Photoprotective Compositions Comprising Synergistic Combination of Sunscreen Active Compounds FIELD OF THE INVENTION The subject invention is directed to compositions for topical application containing a synergistic combination of sunscreen active compounds, and: more particularly to compositions for topical application composing a synergistic combination of octinoxate, octocryene, and aniloxate; BACKGROUND OF THE INVENTION When applied topically, sunscreen compositions impart a film that protects skin against the damaging effects Of exposure to the suns ultraviolet radiation (UVR> Sunscreen active compounds work on skin's surface by Is absorbing IUVR before it can interact with and damage ain, A particular composition's abilty to block UVR is usual y expressed in a sun protection factor or SPF rating. Combinations of sunscreen active compounds are typicaly used in sunscreen composition in order to raise the SPF rating of the composition. 20 U1S. Patent Nos, 030,629 and 5,968,481 assert synergtstic increase in SPF based on combinations of certain sunscreen actve compounds. Further, Andt et al report a synergistic effect based on a combination of organic and inorganic sunscreens covering UVA and UV-B absorption. (V, Andre et al, Cosmetics and Toietries Manufacture Worldwide 2004, pp, 19 25 23. However, as those authors note such synergistic increases in SPF are not completely understood, nor is it predictable before hand which combination of compounds will demonstrate a synergistic effect in fact. as demonstrated in the experiments herein, a combination of ony two of the three sunscreen actives in the present invention does not show synergistc 30 SPF increases Thus a combination of sunscreen active compounds that demonstrate a synergistic increase in SPF. and thus an enhanced UVR protectective -2 capability over what would be predicted from their use alone, would be useful and desirable These and other objectives are obtained by the invention more fuly described and claimed herein, SUMMARY OF THE NVENTION The subject invention provides a topically applicable sunscreen composition suited for the photoprotection of human skin and/or hair, comprising photoprotecting synergistically effective amounts of octinoxate' 1o octocrylene, and arriloxate, The subject invention also provides a cosmetic composition for topical application to human skin and/or hair, comprising photoprotecting synergistically effective amounts of actinoxata, octocrylene, and amoxate The subject invention further provides a method for protecting human is skin and/or hair against the deleterious effects of solar radiation more particularly ultraviolet radiaton (UVR) comprising topically applying thereto an effective amount of the sunscreen compositions as described herein. DETAILED DESCRIPTtaN 20 The subject invention provides a topically applicable sunscreen composition suited for the photoprotection of human skin and/or hair, comprising photoprotectirg synergisically effective amounts of octinoxate, octocrylens, and amiloxate. Octinoxate, which is also known as Octyi rnethoxycinnamate or ethylhexyl methoxycinnamate, 's listed in Annex Vil of the EU Cosmetics Directive for use as a sunTscreen agent up to a level of 10%. in the United States, it is listed by the USEDA for use at level up to 7.5%. Octocrylene, whose chemical name is 2-ethy hexyl 2-cyano-3,3 diphenyl4-propenoate, is listed by the USFDA for use up to 1 0% and in the EU Cosmetics Directive for use up to 10%. Amiloxate, whose chemical name so is 2-benzoic acid, 2-propnoic acid,3-(4-methoxyphenyl-3~methybuty ester and is also known by 4-Methoxycinnamic acidisoamyl ester or isoamy p nethoxycinnamate, is being reviewed for approval by the USFOA for use up to 10% and is listed in the EU Cosmetics Directive for use up to 10%. It is 3 understood that the compositions of the invention are not limited to these statutory limits but that these limits are provided to illustrate practical limitations on the amount of these sunscreen active agents in products that may be marketed in various counties In one embodiment of the invention, the molar ratio of octinioxate~cttocryene:amiloxate present in the composition may range from O34:02804 to 0. 2&60.28:f40. In another embodiment of the present invention, octinoxate may be present in the composition in an amount from about 1.0 to about 7,5 percent by weight, preferably in an amount from about 4,0 to about 7.5 percent by weight, more preferably in an amount from about 6,5 to about 7.5 percent by weight, In a further embodiment of the invention octocrylene may presentin the composition in an amount from about 1.0 to about 10.0 percent by weight, a. ~ preferably in an amount from about 5.0 to about 10,0 percent by weigh, more preferably in an amount from about 8,0 to about 10,0 percent by weight In a further embodiment of the invention, amiloxate may be present in the composition in an amount from about 10 to about 10.0 percent by weight, preferably in an amount from about 540 to about 10.0 percent by weight, more 2 o preferably in an amount from about 7.6 to about 10.) percent by weight The compositions of the invention containing the synergistic combination of sunscreen actives can comprise any form readily known by those of ordinary skill in the art of preparing cosmetic compositions, in particular compositions containing sunscreen active agents, Examples of s such include, but are not limited to, nonionic vesicie dispersions, emulsions, creams, milks, gels, cream gels, ointments, suspensions, dispersions, powders, solids, sticks, foams or sprays In certainly preferred embodiments, UNe composition can compean anhydrous or aqueous soid or paste, emulsion, suspension, or dispersion. 30 Preferable forms of the compositions include an ol-in-water emulsion, a wate-in1o emulsion, an alcoho solution, or an aerosol formulation inr one embodiment the subctinvention, the compoton can bei "n the form of an aerosol, wherein the composition is- combined with at least one 4 propeflant, which may be any suitable gas that can be compressed or liquefied within a spray dispensing canister and which expands or volatilizes to vapor or gas form upon exposure to ambient temperature and pressure conditions to deliver the composition n an aerosol form, Suitable propellants s include hydrocarbons having I to 6 carbon atoms, including but not limited to methane ethane, propane isopropane. butane, isobutane utane pentane, isopentane, neopentane, pentene, hydrofucrocbons (HFCs), chlorofiuorocarbons(CFCs), nitrogen, ethers including dimethyl ether, and any mixtures thereof. Those of ordinary skill in the art recognize that in a closed 0 o contaIner such as an aluminum can or giass bottle, propel ants such as dimethyl ether condense to the liquid state at ambient temperature. Thus, the composition In the aerosol container is liquid formulation which can contain dissolved propellant, undissolved liquid propellant and gaseous propellant Al of this is under pressure due to the vapor pressure of the propellant, In the 1s practice of the subject invention, the propellant can be present in an amount up to about 90 weight percent, preferably from about 2 weight percent to about 50 weight percent, and more preferably about 5 weight percent to about 40 weight percent, most preferably 30 weight percent, based on the total weight of the aerosol composition, 20 The compositions of the invention can also comidse aerosol foams or so-caled mousse compositions. For example, U.S. Patent No, 6,627,585 describes a mousse-forming cleansing shampoo composition comprising a foamable concentrate comprising at least one surfactant. dispersed particles of' a water-insoluble conditioning agent, an aqueous carrier; and an aerosol 25 propellant, US, Patent No. 6,264,964 describes a cosmetic composition including a crosslinked non-ernulsifying polysiloxane elastomer and a carboxyvinyl polymer which is in the form of an aerosol foam in a pressurized system, The propellant may be introduced into the mousse composition at the time of filling by using a standard aerosol dispenser, e.g. a spray can 30 arrangement The subject invention contemplates the incorporation of the synergistic combination of sunscreen actives in sunscreen and sunblock products and any other topically applied composition where the addition of sunscreen active agents would not detract from the efficacy of the product nor affect the sunscreening ability of the sunscreen active agents. Thus the subject invention also provides a cosmetic composition for topical application to human skin and/or hair, comprising photoprotecting synargisticatly effective s amounts of octinoxate, octocrylene, and amiloxate, Nonimiting examples of such cosmetic compositions may include such products as moisturizers, dteansers, conditioners, shampoo, body wash, styling gel/lotion, eye cream and eye liner, blush, mascara, foundation, nail polish, polish remover, eye shadow, lipstick, lip gloss, 1ip liners, lip balms, makeup remover, nail 10 treatment foot care compositions, acne treatment, redness/rosacea treatment, varicose/spider vein treatment. anti-aging compositions, sunless tanning compositions, after-sun compositions, concealers, hair color and bleaching compositions, skin fading/lighteners, body firming lotion, shaving cream, after shave, relaxer, antiperspirants and deodorants, exfoliants, is scrubs, liquid hand soap, bubble bath, pain and wound treatment compositions. insect repellant, anti-itch and rash cream, styling mousse and foams, perfume, lubricants, body oti, body spray, baby lotion, diaper cream, baby soap, baby shampoo, baby oil, baby wipes, hair-loas treatment, hair spray, depilatory, hair growth inhibitors, hair removal waxes, personal 20 cleansing, cologne, oil controller, and hant aanitizer, The compositions of the present invention may contain a wide range of additionaL optional components which are referred to herein as "Cosmetic components", but which can also incude components generally known as pharmaceutically active agents. The CTFA Cosmetic (ngredient Handbook, 2 sSeventh Edition, 1997 and the Eighth Edition, 2000, which is incorporated by reference herein in its entirety, describes a wide variety of cosiietic and pharmaceutical ingredients commonly used in skin care compositions, which are suitable for use in the compositions of the present invention. Examples of these functional classes disclosed in this reference include: absorbents, 30 abrasives, anticaking agents, antifoaring agents, antioxidants, binders, biological additives, buffering agents, bulking agents, cheating agents, chemical additives, colorants, cosmetic astringents, cosmetic biocides, denaturants, drug astringents, external analgesics, film formoers, fragrance components humectants, pacifying agents, pH adjusters, plasticizers, reducing agents, skin beaching agents skitnoonditioring agents (emolMent humectants, miscellaneous, and occlusive), skin protectants, solvents, foam boosters, hydrotropes. solubilizing agents, suspending agents $ (nonsurfactant) sunscreen agents, ultraviolet fight absorbers, SPF boosters, waterproofing agents, and viscosity increasing agents (aqueous and nonaqueous) in the practice of the invention, the composition may contain one or more additional sunscreen active agents. For purposes of the present to inventon, a sunscreenan aie active"' shal include all of those materials, singly or in combination, that are regarded as acceptable for use as active sunscreening ingredients based on their ability to absorb UV radiation. Such compounds are generally described as being UV-A, UVt-, or UV-AUV-B active agents, Approval by a regulatory agency is generally 5 required for inclusion of active agents in formulations intended for human use. Those active agents which have been or are currently approved for sunscreen use in the United States include organic an( Inorganic substances including, without limitation, para aminobenzoic acid, avobenzone, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octy salicylate, 20 oxybenzone, padimate 0, phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylate, titanium dioxide, zinc oxide, diethanolamine methoxycinnamate, digaloy trioleate, ethyl dihydroxypropyl PASA, glyceryl aminobanzonte, lawsone with dihydroxyacetone, red petrolatum. Examples of additional sunscreen actives that have not yet been approved in the US but 2$ are allowed in formulations sold outside of the US include ethyihexyl riazone, dioctyl butamido triazone, benzylidene malonate polysi oxane, terephthalytidene dicamphor sulfonic acid, disodium phenyl di benzimidazole tetrasulfonate. diethylanino hydroxybenzoyl hexyl benzoate, bis diethylamino hydroxybenzoyl benzoate, bis benzoxazoylphenyl ethylhexylimino triazine, 30 drometrizole trisiloxane, methylene bis-benzotriazolyl tetramethylbutylpheno, and bis4ethythexyloxyphenol methoxyphenytriazine, 4~ methyibenzylidenecamphor, and isopentyl 4-methoxycinnamate, However, as the list of approved sunscreens is currently expanding, those of ordinary skill -7< wRi recognize that the invention is not limited to sunscreen active agents currently approved for human use but is readily applicable to those that may be allowed in the future-. In one embodiment of the invention the additional sunscreen active s agent comprises a photoprotecting effective amount of particulates of atleast one inorganic pigment or nanopigment, nonimiting examples of Ahich include titanium dioxide, inc oxide, iron oxide, zirconium oxide, cerium oxide, or mixture thereof The compositions of the invention may also include material that also 'to increase the SPF of the final composition by such mechanisms as UV radiation scattering and dispersor. Such materials are referred to herein as "UV-radiation scattering agents' and comprise materdas that exhibit UV absorbing activity or exhibit no UV absorbing activity. An example of such UV-radiation scattering agents include polymeric materials, such as the Is product known as SunSpheres (Rohm and Haas; Philadelphia, PA ) which are described by their manufacturer as holow styrene/acrylates copolymer spheres manufactured by emulsion polymeization. The polymer spheres are said to raise SPF values across the UNA and UVB region by dispersing and/or scattering the incident UV radiation throughout the Wm of sunscreen 2o president a sufabe; such as human skirt it is undertood that the spheres cause less UV radiation to penetrate into the skin by redirecting the radiation towards the UV-absorbing sunscreen actives in the sunscreen formulation, where the radiation reacts with the sunscreen active molecules and the energy is dissipated as heat; As used herein, the terms "spheres or 2 t "scattering agents' are not limited by chemical makeup or shape, but comprise any agent tha produces the effect of lengthening the path of incident LIV radiation, increasing the statistics likelihood that the radiation will contact a sunscreen active molecule, Le, a UV absorbing active agent. These materials may alo include UV absorbing materials that also exhibit o scattering properties such as ZnO (examples include Z-Cote" products available from BASF), TiO 2 (examples incdde the SoiavelMproducts available from Unigema (New Castle, DE, USA), compounds such as methylene bis-enzotriazolyi tetramethylbutylpheno("Tinasorb'M available from Ciba Specialty Chemicals, Inc. (Basel, Switzerland ). UV radiation scattering agents are typically present in the formulation in amounts up to about 10% by weight, preferably in ranges of about 0,5% to about 7,0% by weight, in particularly preferred ranges of 3% to about 5% by weight. As used herein, the terms "sunless-tanning agent" or "self-tanning compositions" refer to compositions which, when applied to human skin, impart thereto an appearance similar to that achieved by exposing the skin to natural or artificial sunlight Examples of sunless tan ning active agents are described in U,S. Patent Nos. 6,462,397, 6,26 541. and 6,231,837. Such io sunless tanning compositions typically comprise, in addition to an artificial tanning effective amount of a self tanning agent, effective amounts of a composition coloring agent and a cosmetically acceptable carrier adapted for topical application to human skin, The self tanning agents can also include those compositions generally accepted in the art for application to human 15 skin, and which, when so applied, react therein with amino acids so as to form pigmented products, Such reactions give the skin a brown appearance similar to the color obtained upon exposing it to sunlight for periods of time sufficient to tan the skin. Suitable self tanning agents include, without limitation, alpha hydroxy aldehydes and ketones, glyceraidehyde and related alcohol 20 aldehydes, various indoles, imidazoles and derivatives thereof, and various approved pigmentation agents. Presently preferred herein as self tanning agents are the alpha-hydroxy aldehydes and ketones. Most preferably, the self tanning agent is dihydroxyacetone ("DHA"), Other suitable self tanning agents include, without imitation, methyl glyoxat, glycerol aldehyde, 2$ erythrutose, alloxan, 2,3~dihydroxysuccindialdehyde, 2,3~ dimethoxysuccindialdehyde, 2-aminoa3hydroxy-succlndialdehyde and 2-. benzylamino-3~hydroxysuccindialdehyde. Suitable enulsifiers or surfactants include pharmaceutically acceptable, non-toxic, nonionic, anionic and cationic surfactants, Examples 3o of suitable non-ionic surfactants include glycerol fatty acid esters such as glycerol monostearate, glycol fatty acid esters such as propylene glycot monostearate, polyhydric alcohol fatty acid esters such as polyethylene glycol (400) monooleate, polyoxyethylene fatty acid esters such as polyoxyethyiene -9 (40) stearate, polyoxyethylene fatty alcohol ethers such as polyoxyethyfene (20) stearyl ether, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monAstearate, sorbitan esters such as sorbitan monostesrate, alkyl glycosides such as cetearyl glucoside, fatty acid s ethanolamides and their derivatives such as the diethanolamide of stearic acid, and the like. Examples of suitable anionic surfactants are soaps including alkali soaps, such as sodium, potassium and ammonium salts of aliphatic carboxylic acids, usually fatty acids, such as sodium stearate. Organic amine soaps include organic amine salts of aliphatic carboxylic acids 10 usually fatty acids, such as triethanolamine stearate. Metallic soaps include salts of polyvalent metals and aliphatic carboxylic acids, usually fatty acids, such as aluminium stearate. Other classes of suitable anionic surfactants include sulfated fatty acid alcohols such as sodium lauryl sulfate, sulfated oils such as the sulfuric ester of cinoleic acid disodium salt, and sulfoniated 1 s compounds such as alkyl sultonates including sodium cetane sulfonate, amide sulfonates such as sodium N-nethykN-oleyl laurate, sufonated dibasic acid esters such as sodium dioctyl suifosuccinate, alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl naphthalene sulfonates such a sodium isopropyl naphthalene sulfonate, petroleum sulfonate such as aryl 20 napthalene with alkyl substitutes. Examples of suitable cationic surfactants include amine salts such as octadecyl amrnonium chloride, quartemary armonium compounds such as benzalkonium chloride, An emollient is an oleaginous or oiy substance which helps to smooth and soften the skin, and may also reduce its oughness cracking or citation 2s Typical suitable emollients include mineral oil having a viscosity in the range of 50 to 500 centipoise (cps)' lanolin oil, coconut oil, cocoa butter, olive oil, almond oil. macadamia nut oil, aloe extracts such ale vera lipoquinone, synthetic jojoba oils, natural sonora jojoba ois, safflower ofl corn oil, liquid lanolin, cottonseed oil and peanut oil Preferably, the emollient is a 320 cocoglyceride, wh ich is a mixture of mono, di and triglycerides of cocoa oil, sold under the trade name of Myrital 33 1 from Henkel KGaAor Dicaprylyl Ether available under the trade name Cetiol OE from Henkel KGaA or a GiO C ,Alkyl Benzoate sold under the trade name Finsolv TN from Finetex. One or more emollients may be present ranging in amounts from about 1 percent to about 10 percent bv weight; preferably about 5 percent by weight Another suitable emollient is DC 200 Fluid 350, a silicone fuid, available Dow Coring Corp, Other suitable emollients include squalane, castor oil, polybutene, sweet almond oil, avocado l, calophyllum oil, ricin oil, vitamin E acetate olive oil, silicone oils such as dimethy opolysiloxane and cyclomethicone, linolenic alcohol, oleyl alcohol the oil of cereal germs such as the oil of wheat germ, isopropyl paomitate, octy palmitate, isopropyl myristate, hexadecyl to stearate, butyl stearate, decyl oleate, acety! glycerides, the octanoates and benzoates of (Cit0) alcohols, the octanoates and decanoates of alcohols and polyalcohols such as those of glycol and glyceryl, ricinoleates esters such as isopropyl adipate, hexyl laurate and octyl dodecanoate, dicapryly maleate, hydrogenated vegetable oil, phenyltrimethicone, jojoba oil and aloe vera is extract. Other suitable emorients which are solids or sem-sohds at ambient temperatures may be used, Such solid or semi-solid cosmetic emoitents include glyceryl dilaurate, hydrogenated lanolin, hydroxylated lanolin, acetylated lanolin, petrolaturm, isopropyl lanolate, butyl mydstate, cetyi myrstate, myristyl mydlstate, myistyl lactate, cetyl alocho, Isostearyl alcohol and socetyllanolate. One or more emolfients can optionally be included in the formulation, A humectant is a moistening agent that promotes retention of water due to its hygroscopic properties, Suitable humectants include glycedn 25 polymeric glycols such as polyethylene glycol and polypropylene glyco, mrannitol and sorbitoL. Preferably, the humetant is Sorbtol, 70% USP or polyethylene glydol 400, NF, One or more humectants can optionaly be included In the formulation in amounts from about 1 percent to about 10 percent by weight, preferably about 5 percent by weight. 30 A dry-feel modifier is an agent which when added to an emulsion, imparts a "dry feet" to the skinwhen the emulsion dies. Dry feel modifiers can include talc, kaolin, chalk, zinc oxide, silicone fluids, inorganic salts such as barium sulfate, surface treated silica, precipitated silica, fumed silica such -11 as an Aerosil available from Degussa Inc. of New York, N.Y. USA, Another dry feel modifieris an epichlorohydrn crosslnked plyceryl starch of the type that is disclosed in U. Patent No 648.,9 It may be advantageous to incorporate additonal thickening agents, s such as, for instance, various Carbopols available from Noveon Co Particulary preferred are those agents which would not disrupt the lamellar structure in the formulation of the final product, such as non-ionic thickening agents, The selection of additional thickening agents is well within the skill of one in the art. 10 An "anUoxidan" is a natural or synthetic substance added to the sunscreen to protect from or delay its deterioration due to the action of oxygen in the air (oxidation). They may also reduce oxidation reactions in skin tissue. Anti-oxidants prevent oxidative deterioration which may lead to the generation of rancidity and nonenyzymatic browning reaction products. 15 Typical suitable antioxidants include propyl, octyl and dodecy esters of gallit acid, butylated hydroxyanisole (BHA, usually purchased as a mixture of ortho and neta isomers). butyisted hydroxytoluene (BHT), green tea extract, uric acid, cysteine, pyruvate, nordihydrogualaretic acid, Vitamin A, Vitamin E and Vitamin C and their derivatives. One or more antioxidants can optionally be 20 included in the sunscreen composition in an amount ranging from about 0,001 to about 5 weight percent, preferably about 0,01 to about 0.5 percent, "Chelating agents are substances used to chelate or bind metalic jons, such as with a heterocylic ring structure so that the ion is held by chemical bonds from each of the participating rings. Suitable chelating agents 25 include ethylene diaminetetraacetic acid (EDTA). EDTA disodium, calcium disodium edetate, EDTA trisodium, albumin, transferring, desferoxailne, desferal, desferoxamine mesylate, EDTA tetrasodium and EDTA dipotassium, or combinations of any of these., "Fragrance&s are aromatic substances which can impart an 30 aesthetically pleasing aroma to the sunscreen composition. Typical fragrances include aromatic materials extracted from botanical sources e(i~e. rose petals, gardenia blossoms, jasmine flowers, etc,) which can be used alone or in any combination to create essential oils, Alternatively alcoholic -12 extracts may be prepared for compounding fragrances. However, due to the relatively high costs of obtaining fragrances from natural substances, the modern trend is to use synthetically prepared fragrances, particularQy in high volume products, One or more fragrances can optiona~iy be included in the 5 sunscreen composition in an amount ranging from about 0,001 to about 5 weight percent, preferably about 0,01 to about 0.5 percent by weight, Additional preservatives may also be used if desired and include well known preservative compositions such as benzyl alcohol, pheny ethyl alcohol and benzoic acid, diazolydinyl, urea, chlorphenesin, iodopropyny and butyl 0 carbamate, among others, The compositions of the invention can further comprise skin protecant active agents. Suitable examples include (with preferred weight percent ranges), Alantoin (0.5 to 2 percent); Aluminum hydroxide gel (0.15 to 5 percent); Calamine (1 to 25 percent); Cocoa butter (greater than 50); Cod liver s oi (5 to 14 percent); Colloidal oatmeal; Dimethicone (1 to 30 percent); Glycerin (20 to 45 percent); Hard fat (greater than 50); Kaofn (4 to 20 percent); Lanolin (12,5 to 50 percent); Mineral oil (greater than 50 percent); Petrolatum (greater than 30 percent); Sodium bicarbonate; Topical starch (10 to ,8 percent); White petrolatum (greater than 30 percent); Zinc acetate (0,1 20 to 2 percent); Zinc carbonate (0.2 to 2 percent); and Zinc oxide (I to 25 percent), The compositions of the invention may further include insect repelling components, The most widely used insect repeling active agent for personal care products is N,N-Diethy-m-toluamide, frequently called "DET" and as available in the form of a concentrate containing at least about 95 percent DEE VT Other synthetic chemical repellents include ethyl butytacetylaminoproprionate (also known as 1R 3535), dinethy phthalate, ethyl hexanedol, indalone, di-n-propylsocinchoronate. Wcyloheptene, dicarboximide and tetrahydrofuraidehyde. Certain piant-derived materials 3o also have insect repellent activity, including citronalla oil and other sources of citronella (including lemon grass ol), lmonene, rosemary oil and eucalyptus oitl Choice of an insect repellent for incorporation into the sunscreen emulsion will frequently be influenced by the odor of the repellent, The *13 amount of repellent agent used will depend upon the choice of agent; DEET is useful at high concentrations, such as up to about 15 percent or more, while some of the plant-derived substances are typically used in much lower amounts, such as 0.1 percent or less, Topical application of the compositions of the invention described herein to the hair or skin of a human will provide enhanced protection against deleterious effects of ultraviolet radiation (UVR) Thus, the subject invention further provides a method for protecting human skin and/or hair against the deleterious effects of solar radiation, more particularly UVR, which method 1 o comprises topically applying thereto an effective amount of the sunscreen compositions as described herein. An esthetically benefcial result of exposure of skin to UVR (ie. , light addition wavelengths of fromr 280 nm to 400 nm) is the promotion of tanning of the human epidermis. Another benefit of sun exposure comes from production of vitamin 0 within the skin, UVR is is typically divided into UV-A eightt wavelengths from 320 to 400 nm) and UV-B (wavelengths ranging from 280 to 320 on) regions. Overexposure to UV-B irradiation is generally understood to lead to skin burns and erythema, In addition, overexposure to UV-A radiation may cause a loss of elasticity of the skin and the appearance of wrinkles, promoting premature skin aging. Such 20 irradiation promotes triggerin g of the erythemel reaction or amplIfies this reaction in certain individuals and may even be the source of phototoxic or photoaliergc reactions. It is increasing y believed that overexposure to UV-A may also lead to melanoma, Thus, the application of the composittons of the invention to the skin and/or hair of an individual will provide enhanced UVR 2s photoprotection (UV-A andlor UV-S) of the skin and/or hair of the individual. The compositions of the invention are intended to provide a sun protection factor (SPF) rating of at least 2, with additonal preferable enbod'ments having a sun protection factor of at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at ieast 35, at least 40, at least 45, at 30 least 50, and at least 55, The invention will be further described by means of the following examples, which are not intended to Pmit the invention, as defined by the 14 appended claim, in any manner EXAMPLES $ Formulation of Sunscreen Lotions Several oil-in-water formulations comprising the sunscreen active compounds amiloxate, octinoxate, and octocrylene, indivdually and in various combinations, were tested in in vftro SPF experiments. Tables 1 and 2 list the ingredients for the fomulations containing either one or two sunscreen active 10 used for comparative purposes. Table 3 contains ingredients for forulations that contain combinations of all three sunscreen actves which illustrate the surprising synergy between amiloxate, octinoxate, and octocryiene, All formulatAns were prepared according to the following general method: 1 Keltrol and Veegum were added to the water of Part A in a suitable is container and mixed with mechanical stirrer until completely hydrated, The remainder of the Part A ingredient are then added with mAng tW form the water phase and heated to 165-75 "F 2. In a separate container all of the Part B ingredients are combined and heated to 180-185 OF ,o Tha Part B ingredients are then added to the water phase of Part A mixed well, and cooled slowly to 120-125 OF, 4, The Germaben 11 of Part C is then added and mixed well 6, The formulation is then cooled to room temperature and then Part 0 water is added US to weight, -s Tabe I Formulations Containing SInge Sunscreen Active Pat INC Name Trade Ex. 1 E 2 Ex, 3 Ex. 4 Ex. 5 Name Purired water [ wa 74.75 725 7725 72,25 72.25 A EunIestliby4 ISodli 03 0,30 f,30 0.30 0-30 Suuifata At_ P__opy___en ___ G__yco___ Propyten~e S.00 5.00 5.00 5.00 5£00 Sincate__ UStrfae A XanthanGumF 0,35 0.35 0,35 0.35 0,35 B NeopenylGlyA Lexfeel7 5.00 5,00 5.00 5,00 5100 Dfieptarn ae___ PVP Eko sne Ganex V-220 2.00 ZOO 200 2,00 2,00 S Aracidyl Atcohol Montanov 2.00 2.00 2.00 2,00 2.00 (and) $ehenyt Alcohot 202 (and) Arachidyl Gkutoaide ____ Octinoxate ParsoC 7,50 0 0 00 0,00 0,00 8 mioxteNochtlopan 0,00 5.00 0,00 0.00 10.00 Oc~tcryene Uvintd N 539 0.00 0(00 5.00 10.00 0.00 5Peg.30 ArteceP 135 00 .10 010 0.10 010 Dmtine Dow Ca mlag 100000 O 1. 00 . 1,00 _________-.=. T......... 200 Fttuid, 1350 OST _____ C Propylene glycol Germaben~ iU t0 1.00 1,00 1.00 1.00 (d)Dinolidiniyt urea (ernd) methyl paraben (and) prop I fl Purified Water Water aS OS OS QS OD Tota 100.0 10 01000 o All amountls fisted as pecn weight, 16 Table 2 Formutations Containing Two Sunscreen Actives' Part INi Name Trade Name Ex Ex. 8 '-I urffd water Water 8915 82. 5725 4 A qd00 .3O 00 0 $u fate Gatear~I03 j oetary' soumt ............ . . .. ... . -- --- Propylene GhycOt Prnpyiene 5.0 5.0 50 5.00 G. .yo. - Salcate 41 . ....... 23 Oleptanicate___ PV ce -0 200 700 i00 000 1(10 A(oO 3___ 0E 1000 _____________~ .. __ .......___ I-end) rahVI seOa Qlcrylene Uvnul 5397 00 1.0 1.0 100 0 p hydroste 9~eticoe Dow Corn ng I ---- _ ---- .5 ...... 1.0 .00 p0e 1.00. (and) Oiazolidlnyl paraben (and) propyl praben An amo n ed at ercn Qy$weigh 16 Table 3 Formdations Containing Three Sunscreen Actives' Part Et Nm M EL1 A Puife Wa1 Wtr 6.5 55 69 A m A A Zh etroa CGF 35 100 Gcosie__ ___ B Ot~nx~t Pas2lM2 2A 2~$ 7. 25 G -a d -- --- 2 000 B Ocorene 5 UiUso591 500 1.0 ot Daw C0IW I~ .00 200 Fhad 350 COT C------o d4 ----- { Gtw mati eI an4d Diardlidiiyi asrea (and) r"thyl parabenlrpy fl ptr- i IdW;tit water vS § Total ~ ou~ 00.05 000 A I armounts t erned aS weight SPF Measurements All SPF measurements were conducted using Vro @(MS )c Range~ CT; USA) as the substrate to which the sunscreen formulas were 10 applied, The substrates were hydrated according to the manufacturers - 18 instructions. Test formulatirs were applied to the substrates at 2 rng/cm mounted in 6X7 photographic side mounts (B&H Photo Video, New York NY; USA) and allowed to dry for 20 minutes. An untreated hydrated VitroSkcn@ substrate was also mounted in a slide mount and allowed to air dry for 20 5 minutes to serve as a reference and blank. The in vitro SPF of each formula was determined using an Optometrics SPF 290$ Analzyer (Optometics LLC, Ayer. MA; USA) equipped with a computer-controled XY sampling stage and operated according to the manufacture's instructions, A total of 12 in vitro SPF values were obtained for each formula using a different, non-overlapping xc position on each mounted substrate The resulting in vitro SPF values are shown in Table 4, Alt the $PF values reported are the average of 12 values measured for each formulation. Table 4 Measured vs, Expected SPF Formua Octinoxate Ailoxate Octecrylene Measured Expected Example (% wv) (%wv) (% wiv) SPF (sd)f SPF 7, 10 5 0 2 50 -6( 3 3 5 5,6(04) 4 541D 1-35 (3-0) S ~~10.0 __ 3( -47. j80 (1.3) 191 7 - MO 1 0 0 50,2(3 7 281 S5.0 100 24 (3.3) 24.2 S7 10-0 23 2 10 5 300 (24) 247 7.5 1O 42, 0 5&9) 34,' 12 7.5 1 00 10.0 i 482 (5 .) $9 2 - . - ............ i Measued S presents the mea othe diftere t deterMinatins. Expected SPF values reported for Examples 6-12 were cacuated by adding the sum of the individual SPPs fomrn each sunscreen at the same concentration, , -g The results in Table 4 dearly demonstrate that a unique synergy exists for the combination of sunscreen actives of the inventionas demonstrated for example in formulas 1042 containing various levels of al three sunscreen s actives. Formulas 10-12 increase SPF values by 5 to 9 SPF units relative to the SPF's expected from the arithmetic sum of the SPFs from individual sunscreen actives at the same concentrations. In contrast, measured SPF values of formulas 6-9 containing two sunscreen actives remain about the same as the expected SPF values, confirming that the synergies observed for i the combination of al three sunscreen actives do not derive from any possible combination of the two sunscreen actives. The synergistic effect in SPF performance only exists for combinations of all three sunscreen actives in the same formula. In addition to the ol-in-water emulsions described above, additional representative examples of photoprotective compositions according to the invention can be made for example as watergn-oil emulsions and alcohol spray compositons. Representative Examples 13 (waterln-on emulion) and 14 alcoholl spAy) are described below.
-20 Table 5 Water4h0i) EmtdskOn Formulation (Ex. i3) Part No. INCI Name Trade Name Wt. %(w) A 2 O Persol MCX A IrnItoxEo Neo~enopan G-10O0ld A 3 Octocrylne UnvfnslNS9T 10,0 4 BishyroxythyApropyi 0C q62 CabinoI Fluid 4.00 Um ethconR A 8 Cycoopnsiane (and) Dow Gorring 9011I Sicone 5.00 IPEGA2 Dnethicone Eaostomier Croepolymer -6 T-- opheroi d) -,alpha Tocopherol 0 20 & 7Purified Water Water :7 S Propylene Glycol j Propylene Glycol 5.00 0 Polyamninopropyl 8iguanIde Ceomad C0 t00 B 10 Sodigm Chloride Sodium Ch1o4d®05 a 11 Chlorpheaesin 3-4-Chlrphenoxyfl 2- 030 ______Tot ij100.00 - ------- The water-rin-oI formulation above can be prepared by first adding the oil phase ingredient of part A in a container large enough to hold the entire batch and mixing until uniform. Next, in a separate container add the water of part B followed by the remaining ingredients of Pard B 'n the listed order anid to mix well. Finally, The water phase of the second step can be added slowly to the oil phase of step one with slow mixing until all of the aqueous phase has been added and then the mixing speed is increased for rapid mixing to complete the emulsification and set the lotion composition.
-21 Table 6 Aloohol Spray Formulation (Ex. 14) Part INCI Name Trade Name Wt. % j I (wtw) A 1I _Otinoxate Parsol MCX "7.0 A 2 Am-oate Neoteliopan & 00 1000 A 3 Octocrylene Uvinu N 53T T S.00 A 4 SD Alcohol 40 SD Alcohol 40 79,30 A B AcrylatePOctylacryiamide Oernac y7g 00 Copolymer A r Fragrance Fragrance 0,20 Total 100,00 s The compasion is prepared by adding al ingredients to a suitable sized container in the order lsted and mhxng until uniform. The compositons cn then be loaded, for example, into a pump botle for spray application to the skin and/or hair 10 The comnpostons of the invention can also be prepared as aerosol formulations for application as a spray to the skin and/or hair The folowing composition in Table 7 (Example 15) is an example of the production of an aerosol formulation according t.o the subject invention, 22 Table 7 Aerosol Lotion Formulation Part diMC Name Trade Name W %w/w) Pufied wr41,33 A sodum Ceteary Sodium 0,21 Stdfate Caearyl ____________ Sufhle ____ A ropyiena Glytol Propyano: 3.50 {Silicate _ _ _ _ _ _ _ _ A Xdhan Gum Ketrol CGF 0,24 B PVP Estosene Gnex V-220 14 Copolymer I MB (end) Behenyl Akcohol (and) AraPhidy Glucoskde __ we Ocinoxt aro OX52 B Amtskte Noheliopati 7,00 5-1000 _____ __ B t Octocrybene Uvinul N 539 T 7,00 Psg~- ~~~~^~ el siP 13 0.0? O imnethicono Dlow Comirng 0.70 E Mrnethy1 Ether TOT Th aerosol loi listed in Table Pp cynan be easily prepared by ombiningth lotion torm ,u Wpon described herein with a corn fl d loaded J4t a suitable container to allow for storage until applied, in the above Example 15, 70% of the otion described in Example 12 can be combined with a to common propetlant, in this case 30% dimethyl ether, in a closed container, such as an aluminum can or glass bottle. To prepare the aerosol formulation, the emulsion is arowed to cool to room temperature and then weighed io the appropriate container such as an - 23-~ aluminum aerosol can or glass bottle. The appropriate valve, dip tube and actuator are placed in the can or bottle and the system Is crimped and Sealed using a hand crimper designed for the specific diameter of the can or botte. The sealed assenbly is then immersed in an ice bath, Vhile the assembly is maintained at or near 0*C, the propellant is introduced into the can or bottle from a gas cylinder containing the dimethyt ether by depressing the actuator stern and aHowing the gas to flow into the aerosol can or bottle, This transfer occurs because the pressure inside the aersol can or bottle at P'C is less than the pressure in the gas cylinder at ambient temperature, The can or i bottle can be periodically weighed to determine the amount of propellant that has been added. Although certeln present preferred embodiments of the invention have been described herein,, it wi be apparent to those sdUed in the art to is which the invendon pertains that variations and modifications of the described embodiments may be made without departing from the spirit and scope of the invention It is to be understood that, if any prior art publication is referred to 20 herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country. In the claims which follow and in the preceding description of the 25 invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.