Agrochemical composition

Abstract

The present invention relates to agrochemical compositions, methods of making the agrochemical compositions, agrochemical formulations, methods of making the agrochemical formulations, and methods of protecting crops using the agrochemical formulations.

Description

Technical Field

[0001] The present invention relates to an agrochemical composition, a method for producing the agrochemical composition, an agrochemical formulation, a method for producing the agrochemical formulation, and a method for protecting crops using the agrochemical formulation. Background Art

[0002] Agrochemical formulations are conventionally used for protecting crops. Among these agrochemical formulations, capsule suspensions are formulations comprising a dispersion of an agrochemically active ingredient, the droplets of which are contained in the form of microcapsules in a polymer wall.

[0003] Such microcapsule formulations are typically formed by interfacial polymerization using monomers that react at the droplet interface to form a polymer composed of a polyurea shell. In addition to providing protection from chemical or photodegradation (if desired), they also provide controlled release of the active substance upon application. The incorporation of synthetic polymers in such formulations inevitably leads to the introduction of non-biodegradable polymers in the form of microscopic plastic particles, known as microplastics, which have been linked to causing environmental damage when such products are applied to crops. A further disadvantage of such capsule suspensions is the need for additional ingredients to prevent premature release of the active substance during storage and subsequent degradation of the product's physical properties prior to use.

[0004] In “Ethyl cellulose polymer microspheres for controlled release ofnorfluazon”, Jose IPerez- Esmeralda Morillo, Celia Maqueda, and Juan MGines Pest Management Sci 57:688-694 (2001), DOI:10.1002 / ps.339, describe the preparation of microcapsules using a solvent evaporation technique. In this method, the agrochemical active ingredient and a polymer are co-dissolved in a volatile, water-immiscible solvent, such as chloroform and o-xylene. This solution is then emulsified into an aqueous phase, and the microspheres are collected after solvent diffusion / evaporation and polymer precipitation. This complex process involves the use of non-biodegradable solvents, their evaporation, and subsequent filtration, washing, and drying of the resulting microcapsules.

[0005] It is an object of the present invention to overcome at least some of the disadvantages of the prior art, or to provide a commercially useful alternative thereto.

[0006] Another object of the present invention is to provide stable compositions of agrochemical active ingredients that form microcapsules when diluted with water just before application and / or that avoid the use of non-biodegradable polymers that lead to the introduction of microplastics into the environment.

[0007] Another object of the present invention is to provide such a composition which, upon dilution with water, forms microcapsules without evaporation of the solvent used to dissolve the biodegradable polymer and / or without subsequent isolation and / or drying of the microcapsules.

[0008] Another object of the present invention is to provide a biodegradable formulation comprising a microcapsule suspension of an agrochemical active ingredient, which effectively reduces the amount of the agrochemical active ingredient lost due to volatility to a level comparable to that of known capsule suspension formulations (e.g. Standard The results were similar to those of the oxadiazon CS formulation.

[0009] Another object of the present invention is to provide a biodegradable formulation comprising a microcapsule suspension of an agrochemical active ingredient, said biodegradable formulation being comparable to known capsule suspension formulations (e.g. ) provides equivalent or improved control of weeds, pests, insects, etc., i.e., efficacy. Summary of the Invention

[0010] In a first aspect, the present invention provides a composition comprising:

[0011] Agrochemical active ingredients;

[0012] water-miscible organic solvents;

[0013] a first water-immiscible organic solvent;

[0014] emulsifiers;

[0015] biodegradable polymers; and

[0016] an optional second water-immiscible organic solvent;

[0017] The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0018] In a second aspect, the present invention provides a method of making the composition of the first aspect, the method comprising:

[0019] The biodegradable polymer is combined with a first water-immiscible organic solvent to form

[0020] forming a first mixture;

[0021] adding a water-miscible organic solvent and optionally a second water-immiscible organic solvent to the first mixture to form a second mixture;

[0022] adding an agrochemical active ingredient to the second mixture to form a third mixture; and adding an emulsifier to the third mixture;

[0023] The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0024] In a third aspect, the present invention provides a method of making the composition of the first aspect, the method comprising:

[0025] combining a biodegradable polymer with a water-miscible organic solvent to form a first mixture;

[0026] adding a first water-immiscible organic solvent and optionally a second water-immiscible organic solvent to the first solution to form a second mixture;

[0027] adding an agrochemical active ingredient to the second mixture to form a third mixture; and adding an emulsifier to the third mixture;

[0028] The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0029] In a fourth aspect, the present invention provides a formulation comprising:

[0030] water;

[0031] Agrochemical active ingredients;

[0032] water-miscible organic solvents;

[0033] a first water-immiscible organic solvent;

[0034] emulsifiers;

[0035] biodegradable polymers; and

[0036] an optional second water-immiscible organic solvent;

[0037] wherein the agrochemical active ingredient is soluble in a water-miscible organic solvent and / or a first water-immiscible organic solvent and / or a mixture of a water-miscible organic solvent and a first water-immiscible organic solvent;

[0038] wherein the formulation comprises microcapsules having a wall formed at least in part from a biodegradable polymer, wherein the microcapsules contain at least a portion of the agrochemically active ingredient;

[0039] The D50 median diameter of the microcapsules is 5 μm to 50 μm.

[0040] In a fifth aspect, the present invention provides a method of making the formulation of the fourth aspect, the method comprising:

[0041] The composition of the first aspect is added to water.

[0042] In a sixth aspect, the present invention provides a method of protecting crops, the method comprising applying the formulation of the fourth aspect to the crops.

[0043] In a seventh aspect, the present invention provides a method of making the composition of the first aspect, the method comprising:

[0044] combining a biodegradable polymer with a first water-immiscible organic solvent to form a first mixture;

[0045] adding a water-miscible organic solvent and optionally a second water-immiscible organic solvent to the first mixture to form a second mixture;

[0046] adding an emulsifier to the second mixture to form a third mixture; and

[0047] adding an agrochemical active ingredient to the third mixture;

[0048] The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0049] In an eighth aspect, the present invention provides a method of making the composition of the first aspect, the method comprising:

[0050] combining a biodegradable polymer with a water-miscible organic solvent to form a first mixture;

[0051] adding a first water-immiscible organic solvent and optionally a second water-immiscible organic solvent to the first solution to form a second mixture;

[0052] adding an emulsifier to the second mixture to form a third mixture;

[0053] adding an agrochemical active ingredient to the third mixture;

[0054] The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0055] In a ninth aspect, the present invention provides a composition for admixture with an agrochemical active ingredient, the composition comprising:

[0056] water-miscible organic solvents;

[0057] a first water-immiscible organic solvent;

[0058] emulsifiers;

[0059] biodegradable polymers; and

[0060] an optional second water-immiscible organic solvent;

[0061] The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0062] It has now been discovered that a composition containing an agrochemical active ingredient can form biodegradable microcapsules when diluted in water, provided that the formulation is prepared using a biodegradable polymer, a water-miscible organic solvent, a first water-immiscible organic solvent, and an emulsifier. Such microcapsules reduce the volatility of the agrochemical active ingredient and provide protection from degradation when the formulation is applied to crops.

[0063] The present invention involves dissolving an agrochemical active ingredient in a biodegradable polymer and a mixture of a water-miscible organic solvent and a first water-immiscible organic solvent, and adding an emulsifier that provides a fine emulsion upon dilution in water. Unexpectedly, without wishing to be bound by theory, upon dilution in water, the biodegradable polymer precipitates out of solution, forming a film at the interface of the emulsion droplets, thereby producing microcapsules of the agrochemical active ingredient contained in the water-miscible solvent and / or the first water-immiscible solvent.

[0064] Advantageously, the compositions and formulations of the present invention have reduced or similar levels of agrochemical active ingredients (e.g., isocyanate, hydroxypropyltrimonium chloride ... The invention aims to reduce the volatility of oxadiazine (oxadiazine and acetochlor) while maintaining the weed control and crop safety aspects of such formulations.

[0065] Advantageously, the compositions and formulations of the present invention provide a reduced rate of degradation compared to known formulations, thereby extending the residual activity of the agrochemical active ingredient and thereby reducing the application rate required for effective pest control.

[0066] Advantageously, with known capsule suspension formulations such as In comparison, the compositions and formulations of the present invention provide equivalent or improved control, ie efficacy, of weeds, pests, insects, etc.

[0067] Additional preferred embodiments of the compositions, formulations, and methods provided herein appear throughout the specification and particularly in the examples.

[0068] Unless expressly indicated to the contrary, each aspect or embodiment as defined herein may be combined with any other aspect or embodiment. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous. DETAILED DESCRIPTION

[0069] Unless otherwise defined herein, scientific and technical terms used in connection with the present invention shall have the meanings commonly understood by those of ordinary skill in the art. The meaning and scope of the terms should be clear, however, in the event of any potential ambiguity, the definitions provided herein take precedence over any dictionary or external definitions.

[0070] As used in the specification and appended claims, the following terms have the indicated meanings unless indicated to the contrary:

[0071] As used herein, the term "agrochemical active ingredient" refers to an ingredient that is active against crop pests and diseases and / or promotes plant growth in agriculture. For example, the term "agrochemical active ingredient" includes biologically active ingredients or plant protection products, such as herbicides, insecticides, fungicides, etc.

[0072] As used herein, the term "water-miscible organic solvent" refers to an organic solvent that can be mixed with water in any ratio without separating into multiple phases, such as into two phases.

[0073] In contrast, as used herein, the term "water-immiscible organic solvent" refers to an organic solvent that is not miscible with water in any ratio without separating into multiple phases, such as into two phases.

[0074] As used herein, the term "biodegradable" refers to an entity that is broken down by natural factors such as microorganisms (eg, bacteria and fungi) and / or abiotic factors such as temperature, UV light, oxygen, etc., such that new biomass is formed.

[0075] For example, as used herein, a biodegradable polymer is a polymer that can be broken down by natural factors such as microorganisms (eg, bacteria and fungi) and / or abiotic factors such as temperature, UV light, oxygen, etc., such that new biomass is formed.

[0076] For example, as used herein, a biodegradable organic solvent is an organic solvent that can be broken down by natural factors such as microorganisms (eg, bacteria and fungi) and / or abiotic factors such as temperature, UV light, oxygen, etc., such that new biomass is formed.

[0077] As used herein, the term "soluble" with respect to a chemical entity means that the entity is soluble in a solvent such that the entity cannot be recovered by ordinary filtration means, and at least 30 parts of the entity dissolve in 100 parts of the solvent. For example, if the agrochemical active ingredient is soluble in a water-miscible organic solvent and / or a first water-immiscible organic solvent and / or a mixture of a water-miscible organic solvent and a first water-immiscible organic solvent, this means that at least 30 parts of the agrochemical active ingredient dissolve in 100 parts of the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or the mixture of a water-miscible organic solvent and a first water-immiscible organic solvent.

[0078] As used herein, the term "emulsifier" refers to an agent that allows the aqueous and organic phases to be blended into an emulsion.

[0079] As used herein, the unit "w / w %" means weight percent based on the total weight of the composition.

[0080] Thus, in a first aspect, there is provided a composition comprising:

[0081] Agrochemical active ingredients;

[0082] water-miscible organic solvents;

[0083] a first water-immiscible organic solvent;

[0084] emulsifiers;

[0085] biodegradable polymers; and

[0086] an optional second water-immiscible organic solvent;

[0087] The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0088] Preferably, the agrochemical active ingredient comprises a herbicide, an insecticide and / or a fungicide. More preferably, the agrochemical active ingredient comprises a herbicide. In one embodiment, the agrochemical active ingredient comprises a herbicide that is effective in controlling or reducing the growth of chickweed.

[0089] In a preferred embodiment, the active ingredient comprises chloroacetanilide. In one embodiment, the agrochemical active ingredient comprises a chloroacetanilide effective to control or reduce the growth of chickweed. In a preferred embodiment, the chloroacetanilide comprises acetochlor.

[0090] In a preferred embodiment, the agrochemical active ingredient comprises an isocyanate. In a preferred embodiment, the agrochemical active ingredients include isoflurane and / or acetochlor. In another preferred embodiment, the agrochemical active ingredient is In a preferred embodiment, the agrochemical active ingredient comprises acetochlor. In another preferred embodiment, the active ingredient consists of acetochlor.

[0091] different Herbicide is a commercially available agricultural herbicide with the chemical formula:

[0092]

[0093] CAS No. 81777-89-1.

[0094] Acetochlor is a commercially available agricultural herbicide having the chemical formula:

[0095]

[0096] CAS No. 34256-82-1.

[0097] Preferably, the agrochemical active ingredient is present in an amount of 30 w / w% to 50 w / w%, more preferably 32 w / w% to 50 w / w%, more preferably 32 w / w% to 49 w / w%, most preferably 35 w / w% to 48 w / w%. Preferably, when the agrochemical active ingredient comprises isocyanate, Isopropylamine Preferably, when the agrochemical active ingredient comprises or consists of acetochlor, the agrochemical active ingredient is present in an amount of 30 w / w% to 50 w / w%, more preferably 32 w / w% to 49 w / w%, and most preferably 35 w / w% to 48 w / w%. Preferably, when the agrochemical active ingredient comprises or consists of acetochlor, the agrochemical active ingredient is present in an amount of 30 w / w% to 50 w / w%, more preferably 35 w / w% to 50 w / w%, and most preferably 38 w / w% to 50 w / w%.

[0098] Preferably, the biodegradable polymer has a dynamic viscosity of 2.0 mPa.s to 20.0 mPa.s. More preferably, the biodegradable polymer has a dynamic viscosity of 3.0 mPa.s to 18.0 mPa.s, or 4.0 mPa.s to 16.0 mPa.s, or 5.0 mPa.s to 15.0 mPa.s, or 6.0 mPa.s to 14.0 mPa.s, or 7.0 mPa.s to 13.0 mPa.s. Still more preferably, the biodegradable polymer has a dynamic viscosity of 8.0 mPa.s to 12.0 mPa.s, or 9.0 mPa.s to 11.0 mPa.s. The dynamic viscosity of the biodegradable polymer is measured by preparing a 5 weight / weight percent solution of the biodegradable polymer in 80% toluene / 20% ethanol at 25°C. Without wishing to be bound by theory, it is believed that biodegradable polymers having dynamic viscosities within these preferred ranges help promote the formation of stable microcapsules of the desired size (eg, 5 μm to 50 μm) upon dilution with water.

[0099] Preferably, the biodegradable polymer comprises a polysaccharide. More preferably, the biodegradable polymer comprises cellulose and / or starch. Still more preferably, the biodegradable polymer comprises ethyl cellulose. In another preferred embodiment, the biodegradable polymer consists of ethyl cellulose. For example, ethyl cellulose is available under the trade name Ethocel TM Standard 10 Premium is commercially available from Dupont. TM Standard 10 Premium is Ethocel TM Standard 10 Premium has a dynamic viscosity of 9.0 to 11.0 mPa.s as a 5 weight / weight % solution in 80% toluene / 20% ethanol at 25°C when measured using an Ubbelohde viscometer, specifically an Anton-Parr MCR 102 viscometer.

[0100] Preferably, the biodegradable polymer is present in an amount of 1% to 5% w / w, more preferably 1.5% to 4.5% w / w, and most preferably 2.0% to 4.0% w / w. Without wishing to be bound by theory, it is believed that the presence of the biodegradable polymer in these preferred ranges helps promote the formation of stable microcapsules of the desired size (e.g., 5 to 50 μm) upon dilution with water.

[0101] Preferably, the water-miscible organic solvent has a dynamic viscosity at 25°C of 2 to 10 mPa.s. More preferably, the water-miscible organic solvent has a dynamic viscosity at 25°C of 3 to 8 mPa.s. Still more preferably, the water-miscible organic solvent has a dynamic viscosity at 25°C of 4 to 7 mPa.s. Most preferably, the water-miscible organic solvent has a dynamic viscosity at 25°C of 4 to 6 mPa.s. Without wishing to be bound by theory, it is believed that dynamic viscosities within these preferred ranges help promote the formation of stable microcapsules of the desired size (e.g., 5 to 50 μm) upon dilution with water.

[0102] Preferably, the water-miscible organic solvent is biodegradable.Use of a biodegradable solvent avoids the need to evaporate the solvent used to dissolve the biodegradable polymer and / or the agrochemical active ingredient and subsequently isolate and dry the microcapsules.

[0103] In a preferred embodiment, the water-miscible organic solvent comprises 2-hydroxy-N,N-dimethyl-propionamide. In another preferred embodiment, the water-miscible organic solvent consists of 2-hydroxy-N,N-dimethyl-propionamide. For example, 2-hydroxy-N,N-dimethyl-propionamide is available from BTC / BASF under the trade name AMD 3L is commercially available and has a dynamic viscosity of about 5.1 mPa·s at 25°C.

[0104] Preferably, the water-miscible organic solvent is present in an amount of 2% to 20% by weight. More preferably, the water-miscible organic solvent is present in an amount of 4% to 15% by weight. Most preferably, the water-miscible organic solvent is present in an amount of 5% to 13% by weight. Without wishing to be bound by theory, it is believed that the presence of a water-miscible organic solvent in these preferred ranges helps promote the formation of stable microcapsules of the desired size (e.g., 5 to 50 μm) upon dilution with water.

[0105] Preferably, the molecular weight of the first water-immiscible organic solvent is from 100 g / mol to 300 g / mol. More preferably, the molecular weight of the first water-immiscible organic solvent is from 110 g / mol to 250 g / mol. More preferably, the molecular weight of the first water-immiscible organic solvent is from 120 g / mol to 225 g / mol. Without wishing to be bound by theory, it is believed that molecular weights within these preferred ranges help promote the formation of stable microcapsules of the desired size (e.g., 5 μm to 50 μm) upon dilution with water.

[0106] In a preferred embodiment, the molecular weight of the first water-immiscible organic solvent is from 130 g / mol to 160 g / mol. In an alternative preferred embodiment, the molecular weight of the first water-immiscible organic solvent is from 185 g / mol to 215 g / mol.

[0107] More preferably, the first water-immiscible organic solvent has a dynamic viscosity at 20°C of 1.0 mPa.s to 20.0 mPa.s. More preferably, the first water-immiscible organic solvent has a dynamic viscosity at 20°C of 3.0 mPa.s to 10.0 mPa.s. Still more preferably, the first water-immiscible organic solvent has a dynamic viscosity at 20°C of 3.5 mPa.s to 8.0 mPa.s. Without wishing to be bound by theory, it is believed that dynamic viscosities within these preferred ranges help promote the formation of stable microcapsules of the desired size (e.g., 5 μm to 50 μm) upon dilution with water.

[0108] In a preferred embodiment, the first water-immiscible organic solvent has a dynamic viscosity of 3.0 mPa.s to 5.0 mPa.s at 20° C., or a dynamic viscosity of 3.5 mPa.s to 4.5 mPa.s at 20° C. In an alternative preferred embodiment, the first water-immiscible organic solvent has a dynamic viscosity of 6.5 mPa.s to 8.5 mPa.s at 20° C., or a dynamic viscosity of 7.0 mPa.s to 8.0 mPa.s at 20° C.

[0109] Preferably, the first water-immiscible organic solvent is biodegradable.Use of a biodegradable solvent avoids the need to evaporate the solvent used to dissolve the biodegradable polymer and / or the agrochemical active ingredient and subsequently isolate and dry the microcapsules.

[0110] Preferably, the first water-immiscible organic solvent comprises n-butyl L-lactate or 2-ethylhexyl L-lactate. For example, n-butyl L-lactate is available from Corbion under the trade name BL commercially available. BL has a molecular weight of 146 g / mol and a dynamic viscosity of 3.9 mPa.s at 20° C. For example, 2-ethylhexyl L-lactate is available from Corbion under the trade name EHL commercially available. EHL has a molecular weight of 202 g / mol and a dynamic viscosity at 20° C. of 7.6 mPa·s.

[0111] Preferably, the first water-immiscible organic solvent is present in an amount of 10% to 50% by weight. More preferably, the first water-immiscible organic solvent is present in an amount of 15% to 45% by weight. Most preferably, the first water-immiscible organic solvent is present in an amount of 20% to 40% by weight. Without wishing to be bound by theory, it is believed that the presence of the first water-immiscible organic solvent in these preferred ranges helps promote the formation of stable microcapsules of the desired size (e.g., 5 to 50 μm) upon dilution with water.

[0112] In a preferred embodiment, the composition comprises a second water-immiscible organic solvent, wherein the second water-immiscible organic solvent comprises n-butyl L-lactate or 2-ethylhexyl L-lactate, with the proviso that the first water-immiscible organic solvent is different from the second water-immiscible organic solvent.

[0113] Preferably, the second water-immiscible organic solvent is biodegradable.Use of a biodegradable solvent avoids the need to evaporate the solvent used to dissolve the biodegradable polymer and / or the agrochemical active ingredient and subsequently isolate and dry the microcapsules.

[0114] Preferably, the second water-immiscible organic solvent is present in an amount of 0% to 10% by weight. More preferably, the second water-immiscible organic solvent is present in an amount of 0% to 7.5% by weight. Most preferably, the second water-immiscible organic solvent is present in an amount of 0% to 5.0% by weight.

[0115] Alternatively, if present, the second water-immiscible organic solvent is preferably present in an amount of 0.5 w / w% to 10 w / w%, more preferably 1.0 w / w% to 7.5 w / w%, and most preferably 1.4 w / w% to 5.0 w / w% or 2.0 w / w% to 5.0 w / w%.

[0116] Preferably, the total amount of water-immiscible organic solvent in the composition is from 10% to 60% by weight. More preferably, the total amount of water-immiscible organic solvent in the composition is from 15% to 50% by weight. Most preferably, the total amount of water-immiscible organic solvent in the composition is from 20% to 40% by weight.

[0117] Preferably, the weight ratio of the water-miscible organic solvent to the first water-immiscible organic solvent and the second water-immiscible organic solvent is from 1:10 to 1:1. More preferably, the weight ratio of the water-miscible organic solvent to the first water-immiscible organic solvent and the second water-immiscible organic solvent is from 1:8 to 1:1.5. More preferably, the weight ratio of the water-miscible organic solvent to the first water-immiscible organic solvent and the second water-immiscible organic solvent is from 1:5 to 1:2. Most preferably, the weight ratio of the water-miscible organic solvent to the first water-immiscible organic solvent and the second water-immiscible organic solvent is from 1:4 to 1:3. Without wishing to be bound by theory, it is believed that the weight ratio of the water-miscible organic solvent to the first water-immiscible organic solvent and the second water-immiscible organic solvent within these preferred ranges helps promote the formation of stable microcapsules of the desired size (e.g., 5 μm to 50 μm) upon dilution with water.

[0118] Preferably, the emulsifier has a dynamic viscosity at 20°C of 500 to 2500 mPa.s, or a dynamic viscosity at 20°C of 750 to 2000 mPa.s. More preferably, the emulsifier has a dynamic viscosity at 20°C of 1000 to 1800 mPa.s. Most preferably, the emulsifier has a dynamic viscosity at 20°C of 1100 to 1500 mPa.s.

[0119] Preferably, the emulsifier comprises ethoxylated propoxylated polyarylphenol. In another preferred embodiment, the emulsifier consists of ethoxylated propoxylated polyarylphenol. The ethoxylated propoxylated polyarylphenol has a dynamic viscosity of 1300 mPa.s at 20°C and is available from Azelis under the trade name Without wishing to be bound by theory, it is believed that being an emulsifier for the ethoxylated propoxylated polyarylphenol helps promote the formation of stable microcapsules of the desired size (eg, 5 to 50 μm) upon dilution with water.

[0120] Preferably, the emulsifier is biodegradable.

[0121] Preferably, the emulsifier is present in an amount of 5 w / w% to 30 w / w%. More preferably, the emulsifier is present in an amount of 7.5 w / w% to 27.5 w / w%. More preferably, the emulsifier is present in an amount of 10 w / w% to 25 w / w%. Most preferably, the emulsifier is present in an amount of 12 w / w% to 22.5 w / w% or 12 w / w% to 20 w / w%. Without wishing to be bound by theory, it is believed that the emulsifier present in these preferred ranges helps to promote the formation of stable microcapsules of desired size (e.g., 5 μm to 50 μm) when diluted with water.

[0122] Preferably, the composition also comprises a UV stabilizer.

[0123] Preferably, when the composition of the first aspect as described above is added to water, microcapsules having a median diameter of 5 pm to 50 pm are formed, wherein the microcapsules have a wall formed at least in part from a biodegradable polymer, wherein the microcapsules comprise at least a portion of an agrochemically active ingredient. More preferably, when the composition of the first aspect as described above is added to water, microcapsules having a median diameter of 5 pm to 50 pm are formed, wherein the microcapsules have a wall formed from a biodegradable polymer, wherein the microcapsules comprise an agrochemically active ingredient.

[0124] Preferably, the composition comprises, consists essentially of, or consists of:

[0125] 30 to 50 weight / weight % of an agrochemically active ingredient;

[0126] 2 to 20 weight / weight % of a water-miscible organic solvent;

[0127] 10 to 50 weight / weight % of a first water-immiscible organic solvent;

[0128] 10 to 25 weight / weight % of an emulsifier;

[0129] 1 to 5 weight / weight % of a biodegradable polymer; and

[0130] 0 to 10 weight / weight % of a second water-immiscible organic solvent.

[0131] More preferably, the composition comprises, consists essentially of, or consists of:

[0132] 32 to 50 weight / weight % of an agrochemically active ingredient;

[0133] 4 to 15 weight / weight % of a water-miscible organic solvent;

[0134] 15 to 45 weight / weight % of a first water-immiscible organic solvent;

[0135] 10 to 25 weight / weight % of an emulsifier;

[0136] 1.5 to 4.5 weight / weight % of a biodegradable polymer; and

[0137] 0 to 7.5 weight / weight % of a second water-immiscible organic solvent.

[0138] More preferably, the composition comprises, consists essentially of, or consists of:

[0139] 32 to 49 weight / weight percent of an agrochemically active ingredient;

[0140] 4 to 15 weight / weight percent of a water-miscible organic solvent;

[0141] 15 to 45 weight / weight percent of a first water-immiscible organic solvent;

[0142] 10 to 25 weight / weight percent of an emulsifying agent;

[0143] 1.5 to 4.5 weight / weight percent of a biodegradable polymer; and

[0144] 0 to 7.5 weight / weight percent of a second water-immiscible organic solvent.

[0145] Most preferably, the composition comprises, consists essentially of, or consists of:

[0146] 35 to 48 weight / weight percent of an agrochemically active ingredient;

[0147] 5 to 13 weight / weight percent of a water-miscible organic solvent;

[0148] 20 to 40 weight / weight percent of a first water-immiscible organic solvent;

[0149] 12 to 20 weight / weight percent of an emulsifying agent;

[0150] 2.0 to 4.0 weight / weight percent of a biodegradable polymer; and

[0151] 0 to 5.0 weight / weight percent of a second water-immiscible organic solvent.

[0152] Alternatively, most preferably, the composition comprises, consists essentially of, or consists of:

[0153] 35 to 50 weight / weight percent of an agrochemically active ingredient;

[0154] 5 to 13 weight / weight percent of a water-miscible organic solvent;

[0155] 20 to 40 weight / weight percent of a first water-immiscible organic solvent;

[0156] 12 to 22.5 weight / weight % of an emulsifier;

[0157] 2.0 to 4.0 weight / weight % of a biodegradable polymer; and

[0158] 0 to 5.0 weight / weight % of a second water-immiscible organic solvent.

[0159] In a preferred embodiment, the composition consists essentially of:

[0160] an agrochemically active ingredient;

[0161] a water-miscible organic solvent;

[0162] a first water-immiscible organic solvent;

[0163] an emulsifier;

[0164] a biodegradable polymer;

[0165] an optional second water-immiscible organic solvent; and

[0166] an optional U.V. stabilizer;

[0167] wherein the agrochemically active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0168] In a preferred embodiment, the composition consists essentially of:

[0169] an agrochemically active ingredient;

[0170] a water-miscible organic solvent;

[0171] a first water-immiscible organic solvent;

[0172] an emulsifier;

[0173] a biodegradable polymer;

[0174] an optional second water-immiscible organic solvent; and

[0175] an optional U.V. stabilizer;

[0176] wherein the agrochemically active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0177] Preferably, the composition is free of non-biodegradable polymers.

[0178] Preferably, the composition is free of non-biodegradable organic solvents.

[0179] Preferably, the composition is free of non-biodegradable emulsifiers.

[0180] Preferably, the composition contains no non-biodegradable polymers, and no non-biodegradable organic solvents, and no non-biodegradable emulsifiers.

[0181] Preferably, the composition of the first aspect is a clear (ie transparent) solution.

[0182] Each of the agrochemical active ingredient, the water-miscible organic solvent, the first water-immiscible organic solvent, the emulsifier, the biodegradable polymer; and the optional second water-immiscible organic solvent is chemically different from each other. For example, the water-immiscible organic solvent is chemically different from the emulsifier.

[0183] In a second aspect, the present invention provides a method of making the composition of the first aspect, the method comprising:

[0184] combining a biodegradable polymer with a first water-immiscible organic solvent to form a first mixture;

[0185] adding a water-miscible organic solvent and optionally a second water-immiscible organic solvent to the first mixture to form a second mixture;

[0186] adding the agrochemically active ingredient to the second mixture to form a third mixture; and

[0187] adding an emulsifier to the third mixture;

[0188] The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0189] Preferred features of the agrochemically active ingredient, water-miscible organic solvent, first water-immiscible organic solvent, emulsifier, biodegradable polymer and optional second water-immiscible organic solvent are as described above in relation to the composition of the first aspect.

[0190] Preferably, the composition formed by the method of the second aspect is a clear solution.

[0191] Preferably, the method does not comprise evaporating or otherwise removing the first water-immiscible organic solvent and / or the water-miscible organic solvent and / or the optional second water-immiscible organic solvent. More preferably, the method does not comprise evaporating or otherwise removing any of the first water-immiscible organic solvent, the water-miscible organic solvent and the optional second water-immiscible organic solvent.

[0192] In a third aspect, the present invention provides a method of making the composition of the first aspect, the method comprising:

[0193] combining a biodegradable polymer with a water-miscible organic solvent to form a first mixture;

[0194] adding a first water-immiscible organic solvent and optionally a second water-immiscible organic solvent to the first solution to form a second mixture;

[0195] adding the agrochemically active ingredient to the second mixture to form a third mixture; and

[0196] adding an emulsifier to the third mixture;

[0197] The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0198] Preferred features of the agrochemically active ingredient, water-miscible organic solvent, first water-immiscible organic solvent, emulsifier, biodegradable polymer and optional second water-immiscible organic solvent are as described above in relation to the composition of the first aspect.

[0199] Preferably, the composition formed by the method of the third aspect is a clear solution.

[0200] Preferably, the method does not comprise evaporating or otherwise removing the first water-immiscible organic solvent and / or the water-miscible organic solvent and / or the optional second water-immiscible organic solvent. More preferably, the method does not comprise evaporating or otherwise removing any of the first water-immiscible organic solvent, the water-miscible organic solvent and the optional second water-immiscible organic solvent.

[0201] In a fourth aspect, the present invention provides a formulation comprising:

[0202] water;

[0203] Agrochemical active ingredients;

[0204] water-miscible organic solvents;

[0205] a first water-immiscible organic solvent;

[0206] emulsifiers;

[0207] biodegradable polymers; and

[0208] an optional second water-immiscible organic solvent;

[0209] wherein the agrochemical active ingredient is soluble in a water-miscible organic solvent and / or a first water-immiscible organic solvent and / or a mixture of a water-miscible organic solvent and a first water-immiscible organic solvent;

[0210] wherein the formulation comprises microcapsules having a wall formed at least in part from a biodegradable polymer, wherein the microcapsules contain at least a portion of the agrochemically active ingredient;

[0211] The median diameter of the microcapsules is 5 μm to 50 μm.

[0212] Preferred characteristics of the agrochemically active ingredient, the water-miscible organic solvent, the first water-immiscible organic solvent, the emulsifier, the biodegradable polymer; and the optional second water-immiscible organic solvent are as described above in relation to the composition of the first aspect.

[0213] Preferably, the formulation comprises microcapsules having a wall formed from a biodegradable polymer, wherein the microcapsules contain the agrochemical active ingredient.

[0214] Preferably, the D50 median diameter of the microcapsules is from 10 μm to 30 μm, more preferably from 10 μm to 20 μm.

[0215] Preferably, the formulation is free of non-biodegradable polymers.

[0216] Preferably, the formulation is free of non-biodegradable organic solvents.

[0217] Preferably, the formulation is free of non-biodegradable emulsifiers.

[0218] Preferably, the formulation contains no non-biodegradable polymers, and no non-biodegradable organic solvents, and no non-biodegradable emulsifiers.

[0219] In a preferred embodiment, the formulation consists essentially of, or consists of:

[0220] water;

[0221] Agrochemical active ingredients;

[0222] water-miscible organic solvents;

[0223] a first water-immiscible organic solvent;

[0224] emulsifiers;

[0225] biodegradable polymers; and

[0226] an optional second water-immiscible organic solvent;

[0227] Optional UV stabilizer;

[0228] wherein the agrochemical active ingredient is soluble in a water-miscible organic solvent and / or a first water-immiscible organic solvent and / or a mixture of a water-miscible organic solvent and a first water-immiscible organic solvent;

[0229] wherein the formulation comprises microcapsules having a wall formed at least in part from a biodegradable polymer, wherein the microcapsules contain at least a portion of the agrochemically active ingredient;

[0230] The median diameter of the microcapsules is 5 μm to 50 μm.

[0231] In a fifth aspect, the present invention provides a method of making the formulation of the fourth aspect, the method comprising:

[0232] The composition of the first aspect is added to water.

[0233] Preferably, the method of making the formulation of the fourth aspect does not comprise evaporating or otherwise removing the first water-immiscible organic solvent and / or the water-miscible organic solvent and / or the optional second water-immiscible organic solvent. More preferably, the method does not comprise evaporating or otherwise removing any of the first water-immiscible organic solvent, the water-miscible organic solvent and the optional second water-immiscible organic solvent.

[0234] Preferably, the method of making the formulation of the fourth aspect does not comprise filtering and / or washing and / or drying the microcapsules. More preferably, the method does not comprise any of filtering, washing and drying the microcapsules.

[0235] Preferably, the method of making the formulation of the fourth aspect consists of adding the composition of the first aspect to water.

[0236] In a sixth aspect, the present invention provides a method of protecting crops, the method comprising applying the formulation of the fourth aspect to the crops.

[0237] In a preferred embodiment, the crop comprises oilseed rape.

[0238] In a seventh aspect, the present invention provides a method of making the composition of the first aspect, the method comprising:

[0239] combining a biodegradable polymer with a first water-immiscible organic solvent to form a first mixture;

[0240] adding a water-miscible organic solvent and optionally a second water-immiscible organic solvent to the first mixture to form a second mixture;

[0241] adding an emulsifier to the second mixture to form a third mixture; and

[0242] adding an agrochemically active ingredient to the third mixture;

[0243] wherein the agrochemically active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0244] Preferred features of the agrochemically active ingredient, the water-miscible organic solvent, the first water-immiscible organic solvent, the emulsifier, the biodegradable polymer and the optional second water-immiscible organic solvent are as described above in relation to the composition of the first aspect.

[0245] Preferably, the composition formed by the method of the seventh aspect is a clear solution.

[0246] Preferably, the method does not comprise evaporating or otherwise removing the first water-immiscible organic solvent and / or the water-miscible organic solvent and / or the optional second water-immiscible organic solvent. More preferably, the method does not comprise evaporating or otherwise removing any of the first water-immiscible organic solvent, the water-miscible organic solvent and the optional second water-immiscible organic solvent.

[0247] In an eighth aspect, the present application provides a method of manufacturing the composition of the first aspect, the method comprising:

[0248] combining the biodegradable polymer with the water-miscible organic solvent to form a first mixture;

[0249] adding the first water-immiscible organic solvent and the optional second water-immiscible organic solvent to the first solution to form a second mixture;

[0250] adding the emulsifier to the second mixture to form a third mixture;

[0251] adding an agrochemically active ingredient to the third mixture;

[0252] wherein the agrochemically active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0253] Preferred features of the agrochemically active ingredient, the water-miscible organic solvent, the first water-immiscible organic solvent, the emulsifier, the biodegradable polymer and the optional second water-immiscible organic solvent are as described above in relation to the composition of the first aspect.

[0254] Preferably, the composition formed by the method of the eighth aspect is a clear solution.

[0255] Preferably, the method does not comprise evaporating or otherwise removing the first water-immiscible organic solvent and / or the water-miscible organic solvent and / or the optional second water-immiscible organic solvent. More preferably, the method does not comprise evaporating or otherwise removing any of the first water-immiscible organic solvent, the water-miscible organic solvent and the optional second water-immiscible organic solvent.

[0256] In a ninth aspect, the present invention provides a composition for admixture with an agrochemical active ingredient, the composition comprising:

[0257] water-miscible organic solvents;

[0258] a first water-immiscible organic solvent;

[0259] emulsifiers;

[0260] biodegradable polymers; and

[0261] an optional second water-immiscible organic solvent;

[0262] The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

[0263] The composition of the first aspect can be formed by mixing the composition of the ninth aspect with an agrochemical active ingredient. Preferably, the composition of the ninth aspect is emulsified with the agrochemical active ingredient to produce the composition of the first aspect.

[0264] Preferably, before mixing with the agrochemical active ingredient, the composition of the ninth aspect comprises:

[0265] 10% to 20% w / w of a water-miscible organic solvent;

[0266] 40 w / w% to 60 w / w% of a first water-immiscible organic solvent;

[0267] 15 w / w% to 40 w / w% emulsifier;

[0268] 4% to 6% w / w of a biodegradable polymer; and

[0269] 0% to 10% w / w of a second water-immiscible organic solvent.

[0270] Preferably, the composition of the ninth aspect is used with A mixture of agrochemical active ingredients of chlorpyrifos and / or acetochlor.

[0271] When introducing elements of the disclosure or the preferred embodiments thereof, the articles "a", "an", "the" and "said" are intended to mean that there are one or more of the elements. The terms "comprising", "including" and "having" are intended to be inclusive and allow for additional elements.

[0272] The foregoing detailed description has been presented for purposes of illustration and description. It is not intended to be limiting, as the scope of the appended claims is to be given their broadest construction. Many alterations, modifications, and variations will be apparent to an ordinarily skilled artisan having the benefit of this disclosure, and it is contemplated to embody within this description those alternatives that currently exist or are later developed.

[0273] These and other aspects of the present application will now be described with reference to the accompanying drawings, of which:

[0274] Figures la to lh show a comparison of standard oxadiazon CS formulation and oxadiazon ICS formulations of the present application on oilseed rape plants at four different application rates after 14 days. Figures la to lh show a comparison of standard oxadiazon CS formulation and oxadiazon ICS formulations of the present application on oilseed rape plants at four different application rates after 14 days. Figures la to lh show a comparison of standard oxadiazon CS formulation and oxadiazon ICS formulations of the present application on oilseed rape plants at four different application rates after 14 days.

[0275] Figures 2a to 2h show a comparison of standard oxadiazon CS formulation and oxadiazon ICS formulations of the present application on Stellaria media at four different application rates after 17 days. Figures 2a to 2h show a comparison of standard oxadiazon CS formulation and oxadiazon ICS formulations of the present application on Stellaria media at four different application rates after 17 days. Figures 2a to 2h show a comparison of standard oxadiazon CS formulation and oxadiazon ICS formulations of the present application on Stellaria media at four different application rates after 17 days.

[0276] Experimental section

[0277] Dynamic viscosity is measured at 25°C using a standard viscometer such as an Ubbelohde viscometer or an Anton-Parr MCR 102 viscometer, unless otherwise stated.

[0278] Ethocel used in the examples TM The dynamic viscosity of Standard 10 Premium is measured in the form of a 5% w / w solution in 80% toluene / 20% ethanol at 25°C and measured using an Anton-Parr MCR 102 viscometer. TM The dynamic viscosity of Standard 10 Premium is measured in the form of a 5% w / w solution in 80% toluene / 20% ethanol at 25°C and measured using an Anton-Parr MCR 102 viscometer.

[0279] The median diameter (D50 median particle size) of the microcapsules is measured by laser diffraction using a Malvern 300 Mastersizer.

[0280] Solubility is measured at 20°C using OECD Test Guideline 105.

[0281] Example

[0282] The invention will now be described with respect to several embodiments.

[0283] Example 1

[0284] different Oxychloride 360g / l in situ capsule suspension concentrate (ICS) formulation (Formulation A)

[0285]

[0286] Preparation method

[0287] Ethocel 10 was weighed into a 10 mL sample vial containing Purasolv BL. The vial was sealed with a lid and transferred to a magnetic stirring hot plate and mixed using a stirring bar at 600 rpm. The mixture was stirred at room temperature for 30 minutes.

[0288] Add Agnique AMD3L to the mixture followed by Iso The mixture was stirred on a magnetic stirring hot plate for 3 hours, after which Soprophor 796 / P was added. The mixture was stirred until the ethylcellulose was completely dissolved.

[0289] Example 2

[0290] different Oxychloride 360g / l in situ capsule suspension concentrate (ICS) formulation (Formulation B)

[0291]

[0292] Preparation method

[0293] Ethocel 10 was weighed into a 10 mL sample vial containing Purasolv EHL. The vial was sealed with a lid and transferred to a magnetic stirring hot plate and mixed using a stirring bar at 600 rpm. The mixture was stirred at room temperature for 30 minutes.

[0294] Purasolv BL and Agnique AMD3L were added to the mixture followed by the addition of The mixture was stirred on a magnetic stirring hot plate for 3 hours, after which Soprophor 796 / P was added. The mixture was stirred until the ethylcellulose was completely dissolved.

[0295] Example 3

[0296] different Oxychloride 360g / l in situ capsule suspension concentrate (ICS) formulation (Formulation C)

[0297]

[0298] Preparation method

[0299] Ethocel 10 was weighed into a 10 mL sample vial containing Purasolv EHL. The vial was sealed with a lid and transferred to a magnetic stirring hot plate and mixed using a stirring bar at 600 rpm. The mixture was stirred at room temperature for 30 minutes.

[0300] Purasolv BL and Agnique AMD3L were added to the mixture followed by the addition of The mixture was stirred on a magnetic stirring hot plate for 3 hours, after which Soprophor 796 / P was added. The mixture was stirred until the ethylcellulose was completely dissolved.

[0301] Example 4

[0302] different Oxychloride 360g / l in situ capsule suspension concentrate (ICS) formulation (Formulation D)

[0303]

[0304] Preparation method

[0305] Ethocel 10 was weighed into a 10 mL sample vial containing Purasolv EHL. The vial was sealed with a lid and transferred to a magnetic stirring hot plate and mixed using a stirring bar at 600 rpm. The mixture was stirred at room temperature for 30 minutes.

[0306] Purasolv BL and Agnique AMD3L were added to the mixture followed by the addition of The mixture was stirred on a magnetic stirring hot plate for 3 hours, after which Soprophor 796 / P was added. The mixture was stirred until the ethylcellulose was completely dissolved.

[0307] Example 5

[0308] different Oxychloride 360g / l in situ capsule suspension concentrate (ICS) formulation (Formulation E)

[0309]

[0310] Preparation method

[0311] Ethocel 10 was weighed out into a 10 mL sample vial containing Purasolv EHL. The vial was sealed with a cap and transferred to a magnetic stir heating station and mixed using a stir bar at 600 rpm. The mixture was allowed to stir at room temperature for 30 minutes.

[0312] To the mixture was added Purasolv BL and Agnique AMD3L followed by carboxin and the mixture was stirred on a magnetic stir heating station for 3 hours after which Soprophor 796 / P was added. The mixture was stirred until the ethyl cellulose was completely dissolved.

[0313] Example 6

[0314] carboxin 360 g / l in situ capsule suspension concentrate (ICS) formulation (Formulation F)

[0315]

[0316] Preparation method Ethocel 10 was weighed out into a 10 mL sample vial containing Purasolv EHL. The vial was sealed with a cap and transferred to a magnetic stir heating station and mixed using a stir bar at 600 rpm. The mixture was allowed to stir at room temperature for 30 minutes.

[0317] To the mixture was added Purasolv BL and Agnique AMD3L followed by

[0318] carboxin and the mixture was stirred on a magnetic stir heating station for 3 hours after which Soprophor 796 / P was added. The mixture was stirred until the ethyl cellulose was completely dissolved.

[0319] Example 7 carboxin 360 g / l in situ capsule suspension concentrate (ICS) formulation (Formulation G)

[0320]

[0321]

[0322] Preparation method

[0323] ​​Ethocel 10 was weighed into a 10 mL sample vial containing Purasolv EHL. The vial was sealed with a lid and transferred to a magnetic stirring hot plate and mixed using a stirring bar at 600 rpm. The mixture was stirred at room temperature for 30 minutes.

[0324] Purasolv BL and Agnique AMD3L were added to the mixture followed by the addition of The mixture was stirred on a magnetic stirring hot plate for 3 hours, after which Soprophor 796 / P was added. The mixture was stirred until the ethylcellulose was completely dissolved.

[0325] Example 8

[0326] different Oxalazine 480g / l in situ capsule suspension concentrate (ICS) formulation (Formulation H)

[0327]

[0328] Preparation method

[0329] Ethocel 10 was weighed into a 10 mL sample vial containing Purasolv EHL. The vial was sealed with a lid and transferred to a magnetic stirring hot plate and mixed using a stirring bar at 600 rpm. The mixture was stirred at room temperature for 30 minutes.

[0330] Purasolv BL and Agnique AMD3L were added to the mixture followed by the addition of The mixture was stirred on a magnetic stirring hot plate for 3 hours, after which Soprophor 796 / P was added. The mixture was stirred until the ethylcellulose was completely dissolved.

[0331] Example 9

[0332] Acetochlor 360 g / l in situ capsule suspension concentrate (ICS) formulation (Formulation I)

[0333]

[0334] Preparation method

[0335] Weigh Ethocel 10 into a 10 mL sample vial. Add Purasolv BL, Agnique AMD3L, Purasolv EHL, and a stir bar to the vial. Seal the vial with a lid, transfer it to a magnetic stirring hot plate, and mix with a stir bar at 600 rpm. Stir the mixture at 40°C for 30 minutes.

[0336] Acetochlor was added to the mixture, and the mixture was stirred at 40° C. on a magnetic stirring hot plate for 3 hours before the addition of Soprophor 796 / P. The mixture was stirred at room temperature until the ethylcellulose was completely dissolved and the solution was homogeneous.

[0337] Example 10

[0338] Acetochlor 480 g / l in situ capsule suspension concentrate (ICS) formulation (Formulation J)

[0339]

[0340] Preparation method

[0341] Weigh Ethocel 10 into a 10 mL sample vial. Add Purasolv BL, Agnique AMD3L, Purasolv EHL, and a stir bar to the vial. Seal the vial with a lid, transfer it to a magnetic stirring hot plate, and mix with a stir bar at 600 rpm. Stir the mixture at 40°C for 30 minutes.

[0342] Acetochlor was added to the mixture, and the mixture was stirred at 40° C. on a magnetic stirring hot plate for 3 hours before the addition of Soprophor 796 / P. The mixture was stirred at room temperature until the ethylcellulose was completely dissolved and the solution was homogeneous.

[0343] Comparative Example 11

[0344] Acetochlor 360g / l Emulsifiable Concentrate (EC) formulation (acetochlor EC control)

[0345]

[0346] Preparation method

[0347] Acetochlor was weighed into a 10 mL sample vial. Purasolv BL, Agnique AMD3L, Purasolv EHL, Soprophor 796 / P, and a stir bar were added to the vial. The vial was sealed with a lid, transferred to a magnetic stirring hot plate, and mixed at 600 rpm using a stir bar. The mixture was mixed until uniform.

[0348] Vapor studies

[0349] The following method is used to deal with the Laboratory testing of the volatility of an in situ capsule suspension (ICS) formulation of oxadiazon. Sufficient unsterilized topsoil for the test was passed through a 14 mesh sieve twice to remove large particles and debris. Fine particles were then removed through a 30 mesh sieve, leaving topsoil of medium-sized particles. In a tray measuring 32.4 cm × 45.7 × 1.9 cm, 240 grams of this medium-sized topsoil was evenly spread to a thickness of about one to two millimeters over an area of ​​about 27.9 cm × 41.3 cm. The topsoil was then sprayed with enough isoflurane to remove the fine particles. The oxadiazol test formulation was prepared to provide 0.0712 grams of active ingredient in 20 mL of water. The chlorpyrifos test formulation was applied to the soil at a rate of 1.0 kg ai (active ingredient) / hectare. Immediately after treatment, the soil was sealed in glass jars where it was briefly retained until use.

[0350] For different To prepare the oxadiazol test formulation, four 22 mm × 300 mm glass chromatography columns (each including a coarse sintered glass barrier at the bottom) were connected to a multi-port air manifold by their bottom ends, which delivered equal air pressure to multiple columns simultaneously. 59 grams of treated topsoil was placed in each of the four columns, filling a column length of approximately 200 mm. After soil treatment, once the columns were installed, a slow air flow (0.5 liters / minute / column) from the multi-port air manifold was passed through the soil in each column, and then bubbled through a mixture of acetonitrile: water (80:20), resulting in the volatile isocyanate. The oxadiazolidine was dissolved in the solvent. The time between soil treatment and the start of airflow was about one hour. The airflow lasted for about 20 hours. A 1 mL aliquot of the solution was analyzed for isocyanate using a standard high performance liquid chromatography (HPLC) assay. Oxychloride content.

[0351] Record the total amount of each sample in micrograms. The oxadiazol content was compared with the isoflurane content of the samples applied to the soil. The oxadiazol content was compared (in percentage).

[0352] The test results given in Table 1 show that the ICS formulation of the present invention effectively reduces the amount of foreign matter lost due to volatility. The amount of oxadiazol is reduced to (Standard The results were similar to those of the oxadiazon CS formulation.

[0353] Table 1

[0354]

[0355] Laboratory testing of the volatility of an in situ capsule suspension (ICS) formulation of acetochlor was performed in the following manner. Enough unsterilized topsoil for the test was passed through a 14-mesh sieve twice to remove large particles and debris. Fine particles were then removed through a 30-mesh sieve, leaving topsoil of medium-sized particles. In a tray measuring 32.4 cm × 45.7 × 1.9 cm, 240 grams of this medium-sized topsoil was evenly spread to a thickness of about one to two millimeters over an area of ​​about 27.9 cm × 41.3 cm. The topsoil was then sprayed with enough acetochlor test formulations to provide 0.0712 grams of active ingredient in 20 mL of water. In this way, the acetochlor test formulation was applied to the soil at a rate of 1.0 kg ai (active ingredient) / hectare. Immediately after treatment, the soil was enclosed in a glass jar where it was briefly retained until use.

[0356] For each acetochlor test formulation, four 22mm × 300mm glass chromatographic columns (each comprising a coarse sintered glass barrier at the bottom) are connected to a multiport air manifold by their bottom ends, which delivers equal air pressure to multiple posts simultaneously. 40 grams of treated topsoil are placed in each of the four posts, filling a column length of approximately 200mm. After soil treatment, once the post is installed, a slow airflow (0.25 liters / minute / post) from the multiport air manifold is immediately passed through the soil in each post, then bubbled through a mixture of acetonitrile: water (80:20), causing the volatile acetochlor to dissolve in the solvent. The time between soil treatment and the start of airflow is approximately one hour. Airflow lasts for approximately 20 hours. The acetochlor content of 1mL aliquots of the solution is analyzed using standard high performance liquid chromatography (HPLC).

[0357] The total acetochlor content in each sample was recorded in micrograms and compared to the acetochlor content of the sample applied to the soil (as a percentage).

[0358] The test results given in Table 2 show that the ICS formulation of the present invention effectively reduces the amount of acetochlor lost due to volatility to a greater extent than the acetochlor EC formulation containing the same solvent and emulsifier but without ethylcellulose.

[0359] Table 2

[0360]

[0361] Crop safety studies

[0362] The following method was used to determine the effect of application of an The phytotoxicity of oxalool ICS preparations is relative to that of standard isocyanate. Testing of the Phytotoxicity of the Formulations of CS. Formulation A was tested on rapeseed (Brassica napus) using a LED hydroponic system A-03 supplied by AQUA, with 4 seeds each sown in 7 replicated units of plant sponges, providing continuous watering and LED lighting (16 hours on, 8 hours off in a 24-hour cycle). Five such hydroponic tanks were set up with 5 liters of water containing a nutrient solution (50 ml containing a total of N 23%, P2O5 9%, K2O 30%, MgO 7%, CaO 15%, EDTA-FE 0.3%, EDTA-Mn 0.06%, EDTA-Cu 0.005%, EDTA-Zn 0.01%, B 0.1%) and different concentrations of formulation A (0.129 ml - equivalent to 1 / 64 of the use rate, 0.064 ml - equivalent to 1 / 128 of the use rate, 0.032 ml - equivalent to 1 / 256 of the use rate, 0.016 ml - equivalent to 1 / 512 of the use rate), and the phytotoxic effects on the growth of rapeseed plants were evaluated after 14 days. An untreated control was also included in the test.

[0363] Standard isocyanate prepared by conventional interfacial polymerization The test was repeated with the oxadiazon CS formulation (diluted in the nutrient solution at the same ratio). To prevent cross-contamination, a plastic cover was placed around each tank, which was replaced before each new test formulation was applied to the nutrient solution. The test was evaluated by observing the phytotoxic effects on the rape plants on the 14th day after treatment.

[0364] As shown in Figures 1a to 1h, the phytotoxic effects were compared on day 14. Figure 1a shows the effect of the application rate of 1 / 64N on the plant by (comparison with) standard isocyanate. Figure 1c shows the results of the treatment of rapeseed plants with the CS formulation of chlorpyrifos at an application rate of 1 / 128N. Figure 1e shows the results of a comparison of the results of a 1 / 256N application rate on rapeseed plants treated with a standard isocyanate CS formulation. Figure 1g shows the results of the treatment of rapeseed plants with the application rate of 1 / 512N and the treatment of rapeseed plants with the standard isocyanate CS formulation. Figure 1b shows the rape plants treated with the CS formulation of chlorpyrifos at an application rate of 1 / 64N. Figure 1d shows the rape plants treated with the isoflurane ICS formulation at an application rate of 1 / 128N. Figure 1f shows the rape plants treated with the ICS formulation of chlorpyrifos at an application rate of 1 / 256N. Figure 1h shows the application rate of 1 / 512N treated with isoflurane ICS formulations. Rapeseed plants treated with a chlorpyrifos ICS formulation.

[0365] The chlorosis and vigorous growth areas of rapeseed were observed and compared between the tested preparations. Compared with the chlorfenapyr CS product, Formulation A provided equivalent crop safety.

[0366] Potency studies

[0367] The following was done to determine the difference relative to the standard The efficacy of oxadiazon CS formulations applied to weeds Testing of the efficacy of the oxadiazine ICS formulation. One trial of Formulation A was conducted on chickweed seeds (Stellaria media) using an LED hydroponic system A-03 supplied by AQUA, with 4 seeds each sown in 7 separate replicates of planted sponges, provided with continuous watering and LED lighting (16 hours on, 8 hours off in a 24 hour cycle). Five such hydroponic tanks were set up with 5 liters of water containing a nutrient solution (50 ml containing a total of 23% N, 9% P2O5, 30% K2O, 7% MgO, 15% CaO, 0.3% EDTA-FE, 0.06% EDTA-Mn, 0.005% EDTA-Cu, 0.01% EDTA-Zn, 0.1% B) and different concentrations of formulation A (0.129 ml - equivalent to 1 / 64 of the use rate, 0.064 ml - equivalent to 1 / 128 of the use rate, 0.032 ml - equivalent to 1 / 256 of the use rate, 0.016 ml - equivalent to 1 / 512 of the use rate), and the effect on chickweed growth was evaluated after 17 days. An untreated control was also included in the experiment.

[0368] Standard isocyanate prepared by conventional interfacial polymerization The test was repeated with a CS formulation of chlorpyrifos (diluted in the nutrient solution at the same ratio). To prevent cross-contamination, a plastic cover was placed around each tank, which was replaced before each new test formulation was applied to the nutrient solution. The test was evaluated 17 days after treatment by observing the effects on chickweed.

[0369] The effect of different application rates was compared at day 17 as shown in Figures 2a to 2h. Figure 2a shows the effect of (comparative) standard Iso treated with the Isoxaben CS formulation at an application rate of 1 / 128 N. Figure 2c shows the effect of (comparative) standard Iso treated with the Isoxaben CS formulation at an application rate of 1 / 128 N. Figure 2c shows the effect of (comparative) standard Iso treated with the Isoxaben CS formulation at an application rate of 1 / 128 N. Figure 2c shows the effect of (comparative) standard Iso treated with the Isoxaben CS formulation at an application rate of 1 / 128 N. Figure 2c shows the effect of (comparative) standard Iso treated with the Isoxaben CS formulation at an application rate of 1 / 128 N. Figure 2c shows the effect of (comparative) standard Iso treated with the Isoxaben CS formulation at an application rate of 1 / 128 N. Figure 2c shows the effect of (comparative) standard Iso treated with the Isoxaben CS formulation at an application rate of 1 / 128 N. Figure 2c shows the effect of (comparative) standard Iso treated with the Isoxaben CS formulation at an application rate of 1 / 128 N. Figure 2c shows the effect of (comparative) standard Iso

[0370] The test results show that the inventive formulation A provides equivalent control compared to (comparative) standard Iso treated with the Isoxaben CS formulation at an application rate of 1 / 128 N. Figure 2c shows the effect of (comparative) standard Iso

Claims

1. A composition comprising: Agrochemical active ingredients; water-miscible organic solvents; a first water-immiscible organic solvent; emulsifiers; biodegradable polymers; and an optional second water-immiscible organic solvent; The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

2. The composition according to claim 1, wherein the composition comprises: 30% to 50% by weight of the agrochemical active ingredient; 2 w / w % to 20 w / w % of said water-miscible organic solvent; 10% to 50% by weight of the first water-immiscible organic solvent; 10 w / w% to 25 w / w% of said emulsifier; 1 w / w% to 5 w / w% of said biodegradable polymer; and 0% to 10% by weight of the second water-immiscible organic solvent.

3. The composition according to any one of the preceding claims, wherein the agrochemically active ingredient comprises a herbicide, an insecticide and / or a fungicide.

4. A composition according to any one of the preceding claims, wherein the agrochemically active ingredient comprises a herbicide.

5. A composition according to any one of the preceding claims, wherein the agrochemical active ingredient comprises an isocyanate. Herbicide.

6. A composition according to any one of the preceding claims, wherein the agrochemically active ingredient comprises acetochlor.

7. The composition according to any one of the preceding claims, wherein the biodegradable polymer has a dynamic viscosity of 2.0 mPa.s to 20.0 mPa.s.

8. The composition of any preceding claim, wherein the biodegradable polymer comprises a polysaccharide.

9. A composition according to any preceding claim, wherein the biodegradable polymer comprises cellulose and / or starch.

10. The composition of any preceding claim, wherein the biodegradable polymer comprises ethylcellulose.

11. The composition according to any one of the preceding claims, wherein the water-miscible organic solvent has a dynamic viscosity at 25°C of 2 to 10 mPa.s.

12. The composition of any one of the preceding claims, wherein the water-miscible organic solvent comprises 2-hydroxy-N,N-dimethyl-propionamide.

13. The composition of any one of the preceding claims, wherein the first water-immiscible organic solvent has a molecular weight of 100 to 300 g / mol.

14. The composition of any one of the preceding claims, wherein the first water-immiscible organic solvent has a dynamic viscosity at 20°C of 3.0 mPa.s to 10.0 mPa.s.

15. The composition of any one of the preceding claims, wherein the first water-immiscible organic solvent comprises n-butyl L-lactate or 2-ethylhexyl L-lactate.

16. The composition of any one of the preceding claims, wherein the composition comprises a second water-immiscible organic solvent, wherein the second water-immiscible organic solvent comprises n-butyl L-lactate or 2-ethylhexyl L-lactate, with the proviso that the first water-immiscible organic solvent is different from the second water-immiscible organic solvent.

17. A composition according to any preceding claim, wherein the emulsifier has a dynamic viscosity at 20°C of from 1100 mPa.s to 1500 mPa.s.

18. The composition of any preceding claim, wherein the emulsifier comprises an ethoxylated propoxylated polyarylphenol.

19. The composition of any preceding claim further comprising a UV stabilizer.

20. The composition of any one of the preceding claims, wherein the weight ratio of the water-miscible organic solvent: the first water-immiscible organic solvent and the second water-immiscible organic solvent is from 1:5 to 1:

2.

21. The composition according to any one of the preceding claims, wherein when the composition is added to water, microcapsules having a D50 median diameter of 5 to 50 μm are formed, wherein the microcapsules have a wall formed at least in part from the biodegradable polymer, wherein the microcapsules contain at least a portion of the agrochemically active ingredient.

22. A method of making a composition according to any one of the preceding claims, the method comprising: combining a biodegradable polymer with a first water-immiscible organic solvent to form a first mixture; adding a water-miscible organic solvent and optionally a second water-immiscible organic solvent to the first mixture to form a second mixture; adding an agrochemically active ingredient to the second mixture to form a third mixture; and adding an emulsifier to the third mixture; The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

23. A method of making a composition according to any one of claims 1 to 21, comprising: combining a biodegradable polymer with a water-miscible organic solvent to form a first mixture; adding a first water-immiscible organic solvent and optionally a second water-immiscible organic solvent to the first solution to form a second mixture; adding an agrochemically active ingredient to the second mixture to form a third mixture; and adding an emulsifier to the third mixture; The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

24. A method of making a composition according to any one of claims 1 to 21, comprising: combining a biodegradable polymer with a first water-immiscible organic solvent to form a first mixture; adding a water-miscible organic solvent and optionally a second water-immiscible organic solvent to the first mixture to form a second mixture; adding an emulsifier to the second mixture to form a third mixture; and adding an agrochemical active ingredient to the third mixture; The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

25. A method of making a composition according to any one of claims 1 to 21, comprising: combining a biodegradable polymer with a water-miscible organic solvent to form a first mixture; adding a first water-immiscible organic solvent and optionally a second water-immiscible organic solvent to the first solution to form a second mixture; adding an emulsifier to the second mixture to form a third mixture; adding an agrochemical active ingredient to the third mixture; The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

26. A preparation comprising: water; Agrochemical active ingredients; water-miscible organic solvents; a first water-immiscible organic solvent; emulsifiers; biodegradable polymers; and an optional second water-immiscible organic solvent; wherein the agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent; wherein the formulation comprises microcapsules having a wall formed at least in part from the biodegradable polymer, wherein the microcapsules contain at least a portion of the agrochemically active ingredient; The D50 median diameter of the microcapsules is 5 μm to 50 μm.

27. A method of making a formulation according to claim 26, the method comprising adding a composition according to any one of claims 1 to 21 to water.

28. A method of protecting crops, the method comprising applying a formulation according to claim 26 to the crops.

29. A composition for mixing with an agrochemical active ingredient, the composition comprising: water-miscible organic solvents; a first water-immiscible organic solvent; emulsifiers; biodegradable polymers; and an optional second water-immiscible organic solvent; The agrochemical active ingredient is soluble in the water-miscible organic solvent and / or the first water-immiscible organic solvent and / or a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent.

30. The composition of claim 29, wherein the composition comprises: 10% to 20% w / w of said water-miscible organic solvent; 40% to 60% w / w of the first water-immiscible organic solvent; 15 w / w% to 40 w / w% of said emulsifier; 4% to 6% w / w of said biodegradable polymer; and 0% to 10% by weight of the second water-immiscible organic solvent.

31. The composition of claim 30, wherein the composition is for mixing with an agrochemical active ingredient comprising an isocyanate. oxadiazon and / or acetochlor.

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