Title of Invention	METHOD FOR SPRAY DRYING COMPOSITIONS
Abstract	The invention provides a method comprising the steps of: (i) providing an emulsion of: a) an aqueous solvent, such as water, b) a carrier material dispersible or soluble in (a), said carrier material being solid at ambient temperature, and preferably being a polymer and inorganic salt or a surfactant, c) a volatile second liquid phase (for example, chloroform) which is not miscible with (a), and d) a material which is dispersible or soluble in (c) but not in (a), and, (ii) Drying the emulsion at above ambient temperature (preferably by spray drying) to simultaneously remove (a) and (c) and thereby obtain the material (b) in solid form with (d) dispersed therein.

Title of Invention

METHOD FOR SPRAY DRYING COMPOSITIONS

Abstract

The invention provides a method comprising the steps of: (i) providing an emulsion of: a) an aqueous solvent, such as water, b) a carrier material dispersible or soluble in (a), said carrier material being solid at ambient temperature, and preferably being a polymer and inorganic salt or a surfactant, c) a volatile second liquid phase (for example, chloroform) which is not miscible with (a), and d) a material which is dispersible or soluble in (c) but not in (a), and, (ii) Drying the emulsion at above ambient temperature (preferably by spray drying) to simultaneously remove (a) and (c) and thereby obtain the material (b) in solid form with (d) dispersed therein.

Full Text	FORM2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See section 10; rule 13) 1. Title of the invention - SPRAY DRIED COMPOSITIONS 2. Applicant(s) (a) NAME : UNILEVER PLC (b) NATIONALITY : A British Company (c) ADDRESS : Unilever House, Blackfriars, London EC4P 4BQ,United Kingdom 3. PREAMBLE TO THE DESCRIPTION The following specification particularly describes the invention and the manner in which it is to be performed: WO 2006/079409 PCT/EP2005/013933 - 1 - IMPROVEMENTS RELATING TO RAPIDLY DISSOLVING COMPOSITIONS Technical Field: The present invention relates to dried compositions which dissolve rapidly in water. Background to the Invention: Many useful materials are water-insoluble. These include, without limitation, many dyestuffs (i.e. pigments), some fluorescer materials and many pharmaceutical materials. In some circumstances it is possible to disperse these materials in water by processes involving fine comminution, but this can be expensive and time-consuming. Our co-pending international patent application PCT/GB03/03226 describes the formation of solid, porous beads comprising a three dimensional open-cell lattice of a water-soluble polymeric material. These are typically templated' materials formed by the removal of both water and a non-aqueous dispersed phase from a high internal phase emulsion (HIPE) which has a polymer dissolved in the aqueous phase. The beads are formed by dropping the HIPE emulsion into a low temperature fluid such as liquid nitrogen, then freeze-drying the particles formed to remove the bulk of the aqueous phase and the dispersed phase. This leaves behind the polymer in the form of a ‘skeletal' structure. WO 2006/079409 PCT/EP2005/013933 - 2 - The beads dissolve rapidly in water and have the remarkable property that a water-insoluble component dispersed in the dispersed phase of the emulsion prior to freezing and drying can also be dispersed in water on solution of the polymer skeleton of the beads. The production process for the beads and related materials is complex. It requires the use of liquid gasses and vacuum equipment. Throughput is relatively low. There is a clear need to devise a simpler and cheaper process. Past workers have looked at ways of delivering water-insoluble materials such as carotenoids. US 3998753 (Antoshkiw et al., 1974) discloses a method of preparing a water-dispersible carotenoid composition which comprises the steps of forming an emulsion of the carotenoid in a volatile solvent (such as chloroform) and various structurants (such as gelatine) in water. This emulsion is heated with high-speed mixing to drive off the volatile solvent and the resulting emulsion product can be used as is. Optionally, the solvent-free product may be further processed by spray drying to remove the water and give a dry product. US 4213900 (Daubach et al., 1978) takes a different approach. 5 Here formic acid, formamide, N-methylformamide, butyrolactone, ethylene or propylene glycols are used as solubilising agents for water-insoluble dyes. Once a solution has been formed it can be spray-dried to form a fine powder which can be dispersed in water. - 3 - Pamujula et al. (Journal of Pharmacy and Pharmacology, 2004, 56: 1119-1125) disclose a process for the production of spray dried poly(lactide-co-glycolide) (PLGA) carrier particles containing the cytoprotective drug amifostine. In the procedure described the drug was dissolved in water and emulsified with a solution of PLGA carrier in a water-immiscible solvent (dichloromethane) . This was spray-dried to remove the majority of the solvent and obtain nanoparticles, which were then freeze-dried to remove any residual solvent. The final product of the process was in the form of nanoparticles having a median size of 240-257 nm. Several other methods are known which result in a dry emulsion'. For example Dollo et al (Eur. J. of Pharmaceutical Sciences, 19, issue 4 pages 273-280) discloses a physically stabilised dry emulsion with a lipophilic drug dissolved in the oil phase. Hansen, Holm and Schultz (Int J. Pharmaceutics, 287, issue 1-2, 9th December 2004, pages 55-66) disclose a process for preparing powders containing a poorly water-soluble drug dissolved in (nonvolatile) medium chain triglyceride, by spray drying o/w emulsions. The products of this process would still contain the 'solvent' for the drug, i.e. non-volatile medium chain triglyceride. Thus the product of the spray drying process can be described as a 'dry emulsion' which will reform the initial emulsion on addition of water. DE 2122662 (BASF, 1972) discloses a process for obtaining a water-insoluble dye dispersion with practically the same degree of dispersion as that produced by -'wet miiling of. the dye. This process involves mixing "the dye with a surfactant, water^ and a water-immiscible ..solvent, subjecting the mixture AMENDED SHEET - 3a to heat and/or pressure and spray drying the treated mixture. AMENDED SHEET _ 4 _ Brief Description of the Invention: We have now determined that spray drying can be used instead of freeze drying to obtain solid, rapidly dissolving materials directly from an emulsion. Accordingly a first aspect of the present invention provides a method comprising the steps of: (i) providing an emulsion of: a) an aqueous solvent, b) a carrier material dispersible or soluble in (a), said carrier material being solid at ambient temperature, c) a volatile second liquid phase which is not miscible with (a), and d) a material which is dispersible or soluble in (c) but not in (a), and, (ii) Drying the emulsion above ambient temperature to simultaneously remove (a) and (c) and thereby obtain the carrier material (b) in solid form with (d) dispersed therein, said dispersion of '(d) being a nano-scale dispersion, preferably with a maximum particle : size of at most 615nm. 4a - The aqueous solvent (a) is generally and preferably water, but may comprise an electrolyte solution or a mixture of hydrophilic solvents. - 5 - Advantageously, both the aqueous solvent (a) and the volatile, water-immiscible second liquid phase (c) are simultaneously removed during the drying process, and no separate removal step for either the second liquid phase 5 (e.g. by boiling it off) or the aqueous solvent (e.g. by freeze drying) is needed. By volatile' here is meant that the second liquid phase is sufficiently volatile to be removed as a vapour phase during the drying process. ‘Burning-off of one of the solvents is not required in the method of the invention. By far the most preferred method for drying of the intermediate emulsion is by spray drying. This is particularly effective at removing both the aqueous and non- aqueous volatile components to leave the carrier and the ‘payload' material behind in a fine particulate form. Drying is preferably conducted at a temperature well above ambient (taken as 25 Celsius). It is particularly preferred that drying is conducted at above 80 and more preferably above 100 Celsius. In the case of a spray drying apparatus this means that the inlet temperature of the spray drying apparatus is, for example, above 100 Celsius. Particularly preferred drying conditions are those in which the drying temperature is above both the boiling point of water and the boiling point of the volatile second liquid phase. The final structure of the material obtained is not well understood. However it is believed that ".removal by drying of the aqueous solvent and the second liquid phase results in a very fine, nano-scale WO 2006/079409 PCT/EP2005/013933 - 6 - dispersion of the water insoluble material (d) through the water-soluble carrier material (b) . It is believed that the resulting dry materials are not encapsulates, as discrete bodies of the water-immiscible materials (d) are not present in the dry product. Neither are the dry materials %dry emulsions' as little or none of the volatile solvent comprising the 'oil' phase of the emulsion remains after the drying step. On addition of water to the dry product the emulsion is not reformed, as it would be with a ‘dry emulsion'. On admixture of the carrier material with water, the carrier (b) dissolves and the water insoluble material (d) is dispersed through the water in sufficiently fine form that it behaves like a soluble material in many respects. Surprisingly, the effectiveness of materials delivered in this way is hardly reduced as compared with materials delivered using an emulsion- templated, freeze-drying preparation method. Detailed Description of the Invention: In order that the present invention may be better understood and carried forth into practice, it is described below with reference to various preferred features and particular embodiments. Carrier Material: The carrier material is water soluble, which includes the formation of structured aqueous phases as well as true ionic WO 2006/079409 PCT/EP2005/013933 - 7 - solution of molecularly mono-disperse species. The carrier material preferably comprises an inorganic material, surfactant, a polymer or may be a mixture of two or more the these. It is envisaged that other non-polymeric, organic, water-soluble .materials such as sugars can be used as the carrier. However the carrier materials specifically mentioned herein are preferred. Polymeric Carrier Materials: When present, the polymeric carrier material is a material that would be considered as "water soluble" by those skilled in the art i.e. if it forms a homogeneous solution in water. Water soluble polymers generally possess pendant polar or ionizable groups (e.g. -C=0, -OH, -N(RX) (R2) in which Ra and R2, which may be the same or different, are independently H or (CI to C4)alkyl, -N(R3) (R4) (Rs)+ in which R3, R4 and R5 which may be the same or different, are independently H or (CI to C4)alkyl, -CON(R6) (R7) in which R6 and R7, which may be the same or different, are H or (CI to C4) alkyl, -CH2CH20-, -C02H or salts thereof, -S03H or salts thereof groups) on a backbone chain which may be hydrophobic. If water-soluble polymeric carrier materials are incorporated into the products of the present invention, the time taken for the products to dissolve or disperse may be significantly reduced, as compared with 'off-the-shelf samples of the polymeric carrier materials. It is believed that this is due to the structural result of, in particular, the spray-drying process. The same is believed to be true of other carrier materials. The nature of the products should WO 2006/079409 PCT/EP2005/013933 - 8- be such that the dissolution or dispersion of the products in a large excess of water preferably occurs in less than three minutes, more preferably less than two minutes, most preferably less than one minute. The particle size and distributions of the ‘payload' material can be tailored by choosing different water-soluble polymers and polymers with different molecular weights. This allows some control over the activity/availability of the payload material'. Examples of suitable water-soluble polymeric carrier materials include: (a) natural polymers (for example naturally occurring gums such as guar gum or locust bean gum or a polysaccharide such as dextran; (b) cellulose derivatives for example xanthan gum, xyloglucan, cellulose acetate, methylcellulose, methyl- ethylcellulose, hydroxyethylcellulose, hydroxyethylmethyl - cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose (HPMC), hydroxypropylbutylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose and its salts (eg the sodium salt - SCMC), or carboxymethylhydroxyethylcellulose and its salts (for example the sodium salt); (c) homopolymers of any one of the monomers listed in Table 1 below; WO 2006/079409 PCT7EP2005/013933 (d) copolymers prepared from two or more monomers listed in Table 1 below; (e) mixtures thereof Table 1 vinyl alcohol, acrylic acid, methacrylic acid acrylamide, methacrylamide acrylamide methylpropane sulphonates aminoalkylacrylates aminoalkylmethacrylates hydroxyethylacrylate hydroxyethylmethylacrylate vinyl pyrrolidone vinyl imidazole vinyl amines vinyl pyridine ethyleneglycol and other alkylene glycols ethylene oxide and other alkylene oxides ethylene imine styrenesulphonates ethyleneglycolacrylates ethyleneglycol methacrylate When the polymeric material is a copolymer it may be a statistical copolymer (heretofore also known as a random WO 2006/079409 PCT/EP2005/013933 - 10 - copolymer), a block copolymer, a graft copolymer or a hyperbranched copolymer. Comonomers other than those listed in Table 1 may also be included in addition to those listed if their presence does not destroy the water soluble or water dispersible nature of the resulting polymeric material. Examples of suitable homopolymers include polyvinylalcohol, polyacrylic acid, polymethacrylic acid, polyacrylamides (such as poly-N-isopropylacrylamide) , polymethacrylamide; polyacrylamines, polymethylacrylamines, (such as polydimethylaminoethylmeth-acrylate and poly-N-morpholinoethylmethacrylate, polyvinyl-pyrrolidone, polyvinylimidazole, polyvinylpyridine, polyethylene-imine and ethoxylated derivatives thereof. Polyvinylalcohol is a particularly preferred carrier material. Surfactant Carrier Materials: Where the carrier material is a surfactant, the surfactant may be non-ionic, anionic, cationic, amphoteric or zwitterionic. Examples of suitable non-ionic surfactants include ethoxylated triglycerides; fatty alcohol ethoxylates; alkylphenol ethoxylates; fatty acid ethoxylates; fatty amide ethoxylates; fatty amine ethoxylates; sorbitan alkanoates; ethylated sorbitan alkanoates; alkyl ethoxylates; Pluronics™; alkyl polyglucosides; stearol ethoxylates; alkyl polyglycosides. - 11 - Examples of suitable anionic surfactants include alkylether sulfates; alkylether carboxylates; alkylbenzene sulfonates; alkylether phosphates; dialkyl sulfosuccinates; alkyl sulfonates; soaps; alkyl sulfates; alkyl carboxylates; alkyl phosphates; paraffin sulfonates; secondaryn-alkane sulfonates; alpha-olefin sulfonates; isethionate sulfonates. Examples of suitable cationic surfactants include fatty amine salts; fatty diamine salts; quaternary ammonium compounds; phosphonium surfactants; sulfonium surfactants; sulfonxonium surfactants. Examples of suitable zwitterionic surfactants include N-alkyl derivatives of amino acids (such as glycine, betaine, aminopropionic acid); imidazoline surfactants; amine oxides; amidobetaines. Mixtures of surfactants may be used. In such mixtures there may be individual components which are liquid, provided that the carrier material overall, is a solid. Anionic surfactants are particularly preferred as carrier materials. Inorganic Carrier Materials: The carrier material can also be an water-soluble inorganic material which is neither a surfactant nor a polymer. Simple •organic salts have been, found suitable, particularly in ^admixture with polynieric- and/or surfactant carrier materials as described above. Suitable salts include carbonate, AMENDED SHEET WO 2006/079409 PCT/EP2005/013933 - 12 - bicarbonates, halides, sulphates, nitrates and acetates, particularly soluble salts of sodium, potassium and magnesium. Preferred materials include, sodium carbonate, sodium bicarbonate and sodium sulphate. These materials have the advantage that they are cheap and physiologically acceptable. They are also relatively inert as well as compatible with many materials found in household and pharmaceutical products. In general spray-dried samples containing an inorganic carrier material gave smaller particle sizes on re-dissolution than comparative freeze-dried samples. Mixtures of carrier materials are advantageous. Preferred mixtures include combinations of inorganic salts and surfactants and polymers and surfactants. Where inorganic salts are present the carrier material typically comprise 10-50%wt surfactant and 90-50%wt of the inorganic salt. Second liquid phase: The compositions of the invention comprise a volatile, second liquid phase, which is not miscible with the aqueous solvent. The second liquid phase of the emulsion may be selected from one or more from the following group of volatile organic solvents: alkanes, such as heptane, n-hexane, isooctane, dodecane, 3 decane; WO 2006/079409 PCT7EP2005/013933 - 13 - • cyclic hydrocarbons, such as toluene, xylene, cyclohexane; • halogenated alkanes ,such as dichloromethane, dichoroethane, trichloromethane (chloroform) , fluoro- trichloromethane and tetrachloroethane; • esters such as ethyl acetate; • ketones such as 2-butanone; • ethers such as diethyl ether; • volatile cyclic silicones such as either linear or cyclomethicones containing from 4 to 6 silicon units. Suitable examples include DC245 and DC345, both of which are available from Dow Corning Inc. Preferred second liquid phases have a boiling point of less than 150 Celsius and, more preferably, have a boiling point of less than 100 Celsius, so as to facilitate drying, particularly spray-drying under practical conditions and without use of specialised equipment. Preferred second liquid phase material are non-flammable, or have a flash point above the temperatures encountered in the method of the invention. Preferably, the second liquid phase comprises from about 10 % to about 95 % v/v of the emulsion, more preferably from about 20 % to about 80 % v/v. WO 2006/079409 PCT/EP2005/013933 - 14 - Particularly preferred solvents are halogenated solvents, more preferably chlorine-containing solvents, most preferably solvents selected from (di- or tri-chloromethane). Materials as carriers: The products of the present invention include 'payload' materials to be dispersed when the products are partially dissolved in an aqueous medium. These are water-insoluble materials, which are soluble in the second liquid phase. Dispersion into an aqueous medium of such hydrophobic materials is much improved in the products of the invention. These hydrophobic materials are dissolved in the discontinuous phase of the emulsion prior to drying. The present invention also includes, in a further aspect, solutions or dispersions comprising the carrier (preferably surfactant, polymer or inorganic salt) and a hydrophobic material formed by exposing to an aqueous medium products according to the present invention, wherein said products comprise the hydrophobic material and are obtainable by means of the method of the present invention. The present invention is susceptible of a very broad range of applications as regards the choice of hydrophobic material to be carried. The embodiments mentioned below are selected from a range of applications including, home and personal care products, agrochemicals and pharmaceuticals, perfumes and flavourings, inks and dyes and other applications. The list is not intended to be limiting. WO 2006/079409 PCT7EP2005/013933 - 15 - For example, there are many instances in personal care products such as deodorants, skin and hair cleaning or care products or in household products such as laundry cleaning and care products or household cleaning or care products for hard and soft surfaces where it is desirable to administer hydrophobic materials in an aqueous environment. Because of the hydrophobic nature of these materials they are often difficult to disperse in an aqueous environment. The use of the products of the present invention facilitates this dispersion and in many cases enables hydrophobic materials to be dispersed more effectively than previously. It may be required to disperse the hydrophobic materials at the point where a formulation is being used. In this case the materials of the present invention will be contained in a formulation until it is used by exposing it to an aqueous environment, at which time the water-soluble/dispersible carrier forming the product will release the hydrophobic material. Particularly preferred products according to the present invention comprise a water-insoluble, pharmaceutically active substance and a water-soluble physiologically acceptable carrier. As well as finding advantageous application at the point of use, the products of the present invention may be used to introduce hydrophobic materials into formulations, for example, liquid formulations during the manufacture of these formulations. In this case the products of the present invention will, on contact an aqueous environment, release the hydrophobic material in a form in which it can be more readily incorporated into the product being manufactured. WO 2006/079409 PCT/EP2005/013933 - 16 - The products of the present invention may be used to transport materials to sites where they can be incorporated into formulations. By converting liquids into products according to the invention, the need to transport large amounts of liquids can be avoided resulting in significant cost savings and safer transport of materials, which are potentially hazardous when transported in a liquid form. Materials which would be potentially unstable if stored or transported in liquid form may be incorporated into the products of the present invention and stored or transported with less risk of degradation. It is envisaged that incorporation of potentially unstable hydrophobic materials, for example vaccines, vitamins or perfume components, into the products of the present invention will protect them from degradation during storage prior to use. For example, a so-called pro-fragrance incorporated into a dry carrier material according to the invention is expected to exhibit reduced hydrolysis as compared with the same material in solution or exposed to moist air. Some specific examples of products in which the products of the present invention may be used are given below. These are given as examples only and are not intended to limit the applicability of the present invention. Those skilled in the art will however realise that the materials of the present invention will have utility in other areas not specifically exemplified herein. WO 2006/079409 PCT/EP2005/013933 - 17 - Hydrophobic materials that are released from the products of the present invention at the time of use may include:- • antimicrobial agents, for example: Triclosan™, climbazole, octapyrox, ketoconizole, phthalimoperoxyhexanoic acid (PAP), quaternary ammonium compounds; • antidandruff agents for example: zinc pyrithione; • skin lightening agents for example 4-ethylresorcinol; • fluorescing agents for example: 2,5-bis(2-benzoxazolyl) thiophene for use on fabrics (such as cotton, nylon, polycotton or polyester)in laundry products; • skin conditioning agents, for example cholesterol; • antifoaming agents for example isoparrafin • hair conditioning agents for example quaternary ammonium compounds, protein hydrolysates, peptides, ceramides and hydrophobic conditioning oils for example hydrocarbon oils such as paraffin oils and/or mineral oils, fatty esters such as mono-, di-, and triglycerides, silicone oils such as polydimethylsiloxanes (e.g. dimethicone) and mixtures thereof; • fabric conditioning agents for example quaternary ammonium compounds having 1 to 3, preferably 2 optionally substituted (C8-C24) alk(en)yl chains attached to the WO 2006/079409 PCT/EP2005/013933 - 18 - nitrogen atom by one or more ester groups; hydrophobic monoparticles such as a sucrose polyester for example sucrose tetra-tallowate; silicones for example polydimethylsiloxane; • thickening agents for example hydrophobically modified cellulose ethers such as modified hydroxyethylcelluloses; • dyes for example dyes intended to change the colour of fabrics, fibres, skin or hair; • UV protecting agents such as sunscreens for example octyl methoxycinnamate (Parsol MCX), butyl methoxydibenzoylmethane (Parsol 1789) and benzophenone-3 (Uvinul M-40), ferulic acid; • bleach or bleach precursors for example 6-N- phthalimidoperoxyhexanoic acid (PAP) or photobleaching compounds. Dispersing the bleach from the porous bodies of the present invention results in the bleach being more finely dispersed and reduces the spot damage seen when larger particles of the bleach contact a fabric; • antioxidants for example hydrophobic vitamins such as vitamin E, retinol, antioxiants based on hydroxytoluene such as Irganox™ or commercially available antioxidants such as the Trollox™ series. • insecticides, pesticides, herbicides and other agrochemicals, for example those that are stored as solid WO 2006/079409 PCT/EP2005/013933 - 19 - compositions before use but which are made up into liquid for spraying (or other application) onto animals or crops; • perfumes or flavourings or precursors thereto; • pharmaceutical^ or veterinary active materials. Compositions of the present invention may have additional specific advantages. For example, there is a need for pharmaceutical compositions, which can be taken by the consumer without the need to ingest the composition with a drink such as water. These compositions interact with the moisture in the oral cavity to release the active ingredient, which is then ingested by the consumer. By incorporating the pharmaceutically or veterinary active molecule in the products of the present invention, pharmaceutical compositions which meet this need can be prepared. In a similar way to that described above pharmaceutical and veterinary active ingredients may be formulated so that they release the active material into the nasal, ocular, pulmonary or rectal cavities or on the skin where they may act topically or they may be absorbed trans-dermally to act systemically. By using the appropriate polymeric material in the products of the present invention, materials can be made that remain intact until the conditions (for example temperature or pH) change to those under which dispersion can occur. Thus dispersion can be delayed until a certain temperature has been reached or until the pH has changed to a suitable value such as- would occur as the products pass down the GI tract. WO 2006/079409 PCT/EP2005/013933 - 20 - Acidity in the GI tract reduces down the GI tract and materials which disperse hydrophobic actives only when the materials are exposed to higher pH conditions enable pharmaceutically or veterinary active materials to be released only in the intestine having passed through the stomach intact. Further examples of situations where the products of the present invention are used to incorporate a hydrophobic 0 material into a formulation during the manufacture of that product include:- • the introduction of hydrophobic materials such as fluorescers; enzymes; bleaches; hydrophobic polymers for example hydrophobically modified polyacrylates, silicones, hydrophobically modified polyvinylpyrrolidone, sulpha alkyl polysaccharides, Jaguar and JR polymers; fatty alcohols or acids; dyes for example shading dyes or black dyes for colour recovery into laundry products; • the use of products according to the present invention containing hydrophobic dyes in the manufacture of water soluble Inkjet compositions; • the introduction of products containing different hydrophobic materials enables a manufacturer to produce a single base formulation into which the desired hydrophobic materials may be introduced by the use of the appropriate product of the present invention; WO 2006/079409 PCT/EP2005/013933 - 21 - • the use of products containing hydrophobic polymers which disperse into water to form a latex. The use of such latexes containing appropriate hydrophobic polymers deposited onto fabric imparts crease resistance or easy- iron properties to fabric. The materials of the present invention may include within carrier material, water-soluble materials, which will be dispersed when the bodies are dispersed in an aqueous medium. The water-soluble materials may be incorporated into the lattice by dissolving them in the liquid medium from which they are made. Examples of suitable water soluble materials include:- • Water soluble vitamins such as vitamin C; • water soluble fluorescers such as the 4,4'-bis(sulfo- styryl)biphenyl disodium salt (sold under the trade name Tinopal CBS-X; • activated aluminium chlorohydrate; • transition metal complexes used as bleaching catalysts; • water soluble polymers and oligomers such as polyesters isophthalic acid), gerol, xanthan gum, or polyacrylates; diethylenetriamine-pentaacetic acid (DTPA); or mixtures thereof WO 2006/079409 PCT/EP2005/013933 - 22 - In some cases the water-soluble carrier material itself may not be inert but may also have useful activity. For example, the carriers suggested above include materials which are known to be active as detergency builders (sodium carbonate) or as an antacid (sodium bicarbonate). Method of Preparation: As noted above, the method for preparing the products of the invention comprises drying an emulsion containing an aqueous phase comprising a carrier and a volatile 'oil' phase comprising a 'payload' material. As noted above, the preferred method of drying is spray drying. Preferably, the volatile oil phase comprises from about 10 % to about 95 % v/v of the emulsion, more preferably from about 20 % to about 68 % v/v. The emulsions are typically prepared under conditions which are well known to those skilled in the art, for example, by using a magnetic stirring bar, a homogeniser, or a rotational mechanical stirrer. The emulsions need not be particularly stable, provided that they do not undergo extensive phase separation prior to the drying step. Homogenisation using a high-shear mixing device is a particularly preferred way to make an emulsion in which the aqueous phase is the continuous phase. It is believed that this avoidance of coarse emulsion and reduction of the 30 droplet size of the dispersed phase of the emulsion, results in an improved dispersion of the ‘payload' material in the WO 2006/079409 PCT/EP2005/013933 - 23 - dry product. In a preferred method according to the invention a water-continuous emulsion is prepared with an average dispersed-phase droplet size (using the Malvern peak intensity) of between 500nm and 3 000nm. We have found that an 'Ultra-Turrux' T25 type laboratory homogeniser (or equivalent) gives a suitable emulsion when operated for more than a minute at above 10,000 rpm. In preferred embodiments of the invention, there is a directional relation between the emulsion droplet size and the size of the particles of the 'payload' material, which can be detected after dispersion of the materials of the invention in aqueous solution. We have determined that an increase in the speed of homogenisation for precursor emulsions can decrease final particle size after re-dissolution. It is believed that the re-dissolved particle size can be reduced by nearly one half when the homogenisation speed increased from 13,500 rpm to 21,500 rpm. The homogenisation time also plays an important role in controlling re-dissolved particle size. The particle size again decreases when increase the homogenisation time, and the particle size distribution becomes broader at the same time. For an intermediate emulsion size range of 500-3 00 0nm the re-dispersed particle size range is typically 180-300nm. Spray drying, the most preferred method of drying the emulsion, is well known to those versed in the art. In the case of the present invention some care must be taken due to WO 2006/079409 PCT/EP2005/013933 - 24 - the presence of a volatile non-aqueous solvent in the emulsion being dried. In order to reduce the risk of explosion when a flammable solvent is being used, an inert gas, for example nitrogen, can be employed as the drying medium in a so-called closed spray-drying system. The solvent can be recovered a re-used. We have found that the 'Buchi' B-2 90 type laboratory spray drying apparatus is suitable. The product form obtained form the preferred spray drying process is a powder. As noted above, the precise microstructure of this powder is unclear. This powder can be incorporated into tablets, either by simple compression (where the carrier material is sticky enough) or following the addition of excipients and or tableting agents. The present invention will now be more particularly described, by way of example only, with reference to the accompanying Examples. Examples: Particle sizing A method of particle sizing for the dispersed products of the present invention used in the following examples employs a dynamic light scattering instrument (Nano S, manufactured by Malvern Instruments UK). Transmission electron microscope images and field flow fractionation techniques have been WO 2006/079409 PCT/EP2005/013933 - 25 - used to confirm some particle sizing data. Specifically, the Malvern Instruments Nano S uses a red (633nm) 4mW Helium-Neon laser to illuminate a standard optical quality UV curvette containing a suspension of material. The viscosity of the sample can be measured with a Viscolite 700 portable viscometer (manufactured by Hydramotion UK) prior to analysis with the Malvern Instruments Nano S. Example 1: In this example the emulsion that was spray dried comprised the water insoluble dye 'Sudan Red 7b' (CI 26050) and the water-soluble structuring agents are polyvinyl alcohol (PVA) and sodium dodecyl sulphonate (SDS) . The emulsion was made up as shown in the table below: Table 2 1 Sudan Red 7b PVA SDS Cyclohexane DI Water 1 1 0.1 g 2.0 g 5.0 g 12 0ml 40ml PVA was dissolved in 40ml water with stirring and once the entire polymer was dissolved the SDS was added. The red dye/cyclohexane solution was made up separately and added to the aqueous solution slowly over 10 minutes. Once all the dye was been added, stirring was continued for a further 5 minutes. Stirring and emulsification was achieved by means of a magnetic stir bar and stirrer. WO 2006/079409 PCT/EP2005/013933 - 26 The emulsion was spray dried using a Buchi™ laboratory spray dryer (fitted with a Schlick™ nozzle) housed in a laboratory fume cupboard. The emulsion was stirred continuously using a magnetic stirrer whilst spray drying. The following spray drying conditions were employed: Inlet temperature Atomisation pressure Liquid feed rate Outlet temperature (start) filter bag pressure (start) 120°C 3.0 bar 3.OmL/Min 60°C -40mbar Example 2; In this example the emulsion that was spray dried comprised the water-insoluble antimicrobial Triclosan'™ and the water-soluble structuring agent polyvinyl alcohol. The emulsion was made up as shown in the table below: Table 3 Triclosan 8.13 PVA 54.4g Cyclohexane 563ml DI Water 1875ml The PVA was dissolved in the deionised water. The Triclosan was dissolved in the cyclohexane. The Triclosan solution was added to the PVA solution over a period of 1 minute with continuous homogenisation (using an IKA ultra-Turrax™ T25 WO 2006/079409 PCT/EP2005/013933 - 27 - homogeniser at 6000rpm) and then further homogenised for a further 2 minutes (total of 3 minutes). The emulsion was spray dried using a Buchi laboratory spray dryer (fitted with a Schlick nozzle) housed in a laboratory fume cupboard. The emulsion was stirred continuously using a magnetic stirrer whilst spray drying. The following spray drying conditions were employed: Inlet temperature 90°C Atomisation pressure 4.0 bar Liquid feed rate 3.OmL/Min Outlet temperature (start) 60°C filter bag pressure (start) -40mbar 31.7 grams of material were collected. In this case a hazy dispersion is formed on addition of spray dried material to water. After several hours an optically clear and colourless dispersion is obtained. Example 3; In this example the emulsion that was spray dried comprised the water insoluble antimicrobial ‘Triclosan'™ and the water soluble structuring agents polyvinyl alcohol and Brij 78™. The emulsion was made up as shown in the table below: WO 2006/079409 PCT7EP2005/013933 - 28 - Table 4 ! Triclosan Brij 78 PVA Cyclohexane DI Water j 6.0g 15.4g 38. 5g 78na 770ml■, The PVA was dissolved in the de-ionised water. When the PVA was dissolved the Brij-78 was added and allowed to dissolve. Triclosan was dissolved in the cyclohexane. The Triclosan solution was added (over 3 0 seconds) to the solution of PVA/Brij 78 with continuous homogenisation (using an IKA ultra-Turrax T25 homogeniser at 6000rpm) . The emulsion was further homogenised for a further 3 0 seconds (total of one minute). The emulsion was spray dried using a Buchi laboratory spray dryer (fitted with a Schlick nozzle) housed in a laboratory fume cupboard. The emulsion was stirred continuously using a magnetic stirrer whilst spray drying. The following spray drying conditions were employed: Inlet temperature 85°C Atomisation pressure 4.0 bar Liquid feed rate 3.OmL/Min Outlet temperature (start) 55°C filter bag pressure (start) -40mbar 32.4 grams of material was collected. WO 2006/079409 PCT/EP2005/013933 - 29 -Examples 4-13: In this example the emulsion that was spray dried comprised the water insoluble antimicrobial ‘Triclosan'TM and the water soluble structuring agent SDS. A range of solvents, as listed below was employed. Table 5 Example Solvent Boiling Point Solvent Type 4 Pentane 3 6°C Alkane 5 Hexane 69°C Alkane 6 Heptane 98°C Alkane 7 Octane 125°C Alkane 8 Nonane ~150°C Alkane 9 Chloroform 61°C Chlorinated solvent 10 t-Butylmethyl ether 55°C Ethers 11 Cyclohexane 81°C Cyclic solvents 12 Ethyl Acetate 77°C Ester 13 Toluene 110°C Aromatic solvents The following solutions were made: SDS 8.9g dissolved in 125ml water Triclosan 1.lg dissolved in 125ml organic solvent The Triclosan solution was slowly added to the SDS solution over a 30 second period, with continuous homogenisation using a IKA ultra-Turrax T25 homogeniser (6,000rpm) . After addition, homogenisation is continued for a further 90 seconds (2 minutes in total). WO 2006/079409 PCT/EP2005/013933 - 30 Each emulsion was spray dried using a Buchi laboratory spray dryer (fitted with a Schlick nozzle) housed in a laboratory fume cupboard. During spray drying the emulsion was stirred continuously using a magnetic stirrer. The following spray drying conditions were used: Inlet temperature Atomisation pressure Liquid feed rate Outlet temperature (start) filter bag pressure (start) 90°C 3.Obar 3.OmL/min Varies with solvent -40mbar Example 14; In this example the emulsion that was spray dried comprised the water insoluble fluorescer "Tinopal SOP'™ and the water-soluble structuring agent CocoPAS (sodium lauryl sulphate, EMAL 10PHD, ex Kao) . The emulsion was made up as shown in the table below: Table 6 ED Tinopal SOP l.Og Cocopas 9.0g Dichloromethane 120ml DI Water 120ml The CocoPAS was dissolved in the de-ionised water. The Tinopal SOP was dissolved in the dichloromethane. WO 2006/079409 PCT7EP2005/013933 31 The dichloromethane solution was added (over 3 0 seconds) to the aqueous solution of cocoPAS with continuous homogenisation (using an IKA ultra-Turrax T25 homogeniser at 6000rpm) for a total of 1 minute. The resulting emulsion was spray dried using a Buchi laboratory spray dryer (fitted with a Schlick nozzle) housed in a laboratory fume cupboard. The emulsion was stirred continuously using a magnetic stirrer whilst spray drying. The following spray drying conditions were employed: Inlet temperature 12 0°C Atomisation pressure 3.0 bar Liquid feed rate 4.0mL/Min Outlet temperature (start) 66°C filter bag pressure (start) -4 0mbar 3.84g of material was collected Example 15; In order to compare the effectiveness of compositions of the invention with those prepared by freeze-dry methods, the performance of the product obtained in example 14 was compared with a product obtained by a freeze drying method. To prepare the freeze dried product, 9g of CocoPAS (sodium lauryl sulphate, EMAL 10PHD, ex Kao) was dissolved in 120 ml of water. To this aqueous solution was added 1.Og of Tinopal™ SOP in 120ml of dichloromethane with vigorous WO 2006/079409 PCT/EP2005/013933 - 32 - stirring. The emulsion formed was sprayed into liquid nitrogen using a trigger spray and the resulting frozen powder was freeze-dried (Edwards Supermodulyo, operated with an average vacuum of 0.2mbar and at -50 °C) to form a powder. Samples of the 10% loaded product were added to Brilhante™ (ex Gessy Lever, 2004) base formulation, without any fluorescer present. The composition thus obtained was used to launder untreated cloth monitors. The change in Ganz whiteness (Delta G) on cloth monitors was measured after each wash. Measurements were performed for cotton, nylon and polyester. Results for the method of the invention (in bold, and marked ‘spray dried') and the comparative tests (marked 'freeze dried') are shown in the table below: Table 7 Cloth Type Preparation Ganzafter1st wash Ganzafter2nd wash Ganzafter3rd wash53.14 Nylon Freeze dried 33.35 46.84 Nylon Spray dried 38.17 50.05 56.14 Polyester Freeze dried 9.11 12.46 14.74 Polyester Spray dried 12.05 15.23 16.73 Cotton Freeze dried 21.68 26.43 30.36 Cotton Spray dried 25.39 32.64 34.71 Higher ‘Ganz' figures are obtained when fluorescer is more effectively deposited. Products prepared according to the method of the invention show better performance than those prepared by the freeze-drying method. WO 2006/079409 PCT/EP2005/013933 - 33 - Example 16: In order to demonstrate the effect of choice of water soluble polymers on particle size and distributions, several different water soluble polymers with different molecular weights, including polyvinyl alcohol (PVA), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl cellulose (HEC), and polyvinylpyrrolidone (PVP) were employed. Table 8 lists the polymers. Table 8 Polymer Molecular weight, mol/1 Producer PVA Mw 9,000-10,000 Aldrich HPMC Mw 10,000 Aldrich HEC Mw 90,000 Aldrich PVP Mw 10,000 Aldrich Mw 24,000 Fluka Mw 55,000 Fluka Mw 360,000 Fluka In this example, Oil red O (OR) was used as a model for active compound, and sodium dodecylsulfate (SDS) was used as a surfactant carrier. 0.25 g OR was dissolved in 50 ml chloroform as oil phase, and 1.0 g SDS and 1.0 g PVP were dissolved in 50 ml water as aqueous phase. The oil phase was added dropwise into aqueous phase with overhead stirring (IKA EUROSTAR) at 600 rpm for 2 min. WO 2006/079409 PCT/EP2005/013933 - 33 - Example 16: In order to demonstrate the effect of choice of water soluble polymers on particle size and distributions, several different water soluble polymers with different molecular weights, including polyvinyl alcohol (PVA), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl cellulose (HEC), and polyvinylpyrrolidone (PVP) were employed. Table 8 lists the polymers. Table 8 \| Polymer Molecular weight, mol/1 Producer PVA Mw 9,000-10,000 Aldrich 1 HPMC Mw 10,000 Aldrich HEC Mw 90,000 Aldrich PVP Mw 10,000 Aldrich Mw 24,000 Fluka Mw 55,000 Fluka Mw 360,000 Fluka In this example, Oil red O (OR) was used as a model for active compound, and sodium dodecylsulfate (SDS) was used as a surfactant carrier. 0.25 g OR was dissolved in 50 ml chloroform as oil phase, and 1.0 g SDS and 1.0 g PVP were dissolved in 50 ml water as aqueous phase. The oil phase was added dropwise into aqueous phase with overhead stirring (IKA EUROSTAR) at 600 rpm for 2 min. WO 2006/079409 PCT/EP2005/013933 - 34 - The coarse emulsion was then further treated with a homogenizer (IKA T25 basic Ultra-Turrax) at 17,500 rpm for 5 min. The resulting fine emulsion was then spray dried at 125 5 °C with a Buchi Mini spray dryer B-2 90 to obtain products according to the present invention. Spray drying conditions were Inlet temp.: 125 °C; Aspiration rate: 100%; Pump rate: 3.62ml/min. A sample of the dry powder was then dispersed into distilled water and the nanoparticle size was measured with Malvern Nano-S. Details concerning these experiments and their results are summarized in Table 9. PhR=phase ratio, oil phase/aqueous phase 15 PS=average particle size PDI=polydispersity index Table 9 Sample Oil Phase Aqueous phase PhR, v/v PS,ma PDI OR, mg/ml SDS, mg/ml PVP, mg/ml WP-141 5.0 20.0 Mw 10,000 20.0 50/50 255 1.016 WP-142 Mw 29,000 220 1.103 WP-143 Mw 55,000 255 1.133 WP-144 Mw 360,000 295 ,12s \| WO 2006/079409 PCT/EP2005/013933 - 35 - In further examples 0.25 g OR was dissolved in 50 ml chloroform as oil phase, and 1.0 g SDS and 1.0 g water soluble polymer (PVP (Mw 29,000), PVA, HPMC, or HEC) were dissolved in 50 ml water as aqueous phase. The oil phase was added dropwise into aqueous phase with overhead stirring at 600 rpm for 2 min. The coarse emulsion was further treated with a homogenizer at 17,500 rpm for 5 min. The resulting fine emulsion was then spray dried at 125 °C with a Buchi Mini spray dryer B-290 (Inlet temp.: 125 °C; Aspiration rate: 100%; Pump rate: 3.62ml/min.) A sample of the dry powder was then dispersed into distilled water and the nanoparticle size was measured with Malvern Nano-S. Details concerning these experiments and their results are summarized in Table 10. Table 10 Oil Phase Aqueous phase PhR, v/v PS, nm PDI Sample OR, mg/ml SDS, mg/ml Water solublepolymer,mg/ml WP-142 5.0 20.0 PVP 20.0 50/50 220 1.103 WP-145 PVA 220 1.240 WP-146 HPMC 164 1.012 WP-147 HEC 342 1.567 In this example HPMC (Mw 10,000) gave the smallest particle size and narrowest poly-dispersity, PVA (9-10k MW) gave similar particle size to PVP but broader particle size WO 2006/079409 PCT/EP2005/013933 - 36 - distributions, and HEC (MW 90k) gave the largest particle size and the broadest particle size distributions. In yet further examples 0.25 g OR was dissolved in 50 ml chloroform as oil phase, and 1.0 g SDS was dissolved in 50 ml water with different water soluble polymers (PVP (Mw 29,000), PVA (Mw 10,000), and HPMC (Mw 10,000)) with different concentrations (20mg/ml, 15mg/ml, lOmg/ml, and 5mg/ml) as aqueous phase. The oil phase was added dropwise into the aqueous phase with overhead stirring at 600 rpm for 2 min. The coarse emulsion was further treated with a homogenizer at 17,500 rpm for 5 min. The resulting fine emulsion was then spray dried at 125 °C with a Buchi Mini spray dryer B-290 (Inlet temp.: 125 °C; Aspiration rate: 100%; Pump rate: 3.62ml/min). A sample of the dry powder was then dispersed into distilled water and the dispersed particle size was measured with Malvern Nano-S. Details concerning these experiments and their results are summarized in Table 11. WO 2006/079409 PCT/EP2005/013933 - 37 - Table 11 Sample Oil Phase Aqueous phase PhR, v/v PS,nm PDI OR, mg/ml SDS, mg/ml Water soluble po lymer, mg/ml WP-142 5.0 20.0 PVP 20.0 50/50 220 1.103 WP-145 PVA 220 1.240 WP-146 HPMC 164 1.012 WP-148 PVP 15.0 295 1.026 WP-149 PVA 255 1.027 WP-150 HPMC 164 1.067 WP-151 PVP 10.0 585 1.309 WP-152 PVA 255 1.137 WP-153 HPMC 220 1.180 WP-154 PVP 5.0 615 1.314 WP-155 PVA 342 1.230 WP-156 HPMC 396 1.764 Example 17: 0.25 g OR was dissolved in 60 ml chloroform as oil phase, and 4.05 g SDS and 7.0 g PVA (Mw 10,000) were dissolved in 140 ml water as aqueous phase. The oil phase was added dropwise into aqueous phase with overhead stirring at 600 rpm for 2 0 min. Half the volume of the coarse emulsion obtained was further treated with a homogenizer at 17,500 rpm for 5 min. WO 2006/079409 PCT/EP2005/013933 - 38 - The coarse emulsion and the fine emulsion were then each spray dried at 12 0 °C with a Buchi Mini spray dryer B-290 respectively (inlet temp.: 120 °C; Aspiration rate: 100%; Pump rate: 5.90 ml/min.). Samples of the dry powders were dispersed into distilled water and the particle size was measured with Malvern Nano-S. Details concerning these experiments and their results are summarised in Table 12. In a separate preparation 0.20 g OR was dissolved in 50 ml chloroform as oil phase, and 1.45 g SDS and 2.50 g PVA (Mw 10,000) were dissolved in 50 ml water as aqueous phase. The oil phase was added dropwise into aqueous phase with overhead stirring at 600 rpm for 2 min. The coarse emulsion was further treated with a homogeniser at 17,500 rpm for 5 min. This fine emulsion was then spray dried at 12 0 °C with a Buchi Mini spray dryer B-290 (inlet temp.: 120 °C; Aspiration rate: 100%; Pump rate: 5.90 ml/min.). The dry powder was then dispersed into distilled water and the particle size was measured with Malvern Nano-S. Details concerning these experiments and their results are also summarised in Table 12. WO 2006/079409 PCT/EP2005/013933 - 39 - Table 12 Sample Oil Phase Aqueous phase PhR, v/v Process PS, nm PDI OR, mg/ml SDS, mg/m1 PVA, mg/ml WP-101 4.0 29.0 50.0- 30/70 Stir 264 1.112 WP-102 Homogenise 89 1.012 [WP-103 50/50 123 1.019 Example 18: 0.25 g OR was dissolved in 50 ml chloroform as oil phase, and 1.0 g SDS and 1.0 g PVP (Mw 29,000) were dissolved in 50 ml water as aqueous phase. The oil phase was added dropwise into the aqueous phase with overhead stirring at 600 rpm for 2 min. The coarse emulsion was further treated with a homogeniser at different speed to obtain a series of finer emulsions. These finer emulsions were then spray dried at 125 °C with a Buchi Mini spray dryer B-290 (inlet temp.: 125 °C; Aspiration rate: 100%; Pump rate: 3.62 ml/min). The dry powder was then dispersed into distilled water and the nanoparticle size was measured with Malvern Nano-S. Details concerning these experiments and their results are summarized in Table 13 (HS=Homogenization speed, Ht=Homogenization time) WO 2006/079409 PCT/EP2005/013933 - 40 - Table 13 Sample Oil Phase Aqueous phase PhR, v/v HS,rpm Ht, min PS,nm PDI OR, mg/ml SDS, mg/ml PVA, mg/ml WP-157 4.0 29.0 50.0 50/50 13,500 2 347 1.037 WP-158 17,500 2 279 1.043 WP-142 17,500 5 220 1.103 WP-159 21,500 2 190 1.014 Example 19: Preparations have been made into tablet form by means of a tablet maker which has four parts. Three used to form the tablet and one to achieve compression. The parts used for tablet formation are an inverted WU" shape with a hole in the top, into which fits a solid cylinder with arms at the top and a solid rectangle that fits into the inverted U. Tablets are formed, with the U and rectangle assembled, by adding powder to the hole in the inverted U and carefully placing the cylinder into the hole. The assembly is then placed in the compression part, where the screw thread acts on the cylinder compacting the powder. The tablet is released by removing the rectangular and cylindrical blocks. Spray dried powder prepared from cocoPAS, sodium sulphate and fat red dye was made into a 0.5g tablet using this apparatus. When a similar freeze dried powder was used, (cocoPAS, sodium chloride, fat red dye), a 0.06g tablet was formed. WO 2006/079409 PCT/EP2005/013933 - 41 - Tablet and powder behave differently in terms of dissolution times and clarity of solution. Example 20: A product comprising sodium sulphate was made by dissolving 0.5g CocoPAS in 12 ml water and adding 0.5g sodium sulphate. O.Olg Fat red 7B dye was dissolved in cyclohexane, added to the aqueous solution to form an emulsion and freeze dried as a powder. Other similar powders, varying the CocoPAS : Sodium sulphate ratio from 60:40 to 90:10 gradually, were made in the same way. A similar set of samples containing sodium carbonate was also made. All powders re-dissolved in water to give a clear solution. Without sodium carbonate, dissolution took about 20 seconds, with sodium carbonate, the time increased to 1 to 2 minutes. A CocoPAS:NaS04, 50:50 ratio powder was made, this time forming the emulsion using a homogeniser and spray drying; for comparison of particle size, which gave a Z (Malvern) average of 57.3 and a poly-dispersity of 0.39. For a 20:80 cocoPAS:Na2S04 sample the particle size Z (Malvern) average was 115 and a poly-dispersity of 0.126. For freeze dried samples, the particle size would appear to decrease as the amount of filler increases, for sodium sulphate, range Zave. 200 0, polydispersity 0.746 (50:50) to Zave. 609, polydispersity 0.492 (10:90). WO 2006/079409 PCT/EP2005/013933 - 42 - Other inorganic fillers included sodium carbonate, sodium chloride, magnesium chloride, magnesium acetate, calcium chloride and sucrose; these tended not to give clear solutions. Whereas sodium bicarbonate, sodium acetate and magnesium sulphate (at 50:50) gave clear re-dispersions. All these were prepared in a PVA/SDS system. Particle sizes varied between Zave. 1380, polydispersity 0.6 and Zave. 771, polydispersity 0.48 for the sodium salt fillers. The preparations containing magnesium salts at 50:50 in PVA/SDS, gave particle sizes that ranged between Zave. 72.9, polydispersity 0.402 and Zave. 672, polydispersity 0.655. Magnesium sulphate was also made at the 20:80 ratio, but unlike sodium sulphate, due to it not giving a clear solution, the particle size Zave.(255) polydispersity 0.375 was greater than the 50:50 ratio Zave. (72.9) polydispersity 0.402. The particle size data for magnesium salts, for all but the acetate, gave more than one peak size. Calcium chloride and sucrose were also used as bulking agents; they gave particle sizes of Zave .892, polydispersity 0.593 and Zave.338, polydispersity 0.489 respectively. Polymer only i.e. PVA with sodium sulphate filler (50:50) has been prepared as a freeze dried powder. It was slow to re-dissolve; time, 7 minutes, gave a clear solution and particle size Zave. 467, polydispersity 0.557 and had 2 peaks. WO 2006/079409 PCT/EP2005/013933 - 43 -Example 21: 0.037 g of the hydrophobic polymer polycaprolactone was dissolved in 15 ml chloroform as oil phase, and 0.26 g SDS and 0.45 g PVA (Mw 10,000) were dissolved in 15 ml water as aqueous phase. The oil phase was added dropwise into the aqueous phase and homogenised for 2 min. The emulsion was spray dried at 150 °C with a Buchi Mini spray dryer B-290 respectively (inlet temp.: 150 °C; Aspiration rate: 100%; Pump rate: 7.20 ml/min.). A sample of the dry powders were then dispersed into distilled water (10mg/ml) and the resulting particle size was measured with Malvern Nano-S. The particles were 162nm with a standard deviation of 2.14nm and a poly-dispersity of 0.131 Example 22: 0.5 g of the hydrophobic polymer Eudragit™ EPO was dissolved in 60 ml chloroform as oil phase, and 10 g PVA (Mw 10,000) were dissolved in 120 ml water as aqueous phase. The oil phase was added dropwise into the aqueous phase and homogenised for 1 min. The emulsion was spray dried at 90 °C with a Buchi Mini spray dryer B-290 respectively (inlet temp.: 90 °C; Aspiration rate: 100%; Pump rate: 3 ml/min.). A sample of the dry powders were then dispersed into distilled water (lOmg/ml) and the resulting particle size was measured with Malvern Nano-S. The particles were 520nm. - 44 - CLAIMS 1. A method comprising the steps of: i) providing an emulsion of: a) an aqueous solvent, b) a carrier material dispersible or soluble in 10 (a) , said carrier material being solid at ambient temperature, c) a volatile second liquid phase which is not miscible with (a) , d) a material which is dispersible or soluble in (c) but not in (a) , and, ii) drying the emulsion above ambient temperature to simultaneously remove (a) and (c) and thereby obtain the material (b) in solid form with (d) dispersed therein, said dispersion of (d) being a nano-scale dispersion, preferably with a maximum particle size of at most 615nm. A method according to claim 1 wherein the aqueous solvent (a) is water. AMENDED SHEET - 45 - 3. A method according to claim 1 or 2 wherein the carrier material (b) comprises a polymer. 4. A method according to claim 3 wherein the carrier material is polyvinyl alcohol. 5 . A method according to claim 1 or 2 wherein the carrier material (b) comprises a surfactant. 6. A method according to claim 5 wherein the carrier material (b) comprises an anionic surfactant. 7. A method according to any of claims 1 to 6 wherein the volatile second liquid phase (c) has a boiling point of less than 150 Celsius, preferably less than 100 Celsius. 8. A method according to claim 7 wherein the volatile second liquid phase (c) is selected from: alkanes, chlorinated solvents, ethers, cyclic solvents, esters and aromatic solvents. 9. A method according to any of claims 1 to 8 wherein the volatile second liquid phase comprises from 10 % to 95 % v/v of the emulsion, preferably from 20 % to 68 % v/v. 1.0;. A method according toany one of claims 1 to" 9 'wherein the drying method is spray drying. AMENDED SHEET - 46 - 11. A product obtainable by the method of any one of claims 1-10. 12. A product according to claim 11 which comprises as (d) a water-insoluble, pharmaceutically active substance and as (b) a water-soluble physiologically acceptable carrier. 13 . A product according to claim 11 or 12 wherein the material-(d) has a particle size of not more than 300nm, preferably 180-300nm. 14. A product according to claim 11 which comprises as (d) 15 an antimicrobial agent, an antidandruff agent, a skin-lightening agent, a fluorescing agent, a skin-conditioning agent, an antifoaming agent, a hair conditioning agent, a fabric conditioning agent, a thickening agent, a UV protecting agent, a bleach or bleach precursor, an antioxidant, an insecticide, pesticide, herbicide or other agrochemical, a perfume or a flavouring. AMENDED SHEET

Full Text

FORM2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
1. Title of the invention - SPRAY DRIED COMPOSITIONS
2. Applicant(s)
(a) NAME : UNILEVER PLC
(b) NATIONALITY : A British Company
(c) ADDRESS : Unilever House, Blackfriars, London EC4P 4BQ,United Kingdom
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed:

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IMPROVEMENTS RELATING TO RAPIDLY DISSOLVING COMPOSITIONS
Technical Field:
The present invention relates to dried compositions which dissolve rapidly in water.

Background to the Invention:
Many useful materials are water-insoluble. These include, without
limitation, many dyestuffs (i.e. pigments), some fluorescer materials and many pharmaceutical materials. In some circumstances it is possible to disperse these materials in water by processes involving fine comminution, but this can be expensive and time-consuming.

Our co-pending international patent application PCT/GB03/03226 describes the formation of solid, porous beads comprising a three dimensional open-cell lattice of a water-soluble polymeric material. These are typically templated' materials formed by
the removal of both water and a non-aqueous dispersed phase from a high internal phase emulsion (HIPE) which has a polymer dissolved in the aqueous phase. The beads are formed by dropping the HIPE emulsion into a low temperature fluid such as liquid nitrogen, then freeze-drying the particles formed to remove the
bulk of the aqueous phase and the dispersed phase. This leaves behind the polymer in the form of a ‘skeletal' structure.

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The beads dissolve rapidly in water and have the remarkable property that a water-insoluble component dispersed in the dispersed phase of the emulsion prior to freezing and drying can also be dispersed in water on solution of the polymer skeleton of the beads.
The production process for the beads and related materials is complex. It requires the use of liquid gasses and vacuum equipment. Throughput is relatively low. There is a clear need to devise a simpler and cheaper process.
Past workers have looked at ways of delivering water-insoluble materials such as carotenoids. US 3998753 (Antoshkiw et al., 1974) discloses a method of preparing a water-dispersible
carotenoid composition which comprises the steps of forming an emulsion of the carotenoid in a volatile solvent (such as chloroform) and various structurants (such as gelatine) in water. This emulsion is heated with high-speed mixing to drive off the volatile solvent and the resulting emulsion product can be used
as is. Optionally, the solvent-free product may be further processed by spray drying to remove the water and give a dry product.
US 4213900 (Daubach et al., 1978) takes a different approach. 5 Here formic acid, formamide, N-methylformamide, butyrolactone, ethylene or propylene glycols are used as solubilising agents for water-insoluble dyes. Once a solution has been formed it can be spray-dried to form a fine powder which can be dispersed in water.

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Pamujula et al. (Journal of Pharmacy and Pharmacology, 2004, 56: 1119-1125) disclose a process for the production of spray dried poly(lactide-co-glycolide) (PLGA) carrier particles containing the cytoprotective drug amifostine. In the procedure described the drug was dissolved in water and emulsified with a solution of PLGA carrier in a water-immiscible solvent (dichloromethane) . This was spray-dried to remove the majority of the solvent and obtain nanoparticles, which were then freeze-dried to remove any residual solvent. The final product of the process was in the form of nanoparticles having a median size of 240-257 nm.
Several other methods are known which result in a dry emulsion'. For example Dollo et al (Eur. J. of Pharmaceutical Sciences, 19, issue 4 pages 273-280) discloses a physically stabilised dry emulsion with a lipophilic drug dissolved in the oil phase.
Hansen, Holm and Schultz (Int J. Pharmaceutics, 287, issue 1-2, 9th December 2004, pages 55-66) disclose a process for preparing powders containing a poorly water-soluble drug dissolved in (nonvolatile) medium chain triglyceride, by spray drying o/w emulsions. The products of this process would still contain the 'solvent' for the drug, i.e. non-volatile medium chain triglyceride. Thus the product of the spray drying process can be described as a 'dry emulsion' which will reform the initial emulsion on addition of water.
DE 2122662 (BASF, 1972) discloses a process for obtaining a water-insoluble dye dispersion with practically the same degree of dispersion as that produced by -'wet miiling of. the dye. This process involves mixing "the dye with a surfactant, water^ and a water-immiscible ..solvent, subjecting the mixture

AMENDED SHEET

- 3a
to heat and/or pressure and spray drying the treated mixture.
AMENDED SHEET

_ 4 _
Brief Description of the Invention:
We have now determined that spray drying can be used instead of freeze drying to obtain solid, rapidly dissolving materials directly from an emulsion.
Accordingly a first aspect of the present invention provides a method comprising the steps of:
(i) providing an emulsion of:
a) an aqueous solvent,
b) a carrier material dispersible or soluble in (a), said carrier material being solid at ambient
temperature,
c) a volatile second liquid phase which is not
miscible with (a), and

d) a material which is dispersible or soluble in (c)
but not in (a), and,
(ii) Drying the emulsion above ambient temperature to simultaneously remove (a) and (c) and thereby obtain the carrier material (b) in solid form with (d) dispersed therein, said dispersion of '(d) being a nano-scale dispersion, preferably with a maximum particle : size of at most 615nm.

4a -
The aqueous solvent (a) is generally and preferably water, but may comprise an electrolyte solution or a mixture of hydrophilic solvents.

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Advantageously, both the aqueous solvent (a) and the volatile, water-immiscible second liquid phase (c) are simultaneously removed during the drying process, and no separate removal step for either the second liquid phase 5 (e.g. by boiling it off) or the aqueous solvent (e.g. by freeze drying) is needed. By volatile' here is meant that the second liquid phase is sufficiently volatile to be removed as a vapour phase during the drying process. ‘Burning-off of one of the solvents is not required in the method of the invention.
By far the most preferred method for drying of the intermediate emulsion is by spray drying. This is particularly effective at removing both the aqueous and non- aqueous volatile components to leave the carrier and the ‘payload' material behind in a fine particulate form.
Drying is preferably conducted at a temperature well above ambient (taken as 25 Celsius). It is particularly preferred
that drying is conducted at above 80 and more preferably above 100 Celsius. In the case of a spray drying apparatus this means that the inlet temperature of the spray drying apparatus is, for example, above 100 Celsius. Particularly preferred drying conditions are those in which the drying
temperature is above both the boiling point of water and the boiling point of the volatile second liquid phase.
The final structure of the material obtained is not well understood. However it is believed that ".removal by drying of the aqueous solvent and the second liquid phase results in a very fine, nano-scale

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dispersion of the water insoluble material (d) through the water-soluble carrier material (b) . It is believed that the resulting dry materials are not encapsulates, as discrete bodies of the water-immiscible materials (d) are not present in the dry product. Neither are the dry materials %dry emulsions' as little or none of the volatile solvent comprising the 'oil' phase of the emulsion remains after the drying step. On addition of water to the dry product the emulsion is not reformed, as it would be with a ‘dry emulsion'.
On admixture of the carrier material with water, the carrier (b) dissolves and the water insoluble material (d) is dispersed through the water in sufficiently fine form that
it behaves like a soluble material in many respects.
Surprisingly, the effectiveness of materials delivered in this way is hardly reduced as compared with materials delivered using an emulsion- templated, freeze-drying preparation method.

Detailed Description of the Invention:
In order that the present invention may be better understood and carried forth into practice, it is described below with reference to various preferred features and particular embodiments.
Carrier Material:
The carrier material is water soluble, which includes the
formation of structured aqueous phases as well as true ionic

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solution of molecularly mono-disperse species. The carrier material preferably comprises an inorganic material, surfactant, a polymer or may be a mixture of two or more the these. It is envisaged that other non-polymeric, organic, water-soluble .materials such as sugars can be used as the carrier. However the carrier materials specifically mentioned herein are preferred.
Polymeric Carrier Materials:

When present, the polymeric carrier material is a material that would be considered as "water soluble" by those skilled in the art i.e. if it forms a homogeneous solution in water. Water soluble polymers generally possess pendant polar or
ionizable groups (e.g. -C=0, -OH, -N(RX) (R2) in which Ra and R2, which may be the same or different, are independently H or (CI to C4)alkyl, -N(R3) (R4) (Rs)+ in which R3, R4 and R5 which may be the same or different, are independently H or (CI to C4)alkyl, -CON(R6) (R7) in which R6 and R7, which may
be the same or different, are H or (CI to C4) alkyl, -CH2CH20-, -C02H or salts thereof, -S03H or salts thereof groups) on a backbone chain which may be hydrophobic.
If water-soluble polymeric carrier materials are incorporated into the products of the present invention, the time taken for the products to dissolve or disperse may be significantly reduced, as compared with 'off-the-shelf samples of the polymeric carrier materials. It is believed that this is due to the structural result of, in particular, the spray-drying process. The same is believed to be true of other carrier materials. The nature of the products should

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be such that the dissolution or dispersion of the products in a large excess of water preferably occurs in less than three minutes, more preferably less than two minutes, most preferably less than one minute.
The particle size and distributions of the ‘payload' material can be tailored by choosing different water-soluble polymers and polymers with different molecular weights. This allows some control over the activity/availability of the *payload material'.
Examples of suitable water-soluble polymeric carrier materials include:
(a) natural polymers (for example naturally occurring gums such as guar gum or locust bean gum or a polysaccharide such as dextran;
(b) cellulose derivatives for example xanthan gum, xyloglucan, cellulose acetate, methylcellulose, methyl-
ethylcellulose, hydroxyethylcellulose,
hydroxyethylmethyl - cellulose, hydroxypropylcellulose,
hydroxypropylmethylcellulose (HPMC),
hydroxypropylbutylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose and
its salts (eg the sodium salt - SCMC), or
carboxymethylhydroxyethylcellulose and its salts (for
example the sodium salt);
(c) homopolymers of any one of the monomers listed in Table 1 below;

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(d) copolymers prepared from two or more monomers listed in
Table 1 below;
(e) mixtures thereof

Table 1
vinyl alcohol,
acrylic acid, methacrylic acid
acrylamide,
methacrylamide
acrylamide methylpropane sulphonates
aminoalkylacrylates aminoalkylmethacrylates
hydroxyethylacrylate
hydroxyethylmethylacrylate
vinyl pyrrolidone
vinyl imidazole vinyl amines
vinyl pyridine
ethyleneglycol and other alkylene glycols
ethylene oxide and other alkylene oxides
ethylene imine styrenesulphonates
ethyleneglycolacrylates
ethyleneglycol methacrylate
When the polymeric material is a copolymer it may be a
statistical copolymer (heretofore also known as a random

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copolymer), a block copolymer, a graft copolymer or a hyperbranched copolymer. Comonomers other than those listed in Table 1 may also be included in addition to those listed if their presence does not destroy the water soluble or water dispersible nature of the resulting polymeric material.
Examples of suitable homopolymers include polyvinylalcohol, polyacrylic acid, polymethacrylic acid, polyacrylamides
(such as poly-N-isopropylacrylamide) , polymethacrylamide; polyacrylamines, polymethylacrylamines, (such as polydimethylaminoethylmeth-acrylate and poly-N-morpholinoethylmethacrylate, polyvinyl-pyrrolidone, polyvinylimidazole, polyvinylpyridine, polyethylene-imine
and ethoxylated derivatives thereof. Polyvinylalcohol is a particularly preferred carrier material.
Surfactant Carrier Materials:
Where the carrier material is a surfactant, the surfactant may be non-ionic, anionic, cationic, amphoteric or zwitterionic.
Examples of suitable non-ionic surfactants include ethoxylated triglycerides; fatty alcohol ethoxylates;
alkylphenol ethoxylates; fatty acid ethoxylates; fatty amide
ethoxylates; fatty amine ethoxylates; sorbitan alkanoates;
ethylated sorbitan alkanoates; alkyl ethoxylates;
Pluronics™; alkyl polyglucosides; stearol ethoxylates; alkyl polyglycosides.

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Examples of suitable anionic surfactants include alkylether sulfates; alkylether carboxylates; alkylbenzene sulfonates; alkylether phosphates; dialkyl sulfosuccinates; alkyl sulfonates; soaps; alkyl sulfates; alkyl carboxylates; alkyl phosphates; paraffin sulfonates; secondaryn-alkane
sulfonates; alpha-olefin sulfonates; isethionate sulfonates.
Examples of suitable cationic surfactants include fatty amine salts; fatty diamine salts; quaternary ammonium compounds; phosphonium surfactants; sulfonium surfactants; sulfonxonium surfactants.
Examples of suitable zwitterionic surfactants include N-alkyl derivatives of amino acids (such as glycine, betaine, aminopropionic acid); imidazoline surfactants; amine oxides; amidobetaines.
Mixtures of surfactants may be used. In such mixtures there may be individual components which are liquid, provided that the carrier material overall, is a solid.
Anionic surfactants are particularly preferred as carrier materials.
Inorganic Carrier Materials:
The carrier material can also be an water-soluble inorganic material which is neither a surfactant nor a polymer. Simple •organic salts have been, found suitable, particularly in ^admixture with polynieric- and/or surfactant carrier materials as described above. Suitable salts include carbonate,
AMENDED SHEET

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bicarbonates, halides, sulphates, nitrates and acetates, particularly soluble salts of sodium, potassium and magnesium. Preferred materials include, sodium carbonate, sodium bicarbonate and sodium sulphate. These materials have the advantage that they are cheap and physiologically acceptable. They are also relatively inert as well as compatible with many materials found in household and pharmaceutical products. In general spray-dried samples containing an inorganic carrier material gave smaller particle sizes on re-dissolution than comparative freeze-dried samples.
Mixtures of carrier materials are advantageous. Preferred mixtures include combinations of inorganic salts and surfactants and polymers and surfactants. Where inorganic salts are present the carrier material typically comprise 10-50%wt surfactant and 90-50%wt of the inorganic salt.
Second liquid phase:

The compositions of the invention comprise a volatile, second liquid phase, which is not miscible with the aqueous solvent.
The second liquid phase of the emulsion may be selected from one or more from the following group of volatile organic solvents:
alkanes, such as heptane, n-hexane, isooctane, dodecane, 3 decane;

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• cyclic hydrocarbons, such as toluene, xylene, cyclohexane;
• halogenated alkanes ,such as dichloromethane, dichoroethane, trichloromethane (chloroform) , fluoro-
trichloromethane and tetrachloroethane;
• esters such as ethyl acetate;
• ketones such as 2-butanone;
• ethers such as diethyl ether;
• volatile cyclic silicones such as either linear or
cyclomethicones containing from 4 to 6 silicon units.
Suitable examples include DC245 and DC345, both of which are available from Dow Corning Inc.
Preferred second liquid phases have a boiling point of less than 150 Celsius and, more preferably, have a boiling point
of less than 100 Celsius, so as to facilitate drying,
particularly spray-drying under practical conditions and without use of specialised equipment. Preferred second liquid phase material are non-flammable, or have a flash point above the temperatures encountered in the method of
the invention.
Preferably, the second liquid phase comprises from about 10 % to about 95 % v/v of the emulsion, more preferably from about 20 % to about 80 % v/v.

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Particularly preferred solvents are halogenated solvents, more preferably chlorine-containing solvents, most preferably solvents selected from (di- or tri-chloromethane).
Materials as carriers:
The products of the present invention include 'payload' materials to be dispersed when the products are partially dissolved in an
aqueous medium. These are water-insoluble materials, which are soluble in the second liquid phase. Dispersion into an aqueous medium of such hydrophobic materials is much improved in the products of the invention. These hydrophobic materials are dissolved in the discontinuous phase of the emulsion prior to
drying.
The present invention also includes, in a further aspect, solutions or dispersions comprising the carrier (preferably surfactant, polymer or inorganic salt) and a hydrophobic material formed by exposing to an aqueous medium products according to the present invention, wherein said products comprise the hydrophobic material and are obtainable by means of the method of the present invention.
The present invention is susceptible of a very broad range of applications as regards the choice of hydrophobic material to be carried. The embodiments mentioned below are selected from a range of applications including, home and personal care products, agrochemicals and pharmaceuticals,
perfumes and flavourings, inks and dyes and other
applications. The list is not intended to be limiting.

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For example, there are many instances in personal care products such as deodorants, skin and hair cleaning or care products or in household products such as laundry cleaning and care products or household cleaning or care products for hard and soft surfaces where it is desirable to administer hydrophobic materials in an aqueous environment. Because of the hydrophobic nature of these materials they are often difficult to disperse in an aqueous environment. The use of the products of the present invention facilitates this dispersion and in many cases enables hydrophobic materials to be dispersed more effectively than previously.
It may be required to disperse the hydrophobic materials at the point where a formulation is being used. In this case the materials of the present invention will be contained in a formulation until it is used by exposing it to an aqueous
environment, at which time the water-soluble/dispersible carrier forming the product will release the hydrophobic material.
Particularly preferred products according to the present
invention comprise a water-insoluble, pharmaceutically
active substance and a water-soluble physiologically acceptable carrier.
As well as finding advantageous application at the point of use, the products of the present invention may be used to introduce hydrophobic materials into formulations, for example, liquid formulations during the manufacture of these formulations. In this case the products of the present invention will, on contact an aqueous environment, release
the hydrophobic material in a form in which it can be more
readily incorporated into the product being manufactured.

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The products of the present invention may be used to transport materials to sites where they can be incorporated into formulations. By converting liquids into products according to the invention, the need to transport large amounts of liquids can be avoided resulting in significant cost savings and safer transport of materials, which are potentially hazardous when transported in a liquid form. Materials which would be potentially unstable if stored or transported in liquid form may be incorporated into the
products of the present invention and stored or transported with less risk of degradation.
It is envisaged that incorporation of potentially unstable hydrophobic materials, for example vaccines, vitamins or perfume components, into the products of the present invention will protect them from degradation during storage prior to use. For example, a so-called pro-fragrance incorporated into a dry carrier material according to the invention is expected to exhibit reduced hydrolysis as
compared with the same material in solution or exposed to moist air.
Some specific examples of products in which the products of the present invention may be used are given below. These
are given as examples only and are not intended to limit the applicability of the present invention. Those skilled in the art will however realise that the materials of the present invention will have utility in other areas not specifically exemplified herein.

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Hydrophobic materials that are released from the products of the present invention at the time of use may include:-
• antimicrobial agents, for example: Triclosan™, climbazole,
octapyrox, ketoconizole, phthalimoperoxyhexanoic acid
(PAP), quaternary ammonium compounds;
• antidandruff agents for example: zinc pyrithione;
• skin lightening agents for example 4-ethylresorcinol;
• fluorescing agents for example: 2,5-bis(2-benzoxazolyl)
thiophene for use on fabrics (such as cotton, nylon,
polycotton or polyester)in laundry products;

• skin conditioning agents, for example cholesterol;
• antifoaming agents for example isoparrafin
• hair conditioning agents for example quaternary ammonium compounds, protein hydrolysates, peptides, ceramides and hydrophobic conditioning oils for example hydrocarbon oils such as paraffin oils and/or mineral oils, fatty esters such as mono-, di-, and triglycerides, silicone oils such
as polydimethylsiloxanes (e.g. dimethicone) and mixtures thereof;
• fabric conditioning agents for example quaternary ammonium
compounds having 1 to 3, preferably 2 optionally
substituted (C8-C24) alk(en)yl chains attached to the

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nitrogen atom by one or more ester groups; hydrophobic monoparticles such as a sucrose polyester for example sucrose tetra-tallowate; silicones for example polydimethylsiloxane;

• thickening agents for example hydrophobically modified
cellulose ethers such as modified hydroxyethylcelluloses;
• dyes for example dyes intended to change the colour of
fabrics, fibres, skin or hair;
• UV protecting agents such as sunscreens for example octyl
methoxycinnamate (Parsol MCX), butyl
methoxydibenzoylmethane (Parsol 1789) and benzophenone-3
(Uvinul M-40), ferulic acid;
• bleach or bleach precursors for example 6-N-
phthalimidoperoxyhexanoic acid (PAP) or photobleaching
compounds. Dispersing the bleach from the porous bodies
of the present invention results in the bleach being more finely dispersed and reduces the spot damage seen when larger particles of the bleach contact a fabric;
• antioxidants for example hydrophobic vitamins such as
vitamin E, retinol, antioxiants based on hydroxytoluene such as Irganox™ or commercially available antioxidants such as the Trollox™ series.
• insecticides, pesticides, herbicides and other
agrochemicals, for example those that are stored as solid

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compositions before use but which are made up into liquid for spraying (or other application) onto animals or crops;
• perfumes or flavourings or precursors thereto;
• pharmaceutical^ or veterinary active materials.
Compositions of the present invention may have additional specific advantages. For example, there is a need for
pharmaceutical compositions, which can be taken by the
consumer without the need to ingest the composition with a drink such as water. These compositions interact with the moisture in the oral cavity to release the active ingredient, which is then ingested by the consumer. By
incorporating the pharmaceutically or veterinary active molecule in the products of the present invention, pharmaceutical compositions which meet this need can be prepared. In a similar way to that described above pharmaceutical and veterinary active ingredients may be
formulated so that they release the active material into the
nasal, ocular, pulmonary or rectal cavities or on the skin where they may act topically or they may be absorbed trans-dermally to act systemically.
By using the appropriate polymeric material in the products of the present invention, materials can be made that remain intact until the conditions (for example temperature or pH) change to those under which dispersion can occur. Thus dispersion can be delayed until a certain temperature has
been reached or until the pH has changed to a suitable value
such as- would occur as the products pass down the GI tract.

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Acidity in the GI tract reduces down the GI tract and materials which disperse hydrophobic actives only when the materials are exposed to higher pH conditions enable pharmaceutically or veterinary active materials to be released only in the intestine having passed through the stomach intact.
Further examples of situations where the products of the present invention are used to incorporate a hydrophobic 0 material into a formulation during the manufacture of that product include:-
• the introduction of hydrophobic materials such as
fluorescers; enzymes; bleaches; hydrophobic polymers for
example hydrophobically modified polyacrylates, silicones, hydrophobically modified polyvinylpyrrolidone, sulpha alkyl polysaccharides, Jaguar and JR polymers; fatty alcohols or acids; dyes for example shading dyes or black dyes for colour recovery into laundry products;

• the use of products according to the present invention
containing hydrophobic dyes in the manufacture of water
soluble Inkjet compositions;
• the introduction of products containing different
hydrophobic materials enables a manufacturer to produce a single base formulation into which the desired hydrophobic materials may be introduced by the use of the appropriate product of the present invention;

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• the use of products containing hydrophobic polymers which
disperse into water to form a latex. The use of such
latexes containing appropriate hydrophobic polymers
deposited onto fabric imparts crease resistance or easy-
iron properties to fabric.
The materials of the present invention may include within carrier material, water-soluble materials, which will be dispersed when the bodies are dispersed in an aqueous medium. The water-soluble materials may be incorporated into the lattice by dissolving them in the liquid medium from which they are made.
Examples of suitable water soluble materials include:- • Water soluble vitamins such as vitamin C;
• water soluble fluorescers such as the 4,4'-bis(sulfo-
styryl)biphenyl disodium salt (sold under the trade name
Tinopal CBS-X;

• activated aluminium chlorohydrate;
• transition metal complexes used as bleaching catalysts;
• water soluble polymers and oligomers such as polyesters isophthalic acid), gerol, xanthan gum, or polyacrylates; diethylenetriamine-pentaacetic acid (DTPA);
or mixtures thereof

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In some cases the water-soluble carrier material itself may not be inert but may also have useful activity. For example, the carriers suggested above include materials which are known to be active as detergency builders (sodium carbonate) or as an antacid (sodium bicarbonate).
Method of Preparation:
As noted above, the method for preparing the products of the invention comprises drying an emulsion containing an aqueous phase comprising a carrier and a volatile 'oil' phase comprising a 'payload' material. As noted above, the preferred method of drying is spray drying.
Preferably, the volatile oil phase comprises from about 10 % to about 95 % v/v of the emulsion, more preferably from about 20 % to about 68 % v/v.
The emulsions are typically prepared under conditions which are well known to those skilled in the art, for example, by using a magnetic stirring bar, a homogeniser, or a rotational mechanical stirrer. The emulsions need not be particularly stable, provided that they do not undergo extensive phase separation prior to the drying step.
Homogenisation using a high-shear mixing device is a particularly preferred way to make an emulsion in which the aqueous phase is the continuous phase. It is believed that this avoidance of coarse emulsion and reduction of the 30 droplet size of the dispersed phase of the emulsion, results in an improved dispersion of the ‘payload' material in the

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dry product. In a preferred method according to the invention a water-continuous emulsion is prepared with an average dispersed-phase droplet size (using the Malvern peak intensity) of between 500nm and 3 000nm. We have found that an 'Ultra-Turrux' T25 type laboratory homogeniser (or
equivalent) gives a suitable emulsion when operated for more than a minute at above 10,000 rpm.
In preferred embodiments of the invention, there is a directional relation between the emulsion droplet size and the size of the particles of the 'payload' material, which can be detected after dispersion of the materials of the invention in aqueous solution. We have determined that an increase in the speed of homogenisation for precursor emulsions can decrease final particle size after re-dissolution.
It is believed that the re-dissolved particle size can be reduced by nearly one half when the homogenisation speed
increased from 13,500 rpm to 21,500 rpm. The homogenisation time also plays an important role in controlling re-dissolved particle size. The particle size again decreases when increase the homogenisation time, and the particle size distribution becomes broader at the same time.

For an intermediate emulsion size range of 500-3 00 0nm the re-dispersed particle size range is typically 180-300nm.
Spray drying, the most preferred method of drying the emulsion, is well known to those versed in the art. In the case of the present invention some care must be taken due to

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the presence of a volatile non-aqueous solvent in the emulsion being dried. In order to reduce the risk of explosion when a flammable solvent is being used, an inert gas, for example nitrogen, can be employed as the drying medium in a so-called closed spray-drying system. The solvent can be recovered a re-used.
We have found that the 'Buchi' B-2 90 type laboratory spray drying apparatus is suitable.

The product form obtained form the preferred spray drying process is a powder. As noted above, the precise microstructure of this powder is unclear. This powder can be incorporated into tablets, either by simple compression
(where the carrier material is sticky enough) or following the addition of excipients and or tableting agents.
The present invention will now be more particularly described, by way of example only, with reference to the accompanying Examples.
Examples:
Particle sizing
A method of particle sizing for the dispersed products of the present invention used in the following examples employs a dynamic light scattering instrument (Nano S, manufactured by Malvern Instruments UK). Transmission electron microscope images and field flow fractionation techniques have been

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used to confirm some particle sizing data. Specifically, the Malvern Instruments Nano S uses a red (633nm) 4mW Helium-Neon laser to illuminate a standard optical quality UV curvette containing a suspension of material. The viscosity of the sample can be measured with a Viscolite 700 portable viscometer (manufactured by Hydramotion UK) prior to analysis with the Malvern Instruments Nano S.
Example 1:

In this example the emulsion that was spray dried comprised the water insoluble dye 'Sudan Red 7b' (CI 26050) and the water-soluble structuring agents are polyvinyl alcohol (PVA) and sodium dodecyl sulphonate (SDS) . The emulsion was made
up as shown in the table below:
Table 2

1 Sudan Red 7b PVA SDS Cyclohexane DI Water 1
1 0.1 g 2.0 g 5.0 g 12 0ml 40ml
PVA was dissolved in 40ml water with stirring and once the entire polymer was dissolved the SDS was added. The red dye/cyclohexane solution was made up separately and added to the aqueous solution slowly over 10 minutes. Once all the dye was been added, stirring was continued for a further 5 minutes. Stirring and emulsification was achieved by means of a magnetic stir bar and stirrer.

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The emulsion was spray dried using a Buchi™ laboratory spray dryer (fitted with a Schlick™ nozzle) housed in a laboratory fume cupboard. The emulsion was stirred continuously using a magnetic stirrer whilst spray drying. The following spray drying conditions were employed:

Inlet temperature Atomisation pressure Liquid feed rate Outlet temperature (start) filter bag pressure (start)

120°C 3.0 bar 3.OmL/Min 60°C -40mbar

Example 2;
In this example the emulsion that was spray dried comprised the water-insoluble antimicrobial *Triclosan'™ and the water-soluble structuring agent polyvinyl alcohol. The emulsion was made up as shown in the table below:

Table 3

Triclosan
8.13

PVA
54.4g

Cyclohexane
563ml

DI Water
1875ml

The PVA was dissolved in the deionised water. The Triclosan was dissolved in the cyclohexane. The Triclosan solution was added to the PVA solution over a period of 1 minute with continuous homogenisation (using an IKA ultra-Turrax™ T25
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homogeniser at 6000rpm) and then further homogenised for a further 2 minutes (total of 3 minutes).
The emulsion was spray dried using a Buchi laboratory spray dryer (fitted with a Schlick nozzle) housed in a laboratory fume cupboard. The emulsion was stirred continuously using a magnetic stirrer whilst spray drying. The following spray drying conditions were employed:
Inlet temperature 90°C
Atomisation pressure 4.0 bar
Liquid feed rate 3.OmL/Min
Outlet temperature (start) 60°C
filter bag pressure (start) -40mbar

31.7 grams of material were collected. In this case a hazy dispersion is formed on addition of spray dried material to water. After several hours an optically clear and colourless dispersion is obtained.

Example 3;
In this example the emulsion that was spray dried comprised the water insoluble antimicrobial ‘Triclosan'™ and the water soluble structuring agents polyvinyl alcohol and Brij 78™. The emulsion was made up as shown in the table below:

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Table 4

! Triclosan Brij 78 PVA Cyclohexane DI Water
j 6.0g 15.4g 38. 5g 78na 770ml■,
The PVA was dissolved in the de-ionised water. When the PVA was dissolved the Brij-78 was added and allowed to dissolve. Triclosan was dissolved in the cyclohexane. The Triclosan solution was added (over 3 0 seconds) to the solution of PVA/Brij 78 with continuous homogenisation (using an IKA ultra-Turrax T25 homogeniser at 6000rpm) . The emulsion was further homogenised for a further 3 0 seconds (total of one minute).
The emulsion was spray dried using a Buchi laboratory spray dryer (fitted with a Schlick nozzle) housed in a laboratory fume cupboard. The emulsion was stirred continuously using a magnetic stirrer whilst spray drying. The following spray drying conditions were employed:
Inlet temperature 85°C
Atomisation pressure 4.0 bar
Liquid feed rate 3.OmL/Min
Outlet temperature (start) 55°C
filter bag pressure (start) -40mbar

32.4 grams of material was collected.

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In this example the emulsion that was spray dried comprised the water insoluble antimicrobial ‘Triclosan'TM and the water soluble structuring agent SDS. A range of solvents, as listed below was employed.
Table 5

Example Solvent Boiling Point Solvent Type
4 Pentane 3 6°C Alkane
5 Hexane 69°C Alkane
6 Heptane 98°C Alkane
7 Octane 125°C Alkane
8 Nonane ~150°C Alkane
9 Chloroform 61°C Chlorinated solvent
10 t-Butylmethyl ether 55°C Ethers
11 Cyclohexane 81°C Cyclic solvents
12 Ethyl Acetate 77°C Ester
13 Toluene 110°C Aromatic solvents
The following solutions were made:
SDS 8.9g dissolved in 125ml water Triclosan 1.lg dissolved in 125ml organic solvent
The Triclosan solution was slowly added to the SDS solution over a 30 second period, with continuous homogenisation using a IKA ultra-Turrax T25 homogeniser (6,000rpm) . After addition, homogenisation is continued for a further 90 seconds (2 minutes in total).

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Each emulsion was spray dried using a Buchi laboratory spray dryer (fitted with a Schlick nozzle) housed in a laboratory fume cupboard. During spray drying the emulsion was stirred continuously using a magnetic stirrer. The following spray drying conditions were used:

Inlet temperature Atomisation pressure Liquid feed rate Outlet temperature (start) filter bag pressure (start)

90°C
3.Obar
3.OmL/min
Varies with solvent
-40mbar

Example 14;
In this example the emulsion that was spray dried comprised the water insoluble fluorescer "Tinopal SOP'™ and the water-soluble structuring agent CocoPAS (sodium lauryl sulphate, EMAL 10PHD, ex Kao) . The emulsion was made up as shown in the table below:

Table 6

ED
Tinopal SOP
l.Og

Cocopas
9.0g

Dichloromethane
120ml

DI Water
120ml

The CocoPAS was dissolved in the de-ionised water. The Tinopal SOP was dissolved in the dichloromethane.

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The dichloromethane solution was added (over 3 0 seconds) to the aqueous solution of cocoPAS with continuous homogenisation (using an IKA ultra-Turrax T25 homogeniser at 6000rpm) for a total of 1 minute.
The resulting emulsion was spray dried using a Buchi laboratory spray dryer (fitted with a Schlick nozzle) housed in a laboratory fume cupboard. The emulsion was stirred continuously using a magnetic stirrer whilst spray drying. The following spray drying conditions were employed:
Inlet temperature 12 0°C
Atomisation pressure 3.0 bar
Liquid feed rate 4.0mL/Min
Outlet temperature (start) 66°C
filter bag pressure (start) -4 0mbar
3.84g of material was collected

Example 15;
In order to compare the effectiveness of compositions of the invention with those prepared by freeze-dry methods, the performance of the product obtained in example 14 was
compared with a product obtained by a freeze drying method.
To prepare the freeze dried product, 9g of CocoPAS (sodium lauryl sulphate, EMAL 10PHD, ex Kao) was dissolved in 120 ml of water. To this aqueous solution was added 1.Og of Tinopal™ SOP in 120ml of dichloromethane with vigorous

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stirring. The emulsion formed was sprayed into liquid nitrogen using a trigger spray and the resulting frozen powder was freeze-dried (Edwards Supermodulyo, operated with an average vacuum of 0.2mbar and at -50 °C) to form a powder.
Samples of the 10% loaded product were added to Brilhante™
(ex Gessy Lever, 2004) base formulation, without any
fluorescer present. The composition thus obtained was used
to launder untreated cloth monitors. The change in Ganz whiteness (Delta G) on cloth monitors was measured after each wash. Measurements were performed for cotton, nylon and polyester. Results for the method of the invention (in bold, and marked ‘spray dried') and the comparative tests (marked
'freeze dried') are shown in the table below:
Table 7

Cloth Type Preparation Ganzafter1st wash Ganzafter2nd wash Ganzafter3rd wash53.14
Nylon Freeze dried 33.35 46.84
Nylon Spray dried 38.17 50.05 56.14
Polyester Freeze dried 9.11 12.46 14.74
Polyester Spray dried 12.05 15.23 16.73
Cotton Freeze dried 21.68 26.43 30.36
Cotton Spray dried 25.39 32.64 34.71
Higher ‘Ganz' figures are obtained when fluorescer is more effectively deposited. Products prepared according to the method of the invention show better performance than those prepared by the freeze-drying method.

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Example 16:
In order to demonstrate the effect of choice of water soluble polymers on particle size and distributions, several different water soluble polymers with different molecular weights, including polyvinyl alcohol (PVA), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl cellulose (HEC), and polyvinylpyrrolidone (PVP) were employed. Table 8 lists the polymers.
Table 8

Polymer Molecular weight, mol/1 Producer
PVA Mw 9,000-10,000 Aldrich
HPMC Mw 10,000 Aldrich
HEC Mw 90,000 Aldrich
PVP Mw 10,000 Aldrich
Mw 24,000 Fluka
Mw 55,000 Fluka
Mw 360,000 Fluka
In this example, Oil red O (OR) was used as a model for active compound, and sodium dodecylsulfate (SDS) was used as a surfactant carrier.

0.25 g OR was dissolved in 50 ml chloroform as oil phase, and 1.0 g SDS and 1.0 g PVP were dissolved in 50 ml water as aqueous phase. The oil phase was added dropwise into aqueous phase with overhead stirring (IKA EUROSTAR) at 600 rpm for 2
min.

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Example 16:
In order to demonstrate the effect of choice of water soluble polymers on particle size and distributions, several different water soluble polymers with different molecular weights, including polyvinyl alcohol (PVA), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl cellulose (HEC), and polyvinylpyrrolidone (PVP) were employed. Table 8 lists the polymers.
Table 8

| Polymer Molecular weight, mol/1 Producer
PVA Mw 9,000-10,000 Aldrich 1
HPMC Mw 10,000 Aldrich
HEC Mw 90,000 Aldrich
PVP Mw 10,000 Aldrich
Mw 24,000 Fluka
Mw 55,000 Fluka
Mw 360,000 Fluka
In this example, Oil red O (OR) was used as a model for active compound, and sodium dodecylsulfate (SDS) was used as a surfactant carrier.

0.25 g OR was dissolved in 50 ml chloroform as oil phase, and 1.0 g SDS and 1.0 g PVP were dissolved in 50 ml water as aqueous phase. The oil phase was added dropwise into aqueous phase with overhead stirring (IKA EUROSTAR) at 600 rpm for 2
min.

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The coarse emulsion was then further treated with a homogenizer (IKA T25 basic Ultra-Turrax) at 17,500 rpm for 5 min. The resulting fine emulsion was then spray dried at 125 5 °C with a Buchi Mini spray dryer B-2 90 to obtain products according to the present invention. Spray drying conditions were Inlet temp.: 125 °C; Aspiration rate: 100%; Pump rate: 3.62ml/min.
A sample of the dry powder was then dispersed into distilled water and the nanoparticle size was measured with Malvern Nano-S. Details concerning these experiments and their results are summarized in Table 9.
PhR=phase ratio, oil phase/aqueous phase 15 PS=average particle size PDI=polydispersity index
Table 9

Sample Oil Phase Aqueous phase PhR, v/v PS,ma PDI
OR, mg/ml SDS, mg/ml PVP, mg/ml
WP-141 5.0 20.0 Mw 10,000 20.0 50/50 255 1.016
WP-142 Mw 29,000 220 1.103
WP-143 Mw 55,000 255 1.133
WP-144 Mw 360,000 295 ,12s |

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In further examples 0.25 g OR was dissolved in 50 ml chloroform as oil phase, and 1.0 g SDS and 1.0 g water soluble polymer (PVP (Mw 29,000), PVA, HPMC, or HEC) were dissolved in 50 ml water as aqueous phase. The oil phase was added dropwise into aqueous phase with overhead stirring at 600 rpm for 2 min. The coarse emulsion was further treated with a homogenizer at 17,500 rpm for 5 min. The resulting fine emulsion was then spray dried at 125 °C with a Buchi Mini spray dryer B-290 (Inlet temp.: 125 °C; Aspiration rate: 100%; Pump rate: 3.62ml/min.)
A sample of the dry powder was then dispersed into distilled water and the nanoparticle size was measured with Malvern Nano-S. Details concerning these experiments and their results are summarized in Table 10.
Table 10

Oil Phase Aqueous phase PhR, v/v PS, nm PDI
Sample OR, mg/ml SDS, mg/ml Water solublepolymer,mg/ml
WP-142 5.0 20.0 PVP 20.0 50/50 220 1.103
WP-145 PVA 220 1.240
WP-146 HPMC 164 1.012
WP-147 HEC 342 1.567
In this example HPMC (Mw 10,000) gave the smallest particle size and narrowest poly-dispersity, PVA (9-10k MW) gave similar particle size to PVP but broader particle size

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distributions, and HEC (MW 90k) gave the largest particle size and the broadest particle size distributions.
In yet further examples 0.25 g OR was dissolved in 50 ml chloroform as oil phase, and 1.0 g SDS was dissolved in 50 ml water with different water soluble polymers (PVP (Mw 29,000), PVA (Mw 10,000), and HPMC (Mw 10,000)) with different concentrations (20mg/ml, 15mg/ml, lOmg/ml, and 5mg/ml) as aqueous phase. The oil phase was added dropwise into the aqueous phase with overhead stirring at 600 rpm for 2 min. The coarse emulsion was further treated with a homogenizer at 17,500 rpm for 5 min.
The resulting fine emulsion was then spray dried at 125 °C with a Buchi Mini spray dryer B-290 (Inlet temp.: 125 °C; Aspiration rate: 100%; Pump rate: 3.62ml/min).
A sample of the dry powder was then dispersed into distilled water and the dispersed particle size was measured with Malvern Nano-S. Details concerning these experiments and their results are summarized in Table 11.

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Table 11

Sample Oil Phase Aqueous phase PhR, v/v PS,nm PDI
OR, mg/ml SDS, mg/ml Water soluble po lymer, mg/ml
WP-142 5.0 20.0 PVP 20.0 50/50 220 1.103
WP-145 PVA 220 1.240
WP-146 HPMC 164 1.012
WP-148 PVP 15.0 295 1.026
WP-149 PVA 255 1.027
WP-150 HPMC 164 1.067
WP-151 PVP 10.0 585 1.309
WP-152 PVA 255 1.137
WP-153 HPMC 220 1.180
WP-154 PVP 5.0 615 1.314
WP-155 PVA 342 1.230
WP-156 HPMC 396 1.764
Example 17:
0.25 g OR was dissolved in 60 ml chloroform as oil phase, and 4.05 g SDS and 7.0 g PVA (Mw 10,000) were dissolved in 140 ml water as aqueous phase. The oil phase was added
dropwise into aqueous phase with overhead stirring at 600 rpm for 2 0 min. Half the volume of the coarse emulsion obtained was further treated with a homogenizer at 17,500 rpm for 5 min.

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The coarse emulsion and the fine emulsion were then each spray dried at 12 0 °C with a Buchi Mini spray dryer B-290 respectively (inlet temp.: 120 °C; Aspiration rate: 100%; Pump rate: 5.90 ml/min.). Samples of the dry powders were dispersed into distilled water and the particle size was measured with Malvern Nano-S. Details concerning these experiments and their results are summarised in Table 12.
In a separate preparation 0.20 g OR was dissolved in 50 ml chloroform as oil phase, and 1.45 g SDS and 2.50 g PVA (Mw 10,000) were dissolved in 50 ml water as aqueous phase. The oil phase was added dropwise into aqueous phase with overhead stirring at 600 rpm for 2 min. The coarse emulsion was further treated with a homogeniser at 17,500 rpm for 5 min.
This fine emulsion was then spray dried at 12 0 °C with a Buchi Mini spray dryer B-290 (inlet temp.: 120 °C; Aspiration rate: 100%; Pump rate: 5.90 ml/min.). The dry powder was then dispersed into distilled water and the particle size was measured with Malvern Nano-S. Details concerning these experiments and their results are also summarised in Table 12.

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Table 12

Sample Oil Phase Aqueous phase PhR, v/v Process PS, nm PDI
OR, mg/ml SDS, mg/m1 PVA, mg/ml
WP-101 4.0 29.0 50.0- 30/70 Stir 264 1.112
WP-102 Homogenise 89 1.012
[WP-103 50/50 123 1.019
Example 18:
0.25 g OR was dissolved in 50 ml chloroform as oil phase, and 1.0 g SDS and 1.0 g PVP (Mw 29,000) were dissolved in 50 ml water as aqueous phase. The oil phase was added dropwise into the aqueous phase with overhead stirring at 600 rpm for 2 min. The coarse emulsion was further treated with a homogeniser at different speed to obtain a series of finer emulsions. These finer emulsions were then spray dried at 125 °C with a Buchi Mini spray dryer B-290 (inlet temp.: 125 °C; Aspiration rate: 100%; Pump rate: 3.62 ml/min).

The dry powder was then dispersed into distilled water and the nanoparticle size was measured with Malvern Nano-S. Details concerning these experiments and their results are summarized in Table 13 (HS=Homogenization speed,
Ht=Homogenization time)

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Table 13

Sample Oil Phase Aqueous phase PhR, v/v HS,rpm Ht, min PS,nm PDI
OR, mg/ml SDS, mg/ml PVA, mg/ml
WP-157 4.0 29.0 50.0 50/50 13,500 2 347 1.037
WP-158 17,500 2 279 1.043
WP-142 17,500 5 220 1.103
WP-159 21,500 2 190 1.014
Example 19:
Preparations have been made into tablet form by means of a tablet maker which has four parts. Three used to form the tablet and one to achieve compression. The parts used for tablet formation are an inverted WU" shape with a hole in the top, into which fits a solid cylinder with arms at the top and a solid rectangle that fits into the inverted U. Tablets are formed, with the U and rectangle assembled, by adding powder to the hole in the inverted U and carefully placing the cylinder into the hole. The assembly is then placed in the compression part, where the screw thread acts on the cylinder compacting the powder. The tablet is released by removing the rectangular and cylindrical blocks.
Spray dried powder prepared from cocoPAS, sodium sulphate and fat red dye was made into a 0.5g tablet using this apparatus. When a similar freeze dried powder was used, (cocoPAS, sodium chloride, fat red dye), a 0.06g tablet was formed.

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Tablet and powder behave differently in terms of dissolution times and clarity of solution.
Example 20:
A product comprising sodium sulphate was made by dissolving 0.5g CocoPAS in 12 ml water and adding 0.5g sodium sulphate. O.Olg Fat red 7B dye was dissolved in cyclohexane, added to
the aqueous solution to form an emulsion and freeze dried as a powder. Other similar powders, varying the CocoPAS : Sodium sulphate ratio from 60:40 to 90:10 gradually, were made in the same way. A similar set of samples containing sodium carbonate was also made. All powders re-dissolved in
water to give a clear solution. Without sodium carbonate, dissolution took about 20 seconds, with sodium carbonate, the time increased to 1 to 2 minutes.
A CocoPAS:NaS04, 50:50 ratio powder was made, this time forming the emulsion using a homogeniser and spray drying; for comparison of particle size, which gave a Z (Malvern) average of 57.3 and a poly-dispersity of 0.39. For a 20:80 cocoPAS:Na2S04 sample the particle size Z (Malvern) average was 115 and a poly-dispersity of 0.126.
For freeze dried samples, the particle size would appear to decrease as the amount of filler increases, for sodium sulphate, range Zave. 200 0, polydispersity 0.746 (50:50) to Zave. 609, polydispersity 0.492 (10:90).

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Other inorganic fillers included sodium carbonate, sodium chloride, magnesium chloride, magnesium acetate, calcium chloride and sucrose; these tended not to give clear solutions. Whereas sodium bicarbonate, sodium acetate and magnesium sulphate (at 50:50) gave clear re-dispersions. All these were prepared in a PVA/SDS system. Particle sizes varied between Zave. 1380, polydispersity 0.6 and Zave. 771, polydispersity 0.48 for the sodium salt fillers.
The preparations containing magnesium salts at 50:50 in PVA/SDS, gave particle sizes that ranged between Zave. 72.9, polydispersity 0.402 and Zave. 672, polydispersity 0.655. Magnesium sulphate was also made at the 20:80 ratio, but unlike sodium sulphate, due to it not giving a clear
solution, the particle size Zave.(255) polydispersity 0.375 was greater than the 50:50 ratio Zave. (72.9) polydispersity 0.402. The particle size data for magnesium salts, for all but the acetate, gave more than one peak size.

Calcium chloride and sucrose were also used as bulking agents; they gave particle sizes of Zave .892, polydispersity 0.593 and Zave.338, polydispersity 0.489 respectively.

Polymer only i.e. PVA with sodium sulphate filler (50:50) has been prepared as a freeze dried powder. It was slow to re-dissolve; time, 7 minutes, gave a clear solution and particle size Zave. 467, polydispersity 0.557 and had 2
peaks.

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0.037 g of the hydrophobic polymer polycaprolactone was dissolved in 15 ml chloroform as oil phase, and 0.26 g SDS and 0.45 g PVA (Mw 10,000) were dissolved in 15 ml water as aqueous phase. The oil phase was added dropwise into the aqueous phase and homogenised for 2 min.
The emulsion was spray dried at 150 °C with a Buchi Mini spray dryer B-290 respectively (inlet temp.: 150 °C;
Aspiration rate: 100%; Pump rate: 7.20 ml/min.). A sample of the dry powders were then dispersed into distilled water (10mg/ml) and the resulting particle size was measured with Malvern Nano-S. The particles were 162nm with a standard deviation of 2.14nm and a poly-dispersity of 0.131
Example 22:
0.5 g of the hydrophobic polymer Eudragit™ EPO was dissolved in 60 ml chloroform as oil phase, and 10 g PVA (Mw 10,000) were dissolved in 120 ml water as aqueous phase. The oil phase was added dropwise into the aqueous phase and homogenised for 1 min.
The emulsion was spray dried at 90 °C with a Buchi Mini spray dryer B-290 respectively (inlet temp.: 90 °C; Aspiration rate: 100%; Pump rate: 3 ml/min.). A sample of the dry powders were then dispersed into distilled water (lOmg/ml) and the resulting particle size was measured with
Malvern Nano-S. The particles were 520nm.

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CLAIMS
1. A method comprising the steps of: i) providing an emulsion of:
a) an aqueous solvent,
b) a carrier material dispersible or soluble in 10 (a) , said carrier material being solid at
ambient temperature,
c) a volatile second liquid phase which is not
miscible with (a) ,

d) a material which is dispersible or soluble in
(c) but not in (a) , and,
ii) drying the emulsion above ambient temperature to
simultaneously remove (a) and (c) and thereby
obtain the material (b) in solid form with (d) dispersed therein, said dispersion of (d) being a nano-scale dispersion, preferably with a maximum particle size of at most 615nm.

A method according to claim 1 wherein the aqueous solvent (a) is water.
AMENDED SHEET

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3. A method according to claim 1 or 2 wherein the carrier
material (b) comprises a polymer.
4. A method according to claim 3 wherein the carrier
material is polyvinyl alcohol.
5 . A method according to claim 1 or 2 wherein the carrier material (b) comprises a surfactant.
6. A method according to claim 5 wherein the carrier material (b) comprises an anionic surfactant.
7. A method according to any of claims 1 to 6 wherein the
volatile second liquid phase (c) has a boiling point of
less than 150 Celsius, preferably less than 100 Celsius.
8. A method according to claim 7 wherein the volatile
second liquid phase (c) is selected from: alkanes,
chlorinated solvents, ethers, cyclic solvents, esters and aromatic solvents.
9. A method according to any of claims 1 to 8 wherein the
volatile second liquid phase comprises from 10 % to 95
% v/v of the emulsion, preferably from 20 % to 68 % v/v.
1.0;. A method according toany one of claims 1 to" 9 'wherein the drying method is spray drying.
AMENDED SHEET

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11. A product obtainable by the method of any one of claims
1-10.
12. A product according to claim 11 which comprises as (d) a water-insoluble, pharmaceutically active substance and as (b) a water-soluble physiologically acceptable carrier.
13 . A product according to claim 11 or 12 wherein the material-(d) has a particle size of not more than 300nm, preferably 180-300nm.
14. A product according to claim 11 which comprises as (d) 15 an antimicrobial agent, an antidandruff agent, a skin-lightening agent, a fluorescing agent, a skin-conditioning agent, an antifoaming agent, a hair conditioning agent, a fabric conditioning agent, a thickening agent, a UV protecting agent, a bleach or
bleach precursor, an antioxidant, an insecticide,
pesticide, herbicide or other agrochemical, a perfume or a flavouring.
AMENDED SHEET

Documents:

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Patent Number

270879

Indian Patent Application Number

1039/MUMNP/2007

PG Journal Number

05/2016

Publication Date

29-Jan-2016

Grant Date

25-Jan-2016

Date of Filing

11-Jul-2007

Name of Patentee

UNILEVER PLC.

Applicant Address

UNILEVER HOUSE, BLACKFRIARS, LONDON, EC4P 4BQ

Inventors:

#	Inventor's Name	Inventor's Address
1	BARNWELL STEPHEN GEORGE	UNILEVER R&D PORT SUNLIGHT, QUARRY ROAD EAST, BEBINGTON, WIRRAL, MERSEYSIDE, CH63 3JW
2	COOPER ANDREW LAN	UNIVERSITY OF LIVERPOOL, DEPARTMENT OF CHEMISTRY, SENATE HOUSE, CROWN STREET, LIVERPOOL, L69 3BX
3	DUNCALF DAVID	36 SANDON CRESCENT, LITTLE NESTON, WIRRAL, CH64 0TU
4	FOSTER ALISON JAYNE	74 VILLAGE ROAD, HIGHER BEBINGTON, WIRRAL, MERSEYSIDE CH63 8QB
5	RANNARD STEVEN PAUL	UNILEVER R&D PORT SUNLIGHT, QUARRY ROAD EAST, BEBINGTON, WIRRAL, MERSEYSIDE CH6 3JW

PCT International Classification Number

C08J3/12 A61K9/16

PCT International Application Number

PCT/EP2005/013933

PCT International Filing date

2005-12-20

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	0501835.3	2005-01-28	U.K.