High-loading agricultural formulation and method for producing same

Abstract

A method of forming an agrochemical formulation is provided that includes: (a) homogenizing a first mixture comprising at least one agrochemical active in water to form a first homogenized mixture; (b) forming a first mill-base by milling the first homogenized mixture; (c) homogenizing a second mixture comprising at least one agrochemical active and the first mill-base to form a second homogenized mixture; (d) bead milling the second homogenized mixture; (e) homogenizing a third mixture comprising an aqueous surfactant solution and a thickener to form a slurry; and (f) combining the slurry with the second mill-base to form an agrochemical formulation, the agrochemical formulation including 57-76% (w / w) agrochemical active, based on the total weight of the formulation.

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates generally to highly concentrated pesticide formulations and methods for their preparation. [Background technology]

[0002] Agrochemical formulations are usually supplied to end users as concentrates and then diluted for use. Adjuvants and agrochemical actives can be added to the tank mix during dilution. However, preferably, the adjuvants and actives are included in the concentrates. When the agrochemical active is insoluble or only partially soluble in water, the concentrates containing the actives are conveniently supplied in the form of suspension concentrates (SCs) in which finely divided solid particles of the agrochemical are suspended in an aqueous formulation. Wetting agents and dispersing agents can also be included in the SCs to moisten and stabilize the solid particles. Thus, SC formulations may typically include solid actives, surfactants, density / viscosity modifier systems, freeze / thaw additives, bactericides, antifoam agents, and water diluents.

[0003] It is important that the solid particles remain suspended in the concentrated formulation without significant separation over long periods of time under typical storage conditions. It is also important to prevent the solid particles dispersed in the SC from forming hard-packed sediments upon storage. Therefore, it is usually necessary to incorporate a suspending or structuring agent into the suspension concentrate. For example, existing structuring agents used in water-based SCs include polysaccharide gums, clays, celluloses, polyacrylates, and xanthan gums.

[0004] The high pesticide loadings in SC formulations and the resulting reduced moisture content present significant problems for formulators, including challenges in maintaining the SC formulation in a flowable form. Formulation flowability is particularly important for seed treatment formulations, which are typically applied using equipment that pumps the formulation onto the seeds. Summary of the Invention [Problem to be solved by the invention]

[0005] Thus, there is a need for pesticide formulations containing high concentrations of active agents that can exhibit suitable viscosity and flow properties during use, that can remain stable against settling, phase separation and / or aggregation for a period of time, and that can be stored without settling of the solid active agents. [Means for solving the problem]

[0006] Provided herein is a method of forming an agrochemical formulation, comprising: (a) homogenizing a first mixture comprising at least one pesticidal active in water to form a first homogenized mixture; (b) a first millbase; (i) bead milling the first homogenized mixture to form first particles having a D90 particle size of about 1 to 75 microns; or (ii) colloidal milling the first homogenized mixture to form first particles having a D50 particle size of about 1 to 75 microns. and forming (c) homogenizing a second mixture comprising at least one pesticidal active and the first mill-base to form a second homogenized mixture; (d) bead milling the second homogenized mixture to form a second mill-base comprising second particles having a D90 particle size of about 1 to 75 microns; (e) homogenizing a third mixture comprising the aqueous surfactant solution and the thickener to form a slurry; (f) combining the slurry with a second millbase to form a pesticide formulation comprising 57-76% (w / w) pesticide active material based on the total weight of the formulation, thereby forming the pesticide formulation. wherein the first mixture comprises 20-70% (w / w) of at least one pesticide active, the balance comprising water and optionally a surfactant, an antifreeze, a biocide, an antifoam agent or combinations thereof, and the second mixture comprises 10-50% (w / w) of the at least one pesticide active, based on the total weight of the second mixture.

[0007] Further provided herein is an agrochemical formulation comprising about 57 to about 76% (w / w), based on the total weight of the formulation, of at least one agrochemical active dispersed in a mixture of water, an aqueous surfactant, and a thickening agent, and in the form of a shear-thinning gel.

[0008] Further provided herein is an article for dispensing the pesticide formulation of the present disclosure, the article comprising a container having an agitator blade attached thereto, and the pesticide formulation of the present disclosure provided within the container and in contact with the agitator blade, the agitator blade configured to promote a phase transition of the pesticide formulation from a gel to a flowable fluid.

[0009] Further provided herein is a kit comprising a container having an agitator blade attached thereto and an agrochemical formulation of the present disclosure.

[0010] Further provided herein is a method of treating a substrate with the pesticide formulation of the present disclosure, the method comprising providing a substrate comprising the pesticide formulation of the present disclosure, agitating the pesticide formulation to promote a phase transition of the pesticide formulation from a gel to a flowable fluid, and applying the flowable fluid to the substrate.

[0011] Further aspects and advantages will be apparent to those of skill in the art from a review of the following detailed description. While the compositions and methods are capable of embodiment in a variety of forms, the following description includes specific embodiments, with the understanding that the disclosure is illustrative and is not intended to limit the invention to the specific embodiments described herein.

[0012] To facilitate a better understanding of the present invention, the following drawings are attached. [Brief description of the drawings]

[0013] [Figure 1] 1 shows syneresis after six months of storage of two pesticide formulations other than those disclosed herein (Formulation A and Formulation B) and a formulation of the disclosure (Example 2). [Diagram 2]1 shows the viscosity after stirring of two pesticide formulations other than those of the present disclosure (Formulation A and Formulation B) and a formulation of the present disclosure (Example 2). [Diagram 3] 1 shows viscosity and syneresis results for four pesticide formulations other than those of the present disclosure (Formulations A, C, D, and E) and a formulation of the present disclosure (Example 5 formulation). [Figure 4] 1 shows viscosity and syneresis results for four pesticide formulations other than those of the present disclosure (Formulations A, C, D, and E) and a formulation of the present disclosure (Example 5 formulation). [Diagram 5] 1 shows storage modulus (G') data for one pesticide formulation other than that of the present disclosure (Formulation D) and a formulation of the present disclosure (Example 5 formulation). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Provided herein are pesticide formulations, methods for forming pesticide formulations, methods for using pesticide formulations, and articles and kits that include pesticide formulations.The pesticide formulations of the present disclosure may have one or more advantages, including but not limited to, providing pesticide formulations with high concentrations of pesticide actives, providing gelled pesticide compositions that can maintain solid pesticide actives dispersed throughout the composition, thereby preventing actives from settling over time, and / or providing pesticide formulations in a stable form that can return to a flowable form when needed for application to a substrate.

[0015] The present disclosure provides an agrochemical formulation comprising a dispersion comprising at least about 57 to about 76% (w / w) of at least one agrochemical active, based on the total weight of the formulation, dispersed in a mixture of water, an aqueous surfactant, and a thickening agent, the formulation being in the form of a shear-thinning gel.

[0016] The term "about" is used according to its ordinary meaning, such as approximately or around. In one embodiment, the term "about" means ±10% of a stated value or range of values. In another embodiment, the term "about" means ±5% of a stated value or range of values. Values ​​or ranges stated in conjunction with the term "about" also explicitly include the specific value and / or range (e.g., for a value stated as "about 40," "40" is also explicitly contemplated).

[0017] All percentages, parts and ratios referred to herein are based on measurements made at about 25° C. unless otherwise specified. All such weights as they pertain to listed ingredients are based on the concentration of the ingredient and, therefore, do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified.

[0018] All ranges described herein include all possible subsets of ranges and any combination of such subset ranges. By default, unless otherwise indicated, ranges include the endpoints described. When a range of values ​​is provided, it is understood that each value between the upper and lower limits of the range and any other stated value or intermediate value within the stated range is encompassed within the disclosure. The upper and lower limits of these smaller ranges may be independently included in the smaller ranges, and are also encompassed within the disclosure, subject to any specifically excluded limits within the stated range. When a stated range includes one or both of the limits, ranges excluding one or both of those included limits are also considered to be part of the disclosure.

[0019] For any numerical values ​​described herein, e.g., as part of a parameter of the described subject matter or a range related to the described subject matter, alternatives that form part of the description are expressly contemplated as functionally equivalent ranges surrounding the particular numerical value (e.g., for a dimension disclosed as "40 microns," a possible alternative embodiment is "about 40 microns").

[0020] "Comprising" as used herein means that various components, materials, or steps can be used in combination in carrying out the present disclosure. Thus, the term "comprising" encompasses the more restrictive terms "consisting essentially of" and "consisting of". The present composition can comprise, consist essentially of, or consist of any of the essential and optional elements disclosed herein. The present invention illustratively disclosed herein can suitably be practiced in the absence of any element or step not expressly disclosed herein.

[0021] The terms "dispersed", "dispersion" and other iterative applications thereof are used according to the usual meaning of a two-phase system comprising a dispersed phase in a dispersion medium. In the formulations of the present disclosure, the dispersed phase comprises a solid pesticide active and the dispersion medium comprises water. The dispersion medium may optionally contain other components dissolved in water, such as, but not limited to, surfactants, defoamers, biocides, antifreeze agents and thickeners.

[0022] As used herein, the term "shear thinning" is used in its usual sense to refer to a material having non-Newtonian behavior, in which the viscosity of the material decreases under shear strain. As used herein, the term "gel" is used in its usual sense to refer to a semi-solid material.

[0023] As used herein and unless otherwise indicated, a "flowable fluid" refers to a composition having a viscosity of about 2000 cP or less. Generally, the composition may be a solution, suspension, or other mixture.

[0024] Pesticide Active Substances The pesticide active may be any chemical or combination of chemicals generally useful in agriculture, such as, but not limited to, insecticides, herbicides, fungicides, algicides, rodenticides, molluscicides, nematicides, fertilizers, soil conditioners, liming and acidifying agents, and plant growth regulators. In an embodiment, the pesticide active comprises an insecticide, herbicide, fungicide, algicide, rodenticide, molluscicide, nematicide, or combination thereof. In an embodiment, the pesticide active comprises an insecticide, herbicide, fungicide, fungicide, or combination thereof. In an embodiment, the pesticide active comprises an insecticide, fungicide, or combination thereof.

[0025] In some embodiments, the active agent has a density in the range of about 0.5 to about 2.5 g / mL, about 0.5 to about 2.0 g / mL, about 0.5 to about 1.5 g / mL, about 0.75 to about 2.5 g / mL, about 0.75 to about 2.0 g / mL, about 0.75 to about 1.5 g / mL, about 1.0 to about 2.5 g / mL, about 1.0 to about 2.0 g / mL, or about 1.0 to about 1.5 g / mL. In some embodiments, the active agent has a density in the range of about 1.0 to about 2.0 g / mL.

[0026] In some embodiments, the active agent has a melting point greater than about 50°C, greater than about 75°C, greater than about 100°C, greater than about 125°C, greater than about 150°C, or greater than about 175°C. In embodiments, the active agent has a melting point greater than about 50°C. In embodiments, the active agent has a melting point greater than about 100°C. In some embodiments, the active agent has a melting point in the range of about 50°C to about 200°C, about 50°C to about 175°C, about 50°C to about 150°C, about 75°C to about 200°C, about 75°C to about 175°C, about 75°C to about 150°C, about 100°C to about 200°C, or about 100°C to about 175°C. In one aspect, the active agent has a melting point in the range of about 50°C to about 200°C. In another aspect, the active agent has a melting point in the range of about 100°C to about 200°C.

[0027] In some embodiments, the active agent has a water solubility of less than about 2000 mg / L, less than about 1750 mg / L, less than about 1500 mg / L, less than about 1250 mg / L, less than about 1000 mg / L, less than about 750 mg / L, less than about 500 mg / L, less than about 250 mg / L, or less than about 100 mg / L. In embodiments, the active agent has a water solubility of less than about 1000 mg / L. In embodiments, the active agent has a water solubility of less than about 100 mg / L.

[0028] In some embodiments, the active agent has a water solubility in the range of about 0.01 mg / L to about 2000 mg / L, about 0.01 mg / L to about 1750 mg / L, about 0.01 mg / L to about 1500 mg / L, about 0.01 mg / L to about 1250 mg / L, about 0.01 mg / L to about 1000 mg / L, about 0.01 mg / L to about 750 mg / L, about 0.01 mg / L to about 500 mg / L, about 0.01 mg / L to about 250 mg / L, or about 0.01 mg / L to about 100 mg / L. In embodiments, the active agent has a water solubility of less than about 1000 mg / L. In embodiments, the active agent has a water solubility in the range of about 0.01 mg / L to about 1000 mg / L. In some embodiments, the active agent has a solubility in water ranging from about 0.01 mg / L to about 100 mg / L.

[0029] In some embodiments, the active substance in the pesticide formulation may be a fungicide. In certain embodiments, the fungicide may be a triazole fungicide. In one embodiment, the triazole fungicide is azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, fluconazole, fluconazole-cis, hexaconazole, imibenconazole, ipconazole, mefentrifluconazole, In one embodiment, the compound is selected from the group consisting of 1-(4-chloro-phenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol, ...

[0030] In another embodiment, the fungicide may be a strobilurin fungicide. In one embodiment, the triazole fungicide is selected from the group consisting of trifloxystrobin, dimoxystrobin, fluoxastrobin, pyraclostrobin, enestrobin, picoxystrobin, azoxystrobin and mandestrobin.

[0031] The fungicide may be selected from any one of the following:

[0032] 1) Inhibitors of ergosterol biosynthesis, for example (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.011) imazalil sulfate, (1.012) ipconazole, (1.013) metconazole, (1.01 4) myclobutanil, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1.019) pyrisoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023) triadimenol, (1.024) tridemorph, (1.025) triticonazole, (1.026) (1R,2S,55)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H- 1,2,4-triazol-1-ylmethyl)-cyclo-pentanol, (1.027) (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.028) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.029) (2R)-2-(1-chlorocyclopropyl)- 4-[1(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.030)(2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl1)-propan-2-ol, (1.031)(2S)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.032) (2S)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.033) (25)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.034) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl) (1.035) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037) 1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl) -1H-1,2,4-triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.039) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.040) 1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluoro-phenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate (1.041) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.043) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.044) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.045) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl )-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.046) 2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.047) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2, 4-Dihydro-3H-1,2,4-triazole-3-thione, (1.048) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethyl-heptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1. 050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.053) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol, (1.055) Mefentrifluconazole, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2, 4-Triazole-3-thione, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.058) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2- Methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060) 5-(allylsulfanyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(allylsulfanyl)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.062) 5-(allylsulfanyl)- 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.063) N'-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.065) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.067) N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.068) N'-(2,5-dimethyl-4-{3-[(2,2,2-trifluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.069) N'-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide,. (1.070) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)-sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.071) N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methylimidoformamide, (1.072) N'-(4-1[3-(difluoromethoxy)-phenyl]-sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.073) N'- (4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.074) N'-[5-bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimidoformamide, (1.075) N'-{4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl-N-ethyl-N-methylimidoformamide (1.076) N'-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.077) N'-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.078) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide -methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.079) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.080) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.081) Ipfentrifluconazole.

[0033] 2) Inhibitors of the respiratory chain at complex I or II, such as (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) isofetamide, (2.010) isopyrazam (anti-epimer enantiomer 1R,4S,9S), (2.011) isopyrazam (anti-epimer enantiomer 1S,4 R,9R), (2.012) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (2.013) isopyrazam (mixture of syn-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR), (2.014) isopyrazam (syn-epimeric enantiomer 1R,4S,9R), (2.015) isopyrazam (syn-epimeric enantiomer 1S,4R,9S), (2.016) isopyrazam (syn-epimeric racemate 1RS,4 SR,9RS), (2.017) Penflufen, (2.018) Penthiopyrad, (2.019) Pydiflumetofen, (2.020) Pyraziflumide, (2.021) Sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide amide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.028) 3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H -inden-4-yl]-1H-pyrazole-4-carboxamide, (2.030) Fluindapyr, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole -4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}-phenyl)ethyl]quinazolin-4-amine, (2.034) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3- (Difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.037) N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038) isoflucipram, (2.039) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041) N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl] -3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.042) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl]-1H-pyrazole-4-carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl]- (2.045) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.048) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carbothioamide, (2.049) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoine.

[0034] 3) Inhibitors of the respiratory chain at complex III, such as (3.001) amethoctrazine, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) methoxystrobin, (3.005) cumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.0 14) Metominostrobin, (3.015) Orysastrobin, (3.016) Picoxystrobin, (3.017) Pyraclostrobin, (3.018) Pyrametstrobin, (3.019) Pyraoxystrobin, (3.020) Trifloxystrobin, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.022) (2E,3Z) -5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.023)(2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024)(2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025)(3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)meth oxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl 2-methylpropanoate, (3.026) mandestrobin, (3.027) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029) Methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate, (3.030) Methyltetraprole, (3.031) Florylpicoxamide.

[0035] 4) Inhibitors of mitosis and cell division, for example (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate methyl, (4.008) zoxamide, (4.009) 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl) )-6-methylpyridazine, (4.011) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.014) 4-(2-bromo -4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1 ,3-dimethyl-1H-pyrazol-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dim-ethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine.

[0036] 5) Compounds capable of multisite action, such as (5.001) Bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper(2+) sulfate, (5.010) dithianone, (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) mancozeb, Nneb, (5.015) metiram, (5.016) metiram zinc, (5.017) oxine copper, (5.018) propineb, (5.019) sulfur preparations containing sulfur and calcium polysulfide, (5.020) thiuram, (5.021) zineb, (5.022) ziram, (5.023) 6-ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][1,4]dithiino[2,3-c][1,2]thiazole-3-carbonitrile.

[0037] 6) Compounds capable of inducing host defense, such as (6.001) acibenzolar-S-methyl, (6.002) isotianil, (6.003) probenazole, (6.004) thiazinil.

[0038] 7) Inhibitors of amino acid and / or protein biosynthesis, such as (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline.

[0039] 8) Inhibitors of ATP production, such as (8.001) Silthiofam.

[0040] 9) Inhibitors of cell wall synthesis, such as (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamide, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4yl)prop-2-en-1-one.

[0041] 10) Inhibitors of lipid and membrane synthesis, such as (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.

[0042] 11) Inhibitors of melanin biosynthesis, such as (11.001) tricyclazole, (11.002) 2,2,2-trifluoroethyl{3-methyl-1-[(4-methylbenzoyl)amino]butan-2-yl}carbamate.

[0043] 12) Inhibitors of nucleic acid synthesis, such as (12.001) benalaxyl, (12.002) benalaxyl-M (chiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).

[0044] 13) Signal transduction inhibitors, such as (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazide, (13.005) quinoxyfen, (13.006) vinclozolin.

[0045] 14) Compounds capable of acting as uncouplers, such as (14.001) fluazinam, (14.002) meptyldinocap.

[0046] 15) Further compounds, for example (15.001) abscisic acid, (15.002) benthiazole, (15.003) bethoxazin, (15.004) capsimycin, (15.005) carvone, (15.006) quinomethionate, (15.007) khufuraneb, (15.008) cyflufenamid, (15.009) cymoxanil, (15.010) cyprosulfamide, (15.011) fluthianil, (15.012) fosetyl-aluminium, (15.013) fosetyl- Calcium, (15.014) fosetyl-sodium, (15.015) methyl isothiocyanate, (15.016) metrafenone, (15.017) mildiomycin, (15.018) natamycin, (15.019) nickel dimethyldithiocarbamate, (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) oxathiapiproline, (15.023) oxyfenthiin, (15.024) pentachlorophenol and salts, (15.025) Phosphorous acid and its salts, (15.026) Propamocarb-fosetylate, (15.027) Pyriophenone (clazaphenone), (15.028) Tebufloquine, (15.029) Tecloftalam, (15.030) Tornifanide, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-( trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.032) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.033) 2-(6-benzylpyridin-2-yl)quinazoline, (15.034) dipimethitrone, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)-piperidin-1-yl]ethanone, (15.036) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazole -3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.037) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]-ethanone, (15.038) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15 .039) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.040) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazole -5-yl}-3-chlorophenyl methanesulfonate, (15.041) Ipflufenoquine, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.043) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.044) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate, (15.045) 2-Phenylphenol and salts, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.047) Quinovumeline, (15.048) 4-Amino-5-fluoropyrimidine-2- 4-amino-5-fluoropyrimidin-2(1H)-one (tautomeric form: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.049) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophene-2-sulfonohydrazide, (15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine, (15.053) 5-fluoro-2-[(4-methylbenzyl)-o oxy]-pyrimidin-4-amine, (15.054) 9-fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazepine, (15.055) but-3-yn-1-yl {6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)-(phenyl)-methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.056) ethyl (2Z)-3-amino-2-cyano-3-phenylacrylate, (15.057) phenazine-1-carboxylic acid, (15.058) proline Pyr 3,4,5-trihydroxybenzoate, (15.059) quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2:1), (15.061) tert-butyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}-carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, (15.063) aminopyrifen.

[0047] All named mixing partners of classes (1) to (15) herein above can be present in the form of the free compounds and / or their agriculturally acceptable salts, if their functional groups allow this.

[0048] In other embodiments, the active substance in the pesticide formulation is an insecticide. The insecticide may be selected from any one of the following:

[0049] (1) Acetylcholinesterase (AChE) inhibitors, such as carbamates, such as aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb or organophosphates, such as acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, Dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famflu, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyaphos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimphos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vamidothion, etc.

[0050] (2) GABA-gated chloride channel blockers, such as cyclodiene-organochlorines, such as chlordane and endosulfan or phenylpyrazoles (fiproles), such as ethiprole and fipronil.

[0051] (3) Sodium channel modulators, for example pyrethroids, such as acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, β-cyfluthrin, cyhalothrin, λ-cyhalothrin, γ-cyhalothrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin, ζ-cypermethrin, cyphenothrin [(1R)-trans-isomer], deltamethrin, empenthrin, fluorothrin [(EZ)-(1R)-isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, fenothrin [(1R)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomer)], tralomethrin and transfluthrin or DDT or methoxychlor, etc.

[0052] (4) Nicotinic acetylcholine receptor (nAChR competitive modulators, such as neonicotinoids, such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or flupyradifurone.

[0053] (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators, such as spinosyns, such as spinetoram and spinosad.

[0054] (6) Glutamate-gated chloride channel (GluCl) allosteric modulators, such as abamectins / milbemycins, such as abamectin, emamectin benzoate, lepimectin, and milbemectin.

[0055] (7) Juvenile hormone mimetics, such as juvenile hormone analogues, such as hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen.

[0056] (8) Miscellaneous nonspecific (multi-site) inhibitors, such as alkyl halides, e.g., methyl bromide and other alkyl halides or chloropicrin or sulfuryl fluoride or borax or tartar emetic or methyl isocyanate generators, e.g., diazomet and metham.

[0057] (9) Chordotonal organ modulators, such as pymetrozine or flonicamide.

[0058] (10) Mite growth inhibitors, such as clofentezine, hexythiazox and diflobidazine or etoxazole.

[0059] (11) Microbial disruptors of insect midgut membranes, such as Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Abl / 35Abl, etc.

[0060] (12) Inhibitors of mitochondrial ATP synthase, such as ATP disruptors, such as diafenthiuron or organotin compounds, such as azocyclotin, cyhexatin and fenbutatin oxide or propargite or tetradifon.

[0061] (13) Uncouplers of oxidative phosphorylation via disruption of the proton gradient, such as chlorfenapyr, DNOC, and sulfuramide.

[0062] (14) Nicotinic acetylcholine receptor channel blockers, such as bensultap, cartap hydrochloride, thiocyclam and thiosultap sodium.

[0063] (15) Chitin biosynthesis inhibitors, type 0, such as bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.

[0064] (16) Chitin biosynthesis inhibitors, type 1, such as buprofezin.

[0065] (17) Molting disruptors (especially for Diptera, i.e., for insects), such as cyromazine.

[0066] (18) Ecdysone receptor agonists, such as chromafenozide, halofenozide, methoxyfenozide and tebufenozide.

[0067] (19) Octopamine receptor agonists, such as amitraz.

[0068] (20) Mitochondrial complex III electron transport inhibitors, such as hydramethylnon, or acequinocyl, or fluacrypyrim.

[0069] (21) Mitochondrial complex I electron transport inhibitors, such as those from the group of METI acaricides and insecticides, such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).

[0070] (22) Voltage-dependent sodium channel blockers, such as indoxacarb or metaflumizone.

[0071] (23) Acetyl-CoA carboxylase inhibitors, such as tetronic acid and tetramic acid derivatives, such as spirodiclofen, spiromesifen and spirotetramat.

[0072] (24) Mitochondrial complex IV electron transport inhibitors, such as phosphines, such as aluminum phosphide, calcium phosphide, phosphine and zinc phosphide or cyanides, such as calcium cyanide, potassium cyanide and sodium cyanide.

[0073] (25) Mitochondrial complex II electron transport inhibitors, such as β-ketonitrile derivatives, such as cyenopyrafen and cyflumetofen, and carboxanilides, such as piflubumid.

[0074] (28) Ryanodine receptor modulators, such as diamides, such as chlorantraniliprole, cyantraniliprole, and flubendiamide.

[0075] For example, afidopiropen, afoxolaner, azadirachtin, benclotiaz, benzoximate, bifenazate, brofuranilide, bromopropylate, quinomethionate, chlorprallethrin, cryolite, cyclaniliprole, cycloxapride, cyhalodiamide, dichloromethiaz, dicofol, epsilon-metofluthrin, epsilon-momfluthrin, flometoquin, fluazaindolizine, fluensulfone, flufenerim, flufenoxystrobin, flufiprole, fluhexafon, fluopyram, and fluralaner. , fluxamethamide, fufenozide, guadipyr, heptafluthrin, imidaclothiz, iprodione, kappa-bifenthrin, kappa-tefluthrin, lotilaner, meperfluthrin, paichongding, pyridalyl, pyrifluquinazone, pyriminostrobin, spirobudiclofen, tetramethylfluthrin, tetraniliprole, tetrachlorantraniliprole, tigoraner, thioxazaphen, thiofluoximate, triflumezopyrim and iodomethane; firmus) (1-1582, BioNeem, VOTIVO®), as well as the following compounds: 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO 2006 / 043635) (CAS 885026-50-6), {1'-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]-5-fluorospiro[indole-3,4'-piperidine]-1(2H)-yl}(2-chloropyridin-4-yl)methanone (known from WO 2003 / 106457) (CAS 637360-23-7), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known from WO 2006 / 003494) (CAS 872999-66-1), 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO 2010 / 052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-ylethyl carbonate (known from EP 2647626) (CAS 1440516-42-6), 4-(but-2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known from WO 2004 / 099160) (CAS 792914-58-0), PF1364 (known from JP 2010 / 018586 A) (CAS 1204776-60-2), N-[(2E)-1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide (known from WO 2012 / 029672) (CAS 1363400-41-2), (3E)-3-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-1,1,1-trifluoro-propan-2-one (known from WO 2013 / 144213) (CAS 1461743-15-6), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known from International Publication No. 2010 / 051926) (CAS 1226889-14-0), 5-bromo-4-chloro-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known from CN103232431) (CAS 1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)-benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxido-3-thietanyl)-benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxide-3-thietanyl)benzamide (known from WO 2013 / 050317A1) (CAS 1332628-83-7), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide, (+)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide and (-)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide (known in WO 2013 / 162715A2, WO 2013 / 162716A2, and U.S. Patent Application Publication No. 2014 / 0213448A1) (CAS 1477923-37-7), 5-[[(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (known from CN101337937A) (CAS 1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thioxomethyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide, (Liudaibenjiaxuanan, known from CN103109816A) (CAS 1232543-85-9; N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (known from WO 2012 / 034403A1) (CAS 1268277-22-0), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from International Publication WO 2011 / 085575A1) (CAS 1233882-22-8), 4[3-[2,6-dichloro-4-[(3,3-dichloro-2-propen-1-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN101337940A) (CAS 110818452-6; (2E)- and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide (known from CN101715774A) (CAS 1232543-85-9); 3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenyl-cyclopropanecarboxylic acid ester (known from CN103524422A) (CAS 1542271-46-4;(4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]-indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylic acid methyl ester (known from CN102391261A) (CAS 1370358-69-2);6-deoxy-3-O-ethyl-2,4-di-O-methyl-,1-[N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1H-1,2,4-triazol-3-yl]phenyl]carbamato]-α-L-mannopyranose (known from US Patent Application Publication No. 2014 / 0275503A1) (CAS 1181213-14-8); 8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-azabicyclo[3.2.1]octane (CAS 1253850-56-4), (8-anti)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-azabicyclo[3.2.1]octane (CAS 933798-27-7), (8-syn)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-azabicyclo[3.2.1]octane (known from WO 2007040280A1 and WO 2007 / 040282A1) (CAS 934001-668), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)thio]-propanamide (known from WO 2015 / 058021A1 and WO 2015 / 058028A1) (CAS 1477919-27-9) and N-[4-(aminothioxomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from CN103265527A) (CAS 1452877-50-7), 5-(1,3-dioxan-2-yl)-4-[[4-(trifluoromethyl)phenyl]methoxy]-pyrimidine (known from WO 2013 / 115391A1) (CAS 1449021-97-9), 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1-methyl-1,8-Diazaspiro[4.5]dec-3-en-2-one (known from WO 2010 / 066780A1 and WO 2011 / 151146A1) (CAS 1229023-34-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decane-2,4-dione (known from WO 2014 / 187846A1) (CAS 1638765-58-8), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl-carbonic acid ethyl ester (known from WO 2010 / 066780A1 and WO 2011151146A1) (CAS 1229023-00-0), N-[1-[(6-chloro-3-pyridinyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoro-acetamide (known from German Patent Application Publication No. 3639877A1 and WO 2012 / 029672A1) (CAS 1363400-41-2), [N(E)]-N-[1-[(6-chloro-3-pyridinyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoro-acetamide (known from WO 2016005276A1), (CAS 1689566-03-7), [N(Z)]-N-[1-[(6-chloro-3-pyridinyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoro-acetamide, (CAS 1702305-40-5), 3-endo-3-[2-propoxy-4-(trifluoromethyl)phenoxy-9-[[5-(trifluoromethyl)-2-pyridinyl]oxy]-9-azabicyclo[3.3.1]nonane (known from WO 2011 / 105506 A1 and WO 2016 / 133011 A1) (CAS 1332838-17-1).

[0076] In certain embodiments, the active agent is a fungicide or insecticide selected from those shown in Table 1.

[0077] [Table 1]

[0078] [Table 2]

[0079] [Table 3]

[0080] In some embodiments, the pesticide formulation is a seed treatment formulation.

[0081] In some embodiments, the active agent is an insecticide selected from the group of abamectin, chlorantraniliprole, clothianidin, cyantraniliprole, ethiprole, fipronil, flubendiamide, flupyradifurone, imidacloprid, methiocarb, spinetoram, spinosad, sulfoxaflor, tefluthrin, thiacloprid, thiamethoxam, thiodicarb, and combinations thereof. In an embodiment, the active agent comprises clothianidin.

[0082] In some embodiments, the active agent is a fungicide selected from the group consisting of azoxystrobin, beta-cyfluthrin, carbendazim, carbendazim, cyproconazole, epoxiconazole, fenamidone, fluazinam, fludioxinil, fluopyram, fluoxastrobin, fluquinconazole, ipconazole, iprodione, isotianil, mefentrifluconazole, metalaxyl, metalaxyl-M, metominostrobin, pencycuron, penflufen, picarbutrazox, picoxystrobin, procymidone, propiconazole, prothioconazole, pyraclostrobin, tebuconazole, triadimenol, trifloxystrobin, and combinations thereof. In one embodiment, the active agent is fluopyram. In another embodiment, the active agent is a triazole fungicide or a strobilurin fungicide.

[0083] In some embodiments, the active agent has a melting point greater than about 35° C., greater than about 40° C., greater than about 45° C., greater than about 50° C., greater than about 55° C., greater than about 60° C., greater than about 65° C., greater than about 70° C., greater than about 75° C., greater than about 80° C., greater than about 85° C., greater than about 90° C., greater than about 95° C., or greater than about 100° C. In other embodiments, the active agent has a melting point greater than about 100° C., greater than about 125° C., or greater than about 150° C.

[0084] Surfactants Generally, the surfactant may be any surfactant capable of wetting and / or stabilizing the solid particles of the pesticide active substance in a suspended form in the aqueous formulation. Generally, the surfactant is provided as an aqueous solution comprising a surfactant and water. In some embodiments, the surfactant is a nonionic surfactant, a cationic surfactant and an anionic surfactant or an amphoteric surfactant. In some embodiments, the surfactant comprises a nonionic surfactant and an anionic surfactant or a combination thereof. In some embodiments, the surfactant is a nonionic surfactant.

[0085] Suitable non-ionic surfactants include, but are not limited to, alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. In embodiments, the non-ionic surfactants may include alkoxylate surfactants, polymeric surfactants, and combinations thereof.

[0086] Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide, preferably ethylene oxide, can be used for alkoxylation. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. In embodiments, the alkoxylate surfactant can be an alcohol, alkylphenol, amine, amide, arylphenol, fatty acid or fatty ester or a combination of the above, and the alkoxylate surfactant is alkoxylated with 1 to 50 equivalents.

[0087] Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of polymeric surfactants may also include homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate. Suitable block polymers are block polymers of AB or ABA type with blocks of polyethylene oxide and polypropylene oxide or block polymers of ABC type with alkanol, polyethylene oxide and polypropylene oxide. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. In embodiments, the polymeric surfactant may be block polymers of AB or ABA type with blocks of polyethylene oxide and polypropylene oxide, block polymers of ABC type with alkanol, polyethylene oxide and polypropylene oxide, comb polymers or combinations of the above. In embodiments, the polymeric surfactant may be block polymers of AB or ABA type with blocks of polyethylene oxide and polypropylene oxide, block polymers of ABC type with alkanol, polyethylene oxide and polypropylene oxide or combinations of the above.

[0088] In one embodiment, the polymeric surfactant is a poloxamer. As used herein, a "poloxamer" is a non-ionic triblock copolymer consisting of a central hydrophobic chain of polyoxypropylene (poly(propylene oxide)) flanked by two hydrophilic chains of polyoxyethylene (poly(ethylene oxide)). Poloxamers include poloxamer 101, poloxamer 105, poloxamer 108, poloxamer 122, poloxamer 123, poloxamer 124, poloxamer 181, poloxamer 182, poloxamer 183, poloxamer 184, poloxamer 185, poloxamer 188, poloxamer 212, poloxamer 215, poloxamer 217, poloxamer 231, poloxamer 234, poloxamer 235. , poloxamer 237, poloxamer 238, poloxamer 282, poloxamer 284, poloxamer 288, poloxamer 331, poloxamer 333, poloxamer 334, poloxamer 335, poloxamer 338, poloxamer 401, poloxamer 402, poloxamer 403, poloxamer 407, poloxamer 105 benzoate, and poloxamer 182 dibenzoate.

[0089] In another embodiment, the polymeric surfactant is an acrylic copolymer solution. In one embodiment, the acrylic copolymer solution is a polymethylmethacrylate-polyethyleneglycol graft copolymer. In some embodiments, the polymeric surfactant comprises a poloxamer, an acrylic copolymer, or a combination thereof.

[0090] Suitable cationic surfactants include, but are not limited to, quaternary surfactants, such as quaternary ammonium compounds having one or two hydrophobic groups or salts of long chain primary amines.

[0091] Suitable anionic surfactants include, but are not limited to, the alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof. In an embodiment, the anionic surfactant comprises sulfonates, carboxylates or combinations thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, ligninsulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols or fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylates.

[0092] In one embodiment, the sulfonate is a sulfonate of condensed naphthalene or a salt thereof. In another aspect, the sulfonate is a naphthalene sulfonate condensate (NSC) or a salt thereof. In an embodiment, the sulfonate includes lignin sulfonate, a sulfonate of condensed naphthalene, a salt of the foregoing, or a combination of the foregoing. In an embodiment, the carboxylate includes an alkyl carboxylate, an alkylphenol ethoxylate, a polycarboxylic acid, a carboxylated alcohol, or a combination thereof.

[0093] Suitable amphoteric surfactants include, but are not limited to, alkyl betaines and imidazolines.Suitable polyelectrolytes are polyacids or polybases.Examples of polyacids include alkali salts of polyacrylic acid or polyacid comb polymers.Examples of polybases include polyvinylamines or polyethyleneamines.

[0094] In some embodiments, the surfactant may be a non-ionic surfactant or an anionic surfactant. In one aspect, the non-ionic surfactant is an alkoxylate surfactant or a polymeric surfactant. In one embodiment, the alkoxylate surfactant is an alcohol, an alkylphenol, an amine, an amide, an arylphenol, a fatty acid, or a fatty acid ester, and the alkoxylate surfactant is alkoxylated with 1 to 50 equivalents. In another embodiment, the polymeric surfactant is a block polymer of the AB or ABA type, including blocks of polyethylene oxide and polypropylene oxide, or the ABC type, including blocks of alkanol, polyethylene oxide, and polypropylene oxide.

[0095] In some embodiments, the polymeric surfactant is a poloxamer or an acrylic copolymer. In yet another aspect, the anionic surfactant is a sulfonate or a carboxylate. In one embodiment, the sulfonate is a lignin sulfonate, a sulfonate of condensed naphthylene or a salt thereof. In another embodiment, the carboxylate is an alkyl carboxylate, an alkylphenol ethoxylate, a polycarboxylic acid or a carboxylated alcohol.

[0096] Thickening / Structuring Agent The formulation of the present disclosure may also include a thickening and / or structuring agent.As used herein and unless otherwise indicated, the terms thickening agent and structuring agent are used interchangeably.The thickening and / or structuring agent may generally be any compound that can prevent or reduce the separation of solid particles of pesticide active substance from the aqueous formulation over a long period of time under typical storage conditions and / or can prevent or reduce the formation of hard-packed sediment of particles of pesticide active substance when the formulation of the present disclosure is stored over a long period of time under typical storage conditions.

[0097] The thickening and / or structuring agent may include polysaccharides, clays, celluloses, polyacrylates, and silicas. Suitable thickening agents include, but are not limited to, starch, xanthan gum, guar gum, locust bean gum, karaya gum, tragacanth gum, arabic gum, methylcellulose, ethylcellulose, methylhydroxyethylcellulose, methylhydroxyethylhydroxypropylcellulose, hydroxypropylmethylcellulose, pectin, agar, arginine, carrageenan, pullulan, and alginates. In embodiments, the thickening and / or structuring agent may include polysaccharides, cellulose, or combinations thereof. In embodiments, the thickening agent may be micro- and / or nanocrystalline cellulose. In embodiments, the thickening and / or structuring agent may include xanthan gum, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, or combinations thereof. In embodiments, the thickening and / or structuring agent may include xanthan gum, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, or combinations thereof. In embodiments, the thickening and / or structuring agent may include xanthan gum.

[0098] Supplementary ingredients The formulations of the present disclosure may include auxiliary ingredients. The auxiliary ingredients may include ingredients that are commonly used in agricultural treatment formulations and known to those skilled in the art. Examples include antioxidants such as ascorbic acid, penetrants, biocides, preservatives, deodorants, fragrances, antifreeze and evaporation inhibitors such as glycerol and ethylene or propylene glycol, sorbitol, mineral oil, processing oil, sodium lactate, fillers, extenders, carriers, colorants including pigments and / or dyes, pH adjusters (buffers, acids and bases), salts such as calcium, magnesium, ammonium, potassium, sodium and / or iron chloride, fertilizers such as ammonium sulfate and ammonium nitrate, urea and processing aids such as dispersants, emulsifiers, wetting agents, defoamers and suspending agents. The aqueous formulations may also contain other active ingredients such as additional fungicides, insecticides, pesticides and / or fertilizers known in the art.

[0099] Suitable defoamers include all conventional defoamers, including those based on silicone and perfluoroalkyl phosphinic and phosphonic acids, in particular silicone defoamers, such as silicone oil.The most common defoamers are from the group of linear polydimethylsiloxanes, which have an average kinematic viscosity of 1000 to 8000 mPas (mPas = millipascal seconds), usually 1200 to 6000 mPas, measured at 25 ° C., and contain silica.Silica includes polysilicic acid, metasilicic acid, orthosilicic acid, silica gel, silicic acid gel, diatomaceous earth, precipitated SiO2, etc.

[0100] Antifoam agents from the group of linear polydimethylsiloxanes have as their chemical backbone the formula HO-[Si(CH3)2-O-] n The end groups are modified by etherification, for example or generally bonded to the group -Si(CH3)3. Non-limiting examples of this type of defoamer are RHODORSIL® Antifoam 416 (Rhodia) and RHODORSIL® Antifoam 481 (Rhodia). Other suitable defoamers are RHODORSIL® 1824, ANTI-MUSSOL 4459-2 (Clamant), Defoamer V 4459 (Clariant), SE Visk and AS EM SE 39 (Wacker). Silicone oils can also be used in the form of emulsions.

[0101] Suitable extenders are, for example, water, polar and non-polar organic chemical liquids, for example from the classes of aromatic and non-aromatic hydrocarbons (paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes, etc.), alcohols and polyols (which may be substituted, etherified and / or esterified as required), ketones (acetone, cyclohexanone, etc.), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).

[0102] When the extender used is water, it is also possible to use, for example, organic solvent as auxiliary solvent.Essentially, suitable liquid solvents are aromatics such as xylene, toluene or alkylnaphthalene, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffin, for example petroleum fractions, mineral oils and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexane, highly polar solvents such as dimethylformamide and dimethylsulfoxide, and water.

[0103] Any suitable carrier can be used. Suitable carriers are in particular ground natural minerals, such as ammonium salts and kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, as well as ground synthetic mineral fertilizers, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes and / or solids. Likewise, mixtures of such monomeric carriers can be used. Suitable carriers for the granules include: ground and fractionated natural minerals, such as calcite, marble, pumice, sepiolite, dolomite, synthetic granules of inorganic and organic foods, granules of organic materials, such as sawdust, paper, coconut shells, corn cobs and tobacco stalks, etc.

[0104] Liquefied gaseous extenders or solvents may be used.Extenders or carriers that are gases at standard temperature and pressure, such as halogenated hydrocarbons, as well as aerosol propellants such as butane, propane, nitrogen and carbon dioxide, are particularly suitable.

[0105] Examples of emulsifiers and / or foaming agents, dispersants or wetting agents with ionic or non-ionic properties or mixtures of these surface-active substances are salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines with substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (preferably alkyl taurates), phosphoric acid esters of polyethoxylated alcohols or phenols, fatty acid esters of polyols and derivatives of compounds containing sulfates, sulfonates and phosphates, such as alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, protein hydrolysates, lignin sulfite waste liquors and methylcellulose. If one of the active compounds and / or one of the inert carriers is not soluble in water and the application is carried out in water, the presence of a surface-active substance is advantageous.

[0106] Further adjuvants which may be present in the formulations and the application forms obtained therefrom include colorants such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyes, for example alizarin dyes, azo dyes and metal phthalocyanine dyes, as well as nutrients and micronutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

[0107] Stabilizers such as low temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents which improve chemical and / or physical stability may also be present.

[0108] Pesticide formulations The pesticide formulations of the present disclosure generally comprise a pesticide active dispersed in a mixture of water, an aqueous surfactant, and a thickening agent. Optionally, the pesticide formulation may comprise any of the adjunct ingredients disclosed herein.

[0109] The pesticide formulations of the present disclosure may generally comprise from about 57% to about 76% (w / w) of at least one pesticide active, based on the total weight of the formulation (i.e., based on the total weight of the dispersion). In embodiments, the pesticide active may be provided in the formulation in an amount ranging from about 57% to about 76% (w / w), about 60% to about 75% (w / w), about 60% to about 70% (w / w), about 62% to about 70% (w / w), or about 65% to about 70% (w / w), based on the total weight of the formulation.

[0110] The pesticide active may be selected from a combination of pesticide actives. As defined above, the pesticide active may be any chemical or combination of chemicals useful in agriculture, such as, but not limited to, insecticides, herbicides, fungicides, algicides, rodenticides, molluscicides, nematicides, fertilizers, soil conditioners, liming and acidifying agents, and plant growth regulators. In an embodiment, the pesticide active comprises an insecticide, herbicide, fungicide, algicide, rodenticide, molluscicide, nematicide, or a combination thereof. In an embodiment, the pesticide active comprises an insecticide, herbicide, fungicide, fungicide, or a combination thereof. In an embodiment, the pesticide active comprises an insecticide, a fungicide, or a combination thereof.

[0111] Additionally or alternatively, the pesticide formulation may be characterized by the concentration of pesticide active in the pesticide formulation. Generally, the concentration of pesticide active in the pesticide formulation is at least 750 g / L. In embodiments, the concentration of pesticide active in the pesticide formulation ranges from about 750 g / L to about 1000 g / L, from about 800 g / L to about 950 g / L, from about 800 g / L to about 900 g / L, or from about 825 g / L to about 875 g / L. Advantageously, the method of the present disclosure can provide an ultra-high loading agricultural formulation comprising at least about 750 g / L of agricultural active, where the active remains dispersed in the aqueous composition, with minimal or no settling or agglomeration of the active.

[0112] The surfactant may be provided in the pesticide formulation of the present disclosure in an amount ranging from about 0.1% to about 10% (w / w) based on the total weight of the pesticide formulation, for example, from about 0.5% to about 10% (w / w), from about 1% to about 9% (w / w), from about 2% to about 8% (w / w), from about 2% to about 6% (w / w), or from about 4% to about 6% (w / w) based on the total weight of the pesticide formulation.

[0113] Thickening and / or structuring agents may be provided in the formulations of the present disclosure in an amount ranging from about 0.01% to about 3% (w / w) based on the total weight of the pesticide formulation, for example, from about 0.01% to about 2% (w / w), from about 0.01% to about 1% (w / w), from about 0.01% to about 0.50% (w / w), from about 0.01% to about 0.20% (w / w), or from about 0.05% to about 0.15% (w / w) based on the total weight of the pesticide formulation.

[0114] The remainder of the pesticide formulation of the present disclosure includes any optional auxiliary ingredients and water. Water may be provided in the pesticide formulation of the present disclosure in an amount ranging from about 10% to about 40% (w / w) based on the total weight of the pesticide formulation, for example, from about 15% to about 35% (w / w), from about 20% to about 35% (w / w), from about 20% to about 30% (w / w), or from about 25% to about 30% (w / w) based on the total weight of the pesticide formulation.

[0115] Upon preparation of the pesticide formulation, it is in the form of a flowable fluid. Advantageously, upon standing of the formulation, the pesticide formulation forms a shear-thinning gel. Without being bound by theory, it is believed that the gel form of the formulation allows the pesticide active to remain stable against settling, phase separation and / or aggregation (i.e., inhibits settling and / or aggregation of the active) during storage and prior to use by the end user. Furthermore, the gel formulation is advantageously shear-thinning, which allows the gel to return to a flowable fluid with moderate agitation.

[0116] In an embodiment, the pesticide formulation in the form of a shear-thinning gel has a viscosity of greater than about 1000 cP, greater than about 1500 cP, or greater than 2000 cP. Generally, upon stirring, the viscosity of the pesticide formulation decreases. In an embodiment, upon stirring, the viscosity of the pesticide formulation decreases and the pesticide formulation becomes a flowable fluid. In an embodiment, the gelled pesticide formulation can be stirred to provide a flowable fluid having a viscosity in the range of about 200 cP to about 1000 cP, about 300 cP to about 900 cP, or about 400 cP to about 800 cP. The gelled pesticide formulation can be stirred under any conditions sufficient to reduce the viscosity of the gelled pesticide formulation. The means of stirring the gelled pesticide formulation to form a flowable fluid are not particularly limited. For example, the container containing the gelled pesticide formulation can be shaken, or the gelled pesticide formulation can be mechanically stirred in the container using, for example, a mixing blade. Suitable mixing blades include, but are not limited to, impellers such as turbines, propellers, hydrofoils, paddles and dispersing blades. Conditions sufficient to reduce the viscosity of the gelled pesticide formulation may include operating the stirring means at a speed of at least 50 revolutions per minute (rpm), at least 75 rpm, at least 100 rpm, at least about 500 rpm, at least about 750 rpm, at least about 1000 rpm and up to about 500 rpm, up to about 750 rpm, up to about 1000 rpm, up to about 1500 rpm or up to about 2000 rpm, for example, in the range of about 50 rpm to about 2000 rpm or about 50 rpm to about 1000 rpm. Those skilled in the art will readily appreciate that as the speed of the stirring means increases, the time required to reduce the gelled pesticide formulation from a first viscosity to a second viscosity decreases. Thus, the stirring speed and stirring time can be selected based on the energy and time available to the end user.

[0117] Method for preparing agrochemical formulations The present disclosure provides a method of forming an agrochemical formulation, comprising: (a) homogenizing a first mixture comprising at least one pesticidal active in water to form a first homogenized mixture; (b) a first millbase; (i) bead milling the first homogenized mixture to form first particles having a D90 particle size of about 1 to 75 microns; or (ii) colloidal milling the first homogenized mixture to form first particles having a D50 particle size of about 1 to 75 microns. and forming the (c) homogenizing a second mixture comprising at least one pesticidal active and the first mill-base to form a second homogenized mixture; (d) bead milling the second homogenized mixture to form a second mill-base comprising second particles having a D90 particle size of about 1 to 75 microns; (e) homogenizing a third mixture comprising the aqueous surfactant solution and the thickener to form a slurry; (f) combining the slurry with a second millbase to form a pesticide formulation comprising 57-76% (w / w) pesticide active material based on the total weight of the formulation, thereby forming the pesticide formulation. wherein the first mixture comprises 20-70% (w / w) of at least one pesticide active, the balance comprising water and optionally a surfactant, an antifreeze, a biocide, an antifoam agent or combinations thereof, and the second mixture comprises 10-50% (w / w) of at least one pesticide active, based on the total weight of the second mixture.

[0118] As used herein and unless otherwise defined, the terms "homogeneous," "homogenize," and other iterations thereof are used in accordance with the ordinary meaning of homogeneity. With specific reference to a mixture of a pesticide active in water, "homogeneous" and other iterations thereof refer to a dispersion of the pesticide active in water in which the pesticide active is substantially uniformly distributed throughout the mixture.

[0119] Methods for homogenizing a mixture are generally known in the art. For example, the first mixture can be homogenized by overhead mixing, impeller mixing, magnetic stirring, or a combination thereof. In an embodiment, the first mixture can be homogenized using an overhead mixer. In an embodiment, the first mixture can be homogenized using magnetic stirring.

[0120] The pesticide active in the first mixture may include any pesticide active disclosed herein. The amount of pesticide active provided by the first mixture may range from about 20% to about 70% (w / w) based on the total weight of the first mixture, such as from about 25% to about 65% (w / w), from about 30% to about 60% (w / w), from about 35% to about 55% (w / w), from about 40% to about 50% (w / w), or from about 45% to about 55% (w / w). The amount of pesticide active provided in the first mixture may also be characterized by the amount of pesticide active in the first mixture relative to the total amount of pesticide active provided in the final composition. The amount of pesticide active provided by the first mixture may range from about 30% to about 75% (w / w) based on the total amount of pesticide active in the final pesticide formulation, for example, from about 30% to about 70%, from about 35% to about 60% (w / w), from about 35% to about 55%, or from about 40% to about 50% (w / w) based on the total amount of pesticide active in the final pesticide formulation, or from about 75% (w / w) or less, from about 70% (w / w) or less, from about 65% (w / w) or less, from about 50% (w / w) or less, from about 48% (w / w) or less, from about 46% (w / w) or less, or from about 44% (w / w) or less, with the remainder of the pesticide active being provided in the second mixture of pesticide active in the second mixture. The first mixture and the first homogenized mixture may further comprise any surfactant and / or any adjunct ingredient disclosed herein. In an embodiment, the first mixture further comprises a surfactant. In an embodiment, the first mixture further comprises a surfactant and one or more of an antifreeze agent, a biocide, and an antifoam agent. The pesticide active and any surfactant and / or any adjunct ingredient can be combined in any order to form the first mixture.

[0121] When included in the first mixture and the first homogenized mixture, the surfactant may be included in an amount ranging from about 0.1% to about 15% (w / w) based on the total weight of the first mixture, e.g., from about 0.5% to about 12% (w / w), from about 1% to about 10% (w / w), from about 2% to about 10% (w / w), from about 3% to about 8% (w / w), from about 4% to about 8% (w / w), from about 5% to about 8% (w / w), from about 6% to about 8% (w / w), or from about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15% (w / w) based on the total weight of the first mixture. When included in the first mixture and the first homogenized mixture, the auxiliary ingredients may be included in a total amount in the range of about 0.1% to about 10% (w / w) based on the total weight of the first mixture, for example, about 0.5% to about 8% (w / w), about 1% to about 6% (w / w), about 2% to about 5% (w / w), about 3% to about 5% (w / w), or about 3.5% (w / w) to about 4.5% (w / w) based on the total weight of the first mixture.

[0122] The first mixture and the first homogenized mixture further comprise water. The water may be provided in any amount suitable to arrive at a final pesticide formulation having an amount of pesticide active material generally ranging from about 57% to about 76% (w / w) based on the total weight of the formulation. In an embodiment, the first mixture and the first homogenized mixture may comprise water in an amount ranging from about 7% to about 80% (w / w) based on the total weight of the first mixture, for example, from about 10% to about 70% (w / w), from about 20% to about 60% (w / w), from about 30% to about 50% (w / w), from about 35% to about 45% (w / w), or from about 40% (w / w) based on the total weight of the first mixture.

[0123] The first homogenized mixture can be milled to form a first mill base comprising first particles of the pesticide active that have a reduced particle size compared to the pesticide active raw material. A variety of techniques can be used to perform the milling, including those described in Nakach et al., Journal of Pharmaceutical Sciences 106(2017)1889-1904 and Loh et al., Asian Journal of Pharmaceutical Sciences 10(2015)255-274, which are incorporated herein by reference. The milling of the first homogenized mixture can be performed using a bead mill or a colloid mill. In one embodiment, the device used to perform the milling is a bead mill. In another embodiment, the device used to perform the milling is a colloid mill. The mills used to perform the methods disclosed herein can be horizontal or vertical.

[0124] In an embodiment, the milling of the first homogenized mixture is carried out using a bead mill until the D90 particle size of the first particles of the pesticide active is in the range of about 1 micron to about 75 microns, e.g., about 1 micron to about 70 microns, about 1 micron to about 65 microns, about 1 micron to about 60 microns, about 1 micron to about 55 microns, about 1 micron to about 50 microns, about 1 micron to about 45 microns, about 1 micron to about 40 microns, about 1 micron to about 35 microns, about 1 micron to about 30 microns, about 1 micron to about 25 microns, about 1 micron to about 20 microns, about 1 micron to about 20 microns, about 1 micron to about 15 microns, about 1 micron to about 10 microns, about 1 micron to about 5 microns, about 3 microns to about 20 microns, about 3 microns to about 15 microns, about 3 microns to about 10 microns, about 3 microns to about 8 microns, or about 4 microns to about 6 microns. In an embodiment, milling is continued until the first particles have a D90 particle size of about 3 microns to about 8 microns In an embodiment, milling is continued until the first particles have a D90 particle size of about 4 microns to about 6 microns.

[0125] In an embodiment, the milling of the first homogenized mixture is carried out using a colloid mill until the D50 particle size of the first particles of the pesticide active is about 1 micron to about 75 microns, e.g., about 1 micron to about 70 microns, about 5 microns to about 70 microns, about 10 microns to about 70 microns, about 15 microns to about 70 microns, about 20 microns to about 70 microns, about 25 microns to about 70 microns, about 30 microns to about 70 microns, about 35 microns to about 65 microns, about 40 microns to about 60 microns, about 45 microns to about 55 microns, or about 50 microns. In an embodiment, the milling is continued until the D50 particle size of the first particles is about 45 microns to about 55 microns. In an embodiment, the milling is continued until the D50 particle size of the first particles is about 48 microns to about 52 microns.

[0126] Particle size may be measured by any method known in the art, such as laser diffraction, FBRM (focused beam reflectometry), UAS (ultrasonic attenuation spectroscopy), PDA (phase Doppler spectroscopy), SFT (spatial filtering technique) or SDV (shadow Doppler velocimetry).

[0127] The second mixture may be homogenized using any method known in the art. For example, the second mixture may be homogenized by overhead mixing, impeller mixing, magnetic stirring, or a combination thereof. In an embodiment, the second mixture may be homogenized using an overhead mixer. In an embodiment, the second mixture may be homogenized using magnetic stirring.

[0128] The pesticide active in the second mixture may include any pesticide active disclosed herein. In an embodiment, the pesticide active in the second mixture is the same active as the first mixture. In an embodiment, the pesticide active in the second mixture is a different active than the first mixture. In an embodiment, the pesticide active in the second mixture includes the same active as the first mixture and a different active than the first mixture. The amount of pesticide active in the second mixture may range from about 20% to about 70% (w / w), for example, from about 25% to about 65% (w / w), from about 20% to about 60% (w / w), from about 25% to about 55% (w / w), from about 30% to about 50% (w / w), or from about 35% to about 45% (w / w), based on the total weight of the second mixture. The amount of pesticide active in the second mixture may also be characterized by the amount of pesticide active in the second mixture relative to the total amount of pesticide active provided in the final composition. The amount of pesticide active in the second mixture may range from about 25% to about 70% (w / w) based on the total amount of pesticide active in the final pesticide formulation, for example, from about 30% to about 70%, from about 40% to about 65%, from about 45% to about 65%, or from about 50% to about 60%, for example, from about 50% (w / w) or more, from about 52% (w / w) or more, from about 54% (w / w) or more, or from about 56% (w / w) or more based on the total amount of pesticide active in the final pesticide formulation, with the remainder of the pesticide active being provided in the first one in the first mixture. The remainder of the second mixture and the second homogenized mixture are comprised of the first millbase and optionally surfactants or other adjuvants. In an embodiment, the second mixture further consists essentially of the pesticide active and the first millbase. In an embodiment, the second mixture further comprises one or more of an antifreeze agent, a biocide, and an antifoam agent.

[0129] The second homogenized mixture can be milled to reduce the particle size of the pesticide active and form a second mill base containing the second particles. A variety of techniques can be used to perform the milling, including those described in Nakach et al., Journal of Pharmaceutical Sciences 106(2017)1889-1904 and Loh et al., Asian Journal of Pharmaceutical Sciences 10(2015)255-274, which are incorporated herein by reference. The milling of the second homogenized mixture can be performed using a bead mill or a colloid mill. In one embodiment, the device used to perform the milling is an annular gap bead mill.

[0130] In an embodiment, the milling of the second homogenized mixture is carried out using a bead mill until the D90 particle size of the second particles of the pesticide active is in the range of about 1 micron to about 75 microns, e.g., about 1 micron to about 70 microns, about 1 micron to about 65 microns, about 1 micron to about 60 microns, about 1 micron to about 55 microns, about 1 micron to about 50 microns, about 1 micron to about 45 microns, about 1 micron to about 40 microns, about 1 micron to about 35 microns, about 1 micron to about 30 microns, about 1 micron to about 25 microns, about 1 micron to about 20 microns, about 1 micron to about 20 microns, about 1 micron to about 15 microns, about 1 micron to about 10 microns, about 1 micron to about 5 microns, about 3 microns to about 20 microns, about 3 microns to about 15 microns, about 3 microns to about 10 microns, about 3 microns to about 8 microns, or about 4 microns to about 6 microns. In an embodiment, milling is continued until the second particles have a D90 particle size of about 3 microns to about 8 microns In an embodiment, milling is continued until the second particles have a D90 particle size of about 4 microns to about 6 microns.

[0131] In some embodiments, the first mixture and / or the second mixture are substantially free of surfactants. As used herein and unless otherwise defined, "substantially free of surfactants" means that the mixture contains less than about 1 wt. %, for example less than about 0.5 wt. %, less than 0.1 wt. %, or less than 0.01 wt. % of surfactant based on the total weight of the mixture. In some embodiments, the first mixture contains surfactants and the second mixture is substantially free of surfactants. In some embodiments, the first mixture and the second mixture are substantially free of surfactants.

[0132] In embodiments where the milling of the first homogenized mixture is carried out in a bead mill, the bead milling can be carried out under any conditions sufficient to reduce the particle size of the pesticide active without degrading the pesticide active. Generally, the bead milling is carried out under wet conditions. In embodiments, the bead milling uses glass beads at a loading of 60-90%, e.g., a loading of 70-85% or a loading of 75-80%. In embodiments, the bead milling uses glass beads at a loading of 75-80%. Generally, as the bead loading decreases, the amount of milling achieved decreases and / or the milling time may increase beyond acceptable time limits. As the bead loading increases, the potential for heat generation increases, which may result in the mixture becoming thick and unworkable. In an embodiment, the glass beads for grinding have a diameter in the range of about 0.50 mm to about 1.25 mm, for example, about 0.60 mm to about 1.15 mm, about 0.65 mm to about 1.10 mm, about 0.70 mm to about 1.05 mm, or about 0.75 mm to about 1.00 mm. In an embodiment, the glass beads have a diameter of about 0.75 mm to about 1.00 mm. In general, as the size of the beads increases, the amount of grinding achieved decreases and / or the grinding time may increase beyond the acceptable time limit. As the size of the beads decreases, it is possible to intensify the grinding, but there is a higher possibility of heat generation and the mixture may thicken and become unprocessable. In an embodiment, the bead mill may operate at about 1500 rpm to about 3500 rpm, for example, about 2000 rpm to about 3000 rpm, or about 2250 rpm to about 2750 rpm, or about 2500 rpm. In an embodiment, the bead mill operates at about 2250 rpm to about 2750 rpm. In general, slower rotation speeds increase processing time and may limit particle size reduction. Higher rotation speeds increase the potential for heat generation, which may result in a thick, unprocessable mixture.

[0133] In embodiments where the grinding of the first homogenized mixture is performed in a colloid mill, the colloid grinding can be performed under any conditions sufficient to reduce the particle size of the pesticide active without degrading the pesticide active. In embodiments, the colloid mill can operate with a gap width in the range of about 0.6 mm to about 0.16 mm, e.g., about 0.5 mm to about 0.16 mm, about 0.4 mm to about 0.16 mm, about 0.3 mm to about 0.16 mm, or about 0.2 mm to about 0.16 mm. In embodiments, the colloid mill can operate with a gap width of about 0.16 mm. In an embodiment, the colloid mill may be operated at a rotation speed in the range of about 1000 rpm to about 20,000 rpm, for example, about 2000 rpm to about 18,000 rpm, about 2000 rpm to about 16,000 rpm, about 2000 rpm to about 14,000 rpm, about 2000 rpm to about 12,000 rpm, about 4000 rpm to about 10,000 rpm, about 6000 rpm to about 10,000 rpm, about 7000 rpm to about 9000 rpm, or about 7500 rpm to about 8500 rpm, or about 6000 rpm, about 8000 rpm, about 10,000 rpm, about 15,000 rpm, or about 20,000 rpm. In an embodiment, the colloid mill may be operated at a rotation speed in the range of about 6000 rpm to about 10,000 rpm. In embodiments, the colloid mill may be operated at a rotational speed ranging from about 7000 rpm to about 9,000 rpm.

[0134] In embodiments where the milling of the second homogenized mixture is carried out in a bead mill, the bead milling can be carried out under any conditions sufficient to reduce the particle size of the pesticide active without degrading the pesticide active. Generally, the bead milling is carried out under wet conditions. In embodiments, the bead milling of the second homogenized mixture uses glass beads at a loading of 25-70%, e.g., a loading of 30-60%, a loading of 30-50%, a loading of 40-50%, or a loading of about 45%. In embodiments, the bead milling of the second homogenized mixture uses glass beads at a loading of 40-50%. In embodiments, the glass beads for milling have a diameter in the range of about 0.50 mm to about 1.25 mm, e.g., about 0.60 mm to about 1.15 mm, about 0.65 mm to about 1.10 mm, about 0.70 mm to about 1.05 mm, or about 0.75 mm to about 1.00 mm. In an embodiment, the glass beads have a diameter of about 0.75 mm to about 1.00 mm. In an embodiment, the bead mill can be operated at about 1500 rpm to about 3500 rpm, such as about 2000 rpm to about 3000 rpm, or about 2250 rpm to about 2750 rpm, or about 2500 rpm. In an embodiment, the bead mill is operated at about 2250 rpm to about 2750 rpm.

[0135] In general, the temperature of the grinding step can be any suitable temperature. As the temperature increases, the likelihood of gelation increases, the likelihood of decomposition of the active substance increases, and the likelihood of heat or heat surge increases. Thus, in an embodiment, the grinding step can be carried out in a mill having a controlled temperature set at about 1°C to about 60°C, for example, about 1°C to about 55°C, about 1°C to about 50°C, about 1°C to about 45°C, about 1°C to about 40°C, about 1°C to about 35°C, about 1°C to about 30°C, about 1°C to about 25°C, or about 1°C to about 20°C. In yet another embodiment, the grinding is carried out in a mill having a controlled temperature set at about 5°C to about 60°C, about 5°C to about 55°C, about 5°C to about 50°C, about 5°C to about 45°C, about 5°C to about 40°C, about 5°C to about 35°C, about 5°C to about 30°C, about 5°C to about 25°C, or about 5°C to about 20°C. In an embodiment, the grinding is carried out in a mill having a controlled temperature set at about 1°C to about 40°C.

[0136] The third mixture may be homogenized using any method known in the art. For example, the third mixture may be homogenized by overhead mixing, impeller mixing, magnetic stirring, or a combination thereof. In an embodiment, the third mixture may be homogenized using an overhead mixer. In an embodiment, the third mixture may be homogenized using magnetic stirring.

[0137] The third mixture generally comprises an aqueous surfactant solution comprising a surfactant and water, and a thickening agent. After homogenizing the third mixture, a slurry is formed in which the thickening agent is dispersed in the surfactant solution. The third mixture may comprise any surfactant disclosed herein and any thickening agent disclosed herein. The surfactant may be provided in an amount ranging from about 5% to about 15% (w / w) based on the total weight of the third mixture, for example, from about 6% to about 14% (w / w), from about 7% to about 13% (w / w), from about 8% to about 12% (w / w), from about 9% to about 11% (w / w), or from about 10% (w / w) based on the total weight of the third mixture. The thickening agent may be provided in an amount ranging from about 0.01% to about 5% (w / w) based on the total weight of the third mixture, for example, about 0.5% to about 4.5% (w / w), about 1.0% to about 4.0% (w / w), about 1.5% to about 3.5% (w / w), or about 2.0% to about 3.0% (w / w) based on the total weight of the third mixture. The remainder of the third mixture may be water, antifreeze, glycerin, propylene glycol, or a combination thereof, provided in an amount ranging from about 81% to about 95% (w / w) based on the total weight of the third mixture, for example, about 83% to about 92% (w / w) or about 85% to about 90% (w / w) based on the total weight of the third mixture. In an embodiment, the remainder of the third mixture is water. In an embodiment, the remainder of the third mixture is glycerin.

[0138] The slurry prepared from the third mixture is combined with the second mill base to form an agrochemical formulation comprising about 57% to about 76% of the agrochemical active material based on the total weight of the agrochemical formulation. The method of combining the third mixture with the second mill base is not particularly limited and may include simply mixing the two compositions at ambient temperature and relative humidity. When combining the third mixture and the mill base of the second mill base, the mixture may be stirred under moderate conditions, for example, at about 200 to 1500 rpm, for up to about 1 hour, for example, about 30 to about 60 minutes.

[0139] The pesticide formulation resulting from the method disclosed herein is described in detail above. As disclosed herein, the pesticide formulation may advantageously comprise a pesticide active at a concentration of at least about 57 to about 76% (w / w) or at least 750 g / L based on the total weight of the formulation. Advantageously, upon formation of the pesticide formulation, the formulation forms a reversible gel when the formulation is allowed to stand at ambient conditions, inhibiting settling and / or aggregation of the pesticide active particles. The reversible gel network comprises a storage modulus (G') of greater than 250 Pa, measured after an equilibration time of 48 hours. Oscillatory measurements of G' are performed in the linear viscoelastic region at a fixed frequency of 0.5 Hz.

[0140] A reversible gel forms a flowable fluid upon agitation and reverts to a gel upon storage. Advantageously, the gel form of the pesticide formulation can be stored for at least 1 month, at least 2 months, at least 3 months, at least 4 months, at least 6 months, or at least 12 months without significant settling, flocculation, and / or syneresis of the gel components. As used herein and unless otherwise defined, "significant" settling, flocculation, and / or syneresis refers to 15% or more of the solid pesticide actives settling from the gel and / or 15% or more of the liquids separating from the gel. In embodiments, the pesticide formulations of the present disclosure exhibit about 12% or less, about 10% or less, or about 8% or less settling, flocculation, and / or syneresis.

[0141] Articles and methods for using the pesticide formulations of the present disclosure Further provided herein is an article for dispensing the pesticide formulation of the present disclosure, the article including a container having a mixing blade attached thereto, and the pesticide formulation of the present disclosure provided within the container and in contact with the mixing blade, the mixing blade configured to promote a phase transition of the pesticide formulation from a gel to a flowable fluid.

[0142] In general, the container can be any container suitable for holding the pesticide formulation in the form of a gel and in the form of a flowable fluid. The container can include a lid portion so that the pesticide formulation can be completely contained. The container can also include a means for dispensing the pesticide formulation from the container. The means for dispensing the pesticide formulation can allow the pesticide formulation to be poured, sprayed, or otherwise dispensed from the container. The means for dispensing the pesticide formulation can include, but are not limited to, valves, hoses, and nozzles. In some embodiments, the substrate to be treated by the pesticide formulation can be added to the container and mixed with the pesticide formulation using a mixing blade.

[0143] The mixing blade is generally configured to promote the phase transition of the pesticide formulation from gel to a flowable fluid. The mixing blade mechanically agitates the gelled pesticide formulation in the container. Suitable mixing blades include, but are not limited to, impellers such as turbines, propellers, hydrofoils, paddles and dispersing blades. The mixing blade can be operatively associated with a controller, such as a mechanical switch or an electrical controller, to control the mixing blade and the speed at which the mixing blade operates. Without being bound by theory, it is believed that only moderate agitation is required to promote the phase transition of the pesticide formulation gel to a flowable fluid. As used herein, "moderate agitation" can be achieved by operating the mixing blade at a speed of at least 60 revolutions per minute (rpm), for example at least 75 rpm or at least 100 rpm.

[0144] Further provided herein is a kit comprising a container fitted with a mixing blade and an agrochemical formulation of the present disclosure. The container can be any container disclosed herein and the mixing blade can be any mixing blade disclosed herein. The agrochemical formulation can be provided in the container or in a separate container and transferred to the container at the time of use. The mixing blade can be configured to promote a phase transition of the agrochemical formulation from a gel to a flowable fluid.

[0145] Further provided herein is a method of treating a substrate with the pesticide formulation of the present disclosure, the method comprising providing the pesticide formulation of the present disclosure and applying a flowable fluid to the substrate. Optionally, the pesticide formulation of the present disclosure may be provided in gel form and agitated to promote phase transition to a flowable fluid prior to applying the flowable pesticide formulation to the substrate.

[0146] In embodiments, the substrate to be treated is plant propagation material, including, but not limited to, cuttings, callus cultures, rhizomes or tubers, fruits, seeds, seedlings, protoplasts, cell cultures, and the like.

[0147] In some embodiments, the pesticide formulation is a seed treatment formulation.These formulations can be used to protect seeds from undesirable microorganisms, such as phytopathogenic microorganisms, such as phytopathogenic fungi or phytopathogenic oomycetes.The term seed as used herein includes dormant seeds, pre-germinated seeds, and seeds with roots and leaves emerged.

[0148] Thus, the present disclosure also relates to a method for protecting seeds against undesirable microorganisms comprising treating the seeds with a formulation of the present disclosure.

[0149] Seed treatment with the formulation of the present disclosure can not only protect the seed from phytopathogenic microorganisms, but also protect the germinating seed, the emerging seedling, and the plant after emergence from the treated seed.Therefore, the present disclosure relates to a method for protecting the seed, germinating the seed, and germinating the seedling.Seed treatment can be carried out before sowing, at the time of sowing, or immediately after sowing.

[0150] When seed treatment is carried out before sowing (for example, so-called seed application), seed treatment can be carried out as follows: Seeds are placed in a mixer with the desired amount of the formulation of the present disclosure, and the seeds and the formulation of the present disclosure are mixed until a uniform distribution is achieved on the seeds. If appropriate, the seeds can then be dried.

[0151] The present disclosure also relates to seeds coated with the formulation of the present disclosure. Optionally, the seeds are treated in a sufficiently stable state so that no damage occurs during treatment. Generally, the seeds can be treated at any time from during harvest to immediately after sowing. It is customary to use seeds that have been separated from the plant and have been freed from the cob, husk, stem, skin, hair or fruit pulp. For example, it is possible to use seeds that have been harvested, washed and dried to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seeds that have been dried, for example treated with water and then dried again, or seeds that have been immediately primed or seeds that have been stored under primed conditions, or pre-germinated seeds, or seeds that have been sown in seedling trays, tapes or papers.

[0152] The amount of the formulation of the present disclosure applied to the seed is typically such that the seed germination is not impaired or the resulting plant is not damaged. In order to achieve optimal seed and germinating plant protection with the minimum amount of active ingredient used, the unique phenotype of the transgenic plant should also be considered when determining the amount of the formulation of the present disclosure applied to the seed.

[0153] The formulations of the present disclosure may be applied directly to seeds as is, i.e., without other ingredients and without dilution. The compositions of the present disclosure may also be applied to seeds.

[0154] The formulation of the present disclosure is suitable for protecting any plant variety.Exemplary seeds are cereals (such as wheat, barley, rye, millet, triticale, oats), canola, corn, cotton, soybean, rice, potato, sunflower, bean, coffee, pea, beet (such as sugar beet and fodder beet), peanut, vegetable (such as tomato, cucumber, onion and lettuce), turf and ornamental plant seeds.

[0155] The formulations of the present disclosure can be used to treat transgenic seeds, particularly those of plants capable of expressing a polypeptide or protein acting against pests, herbicidal damage or abiotic stress, thereby increasing the protective effect. The seeds of plants capable of expressing a polypeptide or protein acting against pests, herbicidal damage or abiotic stress can contain at least one heterologous gene that allows the expression of said polypeptide or protein. These heterologous genes in transgenic seeds can be derived from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. These heterologous genes are preferably derived from Bacillus sp., in which case the gene products are effective against the European corn borer and / or the western corn rootworm. Particularly preferably, the heterologous genes are derived from Bacillus thuringiensis.

[0156] The present disclosure further provides a formulation of crop protection agent and / or insecticide, such as drench, drip and spray liquid, which comprises at least one of the active compounds of the present disclosure, and application forms prepared therefrom.The application forms may contain additional crop protection agent and / or insecticide and / or activity-enhancing adjuvants, such as penetrants, for example vegetable oils, such as rapeseed oil, sunflower oil, for example liquid paraffin, alkyl esters of vegetable fatty acids, such as rapeseed oil or soybean oil methyl ester or alkanol alkoxylates, and / or spreading agents, such as alkylsiloxanes and / or salts, such as organic or inorganic ammonium or phosphonium salts, for example ammonium sulfate, diammonium hydrogen phosphate, and / or retention promoters, such as dioctyl sulfosuccinate or hydroxypropyl guar polymers, and / or humectants, such as glycerol and / or fertilizers, such as ammonium, potassium or phosphorus fertilizers. EXAMPLES

[0157] Example 1: Preparation of ultra-high loading pesticide formulation Clothianidin TC (284.53 g) was combined with surfactant (47.42 g), antifreeze (20.75 g), biocide (2.61 g), antifoam (1.48 g) and water (235.98 g) to form a first mixture. The first mixture was then homogenized using an overhead mixer to form a first homogenized mixture. The first homogenized mixture was bead milled under humid conditions at 30-35°C using glass beads (75-80% loading) having a diameter of 0.75 mm-1.00 mm at 2500 rpm until a D90 particle size of 5 μm was achieved, thereby obtaining a first mill base. Clothianidin TC (368.74 g) was then added to the first mill base (592.76 g) and homogenized to form a second homogenized mixture. The second homogenized mixture was bead milled (30-35 °C, 45% loading, 0.75-1.0 mm glass beads, 2500 rpm) until a D90 particle size of 5 μm was obtained to obtain a second mill base. In a separate container, a surfactant solution in water (3.76 g surfactant; 33.80 g water) was prepared and then combined with xanthan gum (0.94 g) to form a third mixture. The third mixture was homogenized by overhead mixing to produce an aqueous slurry. The aqueous slurry (38.5 g) was combined with the second mill base (961.50 g) to form an agrochemical formulation with a final concentration of total clothianidin TC of 65.33% (w / w) (approximately 800 g / L) based on the total weight of the agrochemical formulation.

[0158] Thus, Example 1 illustrates the preparation of an agrochemical formulation of the present disclosure.

[0159] Example 2: Preparation of ultra-high loading pesticide formulations Clothianidin TC (70% overall in the final formulation) was combined with the same surfactants and adjuvants as in Example 1 and water to form a first mixture. The first mixture was then homogenized using an overhead mixer to form a first homogenized mixture. The first homogenized mixture was colloidally milled at 8000 rpm, 0.159 mm gap and 30-35°C until a D50 particle size of 40 μm was achieved, thereby obtaining a first mill base. Clothianidin TC (30% overall in the final formulation) was then added to the first mill base and homogenized to form a second homogenized mixture. The second homogenized mixture was passed through a colloid mill 1-2 times and then bead milled (45% loading, 0.75-1.0 mm glass beads, 2500 rpm) until a D90 particle size of 6 μm was obtained to obtain a second mill base. In a separate container, a surfactant solution in water (3.76 g surfactant; 33.80 g water) was prepared and then combined with xanthan gum (0.94 g) to form a third mixture. The third mixture was homogenized by overhead mixing to produce an aqueous slurry. The aqueous slurry was combined with the second millbase to form a pesticide formulation having a final concentration of clothianidin TC of about 65% (w / w) (about 885 g / L) based on the total weight of the pesticide formulation.

[0160] Thus, Example 2 illustrates the preparation of an agrochemical formulation of the present disclosure.

[0161] Example 3: Preparation of ultra-high loading pesticide formulations Fluopyram TC (222 g) was combined with surfactant (20.9 g), antifreeze (19.9 g), biocide (1.0 g), antifoam (1.48 g) and water (235.98 g) to form a first mixture. The first mixture was then homogenized using an overhead mixer to form a first homogenized mixture. The first homogenized mixture was bead milled under humid conditions at 30-35°C using glass beads (60% loading) having a diameter of 0.75 mm-1.00 mm at 2500 rpm until a D90 particle size of 6 μm was achieved, thereby obtaining a first mill base. Fluopyram TC (78.3 g) and mefentrifluconazole TC (32 g) were then added to the first mill base and homogenized to form a second homogenized mixture. The second homogenized mixture was bead milled (30-35°C, 60% loading, 0.75-1.0 mm glass beads, 2500 rpm) to a D90 particle size of 6 μm to obtain a second mill base. In a separate container, a 10% mixture of Methocel k200M surfactant in propylene glycol was prepared. The surfactant mixture (1.38 g) was added to the second mill base and homogenized by overhead mixing to form a pesticide formulation with a final concentration of fluopyram and mefentrifluconazole of 66.46% (w / w) (approximately 850 g / L) based on the total weight of the pesticide formulation.

[0162] Example 4: Preparation of pesticide formulations Two pesticide formulations were prepared according to known methods in the art. Formulation A is a pesticide formulation not disclosed herein with a clothianidin TC concentration of about 600 g / L. Formulation B is a pesticide formulation not disclosed herein with a clothianidin TC concentration of about 750 g / L.

[0163] Briefly, formulation A was prepared by combining clothianidin TC, surfactant, water and optional adjuvants to form a first mixture. The first mixture was homogenized using an overhead mixer at 500 rpm, followed by bead milling at 30-35°C using glass beads (75-80% bead loading) having a diameter of 0.75 mm to 1.00 mm at 2500 rpm until a D90 particle size of 5 μm was achieved. Samples were collected in a separate container and a 2% xanthan gum slurry in water was added and homogenized for 1 hour at 500 rpm. The final mixture contained 48% w / w (approximately 600 g / L) clothianidin TC based on the total weight of the pesticide formulation.

[0164] Formulation B was prepared in the same manner as Formulation A, except that the amount of clothianidin included in the mixture resulted in a final formulation with 57.28% w / w (approximately 750 g / L) clothianidin TC based on the total weight of the pesticide formulation.

[0165] Syneresis and sedimentation of each of Formulation A, Formulation B and the formulation prepared in Example 2 were monitored over a period of six months. Syneresis is provided as a percentage and is the mean value at t=0 (H t=0 ) and at different times (H t=x ) for at least t = 4 weeks and t = 26 weeks. The percent syneresis at a given time point is determined as follows: % syneresis = [(H t=0 -H t=x ) / H t=0 ]×100. The results are shown in Figure 1. As shown in Figure 1, after 6 months of storage, formulations A and B showed syneresis (approximately 7% and 2%, respectively), while the formulation of Example 2 showed significantly improved syneresis (0%). After stirring, the viscosity of the formulations was also measured. As shown in Figure 2, after stirring, the formulation of Example 2 is in the form of a flowable fluid with a viscosity similar to that of Formulation B.

[0166] Thus, Example 4 shows that formulations of the present disclosure prepared by the methods of the present disclosure demonstrate improved syneresis at higher concentrations of pesticidal actives than formulations prepared by known methods, while maintaining the ability to be provided as flowable fluids.

[0167] Example 5: Method for preparing ultra-high-load formulations containing two or more active ingredients Briefly, formulation C was prepared by combining clothianidin TC, surfactant, water and optional adjuvants to form a first mixture. The first mixture was homogenized using an overhead mixer at 500 rpm, followed by bead milling at 30-35°C using glass beads (75-80% bead loading) with diameters of 0.75 mm to 1.00 mm at 2500 rpm until a D90 particle size of 5 μm was achieved. Samples were collected in a separate container and Bacillus firmus slurry in water was added and homogenized for 1 hour at 500 rpm. The final mixture contained 40% w / w clothianidin TC and 10% Bacillus firmus based on the total weight of the pesticide formulation or approximately 610 g / L.

[0168] Briefly, formulation D was prepared by combining Fluopyram TC, surfactant, water and optional adjuvants to form a first mixture. The first mixture was homogenized using an overhead mixer at 500 rpm, followed by bead milling at 30-35°C using glass beads (75-80% bead loading) having a diameter of 0.75 mm to 1.00 mm at 2500 rpm until a D90 particle size of 5 μm was achieved. Samples were collected in a separate container and a 2% xanthan gum slurry in water was added and homogenized for 1 hour at 500 rpm. The final mixture contained 48% w / w (approximately 600 g / L) Fluopyram TC based on the total weight of the pesticide formulation.

[0169] Briefly, formulation E was prepared by combining Fluopyram TC, surfactant, water and optional adjuvants to form a first mixture. The first mixture was homogenized using an overhead mixer at 500 rpm, followed by bead milling at 30-35°C using glass beads (75-80% bead loading) having a diameter of 0.75 mm to 1.00 mm at 2500 rpm until a D90 particle size of 5 μm was achieved. Samples were collected in a separate container and a 2% xanthan gum slurry in water was added and homogenized for 1 hour at 500 rpm. The final mixture contained 57.25% w / w (approximately 720 g / L) Fluopyram TC based on the total weight of the pesticide formulation.

[0170] The compositions set forth in Table 2 represent exemplary formulations according to the present invention. Millbase 1a was obtained by combining Fluopyram TC1 with surfactants, antifreeze, biocides, antifoam and water (Table 4). Millbase 1a was then homogenized using an overhead mixer and bead milled under wet conditions using glass beads with diameters of 0.75 mm to 1.00 mm (65% loading) at 2500 rpm until a particle size of 10 μm (D90) was achieved. Fluopyram TC2 and Mefentrifluconazole TC were then added to Millbase 1a (Table 5), homogenized and bead milled in Millbase 1b (65% loading, 0.75-1.0 mm glass beads, 2500 rpm) to a final particle size of 6 μm (D90). In a separate vessel, Methocel K200M was combined with propylene glycol (Table 3) and homogenized by an overhead mixer to create a slurry. As described in Table 6, Methocel 200M slurry, millbase 1b and anhydrous citric acid were combined to achieve a final concentration of 64.86 w / w%.

[0171] [Table 4]

[0172] [Table 5]

[0173] [Table 6]

[0174] [Table 7]

[0175] [Table 8]

[0176] The formulations were analyzed for viscosity, storage modulus (G') and syneresis behavior. Viscosity and storage modulus were measured on an Anton Paar 302e rheometer using a double gap geometry. Viscosity and storage modulus measurements were performed at 20 L / s and 0.5 Hz (72 hours), respectively. Syneresis was determined by dividing the length of the supernatant liquid phase and dividing by the length of the suspended phase. Table 6 shows the viscosity and syneresis results, and Table 7 shows the storage modulus (G') data of the formulations. Figures 3 and 4 show the viscosity and syneresis results for formulations A, C, D, E and Example 5 formulation. Figure 5 shows the storage modulus (G') data for formulations D and Example 5 formulation.

[0177] [Table 9]

[0178] [Table 10]

[0179] The foregoing descriptions are set forth merely for clarity of understanding, and no unnecessary limitations should be understood therefrom, since modifications within the scope of the invention may be apparent to those skilled in the art.

[0180] All patents, publications, and references cited herein are hereby incorporated by reference in their entirety. In the event of a conflict between this disclosure and the incorporated patents, publications, and references, this disclosure shall control.

Claims

1. A method for forming a pesticide formulation, (a) Homogenizing a first mixture containing at least one pesticide active substance in water to form a first homogenized mixture, (b) The first mill base, (i) Grinding the first homogenized mixture with beads to form first particles having a D90 particle size of about 1 to 75 microns, or (ii) Colloidal pulverization of the first homogenized mixture to form first particles having a D50 particle size of about 1 to 75 microns. To be formed by, (c) Homogenizing a second mixture containing at least one pesticide active substance and the first mill base to form a second homogenized mixture, (d) The second homogenized mixture is bead-ground to form a second mill base containing second particles having a D90 particle size of about 1 to 75 microns, (e) Homogenizing a third mixture containing an aqueous surfactant solution and a thickener to form a slurry, (f) A pesticide formulation comprising combining the slurry with the second mill base to form a pesticide formulation containing 57-76% (w / w) of the pesticide active substance based on the total weight of the formulation, thereby forming the pesticide formulation. A method comprising: the first mixture comprising 20-70% (w / w) of the at least one pesticide active substance, the remainder comprising water and optionally a surfactant, antifreeze, biocide, defoamer, or a combination thereof; and the second mixture comprising 10-50% (w / w) of the at least one pesticide active substance based on the total weight of the second mixture.

2. The method according to claim 1, wherein the at least one pesticide active substance in step (a) and the at least one pesticide active substance in step (c) are the same pesticide active substance.

3. The method according to claim 1, wherein the at least one pesticide active substance in step (a) and the at least one pesticide active substance in step (c) are different pesticide active substances.

4. The method according to claim 1, wherein the first mixture and the second mixture are substantially free of surfactants.

5. The method according to claim 1, wherein the active substance has a density in the range of about 1.0 to 2.0 g / mL.

6. The method according to claim 1, wherein the active substance has a melting point of more than approximately 50°C.

7. The method according to claim 1, wherein the active substance has a solubility in water of less than approximately 1000 mg / L.

8. The method according to claim 1, wherein the bead grinding, colloidal grinding, or a combination thereof is carried out in a mill having a controlled temperature set in the range of about 1°C to about 60°C, or about 30°C to about 45°C, or about 30°C to about 35°C.

9. The method according to claim 1, wherein the concentration of the pesticide active substance in the pesticide formulation is at least about 750 g / L.

10. The method according to claim 9, wherein the concentration of the pesticide active substance in the pesticide formulation is in the range of about 750 g / L to about 1000 g / L, about 800 g / L to about 950 g / L, about 800 g / L to about 900 g / L, or about 825 g / L to about 875 g / L.

11. The method according to claim 1, wherein the pesticide formulation is in the form of a gel.

12. The method according to claim 1, wherein the bead grinding in step (b) includes loading beads in the range of about 60% to 90%, about 70% to 90%, or about 75% to 85%.

13. The method according to claim 1, wherein the bead grinding in step (d) includes loading beads in the range of about 25% to 70%, about 30% to 60%, about 35% to 50%, or about 40% to 50%.

14. The method according to claim 1, wherein the pesticide active substance comprises an insecticide selected from the group consisting of abamectin, chlorantraniliprole, clothianidin, cyantraniliprole, ethiprole, fipronil, flubendiamide, flpyradiflon, imidacloprid, methiocarb, spinetram, spinosad, sulfoxaflor, tefluthrin, ticlopride, thiamethoxam, and thiodicarb.

15. The method according to claim 14, wherein the insecticide comprises clothianidin.

16. The method according to claim 1, wherein the at least one pesticide active substance in step (a) and / or (c) comprises clothianidin.

17. The method according to claim 1, wherein the pesticide active substance comprises a fungicide selected from the group consisting of azoxystrobin, β-cyfluthrin, carbendazim, carbendazim, cyproconazole, epoxyconazole, phenamidon, fluazinam, fludioxynil, fluopyram, fluoxastrobin, fluquinconazole, ipconazole, iprodione, isothianil, mefentrifluconazole, metalaxyl, metalaxyl-M, metminostrobin, pencyclon, penflufen, picarbtrazox, picoxystrobin, procymidone, propiconazole, prothioconazole, pyraclostrobin, tebuconazole, triadimenol, and trifloxystrobin.

18. The method according to claim 1, wherein the pesticide active substance comprises at least mefentrifluconazole and fluopyram.

19. The method according to claim 1, wherein the surfactant in the first mixture, the second mixture, the third mixture, or a combination thereof includes a nonionic surfactant, an anionic surfactant, or a combination thereof.

20. The method according to claim 19, wherein the nonionic surfactant includes an alkoxylate surfactant, a polymer surfactant, or a combination thereof.

21. The method according to claim 20, wherein the alkoxylate surfactant comprises an alcohol, an alkylphenol, an amine, an amide, an arylphenol, a fatty acid or a fatty acid ester, or a combination thereof, and the alkoxylate surfactant is alkoxylated in an amount of 1 to 50 equivalents.

22. The method according to claim 20, wherein the polymer surfactant includes an A-B or A-B-A type block polymer containing blocks of polyethylene oxide and polypropylene oxide, an alkanol, an A-B-C type block copolymer containing polyethylene oxide and polypropylene oxide, a comb polymer, or a combination thereof.

23. The method according to claim 20, wherein the polymer surfactant comprises poloxamer or acrylic copolymer.

24. The method according to claim 19, wherein the anionic surfactant comprises a sulfonate or a carboxylate.

25. The method according to claim 24, wherein the sulfonate comprises lignin sulfonate, condensed naphthalene sulfonate, or a salt thereof.

26. The method according to claim 24, wherein the carboxylate includes an alkyl carboxylate, an alkylphenol ethoxylate, a polycarboxylic acid, or a carboxylated alcohol.

27. The method according to claim 1, wherein the pesticide formulation contains at least 65% (w / w) of the pesticide active substance based on the total weight of the formulation.

28. A pesticide preparation manufactured by the method described in any one of claims 1 to 27.

29. A pesticide formulation comprising at least one pesticide active substance in a mixture of water, an aqueous surfactant, and a thickener, at least about 57 to about 76% (w / w) based on the total weight of the formulation, and in the form of a shear-thickened gel.

30. The pesticide formulation according to claim 29, having a viscosity of more than 2000 cP.

31. The pesticide formulation according to claim 29, wherein, upon stirring, the viscosity of the pesticide formulation decreases to a viscosity in the range of approximately 200 cP to approximately 1000 cP or approximately 400 cP to approximately 800 cP.

32. The pesticide formulation according to claim 29, wherein the pesticide active substance has a density in the range of about 1.0 to 2.0 g / mL.

33. The pesticide formulation according to claim 29, wherein the pesticide active substance has a melting point of over 50°C.

34. The pesticide formulation according to claim 29, wherein the pesticide active substance has a water solubility of less than approximately 1000 mg / L.

35. The pesticide formulation according to claim 29, wherein the concentration of the pesticide active substance in the pesticide formulation is at least about 750 g / L.

36. The pesticide formulation according to claim 35, wherein the concentration of the pesticide active substance in the pesticide formulation is in the range of about 750 g / L to about 1000 g / L, about 800 g / L to about 950 g / L, about 800 g / L to about 900 g / L, or about 825 g / L to about 875 g / L.

37. The pesticide formulation according to claim 29, wherein the pesticide active substance comprises an insecticide selected from the group consisting of abamectin, chlorantraniliprole, clothianidin, cyantraniliprole, ethiprole, fipronil, flubendiamide, flupyradiflon, imidacloprid, methiocarb, spinetram, spinosad, sulfoxaflor, tefluthrin, ticlopride, thiamethoxam, and thiodicarb.

38. The pesticide formulation according to claim 37, wherein the insecticide comprises clothianidin.

39. The pesticide formulation according to claim 29, wherein the pesticide active substance comprises a fungicide selected from the group consisting of azoxystrobin, β-cyfluthrin, carbendazim, carbendazim, cyproconazole, epoxyconazole, phenamidon, fluazinam, fludioxynil, fluopyram, fluoxastrobin, fluquinconazole, ipconazole, iprodione, isothianil, mefentrifluconazole, metalaxyl, metalaxyl-M, metminostrobin, pencyclon, penflufen, picarbtrazox, picoxystrobin, procymidone, propiconazole, prothioconazole, pyraclostrobin, tebuconazole, triadimenol, and trifloxystrobin.

40. The pesticide formulation according to claim 29, wherein the pesticide active substance comprises at least mefentrifluconazole and fluopyram.

41. The pesticide formulation according to claim 29, wherein the surfactant includes a nonionic surfactant, an anionic surfactant, or a combination thereof.

42. The pesticide formulation according to claim 29, wherein the nonionic surfactant is an alkoxylate surfactant, a polymer surfactant, or a combination thereof.

43. The agrochemical formulation according to claim 42, wherein the alkoxylate surfactant comprises an alcohol, alkylphenol, amine, amide, arylphenol, fatty acid or fatty acid ester, or a combination thereof, and the alkoxylate surfactant is alkoxylated in an amount of 1 to 50 equivalents.

44. The pesticide formulation according to claim 43, wherein the polymer surfactant is an A-B or A-B-A type block polymer containing blocks of polyethylene oxide and polypropylene oxide, an alkanol, an A-B-C type block copolymer containing polyethylene oxide and polypropylene oxide, a comb-shaped polymer, or a combination thereof.

45. The pesticide formulation according to claim 43, wherein the polymer surfactant comprises poloxamer, acrylic copolymer, or a combination thereof.

46. The pesticide formulation according to claim 41, wherein the anionic surfactant comprises a sulfonate, a carboxylate, or a combination thereof.

47. The pesticide formulation according to claim 46, wherein the sulfonate comprises lignin sulfonate, condensed naphthalene sulfonate, or a salt thereof.

48. The pesticide formulation according to claim 46, wherein the carboxylate comprises an alkyl carboxylate, an alkylphenol ethoxylate, a polycarboxylic acid, a carboxylated alcohol, or a combination thereof.

49. The pesticide formulation according to claim 29, comprising at least 65% (w / w) of the pesticide active substance based on the total weight of the formulation.

50. An article for distributing a pesticide preparation according to any one of claims 29 to 49, A container with a mixing blade attached, A pesticide preparation according to any one of claims 29 to 49, provided in the container and in contact with the mixing blade. An article comprising, wherein the mixing blade is configured to facilitate the phase transition of the pesticide formulation from a gel to a fluid.

51. It's a kit, A container with a mixing blade attached, A pesticide preparation according to any one of claims 29 to 49 A kit that includes this.

52. A method for treating a substrate with a pesticide formulation, comprising applying the pesticide formulation described in any one of claims 29 to 49 to the substrate.

53. The method according to claim 52, further comprising stirring the pesticide formulation to promote the phase transition of the pesticide formulation from a gel to a fluid.

Images