Cosmetic composition

Abstract: A composition for topical application to human skin to provide protection from excessive exposure to ultra-violet rays, comprises: a. an effective amount of ultrafine titanium dioxide as an inorganic sunscreen; b. an effective amount of octyl methoxycinnamate as an organic sunscreen; and c. a cosmetically acceptable vehicle for the sunscreens; the weight concentration of the titanium dioxide and octyl methoxycinnamate being within the region designated A in the accompaning drawing.

Description: FIELD OF THE INVENTION The invention relates to compositions for topical application to human skin to provide enhanced protection from the damaging effects of sunlight. BACKGROUND AND PRIOR ART The damaging effects of sunlight on human skin have been observed since time immemorial and many remedies have been proposed to protect the skin from this damage. In general terms, harmful ultra-violet (UV) rays, particularly those originating from sunlight, which penetrate the upper atmosphere and reach the earth's surface, can be classified into: i. the energy-rich UV-B rays (290-320nm wavelength) which possess an intense physiopathological activity on the skin; these are absorbed just above the dermis and they are responsible for erythema and skin pigmentation, and ii. UV-A rays (320-400nm wavelength) which penetrate deeper into the skin (to the dermis and beyond). Their energy is much lower and the photobiological effects they cause are much more long term in nature, for example, they accelerate skin ageing. Certain organic substances (sunscreens) whose molecules absorb the harmful ultra-violet rays have been proposed for use in mitigating the deleterious effects of ultra-violet radiation. Some of these substances absorb more effectively in UV-A range thereby providing filtering of UV radiation in this range, while others are more effective in the UV-B range. A common problem exists, however, whatever the choice of organic sunscreen, for protection from whichever wavelength of ultra-violet radiation, and this is that physiological damage to the body can occur, following topical application of these sunscreens in quantities necessary to provide effective filtering of harmful ultra-violet radiation. Even those organic sunscreens that are believed to be safe to use in this way, necessarily have safety limits imposed, based on the quantity applied to the skin, which can result in only moderate to poor protection from harmful ultra-violet radiation. Certain inorganic substances have also been proposed for use as sunscreens which physically block exposure of the skin to ultra-violet rays. Notable of these is titanium dioxide having a very small particle size. This grade of titanium dioxide, designated ultrafine TiO₂, affords a good degree of sun blocking potential without the unacceptable skin whitening experienced with the normal pigmentary grade (particle size >300nm). For example, in DE-A-3824999 (The Boots Company PLC), it is proposed to use oil-dispersible titanium dioxide with a mean primary particle size of <100nm in a water-in-oil emulsion as a sunscreen preparation. This reference also suggests that organic sunscreen agents, such as p-aminobenzoic acid and esters thereof, methoxycinnamate, benzophenone, dibenzoylmethanes or salicylates can also be included to improve protection. In spite of this, and other prior proposals, there still exists a need for a highly efficient and thoroughly safe sun protection composition which has a wide spectrum of protection (i.e. both UV-A and UV-B) in the UV region. SUMMARY OF THE INVENTION Applicants have now discovered that by the use of ultrafine titanium dioxide together with a specific organic sunscreen, whose concentration is lower than usual, in a composition adapted for use topically on the skin, synergistically enhanced protection from ultra-violet rays can be attained. DEFINITION OF THE INVENTION Accordingly, the invention provides a composition for topical application to human skin to provide protection from excessive exposure to ultra-violet rays, which comprises: a. an effective amount of ultrafine titanium dioxide; b. an effective amount of octyl methoxycinnamate; and c. a cosmetically acceptable vehicle; the weight concentration of the titanium dioxide and octyl methoxycinnamate being within the region designated C in the accompanying drawing. DISCLOSURE OF THE INVENTION The invention is concerned with a composition suitable for topical application to human skin to provide protection from excessive exposure to ultra-violet rays over a large range of wavelengths, notably covering both the UV-A and UV-B ranges. The composition of the invention comprises a special mixture of an inorganic sunscreen, namely ultrafine titanium dioxide and an organic sunscreen namely octyl methoxycinnamate, which are both conveniently dispersed or distributed in a cosmetically acceptable vehicle. Depending upon the nature of the composition, other sunscreens, skin benefit materials and/or cosmetic adjuncts can optionally be present in the composition. The titanium dioxide The composition according to the invention comprises ultrafine titanium dioxide. Ultrafine titanium dioxide is available as a water-dispersible form and as an oil-dispersible form: either or both forms of titanium dioxide can be employed in the composition according to the invention. By "ultrafine titanium dioxide" is meant titanium dioxide having an average particle size of less than 100nm, preferably from 10 to 40nm and most preferably from 15 to 25nm. Water-dispersible titanium dioxide is ultrafine titanium dioxide, the particles of which are uncoated or which are coated with a material to impart a hydrophilic surface property to the particles. Examples of such materials include aluminium oxide and aluminium silicate. Oil-dispersible titanium dioxide, is ultrafine titanium dioxide, the particles of which exhibit a hydrophobic surface property, and which for this purpose can be coated with metal soaps, such as aluminium stearate, aluminium laurate or zinc stearate, or with organosilicone compounds. The organic sunscreen The composition according to the invention also comprises as the organic sunscreen octyl methoxycinnamate, an example of which is Parsol MCX available from Bernel Chemical Co. The concentration of the titanium dioxide and the octyl methoxycinnamate It is well known to those skilled in the art that different sunscreens can be combined in a formulation to achieve high sun protection factors. Different sunscreens have different absorption coefficients however and as a consequence equal weights of sunscreens do not necessarily give equal sun protection. Given this caveat, it would be expected that combinations of sunscreens would have additive effects such that where: X = the concentration of the first sunscreen required, on its own, to produce an SPF of S. Y = the concentration of the second sunscreen required, on its own, to produce an SPF of S. both sunscreens being formulated in otherwise identical formulations, then the same formulation containing concentrations of: The Accompanying Drawing An extensive series of experiments has been carried out to test this theoretical prediction and it has been established that it does, in fact, hold for most mixtures of octyl methoxycinnamate and ultrafine titanium dioxide, such that the difference between the theoretical erythemally effective UV light transmission (which is equal to 100/SPF) and the actual erythemally effect UV light transmission is less than 1%. However, certain particular mixtures of these sunscreens produce an actual transmission significantly less than that predicted by theory and thereby produce statistically significantly better UV protection than expected. These preferred compositions are defined by the area designated C in the accompanying drawing, Figure 1, in which the ordinate represents % by weight octyl methoxycinnamate in the composition, and the abscissa represents % by weight ultrafine titanium dioxide in the composition. Particularly preferred compositions are defined by area D and especially preferred compositions by area E. By inspection, it can be deduced that the approximate weight concentrations of ultrafine titanium dioxide and octyl methoxycinnamate for each of the designated areas are as follows, bearing in mind that the combined amounts of the titanium dioxide and octyl methoxycinnamate should fall within the appropriate area designated in the drawing. It is also apparent that when the composition contains less than 2% by weight of octyl methoxycinnamate, the amount of protection afforded by the composition following topical application to human skin is very low, whereas when the amount of this ingredient exceeds 10% by weight of the composition then, although the degree of protection against ultra-violet rays afforded by the composition following topical application to skin is substantial, the amount of this ingredient in the composition is sufficiently high to give some cause for anxiety as to the safety in use of this composition when applied topically to human skin. The Cosmetically Acceptable Vehicle The composition according to the invention also comprises a cosmetically acceptable vehicle to act as a dilutant, dispersant or carrier for other materials present in the composition, so as to facilitate their distribution when the composition is applied to the skin and/or hair. Vehicles other than water can include liquid or solid emollients, solvents, humectants, thickeners and powders. Examples of each of these types of vehicle, which can be used singly or as mixtures of one or more vehicles, are as follows: Emollients, such as 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 dimethylpolysiloxane, di-n-butyl sebacate, isopropyl myristate, isopropyl 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, jojoba oil, evening primrose oil, soybean oil, sunflower seed oil, avocado oil, sesame seed oil, coconut oil, arachis oil, castor oil, acetylated lanolin alcohols, petroleum jelly, mineral oil, butyl myristate, isostearic acid, palmitic acid, isopropyl linoleate, lauryl lactate, myristyl lactate, decyl oleate, myristyl myristate; Propellants, such as propane, butane, isobutane, dimethyl ether, carbon dioxide, nitrous oxide; Solvents, such as ethyl alcohol, methylene chloride, isopropanol, acetone, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dimethyl sulphoxide, dimethyl formamide, tetrahydrofuran; Powders, such as chalk, talc, fullers earth, kaolin, starch, gums, colloidal silica sodium polyacrylate, tetra alkyl and/or trialkyl aryl ammonium smectites, chemically modified magnesium aluminium silicate, organically modified montmorillonite clay, hydrated aluminium silicate, fumed silica, carboxyvinyl polymer, sodium carboxymethyl cellulose, ethylene glycol monostearate. The cosmetically acceptable vehicle will usually form from 10 to 99.9%, preferably from 50 to 99% by weight of the emulsion, and can, in the absence of other cosmetic adjuncts, form the balance of the emulsion. OPTIONAL SKIN BENEFIT MATERIALS AND COSMETIC ADJUNCTS A particularly convenient form of the composition according to the invention is an emulsion, in which case an oil or oily material will normally be present, together with an emulsifier to provide either a water-in-oil emulsion or an oil-in-water emulsion, depending largely on the average hydrophilic-lyophilic balance (HLB) of the emulsifier employed. Oil or oily material The composition according to the invention can optionally comprise one or more oils or other materials having the properties of an oil. Examples of suitable oils include mineral oil and vegetable oils, and oil materials, such as those already proposed herein as emollients. Other oils or oily materials include silicone oils, both volatile and non-volatile, such as polydimethyl siloxanes. The oil or oily material, when present for the purposes for forming an emulsion, will normally form up to 90%, preferably from 10 to 80% by volume of the composition. Emulsifier The composition according to the invention can also optionally comprise one or more emulsifiers the choice of which will normally determine whether a water-in-oil or and oil-in-water emulsion is formed. When a water-in-oil emulsion is required, the chosen emulsifier or emulsifiers should normally have an average HLB value of from 1 to 6. When an oil-in-water emulsion is required, a chosen emulsifier or emulsifiers should have an average HLB value of >6. Examples of suitable emulsifiers are set below in Table 1 in which the chemical name of the emulsifiers is given together with an example of a trade name as commercially available, and the average HLB value. The foregoing list of emulsifiers is not intended to be limiting and merely exemplifies selected emulsifiers which are suitable for use in accordance with the invention. It is to be understood that two or more emulsifiers can be employed if desired. The amount of emulsifier or mixtures thereof, to be incorporated in the composition of the invention, when appropriate is from 1 to 50%, preferably from 2 to 20% and most preferably from 2 to 10% by weight of the composition. Water The composition of the invention can also comprise water, usually up to 80%, preferably from 5 to 80% by volume. Silicone Surfactant The composition of the invention can also optionally comprise a high molecular weight silicone surfactant which can also act as an emulsifier, in place of or in addition to the optional emulsifier(s) already mentioned. The silicone surfactant is a high molecular weight polymer of dimethyl polysiloxane with polyoxyethylene and/or polyoxypropylene side chains having a molecular weight of from 10,000 to 50,000 and having the structure: where the groups R′ and R″ are each chosen from -H, C₁₋₁₈ alkyl and a has a value of from 9 to 115, b has a value of from 0 to 50, x has a value of from 133 to 673, y has a value of from 25 to 0.25. Preferably, the dimethyl polysiloxane polymer is one in which: a has a value of from 10 to 114 b has a value of from 0 to 49 x has a value of from 388 to 402 y has a value of from 15 to 0.75 one of groups R′ and R″ being lauryl, and the other having a molcular weight of from 1000 to 5000. A particularly preferred dimethyl polysiloxane polymer is one in which: a has the value 14 b has the value 13 x has the value 249 y has the value 1.25 The dimethyl polysiloxane polymer is conveniently provided as a dispersion in a volatile siloxane, the dispersion comprising, for example, from 1 to 20% by volume of the polymer and from 80 to 99% by volume of the volatile siloxane. Ideally, the dispersion consists of a 10% by volume of the polymer dispersed in the volatile siloxane. Examples of the volatile siloxanes in which the polysiloxane polymer can be dispersed include polydimethyl siloxane (pentamer and/or hexamer). A particularly preferred silicone surfactant is cyclomethicone and dimethicone copolyol, such as DC 3225C Formulation Aid available from DOW CORNING. Another is laurylmethicone copolyol, such as DC Q2-5200, also available from Dow Corning. The amount of silicone surfactant, when present in the composition will normally be up to 25%, preferably from 0.5 to 15% by weight of the emulsion. Further organic sunscreens The emulsion of the invention optionally can comprise one or more organic sunscreens, in addition to octyl methoxycinnamate, further to enhance the benefit of the emulsion in providing protection from the harmful effects of excessive exposure to sunlight. As has already been stated, some organic sunscreens can be harmful to health if applied topically to the skin at a concentration sufficient to screen out effectively radiation from either the UV-A range or the UV-B range. The presence however, of ultrafine titanium dioxide, which can provide a broad spectrum of protection, enables a lower than usual amount of organic sunscreen materials to be used to "top-up" the overall Sun Protection Factor of the emulsion to an exceptionally high level, without the risk of causing the type of skin damage or other health problems that can be associated with the use of higher levels of organic sunscreen materials alone. In view of this, a relatively small amount of a second organic sunscreen optionally can be incorporated into the emulsion of the invention. Examples of suitable further organic sunscreens, in addition to octyl methoxycinnamate, when required, include those set out in Table 2 below, and mixtures thereof. The composition of the invention can accordingly comprise from 0.1 to 10%, preferably from 1 to 5% by weight of an organic sunscreen material. Other Inorganic Sunscreens The emulsion of the invention optionally can comprise an inorganic sunscreen in addition to ultrafine titanium dioxide as herein defined. Examples of other inorganic sunscreens include: zinc oxide, having an average particle size of from 1 to 300nm, iron oxide, having an average particle size of from 1 to 300nm, silica, such as fumed silica, having an average particle size of from 1 to 100nm. It should be noted that silica, when used as an ingredient in the emulsion according to the invention can provide protection from infra-red radiation. Other Cosmetic Adjuncts Examples of conventional adjuncts which can optionally be employed include preservatives, such as para-hydroxy benzoate esters; antioxidants, such butyl hydroxy toluene; humectants, such as glycerol, sorbitol, 2-pyrrolidone-5-carboxylate, dibutylphthalate, gelatin, polyethylene glycol, such as PEG 200-600; buffers, such as lactic acid together with a base such as triethanolamine or sodium hydroxide; waxes, such as beeswax, ozokerite wax, paraffin wax: plant extracts, such as Aloe vera, cornflower, witch hazel, elderflower, cucumber; thickeners; activity enhancers; colourants; and perfumes. Cosmetic adjuncts can form the balance of the composition. Use of the Composition The composition according to the invention is intended primarily as a sun care product for topical application to human skin to protect exposed skin from the harmful effects of excessive exposure to sunlight. In use, a small quantity of the composition, for example from 1 to 5ml, is applied to exposed areas of the skin, from a suitable container or applicator and, if necessary, it is then spread over and/or rubbed into the skin using the hand or fingers or a suitable device. PRODUCT FORM AND PACKAGING The topical skin and/or hair treatment composition of the invention can be formulated as a lotion having a viscosity of from 4,000 to 10,000 mPas, a fluid cream having a viscosity of from 10,000 to 20,000 mPas or a cream having a viscosity of from 20,000 to 100,000 mPas, or above. The composition can be packaged in a suitable container to suit its viscosity and intended use by the consumer. For example, a lotion or fluid cream can be packaged in a bottle or a roll-ball applicator or a propellant-driven aerosol device or a container fitted with a pump suitable for finger operation. When the composition is a cream, it can simply be stored in a non-deformable bottle or squeeze container, such as a tube or a lidded jar. The invention accordingly also provides a closed container containing a cosmetically acceptable composition as herein defined. Method for Determining Concentrations of Octyl Methoxycinnamate and Ultrafine Titanium Dioxide To determine the optimum concentration of the two sunscreens it is necessary to have an accurate and convenient method to measure the Sun Protection Factor (SPF) of a releatively large number of formulations. Any suitable method can be used, including the DIN or FDA approved in vivo methods but the in vitro method described below is particularly accurate and convenient. All formulations used were based on a simple commercial O/W emulsion sunscreen base composition. The method for the in vitro SPF determination of the composition of the invention involves the spectrophotometric scanning of stratum corneum between 400nm and 290nm utilising a Perkin Elmer Lamba 17 spectrophotometer equipped with a diffuse transmission detection system. Transpore® tape is used in place of human skin and the following procedure is followed. i. A piece of the tape is applied to the outer surface of a 0.5 cm quartz cuvette. ii. The quartz cuvette carrying the piece of tape is placed in the light path of the spectrophotometer which for this purpose is fitted with a fluorescence cut-off filter. This filter eliminates the autofluorescence of the tape and filters out all transmissions above 400nm. iii. The tape is scanned from 290 to 400nm and the spectrum obtained is saved as the control. iv. The cuvette with tape is removed from the spectrophotometer and the test material (i.e. sunscreen) is applied to the tape at the rate of 1.5 µl/cm², in accordance with German DIN protocol, and rubbed uniformly across the entire surface of the tape using the finger fitted with a finger stall. v. The applied sunscreen material is allowed to stand for 5 minutes at room temperature (20°C) to enable it to dry, and then the sample is rescanned in the spectrophotometer as before from 290 to 400nm. This spectrum is saved as the test spectrum. No spectral absorbance changes were observed with drying times between 2 and 15 minutes; the 5 minute drying time was therefore adopted as standard. vi. The control spectrum is subtracted from the test spectrum to provide the spectral absorbance of the test sample of sunscreen material and this absorbence is converted to transmission. vii.The in vitro Sun Protection Factor (SPF) is finally calculated from the transmission measurements as described by Diffey et al, in a paper entitled: "A new substrate to measure sunscreen protection factors throughout the ultra-violet spectrum" in J. Soc. Cosmet. Chem. 40 , 127-133 (May/June 1989); see especially page 130. This process provides accurate SPF values for a variety of formulations. From the data for SPF of formulations containing simple sunscreens, values of X and Y in Expression 1, for S values of 1 to 50, are obtained using interpolation or extrapolation where necessary. Actual SPF values are then obtained for mixtures of the two sunscreens with n - O, 0.02, 0.04....1.00 in Expression 1. Again, precise data points are obtained by computer-assisted interpolation and extrapolation of actual data points with the assumption that, within the range of the extrapolation or interpolation, Beer's law is obeyed. Those combinations of the two sunscreens which produce ′actual′ transmission of the erythemally effective UV light (defined as 100/SPF) 1.1%, 1.3%, 1.5%, 1.7% and 1.8% higher than that of the single sunscreens are then plotted as in Figure 1 to define the preferred, particularly preferred and especially preferred areas designated C, D, E on Figure 1. Evidence to confirm superiority of mixtures of ultrafine, titanium dioxide (TiO₂) and octyl methoxycinnamate (Parsol MXC) whose respective weight concentrations both fall within the Area designated A in the accompanying drawing A sunscreen composition prepared as a conventional o/w emulsion containing either 9.15% ultrafine TiO₂ or 5.97% Parsol MCX gives a Sun Protective Factor (SPF) of 10.4 in the in vitro SPF method described hereinbefore. This indicates that the composition transmits 100/10.4 or 9.61% of incident erythemally effective UV light. It would be expected that a similar composition containing (9.15 x 0.3)% TiO₂ and (5.97 x 0.7)% Parsol MCX would be equivalent to the formulation containing either sunscreen alone as above and in fact this is approximately the case as the SPF of the combination is 11.54 giving an erythemally effective UV light transmission of 8.66% - just 0.95% less than predicted. The composition containing 9.15 x 0.3 = 2.74% TiO₂ and 5.97 x 0.7 = 4.2% Parsol MCX lies outside the Area designated A on the accompanying figure, as it provides less than 1% unexpected additional absorbance of erythemally effective UV light. A similar composition prepared containing either 12.6% TiO₂ or 15% Parsol MCX gives an SPF or 23.8 by the in vitro method, an erythemally effective UV light transmission of 4.2% (1/23.8). In this case however a composition containing (0.7 x 12.6)% TiO₂ and (0.3 x 15%) Parsol MCX gives an erythemally effective UV transmission of only 2.46%, an unexpected additional absoption of 1.74% of the erythemally effective UV light. This composition, which falls within the particularly preferred region of the figure, inside line D, containing 0.7 x 12.6 = 8.82% TiO₂ and 0.3 x 15 = 4.5% Parsol MCX gives a highly significant unexpected additional absorption. EXAMPLES The invention is illustrated by the following examples. Example 1 Example 2 This example illustrates a cream according to the invention. Example 3 This example illustrates a lotion according to the invention. Example 4 This example illustrates a lotion according to the invention.

Claims: A composition for topical application to human skin to provide protection from excessive exposure to ultra-violet rays, which comprises: a. an effective amount of titanium dioxide having an average particle size of less than 100mm as an inorganic sunscreen; b. an effective amount of octyl methoxycinnamate as an organic sunscreen; and c. a cosmetically acceptable vehicle for the sunscreens; the weight concentration of the titanium dioxide and octyl methoxycinnamate being within the region designated C in the accompanying drawing. A composition according to claim 1, in which the titanium dioxide is water-dispersible titanium dioxide. A composition according to claim 1, in which the titanium dioxide is oil-dispersible titanium dioxide. A composition according to claim 1, 2 or 3, in which the weight concentration of the titanium dioxide and octyl methoxycinnamate fall within or are encompassed by the region designated D in the accompanying drawing. A composition according to claim 1, 2 or 3, in which the weight concentration of the titanium dioxide and octyl methoxycinnamate fall within the region designated E in the accompanying drawing. A composition according to any preceding claim which is an emulsion. A composition according to any preceding claim which comprises a silicone oil. A composition according to any preceding claim which comprises a silicone surfactant. A composition according to any preceding claim which further comprises a second organic sunscreen. The use of a composition according to any preceding claim, following topical application to human skin or hair, in protecting the skin and hair against damage due to exposure to ultra-violet rays.

Inventors: NICOLL GREGG ALAN, SCOTT IAN RICHARD, NICOLL, GREGG ALAN, SCOTT, IAN RICHARD
Applicants: UNILEVER NV, UNILEVER PLC, UNILEVER N.V.
Application year: 1991
Main classification: A61K7
IPC codes: A61Q17, A61K8