Core-shell microcapsules

Abstract

The present invention relates to core-shell microcapsules, to a method for their preparation and to their use in formulated products.

Description

[0001] CORE-SHELL MICROCAPSULES

[0002] FILED OF THE INVENTION

[0003] The present invention relates to core-shell microcapsules, to a method for their preparation and to their use in formulated products.

[0004] BACKGROUND OF THE INVENTION

[0005] Encapsulation of actives in microcapsules is a well-established technology. The first step in an encapsulation process is typically an emulsification step wherein an active composition comprising the active material plus any carriers, solvents, dissolved polymers and / or other materials is emulsified into the surrounding liquid by stirring. A shell of harder material then typically forms around the emulsified droplet by a reaction between components at the droplet and surrounding liquid interface, resulting in a core-shell microcapsule. Examples include complex coacervation, interfacial polymerization and precipitation from an external phase.

[0006] The emulsification step is a critical first step in this process. This is typically done on a large scale by a bulk emulsification process wherein the active composition is mixed into the surrounding liquid in a stirred tank. This can be a high shear process, especially for high viscosity mixtures, and the more stressed conditions and non-homogenous mixing conditions very often result in a wide range of emulsion droplet sizes at best. More often part of the mixture does not form a plurality of discreet microcapsules at all, but rather forms an undesirable solid mass.

[0007] Recently, the development of microfluidic emulsification devices has allowed the production of highly uniform and well controlled microcapsules due to the very high degree of control in the emulsification process and afterwards arising from the ability to control flow patterns and temperature conditions around individual droplets. For example, it is possible to control the temperature at different points along the channel in a microfluidic reactor. The emulsification can be done at one temperature (typically a higher temperature to achieve lower viscosities) and then the droplets can be rapidly cooled, typically to change viscosity or avoid degradation. This has also allowed a wider range of actives and wall forming components and concentrations to be used. The droplets are typically kept well apart which avoids coalescence, and they are subjected to only very low shear, due to the small dimensions of the microchannels, therefore avoiding the formation of an undesirable solid mass during encapsulation.

[0008] Microfluidics would seem to offer a highly preferred emulsion process and microcapsules made by this manner have been widely reported in the literature. There are, however, issues with the microfluidic production of microcapsules which limit its application. The principal issue is that the production rate through any individual microfluidic nozzle is obviously very low. Processes can use multiple nozzles, but rates will still be limited. This means that bulk emulsification processes still need to be used for many large-scale products.

[0009] One issue that does arise is that not all formulations that can be made into microcapsules via microfluidic processes can be directly transferred into bulk emulsification processes. Bulk emulsification is typically a more intense and less controlled mixing environment, quite different to the controlled environments typical of microfluidic devices. For example, temperatures cannot be quickly changed in a bulk stirred tank, therefore for example, heatsensitive actives can degrade during processing. Unfortunately, this can mean that microcapsule formulations cannot automatically be made by both processes without substantial changes. Formulations that can be made into a microcapsule by a bulk emulsification process can very often be also made by a microfluidics process, but the reverse is not necessarily true. The fact that a composition can be made in a microfluidic process does not automatically mean that it can be made by a bulk process.

[0010] There therefore remains a need for a bulk emulsification process that can operate at large industrial scales, wherein discreet core-shell microcapsules can be formed, preferably wherein high temperature processing is not required.

[0011] WO2019243425 describes a process of forming microcapsules containing a hydrophobic core by a process of complex coacervation, optionally combined with interfacial polymerization and covalent cross-linking for extra reinforcement of the shell layer. The process claimed in WO2019243425 is fundamentally different to that of the present invention.

[0012] In WO2019243425, a hydrophobic core material, which does not contain any wall-forming polymeric material, is dispersed in an aqueous phase comprising a globular protein to form an emulsion. An aqueous polysaccharide-containing solution is then added to this emulsion. Preferably the globular protein is whey protein and the polysaccharide is pectin. The use of whey protein and pectin to form microcapsules by a process of complex coacervation is well known in the art. This interaction is known to be a combination of covalent and non-covalent bonding (see Du et al; Colloids and Surfaces B; Volume 210; Feb 2022; 112253: The complex of whey protein and pectin: Interactions, functional properties and applications in food colloidal systems - A review).

[0013] WO2019243425 does claim globular proteins comprising vegetable proteins but does not provide any details. All of the examples use whey protein and preferably the globular protein is whey protein. It is an inherent need for the type of complex coacervation process described in Claim 1 of WO2019243425 that the globular protein is soluble. Whey, betalactoglobulin, ovalbumin and bovine serum albumin, as specifically claimed in Claim 3, are all soluble proteins. Complex coacervation is well known in the art for forming microcapsules and depends on two soluble but oppositely-charged polymeric materials interacting with each other and the resulting coacervate being deposited at the oil-water interface of the hydrophobic droplets to form a composite shell around the hydrophobic core.

[0014] The globular proteins described in WO2019243425 are not suitable shell materials as claimed in the present invention. WO2019243425 implicitly describes the use of aqueous solutions of soluble globular proteins. The aqueous solubility of the globular proteins specifically claimed in WO2109243425 means that they are not suitable shell materials on their own. In the present invention, the shell material needs to be dispersed / dissolved in a non-aqueous shell solvent. The shell material needs to be more soluble in the shell solvent than in water and this is required for the simple coacervation process of the present invention.

[0015] WO2019243425 claims the addition of an aqueous solution of polysaccharide to the oil-in- water dispersion formed by mixing the hydrophobic active material with the aqueous mixture of globular protein. This means that the polysaccharide solution described in WO2019143425 cannot be described as a primary stabilizer in the context of the present invention. In the present invention, the materials of step (a) and step (b) are non-aqueous. The addition of the primary stabilizer in step (d) helps form an emulsion. In WO2019243425 the polysaccharide is being added to an existing oil-in-water emulsion. Therefore it cannot be described as the primary stabilizer as the emulsion to which it is being added is already stable. WO2023217590 describes an interfacial polymerization process for forming microcapsules. A cross-linking agent - here acyl chloride - is dispersed in the hydrophobic active material which is them emulsified in an aqueous solution of oligopeptides. The acyl chloride migrates to the interface of the oil droplet and covalently reacts with the oligopeptide to form an insoluble microcapsule wall material. The wall material is described as a polyamide. A crosslinking material such as an acyl chloride is not a shell material in the sense of the present invention as it is not capable of forming a microcapsule wall without covalently reacting with other species. In WO2023217950 the wall material is the polyamide formed by the interfacial reaction of the acyl chloride and the oligopeptides. The resulting cross-linked polyamide microcapsule wall material will be very different to the material of the present invention, which is formed by non-covalent interactions of the shell material with the surrounding aqueous phase. Increased cross-linking typically reduces the biodegradability of wall materials.

[0016] US20220250024 describes a similar process to WO2023217590 in that an acyl chloride is added to a hydrophobic active core material and the mixture or solution is then emulsified into an amino-acid containing aqueous solution. Example 1 of US20220250024 describes a process in which colloidal albumin is dispersed in a hydrophobic liquid (benzyl benzoate) and then combined with a solution of acyl chloride in benzyl benzoate. The albumin must be added as a solid. The resulting mixture is then emulsified in an aqueous solution containing an amino compound - in Example 1 L-lysine- to which an additional amino compound is added. The shell material of the microcapsules is a polyamide formed by interfacial polymerization at the oikwater droplet interface due to the covalent reaction of the amino compounds in the aqueous phase with the acyl chloride in the hydrophobic phase. The wall material will inherently have a different form and structure to the present invention due to the different mechanism of wall formation. In the present invention, the primary stabilizer is in the form of a suspension which is combined with the hydrophobic active phase to form an emulsion. The primary stabilizer cannot be in the same phase as the active material as described in US20220250024. Benzyl benzoate is described in the present invention as a possible active material. It is not described as a possible shell solvent or as a possible primary stabilizer solvent. As in WO2023217950, acyl chloride cannot be described as a shell material in the context of the present invention. WO2023274788 describes a variation of the interfacial polymerization processes described in US20220250024 and WO2023217590 to form a polyamide microcapsule wall material. The shell materials of the present invention are not polyamides.

[0017] US2023105666 just describes specific acyl chlorides used to form the polyamide wall material by interfacial polymerization.

[0018] W02023020883 describes a process for making perfume microcapsules where the shell material is formed by the reaction of a polyisocyanate and an aminosilane. This is a covalent cross-linking reaction. The isocyanate and the silane can both be in the oil phase. They only react at the interface of the oil core droplet when they come into contact with water. The resulting polymeric material will be covalently cross-linked and different to the shell material of the present invention. As a cross-linked synthetic material (since the starting materials are not natural materials), the wall of the microcapsules of W02023020883 will be much less biodegradable than the microcapsules of the present invention. The “stabilizer” in W02023020883 is actually the wall material hence it cannot be added separately as in the present invention. The proteins and polysaccharides mentioned in W02023020883 are to form a coacervate adhesive coating onto the formed microcapsules to aid deposition and are not part of the wall material.

[0019] WO2012168144 describes a process in which a polymeric / inorganic composite wall surrounding an oily active droplet core is formed by a two-stage process. The oily active phase is dispersed into a suspension of a protein (preferably gelatine) with a negatively- charged polymer (preferably gum Arabic). The coacervate formed by the interaction of these polymers deposits at the oikwater interface forming the microcapsule wall. Preferably the microcapsule walls are then further cross-linked. This is different to the present invention. The microcapsules are then contacted with a liquid silica precursor to precipitate silica within the coacervate wall material so as to form a composite wall structure.

[0020] The use of a liquid silica precursor is necessary to ensure that the silica precursor can permeate throughout the coacervate wall material. The objective of WO2012168144 was to form robust microcapsules that are more breakable and less deformable than alternative microcapsules. As such, high levels of silica are required and WO2012168144 describes the resulting wall materials as being “rich in silicon”. Biodegradability was not an objective. In the present invention, colloidal silica is described as a possible primary stabiliser of the droplets of active material and shell material. This effect depends on the silica being present as particles and also being present at a low level. The liquid silica precursors of WO2012168144 cannot act as primary stabilisers. There is no inherent mechanism why the microcapsule wall formation of the present invention would lead to stabilising silica particles being embedded within and throughout the shell material in the manner described in WO2012168144.

[0021] SUMMARY OF THE INVENTION

[0022] Viewed from a first aspect, the present invention provides a method for the preparation of a composition of core-shell microcapsules, the method comprising the following steps: a) providing a shell composition comprising one or more shell materials and one or more shell solvents; b) providing a liquid active composition comprising one or more active materials and optionally one or more active material solvents; c) preparing a liquid primary stabiliser composition comprising one or more primary stabilisers and one or more primary stabiliser solvents; d) mixing said shell composition of step a) with said primary stabiliser composition of step b) to result in a core composition; e) mixing said core composition of step d) with said primary stabiliser composition of step c) so as to form an emulsion of the core composition of step d) in the primary stabiliser composition of step c); f) stirring the emulsion of step e) to form a shell wall by non-covalent interaction of at least part of the one or more shell materials at the interface of droplets of the core composition of step d) and an external phase of the primary stabiliser composition of step c) so as to result in a microcapsules composition of coreshell microcapsules in said external phase; g) optionally removing at least part of the external phase of step f).

[0023] Viewed from another aspect, the present invention provides a composition of core-shell microcapsules, wherein the microcapsules are obtained by the method of the present invention. Viewed from a further aspect, the present invention provides a composition of core-shell microcapsules, wherein the microcapsules comprise a core comprising one or more active materials and a shell comprising one or more shell materials and one or more primary stabilisers.

[0024] Viewed from an even further aspect, the present invention provides the use of a composition of core-shell microcapsules of the invention in a formulated product.

[0025] DETAILED DESCRIPTION OF THE INVENTION

[0026] The inventors of the present invention have uncovered a method to prepare a composition of core-shell microcapsules, in which the core-shell structure allows controlled release of the active material when the microcapsules are broken by pressure or shear applied to the dried microcapsule. The method allows for a wide variety of actives to be encapsulated by an easily scalable emulsification process that does not require high temperatures or excessive residence times. The core-shell microcapsules of the present invention are suitable for use in a wider variety of formulated products.

[0027] The present invention is directed to a method for the preparation of a composition of coreshell microcapsules, the method comprising the following steps: a) providing a shell composition comprising one or more shell materials and one or more shell solvents; b) providing a liquid active composition comprising one or more active materials and optionally one or more active material solvents; c) preparing a liquid primary stabiliser composition comprising one or more primary stabilisers and one or more primary stabiliser solvents; d) mixing said shell composition of step a) with said active composition of step b) to result in a core composition; e) mixing said core composition of step d) with said primary stabiliser composition of step c) so as to form an emulsion of the core composition of step d) in the primary stabiliser composition of step c); f) stirring the emulsion of step e) to form a shell wall by non-covalent interaction of at least part of the one or more shell materials at the interface of droplets of the core composition of step d) and an external phase of the primary stabiliser composition of step c) so as to result in a microcapsules composition of core-shell microcapsules in said external phase; g) optionally removing or replacing at least part of the external phase of the microcapsules composition of step f).

[0028] Without wishing to be bound by theory it is believed that in steps e) and f) the shell material in the core composition undergoes anti-solvent interfacial precipitation at the interface between the core composition and the external phase. This interface is stabilised by the primary stabiliser.

[0029] The term “non-covalent interaction” in step f) refers to non-covalent interactions including electrostatic interaction, van der Waals forces, TT-effects, hydrogen bonding and hydrophobic interactions. These interactions may be intramolecular, such as in protein folding, or intermolecular, between molecules. They are key in enabling large molecules to form a defined 3-dimensional structure. Such interactions do not result in breaking or forming covalent bonds.

[0030] Optionally, methods of the present invention further comprise h) adding a secondary stabiliser composition comprising one or more secondary stabilisers and optionally one or more secondary stabiliser solvents to the microcapsules composition of either step f) or step g).

[0031] Optionally, methods of the present invention further comprise i) isolating the microcapsules from the microcapsules composition of either step f), step g) or step h).

[0032] In preferred methods of the present invention, the one or more shell materials are selected from the group consisting of prolamin proteins, glutelin proteins, polysaccharides and polyesters. More preferably, the one or more shell materials are selected from the group consisting of zein, shellac, chitosan, and polyhydroxyalkanoates (PHAs). Most preferred, the one or more shell materials are shellac and / or zein.

[0033] Plant proteins are mainly comprised of globular proteins which are storage proteins and can be classified as albumins (soluble in water), globulins (soluble in dilute salt solutions), prolamins (soluble in aqueous ethanol solutions), and glutelins (soluble in dilute acid / alkaline solutions or insoluble in water). Albumins and globulins are predominately present in all pulses (at greater than 50%) and some pseudo cereals (such as quinoa and amaranth). Globulins represent between about 70 and 78 wt% of the protein found in legume seeds, whereas albumins constitute between about 10 and 20 wt% of the protein. Globulins are the storage proteins of most legume seeds. Globulins have higher molecular weights than albumins and are insoluble in pure water but dissolve in dilute salt solutions. Globulins are typically more water soluble than prolamins.

[0034] The storage proteins from different plants can be classified by their sedimentation coefficient in Svedberg units (S). This coefficient indicates the speed of sedimentation of a macromolecule in a centrifugal field. It should be noted however that some small variations of sedimentations are expected depending on the type of plant and / or the extraction protocol employed. Therefore, the sedimentation coefficient is not intended to be restrictive, but rather serve as a useful guide for the classification of the storage proteins.

[0035] The albumins found in pulse proteins are soluble proteins with a variable molecular mass (-12-28 kDa). Albumin proteins include for example 2S albumins, napins, barley trypsin inhibitor and wheat a-amylase inhibitor. In typical commercial protein isolates there are generally only residual amounts of albumins present as they are generally removed during the protein extraction process.

[0036] The major globulins found in pulses are vicilin (7S) and legumin (11 S). Vicilin (7S) has a trimeric structure with molecular mass (MM) of -175-180 kDa and lacks disulfide bridging. In contrast, legumin (11 S) has a hexameric (MM of -340-360 kDa) quaternary structure composed of 6 subunits (MM of ~60kDa) linked by non-covalent forces. Each subunit pair is comprised of an acidic (MM -40 kDa) and basic (MM -20 kDa) chain joined by a disulfide bond. The ratio of legumin:vicilin (L / V) is not fixed and may vary among different pulse varieties and species. A third globulin pulse protein is convicilin with 3 or 4 subunits each having a MM of -70 kDa and a sedimentation coefficient of -8S. Convicilin is present in lesser amounts as compared to other globulins. Other globulins include for example 2S globulins, conglutin, sfa, edestin, amandin, concanvalin, cruciferin, helianthinin.

[0037] Globulins are typically obtained from soybean, pea, rice, potato, rapeseed, sunflower, lentil, chickpea, bean, fava bean, mung bean, sunflower seed, pumpkin seed, flax, chia, canola, lupine, alfalfa, moringa, borage, hemp seed, and cotton seed; preferably obtained from pea protein, potato protein, rapeseed protein, and / or sunflower protein.

[0038] Prolamins and glutelins make up 85% of protein in the cereal and pseudo cereal families. Prolamins are typically found in wheat, corn, barley and rye whilst glutelins are typically only found in wheat and rice.

[0039] Prolamins are high in proline and glutamine amino acid content. They have a relatively high fraction of non-polar functionalities. They are less abundant than globulins and are found across fewer plant species. They include gliadin from wheat, hordein from barley, secalin from rye, zein (alpha, beta, gamma) from corn, kafirin from sorghum, avenin from oats. Prolamins are typically much less water soluble than globulins.

[0040] Polysaccharides are the most abundant carbohydrates found in food. They are long chain polymeric carbohydrates composed of monosaccharide units bound together by glycosidic linkages. This carbohydrate can react with water (hydrolysis) using amylase enzymes as a catalyst, which produces constituent sugars (monosaccharides, or oligosaccharides). They range in structure from linear to highly branched chains.

[0041] Chitin is the second most abundant polysaccharide occurring in nature after cellulose, and is the material that gives strength to the exoskeletons of crustaceans, insects, and the cell walls of fungi. Through enzymatic or chemical deacetylation chitin can be converted into chitosan. Chitosan is composed of |3-(1 -4)-linked d-glucosamine and N-acetyl-d-glucosamine randomly distributed within the polymer. Although most polysaccharides are usually either neutral or negatively charged in an acidic environment, chitosan is positively charged.

[0042] Gellan gum is an anionic linear polysaccharide composed by approximately, 60% glucose, 20% glucuronic acid, and 20% rhamnose as a repeating unit, and two acyl groups, acetate and glycerate, bound to the glucose residue adjacent to glucuronic. It is a thermally reversible gel with good stability and gel strength that can vary depending on the degree of deacylation. Xanthan gum is a branched polysaccharide that is a common food additive with good emulsification properties and high viscosity.

[0043] Another example of a linear polysaccharide is pullulan composed of maltotriose units, three glucose units connected by a-1 ,4 glycosidic bonds, connected to each other by a-1 ,6 glycosidic bonds Other suitable polysaccharides include agar gum, pectin, alginates, locust bean gum, guar gum, flaxseed gum, carboxymethyl cellulose, methyl cellulose, gum arabic, and carrageenan.

[0044] Starches consist essentially of amylose, a linear polysaccharide, and / or amylopectin, a branched polysaccharide, and in the native form are typically in the form of semi-crystalline granules. A waxy starch consists essentially of amylopectin and lacks an appreciable amount of amylose. Alternatively, some starches are classified as high amylose starches. Sources of starch include but are not limited to fruits, seeds, and rhizomes or tubers of plants, such as wheat starch, potato starch, pea starch, waxy potato starch, maize starch, waxy maize starch, high amylose maize starch, tapioca starch, cassava starch, rye starch, sorghum starch, chickpea starch, soy starch, or a mixture thereof, preferably potato starch.

[0045] Starches may be modified, for example, by enzymes, by heat treatment, oxidation, or reaction with various chemicals and can be selected from acid-treated starch, dextrin, alkaline-modified starch, bleached starch, oxidized starch, enzyme-treated starch, maltodextrin, cyclodextrin monostarch phosphate, distarch phosphate, acetylated starch, hydroxypropylated starch, hydroxyethyl starch, starch sodium octenyl succinate, starch aluminium octenyl succinate or cationic starch, or a mixture thereof, preferably acid-treated starch.

[0046] Shellac is a natural polyester, which mainly contains esters of aleuritic, jalaric, shellolic, and butolic acid. It is a natural resin, the secretion of the lac insect, Laccifer lacca, which is then purified so that the commercial purified shellac resin consists of 85-90% pure shellac, 5-8% shellac wax, and 2-5% impurities. Shellac resin is dried and available as flakes or as a ground powder.

[0047] Polyhydroxyalkanoates (PHA) are aliphatic polyesters produced by fermentation in microorganisms with a range of physical properties.

[0048] In preferred methods of the present invention, the one or more shell materials are bio-based materials.

[0049] In alternatively preferred methods of the present invention, the one or more shell materials are plant materials. In preferred methods of the present invention, the one or more shell solvents are selected from the group consisting of glycols and glycol derivatives, ethyl esters, glycerine esters, alcohols, organic solvents, ionic liquids, fatty acids and fatty acid esters. More preferably, the one or more shell solvents are selected from the group consisting of propylene glycol, dipropylene glycol, ethylene glycol, triethylene glycol, propylene carbonate, ethylene carbonate, triethyl citrate, ethyl lactate, ethyl acetate, glycerol formal, methanol, ethanol, isopropyl alcohol, butanols, acetone, dimethyl sulphoxide, imidazolium-based ionic liquids, myristic acid, lauric acid, palmitic acid, stearic acid, oleic acid and sucrose fatty acid esters. Even more preferably, the one or more shell solvents are selected from the group consisting of glycols. Most preferably, the one or more shell solvents are propylene glycol and / or dipropylene glycol.

[0050] In preferred methods of the present invention, the one or more shell solvents are present as an aqueous mixture of one or more shell solvents.

[0051] In preferred methods of the present invention, the shell solvent is water having a pH greater than 7, more preferably a pH greater than 10.

[0052] In preferred methods of the present invention, the water present in the core composition is an anti-solvent.

[0053] In preferred methods of the present invention, the one or more shell solvents are bio-based materials.

[0054] In alternatively preferred methods of the present invention, the one or more shell solvents are plant materials.

[0055] In preferred methods of the present invention, the one or more active materials are selected from the group consisting of fragrance materials, essential oils, fat soluble vitamins, minerals, flavour materials, agrochemicals, cosmetic ingredients, fatty acids, surface care ingredients, pharmaceutical ingredients, microorganisms including probiotics, and fungal spores. More preferably, the one or more active materials are selected from fragrance materials, flavour materials and probiotics.

[0056] As used herein, the term "fragrance" (used interchangeably with the term “perfume”) refers to the component of a formulation that is capable of imparting or modifying the odour of a product, such as a fabric conditioner or a hair conditioner or a substrate such as fabric or hair. A fragrance is typically used to impart an overall pleasant odour or odour profile to a product either to provide a pleasurable experience, such as a Fine Fragrance, or to provide sensory cues as to the product’s benefit and function, such as a calming effect for a lavender sleep aid, the idea of cleanliness for a laundry product. Fragrance can also be used to mask an unpleasant odour, such as in an insect repellent product, and the term “fragrance” also includes malodour counteractants, materials that reduce the perception of such unpleasant odours. A “fragrance” may be composed of one or more components that can be a single chemical entity, referred to herein as a “fragrance material” (used interchangeably with the term “perfume material”), or a mixture of different “fragrance materials”. Fragrance materials can be created by either synthetic processes or extracted from nature, particularly plants, to obtain naturally occurring plant essential oils and plant extracts such as orange oil. Fragrance materials created by synthetic processes can be either new-to-the-world chemicals or nature-identical fragrance materials. Synthetic and naturally derived fragrance materials can then be blended into fragrances by skilled perfumers, also called noses, for use in consumer products. Fragrance materials can be obtained from specialist fragrance suppliers, known as fragrance houses, as individual chemicals, natural blends or as proprietary specialty blends where the full composition is not disclosed. The individual fragrance materials which comprise a known natural blend can be found by reference to Journals commonly used by those skilled in the art such as "Perfume and Flavourist" or "Journal of Essential Oil Research", or listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA and more recently re-published by Allured Publishing Corporation Illinois (1994) and "Perfume and Flavour Materials of Natural Origin", S. Arctander, Ed., Elizabeth, N.J., 1960. It will be understood that for the purposes of this invention, a “fragrance material” includes a profragrance such as an acetal pro-fragrance, ketal pro-fragrance, ester pro-fragrance, hydrolysable inorganic-organic pro-fragrance, and combinations thereof. The fragrance materials may be released from the pro-fragrances in a number of ways, for example, by hydrolysis, or by a shift in an equilibrium reaction, or by a pH-change, or by enzymatic release, or by UV-radiation.

[0057] A fragrance material can be described in terms of its odour strength, detection threshold, odour saturation and its character. In fragrance encapsulates it is preferable to use fragrance materials with a low odour detection threshold and a high strength so as to maximise the noticeability of even small levels of fragrance encapsulated and released. In order to impart an odour, a fragrance material must be volatile, even if only to a small degree, as it is necessary for the molecule to be airborne to enter the nose, where it gets attached to specific neuroreceptors and elicits a signal within the olfactory system.

[0058] Fragrance materials can be classified according to their volatility. Preferably fragrance materials are liquid at 20°C and atmospheric pressure but occasionally they may be solid and can be blended with other liquid fragrance materials or solvents. Typically, the fragrance industry refers to the volatility and substantivity by loosely categorising materials into one of 3 categories: base notes for the least volatile and most substantive, heart notes for those of moderate volatility and substantivity and top notes for the most volatile and least substantive. This is based on the odour perception of the materials and is quite subjective. One way of objectively classifying the volatility of fragrance materials is according to their vapour pressure.

[0059] As used herein, the term "vapour pressure" means the partial pressure in air at a defined temperature (e.g., 25°C) and standard atmospheric pressure (760 mmHg) for a given chemical species. It defines a chemical species' affinity for the gas phase rather than the liquid or solid state. The higher the vapour pressure the greater the proportion of the material that will, at equilibrium, be in a closed headspace. It is also related to the rate of evaporation of a fragrance material which is defined in an open environment where the material is leaving the system. The vapour pressure can be readily determined according to the reference program ACD / Percepta Desktop Software, Version 14.0 (Build: Aug / 26 / 2021), Advanced Chemistry Development, Inc (ACD / Labs), Toronto, Canada, www.acdlabs.com.

[0060] A physical parameter that is relevant to the encapsulation of a fragrance material is its hydrophobicity, which may be defined in terms of its partition coefficient P. As used herein, the term "partition coefficient" refers to the ratio between the equilibrium concentration of that substance in n-octanol and in water, and is a measure of the differential solubility of said substance between these two solvents. As used herein, the term “logP” refers to the logarithm to the base 10 of the partition coefficient P. The logP can be readily determined according to the reference program ACD / Percepta Desktop Software, Version 14.0 (Build: Aug / 26 / 2021), Advanced Chemistry Development, Inc (ACD / Labs), Toronto, Canada, www.acdlabs.com LogP values are predicted from the SMILE string of fragrance materials molecules. Three different types of logP values can be selected from the software. The logP Classic is based on an algorithm which takes into account a database of experimental logP values while using the principle of isolating carbons. The logP GALAS is based on an algorithm taking into account a database of a training set of compounds as well as adjusting the values with data from structurally close compounds. The consensus logP is a model based on the previous two algorithms, which can be expressed as: consensus logP = a x logP Classic + b x logP GALAS, where a and b are coefficients of the model. The latter value, consensus logP, is the logP value indicated herein.

[0061] Another aspect that is relevant to the encapsulation of a fragrance material is its Hansen Solubility Parameters (HSPs). The term HSP refers to a solubility parameter approach proposed by Charles Hansen first used to predict polymer solubility in a given solvent as described in, The Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient, by Charles Hansen, Danish Technical Press (Copenhagen, 1967). This approach has since been reapplied to many other molecules. The fragrance material (or flavour material or solvent) and its behaviour in the environment are defined by 3 forces: atomic dispersion forces, molecular permanent dipole forces, and molecular hydrogen bonding forces.

[0062] Materials with similar HSP parameters are more likely to be miscible. These forces can be quantified by 3 values: bD, the Hansen dispersion value which relates to the Van der Waals forces (intermolecular forces); bP, the Hansen polarity value which relates to the dipole moment (electrical charges); and bH, the Hansen Hydrogen-bonding ("h-bonding") value. The solubility parameter 5 (MPa1 / 2) is defined as b2= bo2+ bp2+ bn2= EA / , where E is the cohesive energy of a solvent and V is the molar volume. The HSP values for a given material can be obtained from the HSPiP (Hansen Solubility Parameters in Practice) software available from www.hansen-solubility.com through two main different ways. Those values can either be retrieved from the Master Dataset, which comprises over 20,000 materials, by searching by name or CAS number; or be predicted by entering the SMILE string of a given molecule in the DIY section of the software, using the Y-MB (Yamamoto-Molecular Breaking) method. Furthermore, the determination of the HSP sphere relative to a given fragrance material is a good way to predict the solubility preferences within a blend of fragrance materials. The radius Ro of the HSP sphere is defined as Ro = Ra / RED, where Ra is the HSP distance between two molecules (1 and 2) expressed by: Ra2= 4 (boi - bD2)2+ (bpi - bp2)2+ (bm - bH2)2, and RED is the Relative Energy Difference. This RED value can also be extracted from or predicted through the HSPiP software, and a good solvent for a given material should exhibit a RED value lower or equal to 1 , whereas a solvent displaying a RED value greater than 1 should be considered as a bad solvent for the given material. A fragrance material may be selected from an alcohol, an aldehyde, a ketone, an ester, an ether, an acetate, an alkene, a nitrile, a nitrogenous heterocyclic compound, a sulfurous heterocyclic compound, and a Schiff base.

[0063] Preferred aldehyde fragrance materials include, without limitation, alpha- amylcinnamaldehyde, anisic aldehyde, decyl aldehyde, lauric aldehyde, methyl n-nonyl acetaldehyde, methyl octyl acetaldehyde, nonylaldehyde, benzenecarboxaldehyde, neral, geranial, 1,1-diethoxy-3,7-dimethylocta-2,6-diene, 4-isopropylbenzaldehyde, 2,4-dimethyl-3- cyclohexene-1-carboxaldehyde, alpha-methyl-p-isopropyldihydrocinnamaldehyde, 3-(3- isopropylphenyl) butanal, alpha-hexylcinnamaldehyde, 7-hydroxy-3,7-dimethyloctan-1-al, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, octyl aldehyde, phenylacetaldehyde, 2,4- dimethyl-3-cyclohexene-1-carboxaldehyde, hexanal, 3,7-dimethyloctanal, 6,6- dimethylbicyclo[3.1.1]hept-2-ene-2-butanal, nonanal, octanal, 2-nonenal undecenal, 2- methyl-4-(2,6,6-trimethyl-1-cyclohexenyl-1)-2-butenal, 2,6-dimethyloctanal, 3-(p- isopropylphenyl)propionaldehyde, 3-phenyl-4-pentenal citronellal, o / p-ethyl-alpha, alpha, 9- decenal, dimethyldihydrocinnamaldehyde, p-isobutyl-alphamethylydrocinnamaldehyde, cis-4- decen-1-al, 2,5-dimethyl-2-ethenyl-4-hexenal, trans-2-methyl-2-butenal, 3-methylnonanal, alpha-sinensal, 3-phenylbutanal, 2,2-dimethyl-3-phenylpropionaldehyde, m-tertbutyl-alpha- methyldihydrocinnamic aldehyde, geranyl oxyacetaldehyde, trans-4-decen-1-al, methoxycitronellal, and mixtures thereof.

[0064] Preferred ester fragrance materials include, without limitation, allyl cyclohexane-propionate, allyl heptanoate, allyl amyl glycolate, allyl caproate, amyl acetate (n-pentyl acetate), amyl propionate, benzyl acetate, benzyl propionate, benzyl salicylate, cis-3-hexenylacetate, citronellyl acetate, citronellyl propionate, cyclohexyl salicylate, dihydro isojasmonate, dimethyl benzyl carbinyl acetate, ethyl acetate, ethyl acetoacetate, ethyl butyrate, ethyl-2- methyl butryrate, ethyl-2-methyl pentanoate, fenchyl acetate (1 ,3,3-trimethyl-2-norbornanyl acetate), tricyclodecenyl acetate, tricyclodecenyl propionate, geranyl acetate, cis-3-hexenyl isobutyrate, hexyl acetate, cis-3-hexenyl salicylate, n-hexyl salicylate, isobornyl acetate, linalyl acetate, para-tertiary-butyl cyclohexyl acetate, (-)-L-menthyl acetate, ortho-tertiary- butylcyclohexyl acetate, methyl benzoate, methyl dihydro isojasmonate, alpha-methylbenzyl acetate, methyl salicylate, 2-phenylethyl acetate, prenyl acetate, cedryl acetate, cyclabute, phenethyl phenylacetate, terpinyl formate, citronellyl anthranilate, ethyl tricyclo[5.2.1.0- 2,6]decane-2-carboxylate, n-hexyl ethyl acetoacetate, 2-tertbutyl-4-methyl cyclohexyl acetate, formic acid, 3,5,5-trimethylhexyl ester, phenethyl crotonate, cyclogeranyl acetate, geranyl crotonate, ethyl geranate, geranyl isobutyrate, 3,7-dimethyl-ethyl 2-nonynoate-2,6- octadienoic acid methyl ester, citronellyl valerate, 2-hexenylcyclopentanone, cyclohexyl anthranilate, L-citronellyl tiglate, butyl tiglate, pentyl tiglate, geranyl caprylate, 9-decenyl acetate, 2-isopropyl-5-methylhexyl-1 butyrate, n-pentyl benzoate, 2-methylbutyl benzoate (and mixtures thereof with pentyl benzoate), dimethyl benzyl carbinyl propionate, dimethyl benzyl carbinyl acetate, trans-2-hexenyl salicylate, dimethyl benzyl carbinyl isobutyrate, 3,7- dimethyloctyl formate, rhodinyl formate, rhodinyl isovalerate, rhodinyl acetate, rhodinyl butyrate, rhodinyl propionate, cyclohexylethyl acetate, neryl butyrate, tetrahydrogeranyl butyrate, myrcenyl acetate, 2,5-dimethyl-2-ethenylhex-4-enoic acid, methyl ester, 2,4- dimethylcyclohexane-1 -methyl acetate, ocimenyl acetate, linalyl isobutyrate, 6-methyl-5- heptenyl-1 acetate, 4-methyl-2-pentyl acetate, n-pentyl 2-methylbutyrate, propyl acetate, isopropenyl acetate, isopropyl acetate, 1-methylcyclohex-3-ene-carboxylic acid, methyl ester, propyl tiglate, propyl / isobutyl cyclopent- 3-enyl- 1 -acetate (alphavinyl), butyl 2-furoate, ethyl 2- pentenoate, (E)-methyl 3-pentenoate, 3-methoxy-3-methylbutyl acetate, n-pentyl crotonate, n-pentyl isobutyrate, propyl formate, furfuryl butyrate, methyl angelate, methyl pivalate, prenyl caproate, furfuryl propionate, diethyl malate, isopropyl 2-methylbutyrate, dimethyl malonate, bornyl formate, styralyl acetate, 1-(2-furyl)-1-propanone, l-citronellyl acetate, 3,7- dimethyl-1,6-nonadien-3-yl acetate, neryl crotonate, dihydromyrcenyl acetate, tetrahydromyrcenyl acetate, lavandulyl acetate, 4-cyclooctenyl isobutyrate, cyclopentyl isobutyrate, 3-methyl-3-butenyl acetate, allyl acetate, geranyl formate, cis-3-hexenyl caproate, and mixtures thereof.

[0065] Preferred alcohol fragrance materials include, without limitation, benzyl alcohol, beta- gamma-hexenol (2-hexen-1-ol), cedrol, citronellol, cinnamic alcohol, p-cresol, cumic alcohol, dihydromyrcenol, 3,7-dimethyl-1-octanol, dimethyl benzyl carbinol, eucalyptol, eugenol, fenchyl alcohol, geraniol, hydratopic alcohol, isononyl alcohol (3,5,5-trimethyl-1-hexanol), linalool, methyl chavicol (estragole), methyl eugenol (eugenyl methyl ether), nerol, 2-octanol, patchouli alcohol, phenyl hexanol (3-methyl-5-phenyl-1-pentanol), phenethyl alcohol, alphaterpineol, tetrahydrolinalool, tetrahydromyrcenol, 4-methyl-3-decen-5-ol, l-3,7- dimethyloctane-1-ol, 2-(furfuryl-2)-heptanol, 6,8-dimethyl-2-nonanol, ethyl norbornyl cyclohexanol, beta-methyl cyclohexane ethanol, 3,7-dimethyl-(2),6-octen(adien)-1-ol, trans- 2-undecen-1-ol, 2-ethyl-2-prenyl-3-hexenol, isobutyl benzyl carbinol, dimethyl benzyl carbinol, ocimenol, 3,7-dimethyl-1,6-nonadien-3-ol (cis & trans), tetrahydromyrcenol, alphaterpineol, 9-decenol-1, 2-(2-hexenyl)-cyclopentanol, 2,6-dimethyl-2-heptanol, 3-methyl-1- octen-3-ol, 2,6-dimethyl-5-hepten-2-ol, 3,7,9-trimethyl-1 ,6-decadien-3-ol, 3,7-dimethyl-6- nonen-1-ol, 3,7-dimethyl-1-octyn-3-ol, 2,6-dimethyl-1,5,7-octatrienol-3, dihydromyrcenol, 2,6,-trimethyl-5,9-undecadienol, 2,5-dimethyl-2-propylhex-4-enol-1 , (Z)-3-hexenol, o,m,p- methyl-phenylethanol, 2-methyl-5-phenyl-1 -pentanol, 3-methylphenethyl alcohol, para-methyl dimethyl benzyl carbinol, methyl benzyl carbinol, p-methylphenylethanol, 3,7-dimethyl-2- octen-1-ol, 2-methyl-6-methylene-7-octen-4-ol, and mixtures thereof.

[0066] Preferred ketone fragrance materials include, without limitation, oxacycloheptadec- 10-en-2- one, benzylacetone, benzophenone, L-carvone, cis-jasmone, 4-(2,6,6-trimethyl-3- cyclohexen-1-yl)-but-3-en-4-one, ethyl amyl ketone, alpha-ionone, ionone beta, ethanone, octahydro-2, 3, 8, 8-tetramethyl-2-acetonaphthalene, alpha-irone, 1-(5,5-dimethyl-1-cyclo- hexen-1-yl)-4-penten-1-one, 3-nonanone, ethyl hexyl ketone, menthone, 4-methyl- acetophenone, gamma-methyl ionone, methyl pentyl ketone, methyl heptenone (6-methyl-5- hepten-2-one), methyl heptyl ketone, methyl hexyl ketone, delta muscenone, 2-octanone, 2- pentyl-3-methyl-2-cyclopenten-1-one, 2-heptylcyclopentanone, alpha-methylionone, 3- methyl-2-(trans-2-pentenyl)-cyclopentenone, octenyl cyclopentanone, n- amylcyclopentenone, 6-hydroxy-3,7-dimethyloctanoic acid lactone, 2-hydroxy-2-cyclohexen- 1-one, 3-methyl-4-phenyl-3-buten-2-one, 2-pentyl-2,5,5-trimethylcyclopentanone, 2- cyclopentylcyclopentanol-1 , 5-methylhexan-2-one, gamma-dodecalactone, delta- dodecalactone, gamma-nonalactone, delta-nonalactone, gamma-octalactone, delta- undecalactone, gamma-undecalactone, alpha damascene, beta damascene, gamma damascene, delta damascene and mixtures thereof.

[0067] Preferred ether fragrance materials include, without limitation, diphenyl oxide, p-cresyl methyl ether, 4,6,6,7,8,8-hexamethyl-1 ,3,4,6,7,8-hexahydro-cyclopenta(G)-2-benzopyran, betanaphthyl methyl ether, methyl isobutenyl tetrahydropyran, 5-acetyl-1 , 1 ,2, 3,3,6- hexamethylindan (phantolide), 7-acetyl-1 ,1 ,3,4,4,6-hexamethyltetralin (tonalid), 2- phenylethyl-3-methylbut-2-enyl ether, ethyl geranyl ether, phenylethyl isopropyl ether, and mixtures thereof.

[0068] Preferred alkene fragrance materials include, without limitation, allo-ocimene, camphene, beta-caryophyllene, cadinene, diphenylmethane, d-limonene, lymolene, beta-myrcene, paracymene, 2-alpha-pinene, beta-pinene, alpha-terpinene, gamma-terpinene, terpineolene, 7- methyl-3-methylene-1 ,6-octadiene, and mixtures thereof.

[0069] Preferred nitrile fragrance materials include, without limitation, 3,7-dimethyl-6-octenenitrile, 3,7-dimethyl-2(3), 6-nonadienenitrile, (2E,6Z)-2,6-nonadienenitrile, n-dodecane nitrile, and mixtures thereof. Preferred Schiff base fragrance materials include, without limitation, citronellyl nitrile, nonanal / methyl anthranilate, N-octylidene-anthranilic acid methyl ester, hydroxycitronellal / methyl anthranilate, cyclamen aldehyde / methyl anthranilate, methoxyphenylpropanal / methyl anthranilate, ethyl p-aminobenzoate / hydroxycitronellal, citral / methyl anthranilate, 2,4-dimethylcyclohex-3-enecarbaldehyde methyl anthranilate, hydroxycitronellal-indole, and mixtures thereof.

[0070] As used herein, the term "flavour" refers to the component of a formulation that is capable of imparting or modifying the taste and smell of a product, such as a toothpaste or foodstuff. A flavour is typically used to impart an overall pleasant taste and smell, or a taste and smell profile, to a product either to simply provide a pleasurable experience, such as in a foodstuff, or to mask an unpleasant taste or smell, such as in a medicine. It will be understood that for the purposes of this invention, a “flavour material” includes a pro-flavour which may release the flavour material in a number of ways, for example, by hydrolysis, or by a shift in an equilibrium reaction, or by a pH-change, or by enzymatic release. A “flavour material” also includes flavour enhancers used to augment the perception of flavour.

[0071] A flavour or flavour material can be described in terms of its aroma strength, detection threshold and quality. A “flavour” may be composed of one or more components that can be a single chemical entity, referred to herein as a “flavour material”, or a mixture of different “flavour materials”. Flavour materials can be created by either synthetic processes or extracted from nature, particularly from plants, to create naturally occurring plant and animal oils and exudate, such as vanilla. Synthetic and naturally derived flavour materials can then be blended into flavours by skilled flavourists for use in consumer products. Flavour materials can be obtained from specialist flavour suppliers, known as flavour houses, as individual chemicals, natural blends or as proprietary specialty blends where the full composition is not disclosed. The individual flavour materials which comprise a known natural blend can be found by reference to Journals commonly used by those skilled in the art such as "Perfume and Flavourist" or "Journal of Essential Oil Research", or listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA and more recently re-published by Allured Publishing Corporation Illinois (1994); "Perfume and Flavour Materials of Natural Origin", S. Arctander, Ed., Elizabeth, N.J., 1960; and "Flavourings", E. Ziegler and H. Ziegler (ed.), Wiley-VCH Weinheim, 1998. It will be understood that flavours can be volatile or have volatile components which are detected by the nose in the same way as fragrances. As such, flavour materials can also be classified according to their physical characteristics, such as volatility and hydrophobicity, using the methods described above for fragrance materials. Flavour materials can also be described according to their Hansen Solubility Parameters using the methods described above for fragrance materials.

[0072] Sources of flavour materials include essential oils, concretes, absolutes, resins, resinoids, balsams, and tinctures. Preferred flavour materials include anise oil, ethyl-2-methyl butyrate, vanillin, cis-3-heptenol, cis-3-hexenol, trans-2-heptenal, butyl valerate, 2,3-diethyl pyrazine, methylcyclo-pentenolone, benzaldehyde, valerian oil, 3,4-dimeth-oxyphenol, amyl acetate, amyl cinnamate, y-butyryl lactone, trimethyl pyrazine, phenyl acetic acid, isovaleraldehyde, ethyl maltol, ethyl vanillin, ethyl valerate, ethyl butyrate, cocoa extract, coffee extract, peppermint oil, spearmint oil, clove oil, anethol, cardamom oil, Wintergreen oil, cinnamic aldehyde, ethyl-2-methyl valerate, g-hexenyl lactone, 2,4-decadienal, 2,4-heptadienal, methyl thiazole alcohol (4-methyl-5-b-hydroxyethyl thiazole), 2-methyl butanethiol, 4-mercapto-2- butanone, 3-mercapto-2-pentanone, 1-mercapto-2-propane, benzaldehyde, furfural, furfuryl alcohol, 2-mercapto propionic acid, alkyl pyrazine, methyl pyrazine, 2-ethyl-3-methyl pyrazine, tetramethyl pyrazine, polysulfides, dipropyl disulphide, methyl benzyl disulphide, alkyl thiophene, 2,3-dimethyl thiophene, 5-methyl furfural, acetyl furan, 2,4-decadienal, guiacol, phenyl acetaldehyde, b-decalactone, d-limonene, acetoin, amyl acetate, maltol, ethyl butyrate, levulinic acid, piperonal, ethyl acetate, n-octanal, n-pentanal, n-hexanal, diacetyl, monosodium glutamate, monopotassium glutamate, sulfur-containing amino acids, e.g., cysteine, 2-methylfuran-3-thiol, 2-methyldihydrofuran-3-thiol, 2,5-dimethylfuran-3-thiol, tetramethyl pyrazine, propylpropenyl disulphide, propylpropenyl trisulfide, diallyl disulphide, diallyl trisulfide, dipropenyl disulphide, dipropenyl trisulfide, 4-methyl-2-[(methylthio)-ethyl]- 1 ,3-dithiolane, 4,5-dimethyl-2-(methylthiomethyl)-1 ,3-dithiolane, and 4-methyl-2- (methylthiomethyl)-1,3- dithiolane, hop oils, and citrus oils such as lemon, orange, lime, and grapefruit.

[0073] Essential oils possess a strong odour and are produced by aromatic plants as secondary metabolites. They are usually obtained from several plant parts by steam distillation. They are made of a mixture of volatile compounds (between 20 and 100), even if they are, in most cases, characterized by two or three main compounds, representing the major part of the EO (20-70%). As an example, EO of Citrus limon is composed, in majority, of limonene and - pinene. EOs can be composed of molecules of many chemical functionalities such as terpenes and terpenoids (e.g. limonene, linalool); and aromatic and aliphatic molecules (e.g. cinnamaldehyde, safrole). These components are characterized by a low molecular weight and therefore high volatility and fast evaporation. They are also generally very sensitive oxygen and light. This makes it difficult to apply them to crops and fields directly as an agrochemical and therefore encapsulation that releases the EO or its components gradually is advantageous.

[0074] Essential oils were known, for a long time, for their antimicrobial and medicinal properties. The latter have, among others, led to the development of aromatherapy, where they are used as bactericide (e.g., tea tree and cinnamon EOs), fungicide (Lavandula spica EO), or virucides (Cinnamomum camphora).

[0075] In the last 20 years, the antibacterial and antifungal properties of essential oils have been assessed against a large variety of plant pathogens in order to determine their potential as alternative plant protection products (see e.g. Baser, K.H.C.; Buchbauer, G.’s Handbook of Essential Oils, 3rd ed.; ORC Press: Boca Raton, FL, USA, 2020, Chapter 24 provides an overview of the use of EOs in agriculture.

[0076] The complex composition of essential oils is interesting, as they could act as multisite chemicals, lowering the risk of resistance. Alternatively, the antibacterial and antifungal properties can be achieved by extracting major components from the EOs and using a single natural active or a simple mixture of a few natural components. For example, Thymus vulgaris EO main component is thymol and for Rosmarinus officinalis EO it is cineole. These single components can be extracted for use as agricultural actives.

[0077] In preferred methods of the present invention, the active material is an essential oil of natural origin and is selected from the following list of natural plant sources: Abies alba, Abies balsamea, Abies sibirica, Allium sativun, Amyris balsamifera, Anethum graveolens, Aniba rosaeodora var. Amazonica, Apium graveolens var. Dulce, Canarium luzonicum, Carum carvi, Cedrus atlantica, Cedrus deodara, Cinnamomum camphora, Cinnamomum cassia, Cinnamomum zeylanicum, Cinnamosma fragrans, Citrus aurantifolia, Citrus aurantium, Citrus bergamia, Citrus limon, Citrus paradisi, Citrus reticulata, Citrus sinensis, Copaifera officinalis, Coriandrum sativum, Corydothymus capitatus, Cuminum cymincum, Cupressus sempervirens var. Stricta, Cymbopogon citratus, Cymbopogon flexuosus, Cymbopogon giganteus, Cymbopogon martini var. Motia, Cymbopogon nardus, Cymbopogon winterianus, Eucalyptus citriodora, Eucalyptus dives, Eucalyptus globulus, Eucalyptus radiata, Eucalyptus smithii, Eugenia caryophyllus, Foeniculum vulgare, Fokienia hodginsii, Gaultheria fragrantissima, lllicum verum, Juniperus virgiana, Laurus nobilis, Lavendula angustifolia, Lavendula x burnatii clone grosso, Leptospermum petersonii, Litsea citrata, Melaleuca alternifolia, Melaleuca cajputii, Melaleuca quinquenervia, Mentha arvensis, Mentha pulegium, Mentha x citrata, Mentha x piperita, Monarda fistulosa, Myristica fragrans, Myrtus communis, Myrtus communis, Ocimum basilicum, Ocimum sanctum, Origanum compactum, Origanum heracleoticum, Origanum majorana, Pelargonium x asperum, Pimenta racemosa, Pimpinella anisum, Pinus pinaster, Pinus pinaster terebenthine, Pinus sylvestris, Piper nigrum, Rosmarinus officinalis, Salvia lanvandulifolia, Salvia officinalis, Satureja hortensis, Satureja montana, Styrax benzoe, Thuya occidentalis, Thymus mastichina, Thymus satureioides, Thymus vulgaris, Trachyspermum amni, Vanilla fragrans Auct, Vetiveria zizanoides, Zingiber officinale.

[0078] In addition, other Essential Oils with known effects as agrochemicals can be found in Chang Y, Harmon PF, Treadwell DD, Carrillo D, Sarkhosh A and Brecht J K (2022) Biocontrol Potential of Essential Oils in Organic Horticulture Systems: From Farm to Fork. Front. Nutr. 8:805138. Table 1 provides examples of EOs acting against phytopathogenic fungi / oomycetes, Table 2 provides examples of EO acting against phytopathogenic bacteria and Table 4 provides examples of EOs presenting herbicidal properties.

[0079] In preferred methods of the present invention, the main component of Essential Oils maybe extracted from said EOs and then encapsulated. These components may include borneol, camphor, carvacrol, p-caryophyllene, camphene, cinnamaldehyde, cineol, a-curcumene, p- cymene, diallyl di and tri-sulphide, eucalyptol, eugenol, eugenyl acetate, geranial, a- humelene, limonene, myrcene, neral, a-pinene, y-pinene, y-terpinene, terpinolene, a-thujone, thymol, and vanillin.

[0080] In preferred methods of the present invention, the active material can be a nutraceutical material such as vitamins, essential fatty acids, minerals, or probiotics.

[0081] Vitamins can be selected for example from Vitamin A, Vitamin D, Vitamin E, and Vitamin K.

[0082] In preferred methods of the present invention, vitamins can also be present as additives.

[0083] An additive can be included in the microcapsule core to act as an active protectant to reduce any potential degradation of the active material(s) during processing and storage. Preferably, the core additive is an antioxidant or free radical scavenger such as Vitamin E and curcumin. Preferably, the core additive is a pigment such as carotenoids, preferably beta-carotene. Preferably, the core additive is a natural product with a mixture of antioxidants, such as polyphenols, and other compounds such as olive oil and turmeric.

[0084] Essential fatty can be selected for example from flaxseed oil and omega 3 fatty acids. In preferred methods of the present invention, the active material is omega 3 fatty acids.

[0085] Minerals can be selected for example from calcium, zinc, iron and magnesium.

[0086] The vitamins and minerals employed in the present invention may be sourced from a vitamin- containing and / or mineral-containing material. An example of such a material is seaweed.

[0087] Microorganisms include probiotics and spores. They may be in live, inactivated or dormant form. There is a wide range of probiotic strains, but seven core genera of microbial organisms are commonly used, namely Lactobacillus, Bifidobacterium, Saccharomyces, Streptococcus, Enterococcus, Escherichia, and Bacillus.

[0088] Pharmaceutical ingredients include the active materials that produce the intended health effects, including anti-bacterial agents, anti-viral agents, anti-fungal agents, anti-inflammatory agents, anti-cancer agents as well as the excipients or carriers. These ingredients may be natural or synthetic.

[0089] Cosmetic ingredients include anti-acne agents, skin lightening agents, emollients, skin moisturizing agents, skin conditioning agents, wrinkle control agents, hair conditioning agent, dyes and pigments.

[0090] Surface care ingredients including fabric softener actives, surface cleaning actives, antimicrobial agents, paints, lacquers, pigments, dyes and adhesives.

[0091] Agrochemicals are substances used in agriculture, forestry, horticulture and gardening either as pesticides to control pest and diseases, or plant growth promoters. Suitable agrochemicals for use in accordance with the present invention may be solid or liquid at room temperature.

[0092] The term pesticide, or plant protection agent, refers to any substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest. A pesticide may be a chemical substance or biological agent, termed a biopesticide (such as a virus or bacteria). They are used against pests including insects, plant pathogens, weeds, molluscs, birds, mammals, fish, nematodes (roundworms) and microbes that compete with humans for food, destroy property, spread disease or are a nuisance. Pesticides includes biocides which are substances capable of killing different forms of living organisms. Furthermore, the chemical substance maybe derived by synthetic chemistry processes or alternatively extracted from natural sources, such as plant essential oils or single compounds extracted from essential oils.

[0093] Plant growth promoters include plant growth regulators (PGRs), including biological or synthetic or chemical or biological regulators, micronutrients and macronutrients.

[0094] In preferred methods of the present invention, the agrochemical is selected from pesticides, including fungicides, herbicides, insecticides, algicides, molluscicides, miticides and rodenticides, and antimicrobials, including germicides, antibiotics, anti-bacterials, antivirals, antifungals, antiprotozoals and anti-parasites, or combinations thereof.

[0095] A fungicide is a chemical control of fungi. Fungicides are chemical compounds used to prevent the spread of fungi in gardens and crops. Fungicides are also used to fight fungal infections. Fungicides can either be contact or systemic. A contact fungicide kills fungi when in contact with its surface. A systemic fungicide has to be absorbed by the fungus before the fungus dies.

[0096] Examples for suitable fungicides, according to the present invention, encompass the following species: (3-ethoxypropyl)mercury bromide, 2-methoxyethylmercury chloride, 2- phenylphenol, 8-hydroxyquinoline sulphate, 8-phenylmercuri oxyquinoline, acibenzolar, acylamino acid fungicides, acypetacs, aldimorph, aliphatic nitrogen fungicides, allyl alcohol, amide fungicides, ampropylfos, anilazine, anilide fungicides, antibiotic fungicides, aromatic fungicides, aureofungin, azaconazole, azithiram, azoxystrobin, barium polysulphide, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benzalkonium chloride, benzamacril, benzamide fungicides, benzamorf, benzanilide fungicides, benzimidazole fungicides, benzimidazole precursor fungicides, benzimidazolylcarbamate fungicides, benzohydroxamic acid, benzothiazole fungicides, bethoxazin, binapacryl, biphenyl, bitertanol, bithionol, blasticidin-S, Bordeaux mixture, boscalid, bridged diphenyl fungicides, bromuconazole, bupirimate, Burgundy mixture, buthiobate, butylamine, calcium polysulphide, captafol, captan, carbamate fungicides, carbamorph, carbanilate fungicides, carbendazim, carboxin, carpropamid, carvone, Cheshunt mixture, chinomethionat, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chlorodinitronaphthalene, chloroneb, chloropicrin, chlorothalonil, chlorquinox, chlozolinate, ciclopirox, climbazole, clotrimazole, conazole fungicides, conazole fungicides (imidazoles), conazole fungicides (triazoles), copper(ll) acetate, copper(ll) carbonate, basic, copper fungicides, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper(ll) sulphate, copper sulphate, basic, copper zinc chromate, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cyclic dithiocarbamate fungicides, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, DBCP, debacarb, decafentin, dehydroacetic acid, dicarboximide fungicides, dichlofluanid, dichlone, dichlorophen, dichlorophenyl, dicarboximide fungicides, dichlozoline, diclobutrazol, diclocymet, diclomezine, dicloran, diethofencarb, diethyl pyrocarbonate, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinitrophenol fungicides, dinobuton, dinocap, dinocton, dinopenton, dinosulphon, dinoterbon, diphenylamine, dipyrithione, disulphiram, ditalimfos, dithianon, dithiocarbamate fungicides, DNOC, dodemorph, dodicin, dodine, donatodine, drazoxolon, edifenphos, epoxiconazole, etaconazole.etem, ethaboxam, ethirimol, ethoxyquin, ethylmercury 2, 3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etridiazole, famoxadone, fenamidone, fenaminosulph, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, fluopicolide, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulphamide, flutolanil, flutriafol, folpet, formaldehyde, fosetyl, fuberidazole, furalaxyl, furametpyr, furamide fungicides, furanilide fungicides, furcarbanil, furconazole, furconazole- cis, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos, hydrargaphen, hymexazol, imazalil, imibenconazole, imidazole fungicides, iminoctadine, inorganic fungicides, inorganic mercury fungicides, iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isovaledione, kasugamycin, kresoxim-methyl, lime sulphur, mancopper, mancozeb, maneb, mebenil, mecarbinzid, mepanipyrim, mepronil, mercuric chloride, mercuric oxide, mercurous chloride, mercury fungicides, metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, methasulphocarb, methfuroxam, methyl bromide, methyl isothiocyanate, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, metiram, metominostrobin, metrafenone, metsulphovax, milneb, morpholine fungicides, myclobutanil, myclozolin, N-(ethylmercury)-p- toluenesulphonanilide, nabam, natamycin, nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace, organomercury fungicides, organophosphorus fungicides, organotin fungicides, orysastrobin, oxadixyl, oxathiin fungicides, oxazole fungicides, oxine copper, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivative of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, phenylsulphamide fungicides, phosdiphen, phthalide, phthalimide fungicides, picoxystrobin, piperalin, polycarbamate, polymeric dithiocarbamate fungicides, polyoxins, polyoxorim, polysulphide fungicides, potassium azide, potassium polysulphide, potassium thiocyanate, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrazole fungicides, pyrazophos, pyridine fungicides, pyridinitril, pyrifenox, pyrimethanil, pyrimidine fungicides, pyroquilon, pyroxychlor, pyroxyfiir, pyrrole fungicides, quinacetol, quinazamid, quinconazole, quinoline fungicides, quinone fungicides, quinoxaline fungicides, quinoxyfen, quintozene, rabenzazole, salicylanilide, silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulphide, spiroxamine, streptomycin, strobilurin fungicides, sulphonanilide fungicides, sulphur, sultropen, TCMTB, tebuconazole, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thiazole fungicides, thicyofen, thifluzamide, thiocarbamate fungicides, thiochlorfenphim, thiomersal, thiophanate, thiophanate-methyl, thiophene fungicides, thioquinox, thiram, tiadinil, tioxymid, tivedo, tolclofos-methyl, tolnaftate, tolylfluanid, tolylmercury acetate, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazine fungicides, triazole fungicides, triazoxide, tributyltin oxide, trichlamide, tricyclazole, trifloxystrobin, triflumizole, triforine, triticonazole, unclassified fungicides, undecylenic acid, uniconazole, urea fungicides, validamycin, valinamide fungicides, vinclozolin, zarilamid, zinc naphthenate, zineb, ziram, zoxamide, and mixtures thereof.

[0097] An herbicide is a pesticide used to kill unwanted plants, also termed weeds. Selective herbicides kill specific targets while leaving the desired crop relatively unharmed. Some of these act by interfering with the growth of the weed and are often based on plant hormones. Herbicides used to clear waste ground are non-selective and kill all plant material with which they come into contact. Herbicides are widely used in agriculture and in landscape turf management. They are applied in total vegetation control (TVC) programs for maintenance of highways and railroads. Smaller quantities are used in forestry, pasture systems, and management of areas set aside as wildlife habitat.

[0098] Suitable herbicides may be selected from the group comprising: aryloxycarboxylic acid e.g.

[0099] MCPA, aryloxyphenoxypropionates e.g. clodinafop, cyclohexanedione oximes e.g. sethoxydim, hydroxybenzonitriles e.g. bromoxynil, sulphonylureas e.g. nicosulphuron, triazolopyrimidines e.g. penoxsulam, triketiones e.g. mesotriones, triazine herbicides such as metribuzin, hexaxinone, or atrazine; sulphonylurea herbicides such as chlorsulfuron; uracils such as lenacil, bromacil, or terbacil; urea herbicides such as linuron, diuron, siduron, or neburon; acetanilide herbicides such as alachlor, or metolachlor; thiocarbamate herbicides such as benthiocarb, triallate; oxadiazoIone herbicides such as oxadiazon; isoxazolidone herbicides, phenoxyacetic acids; diphenyl ether herbicides such as fluazifop, acifluorfen, bifenox, or oxyfluorfen; dinitro aniline herbicides such as trifluralin; organophosphonate herbicides such as glufosinate salts and esters and glyphosate salts and esters; and / or dihalobenzonitrile herbicides such as bromoxynil, or ioxynil, benzoic acid herbicides, dipyridilium herbicides such as paraquat; and other herbicides such as clomazone, carfentrazone, saflufenacil, cinmethylin and pyroxasulphone. Particularly preferred herbicides may be selected from 2,4-dichlorophenoxyacetic acid (2,4-D), atrazine, cinmethylin, dicamba as benzoic acid, glyphosate, glufosinate, imazapic as imidazolinone, metolachlor as chloroacetamide, picloram, clopyralid, and triclopyr as pyridinecarboxylic acids or synthetic auxins, their respective water soluble salts and esters, and mixtures thereof.

[0100] An insecticide is a pesticide used against insects in all developmental forms, and include ovicides and larvicides used against the eggs and larvae of insects. Insecticides are used in agriculture, medicine, industry and the household.

[0101] Suitable insecticides may include those selected from: chlorinated insecticides such as, for example, Camphechlor, DDT, Hexachloro- cyclohexane, gamma- Hexachlorocyclohexane, Methoxychlor, Pentachlorophenol, TDE, Aldrin, Chlordane, Chlordecone, Dieldrin, Endosulphan, Endrin, Heptachlor, Mirex and their mixtures; organophosphorous compounds such as, for example, Acephate, Azinphos-methyl, Bensulide, Chlorethoxyfos, Chlorpyrifos, Chlorpyriphos-methyl, Diazinon, Dichlorvos (DDVP), Dicrotophos, Dimethoate, Disulphoton, Ethoprop, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Malathion, Methamidophos, Methidathion, Methyl-parathion, Mevinphos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Phorate, Phosalone, Phosmet, Phostebupirim, Pirimiphos-methyl, Profenofos, Terbufos, Tetrachlorvinphos, Tribufos, Trichlorfon and their mixture; carbamates such as, for example, Aldicarb, Carbofuran, Carbaryl, Methomyl, 2-(l- Methylpropyl)phenyl methylcarbamate and their mixtures; pyrethroids such as, for example, Allethrin, Bifenthrin, Deltamethrin, Permethrin, Resmethrin, Sumithrin, Tetramethrin, Tralomethrin, Transfluthrin and their mixtures; plant toxin derived compounds such as, for example, Derris (rotenone), Pyrethrum, Neem (Azadirachtin), Nicotine, Caffeine and their mixture; neonicotinoids such as imidacloprid; abamectin e.g. emamactin; oxadiazines such as indoxacarb; and / or anthranilic diamides such as rynaxypyr.

[0102] Miticides are pesticides that kill mites. Antibiotic miticides, carbamate miticides, formamidine miticides, mite growth regulators, organochlorine, permethrin and organophosphate miticides all belong to this category. Molluscicides are pesticides used to control molluscs, such as moths, slugs and snails. These substances include metaldehyde, methiocarb and aluminium sulphate. A nematicide is a type of chemical pesticide used to kill parasitic nematodes (a phylum of worm).

[0103] Agrochemicals also include plant growth regulators (PGRs). PGRs are synthetic or biological compounds used to modify plant growth such as increasing branching, suppressing shoot growth, increasing return bloom, removing excess fruit, or altering fruit maturity. They can be grouped into five classes: compounds related to auxins, gibberellins and inhibitors of gibberellin biosynthesis, cytokinins, abscisic acid and compounds affecting the ethylene status.

[0104] Agrochemicals also comprise nutrients. The active composition may comprise at least one nutrient. Nutrients refer to chemical elements and compounds which are desired or necessary to promote or improve plant growth. Nutrients generally are described as macronutrients or micronutrients.

[0105] Micronutrients typically refer to trace metals or trace elements, and are often applied in lower doses. Suitable micronutrients include trace elements selected from zinc, boron, chlorine, copper, iron, molybdenum, and manganese.

[0106] The micronutrients may be in a soluble form or be included as insoluble solids, and may in the form of salts or chelates. Preferably, the micronutrient is in the form of a carbonate or oxide. Preferably, the micronutrient may be selected from zinc, calcium, molybdenum or manganese, or magnesium. Particularly preferred micronutrients for use with the present invention may be selected from zinc oxide, manganese carbonate, manganese oxide, or calcium carbonate.

[0107] Macronutrients typically refer to those comprising nitrogen, phosphorus, and potassium, and include fertilisers such as ammonium sulphate, and water conditioning agents. Suitable macronutrients include fertilisers and other nitrogen, phosphorus, or sulphur containing compounds, and water conditioning agents.

[0108] Suitable fertilisers include inorganic fertilisers that provide nutrients such as nitrogen, phosphorus, potassium or sulphur. Examples of such fertilisers include: for nitrogen as the nutrient: nitrates and or ammonium salts such as ammonium nitrate, including in combination with urea e.g. calcium ammonium nitrate, ammonium sulphate nitrate, ammonium phosphates, particularly mono-ammonium phosphate, di-ammonium phosphate and ammonium polyphosphate, ammonium sulphate, and the less commonly used calcium nitrate, sodium nitrate, potassium nitrate and ammonium chloride; for phosphorus as the nutrient: acidic forms of phosphorus such as phosphoric, pyrophosphoric or polyphosphoric acids, but more usually salt forms such as ammonium phosphates, particularly mono-ammonium phosphate, di-ammonium phosphate, and ammonium polyphosphate, potassium phosphates, particularly potassium dihydrogen phosphate and potassium polyphosphate; for sulphur as the nutrient: ammonium sulphate and potassium sulphate, e.g. the mixed sulphate with magnesium.

[0109] The active material may comprise at least one micronutrient and / or at least one macronutrient.

[0110] The use of some of the above described agrochemicals from synthetic origin, and the resulting presence of their residues in food and water, are leading to health safety concerns. Moreover, the use of chemical pesticides affects the environment and the biodiversity. The constant and sometimes inadequate use of chemical pesticides is also responsible for the development of pathogen resistances leading to possible food safety issues.

[0111] Today, the demand for a reduction of agrochemicals, and for the development of alternative ways to protect crops from pathogens and pests, is growing. In response, research and development in the field of biopesticides has grown exponentially in the last 20 years.

[0112] Biopesticides include microorganisms that may be selected from bacteria, cyanobacteria, micro-algae, fungi, viruses, nematodes, protozoa, and yeast in any combination, where such microorganisms are capable of killing undesired living organisms. These microorganisms may be in a dormant or inactivated form or as spores. The microcapsules of this invention may include Bacillus thuringiensi, Bacillus thuringiensis var. kurstaki (Bt), B. thuringien, Bacillus thuringiensis var. tenebrionid, Bacillus thuringiensis var. aizawai, Bacillus thuringiensis japonensis, Bacillus popilliae, Bacillus lentimorbus, Bacillus sphaericus, Bacillus pumilus, Bacillus subtilis, Bacillus firmus, Burkholderia cepacia, Bacillus amyloliquefaciens, Bacillus licheniformis, Erwinia amylovora, Pasteuria penetrans, Pasteuria usage, Psedomonas spp., Streptomyces griseoviridis and Xanthomonas campestris pv. Poannua. and such microorganisms as given in Kumar, J., Ramlal, A., Mallick, D. and Mishra, V. An Overview of Some Biopesticides and Their Importance in Plant Protection for Commercial Acceptance. Plants 2021 , 10, 1185.

[0113] Among the natural alternatives to chemical pesticides, products based on plant extracts and / or plant essential oils (EOs) have received increasing attention because of their generally recognized as safe (GRAS) compounds, due to their very low human toxicity, high volatility, and rapid degradation.

[0114] Active materials for use in this invention, wherein the agrochemical is a biopesticide, EO or EO components, are suitable for use in agrochemical formulations than can be used for plant production that can be certified as organic by organisations such as the USDA (US Department of Agriculture) or Ecocert in Europe.

[0115] In preferred methods of the present invention, the one or more active material solvents are selected from the group consisting of triglyceride oils or waxes, fatty acids, fatty alcohols, fatty acid esters, rosin and its derivatives, hydrocarbon oils, and waxes.

[0116] In preferred methods of the present invention, the one or more active material solvents are present as an aqueous mixture of one or more active material solvents.

[0117] In preferred methods of the present invention, the active material solvent is selected from Miglyol® 840, Miglyol® 812 N, Miglyol® 829, Miglyol® 829 ECO, Miglyol® Coco 810, Miglyol® 810 N, Miglyol® 128, Miglyol® 808, Miglyol® T-C7, Miglyol® 8810, Miglyol® PPG 810, Miglyol® OE, Miglyol® DO, and Miglyol® 818, Abalyn®, benzyl benzoate, diethyl phthalate, isopropyl myristate, triethyl citrate, dipropylene glycol, and propylene glycol, triacetin, glycerin, 1,3 propanediol and combinations thereof. More preferably, the active material solvent is isopropyl myristate and / or Miglyol® 812 N. In preferred methods of the present invention, the active material solvent is a vegetable oil selected from coconut oil, corn oil, canola oil, cottonseed oil, olive oil, palm oil, peanut oil, rapeseed oil, safflower oil, sesame oil, soybean oil, and sunflower oil. Other examples of vegetable oils are given in the CTFA Cosmetic Ingredient Handbook, J.M. Nikitakis (ed.), 1st ed., The Cosmetic, Toiletry and Fragrance Association, Inc., Washington, 1988. A vegetable oil is an oil that comes from plant sources. Alternatively, the solvent is derived from a vegetable oil.

[0118] In preferred methods of the present invention, the active material solvent is a fat or wax having a melting point of less than 60 °C, preferably less than 45 °C, preferably less than 25 °C. Preferably, the wax is selected from Softisan® 100, Softisan® 142, and Softisan® 154, or combinations thereof, preferably Softisan® 100.

[0119] In preferred methods of the present invention, the active material solvent is a rosin resins or rosin esters, wherein at least two rosin acid or rosin acid derivative units are connected by means of at least two ester linkages. Common examples include, but are not limited to, glycerol esters, pentaerythritol esters and (triethylene) glycol esters. Rosin acids comprise a mixture of various rosin acid molecules. Mixtures of this kind that are readily available and occur in nature include, but are not limited to, tall oil rosin, gum rosin or wood rosin. Wood rosin is harvested from the stumps of trees. Gum rosin is collected from the sap of trees in regions such as China and Brazil. Tall oil rosin is a by-product of the Kraft paper process. These natural mixtures may comprise rosin acids of the abietic type and / or the pimaric type such as abietic acid, palustric acid, neoabietic acid, levopimaric acid, pimaric acid, isopimaric acid or dehydroabietic acid, among others, in varying amounts. Suitable rosin resins include, but are not limited to, esters of natural and modified rosins and the hydrogenated derivatives thereof, such as Abalyn®, a methyl ester of wood rosin.

[0120] In preferred methods of the present invention, the one or more active solvents are bio-based materials.

[0121] In alternatively preferred methods of the present invention, the one or more active solvents are plant materials. In preferred methods of the present invention, the one or more primary stabilisers are selected from the group consisting of proteins, polysaccharides, natural based polyisoprenes (such as natural rubber), and mineral particles (including fumed silica, colloidal silica, or diatomaceous earth). More preferably, the one or more primary stabilisers are selected from plant proteins.

[0122] In preferred methods of the present invention, the one or more primary stabilisers are biobased materials.

[0123] In alternatively preferred methods of the present invention, the one or more primary stabilisers are plant materials.

[0124] In preferred methods of the present invention, the one or more primary stabiliser solvents are selected from the group consisting of water, ethanol, organic acids, propylene glycol, dipropylene glycol, ethylene glycol, triethylene glycol, propylene carbonate, ethylene carbonate, triethyl citrate, glycerine acetates, ethyl acetate, ethyl lactate and butanols. More preferably, the primary stabiliser solvent is water.

[0125] In preferred methods of the present invention, the one or more primary stabiliser solvents are bio-based materials.

[0126] In alternatively preferred methods of the present invention, the one or more primary stabiliser solvents are plant materials.

[0127] In preferred methods of the present invention, the mixing in step e) and / or f) is done by one or more of a membrane emulsification or a bulk emulsification process wherein the mixing is achieved through mechanical stirring (low and high shear), ultrasonication, high pressure homogenisation and / or cavitation.

[0128] In preferred methods of the present invention steps e) and f) are carried out at a temperature between 5°C and 40°C, more preferably between 10°C and 30°C.

[0129] In preferred methods of the present invention, steps e) and f) occur consecutively or at the same time. In preferred methods of the present invention, the compositions obtained in steps a) and b) are immiscible.

[0130] In preferred methods of the present invention, the shell composition obtained in step a) has a greater solubility in the liquid active composition of step b) than in water. More preferably, the shell composition obtained in step a) has a greater solubility in the liquid active composition of step b) than in the liquid primary stabiliser composition of step c).

[0131] In preferred methods of the present invention, the one or more shell materials have a greater solubility in the one or more shell solvents than in water. More preferably, the one or more shell materials have a greater solubility in the one or more shell solvents than in the liquid of primary stabiliser composition of step c).

[0132] In preferred methods of the present invention the concentration of shell material in the shell composition of step a) is within the range of 0.1 to 50 weight %, preferably 1 .0 to 33 weight %, more preferably 5.0 to 25 weight %.

[0133] In preferred methods of the present invention, the concentration of the primary stabiliser in the liquid primary stabiliser composition of step c) is within the range of 0.001 to 40 weight %, preferably 0.01 to 33 weight %, more preferably 0.1 to 15 weight %.

[0134] In preferred methods of the present invention, removing at least part of the external phase in step g) can be achieved by one or more of decanting, filtering, sedimentation, freeze drying or evaporation.

[0135] In preferred methods of the present invention, isolating microcapsules in step i) can be achieved by one or more of decanting, filtering, sedimentation, freeze drying or evaporation.

[0136] In preferred methods of the present invention, after steps f), g), h) or i) additional materials such as preservatives may be added to prevent the growth of unwanted microorganisms. In addition, suspending agents, pigments, dyes and opacifiers and other materials maybe added to adjust the aesthetic properties of the microcapsules or the microcapsules composition, such as their visual appearance.

[0137] In preferred methods of the present invention, the one or more secondary stabilisers are selected from the group consisting of proteins, polysaccharides, natural based isoprenes (such as natural rubber), mineral particles (including fumed silica, colloidal silica, or diatomaceous earth) and salts. More preferably, the one or more secondary stabilisers are selected from salts and gellan gum.

[0138] In preferred methods of the present invention, the one or more secondary stabilisers are biobased materials.

[0139] In alternatively preferred methods of the present invention, the one or more secondary stabilisers are plant materials.

[0140] In preferred methods of the present invention, the one or more secondary stabiliser solvents are selected from the group consisting of water, ethanol, organic acids, propylene glycol, dipropylene glycol, ethylene glycol, triethylene glycol, propylene carbonate, ethylene carbonate, triethyl citrate, glycerine acetates, ethyl acetate, ethyl lactate and butanols. More preferably, the secondary stabiliser solvent is water.

[0141] In preferred methods of the present invention, the one or more secondary stabiliser solvents are bio-based materials.

[0142] In alternatively preferred methods of the present invention, the one or more secondary stabiliser solvents are plant materials.

[0143] In preferred methods of the present invention, the liquid active composition of step b) is nonaqueous.

[0144] In preferred methods of the present invention, the primary stabiliser composition of step c) is aqueous.

[0145] The present invention is also directed to a composition of core-shell microcapsules, wherein the microcapsules are obtained by the method hereinbefore described.

[0146] The present invention is also directed to a composition of core-shell microcapsules, wherein the microcapsules comprise a core comprising one or more active materials and a shell comprising one or more shell materials and one or more primary stabilisers. In preferred compositions of the present invention, the one or more active materials are selected from the group consisting of fragrance materials, essential oils, fat soluble vitamins, minerals, flavour materials, agrochemicals, cosmetic ingredients, fatty acids, surface care ingredients, pharmaceutical ingredients, microorganisms including probiotics, and fungal spores. More preferably, the one or more active materials are selected from fragrance materials, flavour materials and probiotics.

[0147] In preferred compositions of the present invention, the one or more shell materials are selected from the group consisting of prolamin proteins, glutelin proteins, polysaccharides and polyesters. More preferably, the one or more shell materials are selected from the group consisting of zein, shellac, chitosan, and polyhydroxyalkanoates (PHAs). Most preferred, the one or more shell materials are shellac and / or zein.

[0148] In preferred compositions of the present invention, the one or more primary stabilisers are selected from the group consisting of proteins, polysaccharides, natural based isoprenes (such as natural rubber), and mineral particles (including fumed silica, colloidal silica, or diatomaceous earth). More preferably, the one or more primary stabilisers are selected from plant proteins.

[0149] In preferred compositions of the present invention, the one or more secondary stabilisers are selected from the group consisting of proteins, polysaccharides, natural based isoprenes (such as natural rubber), mineral particles (including fumed silica, colloidal silica, or diatomaceous earth) and salts. More preferably, the one or more secondary stabilisers are selected from salts and gellan gum.

[0150] In preferred compositions of the present invention, the microcapsules have a core or multiple cores comprising one or more active materials and one or more active material solvents surrounded by a shell comprising one or more shell materials, one or more primary stabilisers and optionally one or more secondary stabilisers. More preferably, the microcapsules have a single core.

[0151] In preferred compositions of the present invention, the microcapsule core comprises 5 to 95 wt%, more preferably 10 to 90 wt%, even more preferably 15 to 80 wt%, most preferably 20 to 75 wt% of the collected wet microcapsules obtained according to the method defined herein. In preferred compositions of the present invention, the microcapsules have a range of sizes measured according to the method herein, preferably with a dso between 5 pm and 500 pm, more preferably between 10 pm and 250 pm, even more preferably between 15 pm and 200 pm, most preferably between 20 pm and 150 pm.

[0152] In preferred compositions of the present invention, the biodegradation percentage based upon 02 consumption of the microcapsules as measured according to ISO-14851 version 2019 after 28 days is 60 to 100% based upon the ratio of the Biological Oxygen Demand (BOD) to the Theoretical Oxygen Demand, more preferably 65 to 100%, even more preferably 70 to 100%, even preferably 75 to 100%, even more preferably 80 to 100%, even more preferably 85 to 100%, most preferably 90 to 100%. claim

[0153] In preferred compositions of the present invention, the microcapsules are edible, preferably wherein the microcapsules are digestible.

[0154] The present invention is also directed to the use of a composition as hereinbefore described in a formulated product wherein the formulated product is a food, beverage, cosmetic, home care product, personal care product, pharmaceutical, industrial product (e.g. paint, adhesive, sandpaper, tape etc.), medical device, biomaterial, or agrochemical.

[0155] BRIEF DESCRIPTION OF THE FIGURES

[0156] Figure 1a - Optical micrograph of Microcapsules 4A.

[0157] Figures 1b and 1c - Confocal micrographs of a Microcapsule 4D.

[0158] Figure 1 d - Optical micrograph of the oil layer of Comparative Example 4.

[0159] Figure 2 - Micrograph of a composition of Microcapsules 5B.

[0160] Figure 3 - Micrograph of Microcapsules 5B dried and then crushed.

[0161] Figure 4 - Micrograph of Microcapsules 5A after 24 hours in fabric conditioner.

[0162] Figure 5 - Micrograph of a Microcapsule 5A after 24 hours in fabric conditioner dried and then crushed.

[0163] Figure 6 - Micrograph of Microcapsules 8A after 24 hours in fabric conditioner.

[0164] Figure 7 - Micrograph of a Microcapsule 8A after 24 hours in fabric conditioner dried and then crushed.

[0165] EXAMPLES References to room temperature in the examples cover typical laboratory temperatures of 19 to 21°C.

[0166] Materials

[0167] Zein, purified was purchased from Fisher Scientific.

[0168] Pea protein Isolate (80% protein, 4 wt% carbohydrate - ProEarth P16109) was purchased from Cambridge Commodities.

[0169] Shellac, ground was purchased from A.F. Suter & Company Ltd, UK.

[0170] Propylene glycol (PG) was purchased from Fisher Scientific.

[0171] Dipropylene glycol (DPG) was purchased from Sigma Aldrich.

[0172] Ethanol Absolute 99.8+%, (EtOH) certified AR for analysis was purchased from Fisher Scientific.

[0173] Acetic acid (glacial 99%) was purchased from Fisher Scientific.

[0174] Hydrochloric acid (HCI) (1 M) was purchased from Fisher Scientific.

[0175] Delta damascene was purchased from Carvansons, UK.

[0176] Isopropyl myristate (I PM) was purchased from Sigma Aldrich.

[0177] Abalyn was purchased from Augustus Oils Ltd, UK.

[0178] Gellan gum (high acyl) was purchased from Special Ingredients Ltd, UK.

[0179] Sodium hydrogen carbonate, certified AR for analysis (NaHCOs) was purchased from Fisher Scientific.

[0180] Calcium sulphate dihydrate (CaSO4.2H2O) was purchased from Fisher Scientific.

[0181] Magnesium sulphate dried (MgSO4) was purchased from Fisher Scientific.

[0182] Potassium Chloride, Extra Pure, SLR, Eur. Ph., (KCI) was purchased from Fisher Scientific. Stepantex VL-90A was obtained from Surfachem, UK.

[0183] Calcium chloride dihydrate was purchased from Fisher Scientific. 1 ,2-Benzothiazol-3(2H)-one was purchased from Fisher Scientific.

[0184] Hard water pH3 was prepared with the following concentrations of salts in deionised (DI) water: 192mg / l of NaHCO3, 120 mg / l CaSO4.2H2O, 120 mg / l MgSO4, 8mg / l KCI. pH was adjusted to 3 with 1 M HCI.

[0185] Single strength Buffer solution was prepared as follows: i. 1 ,904g of citric acid monohydrate and 0.276 g of trisodium citrate dihydrate were weighed out; ii. The mixture was completed to 80 g using DI water; iii. The pH of the solution was adjusted to 3 using 1M HCI and 1M NaOH solutions, and the volume of the solution was completed to 100 g with DI water; iv. 0.38 g of CaCI2 dihydrate was added; v. 0.2 g of sodium benzoate was added; vi. The solution was placed in an ultrasonic bath at 80°C for 5-10 min (i.e. until complete dissolution was observed); vii. The solution was allowed to cool down to 20 °C.

[0186] Double strength buffer was prepared as for single strength buffer but with twice the level of all materials but with the mixture still being completed to 100g.

[0187] Standard fabric conditioner composition

[0188] In some of the following examples, a standard fabric conditioner was employed. This was prepared by mixing the components in Table 1 with an overhead mixer for about 5 minutes at 50°C, then allowing to cool down to 20 °C while mixing.

[0189] Table 1

[0190] Methods

[0191] Total fragrance via Gas chromatography

[0192] Fragrance and fragrance material levels in the microcapsule can be determined by extraction of the fragrance and injection into a Gas Chromatography (GC) column. Quantification is achieved by use of a calibration curve for the given fragrance material diluted in ethanol.

[0193] To measure the total level of fragrance materials in an encapsulate sample, the capsules must first be broken by sonication. For example, 10-50 mg of dried encapsulate or 0.3 - 0.5g of wet encapsulate collected on a 40pm cell strainer in 3.0 g of deionised (DI) water and 10% KOH are vortexed to mix thoroughly. The solution is then sonicated with a Bandelin ultrasonicator, small probe TS104 for 1 - 2 minute at 30% amplitude (around 1.5-3.0 kJ in total). While sonicating, ice is used to keep the temperature below 20 °C to avoid any loss of fragrance through evaporation. An optical microscope as detailed above is used to check visually if the capsules are fully broken. If not, the sonication step is repeated. 8 ml of absolute ethanol is added to the mixture, which is then mixed and centrifuged at 14500rpm for 10 minutes. This mixture is then diluted with absolute ethanol as appropriate and injected into the GC for analysis.

[0194] Optical Microscopy

[0195] Optical microscopy images were obtained using an open Frame microscope equipped with a CellCam 200CR camera, Aura Pro phase contrast illuminator and universal plan fluorite objectives at 4x, 10x and 20x.

[0196] Microcapsule particle size

[0197] The particle size of the final microcapsule was measured using an Anton Paar laser diffraction particle size analyser PSA 1190. The microcapsules composition was added to reverse osmosis water diluted to the required concentration in order to have the desired optical density (normally 2-15% obscuration) for the measurement. The dispersion should be checked via an optical microscope for any larger agglomerates of microcapsules. If these are visible 0.5wt% acetic acid can be added to ensure that the primary particles are well dispersed. The dso quoted is for the volume distribution, as calculated via a general analysis using Mie theory.

[0198] Alternatively, particle size can be measured using optical microscopy (e.g. using an open Frame microscope equipped with a CellCam 200CR camera, Aura Pro phase contrast illuminator and universal plan fluorite objectives at 4x, 10x and 20x). The microcapsule powder is added to either reverse osmosis water or single strength buffer as needed. In such a method, particle sizes are taken from the mean size measurements of 50 microcapsules, for each respective sample. The optical microscope is then calibrated using the grid of a Hirschmann counting chamber, (Fuchs Rosenthal). Using the straight-line tool in Imaged 1.53, particle diameters are measured from two center-edges with the overlay-text feature enabled to avoid repeating capsules.

[0199] Example 1 - Preparation of shell compositions Shell Composition 1A

[0200] 5wt% of zein was dissolved in propylene glycol in an ultrasonic bath at 50°C until full dissolution (between 30 mins and 1 hour) and then left to cool to room temperature to form Shell Composition 1A.

[0201] Shell Composition 1 B

[0202] 20 wt% of ground shellac was dissolved in ethanol in an ultrasonic bath at 50°C for about 1 hour and then left to cool to room temperature to form Shell Composition 1B.

[0203] Shell Composition 1C

[0204] 10 wt% of ground shellac was vortexed in DPG until the powder was well suspended and then placed in an ultrasonic bath at 60°C for about 2 hours and then left to cool to room temperature to form Shell Composition 1C.

[0205] Shell Composition 1 D

[0206] 10 wt% of ground shellac was dissolved in a 1 : 1 weight ratio DPG / ethanol solution, in an ultrasonic bath at 50°C for about 1 hour and then left to cool to room temperature to form Shell Composition 1 D.

[0207] Shell Composition 1 E

[0208] 10 wt% of ground shellac was vortexed in PG until the powder was well suspended and then placed in an ultrasonic bath at 60°C for about 2 hours and then left to cool to room temperature to form Shell Composition 1E.

[0209] Shell Composition 1 F

[0210] 10 wt% of zein was dissolved in propylene glycol in an ultrasonic bath at 50°C for about 1 hour and then left to cool to room temperature to form Shell Composition 1F.

[0211] Shell Composition 1G

[0212] 5 wt% of zein was dissolved in a mixture of 80wt% propylene glycol and 20wt% of reverse osmosis water by immersion in an ultrasonic bath at 50°C for about 1 hour, and then left to cool to room temperature to form Shell Composition 1G.

[0213] Example 2 - Preparation of active compositions

[0214] Active Composition 2A 10 wt% of I PM in delta-damascone, fragrance material with LogP (consensus) of 3.56, was prepared by mixing the IPM into the fragrance at room temperature to form Composition 2A.

[0215] Active Composition 2B Abalyn® was heated in a water bath at 60°C for 30 mins to make less viscous and easier to handle. 10 wt% Abalyn® in delta-damascone, fragrance material with LogP (consensus) of 3.56, was prepared by mixing the Abalyn® into the fragrance at room temperature to form Active Composition 2B. Active Composition 2C

[0216] 10 wt% of IPM in a fragrance oil mixture, comprising five fragrance materials with LogPs (Consensus) ranging from 3.56 to 4.46 in equal weight proportions, was prepared by mixing the IPM into the fragrance oil at room temperature to form Active Composition 2C. Table 2

[0217] Example 3 - Preparation of primary and secondary stabiliser compositions Stabiliser Composition 3A

[0218] A pea protein dispersion was prepared by preparing a protein hydrogel followed by shearing.

[0219] Preparation of the protein hydrogel

[0220] 1120 g of reverse osmosis (RO) water was added to a 2-litre stainless steel container, and 216 g of pea protein isolate was added. The container was placed in a 92 °C water bath and mixed with an overhead stirrer at 1500 rpm. After stirring for 3 minutes, 480g glacial acetic acid was added. The mixture was stirred for 15 minutes at 1500 rpm, then for 30 minutes at 1200 rpm, ensuring that the temperature of the mix surpassed 85 °C for at least 10 minutes. The mixture was poured into trays to a depth of approximately 10 mm, and left at room temperature overnight.

[0221] Application of shear to protein hydrogel

[0222] Shear was then applied to the hydrogel as follows. The protein hydrogel was cut into ~1cm cubes via a low-shear cutting step. The cubes were split between two 75 micron filter bags, which were each then submerged inside a bucket containing 16L of RO water. This formed a coarse protein hydrogel slurry within the filter bag. The hydrogel cubes were left to soak, with agitation from an overhead stirrer at 600-800 rpm, for 90-150 min. This step was performed to reduce the concentration of acetic acid in the hydrogel by diffusion to the continuous aqueous phase. The pH of the wash water was then measured, and if it was above 3.2, soaking was continued for a further 30 minutes. If it was below 2.9, half of the water was drained and replaced with fresh RO water, then soaking was continued for a further 30 minutes. The filter bag was then suspended above the bucket to drain for 5 minutes. The washed gel from both filter bags was transferred to a 5 litre beaker, and homogenized with a Silverson mixer at 5000 rpm for 5 minutes, 6000 rpm for 5 minutes, and 7000 rpm for 5 minutes. The smooth slurry was then transferred to 1 L Nalgene bottles (800 g in each), and exposed to high shear ultrasonication (Hielscher UP500Hdt) with cooling on ice, until 250 kJ had been applied, with shaking every 75 kJ. The hydrogel slurry was then passed through a 200 micron sieve before use. The solids concentration as measured by mass loss on drying was between 9.0 and 11.0 %. The measured pH was 2.9.

[0223] Stabiliser Composition 3B An organic acidic gellan gum solution was prepared by adding 35 g of acetic acid solution at pH3 (about 6.5 wt%) to a 50 ml Falcon tubes. The tube was incubated in an Eppendorf Thermomixer C for about 20 min to allow the liquid to reach the target temperature of at least 90°C. 50.0 mg of gellan gum was carefully weighed and added to the Falcon tube. The tube was tightly closed and the mixture was vortexed at 3000 rpm until no more gellan gum powder remained on the wall of the tube. The suspension was heated and agitated in an Eppendorf Thermomixer C, set to 100°C and 500 rpm, twice for 10 minutes, shaking gently by hand in between.

[0224] Stabiliser Composition 3C

[0225] A neutral gellan gum solution was similarly prepared with 40 g of deionised water added to the Falcon tube. The tube was incubated in an Eppendorf Thermomixer C for about 20 min to allow the liquid to reach the target temperature of at least 90°C. 50.7 mg of gellan gum was carefully weighed and added the Falcon tube. The tube was tightly closed and the mixture was vortexed at 3000 rpm until no more gellan gum powder remained on the wall of the tube. The suspension was heated and agitated in an Eppendorf Thermomixer C, set to 100°C and 500 rpm, twice for 10 minutes, shaking gently by hand in between. The solution was finally acidified to pH 3.0 with 1M HCI.

[0226] Stabiliser Composition 3D

[0227] A buffered solution of gellan gum was prepared by mixing 9.5 mg of gellan gum with 15 g of deionised water in a 50 ml Falcon tube. The suspension was heated and agitated in an Eppendorf Thermomixer C, set to 100°C and 500 rpm, twice for 10 minutes, shaking gently by hand in between. After cooling to room temperature, 15 g of double strength buffer solution was added, and the solution was refrigerated at 4 °C for 24 h.

[0228] Stabiliser Composition 3E

[0229] A pea protein dispersion was prepared by heating, cooling and shearing.

[0230] 336g of Pea Protein Isolate (PPI) was added to 2731g of room temperature reverse osmosis water and placed in a water bath at 90 °C. The mixture was stirred with an overhead stirrer with a propeller impeller at 1700 rpm for around 1 to 2 mins to ensure homogeneous wetting of the PPI powder. 269g of 80% (v / v) acetic acid solution was added to the stirred mixture, a lid placed over the vessel and stirring continued for another 45 mins. The temperature of the mixture was checked. If this was less than 85 °C stirring was continued until this temperature was reached.

[0231] The hot mixture was then transferred to a Silverson mixer and homogenised for 15 mins at 8000 rpm. The vessel was then covered and left to cool until the mixture temperature was below 40 °C which could take several hours, typically overnight.

[0232] Once this temperature was reached the mixture was gently stirred with an overhead mixer with an anchor impeller at 200 rpm for 15 minutes to make the mixture pourable and it was divided into smaller 1 litre batches in bottles.

[0233] Each bottle containing around 860-890g of mixture was sonicated using a Hielscher UIP500hdT whilst in an ice bath to ensure that the mixture temperature remained below 40 °C. This was done at 100 % amplitude until the total energy applied was 175 kJ, over a period of 22-25 minutes. The sonication was stopped a quarter and half-way through the process to manually shake the bottle for a minute to ensure a homogeneous mixture. The mixture was then passed through a 200 micron sieve to produce a homogeneous low viscosity liquid with pH 3.5.

[0234] The mixture was degassed using a Hauschild SpeedMixer DAC 800.2 VAC-P with a vacuum of 3 bar, and a speed ramp of 30 seconds at 1500 rpm, 2 minutes at 1950 rpm, and finally 30 seconds at 1500 rpm. The room temperature mixture was then passed through a laboratory scale high pressure homogeniser (SPCH-EP, Model FPG12805 from Homogenising System Ltd), equipped with a piston gap valve with a 1 mm contact diameter (HPVS-1). once at 250 MPa, with the chiller set at 5°C. The exit mixture temperature ranged between 30 and 40°C and the pH was 3.3. The Stabiliser Composition then cooled to room temperature.

[0235] Example 4 - Zein core-shell fragrance microcapsules prepared with a protein dispersion primary stabiliser

[0236] Preparation of the microcapsules

[0237] Core composition 4A was prepared by mixing Shell Composition 1A and Active Composition 2A at room temperature in the weight ratio 1: 4.

[0238] Core composition 4B was prepared by mixing the Shell Composition 1A and Active Composition 2B at room temperature in the weight ratio 1: 4. Core composition 4C was prepared by mixing the Shell Composition 1A and Active Composition 2C at room temperature in the weight ratio 1:4.

[0239] Core composition 4D was prepared by mixing the Shell Composition 1G and Active Composition 2A at room temperature in the weight ratio 1:4.

[0240] Core composition 4E was prepared by mixing the Shell Composition 1G and Active Composition 2C at room temperature in the weight ratio 1:4.

[0241] 150 g of room temperature Primary Stabiliser Composition 3A or 3E was weighed in a narrow 250 ml beaker. Mechanical agitation was started at 700 rpm with an anchor blade stirrer, placed at about 1 / 3 of the solution height from the bottom of the beaker. 50g of either Core Compositions 4A, 4B, 4C, 4D or 4E was shaken by hand and vortexed at 3000 rpm for a few seconds, before adding straight away to the stirring vessel containing Primary Stabiliser Composition 3A. The formation of a dispersion of microcapsules of Microcapsules Compositions 4A, 4B, 4C, 4D and 4E respectively was visible almost straight away.

[0242] Separately 50g of Core Compositions 4A was shaken by hand and vortexed at 3000 rpm for a few seconds, before adding straight away to the stirring vessel containing Primary Stabiliser Composition 3E. The formation of a dispersion of microcapsules of Microcapsules Composition 4F was visible almost straight away.

[0243] Agitation was maintained for 30 minutes at room temperature for Microcapsules Compositions 4A, 4C, 4D, 4E and 4F and for 2 hours for Microcapsules Composition 4B.

[0244] The resulting microcapsules compositions were transferred to a 1 litre Duran bottle and hard water pH3 was added until the top of the bottle to dilute and separate small microcapsules from any excess stabiliser or shell material.

[0245] The mixtures were first passed through a 250 micron sieve to catch any residual shell or stabiliser materials that might have unexpectedly gelled. This material was discarded.

[0246] The mixtures were then passed through a 38 micron sieve, with the addition of hard water pH3 and swirling of the sieve to get as many of the microcapsules through. The filtrates were transferred to a 1 litre separating funnel and left to separate by gravity. The microcapsules floated to the surface over about 2 hours and a clear separation could be seen. The liquid below the capsules was collected and discarded. The floating microcapsules were collected, rinsed with hard water pH3, and transferred to a smaller 500 ml separating funnel. Again, the microcapsules were left to float to the surface over about 2 hours. The liquid below the microcapsules was collected and discarded. This was repeated until the liquid was clear, indicating that there was no excess fragrance oil or stabiliser or shell material to be washed away. The microcapsules which did not go through the 38 micron sieve were washed thoroughly with hard water pH3, directly on top of the sieve, before being resuspended in hard water pH3 in a 500ml decantation funnel.

[0247] A final wash was carried out with buffer solution with preservative to replace the hard water for both portions of microcapsules, and this slurry was collected and stored in the fridge.

[0248] Characterisation of the microcapsules

[0249] The morphology of the microcapsules was assessed by optical microscopy. Figure 1a shows Microcapsules 4A collected on the 38 micron sieve, with the external structure visible. It consisted of a continuous shell that appeared dark in colour.

[0250] The internal morphology of the microcapsules was assessed by confocal laser scanning microscopy with a HC PL APO CS2 10x / 0.40 DRY objective (Stellaris 5, Leica). Figures 1b and 1c are a confocal microscopy image of the cross-section of an individual Microcapsule 4D that had passed through the 38 micron sieve. A smaller microcapsule was used here to make the cross-section imaging possible. To visualize the active material, i.e. the fragrance material, Nile red was added to the active composition at 0.1 mg / g concentration during the sample preparation. To visualize the shell material, that is the protein, 1 mL of microcapsule solution was stained with 10 pL of 100 mM Thioflavin T solution prior to the imaging. After gentle mixing and equilibration overnight at ambient temperature, 10 pL of the stained sample was placed on a glass coverslip for the observation. The excitation wavelength used for Nile red and Thioflavin T were 510 nm and 405 nm, respectively. The fluorescence images were acquired using sequential scan to minimize the crosstalk and processed by Fiji image analysis software. Figure 1 b shows the fluorescence image of Nile red seen as the bright white core of fragrance oil. Figure 1 c shows the fluorescence image of Thioflavin T seen as the bright white shell of protein material. Taking into account both these figures we can conclude that the encapsulate 4D has an oil-filled core with a thin external shell of protein.

[0251] 50 microlitres of Microcapsules Composition 4B was applied to a glass slide and left to dry at room temperature for at least 24 hours. The dried microcapsules were rubbed with a gloved finger. The microcapsules broke and a noticeable oily slick was visible to the naked eye and the characteristic fruity character of delta damascene was very noticeable. This demonstrates that the microcapsules when left to dry can be broken by moderate friction to release the fragrance active material. Comparative Example 4

[0252] An attempt was made to prepare microcapsules in the absence of a primary stabiliser.

[0253] 150 g of room temperature 6.5wt% acetic acid solution (pH3) was weighed in a narrow 250 ml beaker. Mechanical agitation was started at 550 rpm with an anchor blade stirrer, placed at about 1 / 3 of the solution height from the bottom of the beaker. 50g of Core Composition 4A was shaken by hand and vortexed at 3000 rpm for a few seconds, before adding straight away to the stirring vessel. Agitation was maintained for about 30 minutes at room temperature. Unlike Microcapsules Composition 4A, no visible microcapsules were formed in the absence of a primary stabiliser. When agitation stopped, a thin layer of free oil floated on top of a larger aqueous hazy liquid below. A sample of this floating layer was dried and observed under the microscope as seen in Figure 1d and found to consist of oil that formed droplets on drying.

[0254] Example 5 - Zein core-shell fragrance microcapsules prepared with a protein dispersion primary stabiliser and secondary stabilisation

[0255] Preparation of the microcapsules

[0256] Core Composition 5A was prepared by mixing Shell Composition 1A and Active Composition 2A at room temperature in the weight ratio 1: 4.

[0257] 150 g of room temperature Stabiliser Composition 3A was weighed in a narrow 250 ml beaker. Mechanical agitation was started at 700 rpm with an anchor blade stirrer, placed at about 1 / 3 of the solution height from the bottom of the beaker. 50g of Core Composition 5A was shaken by hand and vortexed at 3000 rpm for a few seconds, before adding straight away to the stirring vessel. The formation of a dispersion of microcapsules was visible almost straight away. Agitation was maintained for about 30 minutes at room temperature.

[0258] The resulting Microcapsules Composition 5A was transferred to a 500ml Duran bottle and hard water pH3 was added until the top of the bottle to dilute and shaken by hand to homogenise it.

[0259] The mixture was transferred to a 1 litre separating funnel by pouring through a 250um sieve. No large aggregates were observed. The mixture was left to separate by gravity and the microcapsules floated to the surface over about 2 hours and a clear separation could be seen. The liquid below the microcapsules was collected and discarded. Hard water pH3 was added again, allowed to separate under gravity and the liquid below the microcapsules was collected and discarded. This was repeated until the liquid was clear indicating that there was no excess fragrance oil or dispersion to be washed away.

[0260] A final wash was carried out with buffer solution with preservative to replace the hard water and Microcapsules Composition 5A were stored in a suspension of single strength buffer.

[0261] Secondary stabilisation of the microcapsules

[0262] Approximately 2 ml of Microcapsules Composition 5A was also pipetted into a Stabiliser Composition 3D and dispersed by hand shaking to form a homogeneous mixture and left at room temperature for 24 hours. The Microcapsules 5B formed were then collected by draining on a 75 pm sieve and washed with hard water pH3 followed by single strength buffer.

[0263] The morphology of the microcapsules was assessed by optical microscopy after washing them in hard water. Figure 2 shows wet Microcapsules 5B where, unlike Figure 1a, the spherical encapsulates appear dark throughout due to the secondary stabilisation by the gellan gum.

[0264] Microcapsules 5B were then left to dry for 24 hours at room temperature on a glass slide. The dry microcapsules were then crushed by pressing another microscope slide on top of the dried sample. The microcapsules broke and released the fragrance oil. The micrograph in Figure 3 shows the crushed encapsulates deformed into an amorphous mass of shell material surrounded by the released fragrance oil.

[0265] Separately approximately 2 ml of Microcapsules Composition 5A was pipetted into Stabiliser Composition 3A and dispersed by hand shaking to form a homogeneous mixture and left at room temperature for 24 hours. The Microcapsules 5C were then collected by draining on a 75 pm sieve and washed with hard water pH3 followed by single strength buffer.

[0266] Stability testing of the microcapsules in fabric conditioner

[0267] Approximately 2 ml of Microcapsules Composition 5A was pipetted into standard fabric conditioner and dispersed by hand shaking to form a homogeneous mixture and left at room temperature for 24 hours. The microcapsules were then collected by draining on a 75 pm sieve and washing with hard water pH3 followed by single strength buffer. After being removed from the fabric conditioner and washed with hard water, the wet microcapsules were observed under the microscope as shown in Figure 4. The microcapsules had maintained their integrity and remained intact after 24 hours in the fabric conditioner.

[0268] The washed microcapsules were also left to dry for 24 hours on a glass slide at room temperature and were then crushed by pressing on top with another microscope slide. Under the microscope the microcapsules were seen to have cracked, opened up and released fragrance oil, as observed in Figure 5.

[0269] Example 6 - Zein core-shell fragrance microcapsules prepared with a gellan gum primary stabiliser

[0270] Preparation of the microcapsules

[0271] Core Composition 6A was prepared by mixing Shell Composition 1A and Active Composition 2A at room temperature in the weight ratio of 1: 4.

[0272] 150 g of either room temperature Stabiliser Composition 3B or 3C was weighed in a narrow 250 ml beaker. Mechanical agitation was started at 700 rpm with an anchor blade stirrer, placed at about 1 / 3 of the solution height from the bottom of the beaker. 50g of Core Composition 6A was shaken by hand and vortexed at 3000 rpm for a few seconds, before adding straight away to the stirring vessel. In both cases the formation of a dispersion of microcapsules was visible almost straight away. Agitation was maintained for about 30 mins at room temperature.

[0273] The resulting Microcapsules Compositions 6A and 6B were transferred to a 500ml Duran bottle and the same volume of hard water pH3 was added to dilute and separate small microcapsules from any excess oil or gellan gum.

[0274] The mixture was poured through a 250 micron sieve into to a 1 litre separating funnel. The microcapsules collected on the sieve were washed with hard water using a wash bottle until most of them had gone through the sieve. This step broke up aggregate of microcapsule and removed a few rare over-sized microcapsules. The remaining microcapsules in the wash water were left to separate by gravity. The microcapsules floated to the surface over about 2 hours and a clear separation could be seen. The liquid below the capsules was collected and discarded. The floating capsules were collected on a 75 pm sieve, rinsed with hard water pH3, several times until liquid collected was clear. A final wash was carried out with buffer solution with preservative to replace the hard water. Microcapsules Composition 6A prepared with Stabiliser Composition 3B and Microcapsules Composition 6B prepared with Stabiliser Composition 3C were stored in a suspension of single strength buffer.

[0275] Example 7 - Shellac core-shell fragrance microcapsules prepared with a protein dispersion primary stabiliser

[0276] Preparation of the microcapsules

[0277] Core Composition 7A was prepared by mixing Shell Composition 1B and Active Composition 2A at room temperature in the weight ratio of 1: 2.

[0278] Core Compositions 7B and 7C were prepared by mixing Shell Composition 1C and 1D respectively with Active Composition 2A at room temperature in the weight ratio of 2:3.

[0279] 150 g of room temperature Stabiliser Composition 3A was weighed in a narrow 250 ml beaker. Mechanical agitation was started at 700 rpm with an anchor blade stirrer, placed at about 1 / 3 of the solution height from the bottom of the beaker. 50g of either Core Compositions 7A, 7B or 7C was shaken by hand and vortexed at 3000 rpm for a few seconds, before adding straight away to the stirring vessel. The formation of a dispersion of microcapsules was visible almost straight away. Agitation was maintained for about 30 minutes at room temperature.

[0280] The resulting Microcapsules Compositions 7A, 7B and 7C were each transferred to a 500ml Duran bottle and the same volume of hard water pH3 was added to dilute and separate small microcapsules from any excess oil and dispersion.

[0281] The mixture was poured through a 250 pm sieve stacked on a 38 micron sieve into to a 1 litre separating funnel. The microcapsules collected on the sieves were washed with hard water pH3 using a wash bottle and collected into hard water pH3. This process was repeated until the remaining microcapsules in the wash water were collected. The microcapsules then went through a second wash with buffer and were collected in buffer. The microcapsules floated to the surface over about 2 hours and a clear separation could be seen. The liquid below the microcapsules was collected and discarded. The floating microcapsules 7A, 7B and 7C were collected and stored in single strength buffer. Example 8 - Shellac core-shell fragrance microcapsules prepared with a protein dispersion primary stabiliser and secondary stabiliser

[0282] Preparation of the microcapsules

[0283] Core Composition 8A was prepared by mixing the Shell Composition 1 E and Active Composition 2A at room temperature in the weight ratio of 2:3.

[0284] 150 g of room temperature Stabiliser Composition 3A was weighed in a narrow 250 ml beaker. Mechanical agitation was started at 700 rpm with an anchor blade stirrer, placed at about 1 / 3 of the solution height from the bottom of the beaker. 50g of Core Composition 8A was placed in a room temperature ultrasonic bath for 5 minutes and then shaken vigorously by hand to form a homogeneous two-phase mixture before adding straight away to the stirring vessel. The formation of a dispersion of microcapsules was visible almost straight away. Agitation was maintained for about 30 minutes at room temperature.

[0285] The resulting Microcapsules Composition 8A was transferred to a 500ml Duran bottle and the same volume of hard water pH3 was added to dilute and separate small microcapsules from any excess oil and dispersion.

[0286] The mixture was poured through a 250 micron sieve stacked on a 38 micron sieve into to a 1 litre separating funnel. The microcapsules collected on the sieves were washed with hard water pH3 using a wash bottle and collected into hard water pH3. This process was repeated until the remaining microcapsules in the wash water were collected. The microcapsules then went through a second wash with buffer and were collected in buffer. The microcapsules floated to the surface over about 2 hours and a clear separation could be seen. The liquid below the microcapsules was collected and discarded. The floating microcapsules 8A were collected and stored in single strength buffer.

[0287] Stability testing of the microcapsules in fabric conditioner

[0288] Approximately 2 ml of Microcapsules Composition 8A was pipetted into standard fabric conditioner and dispersed by hand shaking to form a homogeneous mixture and left at room temperature for 24 hours. The microcapsules were then collected by draining on a 75 pm sieve and washing with hard water pH3 followed by single strength buffer.

[0289] After being removed from the fabric conditioner and washed with hard water, the microcapsules were observed under the microscope in the wet state as shown in Figure 6. The microcapsules maintained their integrity and remained intact after 24 hours in the fabric conditioner.

[0290] The washed microcapsules were also left to dry for 24 hours on a glass slide and then crushed by pressing with another microscope slide on top. As shown in Figure 7 the microcapsule was seen to release fragrance oil.

[0291] Secondary stabilisation of the microcapsules with gellan gum

[0292] Approximately 2 ml of Microcapsules Composition 8A was also pipetted into a Stabiliser Composition 3D and dispersed by hand shaking to form a homogeneous mixture and left at room temperature for 24 hours. The Microcapsules 8B formed were then collected by draining on a 75 pm sieve and washed with hard water pH3 followed by single strength buffer.

[0293] Secondary stabilisation of microcapsules with pea protein dispersion

[0294] Approximately 2 ml of Microcapsules Composition 8A was also pipetted into a Stabiliser Composition 3A and dispersed by hand shaking to form a homogeneous mixture and left at room temperature for 24 hours. The Microcapsules 8C formed were then collected by draining on a 75 pm sieve and washed with hard water pH3 followed by single strength buffer.

[0295] Example 9 - Microcapsule fragrance loading and particle size control

[0296] The total level of fragrance in the microcapsules of the previous examples was measured by the GC method herein and reported in Tables 3 and 4. Microcapsules Compositions 4B, 5A, 6A, 6B, 7A, 7B, 7C and 8A were drained prior to analysis through a 40 micron cell strainer under gravity for about 5 minutes. Any residual moisture on the outside of the cell strainer was absorbed with a tissue prior to analysis. For Microcapsules Compositions 4A, 4C, 4D, 4E and 4F additionally the drained microcapsules were left to air dry for 48 hours prior to analysis.

[0297] The particle size distribution of the microcapsules of the previous examples was measured via laser diffraction according to the method herein and the dso was reported in Tables 3 and 4.

[0298] Table 3 The choice of shell material and shell solvent, as well as primary stabiliser, had a significant effect on the microcapsule fragrance loading and average particle size.

[0299] The highest fragrance loading achieved was 86% for Microcapsules Compositions 4F and 4D, comprising a zein shell with propylene glycol shell solvent and a pea protein containing primary stabiliser.

[0300] The choice of shell solvent also had an impact on the microcapsule oil loading level. For example, Microcapsules Composition 8A with shellac as the shell material, had a loading of 47% when the shell solvent was propylene glycol, whilst for Microcapsules Composition 7B, with dipropylene glycol as the shell solvent, this was lower at 38%.

[0301] Microcapsules Compositions 4A, 4B, 4D, 4F and 5A, all with zein as the shell material and pea protein dispersion as the primary stabiliser composition, were the smallest with a particle size dso below 25 microns. By changing the primary stabiliser to gellan gum in Microcapsules Compositions 6A and 6B the particle size increased to a dso of 152 and 196 microns respectively. The choice of primary stabiliser can control the microcapsule particle size.

[0302] The choice of shell material also had an impact on the microcapsule particle size. When using pea protein dispersion as the primary stabiliser, the microcapsules with zein shell material of Microcapsules Composition 5A were much smaller, with a dso of 22 microns, than the microcapsules with shellac shell material of Microcapsules Composition 7B, with a dso of 69 microns. Table 4

[0303] Microcapsules Composition 4C and 4E demonstrated that high loading levels can also be achieved when encapsulating a fragrance oil which is a mixture of fragrance materials. The fragrance components of Active Composition 2C in Microcapsules Composition 4E were quantified individually via GC and it was found that all the five components of the fragrance were present. Prior to encapsulation these were all 20 wt%, and after encapsulation there was a small loss of the most volatile component, limonene, with 14% present, whilst the remaining components were between 21-22 wt%. This demonstrates that the process can effectively encapsulate a fragrance oil composed of a range of fragrance materials.

[0304] Example 10 - Shellac and zein core-shell fragrance microcapsules prepared with a protein dispersion primary stabiliser

[0305] Preparation of the microcapsules

[0306] Core Composition 10A was prepared by mixing at room temperature Shell Composition 1C with Active Composition 2A in the weight ratio of 2:3 and then with Shell Composition 1F in the weight ratio of 2:3 Shell Composition 1 F: Shell Composition 1C.

[0307] 150 g of room temperature Stabiliser Composition 3A was weighed in a narrow 250 ml beaker. Mechanical agitation was started at 700 rpm with an anchor blade stirrer, placed at about 1 / 3 of the solution height from the bottom of the beaker. 50g of Core Composition 10A was shaken by hand and vortexed at 3000 rpm for a few seconds, before adding straight away to the stirring vessel. The formation of a dispersion of microcapsules was visible almost straight away. Agitation was maintained for about 30 minutes at room temperature.

[0308] The resulting Microcapsules Composition 10A was transferred to a 500ml Duran bottle and the same volume of hard water pH3 was added to dilute and separate small microcapsules from any excess oil and dispersion.

[0309] The mixture was poured through a 250 micron sieve stacked on a 38 micron sieve into to a 1 litre separating funnel. The microcapsules collected on the sieves were washed with hard water pH3 using a wash bottle and collected into hard water pH3. This process was repeated until the remaining microcapsules in the wash water were collected. The microcapsules then went through a second wash with buffer and were collected in buffer. The microcapsules floated to the surface over about 2 hours and a clear separation could be seen. The liquid below the microcapsules was collected and discarded. The floating Microcapsules 10A were collected and stored in single strength buffer.

Claims

CLAIMS1. Method for the preparation of a composition of core-shell microcapsules, the method comprising the following steps: a) providing a shell composition comprising one or more shell materials and one or more shell solvents; b) providing a liquid active composition comprising one or more active materials and optionally one or more active material solvents; c) preparing a liquid primary stabiliser composition comprising one or more primary stabilisers and one or more primary stabiliser solvents; d) mixing said shell composition of step a) with said active composition of step b) to result in a core composition; e) mixing said core composition of step d) with said primary stabiliser composition of step c) so as to form an emulsion of the core composition of step d) in the primary stabiliser composition of step c); f) stirring the emulsion of step e) to form a shell wall by non-covalent interaction of at least part of the one or more shell materials at the interface of droplets of the core composition of step d) and an external phase of the primary stabiliser composition of step c) so as to result in a microcapsules composition of coreshell microcapsules in said external phase; g) optionally removing or replacing at least part of the external phase of the microcapsules composition of step f);2. Method according to claim 1, wherein the method further comprises h) adding a secondary stabiliser composition comprising one or more secondary stabilisers and optionally one or more secondary stabiliser solvents to the microcapsules composition of either step f) or step g).

3. Method according to claim 2, wherein the method further comprises i) isolating the microcapsules from the microcapsules composition of either step f), step g) or step h).

4. Method according to any of claims 1 to 3, wherein the one or more shell materials are selected from the group consisting of prolamin proteins, glutelin proteins, polysaccharides, and polyesters, preferably wherein the one or more shell materialsare selected from zein, shellac, chitosan, and polyhydroxyalkanoates (PHAs), more preferably wherein the one or more shell materials are shellac and / or zein.

5. Method according any of claims 1 to 4, wherein the one or more shell solvents are selected from the group consisting of glycols and glycol derivatives, ethyl esters, glycerine esters, alcohols, organic solvents, ionic liquids, fatty acids and fatty acid esters, preferably wherein the one or more shell solvents are selected from the group consisting of propylene glycol, dipropylene glycol, ethylene glycol, triethylene glycol, propylene carbonate, ethylene carbonate, triethyl citrate, ethyl lactate, ethyl acetate, glycerol formal, methanol, ethanol, isopropyl alcohol, butanols, acetone, dimethyl sulphoxide, imidazolium-based ionic liquids, myristic acid, lauric acid, palmitic acid, stearic acid, oleic acid and sucrose fatty acid esters, even more preferably wherein the one or more shell solvents are selected from the group consisting of glycols, most preferably wherein the one or more shell solvents are propylene glycol and / or dipropylene glycol.

6. Method according to any of claims 1 to 5, wherein the one or more active materials are selected from the group consisting of fragrance materials, essential oils, fat soluble vitamins, minerals, flavour materials, agrochemicals, cosmetic ingredients, fatty acids, surface care ingredients, pharmaceutical ingredients, microorganisms including probiotics and fungal spores, preferably wherein the one or more active materials are selected from fragrance materials, flavour materials and probiotics.

7. Method according to any of claims 1 to 6, wherein the one or more active material solvents are selected from the group consisting of benzyl benzoate, diethyl phthalate, isopropyl myristate, triethyl citrate, dipropylene glycol, and propylene glycol, triacetin, glycerin, 1,3 propanediol and combinations thereof, more preferably wherein the one active material solvent is isopropyl myristate.

8. Method according to any of claims 1 to 7, wherein the one or more primary stabilisers are selected from the group consisting of proteins, polysaccharides, natural based isoprenes, and mineral particles, preferably wherein the one or more primary stabilisers are selected from proteins, more preferably globulin proteins.

9. Method according to any of claims 1 to 8, wherein the one or more primary stabiliser solvents are selected from the group consisting of water, ethanol, organic acids,propylene glycol, dipropylene glycol, ethylene glycol, triethylene glycol, propylene carbonate, ethylene carbonate, triethyl citrate, glycerine acetates, ethyl acetate, ethyl lactate and butanols, preferably wherein the primary stabiliser solvent is water.

10. Method according to any of claims 1 to 9, wherein the mixing in step e) is done by a membrane emulsification or a bulk emulsification process.

11. Method according to any of claims 1 to 10, wherein steps e) and f) are carried out at a temperature between 5°C and 40°C, more preferably between 10°C and 30°C.

12. Method according to any of claims 1 to 11 , wherein the compositions obtained in steps a) and b) are immiscible.

13. Method according to any of claims 1 to 12, wherein the one or more shell materials in step a) have a greater solubility in the liquid active composition of step b) than in water, preferably wherein the shell composition obtained in step a) has a greater solubility in the liquid active composition of step b) than in the liquid primary stabiliser composition of step c).

14. Method according to any of claims 1 to 13, wherein the one or more shell materials have a greater solubility in the one or more shell solvents than in water, preferably wherein the one or more shell materials have a greater solubility in the one or more shell solvents than in the liquid primary stabiliser composition of step c).

15. Method according to any of claims 1 to 14, wherein the concentration of shell material in the shell composition of step a) is within the range of 0.1 to 50 weight %, preferably 1 .0 to 33 weight %, more preferably 5.0 to 25 weight %.

16. Method according to any of claims 1 to 15, wherein the concentration of the primary stabiliser in the liquid primary stabiliser composition of step c) is within the range of 0.001 to 40 weight %, preferably 0.01 to 33 weight %, more preferably 0.1 to 15 weight %.

17. Method according to any of claims 1 to 16, wherein the one or more secondary stabilisers are selected from the group consisting of proteins, polysaccharides, naturalbased isoprenes, mineral particles, and salts, preferably wherein the one or more secondary stabilisers are selected from salts and gellan gum.

18. Method according to any of claims 1 to 17, wherein the one or more secondary stabiliser solvents are selected from the group consisting of water, ethanol, organic acids, propylene glycol, dipropylene glycol, ethylene glycol, triethylene glycol, propylene carbonate, ethylene carbonate, triethyl citrate, glycerine acetates, ethyl acetate, ethyl lactate and butanols, preferably wherein the secondary stabiliser solvent is water.

19. Method according to any of claims 1 to 18, wherein the liquid active composition of step b) is non-aqueous.

20. Method according to any of claims 1 to 18, wherein the liquid primary stabiliser composition of step c) is aqueous.21 . A composition of core-shell microcapsules, wherein the microcapsules are obtained by the method of any of claims 1 to 20.

22. A composition of core-shell microcapsules, wherein the microcapsules comprise a core comprising one or more active materials and a shell comprising one or more shell materials and one or more primary stabilisers.

23. A composition according to claim 22, wherein the shell further comprises one or more secondary stabilisers.

24. A composition according to claim 23, wherein the one or more secondary stabilisers are selected from the group consisting of proteins, polysaccharides, natural based isoprenes, mineral particles, and salts, preferably wherein the one or more secondary stabilisers are selected from salts and gellan gum.

25. A composition according to any of claims 22 to 24, wherein the one or more active materials are selected from the group consisting of fragrance materials, essential oils, fat soluble vitamins, minerals, flavour materials, agrochemicals, cosmetic ingredients, fatty acids, surface care ingredients, pharmaceutical ingredients, microorganismsincluding probiotics, and fungal spores, preferably wherein the one or more active materials are selected from fragrance materials, flavour materials and probiotics.

26. A composition according to any of claims 22 to 25, wherein the one or more shell materials are selected from the group consisting of prolamin proteins, glutelin proteins, polysaccharides, and polyesters, preferably wherein the one or more shell materials are shellac and / or zein.

27. A composition according to any of claims 22 to 26, wherein the one or more primary stabilisers are selected from the group consisting of proteins, polysaccharides, natural based isoprenes, and mineral particles, preferably wherein the one or more primary stabilisers are selected from plant proteins.

28. A composition according to any of claims 22 to 27, wherein the, the biodegradation percentage based upon 02 consumption of the microcapsules as measured according to ISO-14851 version 2019 after 28 days is 60 to 100% based upon the ratio of the Biological Oxygen Demand (BOD) to the Theoretical Oxygen Demand, more preferably 65 to 100%, even more preferably 70 to 100%, even preferably 75 to 100%, even more preferably 80 to 100%, even more preferably 85 to 100%, most preferably 90 to 100%.

29. A composition according to any of claims 22 to 28, wherein the microcapsules are edible, preferably wherein the microcapsules are digestible.

30. A composition according to any of claims 22 to 29, wherein the core is a single core.31 . Use of a composition according to any of claims 21 to 30 in a formulated product, wherein the formulated product is a food, beverage, cosmetic, home care product, personal care product, pharmaceutical, industrial product, medical device, biomaterial, or agrochemical.

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