J3790/C FORM - 2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See Section 10 and Rule 13) HAIR AND/OR SCALP CARE COMPOSITIONS INCORPORATING TERPENOID COMPOUNDS HINDUSTAN UNILEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India The following specification particularly describes the invention and the manner in which it is to be performed WO 2006/097185 PCT/EP2006/001683 HAIR AND/OR SCALP CARE COMPOSITIONS INCORPORATING TERPENOID COMPOUNDS This invention relates to hair and/or scalp care 5 compositions incorporating certain selected terpenoid compounds. The invention also relates to the use of these terpenoid compounds for the treatment and/or prevention of inflammatory skin conditions such as the scalp skin itching and flaking associated with dandruff. 10 Background It is widely believed that Malassezia yeasts, such as Malassezia furfur, are the main cause of dandruff. However, 15 it is unclear why some people suffer from this condition while others do not. What is known is that increasing the level of Malassezia on the scalp does not automatically lead to dandruff. This suggests that Malassezia is necessary but not sufficient to cause the condition. 20 Recent studies have demonstrated that dandruff is associated with changes in scalp skin condition. Dandruff scalp skin has been shown to have decreased levels of stratum corneum lipids such as ceramides, an increased susceptibility to 25 application of topical histamine and a perturbed balance in the levels of inflammatory cytokine markers in the stratum corneum. These findings clearly demonstrate that dandruff is associated with changes in scalp skin condition and that dandruff is multifactorial. It is believed that the 30 weakened scalp skin barrier and perturbed condition of the WO 2006/097185 PCT/EP2006/001683 - 2 - scalp skin renders an individual susceptible to challenge by factors such as Malassezia. The main, if not only, intervention strategy used on the 5 market currently for the treatment of dandruff is the topical application of antifungals such as zinc pyrithione (ZnPTO), octopirox and ketoconazole which are normally delivered from a shampoo. These antifungal agents remove (or at least reduce the level of) the Malassezia from the 10 scalp, and provide effective treatment of the dandruff condition. Although clinically proven to be effective in treating the clinical symptoms of dandruff over.a two to four week 15 period, there remains a need to treat the main symptoms of dandruff more effectively and rapidly. The main symptoms of dandruff are visible skin flakes in the hair and on the shoulders and scalp itch. Scalp itch is perceived as being a particular problem in certain parts of the world, for 20 example it is the main symptom of dandruff in China, South-East Asia and India. As well as treating the clinical signs of dandruff, therefore, there remains a need for providing rapid relief 25 from scalp itch for dandruff sufferers. WO04/00085 describes how cannabinoid receptor (CBR) activators may be useful in hair treatment compositions for the treatment and/or prevention of symptoms of dandruff such 30 as scalp skin itching and flaking. WO 2006/097185 PCT/EP2006/001683 - 3 - The present inventors have found that certain selected terpenoid compounds are capable of acting as CBR activators, and therefore may be used for the treatment and/or prevention of symptoms of dandruff such as scalp skin 5 itching and flaking. The terpenoids, sometimes referred to as isoprenoids, are a class of naturally occurring chemicals derived from five-carbon isoprene units assembled and modified in thousands of 0 ways. Most are multicyclic structures which differ from one another not only in functional groups, but also in their basic carbon skeletons. Terpenoids of different sizes and composition are found in all classes of living things, and are the largest group of natural products- Plant terpenoids 5 are extensively used for their aromatic qualities. There is no suggestion in WO04/00085 that terpenoid compounds (of which over 23,000 have been chemically isolated and reported) would possess such activity. 0 Furthermore it has been observed that the selected terpenoid compounds of the invention are significantly more hydrophilic (with a ClogP < 4.5) than those compounds which have generally been documented in the literature as exhibiting CBR activation. 5 Summary of the invention According to the invention there is provided a hair and/or scalp care composition comprising a terpenoid compound of 0 formula (I), (II) or (III): WO 2006/097185 PCT7EP2006/001683 - 4 - (I) (ID WO 2006/097185 PCT/EP2006/001683 - 5 - R8 O in which Ri to Ru are each, independently, -H,-F,-Cl,-Br,-I,-5 OH, lower alkyl (e.g. Ci_6 alkyl) or lower alkoxy (e.g. C-y-e alkoxy). In another aspect, the invention provides a method of treating and/or preventing inflammatory skin conditions such 10 as the scalp skin itching and flaking associated with dandruff, which method comprises topically applying a composition according to the invention to the hair and/or skin, preferably to the hair and/or scalp. 15 Detailed Description of the Invention and Preferred Embodiments Preferably, Ri to Ru in general formulae (I) to (III) are each independently selected from -OH and -OCH3. WO 2006/097185 PCT/EP2006/001683 - 6 T Specific examples of suitable terpenoid compounds of formula (I), (II) or (III) are: a.compound which has the structural formula (IV) (termed 6-5 hydroxysumatrol): (IV) OCH3 OCH3 10 a compound which has the structural formula (V) (termed isophaseollin): WO 2006/097185 PCT/EP2006/001683 - 7 - (V) ^*\^ a compound which has the structural formula (VI) (termed silandrin): (VI) OCH3 10 WO 2006/097185 PCT/EP2006/001683 - 8 - Preferred is a compound which has the structural formula (V) (isophaseollin). The inventors have found that this compound can activate both of the two similar, but distinct, types of membrane receptor which have been termed Cannabinoid 5 Receptor 1 (CBIR) and Cannabinoid Receptor 2 (CB2R) (Matsuda et al, Nature 346, 561-564 (1990), Munro et al, Nature, 365, 61-65 (1993)). CBIR is by far the predominant form in the central nervous system, whereas both CBIR and CB2R are located in the peripheral tissues, including the skin. 10 Herein a reference to a CBR activator includes either or both CBIR and CB2R activators. The above terpenoid compounds of formula (I), (II) or (III) are natural products and may be obtained from suppliers such 15 as Apin Chemicals Limited (Oxon., OK)., Sigma-Aldrich and Interbioscreens. Mixtures of two or more terpenoid compounds of formula (I), (II) or (III) may also be used in compositions of the 20 invention. The amount of terpenoid compounds of formula (I), (II) or (III) in the compositions of the invention is preferably selected in the range of from 0.05 to 20%, more preferably 25 from 0.1 to 10%, most preferably from 0.25 to 5wt% by weight based on total weight. Preferably, compositions according to the invention comprise from 0.01% to 30% by weight, more preferably 0.1% to 10%, 30 most preferably 0.5 to 2% by weight of an antidandruff agent. By "antidandruff agent" is meant a different compound WO 2006/097185 POVEP2006/001683 - 9 - from the terpenoid compound of formula (I), (II) or (III). Antidandruff agents are compounds that are active against dandruff and are typically antimicrobial agents, preferably antifungal agents. 5 Suitable antidandruff agents include compounds selected from zinc pyrithione, climbazole, ketoconazole, octopirox and mixtures thereof. 10 The preferred antifungal agent is zinc pyrithione (ZnPTO) which, on account of its relative insolubility in aqueous systems, is generally used in hair treatment compositions as a particulate dispersion. The zinc pyrithione may be used in any particle form including, for example, crystalline 15 forms such as platelets and needles and amorphous, regularly or irregularly shaped particles. If zinc pyrithione is present in the composition, a suspending agent is preferably used to prevent or inhibit the settling of the particles out of the composition. The average particle diameter of the 20 zinc pyrithione particles (i.e, their maximum dimension) is typically from about 0.2 to about 50 |Jm, preferably from about 0.4 to about 10 pm, more preferably from 0.4 to lum. Antifungal agents typically display a minimum inhibitory 25 concentration of about 50 mg/ml or less against Malassezia. If the antifungal agent is soluble in aqueous systems, it may be present in solution in a composition used in the invention. WO 2006/097185 PCT/EP2006/001683 - 10 - If the antifungal agent is soluble in aqueous systems, it may be present in solution in a composition used in the invention. 5 Product Forms Compositions of the present invention are typically for topical application to the hair and/or scalp and may be formulated as transparent or opaque emulsions, lotions, 10 creams, pastes or gels. Hair and/or scalp care compositions of the invention may be rinse off products or leave on products. Rinse off products are intended to be substantially rinsed off the hair and/or 15 the scalp of the user with water after use. Leave on products are intended not to be rinsed off the hair and/or the scalp of the user immediately after use (ie, within at least the first 2 hours, preferably at least four hours, after application of the composition). Leave on products 20 include, for example, lotions, creams and hair oils that are intended for topical application to the hair and/or the scalp. Rinse off compositions include shampoos and hair conditioners, as well as hair and/or scalp treatment products which are intended to be left on the hair and/or 25 scalp for up to 2 hours (eg, 5 minutes to 2 hours) before being rinsed off. Preferred product forms are shampoos, conditioners, hair oils and lotions. WO 2006/097185 PCT/EP2006/001683 - 11 - Shampoo Compositions Shampoo compositions according to the invention will typically comprise one or more anionic cleansing surfactants 5 which are cosmetically acceptable and suitable for topical application to the hair. Anionic Cleansing Surfactant 10 Examples of suitable anionic cleansing surfactants are the alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyl succinates," alkyl sulphosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, and alpha- 15 olefin sulphonates, especially their sodium, magnesium, ammonium and mono-, di- and triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18 carbon atoms and may be unsaturated. The alkyl ether sulphates, alkyl ether phosphates and alkyl ether carboxylates may 20 contain from 1 to 10 ethylene oxide or propylene oxide units per molecule. Typical anionic cleansing surfactants for use in shampoo compositions of the invention include sodium oleyl succinate, 25 ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, sodium dodecylbenzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyl isethionate, sodium lauryl isethionate and sodium N-lauryl sarcosinate. The most preferred anionic surfactants are sodium lauryl sulphate, 30 sodium lauryl ether sulphate(n)EO, (where n ranges from 1 to WO 2006/097185 PCT/EP2006/001683 - 12 - 3), ammonium lauryl sulphate and ammonium lauryl ether sulphate(n)EO, (where n ranges from 1 to 3). Mixtures of any of the foregoing anionic cleansing 5 surfactants may also be suitable. The total amount of anionic cleansing surfactant in shampoo compositions of the invention is generally from 5 to 30, preferably from 6 to 20, more preferably from 8 to 16 10 percent by weight of the composition. Co-surfactant Shampoo compositions according to the invention can 15 optionally include co-surfactants, to help impart aesthetic, physical or cleansing properties to the composition. A preferred example is an amphoteric or zwitterionic surfactant, which can be included in an amount ranging from 0 20 to about 8, preferably from 1 to 4 wt%. Examples of amphoteric and zwitterionic surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines), alkyl glycinates, 25 alkyl carboxyglycinates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms. Typical amphoteric and zwitterionic surfactants for use in shampoos of the 30 invention include lauryl amine oxide, cocodimethyl WO 2006/097185 PCT/EP2006/001683 - 13 - sulphopropyl betaine and preferably lauryl betaine, cocamidopropyl betaine and sodium cocamphopropionate. Another preferred example is a nonionic surfactant, which can 5 be included in an amount ranging from 0 to 8, preferably from 2 to 5 percent by weight of the composition. For example, representative nonionic surfactants that can be included in shampoo compositions of the invention include 10 condensation products of aliphatic (Cs - CIB) primary or secondary linear or branched chain alcohols or phenols with alkylene oxides, usually ethylene oxide and generally having from 6 to 30 ethylene oxide groups. 15 Other representative nonionic surfactants include mono- or di-alkyl alkanolamides. Examples include coco mono- or di-ethanolamide and coco mono-isopropanolamide. Further nonionic surfactants which can be included in shampoo 20 compositions of the invention are the alkyl polyglycosides (APGs) . Typically, the APG is one which comprises an alkyl group connected (optionally via a bridging group) to a block of one or more glycosyl groups. Preferred APGs are defined by the following formula: 25 RO - (G)n wherein R is a branched or straight chain alkyl group which may be saturated or unsaturated and G is a saccharide group. 30 WO 2006/097185 PCT/EP2006/001683 - 14 - R may represent a mean .alkyl chain length of from about C5 to about C20« Preferably R represents a mean alkyl chain length of from about Cs to about C12. Most preferably the value of R lies between about 9.5 and about 10.5. G may be selected 5 from C5 or C6 monosaccharide residues, and is preferably a glucoside. G may be selected from the group comprising glucose, xylose, lactose, fructose, mannose and derivatives thereof. Preferably G is glucose. 10 The degree of polymerisation, n, may have a value of from about 1 to about 10 or more. Preferably, the value of n lies in the range of from about 1.1 to about 2. Most preferably the value of n lies in the range of from about 1.3 to about 1.5. 15 Suitable alkyl polyglycosides for use in the invention are commercially available and include for example those materials identified as: Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel. 20 Other sugar-derived nonionic surfactants which can be included in shampoo compositions of the invention include the clO~Ci8 N-alkyl (C1-C6) polyhydroxy fatty acid amides, such as the C12-C18 N-methyl glucamides, as described for example in 25 WO 92 06154 and US 5 194 639, and the N-alkoxy polyhydroxy fatty acid amides, such as Cio-Cis N-(3-methoxypropyl) glucamide. WO 2006/097185 PCT/EP2006/001683 - 15 - A preferred blend of cleansing surfactants is a combination of ammonium lauryl ether sulphate, ammonium lauryl sulphate, PEG 5 cocamide and cocamide MEA (CTFA designations). 5 The shampoo composition can also optionally include one or more cationic co-surfactants included in an amount ranging from 0.01 to 10, more preferably from 0.05 to 5, most preferably from 0.05 to 2 percent by weight of the composition. Useful cationic surfactants are described 10 hereinbelow in relation to conditioner compositions. The total amount of surfactant (including any co-surfactant, and/or any emulsifier) in shampoo compositions of the invention is generally from 5 to 50, preferably from 5 to 15 30, more preferably from 10 to 25 percent by weight of the composition. Cationic Polymer 20 A cationic polymer is a preferred ingredient in shampoo compositions according to the invention, for enhancing conditioning performance of the shampoo. The cationic polymer may be a homopolymer or be formed from 25 two or more types of monomers. The molecular weight of the polymer will generally be between 5 000 and 10 000 000, typically at least 10 000 and preferably in the range 100 000 to about 2 000 000. The polymers will have cationic nitrogen containing groups such as quaternary ammonium or protonated 30 amino groups, or a mixture thereof. WO 2006/097185 PCT7EP2006/001683 - 16 - The cationic nitrogen-containing group will generally be present as a substituent on a fraction of the total monomer units of the cationic polymer. Thus when the polymer is not a homopolymer it can contain spacer non-cationic monomer 5 units. Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of the cationic to non-cationic monomer units is selected to give a polymer having a cationic charge density in the required range. 10 Suitable cationic conditioning polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth)acrylamide, alkyl and dialkyl (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone 15 and vinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably Cl-3 alkyl groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol. 20 The cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general secondary and tertiary amines, especially tertiary, are preferred. 25 Amine substituted vinyl monomers and amines can be polymerized in the amine form and then converted to ammonium by quaternization. 30 The cationic conditioning polymers can comprise mixtures of monomer units derived from amine- and/or quaternary WO 2006/097185 PCT/EP2006/001683 - 17 - ammonium-substituted monomer and/or compatible spacer monomers. Suitable cationic conditioning polymers include, for 5 example: copolymers of l-vinyl-2-pyrrolidine and l-vinyl-3-methyl-imidazolium salt (e.g. chloride salt), referred to in the industry by the Cosmetic, Toiletry, and 10 Fragrance Association, (CTFA) as Polyquaternium-16. This material is commercially available from BASF Wyandotte Corp. (Parsippany, NJ, USA) under the LUVIQUAT tradename (e.g. LUVIQUAT FC 370); 15 copolymers of l-vinyl-2-pyrrolidine and dimethylaminoethyl methacrylate, referred to in the industry (CTFA) as Polyquaternium-11. This material is available commercially from Gaf Corporation (Wayne, NJ, USA) under the GAFQUAT tradename (e.g., GAFQUAT 755N); 20 cationic diallyl quaternary ammonium-containing polymers including, for example, dimethyldiallyammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the 25 industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; mineral acid salts of amino-alkyl esters of homo-and copolymers of unsaturated carboxylic acids having from 3 30 to 5 carbon atoms, (as described in U.S. Patent 4,009,256); WO 2006/097185 PCT/EP2006/001683 - 18 - cationic polyacrylamides(as described in W095/22311). Other cationic conditioning polymers that can be used include cationic polysaccharide polymers, such as cationic 5 cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives. Suitably, such cationic polysaccharide polymers have a charge density in the range from 0.1 to 4 meq/g. 0 Cationic polysaccharide polymers suitable for use in compositions of the invention include those of the formula: A-0-tR-N^R1) TTiijioiiooj EP200bUUlbtt J3790 (C) Amended 12 October 2006 - 31 - Claims: 1. Use of a terpenoid compound of formula (I), (II) or (III) : (I) 10 (ID sceived at the EPO on Oct 12, 2006 18:46:35. Pa AMENDED SHEET 2-10-2006 '7:32 FROMrUNILEUER R&D PATENTS +44151641869 T0:EPO MUNICH EP2006001683 J3790 (C) Amended 12 October 2 006 - 32 - (III) in which Ri to Ru are each, independentlyf -R,-T,-C1,~ Br,-I,-OH, lower alkyl (e.g. Ci-5 alkyl) or lower alkoxy (e.g. Ci-6 alkoxy), in the manufacture of a composition for treating and/or preventing the scalp skin itching. 10 Use according to claim 1 characterised in that the terpenoid compound of formula (I) f (II) or (III) is selected from 6-hydroxysumatrol, isophaseollin, silandrin and mixtures thereof. 15 3. Use according to claim 2 characterised in that the terpenoid compound of formula (I), (II) or (III) is isophaseollin. .•ived at the EPO on Oct 12,2006 18:46:35. Pa AMENDED SHEET t-2-10-2006 J37 90 (C> Amended 12 October 2006 - 33 - 4 . Use according to any preceding claim in which the terpenoid compound is formulated within a composition characterised in that the composition comprises from 5 0.01 to 30% by weight of an antidandruff agent. 5. Use according to Claim 4 characterised in that the antidandruff agent comprises a compound-selected from zinc pyrithione, climbazole,. ketoconazole, octopirox 10 and mixtures thereof. 6. Use according to claim 4 or claim 5 characterised in that the composition is a shampoo composition comprising an anionic cleansing surfactant in an amount 15 of from 5 to 30wt%. 7. Use according to claim 4 or 5 characterised in that tha composition is a conditioner composition comprising a cationic conditioning surfactant in an amount of from 2 0 0.01 to 10wt%. 8. Use according to claim 4 or claim 5 characterised in that tha composition is a hair oil or lotion. 2 5 9. Use according to any preceding claim characterised in that the amount of terpenoid compound of formula (I)r (II) or (III) is from 0.05 to 20% by weight and preferably frcm 0.1 to 10% by weight. Dated this 10th. day of September 2007 HINDUSTAN UNILEVER LIMITED eceived at the EPO on Oct 12, 2006 18:46:35. Pa AMENDED SHEET (S. Venkatramani) Senior Patents Manager