UV PROTECTION COMPOSITIONS

Abstract: The present invention relates to compositions suitable for providing protection against the harmful effects of ultraviolet radiation. The compositions provide excellent efficiency, broad spectrum UV efficacy, and photostability. Methods of use for these compositions are also disclosed. The present compositions comprise: a) an effective amount of UVA-absorbing dibenzoylmethane sunscreen active; b) an effective amount of an aniline derivative, having formula (I) wherein R1, R2, R3, R4 and R5 are independently selected from the group consisting of H, R', OR', COOH, CHO, COOR', CN, SO2R', SO2OR', NO, aryls, OH, SH, NHR', NR'2, SR', I, Cl, F, Br, and combinations thereof; wherein R' is a C1 - C30 straight or branched alkyl or an aryl; wherein R1, R2, R3, R4 and R5 can together form with each other bridged cyclic structures; and c) a suitable carrier.

Description: UV PROTECTION COMPOSITIONS C ROSS RFFERFNCr I O RK1 VTF1) ΛPPLIC IQN I lus application is a C ontinuation-ln-Part ol Application Serial No. 09/174.30"' filed March 2. 1999. w hich is a C ontinued Prosecution Application ol Application Serial Nυ. 09 174.307 filed October 16. 1998. TECHNICAL FIELD The present invention relates to compositions suitable for providing protection against the harmful effects of ultraviolet radiation having excellent efficiency, broad spectrum UV efficacy, and photostability The compositions comprise a UVA-absorbmg dibenzoy nethane sunscreen active, an aniline demam e. and a suitable carrier BACKGROUND OF THE INVENTION It is well known that exposure to sunlight can pose a number of hazards to the skin These damaging effects may result not on y from sunbathing but also from the sunlight exposure associated with daily outdoor activities The major short term hazard of prolonged exposure to sunlight is erythema, I e , sunburn, which primarily results from UVB radiation having a wavelength of from about 290 nm to about 320 nm Over the long term, however, malignant changes in the skin surface often occur Numerous epidemmologic studies demonstrate a strong relationship between sunlight exposure and human skin cancer Another long term hazard of ultraviolet radiation is premature aging of the sk , which is pπmaπh caused by UVA radiation having a wavelength of from about 320 nm to about 400 nm This condition is characterized by wrinkling and pigment changes of the skin, along with other physical changes such as cracking, telangiectasis, solar dermatoses, ecchymoses, and loss of elasticity The adverse effects associated with exposure to UV radiation are more fully discussed m DeSimone, "Sunscreen and Suntan Products," Handbook of Nonprescription Drugs, 7th Ed , Chapter 26, pp 499-51 1 (American Pharmaceutical Association, Washington, D C , 1982), Grove and Forbes, "A Method for Evaluating the Photoprotection Action of Sunscreen Agents Against UV-A Radiation," International Journal of Cosmetic Science. 4, pp 15-24 (1982), and U S Patent No 4,387,089, DePolo, issued June 7, 1983 As a result of the abovementioned hazards associated with sunlight exposure, the general public's interest in the sun protection product market has grown considerably Today, there are not only sunscreen products for sunbathing but there are also a variety of personal care products containmg sunscreens, particularly cosmetic type products which are worn daily "Personal care products" refer to health and cosmetic beauty aid products generally recognized as being formulated for beautifying and grooming the skin and hair For example, personal care products include sunscreen products (e g , lotions, skin creams, etc ), cosmetics, toiletries, and over-the-counter pharmaceutical products intended for topical usage Many conventional sunscreen products, m particular, are deficient, however, due to their inability to provide efficacious protection against broad spectrum UV radiation, 1 e , protection agamst both UVB and UVA radiation Today, most commercially available sunscreen products are efficient at absorbing UV radiation in the 290 nm to 320 nm UVB region such that sunburn of the skin is prevented They are less efficient when it comes to absorbing light which falls m the 320 nm to 400 nm UVA region, which leaves the skin vulnerable to premature s in aging This deficiency is due in part to the limited number of UVA absorbing sunscreen actives which are both commercially available and approved for global use One class of these sunscreen actives includes dibenzoylmethane compounds which provide broad spectrum UV protection and 4-tert-butyl-4'-methoxydιbenzoylmethane, m particular, is also approved for global use Unfortunately, these sunscreens tend to photodegrade upon exposure to UV radiation thereby reducing their UVA efficacy Consequently, sunscreen products which include these compounds are typically more difficult to formulate due to the inherent lack of photostability of dibenzoylmethane compounds One approach to stabilize these types of sunscreens is described in U S Seπal No 07/929,612, Deckner, filed August 13, 1992, involving the use of benzy dene camphor sunscreens to stabilize the dibenzoylmethane compound Such compositions, however, are not currently approved for global use on humans Thus, there is a need for photostabilized compositions suitable for providing protection against the harmful effects of UV radiation to human skin In particular, m the personal care industry, a need remains for sunscreen products having excellent photostability, efficiency, and which provide broad spectrum UV protection (l e , against both UVA and UVB radiation) in a safe and economical manner Likewise, in other industries such as the automotive care, marine vehicle care, household care, animal care, and coatings industries, UV radiation causes undesirable wear and damage Therefore, a need exists for photostabilized compositions suitable for providing protection against the haπnful effects of UV radiation to a variety of objects and or materials prone to sun exposure It has surprisingly now been found that the compositions of the present mvention, which comprise a UVA-absorbmg dibenzoylmethane sunscreen active, an amlme deπvative, and a suitable earner, provide excellent photostability, efficiency, and UV protection efficacy (including both UVA and UVB protection), in a safe and economical manner SUMMARY OF THE INVENTION The present invention relates to a composition suitable for providmg protection against the harmful effects of ultraviolet radiation compnsing a) an effective amount of a UVA-absorbing dibenzoylmethane sunscreen active, b) an effective amount of an aniline deπvative, having the formula R 3 wherein R u R 2 , R 3 , R 4 , and R 5 are independently selected from the group consisting of H, R\ OR', CHO, CN, S0 2 R\ S0 2 OR', NO, aryls, OH,SH, NHR', NR' 2( SR', I, CI, F, Br, and combinations thereof, wherein R' is a C| - C 30 straight or branched alkyl or an aryl, wherein R,, R 2 , R 3 , R 4 , and R 5 can together form with each other bndged cyclic structures; and c) a suitable carrier. In preferred embodiments, the UVA-absorbing dibenzoylmethane sunscreen active and the amlme derivative are present in "safe and effective" amounts and the mole ratio of the UVA-absorbmg dibenzoylmethane sunscreen active to the aniline deπvative is from about 8.1 to about 1 1, more preferably from about 4 1 to about 1 : 1, and most preferably from about 2.1 to about 1 1. The present invention also relates to methods for providing protection to skm from the harmful effects of UV radiation by topical application of such compositions. Furthermore, the present invention relates to methods of stabilizing a UVA-absorbing dibenzoylmethane sunscreen active. DETAILED DESCRIPTION OF THE INVENTION The compositions of the present invention are useful for providing protection against the harmful effects of ultraviolet radiation, especially to human skin The essential components of these compositions are described below Also included is a nonexclusive description of various optional and preferred components useful in embodiments of the present invention. The present invention can comprise, consist of, or consist essentially of any of the required or optional ingredients and/or limitations described herein. All percentages and ratios are calculated on a weight basis unless otherwise indicated. All percentages are calculated based upon the total composition unless otherwise indicated. All molar weights are weight average molecular weights and are given in units of grams per mole. All ingredient levels are in reference to the active level of that ingredient, and are exclusive of solvents, by-products, or other impurities that may be present in commercially available sources, unless otherwise indicated. All measurements made are at ambient room temperature, which is approximately 73 °F, unless otherwise designated. All documents referred to herein, including patents, patent applications, and pπnted publications, are hereby incorporated by reference in their entirety in this disclosure By "safe and effective amount" is meant an amount of a compound, component, or composition (as applicable) sufficient to significantly induce a positive effect (e.g., photoprotection or improvement in photostability), but low enough to avoid senous side effects, (e.g., undue toxicity or allergic reaction), i.e., to provide a reasonable benefit to nsk ratio, within the scope of sound medical judgment By "effective amount" is meant an amount of a compound, component, or composition (as applicable) sufficient to significantly induce a positive effect (e.g., photoprotection or improvement m photostability). UVA-Absorbing Dibenzoylmethane Sunscreen Active The compositions of the present invention compnse a UVA-absorbmg dibenzoylmethane sunscreen active which absorbs UV radiation having a wavelength of from about 320 nm to about 400 nm. Preferred UVA-absorbing dibenzoylmethane sunscreen actives have the general structure wherein R| is a substituent selected from the group consisting of H, OR, and NRR wherein each R is independently H, or d - C 20 straight or branched alkyls, R 2 is selected from the group consisting of H or OH, and is selected from the group consisting of H, or C) - C 20 straight or branched alkyls Even though the dibenzoylmethane chromophore is represented as a 1,3-dιketone, it should be understood that this representation in no way excludes other tautomeric forms of the functional group such as the enol form. Thus, whenever the 1,3-dιketone form is designated, it is understood that all appropriate enol tautomers are also contemplated and included herein These tautomeric enol forms of the dibenzoylmethane chromophore can be represented by the following tautomeric structures wherein R|, R 2 , and R 3 are defined as above. Examples of such UVA-absorbmg dibenzoylmethane sunscreen actives are described in U S. Patent No. 4,489,057, issued to Welters et al. on December 18, 1984 and U. S. Patent No. 4,387,089, issued to Depolo on June 7, 1983, and in Sunscreens Development, Evaluation, and Regulatory Aspects, edited by N. J. Lowe and N. A. Shaath, Marcel Dekker, Inc. (1990). Suitable UVA-absorbing dibenzoylmethane sunscreen actives include, but are not limited to, those selected from the group consisting of 2-methyldιbenzoylmethane, 4-methyldιbenzoylmethane, 4- lsopropyldibenzoylmethane, 4-tert-butyldιbenzoylmethane, 2,4-dιmethyldιbenzoylmethane 2,5- dimethyldibenzoylmethane, 4,4'-dιιsopropylbenzoylmethane, 4-tert-butyl-4'-methoxydιbenzoylmethane, 2- methyl-5-ιsopropyl-4'-methoxydιbenzoylmethane, 2-methyl-5-tert-butyl-4'-methoxydιbenzoylmethane, 2,4- dιmethyl-4'-methoxydιbenzoylmethane, 2,6-dιmethyl-4'tert-butyl-4'methoxydιbenzoylmethane, and mixtures thereof Preferred UVA-absorbing dibenzoylmethane sunscreen actives include those selected from the group consisting of 4-tert-butyl-4'-methoxydιbenzoyhnethane, lsopropyldibenzoylmethane, and mixtures thereof A more preferred UVA-absorbmg dibenzoylmethane sunscreen active is 4-tert-butyl-4'- methoxydibenzoylmethane The sunscreen active, 4-tert-butyl-4'-methoxydιbenzoylmethane, which is also known as butyl methoxydibenzoylmethane or Avobenzone, is commercially available under the names Parsol® 1789 from Givaudan-Roure (International) S A (Basel, Switzerland) and Eusolex® 9020 from Merck & Co , Inc (Whitehouse Station, NJ) The sunscreen 4-ιsopropyldιbenzoylmethane, which is also known as isopropyl dibenzoylmethane, is commercially available from Merck under the name Eusolex 8020 The UVA-absorbing dibenzoylmethane sunscreen active of the instant invention is present m an effective amount, preferably in a safe and effective amount, to provide broad spectrum UV protection either independently or in combination with other UV protective actives which may be present m the composition The composition preferably contains from about 0 01% to about 30%, more preferably from about 0 1% to about 6%, and most preferably from about 1% to about 3%, by weight of the composition, of the UVA- absorbing dibenzoylmethane sunscreen active Exact amounts of the sunscreen active will vary depending upon the desired Sun Protection Factor, l e , the "SPF" of the composition as well as the desired level of UVA protection (SPF is a commonly used measure of photoprotection of a sunscreen against erythema The SPF is defined as the ratio of the ultraviolet energy required to produce minimal erythema on protected skin to that required to produce the same minimal erythema on unprotected skm in the same individual See Federal Register, 43, No 166, pp 38206-38269, August 25, 1978) Aniline Derivative The compositions of the present invention also compπse an aniline deπvative having the formula R 3 wherein R,, R , R 3 , R,, and R 5 are independently selected from the group consisting of H, R', OR', CHO, CN, S0 2 R', SO : OR\ NO, aryls, OH.SH, NHR', NR' 2 , SR', I, CI, F, Br, and combmations thereof, wherem R' is a Ci - C 30 straight or branched alkyl or an aryl, wherem R b R 2 , R 3 , R,, and R 5 can together form with each other bπdged cyclic structures As used herein, "alkyl" means carbon-contaimng chains which may be straight, branched or cyclic, substituted or unsubstituted, saturated, monounsaturated (1 e one double or triple bond m the carbon cham), or polyunsaturated (1 e two or more double bonds m the carbon cham, two or more tnple bonds m the carbon cham, one or more double and one or more triple bonds m the carbon cham) Unless otherwise indicated, alkyl are preferably as follows Preferred alkyl are straight or branched chain, more preferably straight chain Preferred alkyl are mono-, di-, or tπ- substituted, or unsubstituted, most preferably unsubstituted Preferred alkyl are saturated or monounsaturated and, if so, preferably with a double bond, more preferably alkyl are samrated Preferred alkyls are C 1 -C 30 , more preferably CI -CI Q, also more preferably C1 -C4, even more preferably methyl, ethyl and t-butyl, even still more preferably methyl and ethyl, and most preferably methyl Thus the term "substituted alkyl" is included in the definition of alkyl Preferred alkyl substituents fi e substitution on alkyls) include ester, ketone, aldehyde, carboxyhc acid, halo, aryl, ammo, hydroxy, alkoxy, cyano, nitro, amino (including mono- and disubstituted ammo), thiol, and substituted thiol and tπfluoromethyl More preferred alkyl substiments are ester and aryl As used herein the term "alkoxy" includes the above described alkyl radicals attached to the molecule \ ιa oxygen Thus, alkyl not only includes the CI -CI Q alkoxy, but also includes species such as methylenedioxy, ethylenedioxy and other similarly bifunctional, or multifunctional alkoxy substiments These multifunctional substiments can be attached to various places in the molecule and thus form bπdged species For example, species such as dioxolanes, dioxanes and the like are specifically contemplated As used herein "halo" means F, CI, Br, and I Preferred "halos" are F, CI, and Br, more preferably F and CI, most preferably F As used herein, "aryl" or "Ar" means aromatic rings which may be unsubstituted or substituted Preferred aryl are phenyl or naphthyl, especially phenyl Preferred aryl are mono-, di-, tπ- substituted or unsubstituted, more preferred aryl are monosubstituted or unsubstituted, most preferred being unsubstituted Preferred aryl substituents include ester, ketone, aldehyde, carboxyhc acid, alkyl, halo, amino, hydroxy, alkoxy, cyano, nitro and tπfluoromethyl More preferred aryl substiments are alkyl and ester The most preferred aryl is unsubstituted and thus is phenyl Preferably, the aniline deπvative is selected from the group consisting of 4-phenoxyanιhne 2-butylaniline 3,4-(methylenedioxy) aniline p-phenetidine 4-chloro-2-methoxy-5-methylaniline 2,4,6-tπmethyl- 1 ,3-phenylene diamine and mixtures thereof More preferably, the aniline deπvative is selected from the group consisting of 4- phenoxyamline, 2-butylanιhne, 4-chloro-2-metho\y-5-methylanιlιne, and mixtures thereof Suitable amlme deπvatives are commercially available from Aldπch Chemical Co , Inc (Milwaukee, WI) The amlme denvative of the present invention is present in an effective amount, preferably m a safe and effective amount, to reduce the photodegradation of the UVA-absorbmg dibenzoylmethane sunscreen active Photodegradation may be determined by a reduction of the UV absorption capability which in turn may be measured by using standard UV absorption methods Preferred compositions retain at least about 75%, more preferably at least about 85%, and most preferably at least about 95%, of their initial UV absorption after irradiation with approximately 2 J/cm " per desired SPF unit of broad band UV radiation, e g , 30 J/cm * for an SPF 15 composition Preferably, the amlme deπvative is present in an amount such that the mole ratio of the UVA-absorbing dibenzoylmethane sunscreen active to the amlme deπvative is preferably from about 8 1 to about 1 1, more preferably from about 4 1 to about 1 1, and most preferably from about 2 1 to about 1 1 Carrier The compositions of the present invention compπse a suitable earner or vehicle for the UVA- absorbing dibenzoylmethane sunscreen active, the aniline deπvative, and any optional components Suitable carriers are well known in the art and are selected based on the end use application For example, earners of the present invention include, but are not limited to, those suitable for application to skm, hair, nails, animal skin, fur, automobiles, fabrics, manne vehicles, as well as those suitable for incorporation into plastics, metals, etc Preferably, the carriers of the present invention are suitable for application to skin (e g , sunscreens, creams, milks, lotions, masks, serums, etc ), hair and fur (e g , shampoos, hair setting or treatment gels or lotions, shaping/curhng/fixation lacquers or lotions, etc,), and nails (e g , polishes, treatments, etc ) In preferred embodiments, the earner is suitable for application to skin which means that the earner and its components are suitable for use in contact with skm, hair, fur, and nails without undue toxicity, incompatibility, instability, allergic response, and the like within the scope of sound medical judgment Such carriers are well-known to one of ordmary skill in the art, and can mclude one or more compatible liquid or solid filler diluents or vehicles which are suitable for application to skin, hair, fur, and nails The exact amount of earner will depend upon the level of the UVA-absorbmg dibenzoylmethane sunscreen active, the aniline deπvative and any other optional mgredients which one of ordmary skill m the art would classify as distinct from the carrier (e g , other active components) The compositions of the present mvention preferably compπse from about 20% to about 99 8%, more preferably from about 50% to about 99%, and most preferably from 75% to about 95%, by weight of the composition, of a earner The carrier and compositions herem can be formulated in a number of ways, including but not limited to emulsions (in emulsion technology, a composition compπsmg a "dispersed phase" and a "continuous phase," the dispersed phase existing as small particles or droplets that are suspended m and surrounded by a contmuous phase) For example, suitable emulsions mclude oil-in-water, water-in-oil, water-m-oil-m-water, oil-in-water-m-oil, and oil-m-water-in-sihcone emulsions Preferred compositions comprise an oil- -water emulsion The compositions of the present invention can be formulated into a wide vanety of product types, including creams, waxes, pastes, lotions, milks, mousses, gels, oils, tonics, and sprays Preferred compositions are formulated into lotions, creams, gels, and sprays These product forms may be used for a number of applications, including, but not limited to, hand and body lotions, cold creams, facial moistunzers, anti-acne preparations, topical analgesics, make-ups/cosmetics including foundations, eyeshadows, lipsticks, and the like as well as coatings (e g , paints, varnishes, polishes, adhesives, etc ), household care items (e g , detergents, cleansers, fabric conditioners, etc ), automotive and marine v ehicle care items (e g , waxes, etc ), hair care and styling products (e g , shampoos, conditioners, gels, mousses, sprays, etc ), topical animal care items (e g , shampoos, conditioners, skin treatments, etc ) Any additional components required to formulate such products vary with product type and can be routinely chosen by one skilled in the art If compositions of the present invention are formulated as an aerosol and applied to the skm as a spray-on product, a propellant is added to the composition Examples of suitable propellants include chlorofluoπnated lower molecular weight hydrocarbons A more complete disclosure of propellants useful herein can be found m Sagarin, Cosmetics Science and Technology. 2nd Edition, Vol 2, pp 443-465 ( 1972) Optional Components The compositions of the present mvention may contam a variety of other ingredients such as are conventionally used in a given product type provided that they do not unacceptably alter the benefits of the invention In a preferred embodiment, where the composition is to be m contact with human skm, the optional components should be suitable for application to skin, that is, when incorporated mto the composition they are suitable for use in contact with human skin without undue toxicity, incompatibility, instability, allergic response, and the like within the scope of sound medical judgment The CTFA Cosmetic Ingredient Handbook, Second Edition (1992) descnbes a wide vanety of nonlimitmg cosmetic and pharmaceutical ingredients commonly used m the skm care industry, which are suitable for use in the compositions of the present invention Examples of these ingredient classes mclude: abrasives, absorbents, aesthetic components such as fragrances, pigments, colonngs/colorants, essential oils, skm sensates. astringents, etc. (e.g , clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazel distillate), anti-acne agents, anti-caking agents, antifoaming agents, antimicrobial agents (e.g., lodopropyl butylcarbamate), antioxidants, binders, biological additives, buffenng agents, bulking agents, chelating agents, chemical additives, colorants, cosmetic astringents, cosmetic biocides, denaturants, drug astringents, external analgesics, film formers or mateπals, e.g., polymers, for aidmg the film-forming properties and substantivity of the composition (e.g , copolymer of eicosene and vinyl pyrrohdone), opacifying agents, pH adjusters, propellants, reducing agents, sequestrants, skin bleaching and lightening agents (e.g , hydroquinone, kojic acid, ascorbic acid, magnesium ascorbyl phosphate, ascorbyl glucosamine), skin-conditioning agents (e.g., humectants, including miscellaneous and occlusive), skin soothing and or healing agents (e g., panthenol and derivatives (e.g., ethyl panthenol), aloe vera, pantothenic acid and its derivatives, allantom, bisabolol, and dipotassium glycyrrhizinate), skin treating agents, thickeners, and vitamins and deπvatives thereof The compositions of the present invention may contain one or more of such optional components. Preferred compositions optionally contam one or more matenals selected from UVB sunscreen actives, anti- acne actives, vitamin compounds, skin treating agents, humectants, moisturizers, skin conditioners, thickening agents, structunng agents, and emulsifiers. In any embodiment of the present invention, however, the actives useful herein can be categorized by the benefit they provide or by their postulated mode of action. However, it is to be understood that the actives useful herein can in some instances provide more than one benefit or operate via more than one mode of action Therefore, classifications herein are made for the sake of convenience and are not intended to limit the active to that particular application or applications listed. a) UVB Sunscreen Active The compositions of the present mvention may compπse one or more UVB sunscreen actives which absorb UV radiation havmg a wavelength of from about 290 nm to about 320 nm As used herem the UVB sunscreen active means an active other than the UVA-absorbing dibenzoylmethane sunscreen active which itself may possess UVB absorption properties The compositions compπse an amount of the UVB sunscreen active which is safe and effective to provide UVB protection either mdependently or m combination with other UV protective actives which may be present m the composition, preferably from about 0 1% to about 30%, more preferably from about 0 5% to about 25%, and most preferably from about 1% to about 20% by weight of the composition A wide variety of UVB sunscreen actives, including both organic sunscreen actives and inorganic physical sunblocks, are suitable for use herem Nonlimiting examples of such sunscreen actives are described in U S Patent No 5,087,445 issued February 1 1, 1992 to Haffey et al, and U S Patent Nos 5,073.371 and 5,073,372, both issued on December 17, 1991 to Turner et al Nonlimiting examples of suitable physical sunblocks are described in CTFA International Cosmetic Ingredient Dictionary, Sixth Edition, 1995, pp 1026-28 and 1103 Preferred UVB sunscreen actives are selected from the group consisting of 2-phenyl-benzιmιdazole- 5-sulfomc acid, octyl methoxycinnamate, TEA sahcylate, octyl sa cylate, octyl dimethyl PABA, zinc oxide, titanium dioxide, and mixtures thereof A preferred water-soluble organic sunscreen active is 2-phenyl- benzιmιdazole-5-sulfonιc acid while preferred inorganic physical sunblocks are zinc oxide, titanium dioxide, and mixtures thereof Salt and acid-neutralized forms of the acidic sunscreens are also useful herein b) Anti-Acne Actives The compositions of the present invention may comprise one or more anti-acne actives Examples of useful anti-acne actives include resorcmol, sulfur, salicylic acid, erythromycin, zinc, etc Further examples of suitable anti-acne actives are descnbed in further detail in U S Patent No 5,607,980, issued to McAtee et al, on March 4, 1997 c) Vitamin Compounds The compositions of the present invention may comprise vitamin compounds, precursors, and derivatives thereof These vitamin compounds may be in either natural or synthetic form Suitable vitamin compounds include, but are not limited to, Vitamin A (e g , beta carotene, retmoic acid, retinol, retinoids, retinyl palmitate, retinyl propπonate, etc ), Vitamin B (e g , niacin, niacinamide, nboflavin, pantothenic acid, etc ) Vitamin C (e g , ascorbic acid, etc ), Vitamin D (e g , ergosterol, ergocalciferol, cholecalciferol, etc ), Vitamin E (e g , tocopherol acetate, etc ), and Vitamin K (e g , phytonadione, menadione, phthiocol, etc ) compounds In particular, the compositions of the present invention may compπse a safe and effective amount of a vitamin B3 compound Vitamin B 3 compounds are particularly useful for regulating skin condition as descnbed in co-pendmg U. S Application Senal No 08/834,010, filed Apnl 1 1, 1997 (corresponding to international publication WO 97/39733 Al, published October 30, 1997) which is incorporated by reference herem in its entirety. The compositions of the present invention preferably compnse from about 0.01% to about 50%, more preferably from about 0.1% to about 10%, even more preferably from about 0.5% to about 10%, and still more preferably from about 1% to about 5%, most preferably from about 2% to about 5%, of the vitamin B3 compound As used herein, "vitamin B3 compound" means a compound having the formula- wherein R is - CONH2 (i.e., niacinamide), - COOH (i.e , mcotimc acid) or - CH2OH (i.e., nicotinyl alcohol), derivatives thereof, and salts of any of the foregoing. Exemplary derivatives of the foregoing vitamin B3 compounds include mcotinic acid esters, including non-vasodilating esters of mcotinic acid, nicotinyl amino acids, nicotinyl alcohol esters of carboxyhc acids, mcotinic acid N-oxide and niacinamide N-oxide. Examples of suitable vitamin B3 compounds are well known in the art and are commercially available from a number of sources, e.g., the Sigma Chemical Company (St. Louis, MO); ICN Biomedicals, Inc ( Irvin, CA) and Aldπch Chemical Company (Milwaukee, WI). The vitamin compounds may be included as the substantially pure material, or as an extract obtained by suitable physical and/or chemical isolation from natural (e.g., plant) sources d) Skin Treating Agent The compositions of the present invention may contain one or more skin treating agents. Suitable skm treating agents include those effective for preventing, retarding, arresting, and/or reversing skin wnnkles Examples of suitable skm treating agents include, but are not limited to, alpha-hydroxy acids such as lactic acid and glycohc acid and beta-hydroxy acids such as salicylic acid. e) Structuring Agent The compositions of the present invention may contain a structunng agent such as are known in the art. Strucmring agents are particularly preferred m the oil-in-water emulsions of the present invention. Without being limited by theory, it is believed that the structunng agent assists in providing rheological charactenstics to the composition which contribute to the stability of the composition For example, the strucmring agent tends to assist in the formation of the liquid crystalline gel network structures. The structuring agent may also function as an emulsifier or surfactant. Preferred compositions of this mvention compπse from about 0.5% to about 20%, more preferably from about 1% to about 10%, most preferably from about 1% to about 5%, of one or more strucmring agents The preferred structunng agents of the present invention are selected from the group consisting of steaπc acid, palmitic acid, stearyl alcohol, cetyl alcohol, behenyl alcohol, steaπc acid, palmitic acid, the polyethylene glycol ether of stearyl alcohol havmg an average of about 1 to about 21 ethylene oxide units, the polyethylene glycol ether of cetyl alcohol havmg an average of about 1 to about 5 ethylene oxide units, and mixtures thereof More preferred structunng agents of the present mvention are selected from the group consisting of stearyl alcohol, cetyl alcohol, behenyl alcohol, the polyethylene glycol ether of stearyl alcohol havmg an average of about 2 ethylene oxide units (steareth-2), the polyethylene glycol ether of stearyl alcohol having an average of about 21 ethylene oxide units (steareth-21), the polyethylene glycol ether of cetyl alcohol having an average of about 2 ethylene oxide units, and mixtures thereof Even more preferred structuring agents are selected from the group consisting of steaπc acid, palmitic acid, stearyl alcohol, cetyl alcohol, behenyl alcohol, steareth-2, steareth-21, and mixtures thereof f) Thickening Agent (including thickeners and gelling agents) The compositions of the present invention can compπse one or more thickening agents, preferably from about 0 1% to about 5%, more preferably from about 0 1% to about 3%, and most preferably from about 0 25% to about 2%, by weight of the composition Nonlimiting classes of thickening agents include those selected from the group consisting of (I) Carboxyhc Acid Polymers These polymers are crosshnked compounds containmg one or more monomers derived from acrylic acid, substituted acrylic acids, and salts and esters of these acrylic acids and the substituted acrylic acids, wherein the crosslinking agent contains two or more carbon-carbon double bonds and is deπved from a polyhydπc alcohol Polymers useful in the present invention are more fully descπbed in U S Patent No 5,087,445, to Haffey et al, issued February 11, 1992, U S Patent No 4.509,949, to Huang et al, issued April 5, 1985, U S Patent No 2,798,053, to Brown, issued July 2, 1957, and in CTFA International Cosmetic Ingredient Dictionary, Fourth Edition, 1991, pp 12 and 80 Examples of commercially available carboxyhc acid polymers useful herein include the carbomers, which are homopolymers of acrylic acid crosshnked with allyl ethers of sucrose or pentaerytntol The carbomers are available as the Carbopol® 900 series from B F Goodrich (e g , Carbopol® 954) In addition, other suitable carboxyhc acid polymenc agents include copolymers of Cjø.30 alkyl acrylates with one or more monomers of acrylic acid, methacry c acid, or one of their short chain (l e , Cι _4 alcohol) esters, wherein the crosslinking agent is an allyl ether of sucrose or pentaerytntol These copolymers are known as acrylates/C 10 - 30 alkyl acrylate crosspolymers and are commercially available as Carbopol® 1342, Carbopol® 1382, Pemulen TR-1, and Pemulen TR-2, from B F Goodnch In other words, examples of carboxyhc acid polymer thickeners useful herein are those selected from the group consisting of carbomers, acrylates/Cio-C 30 alkyl acrylate crosspolymers, and mixtures thereof (n) Crosslinked Polyacrylate Polymers The compositions of the present mvention can optionally compnse crosslinked polyacrylate polymers useful as thickeners or gelling agents mcludmg both catiomc and nonionic polymers, with the catiomcs bemg generally preferred Examples of useful crosslinked nonionic polyacrylate polymers and crosshnked catiomc polyacrylate polymers are those descnbed in U. S. Patent No. 5,100,660, to Hawe et al, issued March 31, 1992; U. S. Patent No. 4,849,484, to Heard, issued July 18, 1989; U. S. Patent No. 4,835,206, to Farrar et al, issued May 30, 1989; U.S. Patent No. 4,628,078 to Glover et al issued December 9, 1986; U.S Patent No. 4,599,379 to Flesher et al issued July 8, 1986; and EP 228,868, to Farrar et al, published July 15, 1987. (in) Polyacrylamide Polymers The compositions of the present invention can optionally compπse polyacrylamide polymers, especially nonionic polyacrylamide polymers including substituted branched or unbranched polymers. Most preferred among these polyacrylamide polymers is the nomonic polymer given the CTFA designation polyacrylamide and isoparaffin and laureth-7, available under the Tradename Sepigel 305 from Seppic Corporation (Fairfield, NJ). Other polyacrylamide polymers useful herein include multi-block copolymers of acrylamides and substituted acrylamides with acrylic acids and substituted acrylic acids. Commercially available examples of these multi-block copolymers include Hypan SR150H, SS500V, SS500W, SSSA100H, from Lipo Chemicals, Inc., (Patterson, NJ). (IV) Polysacchaπdes A wide variety of polysacchaπdes are useful herein "Polysacchandes" refer to gelling agents which contam a backbone of repeating sugar (i.e., carbohydrate) units. Nonlimiting examples of polysacchaπde gelling agents clude those selected from the group consisting of cellulose, carboxymethyl hydroxyethylcellulose, cellulose acetate propionate carboxylate, hydroxyethylcellulose, hydroxyethyl ethylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose, methyl hydroxyethylcellulose, microcrystalhne cellulose, sodium cellulose sulfate, and mixtures thereof. Also useful herein are the alkyl substituted celluloses. In these polymers, the hydroxy groups of the cellulose polymer is hydroxyalkylated (preferably hydroxyethylated or hydroxypropylated) to form a hydroxyalkylated cellulose which is then further modified with a Cιo-C 30 straight cham or branched cham alkyl group through an ether linkage. Typically these polymers are ethers of Cιo-C 30 straight or branched cham alcohols with hydroxyalkylcelluloses. Examples of alkyl groups useful herein mclude those selected from the group consisting of stearyl, isostearyl, lauryl, myπstyl, cetyl, lsocetyl, cocoyl (i.e. alkyl groups deπved from the alcohols of coconut oil), palmityl, oleyl, noleyl, linolenyl, πcinoleyl, behenyl, and mixtures thereof. Preferred among the alkyl hydroxyalkyl cellulose ethers is the matenal given the CTFA designation cetyl hydroxyethylcellulose, which is the ether of cetyl alcohol and hydroxyethylcellulose. This matenal is sold under the tradename Natrosol® CS Plus from Aqualon Corporation (Wilmington, DE). Other useful polysacchandes include scleroglucans compnsmg a lmear chain of (1-3) linked glucose units with a (1-6) linked glucose every three units, a commercially available example of which is Clearogel™ CS1 1 from Michel Mercier Products Inc (Mountainside, NJ) (v) Gums Other thickening and gelling agents useful herein mclude matenals which are pnmanly denved from natural sources Nonlimiting examples of these gelling agent gums mclude mateπals selected from the group consisting of acacia, agar, algin, alginic acid, ammonium algmate, amylopectin, calcium algmate, calcium carrageenan, carnitine, canageenan, dextnn, gelatin, gellan gum, guar gum, guar hydroxypropyltnmonium chloride, hectoπte, hyaluroinic acid, hydrated silica, hydroxypropyl chitosan, hydroxypropyl guar, karaya gum, kelp, locust bean gum, natto gum, potassium algmate, potassium canageenan, propylene glycol algmate, sclerotium gum, sodium carboyxmethyl dextran, sodium canageenan, tragacanth gum, xanthan gum. and mixtures thereof Prefeπed compositions of the present invention include a thickening agent selected from the group consisting of carboxyhc acid polymers, crosslinked polyacrylate polymers, polyacrylamide polymers, and mixtures thereof, more preferably selected from the group consisting of carboxyhc acid polymers, polyacrylamide polymers, and mixtures thereof g) Humectants, Moisturizers, and Skin Conditioners Prefeπed compositions optionally comprise one or more humectants, moistuπzers, or skm conditioners A variety of these mateπals can be employed and each can be present at a level of from about 0 01% to about 20%, more preferably from about 0 1% to about 10%, and most preferably from about 0 5% to about 7% These mateπals include, but are not limited to, guamdine, glycohc acid and glycolate salts (e g ammonium and quaternary alkyl ammonium), salicylic acid, lactic acid and lactate salts (e g , ammonium and quaternary alkyl ammonium), aloe vera m any of its vanety of forms (e g , aloe vera gel), polyhydroxy alcohols such as sorbitol, glycerol, hexanetπol, propylene glycol, butylene glycol, hexylene glycol and the like, polyethylene glycols, sugars and starches, sugar and starch denvatives (e g , alkoxylated glucose), hyaluro c acid, lactamide monoethanolamine, acetamide monoethanolamine, and mixtures thereof Also useful herem are the propoxylated glycerols descnbed in U S Patent No 4,976,953, to On et al, issued December 11, 1990 Also useful are various C|-C 30 monoesters and polyesters of sugars and related mateπals These esters are derived from a sugar or polyol moiety and one or more carboxyhc acid moieties Such ester mateπals are further described in, U S Patent No 2,831 ,854, U S Patent No 4,005,196, to Jandacek, issued January 25, 1977, U S Patent No 4,005, 195, to Jandacek, issued January 25, 1977, U S Patent No 5,306,516, to Letton et al, issued April 26, 1994, U S Patent No 5,306,515, to Letton et al, issued Apπl 26, 1994, U S Patent No 5,305,514, to Letton et al, issued Apπl 26, 1994, U S Patent No 4,797,300, to Jandacek et al, issued January 10, 1989, U S Patent No 3,963,699, to Rrzzi et al, issued June 15, 1976, U S Patent No 4,518,772, to Volpenhein, issued May 21, 1985, and U S Patent No 4,517,360, to Volpenhem, issued May 21, 1985 h) Emulsifiers The compositions of the present invention can compnse one or more emulsifiers, e g , to reduce the mterfacial tension between phases and improve the formulation and stability of an emulsion Suitable emulsifiers include a wide vanety of nonionic, catiomc, amonic, and zwitteπomc emulsifiers See McCutcheon's, Detergents and Emulsifiers, North Amencan Edition (1986), published by Allured Publishing Corporation, U S Patent No 5,01 1 ,681 issued to Ciotti et al on April 30, 1991 , U S Patent No 4,421 ,769 issued to Dixon et al on December 20, 1983, and U S Patent No 3,755,560 issued to Dickert et al on August 28, 1973 Suitable emulsifier types include esters of glycerin, esters of propylene glycol, fatty acid esters of polyethylene glycol, fatty acid esters of polypropylene glycol, esters of sorbitol, esters of sorbitan anhydrides, carboxyhc acid copolymers, esters and ethers of glucose, ethoxylated ethers, ethoxylated alcohols, alkyl phosphates, polyoxyethylene fatty ether phosphates, fatty acid amides, acyl lactylates, soaps and mixtures thereof Suitable emulsifiers include, but are not limited to, TEA stearate, DEA oleth-3 phosphate, polyethylene glycol 20 sorbitan monolaurate (polysorbate 20), polyethylene glycol 5 soya sterol, steareth-2, steareth-20, steareth-21, ceteareth-20, PPG-2 methyl glucose ether distearate, ceteth-10, polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamme cetyl phosphate, polysorbate 60, glyceryl stearate, PEG- 100 stearate, and mixtures thereof Prefeπed emulsifiers are steareth-2, steareth-21, TEA stearate, diethanolamme cetyl phosphate, potassium cetyl phosphate, and mixtures thereof The emulsifier can be used indi idually or as a mixture of two or more and comprises from about 0 1% to about 10%, more preferably from about 0 15% to about 7%, and most preferably from about 0 25% to about 5% of the compositions of the present invention Methods For Providing Protection From UV Radiation The compositions of the present invention are suitable for providing protection against the harmful effects of ultraviolet radiation, preferably in personal care products More preferably, the compositions of the present mvention are suitable for use as sunscreens to provide protection to human skin from the harmful effects of UV radiation which include, but are not limited to, sunburn and premature aging of the skin The present invention therefore also further relates to methods of protecting human skin from the harmful effects of UV radiation Such methods generally involve attenuating or reducing the amount of UV radiation which reaches the skin's surface To protect the skm from UV radiation, a safe and effective (photoprotective) amount of the composition is topically applied to the skin "Topical application" refers to application of the present compositions by spreading, spraying, etc onto the surface of the skm The exact amount applied may vary depending on the level of UV protection desired From about 0 5 mg of composition per cm^ of skin to about 25 mg of composition per cm^ of skin are typically applied EXAMPLES The following examples further descnbe and demonstrate embodiments within the scope of the present invention The examples are given solely for the purpose of illustration and are not to be construed as limitations on the present invention, as many vanations thereof are possible without departing from the spirit and scope of the invention The following sunscreen products are representative of the present mvention. ' Available as Pemulen TR-1 from B F Goodnch Prepare a water phase by combinmg the water, Carbomer 980 or Carbomer 954, acrylate 505 copolymer, disodium EDTA, methyl paraben. and glycenn in an appropriate vessel with mixing and heatmg to 75°C Prepare the oil phase by combining octyl methoxycinnamate, octyl sahcylate, isopiopyl mvnstate. propyl paraben, 4-phenoxyanιlιne, 4-chloro-2-methoxy-5-methylanιlιne, 4-t-butyl-4'- methoxyldibenzoylmethane, DEA oleth-3-phosphate, stearic acid, cetyl alcohol, and cetyl palmitate in a separate vessel with mixing and heatmg to 75°C Next, mix the oil phase into the water phase with shearing 510 to form an emulsion Cool the emulsion with shearing to 60°C and add the tπethanolamine Slowly stir the emulsion and cool to 30 - 35°C and package as desired

Claims: WHAT IS CLAIMED IS : 1 A composition suitable for providing protection against the harmful effects of ultraviolet radiation characterized in that said composition comprises a) an effective amount of a UVA-absorbing dibenzoylmethane sunscreen active, b) an effective amount of an aniline derivative havmg the formula R 3 wherein R R 2 , R 3 , R 4 , and R 5 are independently selected from the group consisting of H, R', OR', CHO. CN, SO : R', S0 2 OR', NO, aryls. OH, SH, NHR', NR' 2 , SR', I, CI F, Br, and combinations thereof, wherein R' is a d - C 30 straight or branched alkyl or an aryl, wherein R,, R 2 , R 3 , R « , and R 5 can together form ith each other bndged cyclic structures, and c) a suitable carrier 1 The composition of Claim 1 wherein the UVA-absorbing dibenzoylmethane sunscreen active and the aniline deriv ative are present in a safe amount The composition of any of the precedmg claims wherein the aniline deπvativ e is selected from the group consisting of 4-phenoxyanιhne, 2-butylanιhne, 3,4-(methylenedιoxy) aniline, p-phenetidme, 2,4,6-tnmethyl-l ,3-phenylene diaπune, 4-chloro-2-methoxy-5-methylanιhne, and mixtures thereof The composition of any of the preceding claims wherein the UVA-absorbing dibenzoylmethane sunscreen active is selected from the group consisting of 2-methyldιbenzoylmethane, 4- methyldibenzoylmethane, 4-ιsopropyldιbenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4- dimethyldibenzoylmethane, 2,5-dιmethyldιbenzoylmethane, 4,4'-dnsopropylbenzoylmethane, 4-tert- butyl-4'-methoxydιbenzoylmethane, 2-methyl-5-ιsopropyl-4'-methoxydιbenzoylmethane, 2-methyl-5- tert-butyl-4'-methoxydιbenzoylmethane, 2,4-dιmethyl-4'-methoxydιbenzoylmethane, 2,6-dιmethyl- 4'tert-butyl-4'methoxydibenzoylmethane, and mixmres thereof O 00/23041 20 5 The composition of any of the precedmg claims wherem the UVA-absorbmg dibenzoylmethane sunscreen active is selected from the group consistmg of 4-tert-butyl-4 , -methoxydibenzoylmethane, lsopropyldibenzoylmethane, and mixtures thereof. 6. The composition of any of the preceding claims wherem the UVA-absorbmg dibenzoylmethane sunscreen active is 4-tert-butyl-4'-methoxydιbenzoylmethane. 7 The composition of any of the preceding claims wherein the composition compnses from about 0.01% to about 30%, by weight of the composition, of the UVA-absorbmg dibenzoylmethane sunscreen active. 8 The composition of any of the preceding claims wherem the mole ratio of the UVA-absorbmg dibenzoylmethane sunscreen active to the aniline denvative is from about 8.1 to about 1.1 A method for providing protection against the harmful effects of ultraviolet radiation characterized in that said method comprises applying a safe and effective amount of the composition of any of the preceding claims to skm. 10 A method of stabilizing a UVA-absorbmg dibenzoylmethane sunscreen active characterized in that said method comprises combining an effective amount of a UVA-absorb g dibenzoylmethane sunscreen active with an effective amount of an aniline derivative having the formula R 3 wherein R h R 2 , R 3 , R,, and R 5 are independently selected from the group consistmg of H, R', OR', CHO, CN, S0 2 R', S0 2 OR\ NO, aryls, OH, SH, NHR', NR' 2 , SR', I, CI, F, Br, and combmations thereof, wherem R' is a C, - C 30 straight or branched alkyl or an aryl; wherein R b R 2 , R 3 , R,, and R 5 can together form with each other bridged cyclic structures.

Inventors: ROBINSON LARRY RICHARD, ROBINSON, LARRY, RICHARD
Applicants: PROCTER & GAMBLE, THE PROCTER & GAMBLE COMPANY
Application year: 1999
Main classification: A61K7
IPC codes: A61K8, A61Q17