GB2626306A

GB2626306A - Agrochemical compositions

Info

Publication number: GB2626306A
Application number: GB2300332.0A
Authority: GB
Inventors: Misslebrook John
Original assignee: Delsys Tech Ltd
Current assignee: Delsys Technology Ltd
Priority date: 2023-01-10
Filing date: 2023-01-10
Publication date: 2024-07-24

Abstract

A composition comprising an agrochemical active ingredient (pref. 30-50 %w/w); a water-miscible organic solvent (2-20 wt.%, e.g. 2-hydroxy-N,N-dimethyl-propanamide); a first water-immiscible organic solvent (10 to 50 per cent by weight, e.g. n-butyl L-lactate or 2-ethylhexyl L-lactate); an emulsifier (10-25 w/w%, e.g. ethoxylated propoxylated polyarylphenol), a biodegradable polymer (1 to 5 weight per cent, which may comprise ethyl cellulose or a starch); and optionally a second water-immiscible organic solvent (0-10 %w/w); wherein the agrochemical active is soluble in the water-miscible organic solvent, the water immiscible-organic solvent and/or a mixture of the water-miscible and water-immiscible organic solvents. The agrochemical active is preferably a herbicide, e.g. clomazone. Also claimed are methods of making a composition as discussed comprising combining a biodegradeable polymer with a water-immiscible organic solvent, subsequently adding water-miscible organic solvent, then adding, sequentially, agrochem active and emulsifier, and a method of protecting crops, said method comprising applying a composition as disclosed to crops.

Description

Intellectual Property Office Application No GI32300332.0 RTM Date:3 July 2023 The following terms are registered trade marks and should be read as such wherever they occur in this document: Ethocel Purasolv Agnique Intellectual Property Office is an operating name of the Patent Office www.gov.uk/ipo

AGROCHEMICAL COMPOSITIONS

FIELD OF INVENTION

The present invention relates to an agrochemical composition, methods of making the agrochemical composition, an agrochemical formulation, a method of making the agrochemical formulation, and a method of protecting crops using the agrochemical formulation.

BACKGROUND

Agrochemical formulations are routinely used to protect crops. Among these agrochemical formulations are capsule suspensions, which are formulations comprising a dispersion of an agrochemical active ingredient, droplets of which are contained in a polymer wall in the form of microcapsules.

Such microcapsule formulations are usually formed by interfacial polymerization using monomers that react at the droplet interface to form polymers that consist of polyurea shells, providing control of the release of the active on application, in addition to offering protection, if required, from chemical or photo-degradation. 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, that are associated with causing environmental harm, when such products are applied to crops. A further disadvantage of such capsule suspensions is that additional ingredients are required to prevent the premature release of the active during storage and the subsequent degradation of the physical properties of the product prior to use.

In "Ethyl cellulose polymer microspheres for controlled release of norfluazon", Jose I Perez-Martinez, Esmeralda Morillo, Celia Maqueda and Juan M Gines Pest Manag Sci 57:688-694 (2001), DOI: 10.1002/ps.339, microcapsules were prepared by a solvent evaporation technique.

In this method the agrochemical active ingredient and polymer were co-dissolved in volatile water-immiscible solvents such as chloroform and o-xylene. This solution was then emulsified into the aqueous phase and microspheres were collected after solvent diffusion/evaporation and polymer precipitation. This complicated process involves non-biodegradable solvents, their evaporation and the subsequent filtering, washing and drying of the microcapsules thus formed.

It is one 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.

It is a further object of the present invention to provide a stable composition of agrochemical active ingredients that form microcapsules on dilution with water, just prior to application, and/or which avoids the use of non-biodegradable polymers that lead to the introduction of microplastics into the environment.

It is a further object of the present invention to provide a composition which forms microcapsules on dilution with water, without requiring the evaporation of solvents to dissolve the biodegradable polymer and/or the subsequent separation and/or drying of the microcapsules.

It is a further object of the present invention to provide a biodegradable formulation comprising a microcapsule suspension of agrochemical active ingredients which is effective in reducing the amount of agrochemical active ingredient lost by volatility to a similar extent as known capsule suspension formulations, such as Clomate®, a standard clomazone CS formulation.

It is a further object of the present invention to provide a biodegradable formulation comprising a microcapsule suspension of agrochemical active ingredients that provides equivalent or improved control, i.e., efficacy to weeds, pests, insects, etc., compared to known capsule suspension formulations, such as Clomate®.

SUMMARY OF INVENTION

In a first aspect the invention provides a composition comprising an agrochemical active ingredient; a water-miscible organic solvent; a first water-immiscible organic solvent; an emulsifier; a biodegradable polymer; and optionally a 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 In a second aspect the invention provides a method of making the composition of the first aspect, 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 agrochemical active ingredient to the second mixture to form a third mixture; and adding an emulsifier to the third mixture; 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.

In a third aspect the invention provides a method of making the composition of the first aspect, the method comprising combining a biodegradable polymer with a water-miscible organic solvent to form a first mixture; adding first water-immiscible organic solvent and optionally a second water-immiscible organic solvent to the first solution to form a second mixture; adding an agrochemical active ingredient to the second mixture to form a third mixture; and adding an emulsifier to the third mixture; 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.

In a fourth aspect the invention provides a formulation comprising water, an agrochemical active ingredient; a water-miscible organic solvent; a first water-immiscible organic solvent; an emulsifier; a biodegradable polymer; and optionally a 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 4 -a mixture of the water-miscible organic solvent and the first water-immiscible organic solvent; wherein the formulation comprises microcapsules having a wall at least partially formed from the biodegradable polymer, wherein the microcapsules contain at least a portion of the agrochemical active ingredient; wherein the microcapsules have a D50 median diameter of 5 to 50 pm.

In a fifth aspect the invention provides a method of making the formulation of the fourth aspect, the method comprising adding the composition of the first aspect to water.

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

It has now been found that compositions comprising agrochemical active ingredients can form biodegradable microcapsules on dilution in water, provided that a biodegradable polymer, a water-miscible organic solvent, a first water-immiscible organic solvent, and an emulsifier are used to prepare the formulation. Such microcapsules reduce the volatility of the agrochemical active ingredient and provide protection from degradation when the formulation is applied to the crop.

The invention involves the dissolution of an agrochemical active ingredient into a mixture of a biodegradable polymer and water-miscible and first water-immiscible organic solvents and adding an emulsifier, which provides a fine emulsion on dilution in water. Surprisingly, without wishing to be bound by theory, on dilution in water, the biodegradable polymer precipitates out of solution to form a film at the emulsion droplet interface, thus producing microcapsules of the agrochemical active ingredient contained in the water-miscible and/or the first water-immiscible solvent.

Advantageously, the inventive compositions and formulations have reduced or similar volatility of an agrochemical active ingredient, e.g., clomazone, when compared to a capsule suspension formulation of the same active prepared by interfacial polymerization, while maintaining the weed control and crop safety aspects of such a formulation.

Advantageously the inventive compositions and formulations provide a reduction in the rate of degradation compared to known formulations, thus extending the residual activity of the

-

agrochemical active ingredient and thereby reducing the application rate required for effective pest control.

Advantageously the inventive compositions and formulations provide equivalent or improved control, i.e., efficacy to weeds, pests, insects, etc., compared to known capsule suspension formulations, such as Clomate®.

Other preferred embodiments of the compositions, formulations, and methods provided herein appear throughout the specification and in particular in the examples.

Each aspect or embodiment as defined herein may be combined with any other aspect(s) or embodiment(s) unless clearly indicated to the contrary. 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 OF THE INVENTION

Unless otherwise defined herein, scientific and technical terms used in connection with the present invention shall have the meanings that are 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 latent ambiguity, definitions provided herein take precedence over any dictionary or extrinsic definition.

As used in the specification and the appended claims, unless specified to the contrary, the following terms have the meaning indicated: As used herein, the term "agrochemical active ingredient" refers to an ingredient which is active against crop pests and diseases and/or which promote plant growth in agriculture. For example, the term "agrochemical active ingredient" includes biologically active ingredients or plant protection products such as herbicides, insecticides, fungicides, and the like.

As used herein, the term "water-miscible organic solvent" refers to an organic solvent that is capable of mixing with water in any ratio without separation into multiple phases, such as into two phases. 6 -

Conversely, as used herein, the term "water-immiscible organic solvent" refers to an organic solvent that is not capable of mixing with water in any ratio without separation into multiple phases, such as into two phases.

As used herein, the term "biodegradable" refers to breakdown of an entity by natural factors, such as microbes (e.g., bacteria and fungi), and/or abiotic elements such as temperature, U.V. light, oxygen, etc., such that a new biomass is formed.

For example, a biodegradable polymer, as used herein, is a polymer which can be broken down by natural factors, such as microbes (e.g., bacteria and fungi), and/or abiotic elements such as temperature, U.V. light, oxygen, etc., such that a new biomass is formed A biodegradable organic solvent, for example, as used herein, is an organic solvent which can be broken down by natural factors, such as microbes (e.g., bacteria and fungi), and/or abiotic elements such as temperature, U.V. light, oxygen, etc., such that a new biomass is formed.

As used herein, the term "soluble", in relation to a chemical entity, means that the entity is dissolvable in a solvent, such that the entity cannot be recovered by ordinary filtering means and at least 30 parts of the entity dissolves in 100 parts of the solvent. For example, 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, meaning that at least 30 parts of the agrochemical active ingredient dissolves in 100 parts of 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.

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

As used herein, the unit "%w/w" means the weight percentage based on the total weight of the composition.

Accordingly, in a first aspect there is provided a composition comprising an agrochemical active ingredient; a water-miscible organic solvent; a first water-immiscible organic solvent; an emulsifier; 7 -a biodegradable polymer; and optionally a 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 Preferably, the agrochemical active ingredient comprises a herbicide, 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.

In one preferable embodiment, the agrochemical active ingredient comprises clomazone. In a further preferable embodiment, the agrochemical active ingredient consists of clomazone.

Clomazone is a commercially available agricultural herbicide with the chemical formula: Cl 0 0J tH Preferably, the agrochemical active ingredient is present in an amount of 30 to 50 %w/w, more preferably 32 to 49 %w/w, most preferably 35 to 48 %w/w.

Preferably, the biodegradable polymer has a dynamic viscosity of 2.0 to 20.0 mPa.s. More preferably, the biodegradable polymer has a dynamic viscosity of 3.0 to 18.0 mPa.s, or 4.0 to 16.0 mPa.s, or 5.0 to 15.0 mPa.s, or 6.0 to 14.0 mPa.s, or 7.0 to 13.0 mPa.s. More preferably still, the biodegradable polymer has a dynamic viscosity of 8.0 to 12.0 mPa.s, or 9.0 to 11.0 mPa.s. Dynamic viscosity of the biodegradable polymer is measured by preparing a 5 %w/w solution of the biodegradable polymer in 80% toluene/20% ethanol, at 25 °C. Without wishing to be bound by theory, it is thought that a biodegradable polymer having a dynamic viscosity in these preferred ranges helps to promote the formation of stable microcapsules of a desired size (e.g., 5 to 50 pm), on dilution with water.

Preferably, the biodegradable polymer comprises a polysaccharide. More preferably, the biodegradable polymer comprises a cellulose and/or a starch. More preferably still, the biodegradable polymer comprises ethyl cellulose. In a further preferable embodiment, the biodegradable polymer consists of ethyl cellulose. Ethyl cellulose is commercially available 8 -under the tradename EthocelTM Standard 10 Premium, from Dupont, for example. EthocelTM Standard 10 Premium has a dynamic viscosity of 9.0 to 11.0 mPa.s, when in the form of a 5 %w/w solution of the EthocelTM Standard 10 Premium in 80% toluene/20% ethanol, at 25 °C and measured using a Ubbelohde viscometer, specifically an Anton-Parr MCR 102 viscometer.

Preferably, the biodegradable polymer is present in an amount of 1 to 5 °/0w/w, more preferably 1.5 to 4.5 %w/w, most preferably 2.0 to 4.0 %w/w. Without wishing to be bound by theory, it is thought that a biodegradable polymer being present in these preferred ranges helps to promote the formation of stable microcapsules of a desired size (e.g., 5 to 50 km), on dilution with water.

Preferably, the water-miscible organic solvent has a dynamic viscosity of 2 to 10 mPa.s at 25 °C. More preferably, the water-miscible organic solvent has a dynamic viscosity of 3 to 8 mPa.s at 25 °C. More preferably still, the water-miscible organic solvent has a dynamic viscosity of 4 to 7 mPa.s at 25 °C. Most preferably, the water-miscible organic solvent has a dynamic viscosity of 4 to 6 mPa.s at 25°C. Without wishing to be bound by theory, it is thought that a dynamic viscosity in these preferred ranges helps to promote the formation of stable microcapsules of a desired size (e.g., 5 to 50 pm), on dilution with water.

Preferably, the water-miscible organic solvent is biodegradable. Using biodegradable solvents avoids the need for the evaporation of the solvents used to dissolve the biodegradable polymer and/or the agrochemical active ingredient, and the subsequent separation and drying of the microcapsules.

In one preferable embodiment, the water-miscible organic solvent comprises 2-hydroxy-N,N-dimethyl-propanamide. In a further preferable embodiment, the water-miscible organic solvent consists of 2-hydroxy-N,N-dimethyl-propanamide. 2-hydroxy-N,N-dimethyl-propanamide is commercially available under the tradename Agnique® AMD 3L, from BTC / BASF, for example, with a dynamic viscosity of around 5.1 mPa.s at 25°C.

Preferably, the water-miscible organic solvent is present in an amount of 2 to 20 °/0w/w. More preferably, the water-miscible organic solvent is present in an amount of 4 to 15 %w/w. Most preferably, the water-miscible organic solvent is present in an amount of 5 to 13 %w/w. Without wishing to be bound by theory, it is thought that a water-miscible organic solvent being present in these preferred ranges helps to promote the formation of stable microcapsules of a desired size (e.g., 5 to 50 pm), on dilution with water.

Preferably, the first water-immiscible organic solvent has a molecular weight of 100 to 300 g/mol. More preferably, the first water-immiscible organic solvent has a molecular weight of 110 to 250 g/mol. More preferably, the first water-immiscible organic solvent has a molecular weight of 120 to 225 g/mol. Without wishing to be bound by theory, it is thought that a molecular weight in these preferred ranges helps to promote the formation of stable microcapsules of a desired size (e.g., 5 to 50 pm), on dilution with water.

In one preferable embodiment, the first water-immiscible organic solvent has a molecular weight of 130 to 160 g/mol. In an alternative, preferable embodiment, the first water-immiscible organic solvent has a molecular weight of 185 to 215 g/mol.

Preferably, the first water-immiscible organic solvent has a dynamic viscosity of 1.0 to 20.0 mPa.s at 20 °C. More preferably, the first water-immiscible organic solvent has a dynamic viscosity of 3.0 to 10.0 mPa.s at 20°C. More preferably still, the first water-immiscible organic solvent has a dynamic viscosity of 3.5 to 8.0 mPa.s at 20°C. Without wishing to be bound by theory, it is thought that a dynamic viscosity in these preferred ranges helps to promote the formation of stable microcapsules of a desired size (e.g., 5 to 50 pm), on dilution with water.

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

Preferably, the first water-immiscible organic solvent is biodegradable. Using biodegradable solvents avoids the need for the evaporation of the solvents used to dissolve the biodegradable polymer and/or the agrochemical active ingredient, and the subsequent separation and drying of the microcapsules.

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

Preferably, the first water-immiscible organic solvent is present in an amount of 10 to 50 %w/w. More preferably, the first water-immiscible organic solvent is present in an amount of 15 to 45 -10 - %w/w. Most preferably, the first water-immiscible organic solvent is present in an amount of 20 to 40 %w/w. Without wishing to be bound by theory, it is thought that a first water-immiscible organic solvent being present in these preferred ranges helps to promote the formation of stable microcapsules of a desired size (e.g., 5 to 50 pm), on dilution with water.

In one preferable embodiment, the composition comprises a second water-immiscible organic solvent, wherein the second water-immiscible organic solvent comprises n-butyl [-lactate or 2-ethyl hexyl L-lactate, with the proviso that the first water-immiscible organic solvent is different from the second water-immiscible organic solvent.

Preferably, the second water-immiscible organic solvent is biodegradable. Using biodegradable solvents avoids the need for the evaporation of the solvents used to dissolve the biodegradable polymer and/or the agrochemical active ingredient, and the subsequent separation and drying of the microcapsules.

Preferably, the second water-immiscible organic solvent is present in an amount of 0 to 10 %w/w. More preferably, the second water-immiscible organic solvent is present in an amount of 0 to 7.5 %w/w. Most preferably, the second water-immiscible organic solvent is present in an amount of 0 to 5.0 %w/w.

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

Preferably, the total amount of water-immiscible organic solvent in the composition is 10 to 60 %w/w. More preferably, the total amount of water-immiscible organic solvent in the composition is 15 to 50 %w/w. Most preferably, the total amount of water-immiscible organic solvent in the composition is 20 to 40 %w/w.

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 10 15 20 wishing to be bound by theory, it is thought that a weight ratio of the water-miscible organic solvent to the first water-immiscible organic solvent and the second water-immiscible organic solvent in these preferred ranges helps to promote the formation of stable microcapsules of a desired size (e.g., 5 to 50 pm), on dilution with water.

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

Preferably, the emulsifier comprises ethoxylated propoxylated polyarylphenol. In a further preferable embodiment, the emulsifier consists of ethoxylated propoxylated polyarylphenol. Ethoxylated propoxylated polyarylphenol, has a dynamic viscosity of 1300 mPa.s at 2000 and is available under the tradename Soprophor0 796/P, from Azelis. Without wishing to be bound by theory, it is thought that an emulsifier being ethoxylated propoxylated polyarylphenol helps to promote the formation of stable microcapsules of a desired size (e.g., 5 to 50 pm), on dilution with water.

Preferably, the emulsifier is biodegradable.

Preferably, the emulsifier is present in an amount of 5 to 30 %w/w. More preferably, the emulsifier is present in an amount of 7.5 to 27.5 %w/w. More preferably, the emulsifier is present in an amount of 10 to 25 %w/w. Most preferably, the emulsifier is present in an amount of 12 to 20 %w/w. Without wishing to be bound by theory, it is thought that an emulsifier being present in these preferred ranges helps to promote the formation of stable microcapsules of a desired size (e.g., 5 to 50 pm), on dilution with water.

Preferably, the composition further comprises a U.V. stabiliser.

Preferably, when the composition of the first aspect, as described above, is added to water, microcapsules having a median diameter of 5 to 50 pm are formed, wherein the microcapsules have a wall at least partially formed from the biodegradable polymer, wherein the microcapsules contain at least a portion of the agrochemical 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 to 50 pm are formed, wherein the microcapsules have a wall formed from the biodegradable polymer, wherein the microcapsules contain the agrochemical active ingredient.

-12 -Preferably the composition comprises to 50 %w/w of the agrochemical active ingredient; 2 to 20 %w/w of the water-miscible organic solvent; 10 to 50 %w/w of the first water-immiscible organic solvent to 25 %w/w of the emulsifier; 1 to 5 %w/w of the biodegradable polymer; and 0 to 10 %w/w of the second water-immiscible organic solvent.

More preferably the composition comprises 32 to 49 %w/w of the agrochemical active ingredient; 4 to 15 %w/w of the water-miscible organic solvent; 15 to 45 %w/w of the first water-immiscible organic solvent 10 to 25 %w/w of the emulsifier; 1.5 to 4.5 %w/w of the biodegradable polymer; and 0 to 7.5 %w/w of the second water-immiscible organic solvent.

Most preferably the composition comprises to 48 %w/w of the agrochemical active ingredient; 5 to 13 %w/w of the water-miscible organic solvent; to 40 %w/w of the first water-immiscible organic solvent 12 to 20 %w/w of the emulsifier; 2.0 to 4.0 %w/w of the biodegradable polymer; and 0 to 5.0 %w/w of the second water-immiscible organic solvent.

In a preferable embodiment, the composition consists essentially of an agrochemical active ingredient; a water-miscible organic solvent; a first water-immiscible organic solvent; an emulsifier; a biodegradable polymer; optionally a second water-immiscible organic solvent; and optionally a U.V. stabiliser; 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.

-13 -In a preferable embodiment, the composition consists of an agrochemical active ingredient; a water-miscible organic solvent; a first water-immiscible organic solvent; an emulsifier; a biodegradable polymer; optionally a second water-immiscible organic solvent; and optionally a U.V. stabiliser; 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.

Preferably the composition is free of non-biodegradable polymers.

Preferably the composition is free of non-biodegradable organic solvents.

Preferably the composition is free of non-biodegradable emulsifiers.

Preferably, the composition is free of non-biodegradable polymers, and free of non-biodegradable organic solvents, and free of non-biodegradable emulsifiers.

Preferably, the composition of the first aspect is a clear solution.

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 are chemically different from each other. For example, the water-immiscible organic solvent is chemically different from the emulsifier.

In a second aspect the invention provides a method of making the composition of the first aspect, 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; -14 -adding an agrochemical active ingredient to the second mixture to form a third mixture; and adding an emulsifier to the third mixture; 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.

Preferred features 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 are as described above with regard to the composition of the first aspect.

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

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.

In a fourth aspect the invention provides a formulation comprising -15 -water, an agrochemical active ingredient; a water-miscible organic solvent; a first water-immiscible organic solvent; an emulsifier; a biodegradable polymer; and optionally a 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 at least partially formed from the biodegradable polymer, wherein the microcapsules contain at least a portion of the agrochemical active ingredient; wherein the microcapsules have a median diameter of 5 to 50 pm.

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

Preferably, the microcapsules have a D50 median diameter of 10 to 30 pm, more preferably 10 to 20 pm.

Preferably the formulation is free of non-biodegradable polymers.

Preferably the formulation is free of non-biodegradable organic solvents.

Preferably the formulation is free of non-biodegradable emulsifiers.

Preferably, the formulation is free of non-biodegradable polymers, and free of non-biodegradable organic solvents, and free of non-biodegradable emulsifiers.

In one preferable embodiment, the formulation consists essentially of, or consists of -16 -water, an agrochemical active ingredient; a water-miscible organic solvent; a first water-immiscible organic solvent; an emulsifier; a biodegradable polymer; and optionally a second water-immiscible organic solvent; optionally a U.V. stabiliser; 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 at least partially formed from the biodegradable polymer, wherein the microcapsules contain at least a portion of the agrochemical active ingredient; wherein the microcapsules have a median diameter of 5 to 50 pm.

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.

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

-17 -In one preferable embodiment, the crops comprise rape.

When introducing elements of the present disclosure or the preferred embodiments(s) 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 mean that there may be additional elements other than the listed elements.

The foregoing detailed description has been provided by way of explanation and illustration, and is not intended to limit the scope of the appended claims. Many variations in the presently preferred embodiments illustrated herein will be apparent to one of ordinary skill in the art, and remain within the scope of the appended claims and their equivalents.

These and other aspects of the invention will now be described with reference to the accompanying Figures, in which: Figures la to lh show phytotoxic effects of a comparative standard clomazone CS formulation and an inventive clomazone ICS formulation on rape plants after 14 days, at four different application rates. Figures 1a to lh are discussed in more detail in the Example section below.

Figures 2a to 2h show efficacy of a comparative standard clomazone CS formulation and an inventive clomazone ICS formulation on chickweed after 17 days, at four different application rates. Figures 2a to 2h are discussed in more detail in the Example section below.

EXPERIMENTAL SECTION

Unless otherwise indicated, dynamic viscosity was measured at 25 °C using a standard viscometer, e.g., a Ubbelohde viscometer or an Anton-Parr MCR 102 viscometer.

The dynamic viscosity of the EthocelTM Standard 10 Premium used in the Examples was measured in the form of as %w/w solution of the EthocelTM Standard 10 Premium in 80% toluene/20% ethanol, at 25 °C and measured using an Anton-Parr MCR 102 viscometer.

Median diameter (D50 median particle size) of microcapsules was measured by laser diffraction using a Malvern 300 Mastersizer.

Solubility is measured at 20 °C, using OECD Test Guideline 105 -18 -

EXAMPLES

The present invention will now be described in relation to several examples.

Example 1

Clomazone 360g/I In-situ Capsule Suspension Concentrate (ICS) Formulation (Formulation A) Chemical name Tradename CAS Function Content (g/I) Content (%w/w) Clomazone Clomazone 81777-89-1 Active substance 360.0 36.21 Ethyl cellulose EthocelTM 10 9004-57-3 Wall forming component 35 3.45 Ethoxylated propoxylated polyarylphenol Soprophor® 796/P 70880-56-7 Emulsifier 126.8 12.50 n-Butyl L-lactate Purasolv0 BL 34451-19-9 Solvent 373.7 36.84 (Water immiscible) Propanamide, 2-hydroxy-N,N-dimethyl- Agnique0 AMD3L 35123-06-9 Solvent to 1 litre 11.00 (Water miscible) Method of Preparation The Ethocel 10 was weighed out into a 10 mL sample vial in which the Purasolv BL was contained. The vial was sealed with a lid and transferred to a magnetic heater/stirrer plate and mixed using a stirrer bar at a rotation speed of 600 rpm. The mixture was allowed to stir for 30 min at RT.

To the mixture was added Agnique AMD3L, followed by clomazone and the mixture stirred on the magnetic heater/stirrer plate for 3 hrs after which the Soprophor 796/P was added. The mixture was stirred until the ethyl cellulose had completely dissolved.

Example 2

Clomazone 360g/I In situ Capsule Suspension Concentrate (ICS) Formulation (Formulation B) Chemical name Tradename CAS Function Content (g/1) Content (94w/w) Clomazone Clomazone 81777-89-1 Active substance 360.0 36.80 -19 -Ethyl cellulose EthocelTM 10 9004-57-3 Wall forming component 35.4 3.55 Ethoxylated propoxylated polyarylphenol Soprophore 796/P 70880-56-7 Emulsifier 124.8 12.50 n-Butyl L-lactate Purasolv® BL 34451-19-9 Solvent (Water immiscible) 47.1 4.72 2-Ethyl hexyl L-lactate Purasolv® EHL 186817-80-1 Solvent (Water immiscible) 329.4 33.00 Propanamide, 2-hydroxy-N,N-dimethyl- Agnigue0 AMD3L 35123-06-9 Solvent to 1 litre 9.43 (Water miscible) Method of Preparation The Ethocel 10 was weighed out into a 10 mL sample vial in which the Purasolv EHL was contained. The vial was sealed with a lid and transferred to a magnetic heater/stirrer plate and mixed using a stirrer bar at a rotation speed of 600 rpm. The mixture was allowed to stir for 30 min at RT.

To the mixture was added Purasolv BL and Agnique AMD3L, followed by clomazone and the mixture stirred on the magnetic heater/stirrer plate for 3 hrs after which the Soprophor 796/P was added. The mixture was stirred until the ethyl cellulose had completely dissolved.

Example 3

Clomazone 360g/I In-situ Capsule Suspension Concentrate (ICS) Formulation (Formulation C) Chemical name Tradename CAS Function Content (WO Content (kw/w) Clomazone Clomazone 81777-89-1 Active substance 360.0 36.25 Ethyl cellulose EthocelTM 10 9004-57-3 Wall forming component 31.1 3.06 Ethoxylated propoxylated polyarylphenol Soprophor0 796/P 70880-56-7 Emulsifier 202.7 20.00 n-Butyl L-lactate Purasolv® BL 34451-19-9 Solvent 41.2 4.07 (Water immiscible) 2-Ethyl hexyl L-lactate Purasolv® EHL 186817-80-1 Solvent 288.6 28.48 (Water immiscible) Propanamide, 2-hydroxy-N,N-dimethyl- Agnigue® AMD3L 35123-06-9 Solvent to 1 litre 8.14 (Water miscible) -20 -Method of Preparation The Ethocel 10 was weighed out into a 10 mL sample vial in which the Purasolv EHL was contained. The vial was sealed with a lid and transferred to a magnetic heater/stirrer plate and mixed using a stirrer bar at a rotation speed of 600 rpm. The mixture was allowed to stir for 30 min at RT.

Example 4

Clomazone 360g/I In-situ Capsule Suspension Concentrate (ICS) Formulation (Formulation D) Chemical name Tradename CAS Function Content (9/4 Content (cYonew) Clomazone Clomazone 81777-89-1 Active substance 360.0 36.75 Ethyl cellulose EthocelTM 10 9004-57-3 Wall forming component 35.5 3.55 Ethoxylated propoxylated polyarylphenol Soprophor® 796/P 70880-56-7 Emulsifier 124.9 12.50 n-Butyl L-lactate Purasolv® BL 34451-19-9 Solvent (Water immiscible) 23.6 2.36 2-Ethyl hexyl L-lactate Purasolv® EHL 186817-80-1 Solvent (Water immiscible) 330.2 33.04 Propanamide, 2-hydroxy-N,N-dimethyl- Agnique® AMD3L 35123-06-9 Solvent (Water miscible) to 1 litre 11.80 Method of Preparation The Ethocel 10 was weighed out into a 10 mL sample vial in which the Purasolv EHL was contained. The vial was sealed with a lid and transferred to a magnetic heater/stirrer plate and mixed using a stirrer bar at a rotation speed of 600 rpm. The mixture was allowed to stir for 30 min at RT.

-21 -

Example 5

Clomazone 360g/I In-situ Capsule Suspension Concentrate (ICS) Formulation (Formulation E) Chemical name Tradename CAS Function Content (g/I) Content (%w/w) Clomazone Clomazone 81777-89-1 Active substance 360.0 36.78 Ethyl cellulose EthocelTM 10 9004-57-3 Wall forming component 35.5 3.54 Ethoxylated propoxylated polyarylphenol Soprophore 796/P 70880-56-7 Emulsifier 124.9 12.50 n-Butyl L-lactate Purasolv® BL 34451-19-9 Solvent (Water immiscible) 35.4 3.53 2-Ethyl hexyl L-lactate Purasolv® EHL 186817-80-1 Solvent (Water immiscible) 329.8 33.02 Propanamide, 2-hydroxy-N,N-dimethyl- Agnigue® AMD3L 35123-06-9 Solvent (Water miscible) to 1 litre 10.63 Method of Preparation The Ethocel 10 was weighed out into a 10 mL sample vial in which the Purasolv EHL was contained. The vial was sealed with a lid and transferred to a magnetic heater/stirrer plate and mixed using a stirrer bar at a rotation speed of 600 rpm. The mixture was allowed to stir for 30 min at RT.

Example 6

Clomazone 360g/I In-situ Capsule Suspension Concentrate (ICS) Formulation (Formulat on F) Chemical name Tradename CAS Function Content (g/I) Content (%w/w) Clomazone Clomazone 81777-89-1 Active substance 360.0 36.80 Ethyl cellulose EthocelTM 10 9004-57-3 Wall forming component 35.5 3.54 -22 -Ethoxylated propoxylated polyarylphenol Soprophor® 796/P 70880-56-7 Emulsifier 124.8 12.50 n-Butyl L-lactate Purasolv® BL 34451-19-9 Solvent (Water immiscible) 23.5 2.36 2-Ethyl hexyl L-lactate Purasolv® EHL 186817-80-1 Solvent (Water immiscible) 341.4 34.19 Propanamide, 2-hydroxy-N,N-dimethyl- Agnique® AMD3L 35123-06-9 Solvent (Water miscible) to 1 litre 10.61 Method of Preparation The Ethocel 10 was weighed out into a 10 mL sample vial in which the Purasolv EHL was contained. The vial was sealed with a lid and transferred to a magnetic heater/stirrer plate and mixed using a stirrer bar at a rotation speed of 600 rpm. The mixture was allowed to stir for 30 min at RT.

Example 7

Clomazone 360g/I In-situ Capsule Suspension Concentrate (ICS) Formulation (Formulation G) Chemical name Tradename CAS Function Content (WO Content (c/ow/w) Clomazone Clomazone 81777-89-1 Active substance 360.0 36.23 Ethyl cellulose EthocelTM 10 9004-57-3 Wall forming component 31.1 3.06 Ethoxylated propoxylated polyarylphenol Soprophor® 796/P 70880-56-7 Emulsifier 202.8 20.00 n-Butyl L-lactate Purasolv® BL 34451-19-9 Solvent (Water immiscible) 31.0 3.05 2-Ethyl hexyl L-lactate Purasolv® EHL 186817-80-1 Solvent (Water immiscible) 288.9 28.49 Propanamide, 2-hydroxy-N,N-dimethyl- Agnique0 AMD3L 35123-06-9 Solvent (Water miscible) to 1 litre 9.17 -23 -Method of Preparation The Ethocel 10 was weighed out into a 10 mL sample vial in which the Purasolv EHL was contained. The vial was sealed with a lid and transferred to a magnetic heater/stirrer plate and mixed using a stirrer bar at a rotation speed of 600 rpm. The mixture was allowed to stir for 30 min at RT.

Example 8

Clomazone 480g/I In-situ Capsule Suspension Concentrate (ICS) Formulation (Formulation H) Chemical name Tradename CAS Function Content (WO Content (%w/w) Clomazone Clomazone 81777-89-1 Active substance 480.0 46.78 Ethyl cellulose EthocelTM 10 9004-57-3 Wall forming component 24.4 2.33 Ethoxylated propoxylated polyarylphenol Soprophor® 796/P 70880-56-7 Emulsifier 209.4 20.00 n-Butyl L-lactate Purasolv® BL 34451-19-9 Solvent (Water immiscible) 32.4 3.09 2-Ethyl hexyl L-lactate Purasolv® EHL 186817-80-1 Solvent (Water immiscible) 226.5 21.63 Propanamide, 2-hydroxy-N,N-dimethyl- Agnique® AMD3L 35123-06-9 Solvent (Water miscible) to 1 litre 6.17 Method of Preparation The Ethocel 10 was weighed out into a 10 mL sample vial in which the Purasolv EHL was contained. The vial was sealed with a lid and transferred to a magnetic heater/stirrer plate and mixed using a stirrer bar at a rotation speed of 600 rpm. The mixture was allowed to stir for 30 min at RT.

-24 -To the mixture was added Purasolv BL and Agnique AMD3L, followed by clomazone and the mixture stirred on the magnetic heater/stirrer plate for 3 hrs after which the Soprophor 796/P was added. The mixture was stirred until the ethyl cellulose had completely dissolved.

Volatility Studies Laboratory tests for the volatility of in-situ capsule suspension (ICS) formulation of clomazone was carried out in the following manner. Sufficient unsterilized topsoil to conduct the test was passed twice through a 14-mesh sieve to remove large particles and debris. The fine particles were then removed through a 30-mesh sieve, leaving behind topsoil of intermediate-sized particles. This intermediate-sized topsoil, 240 grams, was spread uniformly to a thickness of about one to two millimeters over an area of about 27.9 cm. x 41.3 cm in a tray measuring 32.4 cm x 45.7 x 1.9 cm. The topsoil was then sprayed with sufficient clomazone test formulation to provide 0.0712 gm of active ingredient in 20 mL of water. In this manner the clomazone test formulation was applied to the soil at a rate of 1.0 kg a.i. (active ingredient)/ha. Immediately after treatment, the soil was enclosed in a glass jar, where it remained briefly until used.

For each clomazone test formulation, four 22 mm X 300 mm glass chromatography columns, each containing a coarse sintered glass barrier at the bottom, were connected through their bottom ends to a multi-port air manifold, which delivered equal air pressure simultaneously to a number of columns. In each of the four columns was placed 59 gms of the treated topsoil, which filled about 200 mm of the column length. As soon after the soil treatment as the columns could be set up, a slow stream of air (0.5 liters per minute per column) from the multi-port air manifold was passed through the soil in each column and then bubbled through a mixture of 80:20 acetonitrile:water, causing the volatilized clomazone to dissolve in the solvent. The time between the soil treatment and the start of the air flow was about one hour. The air flow was continued for about 20 hours. A 1 mL aliquot of this solution was analyzed for clomazone content using a standard high-performance liquid chromatography assay method (HPLC).

The total clomazone content expressed in micrograms, of each sample was recorded and compared to the clomazone content of the sample applied to the soil in percentage terms.

The test results, given in Table 1, show that the ICS formulation of the present invention is effective in reducing the amount of clomazone lost by volatility to the same extent as Clomate", a standard clomazone CS formulation.

-25 -

Table 1

h experiments with 0.5 L/min flow rate, in line flowmeter and air drier Column 1 Column 2 Column 3 Column 4 Average Clomate 0.32 0.35 0.34 0.42 0.36 Formulation A 0.27 0.34 0.29 0.32 0.31 Formulation B 0.36 0.31 0.30 0.30 0.32 Formulation C 0.29 0.31 0.30 0.30 0.30 Formulation D 0.31 0.34 0.28 0.36 0.32 Formulation E 0.31 0.33 0.29 0.31 0.31 Formulation F 0.34 0.32 0.28 0.31 0.31 Formulation G 0.33 0.33 0.27 0.32 0.31 Formulation H 0.40 0.34 0.30 0.33 0.34 Crop Safety Studies Tests to determine the phytotoxicity of clomazone ICS formulation applied to crops relative to that of the standard, clomazone CS formulation were carried out as follows. One trial on Formulation A was conducted on rape seeds (Brassica napus), in which 4 seeds each were sown in 7 individual plant sponge replicates, using a LED Hydroponic System A-03, supplied by AQUA, providing constant watering and LED lighting (16 hours on, 8 hours off in 24 hour cycle). 5 such hydroponic tanks were set up with 5 litres water containing nutrient solution (50m1 containing Total N 23%, P205 9%, K20 30%, MgO 7%, CaO 15%, EDTA-FE 0.3%, EDTA-Mn 0.06%, EDTA-Cu 0.005%, EDTA-Zn 0.01%, B 0.1%) together with varying concentrations of Formulation A (0.129ml -equivalent to 1/64 of use rate, 0.064m1 -equivalent to 1/128 of use rate, 0.032m1-equivalent to 1/256 of use rate, 0.016m1-equivalent to 1/512 of use rate) and the phytotoxic effects on the growth of the rape crop was assessed after 14 days. Untreated control was also included in the trial.

The trial was repeated with a standard clomazone CS formulation prepared by conventional interfacial polymerization, diluted in the nutrient solution at the same rates. To prevent cross-contamination, a plastic sleeve was placed around each tank, which was replaced before applying each new test formulation to the nutrient solution. The test was evaluated at 14 days after treatment by observing the phytotoxic effects on the rape plants.

The phytotoxic effects were compared at 14 days, as shown in Figures la to lh. Fig la shows the rape plants treated with the (comparative) standard clomazone CS formulation at an application rate of 1/64N. Fig 1c shows the rape plants treated with the (comparative) standard clomazone CS formulation at an application rate of 1/128N. Fig le shows the rape plants treated with the (comparative) standard clomazone CS formulation at an application rate of -26 - 1/256N. Fig lg shows the rape plants treated with the (comparative) standard clomazone CS formulation at an application rate of 1/512N. Fig lb shows the rape plants treated with the (inventive) clomazone ICS formulation at an application rate of 1/64N. Fig ld shows the rape plants treated with the (inventive) clomazone ICS formulation at an application rate of 1/128N.

Fig lf shows the rape plants treated with the (inventive) clomazone ICS formulation at an application rate of 1/256N. Fig lh shows the rape plants treated with the (inventive) clomazone ICS formulation at an application rate of 1/512N.

The areas of chlorosis and vigour of the rape was observed and compared between test formulations. The tests show that Formulation A provided equivalent crop safety compared to the standard clomazone CS product.

Efficacy Studies Tests to determine the efficacy of clomazone ICS formulation applied to weeds relative to that of the standard, clomazone CS formulation were carried out as follows. One trial on Formulation A was conducted on chickweed seeds (Ste//aria media), in which 4 seeds each were sown in 7 individual plant sponge replicates, using a LED Hydroponic System A-03, supplied by AQUA, providing constant watering and LED lighting (16 hours on, 8 hours off in 24 hour cycle). 5 such hydroponic tanks were set up with 5 litres water containing nutrient solution (50m1 containing Total N 23%, P2059%, K20 30%, MgO 7%, CaO 15%, EDTA-FE 0.3%, EDTA-Mn 0.06%, EDTA-Cu 0.005%, EDTA-Zn 0.01%, B 0.1%) together with varying concentrations of Formulation A (0.129m1 -equivalent to 1/64 of use rate, 0.064m1 -equivalent to 1/128 of use rate, 0.032m1 -equivalent to 1/256 of use rate, 0.01 6m1 -equivalent to 1/512 of use rate) and the effects on the growth of the chickweed was assessed after 17 days. Untreated control was also included in the trial.

The trial was repeated with a standard clomazone CS formulation prepared by conventional interfacial polymerization, diluted in the nutrient solution at the same rates. To prevent cross-contamination, a plastic sleeve was placed around each tank, which was replaced before applying each new test formulation to the nutrient solution. The test was evaluated at 17 days after treatment by observing the effects on the chickweed.

The effects of the different applications rates were compared at 17 days, as shown in Figures 2a to 2h. Fig 2a shows the chickweed treated with the (comparative) standard clomazone CS formulation at an application rate of 1/64N. Fig 2c shows the chickweed treated with the (comparative) standard clomazone CS formulation at an application rate of 1/128N. Fig 2e shows the chickweed treated with the (comparative) standard clomazone CS formulation at an -27 -application rate of 1/256N. Fig 2g shows the chickweed treated with the (comparative) standard clomazone CS formulation at an application rate of 1/512N. Fig 2b shows the chickweed treated with the (inventive) clomazone ICS formulation at an application rate of 1/64N. Fig 2d shows the chickweed treated with the (inventive) clomazone ICS formulation at an application rate of 1/128N. Fig 2f shows the chickweed treated with the (inventive) clomazone ICS formulation at an application rate of 1/256N. Fig 2h shows the chickweed treated with the (inventive) clomazone ICS formulation at an application rate of 1/512N.

The test results show that inventive Formulation A provided equivalent control compared to the (comparative) standard clomazone CS product.

Claims

-28 -CLAIMS: 1. A composition comprising an agrochemical active ingredient; a water-miscible organic solvent; a first water-immiscible organic solvent; an emulsifier; a biodegradable polymer; and optionally a 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.
2. The composition of claim 1, wherein the composition comprises to 50 %w/w of the agrochemical active ingredient; 2 to 20 %w/w of the water-miscible organic solvent; to 50 %w/w of the first water-immiscible organic solvent to 25 %w/w of the emulsifier; 1 to 5 %w/w of the biodegradable polymer; and 0 to 10 %w/w of the second water-immiscible organic solvent.
3. The composition of any of the preceding claims, wherein the agrochemical active ingredient comprises a herbicide, insecticide, and/or a fungicide.
4. The composition of any of the preceding claims, wherein the agrochemical active ingredient comprises a herbicide.
5. The composition of any of the preceding claims, wherein the agrochemical active ingredient comprises clomazone.
6. The composition of any of the preceding claims, wherein the biodegradable polymer has a dynamic viscosity of 2.0 to 20.0 mPa.s.
7. The composition of any of the preceding claims, wherein the biodegradable polymer comprises a polysaccharide.
-29 - 8. The composition of any of the preceding claims, wherein the biodegradable polymer comprises a cellulose and/or a starch.
9. The composition of any of the preceding claims, wherein the biodegradable polymer comprises ethyl cellulose.
10. The composition of any of the preceding claims, wherein the water-miscible organic solvent has a dynamic viscosity of 2 to 10 mPa.s at 25 °C.
11. The composition of any of the preceding claims, wherein the water-miscible organic solvent comprises 2-hydroxy-N,N-dimethyl-propanamide.
12. The composition of any of the preceding claims, wherein the first water-immiscible organic solvent has a molecular weight of 100 to 300 g/mol.
13. The composition of any of the preceding claims, wherein the first water-immiscible organic solvent has a dynamic viscosity of 3.0 to 10.0 mPa.s at 20 °C.
14. The composition of any of the preceding claims, wherein the first water-immiscible organic solvent comprises n-butyl L-lactate or 2-ethylhexyl L-lactate.
15. The composition of any 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-ethyl hexyl L-lactate, with the proviso that the first water-immiscible organic solvent is different from the second water-immiscible organic solvent.
16. The composition of any of the preceding claims, wherein the emulsifier has a dynamic viscosity of 1100 to 1500 mPa.s at 20 °C.
17. The composition of any of the preceding claims, wherein the emulsifier comprises ethoxylated propoxylated polyarylphenol.
18. The composition of any of the preceding claims, further comprising a U.V. stabiliser.
19. The composition of any of the preceding claims, wherein 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.
-30 - 20. The composition of any of the preceding claims, wherein when the composition is added to water, microcapsules having a D50 median diameter of 5 to 50 pm are formed, wherein the microcapsules have a wall at least partially formed from the biodegradable polymer, wherein the microcapsules contain at least a portion of the agrochemical active ingredient.
21. A method of making the composition of any 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 agrochemical active ingredient to the second mixture to form a third mixture; and adding an emulsifier to the third mixture; 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.
22. A method of making the composition of any of the preceding claims, the method comprising combining a biodegradable polymer with a water-miscible organic solvent to form a first mixture; adding first water-immiscible organic solvent and optionally a second water-immiscible organic solvent to the first solution to form a second mixture; adding an agrochemical active ingredient to the second mixture to form a third mixture; and adding an emulsifier to the third mixture; 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.
23. A formulation comprising water, -31 -an agrochemical active ingredient; a water-miscible organic solvent; a first water-immiscible organic solvent; an emulsifier; a biodegradable polymer; and optionally a 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 at least partially formed from the biodegradable polymer, wherein the microcapsules contain at least a portion of the agrochemical active ingredient; wherein the microcapsules have a 050 median diameter of 5 to 50 pm.
24. A method of making the formulation of claim 23, the method comprising adding the composition of any of claims 1 to 20 to water.
25. A method of protecting crops, the method comprising applying the formulation of claim 23 to crops.