GB2431103A - Skin foundation composition - Google Patents

Abstract

The cosmetic composition comprises a transition metal and/or lanthanide doped with metal ions that impart optical absorption characteristics on the oxide. Preferably the dopant ions are Manganese (Mn), Vanadium (V) or Chromium (Cr). The metal oxide is preferably zinc (ZnO) or titanium (TiO2). The composition is intended for use as a skin toning or anti-wrinkle agent.

Description

COSMETIC COMPOSITIONS

The present invention relates to cosmetic compositions, particularly foundation and/or anti-wrinkle skin care compositions.

It is desirable that cosmetic formulations have a colour, or skin tone, that corresponds with, or enhances, the natural skin colour of the wearer. The aim might be to modify colour or to hide blemishes or wrinkles or to make skin look healthy or otherwise obtain uniformity, or any combination of these aims. A variety of pigments has been used in cosmetic formulations to achieve these effects by balancing absorption ans scattering events, for instance iron oxides for absorption or titanium oxide for enhanced scattering. The anti-wrinkle effect that is attainable by the present invention is not fully understood, although it is believed that it results at least in part from a reduction in the visible effect of wrinkles, or other skin surface irregularities, rather than by reducing the wrinkles themselves or by filling them in. This is thought to be due to the precise way in which light is reflected and scattered, giving rise to a soft-focus effect.

However, some of the effect may be due additionally to some filling of the troughs of the wrinkles.

Many cosmetic formulations serve as foundation formulations and have one or more additional functions, for example as perfumes, moisturisers and sunscreens etc. It is clearly desirable that unnecessary complexity in formulation be avoided, and the present invention is able to reduce complexity by making use of a previously unrealized characteristic of certain specific components previously proposed for use in sunscreens.

Other cosmetic formulations which require particulate loading, such as anti- wrinkle creams, are available by use of this invention. In previous cases such formulations would introduce unacceptable skin whitening.

Reference may be made to WO 2004/05 8209 of the present applicant. That document, relevant details of which are set out below, relates to a UV sunscreening composition suitable for cosmetic or topical pharmaceutical use which comprises an amount of one or more organic components which are photosensitive andlor which are degraded and/or in which degradation is induced by another ingredient of the composition, and an amount of Ti02 and. ZnO which has been doped with one or more other elements and/or reduced zinc oxide, this composition having a rate of TJV loss at least 5% less than that of a composition having the same formulation except that it does not contain the said Ti02 and/or ZnO which has been doped with another element or the said reduced zinc oxide.

Although it was known that doped Ti02/ZnO is coloured, and a suggestion is made in WO 2004/058209 that such material can be used in skin lightening compositions, there was no realization that one or more of Ti02, ZnO and CeO2 (or other transition and/or lanthanide metal oxide), doped in particular with one or more of Mn3, V5 or Cr should themselves be used as a skin toning agent and/or a wrinkle-masking agent, particularly in compositions containing substantially no component that significantly masks the absorbance characteristics of the doped material in the visible spectrum or contains other highly scattering particulate material.

Thus, the present invention provides the use as a skin toning agent and/or as a wrinkle-masking agent in a cosmetic formulation of a transition and/or lanthanide metal oxide (particularly one or more of Ti02 ZnO and CeO2) doped with one or more ions (particularly one of more of Mn2, V5 and Cr) that impart optical absorption characteristics to the oxide. Such absorption characteristics will generally be noticeable in addition to the usual, or modified scattering, properties of the material.

The present invention also provides the use of a safe and effective amount of a skin toning agent and/or wrinkle-masking agent in a cosmetic formulation of a transition and/or lanthanide metal oxide doped with one or more ions that impart optical absorption characteristics to the oxide and a safe and effective amount of one or more skincare active agents.

Particularly where the composition is a foundation composition, it is preferably applied to the skin at an amount of 0.05 to 6, more preferably 0.05 to 4, especially 0.05 to 2.5, particularly ito 2.5, often 1.5 to 2.5 mg per sq cm of skin.

As mentioned above, we prefer that the cosmetic formulation contains substantially no component that significantly masks the absorbance characteristics of the doped oxide in the visible spectrum, particularly between 390 and 470 nm, preferably between 290 and 550 nm.

The extent to which the doped oxide provides a toning effect will generally depend on its concentration in the formulation, and we generally prefer the cosmetic formulation to contain from 0.05 to 20, typically 0.1 to 20, more preferably 0.5 to 20, often 0.5 to 10% by weight of the doped Ti02 and/or ZnO and/or CeO2 aridlor other oxide.

The extent to which the doped oxide provides a wrinkle-masking effect will generally depend on its concentration in the formulation, arid we generally prefer the cosmetic formulation to contain from 0.1 to 10% by weight of the doped Ti02 andlor ZnO and/or CeO2 and/or other oxide.

The extent of doping will also have an effect, and we prefer that the doped Ti02 and/or ZnO and/or CeO2 and/or other oxide contain from 0.4 to 1 mole % of Mn3 and/or V5 and/or Cr3 and/or other dopant.

The particle size of material used in formulations is also of importance. The interaction of light with the particle is a balance of absorption and reflection. If the particle size is lower than approximately one fifth of the wavelength of light then reflectance is governed by Raleigh scattering and is proportional to the fourth power of the frequency of the light (i.e. blue light scatters more than red). This particle size range is preferably below approximately 200, especially below 150, usually below 120mm Above this particle size scattering is only weakly frequency-dependent, and is governed by Mie scattering which has a strong forward lobe component. Particles of this size appear as a visible layer on the skin. Absorption is due to the density of energy levels within the electronic structure of the particle, and is responsible for giving colour to the material. It should be appreciated that the appearance of the formulation on the skin is a balance of absorption and scattering, and that various grades of powders can be blended to achieve the required effect.

The formulations achieve maximum effect by utilizing Raleigh rather than Mie scattering. To that end, we prefer that the particles have a particle size of 15 to 200 nm, typically 15 to 150, more preferably 50 to 100 nm. Particle size is given as a diameter in the case of spherical particles, or as the diameter of spherical particles of the same volume in the case of non-spherical particles.

The invention also provides a cosmetic formulation which comprises a transition and/or lanthanide metal oxide (particularly one or more of Ti02, ZnO and CeO2) doped with one or more ions (particularly one of more of Mn2, V5 and Cry) that impart absorption characteristics and a carrier, the formulation containing substantially no component that significantly masks absorption characteristics of the doped oxide in the visible spectrum.

The formulation will in general provide the benefit of sun screening properties as a result of the presence of the doped oxide.

An additional, related, benefit is the stabilisation of the formulation of the foundation.

Degradation of organic agents by UV light can be retarded if the compositions also have present an oxide such as those referred to above that has been doped by another element such as those the ions of which are referred to above.

The organic agents may include additional organic sunscreen agents incorporated into the foundation formulation. Accordingly, the invention disclosed in WO 2004/05 8209 provides a UV sunscreening composition suitable for cosmetic or topical pharmaceutical use referred to above.

A further feature, disclosed in WO 2004/05 8209, resides in the fact that doped Ti02/ZnO is generally coloured. As a result the use of such doped materials causes the composition to absorb more of the visible light which impinges upon it i.e. less visible light is transmitted and reaches the skin. Further in certain countries coloured formulations are advantageous. It was noted that in skin lightening compositions in Japan, a pink colouration is useful in masking uneven colouration of the underlying skin.

In Indonesia a yellow colouration can be seen as attractive. In the present invention, the compositions will in general be skin toning compositions. The use of undoped Ti02 ZnO and CeO2 in cosmetic formulations is limited to low loading therein of the particulate materials. This is due to a "blue-white" tone being imparted to the skin, which is seen as being undesirable. The blue-white colouration is a direct result of Raleigh scattering enhancement of the blue light component. This effect can be mitigated by incorporating doped materials in conjunction with undoped materials to balance the enhanced blue scattering with blue absorption by the doped material. In WO 2004/058209 it was suggested that if colour is to be minimised this can be achieved by coating the particles andlor by controlling the concentration of doping, both as discussed below. In the present invention the doped oxide particles are preferably not coated unless this is necessary for successful formulation.

The optimum amount of the other element in the host lattice may be determined by routine experimentation and in some embodiments is preferably low enough so that the particles are not coloured. Amounts as low as 0.1 mole % or less, for example 0.05 mole %, or as high as 1 mole % or above, for example 5 mole % or 10 mole %, can generally be used. However, we currently prefer 0.4 to 2 mole %.

The particles can be obtained by any one of the standard processes for preparing doped oxides and salts. Thus they can be obtained by a baking technique by combining particles of a host lattice (Ti02/ZnO/Ce02) with a second component in the form of a salt such as a chloride or an oxygencontaining anion such as a perchlorate or a nitrate, in solution or suspension, typically in solution in water, and then baking it, typically at a temperature of at least 3 00 C. Other routes which may be used to prepare the doped materials include a precipitation process of the type described in J. Mat. Sci. (1997) 36, 6001-6008 where solutions of the dopant salt and of an alkoxide of the host metal (Ti/Zn) are mixed, and the mixed solution is then heated to convert the alkoxide to the oxide. Heating is continued until a precipitate of the doped material is obtained. Further details of preparation can be found in WO 99/60994 and WO 01/40114.

Doped Ti02/ZnO/Ce02 can also be obtained by flame pyrolysis or by plasma routes where mixed metal containing precursors at the appropriate level are exposed to a flame or plasma to obtain the desired product.

The rutile form of titania is known to be more photostable than the anatase fonri and is therefore preferred.

The oxide particles used in the present invention may have an inorganic or organic coating. For example, the particles may be coated with oxides of elements such as aluminium, zirconium or silicon, especially silica. The particles of metal oxide may also be coated with one or more organic materials such as polyols, amines, alkanolamines, polymeric organic silicon compounds, for example, RSi[{OSi(Me)2}xOR']3 where R is C1-C10 alkyl, R' is methyl or ethyl and x is an integer of from 4 to 12, hydrophilic polymers such as polyacrylamide, polyacrylic acid, carboxymethyl cellulose and xanthan gum or surfactants such as, for example, TOPO.

Such coatings can have the disadvantageous effect of masking, at least to some extent, any colour which the doped particles may have.

The compositions for cosmetics use are preferably foundation compositions.

However, they may be, for example, skin anti-ageing compositions or antiwrinkle compositions. The compositions may be in the form of, for example, creams, lotions, face powders and preparations for the hands including creams and lotions, moisturising preparations, and gels, serums and sunscreens. The compositions may also be pharmaceutical compositions suitable for topical application. Such compositions are useful, in particular, for patients suffering from disorders of the skin.

The metal oxides are preferably present in such compositions at a concentration of about 0.1 to 25 % by weight, preferably 0.5 to 25, more preferably about 1 to 10 % by weight and yet more preferably about 3 to 8 % by weight, in particular about 4 to 7%, such as 4 to 6% for example about 5%, by weight.

The compositions may be in the form of, for example, lotions, typically with a viscosity of4000 to 10,000 mPas, e.g. thickened lotions, gels, vesicular dispersions, creams, typically a fluid cream with a viscosity of 10,000 to 20,000 mPas or a cream of viscosity 20,000 to 100,000 mPas, milks, powders, solid sticks, and maybe optionally packaged as aerosols and provided in the form of foams or sprays.

The compositions may contain any of the ingredients conventionally used in such formulations including fatty substances, organic solvents, silicones, thickeners, liquid and solid emollients, demulcents, other UVA, TJVB or broad-band sunscreen agents, antifoaming agents, antioxidants such as butyl hydroxy toluene, buffers such as lactic acid with a base such as triethanolamine or sodium hydroxide, plant extracts such as Aloe vera, cornflower, witch hazel, elderfiower and cucumber, activity enhancers, moisturizing agents, and humectants such as glycerol, sorbitol, 2-pyrrolidone-5-carboxylate, dibutylphthalate, gelatin and polyethylene glycol, perfumes, preservatives, such as para-hydroxy benzoate esters, surface-active agents, fillers and thickeners, sequesterants, anionic, cationic, nonionic 1 5 or amphoteric polymers or mixtures thereof, propellants, alkalizing or acidifying agents, colorants and powders, including metal oxide pigments with a particle size of from 100 nm to 20000 nm such as iron oxides along with conventional (undoped) Ti02 and ZnO.

Other ingredients of cosmetic compositions, for example some surfaceactive agents may have the effect of degrading certain organic agents in the presence of UV light. Also Ti02 and ZnO are known to degrade certain organic sunscreens such as avobenzone as well as antioxidants such as vitamins e.g. vitamins A, B, C and E and antiageing factors such as niacinamide, retenoids, coenzyme MEQIO etc. It will be appreciated that it is particularly useful to use the doped oxides with such agents. This is because the oxides specified herein do generally have a positive UV absorptive and free-radical scavenging effect. Thus by using the doped oxide it may be possible to use less antioxidant or make the formulation longer lasting.

The organic solvents are typically chosen from lower alcohols and polyols such as ethanol, isopropanol, propylene glycol, glycerin and sorbitol as well as methylene chloride, acetone, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-ethyl, ether, dimethyl suiphoxide, dimethyl formamide arid tetrahydrofurari.

The fatty substances may consist of an oil or wax or mixture thereof, fatty acids, fatty acid esters, fatty alcohols, vaseline, paraffin, lanolin, hydrogenated lanolin or acetylated lanolin, beeswax, ozokerite wax and paraffin wax.

The oils are typically from animal, vegetable, mineral or synthetic oils and especially hydrogenated palm oil, hydrogenated castor oil, vaseline oil, paraffin oil, Purcellin oil, silicone oil such as polydimethyl siloxanes and isoparaffin.

The waxes are typically animal, fossil, vegetable, mineral or synthetic waxes. Such waxes include beeswax, Carnauba, Candelilla, sugar cane or Japan waxes, ozokerites, Montan wax, microcrystalline waxes, paraffins or silicone waxes and resins.

The fatty acid esters are, for example, isopropyl myristate, isopropyl adipate, isopropyl palmitate, octyl palmitate, C12-C15 fatty alcohol benzoates ("Finsolv TN" from Finetex), oxypropylenated myristic alcohol containing 3 moles of propylene oxide ("Witconol APM" from Witco), capric and caprylic acid triglycerides ("Miglyol 812" from Huls). "Finsolve TN", "Witconol APM" and Miglyol 812" are trade marks.

The compositions may also include silicone elastomers and cross-linked silicones such as Silicone Elastomer 9040 (trade mark) from Dow Corning or Silicone KSG 710 (trade mark) from Shin Etsu.

The compositions may also contain thickeners such as cross-linked or non cross- linked acrylic acid polymers, and particularly polyacrylic acids which are cross-linked using a polyfunctional agent, such as the products sold under the name "Carbopol" (trade mark) by the company Goodrich, cellulose, derivatives such as methylcellulose, hydroxymethylcellulose, hydroxypropyl methylcellulose, sodium salts of carboxymethyl cellulose, or mixtures of cetyistearyl alcohol and oxyethylenated cetyistearyl alcohol containing 33 moles of ethylene oxide.

Desirably, the weight ratio of water-dispersible titanium dioxide to oildispersible titanium dioxide is from 1:4 to 4:1, preferably from 1:2 to 2:1 and ideally about equal weight proportions.

Suitable emollients include stearyl alcohol, glyceryl monoricinoleate, mink oil, cetyl alcohol, isopropyl isostearate, stearic acid, isobutyl palmitate, isocetyl stearate, oleyl alcohol, isopropyl laurate, hexyl laurate, decyl oleate, octadecan-2-ol, isocetyl alcohol, eicosanyl alcohol behenyl alcohol, cetyl palmitate, silicone oils such as dimethylpolysi loxane, di-n-butyl sebacate, isopropyl myristate, i sopropyl palmitate, isopropyl stearate, butyl stearate, polyethylene glycol, triethylene glycol, lanolin, cocoa butter, corn oil, cotton seed oil, olive oil, palm kernel oil, rapeseed oil, safflower seed oil, evening primrose oil, soybean oil, sunflower seed oil, avocado oil, sesame seed oil, coconut oil, arachis oil, caster oil, acetylated lanolin alcohols, petroleum jelly, mineral oil, butyl myristate, isostearic acid, palmitic acid, isopropyl linoleate, lauryl lactate, myristyl lactate, decyl oleate, myristyl myristate.

Suitable propellants include propane, butane, isobutane, dimethyl ether, carbon dioxide, nitrous oxide.

Suitable powders include chalk, talc, fullers earth, kaolin, starch, gums, colloidal silica sodium polyacrylate, tetra alkyl andlor trialkyl aryl ammonium smectites, chemically modified magnesium aluminium silicate, organically modified montmorillonite clay, hydrated aluminium silicate, fumed silica, carboxyvinyl polymer, sodium carboxyrnethyl cellulose, ethylene glycol monostearate.

When the compositions of the present invention are foundation compositions they may be in the form of, for example, suspensions or dispersions in solvents or fatty substances or as emulsions such as creams or milks, in the form of ointments, gels, solid sticks or aerosol foams. The emulsions, which can be oil-in-water or water-in-oil emulsions, may further contain an emulsifier including anionic, nonionic, cationic or amphoteric surface-active agents; for a water-in-oil emulsion the HLB is typically from 1 to 6 while a larger value i.e >6 is desirable for an oil-in-water emulsion. Generally water amounts to up to 80%, typically 5 to 80%, by volume. Specific emulsifiers which can be used include sorbitan trioleate, sorbitari tristearate, glycerol monooleate, glycerol monostearate, glycerol monolaurate, sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate, polyoxyethylene (2) stearyl ether, polyoxyethylene sorbitol beeswax derivative, PEG 200 dilaurate, sorbitan monopalmitate, polyoxyethylen (3.5) nonyl phenol, PEG 200 monostearate, sorbitan monostearate, sorbitan monolaurate, PEG 400 dioleate, polyoxyethylene (5) monostearate, polyoxyethyene (4) sorbitan monostearate, polyoxyethylene (4) lauryl ether, polyoxyethylene (5) sorbitan monooleate, PEG 300 monooleate, polyoxyethylene (20) sorbitan tristearate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (8) monostearate, PEG 400 monooleate, PEG 400 monostearate, polyoxyethylene (10) monooleate, polyoxyethylene (10) stearyl ether, polyoxyethylene (10) cetyl ether, polyoxyethylene (9.3) octyl phenol, polyoxyethylene (4) sorbitan monolaurate, PEG 600 monooleate, PEG 1000 dilaurate, polyoxyethylene sorbitol lanolin derivative, polyoxyethylene (12) lauryl ether, PEG 1500 dioleate, polyoxyethylene (14) laurate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) stearyl ether, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) cetyl ether, polyoxyethylene (25) oxypropylene monostearate, polyoxyethylene (20) sorbitol monolaurate, polyoxyethylene (23) lauryl ether, polyoxyethylene (50) monostearate, and PEG 4000 monostearate. Alternatively the emulsifier can be silicone surfactant such as Abil WE 07 (trade mark) from Goldschmidt AG, especially a dimethyl polysiloxane with polyoxyethylene andlor polyoxypropylene side chains, typically with a molecular weight of 10,000 to 50,000, especially cyclo-methicone and dimethicone copolyol. They may also be provided in the form of vesicular dispersions of ionic or nonionic amphiphilic lipids prepared according to known processes.

It can be advantageous to use both a water-dispersible and an oildispersible Ti02 and/or ZnO and/or CeO2 (etc), at least one of which is doped. It has been found that when an emulsion is spread on the skin it has a tendency to break down into oily and non-oily areas. When the water evaporates the oil-dispersible particles will tend to be in the oily areas thus leaving areas unprotected. This can be avoided by having both hydrophilic and hydrophobic particles in the emulsion so that some are retained in hydrophilic areas and others in hydrophobic areas.

Water-dispersible particles can be uncoated or coated with a material to impart a hydrophilic surface property to the particles. Examples of such materials include aluminium oxide and aluminum silicate. Oil-dispersible particles which exhibit a hydrophobic surface property, are suitably coated with metal soaps such as aluminium stearate, aluminium laurate or zinc stearate, or with organosilicone compounds Organic agents which can be used in the compositions include any conventional sunscreen agent which gives protection against UV light while if there is no other photosensitive component the sunscreen agent is photosensitive and/or is degraded by another ingredient of the composition. Suitable sunscreen agents are listed in the IARC Handbook of Cancer Prevention, vol. 5, Sunscreens, published by the International Agency for Research on Cancer, Lyon, 2001 and include: (a) Para-arninobenzoic acids (PABA), (TJVB absorbers) esters and derivatives thereof, for example amyldimethyl-; ethyldihydroxypropyl-; ethylhexyl dimethyl-; ethyl-; glyceryl-; and 4-bis-(polyethoxy)- PABA.

(b) Cinnamates (UVB) especially esters including methyl cinnamate esters and methoxycinnamate esters such as octylmethoxy cinnamate, ethyl methoxycinnainate, especially 2-ethyihexyl para-methoxycinnamate, isoarnyl p-methoxy cinnamate, or a mixture thereof with diisopropyl cinnamate, 2-ethoxyethyl -4-methoxycinnamate, DEA- methoxycinnamate (diethanolamine salt of para-methoxy hydroxycinnamate) or a,13-di- (para-m ethoxycinnamoyl)-a'-(2-ethylhex anoyl)-glycerin, as well as diisopropyl methylcinnamate; (c) benzophenones (UVA) such as 2,4-dihydroxy-; 2-hydroxy-4-methoxy; 2,2'- dihydroxy-4,4'-dimethoxy-; 2,2'-dihydroxy-4-methoxy-;' 2,2',4,4'- tetrahydroxy-; and 2hydroxy-4-methoxy-4'-methyl-benzophenones,benzenesulphonic acid and its sodium salt; sodium 2,2'-dihydroxy-4,4'-dimethoxy-5 -sulphobenzophenone and oxybenzone; (d) dibenzoylmethanes (UVA) such as butyl methoxydibenzoyl methane, especially 4-tert-butyl-4'methoxydibenzoylmethane; (e) 2-phenylbenzimidazole-5 sulfonic acid UVB and phenyldibenzimidazole sulfonic acid and their salts; (f) alkyl-J3,3-diphenylacrylates (UVB) for example alkyl a-cyano-13, 13- diphenylacrylates such as octocrylene; (g) triazines (IJYB) such as 2,4,6-trianilino--carbo-2-ethyl-hexyl-1-oxy)1,3,5 triazine as well as octyl triazone e.g. ethyihexyltriazone and diethylhexyl butamido triazone.

(h) camphor derivatives (generally UVB) such as 4-rnethylbenzylidene and 3- benzylidene- camphor and terephthalylidene dicamphor sulphonic acid (UVA), benzylidene camphor suiphonic acid, camphor benzalkonium methosulphate and polyacrylamidomethyl benzylidene camphor; (i) organic pigment sunscreening agents such as methylene bis- benzotriazole tetramethyl butylphenol; (j) silicone based sunscreening agents such as dimethicodiethyl benzal malonate.

(k) salicylates (UVB) such as dipropylene glycol-; ethylene glycol-, ethyihexyl-, isopropylbenzyl-, methyl-, phenyl-, 3,3,5-trimethyl- and TEA-salicylate (compound of 2- hydroxybenzoic acid and 2,2'2"-nitrilotris (ethanol)); (I) anthranilates (TJVA) such as menthyl anthranilate as well as bisymidazylate (UVA), dialkyl trioleate (UVB), 5-methyl-2-phenylberizoxazole (IJVB) and urocanic acid (UVB).

Some compounds are effective for both UVA and UVB. These include anisotriazine, methylene bisbenzotriazolyl tetramethylbutyl- phenol and drometrizole trisiloxane (Mexoryl XL).

The organic sunscreen agent(s) are typically present in the compositions at a concentration from 0.1 to 20%, preferably 1 to 10%, and especially 2 to 5%, by weight based on the weight of the composition.

The present invention is further illustrated by the following examples.

Example 1 - Anti-wrinkle Eye Cream %w/w Aqua to 100 Butylene glycol 6 Paraffinum liquidum 5 Dimethicone 2 Petrolutum 2 Cetearyl octanoate 1.8 Cetearyl alcohol 1.6 Glyceiyl stearate 1.5 Cetyl alcohol 1 Prunus dulcis 1 Glycerin 0.57 Hydrogenated vegetalle glycerides citrate 0.5 Tocopheryl acetate 0.5 Bisabolol 0.475 Panthenol 0.45 Sodium phosphate 0.42 PEG-20 stearate 0.4 Isopropyl myristate 0.2 Carbomer 0.15 PEG-12 isostearate 0. 125 Potassium hydroxide 0.051 Buutylmethoxy dibenzyl methane 2.9 Octyl methoxycinnamate 1.9 Optisol 0.5 Preservative q.s.

Method Stage 1 Into the water, citric acid, EDTA, sodium phosphate, disodium phosphate and lactic acid are added and dispersed. Using a homogeniser, carbomer is added and hydrated. The Optisol, Tac and iron oxides are added and homogenised to complete dispersion. The aqueous phase is then heated to 70 C.

Stage2 The paraffinum liquidum, octyl methoxycinnamate, dimethicone, petrolatum, cetearyl octanoate, cetearyl alcohol, glyceryl stearate, cetyl alcohol, hydrogenated vegetable glycerides citrate, tocopheryl acetate, PEG-20 stearate, isopropyl myristate, salicylate, dibenzoyl methane and PEG-12 isostearate are mixed and heated to 70 C to melt the waxes.

Stage 3 Using a homogeniser, stage 2 is added to stage 1 and this is mixed until emulsified and uniform. The emulsion is then cooled to below 35 C using stirring. The remaining materials are then added and mixed. The product is then made to weight using purified water and is stirred until uniform.

Example 2 Anti wrinkle Foundation %w/w Aqua to 100 Butylene glycol 9.8 Cetearyl isononanoate 4.9 Dimethicone 3.2 Glycerin 1.96 Silica 1.9 Caprylic/capric triglyceride 1.67 Paraffinum liquidum 1.67 Petrolatum 1. 67 Hydrogenated coco-glycerides 1.67 Cetearyl octanoate 1.5 Cetearyl alcohol 1.35 Iron Oxides 5 Talc 1 Glyceryl stearate 0.95 PEG-lOO stearate 0.9 Saccharide isomerate 0.54 Lactic acid 0.45 Sodium polyacrylate 0.45 Boron nitride 0.42 Sodium PCA 0.4 Borago officinalis 0.4 Tocopheryl acetate 0.4 PVP/hexadecene copolymer 0.4 PEG-20 stearate 0.33 Glycolic acid 0.2 Sodium stearoyl lactylate 0.2 Isopropyl myristate 0.17 Polyaminopropyl biguanide 0.16 Tetrasodium EDTA 0.1 Xanthan gum 0.1 Citric acid 0.06 Alcohol denat. 0.04 Lecithin 0.037 Optisol 1 Octocrylene 3 Butyl ni ethoxydibenzoyl methane 4.0 Ethyihexyl salicylate 2.5 Diethyihexylbutamido triazone 0.5 Method Stage 1 Into the water, citric acid, EDTA and lactic acid are added and dispersed. Xanthan gum is pre- dispersed in butylene glycol and is added to the bulk. The Optisol, Talc and Iron oxides are then added and homogenised. The aqueous phase is then heated to 70 C.

Stage 2 The cetearyl isononanoate, dimethicone, silica, PVP/hexadecene copolymer, caprylic/capric triglyceride, paraffinum liquidum, petrolatum, hydrogenated coco-glycerides, cetearyl octanoate, cetearyl alcohol, octyl methoxycirmamate, talc, glyceryl stearate, PEG- 100 stearate, butyl methoxydibenzoylmethane, borago officinalis, tocopheryl acetate, sodium stearoyl lactyl ate, isopropyl myristate, salicilate, dibenzoyl methane and Lecithin oil phase are mixed and heated to 70 C to melt the waxes.

Stage 3 Using a homogeniser, stage 2 is added to stage 1 and this is mixed until emulsified and unifonm The emulsion is then cooled to below 35 C using stifling. The remaining materials are then added and mixed. The product is then made to weight using purified water and is stined until uniform.

Example 3 - Anti- wrinkle UV protecting Eye Cream %w/w Aqua to 100 Butylene glycol 6 Paraffinum liquidum 5 Dimethicone 2 Petrolutum 2 Cetearyl octanoate 1.8 Cetearyl alcohol 1.6 Glyceryl stearate 1.5 Cetyl alcohol 1 Prunus dulcis 1 Glycerin 0.57 Hydrogenated vegetable glycerides citrate 0.5 Tocopheryl acetate 0.5 Bisabolol 0.475 Panthenol 0.45 Sodium phosphate 0.42 PEG-20 stearate 0.4 Isopropyl myristate 0.2 Carbomer 0.15 PEG-12 isostearate 0.125 Allantoin 0.1 Tetrasodium EDTA 0.1 Lactic acid 0. 088 Disodium phosphate 0.083 Potassium hydroxide 0.051 Octocrylene 3 Butyl methoxydibenzoyl methane 4.0 Ethylhexyl salicylate 2.5 Diethyihexyl butamido triazone 0.5 Optisol 1.0 Preservative q.s Method Stage 1 Into the water, citric acid, EDTA, sodium phosphate, disodium phosphate and lactic acid are added and dispersed. Using a hornogeniser, carbomer is added and hydrated. The talc, boron nitride and Iron Oxides are added and homogenised. The aqueous phase is then heated to 70 C.

Stage 2 The paraffinum liquidurn, octyl methoxycinnarnate, dimethicone, petrolatum, cetearyl octanoate, cetearyl alcohol, glyceryl stearate, cetyl alcohol, hydrogenated vegetable glycerides citrate, tocopheryl acetate, PEG-20 stearate, isopropyl myristate, salicylate, dibenzoyl methane and PEG-12 isostearate are mixed and heated to 70 C to melt the waxes.

The Optisol is then added and homogenised.

Stage 3 Using a homogeniser, stage 2 is added to stage 1 and this is mixed until emulsified and unifonm The emulsion is then cooled to below 35 C using stirring. The remaining materials, including the are then added and mixed. The product is then made to weight using purified water and is stirred until uniform.

Example 4 anti-wrinkle UV protecting Foundation %w/w Aqua to 100 Butyleneglycol 9.8 Cetearyl isononanoate 4.9 Dimethicone 3.2 Glycerin 1. 96 Silica 1.9 Caprylic/capric triglyceride 1.67 Paraffinum liquidum 1.67 Petrolatum 1.67 Hydrogenated coco-glycerides 1.67 Cetearyl octanoate 1.5 Cetearyl alcohol 1.35 Iron Oxides 7 Talc 1 Glyceryl stearate 0.95 PEG-IOU stearate 0.9 Saccharide isomerate 0.54 Lactic acid 0.45 Sodium polyacrylate 0.45 Boron nitride 0.42 Sodium PCA 0.4 Borago officinalis 0. 4 Tocopheryl acetate 0.4 PVP/hexadecene copo]ymer 0.4 PEG-20 stearate 0. 33 Glycolic acid 0.2 Sodium stearoyl lactylate 0.2 Isopropyl myristate 0. 17 Polyaminopropyl biguanide 0.16 Tetrasodium EDTA 0.1 Xanthan gum 0.1 Citric acid 0.06 Alcohol denat. 0.04 Lecithin 0.037 Preservative q.s Optisol 1 Isodecyl salicylate 10.0 Octocrylene 3 Butyl rnethoxydibenzoyl methane 4.0 Ethyihexyl salicylate 2.5 Diethyihexyl butamido triazone 0.5 Method Stage 1 Into the water, citric acid, EDTA and lactic acid are added and dispersed. Xanthan gum is pre-dispersed in butylene glycol and is added to the bulk. The aqueous phase is then heated to 70 C.

Stage 2 The cetearyl isononanoate, dimethicone, silica, PVP/hexadecene copolymer, caprylic/capric triglyceride, paraffinurn Ii quidum, petrolatum, hydrogenated coco-glycerides, cetearyl octanoate, ceteaiyl alcohol, octyl methoxycinnamate, talc, glyceryl stearate, PEG-100 stearate, butyl methoxydibenzoylmethane, borago officinalis, tocopheryl acetate, sodium stearoyl lactylate, isopropyl myristate, salicilate, dibenzoyl methane and Lecithin oil phase are mixed and heated to 70 C to melt the waxes. The optisol, talc, Boron Nitride and iron oxides are then added arid homogenised.

Stage 3 Using a homogeniser, stage 2 is added to stage 1 and this is mixed until emulsified and uniform. The emulsion is then cooled to below 35 C using stirring. The remaining materials are then added and mixed. The product is then made to weight using purified water and is stined until uniform.

Consumer trial formulations

Optisol example I

Keltrol 0.19 Carbopol 940 0.19 Sequestrene Na4 0.02 Methyl hydroxybenzoate 0.24 Glycerin BP 2.92 1,3-Butylene Glycol 1.46 Optisol 4.86 Water 68.02 Cithrol GMS 2.43 Syncrowax ERLC 1.94 Cetyl Alcohol 1.46 C12-15AB 4.86 Octyl salicylate 2. 43 Parsol MCX 4.86 Parsol 1789 2.92 Propyl hydroxybenzoate 0.15 Caustic potash soln 0.09 Phenonip 0.97 1. Add Carbopol 940 to water with stirring, then heat to 70-75 C. Homogenise until fully dispersed (phase A).

2. Disperse Keltrol in 1,3-butylene glycol (phase B) 3 Add B to A with stirring.

4 Dissolve Sequestrene Na4, Glycerin BP and methyl hydroxybenzoate in A Add Optisol to A, and homogenise until fully dispersed 6 Add Cithrol GMS, Syncrowax ERLC and Cetyl Alcohol to C12-15 alkyl benzoate and heat to 70-75 C until fully melted (phase C).

7 Ensure both oil and water phases are at 70-75 C 8 Just prior to emulisification, add Octyl salicylate, Parsol MCX and Parsol 1789 to phase

C

9 Add phase C to phase A and homogenize Add caustic potash solution 11 Add Phenonip and Propyl hydroxybenzoate

Control example 2

Keltrol 0.19 Carbopol940 0.19 Sequestrene Na4 0.02 Methyl hydroxybenzoate 0.24 GlycerinBP 2.92 1,3-Butylene Glycol 1.46 Titanium Dioxide T805 4.86 Water 68.02 Cithrol GMS 2.43 Syncrowax ERLC 1.94 Cetyl Alcohol 1.46 C12-15AB 4.86 Octyl salicylate 2.43 Parsol MCX 4.86 Parsol 1789 2.92 Propyl hydroxybenzoate 0. 15 Caustic potash soin 0.09 Phenonip 0.97 lAdd Carbopol 940 to water with stirring, then heat to 70-75C. Homogenise until fully dispersed (phase A).

2 Disperse Keltrol in I,3-butylene glycol (phase B) 3 Add B to A with stirring.

4 Dissolve Sequestrene Na4, Glycerin BP and methyl hydroxybenzoate in A Add T805 to A, and homogenise until fully dispersed 6 Add Cithrol GMS, Syncrowax ERLC and Cetyl Alcohol to C 12-15 alkyl benzoate and heat to 70-75C until fully melted (phase C).7 Ensure both oil and water phases are at 70- 75C 8 Just prior to emulisification, add Octyl salicylate, Parsol MCX and Parsol 1789 to phase

C

9 Add phase C to phase A and homogenize Add caustic potash solution 11 Add Phenonip and Propyl hydroxybenzoate Results Ten volunteers each applied one of the creams to each side of their faces, and were then asked to give their views on the products by means of a questionnaire. The responses are summarised in the following table.

________________________________ Optisol 1 Control 2 The Product % % % Agree Disagree Agree Disagree evens my skin tone 80 20 20 80 5...minimises fine lines and wrinkles 80 20 20 80 makes my skin look healthy and 80 20 40 60 natural

Claims (13)

1. The use as a skin toning agent and/or as a wrinkle-masking agent in a cosmetic formulation of a transition and/or lanthanide metal oxide doped with one or more ions that impart optical absorption characteristics to the oxide.

2. The use of a safe and effective amount of a skin toning agent and/or wrinkle- masking agent in a cosmetic formulation of a transition andlor lanthanide metal oxide doped with one or more ions that impart optical absorption characteristics to the oxide and a safe and effective amount of one or more skincare active agents.

3. The use according to claim I or 2, in which the cosmetic formulation is a foundation formulation.

4. The use according to claim 1,2 or 3, in which the formulation includes a sunscreen agent in addition to the doped oxide.

5. The use according to any preceding claim, in which the formulation contains a mixture of doped and undoped particles thereby providing specific optical properties.

6. The use according to claim 5, in which the optical properties reduce the appearance of skin imperfections andlor wrinkles and/or skin blemishes.

7. The use according to any preceding claim, in which the cosmetic formulation contains substantially no component that has significant absorption between 390 and 470nm.

8. The use according to any preceding claim, in which the oxide comprises one or more of TiO,, ZnO and CeO2.

9. The use according to any preceding claim, in which the dopant ion comprises one or more of Mn3, V5 or Cr

10. The use according to any preceding claim, in which the cosmetic formulation contains from 0.05 to 20% by weight of doped Ti02 and/or ZnO and/or CeO2.

11. The use according to any preceding claim, in which the doped oxide comprises Ti02 andlor ZnO containing from 0.4 to 2 mole % of Mn3t

12. The use according to any preceding claim, in which doped Ti02 and/or ZnO andlor CeO2 is present as particles having a particle size of 15 to 150 nm.

13. A cosmetic formulation which comprises a transition and/or lanthanide metal oxide doped with one or more ions that impart absorption characteristics and a carrier, the formulation containing substantially no component that significantly masks absorption characteristics of the doped oxide in the visible spectrum.