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Wo 2011/060099 A2 (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date _ . .. _ 19 May 2011 (19.05.2011) WO 2011/060099 A2 (51) International Patent Classification: Not classified (81) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM, (21) International Application Number: AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, PCT/US2010/056272 CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, (22) International Filing Date: DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, 10 November 2010 (10.1 1.2010) HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, (25) Filing Language: English ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, (26) Publication Language: English NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, (30) Priority Data: TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. 61/259,935 10 November 2009 (10.1 1.2009) U S (84) Designated States (unless otherwise indicated, for every (71) Applicant (for all designated States except US): LABO¬ kind of regional protection available): ARIPO (BW, GH, RATORY SKIN CARE, INC. [US/US]; P.O. Box 7469, GM, KE, LR, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, Tahoe City, California 96145 (US). ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, (72) Inventors; and EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, ΓΓ, LT, LU, (75) Inventors/ Applicants (for US only): MANSOURI, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, Zahra [US/US]; P.O. Box 7469, Tahoe City, California SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, 96145 (US). CANELIDE, Rodica-Tatiana [US/US]; GW, ML, MR, NE, SN, TD, TG). 1455 Adams Drive, Suite 1190, Menlo Park, California 94025 (US). THOMAS, Douglas [US/US]; P.O. Box Published: 7469, Tahoe City, California 96145 (US). OGAWA, Tet- — without international search report and to be republished suro [JP/US]; P.O. Box 7469, Tahoe City, California upon receipt of that report (Rule 48.2(g)) 96145 (US). (74) Agent: FIELD, Bret E.; Bozicevic, Field & Francis, LLP, 1900 University Avenue, Suite 200, East Palo Alto, California 94303 (US). < © o © - - (54) Title: SUNSCREEN COMPOSITIONS COMPRISING UNIFORM, RIGID, SPHERICAL, NANOPOROUS CALCIUM © PHOSPHATE PARTICLES, AND METHODS OF MAKING AND USING THE SAME (57) Abstract: Aspects of the invention include sunscreen formulations that include uniform, rigid, spherical nanoporous calcium ¾ phosphate particles. Also provided are methods of making the sunscreen formulations. The sunscreen formulations find use in sunblocking applications. SUNSCREEN COMPOSITIONS COMPRISING UNIFORM, RIGID, SPHERICAL, NANOPOROUS CALCIUM PHOSPHATE PARTICLES, AND METHODS OF MAKING AND USING THE SAME CROSS-REFERENCE TO RELATED APPLICATIONS Pursuant to 35 U.S.C. § 119 (e), this application claims priority to the filing date of United States Provisional Patent Application Serial No. 61/259,935 filed November 10, 2009; the disclosure of which application is herein incorporated by reference. INTRODUCTION It is well recognized that solar ultraviolet (UV) radiation poses a serious threat to human skin, which may range from the short term hazard like erythema, i.e., sunburn, to long term hazards like skin cancer and/or premature aging of the skin. UV radiation having a wavelength of 290 nm to 320 nm, generally referred to as UVB radiation, is known to cause erythema. In addition, numerous studies point to exposure of unprotected skin to UV radiation having a wavelength of from 320 nm to 400 nm, generally referred to as UVA radiation, as being the primary cause of skin cancer. It is important therefore, that skin is protected from both UVA and UVB radiations to avoid the long and short term deleterious effects of solar radiation. The sun protection factor (SPF) rating system has been developed to help consumers select the appropriate sun protection product for any given outdoor activity involving exposure to the sun. The SPF rating corresponds to a multiplying factor by which the duration of protection by a properly applied sunscreen exceeds the exposure time that causes unprotected skin to darken. Thus, with proper application of an SPF 8 product, a person should be able to remain in the sun without skin darkening for eight times the usual unprotected duration. In recent years, due to the increased public awareness of UV radiation hazards, the use of sun protection products has grown considerably, with consumers preferring products that have high SPF ratings and offer protection over the entire range of UV radiation, i.e., from 290 nm to 400 nm. These products typically contain certain UV- absorbers that are approved for use in sunscreen compositions by regulatory agencies (for example, US Food and Drug Administration (FDA) in the USA and COLIPA in the European Union). These approved UV-absorbers are either organic compounds, referred to in the art as organic UV-absorbers or sunscreens, or inorganic compounds, referred to in the art as inorganic UV-absorbers or sunscreens. At present, approved inorganic UV-absorbers are inorganic oxides such as titanium dioxide (ΤΊ Ο2) and zinc oxide (ZnO). Among these inorganic oxide sunscreens, ZnO is capable of absorbing substantial amounts of UVA-radiation, and hence is often used as a UVA-sunscreen. SUMMARY Aspects of the invention include sunscreen formulations that include uniform, rigid, spherical nanoporous calcium phosphate particles. Also provided are methods of making the sunscreen formulations. The sunscreen formulations find use in sunblocking applications. DETAILED DESCRIPTION Aspects of the invention include sunscreen formulations that include uniform, rigid, spherical nanoporous calcium phosphate particles. Also provided are methods of making the sunscreen formulations. The sunscreen formulations find use in sunblocking applications. Before the present invention is further described, it is to be understood that this invention is not limited to particular embodiments described, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims. Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention. Certain ranges are presented herein with numerical values being preceded by the term "about." The term "about" is used herein to provide literal support for the exact number that it precedes, as well as a number that is near to or approximately the number that the term precedes. In determining whether a number is near to or approximately a specifically recited number, the near or approximating unrecited number may be a number which, in the context in which it is presented, provides the substantial equivalent of the specifically recited number. Methods recited herein may be carried out in any order of the recited events which is logically possible, as well as the recited order of events. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described. All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. It must be noted that as used herein and in the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for use of such exclusive terminology as "solely," "only" and the like in connection with the recitation of claim elements, or use of a "negative" limitation. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as. an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided may be different from the actual publication dates which may need to be independently confirmed. SUNSCREEN FORMULATIONS COMPRISING UNIFORM, RIGID, SPHERICAL, NANOPOROUS CALCIUM PHOSPHATE PARTICLES Aspects of the invention include sunscreen compositions. While the SPF value of sunscreen compositions of the invention may vary, in some instances the compositions have an SPF value of 4 or more, e.g., 8 or more, 15 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, including 70 or more. The compositions may have a UV -A protection value of 1 or more, such as 2 or more, e.g., 2.25 or more, etc., such as 4 or more, e.g., 8 or more, 15 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, including 70 or more.
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