EP1677750A1

EP1677750A1 - Antidandruff shampoo composition

Info

Publication number: EP1677750A1
Application number: EP04790116A
Authority: EP
Inventors: Timothy John Madden; Anand Ramchandra Mahadeshwar; Anthony Moretta; Julia Sarah Rogers; Alun Peter Williams
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2003-10-27
Filing date: 2004-10-01
Publication date: 2006-07-12
Also published as: CN1870970A; TW200518778A; MXPA06004594A; BRPI0415163A; CN1870973A; WO2005046629A1; CN100502832C; JP2007509183A; AR046203A1

Abstract

A shampoo composition comprising: an anti-dandruff agent in an amount of from 0.01% to 10% by weight; beeswax in an amount of from 0.01% to 10% by weight; and a silicone in an amount of from 0.01% to 10% by weight.

Description

_ANTIDANDRUFF SHAMPOO COMPOSITION

This invention relates to shampoo compositions and to the use of components of the compositions.

It is widely believed that Malassezia yeasts, such as Malassezia furfur, are the main cause of dandruff. The main, if not only, intervention strategy used on the market currently for the treatment of dandruff is the topical application of antifungals such as zinc pyrithione (ZnPTO) , climbazole, 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 scalp, and provide effective treatment of the dandruff condition.

Certain compositions used in the treatment of dandruff are perceived as being harsh on the hair, leaving the treated hair dry, rough and difficult to comb.

CA 2078375 describes a shampoo composition for the treatment of headaches and pain comprising specified amounts of natural anti-pain and headache oils as well as beeswax and silicone oil. There is no mention of anti-dandruff agents in CA 2078375 or disclosure regarding the function of the beeswax or silicone oil.

EP 0502616 discloses a mild cosmetic composition comprising an alkylpolyglycoside surfactant, a wax and optionally one or more thickening agents, wherein the composition has a specified viscosity. The wax may be beeswax. EP 0502616 does not, however, describe any anti-dandruff compositions or compositions comprising silicones.

EP 0413417 describes a hair conditioning shampoo comprising a specified anionic detergent, a water insoluble hair conditioning aid such as silicones, polyethylenes, paraffins, isoparaffins, petrolatums, microcrystalline waxes, C₁₈-36 (mixed) fatty acids and/or triglycerides, stearyl stearate and beeswax, a stabiliser and an aqueous medium. The improvement in hair conditioning is stated to be due to the inclusion of the specified anionic detergent.

EP 0471606 discloses stabilized liquid fiber- and skin treating compositions having improved elevated temperature stability due to the inclusion of stabilizing agent which is a long chain alcohol or suitable derivative thereof. The compositions further comprise a liquid medium, an emulsifying agent and a fibre or skin treating material that is insoluble in the liquid medium. Examples of the skin treating material include: petrolatums paraffin waxes; isoparaffins; mineral oils; microcrystalline waxes; beeswaxes; organosilicon compounds, including silicones and aminosilicones; polyethylenes; Cι₈-36 triglycerides; perfumes; sunscreening agents and anti-dandruff agents.

In particular, EP 0471606 describes anti-dandruff compositions comprising specified amounts of an anionic detergent, a water insoluble anti-dandruff agent, a long chain alcohol and water. There remains a need for effective shampoo compositions for treating dandruff which can deliver improved foam quality and which can leave the treated hair with improved conditioned properties such as, for example, smoother feel, greater body and better ease of dry combing without compromising the effectiveness of dandruff treatment.

There also remains a need for shampoo compositions having increased mildness and/or improved foam quality and/or smoothness and/or conditioning benefits.

According to a first aspect of the present invention there is provided a shampoo composition comprising: an anti- dandruff agent in an amount of from 0.01% to 10% by weight; beeswax in an amount of from 0.01% to 10% by weight; and a silicone in an amount of from 0.01% to 10% by weight.

In a further aspect of the present invention, there is provided the use of a combination of beeswax and silicone in a shampoo composition to provide one or more properties selected from increased mildness, improved foam quality, improved conditioning and improved hair manageability benefits. By the term "improved" it is meant that the properties of shampoo compositions comprising a combination of beeswax and silicone according to the invention are superior to shampoo compositions which do not contain the combination of beeswax and silicone.

In a still further aspect of the present invention, there is provided the use of beeswax and silicone in an anti-dandruff shampoo composition to provide improved foam properties and effective deposition of an antidandruff agent.

The present invention relates in part to the surprising finding that a combination of beeswax and a silicone in a shampoo composition can lead to an unexpected improvement in such properties as, for example, mildness, foam quality, conditioning and hair manageability benefits such as smoothness, ease of combing, reduced hair volume and the like.

In particular, the compositions of the present invention can provide shampoos that are mild and yet produce foams that possess properties such as unexpected creaminess. It is known that mild shampoo compositions usually produce foams having lower quality feel and appearance and as a result mild shampoos can be less appealing to the consumer.

Without wishing to be bound by theory, it is believed that there is a synergistic interaction between beeswax and silicone that can lead to the improved hair manageability benefits of the present compositions.

Furthermore, the present invention relates in part to the finding that silicone and beeswax may not interfere with the deposition of anti-dandruff agents from anti-dandruff shampoo compositions in which they are both included and can therefore provide anti-dandruff compositions having, for example, improved foam properties. The anti-dandruff agent may suitably be any anti-dandruff agent known to the person skilled in the art that is capable of treating and/or preventing the formation of dandruff. In particular, the anti-dandruff agent may be any antimicrobial agent that is suitable for the treatment and/or prevention of dandruff.

The anti-dandruff agent may be a single compound or a mixture of two or more compounds .

The anti-dandruff agent is preferably present in an amount of from 0.05% to 5% by weight, more preferably from 0.5% to 2% by weight, particularly preferably from 0.5% to 1% by weight.

The anti-dandruff agent may suitably be particulate or non- particulate and be water-insoluble i.e., not dissolved in the composition at 25°C or water-soluble i.e., dissolved in the composition at 25 °C.

If the anti-dandruff agent is a particulate anti-dandruff agent, it may optionally have a range of sizes that are known in the art to promote deposition onto the hair and/or skin.

In one embodiment, the anti-dandruff agent may comprise fine particles of an insoluble particulate metal pyrithione in which at least about 90% by weight of the particles have a size of 5 microns or less. Preferably, the anti-dandruff agent is selected from the group consisting of: l-hydroxy-2-pyridones, zinc pyrithione, selenium sulfide, sulfur, ketoconazole, dichlorophenyl imidazolodioxalan, clotrimazole, econazole, itraconazole, miconazole, climbazole, oxyconazole, tioconazole, sulconazole, butoconazole, fluconazole, piroctone olamine and mixtures thereof.

It is preferred that the anti-dandruff agent is dissolved in the composition.

In a further preferred embodiment, the anti-dandruff agent contains an azole ring. Preferably, the anti-dandruff agent is selected from the group consisting of ketoconazole and climbazole and mixtures thereof.

In a particularly preferred embodiment, the anti-dandruff agent is climbazole.

The compositions of the invention include beeswax. Beeswax can vary in colour from white to yellow through brown to black depending upon the type of pollen carried by the bees which produce it. Any of these forms may be suitable for the present invention.

By the term "beeswax" it is intended to include natural beeswax obtained from honeycombs in either an unpurified or preferably purified state and synthetic and substitute beeswax, as well as beeswax that has been modified, for example organically modified. The term "synthetic and substitute" beeswax includes substances that have similar properties to those of natural beeswax.

Suitable organically modified beeswaxes include, for example, PEG-8 beeswax, polyglycerol-3 beeswax and siliconized beeswax such as dimethicone copolyol beeswax.

Preferably, the amount of beeswax in the composition is from 0.1% to 5% by weight of the total composition, more preferably from 0.2% to 2.0% by weight, particularly preferably from 0.5% to 1.5% by weight.

In a preferred embodiment of the present invention, the beeswax is suspended in the composition as solid particles.

Particularly preferred forms of beeswax for use in the present invention are processed, refined or white beeswax. In a particularly preferred embodiment, the beeswax is a processed beeswax, such as, for example, that obtainable from Koster Keunen Inc..

The silicone is typically insoluble in the aqueous matrix of the shampoo composition of the invention and so is present in an emulsified form, with the silicone present as dispersed particles.

The silicone is preferably present in an amount of from 0.05% to 5% by weight of the total composition, more preferably from 0.1% to 2% by weight of the total composition. Preferably, the total amount of beeswax and silicone in the composition is greater than 1.0% by weight of the total composition, more preferably greater than 1.1% by weight, such as from 1.2% to 5% by weight.

Preferably, the weight ratio of beeswax to silicone is from 1:4 to 3:1, more preferably from 1.5:1 to 2.5:1. In a particularly preferred embodiment, the weight ratio of beeswax to silicone is about 2:1.

Various methods of making emulsions of particles of silicones for use in the invention are available and are well known and documented in the art. For example, emulsions may be prepared by high shear mechanical mixing of the silicone and water, or by emulsifying the silicone with water and an emulsifier (mixing the silicone into a heated solution of the emulsifier for instance) , or by a combination of mechanical and chemical emulsification. A further suitable technique for preparation of emulsions of particles of silicones is emulsion polymerisation. Emulsion polymerised silicones as such are described in U.S. Pat. No. 2,891,820 (Hyde), U.S. Pat. No. 3,294,725 (Findlay) and U.S. Pat. No. 3,360,491 (Axon) .

The viscosity of the silicone itself (not the emulsion or the final shampoo composition) preferably ranges from 10,000 cps to 5 million cps. The viscosity can be measured by means of a glass capillary viscometer as set out further in Dow Corning Corporate Test Method CTM004 July 20 1970. Suitable silicones include polydiorganosiloxanes, in particular polydimethylsiloxanes which have the CTFA designation dimethicone. An example is dimethicone fluid having a viscosity of up to 100,000 centistokes at 25° C, which is available commercially from the General Electric Company as the Viscasil series and from Dow Corning as the DC 200 series.

Also suitable for use in the compositions of the invention are hydroxy functional silicones, in particular polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol.

A further class of silicones suitable for inclusion in the shampoos of the invention is amino functional silicones. By "amino functional silicone" it is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group.

Amino functional silicones suitable for use in the invention will typically have a mole % amine functionality in the range of from about 0.1 to about 8.0 mole %, preferably from about 0.1 to about 5.0 mole %, most preferably from about 0.1 to about 2.0 mole %.

The viscosity of the amino functional silicone is not particularly critical and can suitable range from about 100 to about 500,000 cst.

Examples of suitable amino functional silicones include polysiloxanes having the CTFA designation "amodimethicone" . Specific examples of amino functional silicones suitable for use in the invention are the aminosilicone oils DC2-8220, DC2-8166, DC2-8466 and DC2-8950-114 (all ex Dow Corning) and GE 1149-75, (ex General Electric Silicones) .

Also suitable are silicone gums. "Silicone gum" denotes polydiorganosiloxanes having a molecular weight of from 200,000 to 1,000,000 and specific examples include dimethicone gums, dimethiconol gums, polydimethyl siloxane/diphenyl/methylvinylsiloxane copolymers, polydimethylsiloxane/methylvinylsiloxane copolymers and mixtures thereof. Examples include those materials described in US Pat. No. 4,152,416 (Spitzer) , and on General Electric Silicone Rubber product Data Sheet SE 30, SE 33, SE 54 and SE 76.

Also suitable for use in the present invention are silicone gums having a slight degree of cross-linking, as are described for example in WO 96/31188. These materials can impart body, volume and stylability to hair, as well as good wet and dry conditioning.

Preferred emulsified silicones for use in compositions of the invention have an average silicone particle size in the composition of less than 100, preferably less than 30, more preferably less than 20 microns, most preferably less than 10 microns.

Particle size may be measured by means of a laser light scattering technique, using a 2600D Particle Sizer from Malvern Instruments. Suitable silicone emulsions for use in the invention are commercially available in a pre-emulsified form. This is particularly preferred since the pre-formed emulsion can be incorporated into the washing composition by simple mixing.

Examples of suitable pre-formed emulsions include emulsions DC2-1766 and DC2-1784, available from Dow Corning. These are emulsions of dimethiconol. Cross-linked silicone gums are also available in a pre-emulsified form, which is advantageous for ease of formulation. A preferred example is the material available from Dow Corning as DC X2-1787, which is an emulsion of cross-linked dimethiconol gum.

A particularly preferred silicone for use in the present invention is SM 555, which can be obtained from GE Silicones. SM 555 is a combination of Dimethiconol and Triethylamine (TEA) Dodecyl Benzene sulphonate. Other combinations of silicones and sulphonates may also be used in the compositions of the invention.

The compositions of the invention preferably comprise one or more cleansing surfactants that are cosmetically acceptable and suitable for topical application to the hair.

Further surfactants may be present as an additional ingredient if sufficient for cleansing purposes is not provided as emulsifier for any emulsified components in the composition, e.g. emulsified silicones. It is preferred that the compositions of the invention comprise at least one surfactant to provide a cleansing benefit.

Preferably the further surfactant is an anionic surfactant.

Suitable cleansing surfactants, which may be used singularly or in combination, are selected from anionic, amphoteric and zwitterionic surfactants, and mixtures thereof. The cleansing surfactant may be the same surfactant as the emulsifier, or may be different.

In one embodiment of the invention, there is provided a shampoo composition comprising: an anionic surfactant in an amount of from 1% to 50% by weight; an amphoteric surfactant in an amount of from 0.1% to 10% by weight; beeswax in an amount of from 0.1% to 10% by weight; and a silicone in an amount of from 0.1% to 10% by weight.

Examples of anionic 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-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 contain from 1 to 10 ethylene oxide or propylene oxide units per molecule. Typical anionic surfactants for use in the compositions of the invention include sodium oleyl succinate, 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, triethanolamine monolauryl phosphate, sodium lauryl ether sulphate 1 EO, 2EO and 3EO, ammonium lauryl sulphate and ammonium lauryl ether sulphate 1EO, 2EO and 3EO.

Examples of amphoteric and zwitterionic surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines) , alkyl glycinates, 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 invention include lauryl amine oxide, cocodimethyl sulphopropyl betaine and preferably lauryl betaine, cocamidopropyl betaine (CAPB) and sodium cocamphopropionate. The composition of the invention can also include co- surfactants, to help impart aesthetic, physical or cleansing properties to the composition. A preferred example is a nonionic surfactant, which can be included in an amount ranging from 0% to about 5% by weight of the total composition.

A preferred combination of surfactants for use in the present invention is sodium lauryl ether sulphate (SLES) 2E0, cocamidopropyl betaine (CAPB) and sodium cocoamphoacetate. SLES is preferably present in an amount of from 5 to 20% by weight, CAPB is preferable present in an amount of from 1 to 5% by weight and sodium cocoamphoacetate is preferably present in an amount of from 1 to 5% by weight.

For example, representative nonionic surfactants that can be included in the compositions of the invention include condensation products of aliphatic (C8 to C18) 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.

Other representative nonionics 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 the 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: 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.

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 C_i2. Most preferably the value of R lies between about 9.5 and about 10.5. G may be selected 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.

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.

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.

The total amount of surfactant (including any co-surfactant, and/or any emulsifier) in the compositions of the invention is generally from 0.1 to 50% by weight, preferably from 5 to 30%, more preferably from 10% to 25% by weight of the total composition.

A cationic deposition polymer is a preferred ingredient in the compositions of the invention, for example for enhancing conditioning performance of the composition of the invention. By "deposition polymer" it is meant an agent which can enhance deposition of, for example, the silicone or anti-dandruff component from the shampoo composition onto the intended site during use, i.e. the hair and/or the scalp. The deposition polymer may be a homopolymer or be formed from 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 amino groups, or a mixture thereof.

The cationic nitrogen-containing group will generally be present as a substituent on a fraction of the total monomer units of the deposition polymer. Thus when the polymer is not a homopolymer it can contain spacer non-cationic monomer 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.

Suitable cationic deposition 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 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.

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.

Amine substituted vinyl monomers and amines can be polymerized in the amine form and then converted to ammonium by quaternization.

The cationic deposition polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers .

Suitable cationic deposition polymers include, for 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 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) ;

- 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) ;

- cationic diallyl quaternary ammonium-containing polymers including, for example, dimethyldiallyammonium chloride homopolymer and copolymers of acrylamide and - IS

dimethyldiallylammonium chloride, referred to in the 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 to 5 carbon atoms, (as described in U.S. Patent 4,009,256);

- cationic polyacrylamides (as described in W095/22311) .

Other cationic deposition polymers that can be used include cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives.

Cationic polysaccharide polymers suitable for use in compositions of the invention include those of the formula:

A-0-[R-N⁺(R¹) (R²) (R³)X^~],

wherein: A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual. R is an alkylene, oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof. R¹, R² and R³ independently represent alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms. The total number of carbon atoms for each cationic moiety (i.e., the sum of carbon atoms in R¹, R² and R³) is preferably about 20 or less, and X is an anionic counterion. Cationic cellulose is available from Amerchol Corp. (Edison, NJ, USA) in their Polymer JR (trade mark) and LR (trade mark) series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 10. Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corp. (Edison, NJ, USA) under the tradename Polymer LM-200.

Other suitable cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers (e.g. as described in U.S. Patent 3,962,418), and copolymers of etherified cellulose and starch (e.g. as described in U.S. Patent 3,958,581) .

A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimonium chloride (Commercially available from Rhodia (formerly Rhone-Poulenc) in their JAGUAR trademark series) .

Examples are JAGUAR C13S, which has a low degree of substitution of the cationic groups and high viscosity. JAGUAR C15, having a moderate degree of substitution and a low viscosity, JAGUAR C17 (high degree of substitution, high viscosity) , JAGUAR C16, which is a hydroxypropylated cationic guar derivative containing a low level of substituent groups as well as cationic quaternary ammonium groups, JAGUAR 162 which is a high transparency, medium viscosity guar having a low degree of substitution and JAGUAR CHT, which is a transparent Jaguar.

Preferably the cationic deposition polymer is selected from cationic cellulose and cationic guar derivatives.

Particularly preferred deposition polymers are JAGUAR CHT, JAGUAR C13S, JAGUAR C15, JAGUAR C17 and JAGUAR C16 and JAGUAR C162.

The cationic deposition polymer will generally be present at levels of from 0.001 to 5%, preferably from about 0.01 to 1%, more preferably from about 0.02% to about 0.5% by weight of the total composition.

Suitable solid active agents that may be incorporated into compositions of the invention include pigment particles, such as solid dyes or colorants suitable for application to hair, and metal colloids.

The shampoos of the present invention may be opacified or pearlised to enhance consumer appeal.

Examples of opacifying agents include higher fatty alcohols (e.g. cetyl, stearyl, arachidyl and behenyl) , solid esters (e.g. cetyl palmitate, glyceryl laurate, stearamide MEA- stearate) , high molecular weight fatty amides and alkanolamides and various fatty acid derivatives such as propylene glycol and polyethylene glycol esters. Inorganic materials used to opacify hair treatment compositions include magnesium aluminium silicate, zinc oxide, and titanium dioxide.

Pearlescing agents typically form thin, platelet-type crystals in the composition, which act like tiny mirrors. This gives the pearl lustre effect. Some of the opacifying agents listed above may also crystallise as pearlescing agents, depending on the media in which they are used and the conditions employed.

Typical pearlescing agents may be selected from C16-C22 fatty acids (e.g. stearic acid, myristic acid, oleic acid and behenic acid) , esters of C16-C22 fatty acid with alcohols and esters of C16-C22 fatty acid incorporating such elements as alkylene glycol units. Suitable alkylene glycol units may include ethylene glycol and propylene glycol. However, higher alkylene chain length glycols may be employed. Suitable higher alkylene chain length glycols include polyethylene glycol and polypropylene glycol.

Examples are polyethylene glycol mono or diesters of C16-C22 fatty acids having from 1 to 7 ethylene oxide units, and ethylene glycol esters of C16-C22 fatty acids. Preferred esters include polyethylene glycol distearates and ethylene glycol distearates. Examples of a polyethylene glycol distearate available commercially are EUPERLAN PK900 (ex Henkel) or GENAPOL TS (ex Hoechst) . An example of an ethylene glycol distearate is EUPERLAN PK3000 (ex Henkel) .

Other pearlescing agents include alkanolamides of fatty acids having from 16 to 22 carbon atoms, (e.g. stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate) ; long chain esters of long chain fatty acids (e.g. stearyl stearate, cetyl palmitate) ; glyceryl esters (e.g. glyceryl distearate) , long chain esters of long chain alkanolamides (e.g. stearamide DEA distearate, stearamide MEA stearate), and alkyl (C18-C22) dimethyl amine oxides (e.g. stearyl dimethyl amine oxide) .

Further suitable pearlescing agents include inorganic materials such as nacreous pigments based on the natural mineral mica. An example is titanium dioxide coated mica. Particles of this material may vary in size from 2 to 150 microns in diameter. In general, smaller particles give rise to a pearly appearance, whereas particles having a larger average diameter will result in a glittery composition.

Suitable titanium dioxide coated mica particles are those sold under the trade names TIMIRON (merck) or FLAMENCO (Mearl) .

The level of opacifying or pearlescing agent employed in compositions of the invention is generally from 0.01 to 20%, preferably 0.01 to 5%, more preferably from 0.02 to 2% by weight of the total composition.

Gas (e.g. air) bubbles represent another type of suspended phase that may be introduced into a shampoo composition for aesthetic purposes. When evenly sized and homogeneously dispersed in the composition, these can enhance consumer appeal. Compositions of this invention may contain any other ingredient normally used in hair treatment formulations. These other ingredients may include viscosity modifiers, preservatives, colouring agents, polyols such as glycerine and polypropylene glycol, chelating agents such as EDTA, antioxidants, fragrances and sunscreens. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally these optional ingredients are included individually at a level of up to about 5% by weight of the total composition.

Preferably, compositions of this invention also contain adjuvants suitable for hair care. Generally such ingredients are included individually at a level of up to

2%, preferably up to 1%, by weight of the total composition.

Among suitable hair care adjuvants, are: (i) natural hair root nutrients, such as amino acids and sugars. Examples of suitable amino acids include arginine, cysteine, glutamine, glutamic acid, isoleucine, leucine, methionine, serine and valine, and/or precursors and derivatives thereof. The amino acids may be added singly, in mixtures, or in the form of peptides, e.g. di- and tripeptides. The amino acids may also be added in the form of a protein hydrolysate, such as a keratin or collagen hydrolysate. Suitable sugars are glucose, dextrose and fructose. These may be added singly or in the form of, e.g. fruit extracts. A particularly preferred combination of natural hair root nutrients for inclusion in compositions of the invention is isoleucine and glucose. A particularly preferred amino acid nutrient is arginine.

(ii) hair fibre benefit agents. Examples are:

- ceramides, for moisturising the fibre and maintaining cuticle integrity. Ceramides are available by extraction from natural sources, or as synthetic ceramides and pseudoceramides. A preferred ceramide is Ceramide II, ex Quest. Mixtures of ceramides may also be suitable, such as Ceramides LS, ex Laboratoires Serobiologiques .

(iii) natural or synthetic oils, such as esters of fatty acids and/or fatty alcohols, containing from 12 to 30 carbon atoms in the ester. An example of a synthetic oil is isopropyl myristate. An example of a natural oil is sunflower seed oil.

The compositions of the invention comprise water, preferably distilled or deionised, preferably in an amount of from 30% by weight to 99.97% by weight of the total composition, more preferably, from 50% to 95% by weight, particularly preferably from 60% to 90% by weight.

The invention will now be further illustrated by the following, non-limiting examples. In the examples and throughout this specification, all percentages are percentages by weight unless otherwise indicated. EXAMPLES :

TESTING SMOOTHNESS AND EASE OF COMBING:

In the following examples the compositions of the invention were compared by 12 panellists in a double-blind switch test study to a comparative commercial composition regarding the properties of smoothness and ease of combing of the hair switch and then scored by the panellists.

SMOOTHNESS TEST PROTOCOL

Low density hair switches treated with the compositions of the present invention or the comparative compositions are presented in pairs to a panel of assessors for comparison. The assessors are asked to "clasp" the switch between the index and fore-fingers and stroke down the length of each switch without looking at the switches and judge which switch feels the smoothest.

Apparatus

1. 6.67g/25cm hair switches (3 per each composition) made from Red Tie Yugoslavian hair. 2. Horizontal bar with clips for suspending hair switches.

3. Test matrix.

4. Panel of assessors.

5. Plastic comb (8 teeth/cm, tooth width 0.025cm). Operator Bias

The test should be conducted double blind to avoid the possibility of the test operator (person conducting the test) influencing the assessor's (person judging the different products) decision.

Procedure

1. Prior to carrying out the test, the switches are balanced to ensure that there are no "rogue" switches within the set. Wash each switch with 2 x 0.5ml 16% SLES 2EO and leave to dry, either in an oven set at 50 °C for 1 hour or at room temperature overnight.

2. According to the test matrix, suspend the switches in pairs from the horizontal bar (first switch on the left) .

3. Ask the panellist to close their eyes and "clasp" the switch between the index and fore fingers of their non- writing hand and stroke down each switch in turn. Then ask the assessor to judge which of the switches felt the smoother. A "no difference" judgement is not allowed.

4. The results are analysed using the computer program VITRO.

5. If no significant differences are found between the set of 3 switches, then proceed to 6. If significant differences are found, identify the "rogue" switch(es). Repeat the balancing procedures with a second wash with 2 x 0.5ml 16% SLES 2EO. If differences are found again, then new switches are required.

6. Treat the switches accordingly with the compositions of the invention and the comparative compositions and repeat steps 2 to 4.

Basic Formulation:

Example 1 :

0.5% beeswax (processed beeswax from Koster Keunen Inc.) and 1.0% SM 555 silicone (from GE Silicones) were added to the basic formulation.

Example 2 :

0.5% beeswax (processed beeswax from Koster Keunen Inc.) and 2.0% SM 555 (from GE Silicones) were added to the basic formulation.

Example 3 :

1.0% beeswax (processed beeswax from Koster Keunen Inc.) and 0.5% SM 555 (from GE Silicones) were added to the basic formulation.

Example 4 : 0.5% beeswax (processed beeswax from Koster Keunen Inc.) and 0.5% SM 555 (from GE Silicones) were added to the basic formulation.

Claims

Claims :

l.A shampoo composition comprising: an anti-dandruff agent in an amount of from 0.01% to 10% by weight; beeswax in an amount of from 0.01% to 10% by weight; and a silicone in an amount of from 0.01% to 10% by weight.

2. Composition according to Claim 1, wherein the weight ratio of beeswax to silicone is from 1:4 to 3:1.

3. Composition according to Claim 1 or 2, wherein the weight ratio of beeswax to silicone is from 1.5:1 to 2.5:1.

4. Composition according to any one of Claims 1 to 3, wherein the weight ratio of beeswax to silicone is about 2:1.

5. Composition according to any one of Claims 1 to 4, wherein the anti-dandruff agent is dissolved in the composition.

6. Composition according to Claim 5, wherein the anti- dandruff agent is selected from the group consisting of ketoconazole, climbazole and mixtures thereof.

7. Composition according to any one of Claims 1 to 6, wherein the anti-dandruff agent is climbazole.

8. Composition according to any one of Claims 1 to 7, which comprises an anionic surfactant.

9. Composition according to any one of Claims 1 to 8, wherein the beeswax is suspended in the composition as solid particles.

10. Composition according to any one of Claims 1 to 9, wherein the total amount of beeswax and silicone in the composition is greater than 1.0% by weight of the total composition.

11. The use of a combination of beeswax and silicone in a shampoo composition to provide one or more properties selected from increased mildness, improved foam quality, improved conditioning and improved hair manageability benefits .

12. The use of beeswax and silicone in an anti-dandruff shampoo composition to provide improved foam properties and effective deposition of an antidandruff agent.

13. Use according to Claim 11 or 12, wherein the weight ratio of beeswax to silicone is from 1:4 to 3:1.