroacetamide selected from the group consisting of: acetochlor, butachlor, dimethenamid, metolachlor or its salts, stereoisomers, esters or solvates, such as dimethenamid or metolachlor or its salts, stereoisomers or solvates. Preferably, the first agrichemically active ingredient is metolachlor or its salts, stereoisomers or solvates.

[0049] The second agrochemical active ingredient is a solid at room temperature and is selected from the group consisting of: [α]-oxyacetamide, [α]-thioacetamide, acetamide, alkylazine, amide, arylpyrrolidone aniline, aryl carboxylate, aryloxyphenoxypropionate (FOP), azolylformamide, benzamide, benzoate, benzofuran, benzoic acid, benzothiadiazinone, benzyl ether, carbamate, carbamate, cyclohexanedione (DIM), dinitroaniline, dinitrophenol, diphenyl ether, diphenyl ether, diphenyl heterocycle, glycine, imidazolinone, isoxazole, isoxazolidone, isoxazoline, nitrile, N-phenyl heterocycle, N-phenyl-imide, N-phenyl-imide, N-phenyl-oxadiazolinone, N-phenyl-triazolinone, other, ethylene oxide, phenylcarbamate, phenoxycarboxylate, phenoxypyridazine, phenyl ether, phenylpyrazole, phenylpyrazoline, phenyl-pyridazine, phosphinic acid, phosphoroamidate, dithiophosphate, pyrazole, pyridazinone, pyridine carboxylate, pyridine, pyridinium, pyridyloxycarboxylate, pyrimidine carboxylate, pyrimidyl benzoate, quinoline carboxylate, sulfonanilide, sulfonylurea, thiocarbamate, triazine, triazinone, triazole, triazolinone, triazolinone, triazolopyrimidine, trione, uracil and urea. N-phenyl-imide is preferred, for example, N-phenyl-imide selected from the group consisting of: flumioxazin, flumiclorac or its salts, stereoisomers, esters or solvates. Preferably, the second agrochemical active ingredient is flumioxazin or its salt or solvate.

[0050] The second agrochemical active ingredient is preferably a PPO inhibitor.

[0051] Typically, the weight ratio of the first agrochemical active ingredient to the N-phenyl-imide ranges between 1:1 and 40:1, for example between 2:1 and 30:1, for example between 3:1 and 28:1 or between 4:1 and 25:1.

[0052] Typically, the weight ratio of the N-phenyl-imide to the arylalkylaryloxyide surfactant ranges between 5:1 and 1:5, for example between 2:1 and 1:4, or between 1:1 and 1:2.

[0053] For example, the weight ratio of the N-phenyl-imide to the sulfonate surfactant ranges between 5:1 and 1:5, for example between 3:1 and 1:3, or between 2:1 and 1:3.

[0054] Alternatively, the second agrochemical active ingredient is selected from the group consisting of glycine and phosphonic acid, preferably phosphonic acid. For example, the second agrochemical active ingredient is selected from the group consisting of: glufosinate and bilanafos, or salts, stereoisomers or solvates thereof. Preferably, the second agrochemical active ingredient is glufosinate, or a salt, stereoisomer or solvate thereof.

[0055] The second agrochemical active ingredient can be an inhibitor of glutamine synthetase.

[0056] Typically, the ratio of the first agrochemical active ingredient to phosphonic acid is included between 1:2 and 10:1, preferably between 1:1 and 6:1, for example between 1:1 and 5:1 or between 1:1 and 4:1.

[0057] For example, the weight ratio of phosphonic acid to an arylalkylaryloxyide surfactant is between 10:1 and 1:2, for example between 5:1 and 1:1, or between 3:1 and 1:1.

[0058] Typically, the weight ratio of phosphonic acid to a sulfonate surfactant is between 20:1 and 1:1, for example between 15:1 and 2:1, or between 12:1 and 2:1.

[0059] The oil dispersions described herein may also contain a safener and / or additional agrochemical active ingredients.

[0060] The formulation may also contain a rheology modifier, such as surface-modified silica, for example silica modified with an alkylsilane. A rheology modifier suitable for the formulations of the present invention is, for example, silica modified with octylmethoxysilane ( R-805; Evonik) or dimethyldichlorosilane ( R-972; Evonik). The amount by weight of the rheology modifier typically is included between 0.1 and 10 wt.% relative to the total weight of the formulation, for example between 1 and 9 wt.%, or for example between 2 and 8 wt.%, or for example between 2 and 7 wt.%.

[0061] The oil dispersions disclosed herein do not require additional surfactants, and thus the surfactant may consist only of:

[0062] - a first surfactant between 0.1 and 10 wt.% relative to the total weight of the formulation, which is selected from sulfonates; and

[0063] - a second surfactant between 1 and 30 wt.% relative to the total weight of the formulation, which is selected from arylalkylaryloxyides.

[0064] For example, the oil dispersion formulation consists only of:

[0065] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water and exceeds 30 wt.% relative to the total weight of the formulation;

[0066] - A second agrochemical active ingredient that is insoluble in the second agrochemical active ingredient and is solid at room temperature and is between 0.5 and 30 wt.% relative to the total weight of the formulation;

[0067] - A first surfactant that is between 0.1 and 10 wt.% relative to the total weight of the formulation and is selected from sulfonates;

[0068] - A second surfactant that is between 1 and 30 wt.% relative to the total weight of the formulation and is selected from arylalkylaryloxyides;

[0069] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0070] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, preferably surface-modified silica; and

[0071] - Optionally, a water-insoluble organic solvent up to 35 wt.% relative to the total weight of the formulation, preferably a vegetable oil or a methylated vegetable oil.

[0072] The formulations disclosed herein admit many combinations of the elements described heretofore in different proportions. Thus, for example, this document covers an agrochemical oil dispersion formulation that comprises:

[0073] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water and is between 30 and 90 wt.% relative to the total weight of the formulation;

[0074] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature and is between 2 and 30 wt.% relative to the total weight of the formulation;

[0075] - A first surfactant that is between 1 and 8 wt.% relative to the total weight of the formulation and is a sulfonate;

[0076] - A second surfactant that is between 5 and 25 wt.% relative to the total weight of the formulation and is selected from arylalkylaryloxyides;

[0077] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0078] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0079] - Optionally, a water-insoluble organic solvent up to 35 wt.% relative to the total weight of the formulation.

[0080] Additional exemplary formulations covered in this document include:

[0081] - A first agrochemical active ingredient that is liquid at room temperature and water-insoluble, between 30 and 80 wt.% relative to the total weight of the formulation;

[0082] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and solid at room temperature, between 2 and 30 wt.% relative to the total weight of the formulation;

[0083] - A first surfactant between 1 and 8 wt.% relative to the total weight of the formulation, which is a sulfonate;

[0084] - A second surfactant between 5 and 25 wt.% relative to the total weight of the formulation, which is selected from arylalkylaryloxyides;

[0085] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0086] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0087] - Optionally, a water-insoluble organic solvent up to 35 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils, methylated vegetable oils, and their mixtures.

[0088] Additional exemplary formulations covered in this document include:

[0089] - A first agrochemical active ingredient that is liquid at room temperature and water-insoluble, between 30 and 80 wt.% relative to the total weight of the formulation;

[0090] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and solid at room temperature, between 2 and 30 wt.% relative to the total weight of the formulation;

[0091] - A first surfactant between 1 and 8 wt.% relative to the total weight of the formulation, which has the formula R-SO 3 - M+ a first surfactant which is a sulfonate of R-SO₃M, where R is an organic residue and M + is a metal cation selected from alkali metals or alkaline earth metals or an ammonium residue;

[0092] - a second surfactant in an amount between 5 and 25 wt.% relative to the total weight of the formulation, selected from arylalkylaryloxides selected from the group consisting of triphenylvinylphenol ethoxylates, triphenylvinylphenol ethoxylate phosphate ethers, and triphenylvinylphenol ethoxylate sulfate ethers;

[0093] - optionally, an antifoaming agent in an amount up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0094] - optionally, a rheology modifier in an amount up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0095] - optionally, a water-insoluble organic solvent in an amount up to 35 wt.% relative to the total weight of the formulation, selected from the group of methylated vegetable oils.

[0096] Additional exemplary formulations covered in this document include:

[0097] - a first agrochemical active ingredient that is liquid at room temperature and water-insoluble in an amount between 30 and 80 wt.% relative to the total weight of the formulation;

[0098] - a second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and solid at room temperature in an amount between 2 and 30 wt.% relative to the total weight of the formulation;

[0099] - a first surfactant which is a sulfonate of R-SO₃M in an amount between 1 and 8 wt.% relative to the total weight of the formulation, where R is an organic residue and M 3 - M + is a metal cation selected from alkali metals or alkaline earth metals or an ammonium residue; + is a metal cation selected from alkali metals or alkaline earth metals or an ammonium residue;

[0100] - a second surfactant in an amount between 5 and 15 wt.% relative to the total weight of the formulation, selected from arylalkylaryloxides selected from the group consisting of triphenylvinylphenol ethoxylates and triphenylvinylphenol ethoxylate phosphate ethers;

[0101] - optionally, an antifoaming agent in an amount up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0102] - Optionally, a rheology modifier up to 6 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0103] - Optionally, a water-insoluble organic solvent up to 35 wt.% relative to the total weight of the formulation, which is selected from the group of methylated vegetable oils.

[0104] Additional exemplary formulations covered in this document include:

[0105] - A first agrochemical active ingredient that is liquid at room temperature and water-insoluble, between 30 and 90 wt.% relative to the total weight of the formulation;

[0106] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and solid at room temperature, between 5 and 30 wt.% relative to the total weight of the formulation, which is selected from the group of glycine and phosphonic acid;

[0107] - A first surfactant between 1 and 8 wt.% relative to the total weight of the formulation, which is a sulfonate;

[0108] - A second surfactant between 5 and 25 wt.% relative to the total weight of the formulation, which is selected from the group of arylalkylaryloxyides;

[0109] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0110] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0111] - Optionally, a water-insoluble organic solvent up to 35 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils and methylated vegetable oils.

[0112] Additional exemplary formulations covered in this document include:

[0113] - A first agrochemical active ingredient that is liquid at room temperature and water-insoluble, between 30 and 90 wt.% relative to the total weight of the formulation, which is selected from the group of [α]-chloroacetamide;

[0114] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and solid at room temperature, between 10 and 25 wt.% relative to the total weight of the formulation, which is selected from the group of glycine and phosphonic acid;

[0115] - A first surfactant between 1 and 8 wt.% relative to the total weight of the formulation, which is a sulfonate;

[0116] - A second surfactant between 15 and 25 wt.% relative to the total weight of the formulation, which is selected from arylalkylaryloxides;

[0117] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0118] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0119] - Optionally, a water-insoluble organic solvent up to 20 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils and methylated vegetable oils.

[0120] Additional exemplary formulations covered in this document include:

[0121] - A first agrochemical active ingredient between 30 and 80 wt.% relative to the total weight of the formulation, which is liquid at room temperature and water-insoluble, and is selected from the group of [α]-chloroacetamides;

[0122] - A second agrochemical active ingredient between 15 and 25 wt.% relative to the total weight of the formulation, which is insoluble in the first agrochemical active ingredient and is solid at room temperature, and is selected from the group of glycine and phosphonic acid;

[0123] - A first surfactant between 1 and 8 wt.% relative to the total weight of the formulation, which is a sulfonate of the formula R-SO 3 - M + wherein R is an organic residue and M + is a metal cation or ammonium residue selected from alkali metals or alkaline earth metals;

[0124] - A second surfactant between 5 and 15 wt.% relative to the total weight of the formulation, which is selected from arylalkylaryloxides, and the arylalkylaryloxides are selected from the group consisting of triphenylvinylphenol ethoxylates and triphenylvinylphenol ethoxylate phosphate ethers;

[0125] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0126] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0127] - Optionally, a water-insoluble organic solvent up to 20 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils and methylated vegetable oils.

[0128] Additional exemplary formulations covered in this document include:

[0129] - A first agrochemical active ingredient that is liquid at room temperature and water-insoluble, between 40 and 80 wt.% relative to the total weight of the formulation, which is selected from the group consisting of: acetochlor, alachlor, butachlor, butenachlor, isobutachlor, acetochlor-methyl, dimethachlor, dimethenamid, pyrazolate, pretilachlor, propachlor, propisochlor, propyzamide, metolachlor, and thenylchlor;

[0130] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, between 15 and 25 wt.% relative to the total weight of the formulation, which is selected from glycine and phosphonic acid;

[0131] - A first surfactant between 1 and 8 wt.% relative to the total weight of the formulation, which is selected from the group consisting of aryl sulfonates, alkyl sulfonates, alkyl aryl sulfonates, dialkyl sulfosuccinates, naphthalene sulfonates, alkyl naphthalene sulfonates, diphenyl sulfonates, α-olefin sulfonates, and mixtures thereof.

[0132] - A second surfactant between 5 and 15 wt.% relative to the total weight of the formulation, which is selected from arylalkylarylalcoxylates, and the arylalkylarylalcoxylates are selected from the group consisting of triphenylvinylphenol ethoxylates, triphenylvinylphenol ethoxylate sulfate ethers, and triphenylvinylphenol ethoxylate phosphate ethers;

[0133] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0134] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0135] - Optionally, a water-insoluble organic solvent between 1 and 15 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils and methylated vegetable oils.

[0136] Additional exemplary formulations covered in this document include:

[0137] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water and is in the range of 30 to 70 wt.% relative to the total weight of the formulation, and is selected from the group consisting of: acetochlor, alachlor, butachlor, butenachlor, isobutachlor, acetochlor-methyl, dimethachlor, dimefuron, pyrazolate, pretilachlor, propachlor, propanil, metolachlor, propyzamide, metolachlor-s, and thenylchlor;

[0138] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature and is in the range of 15 to 25 wt.% relative to the total weight of the formulation, and is selected from phosphonic acid;

[0139] - A first surfactant that is in the range of 1 to 6 wt.% relative to the total weight of the formulation, and is selected from the group consisting of arylsulfonates, alkylsulfonates, alkylarylsulfonates, and mixtures thereof.

[0140] - A second surfactant that is in the range of 5 to 15 wt.% relative to the total weight of the formulation, and is selected from arylalkylarylalcohol alkoxylates, and the arylalkylarylalcohol alkoxylates are selected from the group consisting of triphenylvinylphenol ethoxylates, triphenylvinylphenol ethoxylate sulfate ethers, and triphenylvinylphenol ethoxylate phosphate ethers;

[0141] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0142] - Optionally, a rheology modifier up to 6 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0143] - Optionally, a water-insoluble organic solvent in the range of 10 to 35 wt.% relative to the total weight of the formulation, and is selected from the group of vegetable oils and methylated vegetable oils.

[0144] Additional exemplary formulations covered in this document include:

[0145] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water and is in the range of 30 to 70 wt.% relative to the total weight of the formulation, and is selected from the group consisting of: acetochlor, alachlor, butachlor, butenachlor, isobutachlor, acetochlor-methyl, dimethachlor, dimefuron, pyrazolate, pretilachlor, propachlor, propanil, metolachlor, propyzamide, metolachlor-s, and thenylchlor;

[0146] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, in an amount between 15 and 25 wt.% relative to the total weight of the formulation, selected from the group consisting of glufosinate and bilanafos, or salts, stereoisomers or solvates thereof;

[0147] - A first surfactant in an amount between 1 and 8 wt.% relative to the total weight of the formulation, selected from the group consisting of arylsulfonates, alkylsulfonates, alkylarylsulfonates, dialkylsulfosuccinates, naphthalenesulfonates, alkylnaphthalenesulfonates, diphenylsulfonates, α-olefinsulfonates and mixtures thereof.

[0148] - A second surfactant in an amount between 5 and 15 wt.% relative to the total weight of the formulation, selected from triphenylvinylphenol ethoxylates and triphenylvinylphenol ethoxylate phosphate ethers;

[0149] - Optionally, an antifoaming agent in an amount up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0150] - Optionally, a rheology modifier in an amount up to 6 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0151] - Optionally, a water-insoluble organic solvent in an amount between 10 and 35 wt.% relative to the total weight of the formulation, selected from the group of vegetable oils and methylated vegetable oils.

[0152] Additional exemplary formulations covered in this document include:

[0153] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water, in an amount between 40 and 80 wt.% relative to the total weight of the formulation, selected from the group consisting of acetochlor, alachlor, butachlor, butenachlor, isobutachlor, acetochlor-methyl, dimethachlor, dimethenamid, pyrazolate, pretilachlor, propachlor, napropamide, isopropyl metolachlor, propyzamide and thenylchlor;

[0154] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, in an amount between 15 and 25 wt.% relative to the total weight of the formulation, selected from glufosinate, or salts, stereoisomers or solvates thereof;

[0155] - A first surfactant in an amount between 1 and 8 wt.% relative to the total weight of the formulation, selected from the group consisting of arylsulfonates, alkylsulfonates, alkylarylsulfonates, dialkylsulfosuccinates, naphthalenesulfonates, alkylnaphthalenesulfonates, diphenylsulfonates, α-olefinsulfonates and mixtures thereof.

[0156] - A second surfactant, between 1 and 5 wt.% relative to the total weight of the formulation, selected from triphenylvinylphenol ethoxylated phosphate ethers;

[0157] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0158] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0159] - Optionally, a water-insoluble organic solvent up to 35 wt.% relative to the total weight of the formulation, selected from the group of vegetable oils and methylated vegetable oils.

[0160] Additional exemplary formulations covered in this document include:

[0161] - A first agrochemical active ingredient, liquid at room temperature and water-insoluble, between 30 and 80 wt.% relative to the total weight of the formulation, selected from the group of [α]-chloroacetamides;

[0162] - A second agrochemical active ingredient, insoluble in the first agrochemical active ingredient and solid at room temperature, between 15 and 25 wt.% relative to the total weight of the formulation, selected from the group consisting of phosphonic acids;

[0163] - A first surfactant between 1 and 8 wt.% relative to the total weight of the formulation having the formula R-SO 3 - M + wherein R is an organic residue and M + is a metal cation or ammonium residue selected from alkali metals or alkaline earth metals.

[0164] - A second surfactant between 5 and 15 wt.% relative to the total weight of the formulation, selected from triphenylvinylphenol ethoxylates, triphenylvinylphenol ethoxylate sulfate ethers, and triphenylvinylphenol ethoxylated phosphate ethers;

[0165] - wherein the weight ratio of [α]-chloroacetamide to phosphonic acid is included between 4:1 and 1:1;

[0166] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0167] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0168] - Optionally, a water-insoluble organic solvent between 5 and 20 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils and methylated vegetable oils.

[0169] Additional exemplary formulations covered in this document include:

[0170] - A first agrochemical active ingredient that is liquid at room temperature and water-insoluble between 30 and 80 wt.% relative to the total weight of the formulation, which is selected from the group of [α]-chloroacetamides;

[0171] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and solid at room temperature between 15 and 25 wt.% relative to the total weight of the formulation, which is selected from the group consisting of phosphonic acids;

[0172] - A first surfactant between 1 and 8 wt.% relative to the total weight of the formulation having the formula R-SO 3 - M + wherein R is an organic residue and M + is a metal cation selected from alkali metals or alkaline earth metals or an ammonium residue.

[0173] - A second surfactant between 5 and 15 wt.% relative to the total weight of the formulation, which is selected from triphenylvinylphenol ethoxylates, triphenylvinylphenol ethoxylate sulfate ethers, and triphenylvinylphenol ethoxylate phosphate ethers;

[0174] - wherein the weight ratio of the second surfactant to the first surfactant is between 6:1 and 1:1, preferably between 3:1 and 1:1;

[0175] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0176] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0177] - Optionally, a water-insoluble organic solvent between 5 and 20 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils and methylated vegetable oils.

[0178] Additional exemplary formulations covered in this document include:

[0179] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water, and is selected from the group of [α]-chloroacetamides, in an amount between 30 and 80 wt.% relative to the total weight of the formulation;

[0180] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, and is selected from the group consisting of phosphonic acids, in an amount between 15 and 25 wt.% relative to the total weight of the formulation;

[0181] - A first surfactant having the formula R-SO 3 - M + in an amount between 1 and 8 wt.% relative to the total weight of the formulation, where R is an organic residue and M + is a metal cation selected from alkali metals or alkaline earth metals or an ammonium residue.

[0182] - A second surfactant, in an amount between 5 and 15 wt.% relative to the total weight of the formulation, which is selected from triphenylvinylphenol ethoxylates, triphenylvinylphenol ethoxylate sulfate ethers, and triphenylvinylphenol ethoxylate phosphate ethers;

[0183] - Wherein the weight ratio of [α]-chloroacetamide to phosphonic acid is between 4:1 and 1:1;

[0184] - Wherein the weight ratio of the second surfactant to the first surfactant is between 6:1 and 1:1, preferably between 3:1 and 1:1;

[0185] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0186] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0187] - Optionally, a water-insoluble organic solvent in an amount between 5 and 20 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils and methylated vegetable oils.

[0188] Additional exemplary formulations covered in this document include:

[0189] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water, and is selected from the group of [α]-chloroacetamides, in an amount between 30 and 80 wt.% relative to the total weight of the formulation;

[0190] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, in the range of 15 to 25 wt.% relative to the total weight of the formulation, selected from the group consisting of phosphonic acids;

[0191] - A first surfactant having the formula R-SO 3 - M + in the range of 1 to 8 wt.% relative to the total weight of the formulation, where R is an organic residue and M + is a metal cation selected from alkali metals or alkaline earth metals or an ammonium residue.

[0192] - A second surfactant in the range of 5 to 15 wt.% relative to the total weight of the formulation, selected from triphenylvinylphenol ethoxylates, triphenylvinylphenol ethoxylate sulfate ethers, and triphenylvinylphenol ethoxylate phosphate ethers;

[0193] - Where the weight ratio of [α]-chloroacetamide to the second surfactant is in the range of 10:1 to 1:1;

[0194] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0195] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0196] - Optionally, a water-insoluble organic solvent in the range of 5 to 20 wt.% relative to the total weight of the formulation, selected from the group of vegetable oils and methylated vegetable oils.

[0197] Additional exemplary formulations covered in this document include:

[0198] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water, in the range of 30 to 80 wt.% relative to the total weight of the formulation, selected from the group of [α]-chloroacetamide;

[0199] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, in the range of 15 to 25 wt.% relative to the total weight of the formulation, selected from the group consisting of phosphonic acids;

[0200] - A first surfactant having the formula R-SO 3 - M + in the range of 1 to 8 wt.% relative to the total weight of the formulation, where R is an organic residue and M +is a metal cation selected from alkali metals or alkaline earth metals or an ammonium residue.

[0201] - a second surfactant between 5 and 15 wt.% relative to the total weight of the formulation, selected from triphenylvinylphenol ethoxylates, triphenylvinylphenol ethoxylate sulfate ethers, and triphenylvinylphenol ethoxylate phosphate ethers;

[0202] - wherein the weight ratio of phosphonic acid to the second surfactant is between 3:1 and 1:3, preferably between 3:1 and 1:1;

[0203] - optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0204] - optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0205] - optionally, a water-insoluble organic solvent between 5 and 20 wt.% relative to the total weight of the formulation, selected from the group of vegetable oils and methylated vegetable oils.

[0206] Additional exemplary formulations covered in this document include:

[0207] - a first agrochemical active ingredient between 30 and 80 wt.% relative to the total weight of the formulation, which is liquid at room temperature and water-insoluble, selected from the group of [α]-chloroacetamides;

[0208] - a second agrochemical active ingredient between 15 and 25 wt.% relative to the total weight of the formulation, which is insoluble in the first agrochemical active ingredient and solid at room temperature, selected from the group consisting of phosphonic acid;

[0209] - a first surfactant between 1 and 8 wt.% relative to the total weight of the formulation having the formula R-SO 3 - M + wherein R is an organic residue and M + is a metal cation selected from alkali metals or alkaline earth metals or an ammonium residue.

[0210] - a second surfactant between 5 and 15 wt.% relative to the total weight of the formulation, selected from triphenylvinylphenol ethoxylates, triphenylvinylphenol ethoxylate sulfate ethers, and triphenylvinylphenol ethoxylate phosphate ethers;

[0211] - wherein the weight ratio of [α]-chloroacetamide to the second surfactant is between 10:1 and 1:1;

[0212] - wherein the weight ratio of phosphonic acid to the second surfactant is included between 3:1 and 1:3, preferably between 3:1 and 1:1;

[0213] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0214] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0215] - Optionally, a water-insoluble organic solvent between 5 and 20 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils and methylated vegetable oils.

[0216] Additional exemplary formulations covered in this document include:

[0217] - A first agrochemical active ingredient that is liquid at room temperature and water-insoluble, between 30 and 90 wt.% relative to the total weight of the formulation;

[0218] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and solid at room temperature, between 1 and 10 wt.% relative to the total weight of the formulation, which is selected from N-phenyl-imides;

[0219] - A first surfactant between 1 and 8 wt.% relative to the total weight of the formulation, which is a sulfonate;

[0220] - A second surfactant between 5 and 25 wt.% relative to the total weight of the formulation, which is selected from arylalkylaryloxyides;

[0221] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0222] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0223] - Optionally, a water-insoluble organic solvent up to 35 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils, methylated vegetable oils, and their mixtures.

[0224] Additional exemplary formulations covered in this document include:

[0225] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water, and is selected from the group of [α]-chloroacetamides, in an amount between 30 and 90 wt.% relative to the total weight of the formulation;

[0226] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, and is selected from N-phenyl-imides, in an amount between 1 and 8 wt.% relative to the total weight of the formulation;

[0227] - A first surfactant that is a sulfonate, in an amount between 1 and 8 wt.% relative to the total weight of the formulation;

[0228] - A second surfactant that is selected from arylalkylaryloxyides, in an amount between 5 and 25 wt.% relative to the total weight of the formulation;

[0229] - Optionally, an antifoaming agent, such as silicone (e.g., polydimethylsiloxane with some silica particles), in an amount up to 5 wt.% relative to the total weight of the formulation;

[0230] - Optionally, a rheology modifier, such as a rheology modifier selected from the group of surface-modified silica, in an amount up to 9 wt.% relative to the total weight of the formulation;

[0231] - Optionally, a water-insoluble organic solvent, selected from the group of vegetable oils, methylated vegetable oils, and mixtures thereof, in an amount up to 15 wt.% relative to the total weight of the formulation.

[0232] Additional exemplary formulations covered in this document include:

[0233] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water, and is selected from the group of [α]-chloroacetamides, in an amount between 30 and 80 wt.% relative to the total weight of the formulation;

[0234] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, and is selected from the group consisting of flumioxazin, flumiclorac, or a salt, stereoisomer, ester, or solvate thereof, in an amount between 1 and 8 wt.% relative to the total weight of the formulation;

[0235] - A first surfactant that is a sulfonate of the formula R-SO 3 - M + wherein R is an organic residue and M + is a metal cation selected from alkali metals or alkaline earth metals or an ammonium residue, in an amount between 1 and 8 wt.% relative to the total weight of the formulation;

[0236] - A second surfactant in the range of 5 to 25 wt.% relative to the total weight of the formulation, selected from arylalkylaryloxides, which arylalkylaryloxides are selected from the group consisting of triphenylvinylphenol ethoxylates and triphenylvinylphenol ethoxylate phosphate ethers;

[0237] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0238] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0239] - Optionally, a water-insoluble organic solvent up to 15 wt.% relative to the total weight of the formulation, selected from the group of vegetable oils, methylated vegetable oils, and mixtures thereof.

[0240] Additional exemplary formulations covered in this document include:

[0241] - A first agrochemical active ingredient that is liquid at room temperature and water-insoluble in the range of 40 to 80 wt.% relative to the total weight of the formulation, selected from the group consisting of acetochlor, alachlor, butachlor, butenachlor, isobutachlor, acetochlor-methyl, dimethachlor, dimethenamid, pyrazolamide, clethodim, pretilachlor, propachlor, metolachlor, propyzamide, S-metolachlor, and thenylchlor;

[0242] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and solid at room temperature in the range of 1 to 8 wt.% relative to the total weight of the formulation, selected from the group consisting of flumioxazin, flumiclorac, or salts, stereoisomers, esters, or solvates thereof;

[0243] - A first surfactant in the range of 1 to 8 wt.% relative to the total weight of the formulation, selected from the group consisting of arylsulfonates, alkylsulfonates, alkylarylsulfonates, dialkylsulfosuccinates, naphthalenesulfonates, alkylnaphthalenesulfonates, diphenylsulfonates, alpha-olefinsulfonates, and mixtures thereof;

[0244] - A second surfactant in the range of 5 to 15 wt.% relative to the total weight of the formulation, selected from arylalkylaryloxides, which arylalkylaryloxides are selected from the group consisting of triphenylvinylphenol ethoxylates and triphenylvinylphenol ethoxylate phosphate ethers;

[0245] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0246] - Optionally, a rheology modifier up to 6 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0247] - Optionally, a water-insoluble organic solvent up to 10 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils, methylated vegetable oils, and mixtures thereof.

[0248] Additional exemplary formulations covered in this document include:

[0249] - A first agrochemical active ingredient that is liquid at room temperature and water-insoluble, between 50 and 80 wt.% relative to the total weight of the formulation, which is selected from the group consisting of acetochlor, alachlor, butylate, butachlor, butenachlor, isobutachlor, acetochlor-methyl, dimethachlor, dimepiperate, pyrazolate, pretilachlor, propachlor, propisochlor, propyzamide, metolachlor, and thenylchlor;

[0250] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, between 1 and 8 wt.% relative to the total weight of the formulation, which is selected from N-phenyl-imides;

[0251] - A first surfactant between 1 and 8 wt.% relative to the total weight of the formulation, which is selected from the group consisting of aryl sulfonates, alkyl sulfonates, alkyl aryl sulfonates, dialkyl sulfosuccinates, naphthalene sulfonates, alkyl naphthalene sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, and mixtures thereof;

[0252] - A second surfactant between 1 and 5 wt.% relative to the total weight of the formulation, which is selected from triphenylvinylphenol ethoxylated phosphate ethers;

[0253] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0254] - Optionally, a rheology modifier up to 6 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0255] - Optionally, a water-insoluble organic solvent up to 10 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils, methylated vegetable oils, and mixtures thereof.

[0256] Additional exemplary formulations covered in this document include:

[0257] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water, and is selected from [α]-chloroacetamides, in an amount between 30 and 90 wt.% relative to the total weight of the formulation;

[0258] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, and is selected from N-phenyl-imides, in an amount between 1 and 10 wt.% relative to the total weight of the formulation;

[0259] - A first surfactant that is a sulfonate, in an amount between 1 and 8 wt.% relative to the total weight of the formulation;

[0260] - A second surfactant that is selected from arylalkylaryl alkoxylates, in an amount between 5 and 25 wt.% relative to the total weight of the formulation;

[0261] - Wherein the weight ratio of [α]-chloroacetamide to N-phenyl-imide is between 25:1 and 15:1;

[0262] - Optionally, an antifoaming agent up to 5 wt.% relative to the total weight of the formulation, such as silicone (e.g., polydimethylsiloxane with some silica particles);

[0263] - Optionally, a rheology modifier up to 9 wt.% relative to the total weight of the formulation, such as a rheology modifier selected from the group of surface-modified silica;

[0264] - Optionally, a water-insoluble organic solvent up to 35 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils, methylated vegetable oils, and their mixtures.

[0265] Additional exemplary formulations covered in this document include:

[0266] - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water, and is selected from [α]-chloroacetamides, in an amount between 30 and 90 wt.% relative to the total weight of the formulation;

[0267] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, and is selected from N-phenyl-imides, in an amount between 1 and 10 wt.% relative to the total weight of the formulation;

[0268] - A first surfactant that is a sulfonate, in an amount between 1 and 8 wt.% relative to the total weight of the formulation;

[0269] - A second surfactant that is selected from arylalkylaryl alkoxylates, in an amount between 5 and 25 wt.% relative to the total weight of the formulation;

[0270] - wherein the weight ratio of the second surfactant to the first surfactant is included between 6:1 and 1:1, preferably between 3:1 and 1:1;

[0271] - Optionally, up to 5 wt.% of an antifoaming agent, such as silicone (e.g., polydimethylsiloxane with some silica particles), relative to the total weight of the formulation;

[0272] - Optionally, up to 9 wt.% of a rheology modifier, such as a rheology modifier selected from the group of surface-modified silica, relative to the total weight of the formulation;

[0273] - Optionally, up to 35 wt.% of a water-insoluble organic solvent, selected from the group of vegetable oils, methylated vegetable oils, and mixtures thereof, relative to the total weight of the formulation.

[0274] Additional exemplary formulations covered in this document include:

[0275] - A first agrochemical active ingredient that is liquid at room temperature and water-insoluble, between 30 and 90 wt.% relative to the total weight of the formulation, selected from [α]-chloroacetamide;

[0276] - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and solid at room temperature, between 1 and 10 wt.% relative to the total weight of the formulation, selected from N-phenyl-imide;

[0277] - A first surfactant, which is a sulfonate, between 1 and 8 wt.% relative to the total weight of the formulation;

[0278] - A second surfactant, selected from arylalkylaryloxyides, between 5 and 25 wt.% relative to the total weight of the formulation;

[0279] - wherein the weight ratio of the second surfactant to the first surfactant is included between 6:1 and 1:1, preferably between 3:1 and 1:1;

[0280] - wherein the weight ratio of [α]-chloroacetamide to N-phenyl-imide is included between 25:1 and 15:1;

[0281] - Optionally, up to 5 wt.% of an antifoaming agent, such as silicone (e.g., polydimethylsiloxane with some silica particles), relative to the total weight of the formulation;

[0282] - Optionally, up to 9 wt.% of a rheology modifier, such as a rheology modifier selected from the group of surface-modified silica, relative to the total weight of the formulation;

[0283] - Optionally, up to 35 wt.% of a water-insoluble organic solvent relative to the total weight of the formulation, which is selected from the group consisting of vegetable oils, methylated vegetable oils, and mixtures thereof.

[0284] Methods and applications

[0285] The present invention provides a method for controlling unwanted plants, pests, or diseases, which comprises contacting an effective amount of the oil dispersion described herein with the locus of the unwanted plants, pests, or diseases.

[0286] The method of the present invention is applicable to any unwanted plants, pests, or diseases against which a herbicide, insecticide, or fungicide (preferably a herbicide) has known activity. In the same way, the method of the present invention is applicable to any crop against which a herbicide, insecticide, or fungicide has known protective activity. The method of the present invention is applicable to any crop plant, including but not limited to monocotyledonous plants such as sugarcane, cereals, rice, maize (corn); or dicotyledonous crop plants such as beet (e.g., sugar beet or fodder beet); fruits (e.g., pome fruits, stone fruits, or soft fruits such as apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, or blackberries); leguminous plants (e.g., kidney beans, lentils, peas, or soybeans); oil crops (e.g., rapeseed, mustard, olive, sunflower, coconut, castor oil plant, cocoa bean, or peanut); cucurbitaceous plants (e.g., zucchini, cucumber, or melon); fiber plants (e.g., cotton, flax, or jute); citrus fruits (e.g., oranges, lemons, grapefruits, or tangerines); vegetables (e.g., spinach, lettuce, cabbage, carrots, tomatoes, potatoes, gourds, or peppers); Lauraceae (e.g., avocado, cinnamon, or camphor); tobacco; nuts; coffee; tea; vines; hops; durian; bananas; natural rubber plants; cereals (e.g., wheat or barley); and ornamental plants (e.g., flowers, shrubs, broad-leaved trees, or evergreens such as conifers).

[0287] The oil dispersions described herein are applied to the field in different amounts, depending on the specific active ingredient used, the target crop, and the unwanted plants, pests, or diseases to be controlled. In some embodiments, the active ingredients are each applied in an amount of about 1 g / ha to about 1000 g / ha, or 100 g / ha to about 700 g / ha.

[0288] The oil dispersions described herein can be applied before planting, at the time of planting, or after planting.

[0289] Experiment

[0290]

[0291] Example 1: Combinations of surfactants

[0292] The stability of the formulations was examined using different combinations of surfactants. Compositions A and B were prepared by the following procedure. S-metolachlor (S-Moc), Soprophor BSU, Nansa 70EVM, and Agnique ME 18RD-F were mixed until homogeneously dispersed. Then, the solid second active ingredient (glufosinate) was added and mixed until the solid was fully dispersed in the mixture. Then the rheology modifier (Aerosil) was added and stirred slowly until all of the rheology modifier had entered the mixture. Finally, the antifoaming agent was added and stirred for several minutes until homogeneous. The resulting mixture was milled using a horizontal bead mill until the particle size was below 18 microns, typically requiring 2 full passes. The milled mixture was stirred for 2 hours to ensure homogeneity and remove any air bubbles.

[0293] In each case, the components listed in Table 1 were used and the remaining compositions were prepared using a similar method. The amounts are indicated as weight percentages (wt.%) relative to the total amount of the formulation.

[0294] Composition 1 Composition 2 A B S-Moc 37.5 37.5 37.5 37.5 Glufosinate-ammonium 20 20 20 20 Nansa EVM70 3 2 2 2 Soprophor BSU 20 10 Alkamuls VO2003 20 10 R-972 3 3 4.5 5 Agnique ME 18RD-F 8.25 22.5 16 25.5 Rapeseed oil 8.25 5 Viscosity Paste Paste OK OK

[0295] Table 1

[0296] Only the composition containing the combination of sulfonate (Nansa AVM70) and arylalkylaryl ethoxylate (soprophor BSU) provided an oil dispersion with an appropriate viscosity. Replacing the arylalkylaryl ethoxylate with ethoxylated vegetable oil (Alkamuls VO2003) provided an infeasible mixture.

[0297] Additional surfactants were tested during the search for a stable formulation, and each formulation had the components shown in Table 2. The amounts are indicated as weight percentages (wt.%) relative to the total amount of the formulation.

[0298]

[0299]

[0300] Table 2

[0301] Similarly, only the compositions according to the invention provided formulations with a suitable viscosity. The polymeric amphoteric dispersant (Atlox 4915), nonionic block copolymer (Atlox 4912 or Zephrym PD2206), nonionic random polymer (Atlox 4914), or alkoxylated sorbitan ester (Atlox 1086) did not provide a flowable formulation.

[0302] Example 2: High loading of agrochemical active ingredients

[0303] A series of formulations were prepared in the amounts shown in Table 3 according to the same procedure as in Example 1.

[0304]

[0305]

[0306] Table 3

[0307] As observed in the results, the combinations of surfactants disclosed herein provide stable oil dispersions even at very high concentrations of agrochemical active ingredients.

[0308] Furthermore, the flumioxazin formulation (F) is easy to clean from the tank and provides added benefits when produced on an industrial scale.

Claims

1. - An agrochemical oil dispersion formulation, comprising: - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water and is present in an amount of more than 30 wt.% relative to the total weight of the formulation; - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature and is present in an amount between 0.5 and 30 wt.% relative to the total weight of the formulation; - A first surfactant that is a sulfonate and is present in an amount between 0.1 and 10 wt.% relative to the total weight of the formulation; and - A second surfactant that is selected from arylalkylaryloxyides and is present in an amount between 1 and 30 wt.% relative to the total weight of the formulation.

2. - The formulation according to claim 1, wherein, the first agrochemical active ingredient is an [α]-chloroacetamide selected from the group consisting of: acetochlor, alachlor, butachlor, butenachlor, isobutachlor, acetochlor-methyl, dimethachlor, dimethenamid, pyrazolamide, pretilachlor, propachlor, propanil, metolachlor, pendimethalin, and thenylchlor.

3. - The formulation according to claim 2, wherein, the first agrochemical active ingredient is selected from the group consisting of: dimethenamid, metolachlor, its salts, stereoisomers, and solvates.

4. - The formulation according to any one of the preceding claims, wherein, the second agrochemical active ingredient is selected from the group consisting of N-phenyl-imides, glycine, and phosphonic acids.

5. - The formulation according to claim 4, wherein, the second agrochemical active ingredient is selected from the group consisting of flumioxazin and flufenacet, or its salts, stereoisomers, esters, or solvates.

6. - The formulation according to claim 4, wherein, the second agrochemical active ingredient is selected from the group consisting of glufosinate and bilanafos, or its salts, stereoisomers, or solvates.

7. - The formulation according to any one of the preceding claims, wherein, The first surfactant is a sulfonate having the formula R-SO 3 - M + , where R is an organic residue and M + is a metal cation selected from the group consisting of alkali metals, alkaline earth metals, and ammonium residues.

8. - The formulation according to claim 7, wherein, the first surfactant is a sulfonate selected from the group consisting of: aryl sulfonates, alkyl sulfonates, alkylaryl sulfonates, dialkyl sulfosuccinates, naphthalene sulfonates, alkylnaphthalene sulfonates, diphenyl sulfonates, α-olefin sulfonates, and mixtures thereof.

9. - The formulation according to any one of the preceding claims, wherein, the second surfactant is an arylalkylaryloxyide selected from the group consisting of: triphenylvinylphenol ethoxylate, triphenylvinylphenol ethoxylate phosphate ether, and triphenylvinylphenol ethoxylate sulfate ether.

10. - The formulation according to claim 8 or claim 9, wherein, the first surfactant is an alkylaryl sulfonate, and the second surfactant is triphenylvinylphenol ethoxylate or triphenylvinylphenol ethoxylate phosphate ether.

11. - The formulation according to any one of the preceding claims, which comprises a rheology modifier selected from the group of surface-modified silica.

12. - The formulation according to any one of the preceding claims, which comprises a solvent in an amount between 1 and 35 wt.% relative to the total weight of the formulation, selected from the group consisting of vegetable oils, methylated vegetable oils, and mixtures thereof.

13. - The formulation according to claim 1, which comprises: - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water, in an amount between 30 and 70 wt.% relative to the total weight of the formulation, selected from the group consisting of: acetochlor, alachlor, butachlor, butenachlor, isobutachlor, acetochlor-methyl, dimethachlor, dimepiperate, pyrazolate, pretilachlor, propachlor, propisochlor, propyzamide, metolachlor, and thenylchlor; - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, in an amount between 15 and 25 wt.% relative to the total weight of the formulation, selected from phosphonic acids; - A first surfactant in an amount between 1 and 6 wt.% relative to the total weight of the formulation, selected from the group consisting of aryl sulfonates, alkyl sulfonates, alkyl aryl sulfonates, and mixtures thereof. - A second surfactant in an amount between 5 and 15 wt.% relative to the total weight of the formulation, selected from aryl alkyl aryl alkoxylates, the aryl alkyl aryl alkoxylates being selected from the group consisting of triphenylvinylphenol ethoxylates, triphenylvinylphenol ethoxylate sulfate ethers, and triphenylvinylphenol ethoxylate phosphate ethers; - Optionally, an antifoaming agent in an amount up to 5 wt.% relative to the total weight of the formulation; - Optionally, a rheology modifier in an amount up to 6 wt.% relative to the total weight of the formulation, selected from the group of surface-modified silica; - Optionally, an organic solvent insoluble in water, in an amount between 10 and 35 wt.% relative to the total weight of the formulation, selected from the group of vegetable oils and methylated vegetable oils.

14. - The formulation according to claim 1, which comprises: - A first agrochemical active ingredient that is liquid at room temperature and insoluble in water, in an amount between 30 and 90 wt.% relative to the total weight of the formulation, selected from [α]-chloroacetamide; - A second agrochemical active ingredient that is insoluble in the first agrochemical active ingredient and is solid at room temperature, in an amount between 1 and 10 wt.% relative to the total weight of the formulation, selected from N-phenyl-imides; - A first surfactant in an amount between 1 and 8 wt.% relative to the total weight of the formulation, which is a sulfonate; - A second surfactant in an amount between 5 and 25 wt.% relative to the total weight of the formulation, selected from aryl alkyl aryl alkoxylates; - Wherein the weight ratio of the [α]-chloroacetamide to the N-phenyl-imide is included between 25:1 and 15:1; - An antifoaming agent, optionally up to 5 wt.% relative to the total weight of the formulation; - A rheology modifier, optionally up to 9 wt.% relative to the total weight of the formulation, preferably a rheology modifier selected from the group of surface-modified silica; - Optionally, a water-insoluble organic solvent up to 35 wt.% relative to the total weight of the formulation, which is selected from the group of vegetable oils, methylated vegetable oils, and mixtures thereof.

15. - A method for controlling unwanted plants, pests, or diseases, which comprises contacting an effective amount of the formulation according to any one of claims 1 - 14 with the locus of the unwanted plants, pests, or diseases.

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