Cosmetic composition

Abstract: A composition for topical application to human skin to provide protection from excessive exposure to ultra-violet rays, comprises an effective amount of a sunscreen comprising water-dispersible ultrafine titanium dioxide and oil-dispersible ultrafine titanium dioxide, together with a cosmetically acceptable vehicle for the sunscreen.

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 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. JP 59/172415 (Pola Kasei Kogyo KK) discloses an anti-suntan agent containing fine powdered titanium oxide (average diameter of 10-40 µm, maximum diameter of ≦0.1 µm) to shield the skin from UV radiation, and indomethacin or its salt to suppress/prevent inflammation and melanosis caused by the UV radiation. 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 two different types of ultrafine titanium dioxide 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 a sunscreen comprising a mixture of water-dispersible ultrafine titanium dioxide and oil-dispersible ultrafine titanium dioxide; and b. a cosmetically acceptable vehicle for the sunscreen. 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 wide range of wave lengths, notably covering both the UV-A and the UV-B ranges. The composition of the invention comprises a special mixture of two different grades of ultrafine titanium dioxide which are conveniently dispersed or distributed in a cosmetically acceptable vehicle. Depending upon the nature of the composition, other skin benefit materials and/or cosmetic adjuncts can optionally be present. The titanium dioxide The composition according to the invention comprises ultrafine titanium dioxide in two forms, namely water-dispersible titanium dioxide and oil-dispersible titanium dioxide. Water-dispersible titanium dioxide, in accordance with the invention, 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, in accordance with the invention, 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. By "ultrafine titanium dioxide" is meant particles of titanium dioxide having an average particle size of less than 100nm, preferably from 10 to 40nm and most preferably from 15 to 25nm. It has accordingly been discovered that by topical application to the skin of a mixture of both water-dispersible ultrafine titanium dioxide and oil-dispersible ultrafine titanium dioxide, synergistically enhanced protection of the skin against the harmful effects of both UV-A and UV-B rays is achievable. Evidence to demonstrate this effect will be given later in this specification. It is believed that this unexpected benefit is due to the deposition of each type of titanium dioxide on different regions of the skin surface, water-dispersible titanium dioxide being preferentially retained by hydrophilic regions of the skin's surface, while oil-dispersible titanium dioxide is retained preferentially by hydrophobic regions of the skin's surface. The combined overall effect is that more efficient physical coverage of the skin's surface is attainable and this can be demonstrated by measurement of the Sun Protection Factor (SPF), a property of sunscreens, whose measurement will be described and demonstrated later in this specification. In order to achieve the enhanced, synergistic benefit, as herein described, the weight ratio of water-dispersible titanium dioxide to oil-dispersible titanium dioxide should be from 1:4 to 4:1, preferably from 1:2 to 2:1 and ideally about equal weight proportions. The total amount of titanium dioxide in the composition according to the invention is from 1 to 25%, preferably from 2 to 10% and ideally from 3 to 7% by weight of the composition. Experimental evidence has shown that the synergistic benefit, as described herein, is most pronounced at a total titanium dioxide level of about 5% by weight, and is lost when the titanium level reaches 10% by weight, equal proportions of the water-dispersible and oil-dispersible forms of titanium dioxide being used in this experiment. Likewise, no significant sun protection benefit is shown when the total level of titanium dioxide falls below 1% by weight. 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, 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. Organic sunscreens The emulsion of the invention optionally can comprise an organic sunscreen 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 organic sunscreen optionally can be incorporated into the emulsion of the invention. Examples of suitable organic sunscreens, when required, include those set out in Table 2 below, and mixtures thereof. The emulsion 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 determination of Sun Protection Factor (SPF) in vitro The method for the in vitro SPF determination of the emulsion 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. Guinea pig stratum corneum is used in place of human skin and the following procedure is followed. i. Guinea pig stratum corneum is isolated as fine sheets from guinea pig skin and air dried. ii. A piece of the stratum corneum is applied to the outer surface of a 0.5 cm quartz cuvette using a drop of distilled water to seal the stratum corneum uniformly to the quartz surface. iii. The quartz cuvette carrying the piece of stratum corneum 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 stratum corneum and filters out all transmissions above 400nm. iv. The stratum corneum is scanned from 290 to 400nm and the spectrum obtained is saved as the control. v. The cuvette with stratum corneum is removed from the spectrophotometer and the test material (i.e. sunscreen) is applied to the stratum corneum at the rate of 1.5 µl/cm², in accordance with German DIN protocol, and rubbed uniformly across the entire surface of the skin using the finger fitted with a finger stall. vi. 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. vii. 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. viii.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. Evidence to demonstrate the synergistically enhanced protection of skin against ultra-violet rays with both water-dispersible and oil-dispersible ultrafine titanium dioxide In this experiment, the Sun Protection Factor (SPF) of water-dispersible titanium dioxide and of oil-dispersible titanium dioxide were each measured seperately and as a mixture using the the German DIN technique, as published in "Deutsches Institut für Normung. DIN 67 501 December 1985. The formulations in this experiment were as follows: The results obtained are set out in Table 3 below. The results shown in Table 3 confirm that a proportionally greater benefit in terms of SPF was achieved when the total amount of titanium dioxide in the test formulation was 5% comprising equal weights of each type of titanium dioxide, than when either water-dispersible or oil-dispersible titanium dioxide were each used at the 5% w/w level. This suggested an unexpected (synergistic) response for the mixture. Three further formulations (1A, 2A and 3A) each containing twice the quantity of titanium dioxide, were also tested in a similar manner. The formulations were otherwise similar to Formulations 1, 2 and 3 above, except that the amount of water was reduced by 5% by weight to compensate for a corresponding increase in titanium dioxide. The results obtained are set out in Table 4 below. The results shown in Table 4 apparently show a lack of synergy between the two forms of TiO₂: - this is in fact not the case. It is not correct to assume that the average of the SPF with water dispersible TiO₂ (8.1) and that with oil dispersible TiO₂ (12.3) is the arithmetical mean (10.2). The true average is obtained by converting SPF into an absorbance figure of log (¹/SPF), averaging the absorbance figures and reconverting to an average SPF thus: Thus the mixture of the two types of TiO₂ gives an unexpected additional SPF of 10.5 - 9.98 = 0.5. These results show that mixtures of O/D and W/D TiO₂ give unexpectedly greater SPF than expected by averaging the light absorbances of the two components separately. The effect is proportionately greater at total TiO₂ concentrations of 5% than at 10% but the effect is present at both concentrations. EXAMPLES The invention is further illustrated by the following examples; in each formulation, the titanium dioxide employed was ultrafine titanium dioxide having a mean particle size of from 15 to 25nm. Example 1 This example illustrates a lotion according to the invention. Example 2 This example illustrates a fluid cream according to the invention. Example 3 This example illustrates a cream according to the invention. Example 4 This example illustrates a lotion according to the invention. Example 5 This example illustrates a sunscreen cream in accordance with the invention. Example 6 This example also illustrates a sunscreen cream in accordance with the invention. Example 7 This example illustrates a lotion according to the invention. SPF Data The lotion when tested in vitro produced an SPF of 10.0 (+/- standard error of the mean (SEM) = 0.7). Comparative experiments Experiment 1 The formulation shown in Example 7 was modified by omitting oil-dispersible ultrafine titanium dioxide (2.5% w/w), and replacing it with an equal quantity of additional water-dispersible titanium dioxide, so that the formulation now contained a total of 5% w/w of water-dispersible ultrafine titanium dioxide. The formulation of Experiment 1 was accordingly as follows: SPF Data The lotion when tested in vitro produced an SPF of 7.8 (+/- standard error of the mean (SEM) = 0.3). Experiment 2 The formulation shown in Example 7 was again modified by omitting this time water-dispersible ultrafine titanium dioxide (2.5% w/w) and replacing it with an equal quantity of added oil-dispersible titanium dioxide, so that the formulation now contained a total of 5% w/w oil-dispersible ultrafine titanium dioxide. The formulation of experiment 2 was accordingly as follows: SPF Data The lotion when tested in vitro produced an SPF of 7.9 (+/- standard error of the mean (SEM) = 0.4). Conclusion When comparing the SPF data of the Example 7 formulation, in accordance with the invention, with those of the Experiments of 1 and 2 formulations, which contain either water-dispersible ultrafine titanium dioxide or oil-dispersible ultrafine titanium dioxide, and which are accordingly not in accordance with the invention, it is apparent that for the same quantity of titanium dioxide present in each of the formulations, i.e. 5% by weight, the SPF value for Example 7 formulation is significantly greater than the SPF values of either Experiment 1 or Experiment 2. The demonstrates the superiority of combining in the same formulation the proportion of oil-dispersible ultrafine titanium dioxide with a proportion of water-dispersible ultrafine titanium dioxide.

Claims: A composition for topical application to human skin to provide protection from excessive exposure to ultraviolet rays, which comprises: a. an effective amount of a sunscreen comprising a mixture of water-dispersible titanium dioxide having an average particle size of less than 100 nm and oil-dispersible titanium dioxide having an average particle size of less than 100 nm; and b. a cosmetically acceptable vehicle for the sunscreen. A composition according to claim 1, in which the total amount of titanium dioxide is from 1 to 25% by weight. A composition according to claim 1, in which the total amount of titanium dioxide is from 1 to 10% by weight. A composition according to claim 1, in which the total amount of titanium dioxide is from 3 to 7% by weight. A composition according to any preceding claim, in which the weight ratio of water-dispersible titanium dioxide to oil-dispersible titanium dioxide is from 1:4 to 4:1. A composition according to any preceding claim, in which the weight ratio of water-dispersible titanium dioxide to oil-dispersible titanium dioxide is from 1:2 to 2:1. A composition according to any preceding claim, which is an emulsion. A composition according to any preceding claim, which further comprises a silicone oil. A composition according to any preceding claim, which further comprises a silicone surfactant. A composition according to any preceding claim, which further comprises an organic sunscreen. A composition according to claim 10, in which the organic sunscreen is octyl methoxycinnamate. 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. The use of at least 1% by weight of a mixture of water-dispersible titanium dioxide having an average particle size of less than 100 nm and oil-dispersible titanium dioxide having an average particle size of less than 100 nm, in a composition for topical application to human skin to provide protection from excessive exposure to ultra-violet rays, which composition comprises a major proportion of a cosmetically acceptable vehicle for the titanium dioxide.

Inventors: NICOLL GREGG ALAN, OJO-OSAGIE ANN CAMILLA, SCOTT IAN RICHARD, NICOLL, GREGG ALAN, OJO-OSAGIE, ANN CAMILLA, SCOTT, IAN RICHARD
Applicants: UNILEVER NV, UNILEVER PLC, UNILEVER N.V.
Application year: 1991
Main classification: A61K7
IPC codes: A61Q5, A61K8, A61Q17