US010729633B2

United States Patent (10 ) Patent No.: US 10,729,633 B2 Pan et al. (45 ) Date of Patent : * Aug. 4 , 2020

( 54 ) METHODS FOR BOOSTING UVA (56 ) References Cited PHOTO - PROTECTION USING ANTIOXIDANTS U.S. PATENT DOCUMENTS 10,137,072 B2 * 11/2018 Pan A61K 8/602 (71 ) Applicant: L'OREAL , Paris (FR ) 2014/0170090 A1 6/2014 Thaggard 2016/0106654 A1 * 4/2016 Lewis, II A61K 8/447 ( 72 ) Inventors : Zhi Pan , Ridgewood , NJ (US ) ; 424/59 Anne -Laure Suzanne Bernard , 2016/0367470 A1 * 12/2016 Chiou A61Q 17/04 New - York , NY (US ) ; Yang Deng , 2017/0281499 A1 * 10/2017 Pan A61K 8/498 2017/0281503 A1 * 10/2017 Pan A61K 8/602 Green Brook , NJ (US ) 2017/0281504 A1 * 10/2017 Pan A61K 8/602 ( 73) Assignee : L'OREAL , Paris ( FR ) 2017/0281505 A1 * 10/2017 Pan A61K 8/602 FOREIGN PATENT DOCUMENTS ( * ) Notice : Subject to any disclaimer, the term of this patent is extended or adjusted under 35 FR 2795319 A1 12/2000 U.S.C. 154 (b ) by 0 days . WO WO -2013 /004777 A1 1/2013 This patent is subject to a terminal dis WO WO - 2016 / 166345 Al 10/2016 claimer . OTHER PUBLICATIONS (21 ) Appl. No .: 15 /939,422 International Search Report and Written Opinion dated Jun . 4 , 2019 for corresponding PCT Application No. PCT/ US2019 /023963 . ( 22 ) Filed : Mar. 29 , 2018 Matsui, Mary S. et al. , “ Non - Sunscreen Photoprotection : Antioxi dants Add Value to a Sunscreen , ” Journal of Investigative Derma (65 ) Prior Publication Data tology Symposium Proceedings, vol. 14 , No. 1 , 2009, pp . 56-59 US 2019/0298638 A1 Oct. 3 , 2019 XP055589522 . Oresajo , C. et al ., “ Protective effects of a topical antioxidant mixture ( 51 ) Int. Cl. containing vitamin C , ferulic acid , and phloretin against ultraviolet A61K 8/34 ( 2006.01 ) induced photodamage in human skin ,” Journal of Cosmetic Dermato , A61K 8/35 ( 2006.01) Blackwell Science , Oxford , GB , vol. 7 , No. 4 , 2008, pp . 290-297 A61K 8/365 ( 2006.01) XP008105375 . A61K 8/60 (2006.01 ) A61Q 17/04 ( 2006.01 ) * cited by examiner A61K 8/36 ( 2006.01) A61K 8/37 ( 2006.01 ) Primary Examiner Brian Gulledge A61K 8/40 (2006.01 ) (74 ) Attorney, Agent, or Firm — Polsinelli PC A61K 8/49 ( 2006.01 ) A61K 8/86 ( 2006.01 ) (57 ) ABSTRACT A61K 8/891 ( 2006.01) Methods for providing broad spectrum photo protection to A61K 8/895 ( 2006.01 ) skin using antioxidants that provide UVA protection to skin (52 ) U.S. CI. are described . The methods include topically applying a CPC A61K 8/602 (2013.01 ) ; A61K 8/347 cosmetic composition comprising : ( a ) at least one antioxi ( 2013.01) ; A61K 8/35 ( 2013.01 ) ; A61K 8/36 dant having an Oxygen Radical Absorbance Capacity (2013.01 ) ; A61K 8/365 (2013.01 ); A61K 8/37 (ORAC ) of at least 10,000 umol TE /g and a Hydroxyl (2013.01 ) ; A61K 8/40 ( 2013.01) ; A61K 8/4926 Radical Absorbance Capacity (HORAC ) of at least 2,600 (2013.01 ) ; A61K 8/4953 (2013.01 ); A61K 8/86 umol GAE / g ; ( b ) at least one organic UV filter ; and ( c ) a ( 2013.01 ); A61K 8/891 (2013.01 ) ; A61K 8/895 cosmetically acceptable carrier ; wherein the cosmetic com (2013.01 ) ; A61Q 17/04 ( 2013.01) ; AIK position provides an increase in UVAPPD PF of at least 30 % 2800/30 ( 2013.01) ; A6IK 2800/48 (2013.01 ) ; relative to an otherwise identical cosmetic composition A61K 2800/49 (2013.01 ) ; A61K 2800/522 without the antioxidant (s ) of ( a ) . The disclosure also relates ( 2013.01) to the cosmetic compositions useful in the described meth (58 ) Field of Classification Search ods. None See application file for complete search history . 19 Claims, 1 Drawing Sheet U.S. Patent Aug. 4 , 2020 US 10,729,633 B2

20 PA is een echte PF PA ++

UVAPPD $ A B C FIG . 1 UVAppDPF A 11E F FIG . 2 US 10,729,633 B2 1 2 METHODS FOR BOOSTING UVA the UVA protection provided by the UV filters . The antioxi PHOTO - PROTECTION USING dants that boost UVA photo - protection can be combined ANTIOXIDANTS with UV filters ( e.g., organic UVA and UVB filters ) to provide cosmetic compositions ( such as sunscreen compo 5 sitions ) that provide - a higher level UVA protection that FIELD OF THE DISCLOSURE cannot be achieved by UV filters alone. Also , because the antioxidants can be used together with organic UV filters to The instant disclosure relates to methods and composi boost the overall UVA protection provided by the sunscreen tions for boosting UVA photo -protection using antioxidants composition , the total amountof UVA filters needed to attain to provide broad spectrum photo protection to skin . a desired degree of UVA protection can be reduced . 10 Methods according to the instant disclosure for providing BACKGROUND broad spectrum photo -protection to skin can be carried out by applying to the skin a cosmetic composition comprising : Most individuals are exposed to large amounts of ultra ( a ) at least one antioxidant that boosts photo - protection from violet (UV ) radiation throughout their lifetimes due primar ily to sunlight exposure. Sunlight includes two types ofUV 15 UVACapacity radiation (ORAC having ) of atan leastOxygen 10,000 Radical mol TEAbsorbance/ g and a rays : long wave ultraviolet A (UVA ) and short wave ultra Hydroxyl Radical Absorbance Capacity (HORAC ) of at violet B (UVB ), both of which can damage skin . UVA rays least 2,600 mol GAE / g ; ( b ) at least one organic UV filter ; account for up to 95 percent of the UV radiation reaching the and (c ) a cosmetically acceptable carrier; wherein the cos Earth's surface. Although they are less intense than UVB metic composition provides an increase in UVAPPD PF of at rays , UVA rays are 30 to 50 times more prevalent. They are 20 least 30 % relative to an otherwise identical cosmetic com present with relatively equal intensity during all daylight position without the antioxidant( s ) of ( a ). The method typi hours throughout the year, and can penetrate clouds and cally provides an increase in UVAPPD PF of at least 30 % glass. relative to an otherwise identical cosmetic composition UVA rays penetrate the skin more deeply than UVB rays without the antioxidant( s ) . In some instances, it may be and have long been known to play a major part in skin aging 25 preferable that the at least one antioxidant of ( a ) additionally and wrinkling (photo -aging ), but until recently scientists have a Superoxide Radical Absorbance Capacity (SORAC ) believed that UVA rays did not cause significant damage to of less than 200 U /mg . the epidermis (outermost skin layer ) where most skin can Non - limiting examples of antioxidants that boost photo cers occur. Studies over the past two decades, however, protection from UVA radiation include polydatin , phloretin , show that UVA radiation damages skin cells called kera- 30 resveratrol, ferulic acid , and a mixture thereof. One of more tinocytes in the basal layer of the epidermis . of these antioxidants is combined with one or more UV Both UVA and UVB radiation contribute to skin damage filters , in particular organic UV filters, in a cosmetically that accelerates the appearance ofaging , for example , loss of acceptable carrier. The UV filter( s ) may be UVB filters, skin elasticity and the appearance of wrinkles. This process UVA filters (UVA1 and/ or UVA2 filters ) , and /or inorganic is commonly referred to as photo -aging . As skin ages , the 35 UV filters (UVA and /or UVB filters ). outer skin layer (epidermis ) thins, even though the number Non -limiting examples of UV filters include a para of cells remain largely unchanged . The number of pigment aminobenzoic acid derivative , a salicylic derivative, a cin containing cells (melanocytes ) , however , decreases . There namic derivative , a benzophenone or an aminobenzophe fore , the skin appears pale and translucent. Large pigmented none, an anthranillic derivative , a ß ,ß -diphenylacrylate spots (age spots , liver spots , or lentigos) may appear in 40 derivative, a benzylidenecamphor derivative , a phenylben sun -exposed areas. Changes in the connective tissue reduce zimidazole derivative , a benzotriazole derivative, a triazine the skin's strength and elasticity , which becomes more derivative , a bisresorcinyl triazine, an imidazoline deriva noticeable in sun - exposed areas ( solar elastosis ). Elastosis tive , a benzalmalonate derivative , a 4,4 -diarylbutadiene produces the leathery, weather- beaten appearance common derivative , a benzoxazole derivative , a merocyanine, malo to farmers , sailors , and others who spend a large amount of 45 nitrile or a malonate diphenyl butadiene derivative, a chal time outdoors . cone, and a mixture thereof . Many organic UVB filters are Due to the need for protection from both UVA and UVB known and are more common than UVA filters . UVA filters radiation , sunscreen products designated as “ broad spectrum include , but are not limited to , avobenzone (UVA1 ) , ecamp sunscreens ” have been developed . Sunscreen products that sulate (MEXORYL SX ) (UVA2 ) , and meradimate (menthyl are labeled as “ broad spectrum ” provide protection from 50 anthranilate ). Filters such as dioxybenzone, oxybenzone , both UVA and UVB radiation ; and in the United States these and sulisobenzone provide both UVB and UVA2 protection . products must meet specific requirements set by the Food The cosmetic compositions often include one or more and Drug Administration (FDA ) . The number of known additional components such as solubilizing agents , emulsi UVA filters and especially FDA approved UVA filters is fiers , silicone compounds, thickening agent , fatty com small and therefore products are limited in what UVA filters 55 pounds , fillers , preservatives , etc. can be used to provide broad spectrum protection . In addition to providing broad spectrum photo protection , the cosmetic compositions are useful in methods for pro SUMMARY OF THE DISCLOSURE viding anti- aging benefits to skin ; whitening or preventing darkening of skin ; improving the appearance of skin ; The instant disclosure relates to methods and composi- 60 strengthening skin's natural antioxidant defenses ; diminish tions for providing broad spectrum photo protection to skin , ing the visible signs of skin aging ; and improving skin's i.e. , protection from both UVA and UVB radiation . The radiance and firmness . inventors unexpectedly discovered that certain antioxidants boost the UVA protection provided by UV filters and can BRIEF DESCRIPTION OF THE DRAWINGS therefore be used in cosmetic compositions to increase 65 photo -protection from UVA radiation . Certain antioxidants FIG . 1 is a graph showing : ( A ) the UVAPPD PF of a synergistically interact with UV filters to significantly boost cosmetic composition comprising UV filters but no antioxi US 10,729,633 B2 3 4 dants that boost UVA photo -protection ; ( B ) a cosmetic (a ) at least one antioxidant that boosts UVA photo -pro composition comprising UV filters and baicalin ; and ( C ) a tection having: cosmetic composition comprising UV filters and polydatin ; i. an Oxygen Radical Absorbance Capacity (ORAC ) of at and least 10,000 umol TE / g ; and FIG . 2 is a graph showing : ( A ) the UVAPPD PF of a 5 ii . a Hydroxyl Radical Absorbance Capacity (HORAC ) of cosmetic composition comprising UV filters but no antioxi at least 2,600 umol GAE /g ; dants that boost UVA photo -protection ; ( D ) a cosmetic ( b ) at least one organic UV filter ; and composition comprising UV filters and ferulic acid ; ( E ) a (© ) a cosmetically acceptable carrier ; cosmetic composition comprising UV filters and resveratrol; wherein the cosmetic composition provides an increase in 10 UVAPPD PF of at least 30 % relative to an otherwise and ( F ) a cosmetic composition comprising UV filters and identical cosmetic composition without the anti phloretin . oxidant( s ) of ( a ) . In some instances, the at least one It should be understood that the various aspects of the antioxidant of ( a ) may have a Superoxide Radical present disclosure are not limited to the arrangements and Absorbance Capacity (SORAC ) of less than 200 U /mg . instrumentality shown in the figures . 15 The cosmetic compositions comprising the antioxidant( s ) that boosts photo -protection from UVA radiation increase DETAILED DESCRIPTION OF THE the in UVAPPD PF of the cosmetic composition by at least DISCLOSURE 40 , 50 , 60 , 70 , 80 , 90 , 100 , 110 , 120 , 130 , 140 , 150 , 160 , The methods and cosmetic compositions of the present 170 , 180 , 190 , or 200 % , relative to an otherwise identical disclosure provide broad spectrum photo -protection from 20 cosmetic composition without the antioxidant ( s ). A maxi UV radiation . The term “ broad spectrum photo -protection ” mum percent increase in UVAPPD PF may be 100 , 120 , 150 , means photo -protection from both UVA and UVB radiation . 180 , 200 , 220 , 250 , 270 , or 300 % ( e.g., the percent increase Sun Protection Factor (SPF ) indicates a sunscreen's ability in UVAPPD PF may be from at least 30 % to 300 % , relative to protect against UVB rays but does not adequately desig to an otherwise identical cosmetic composition without the nate to what extent ( if any ) a sunscreen composition protects 25 antioxidant( s ) ) . against UVA radiation . SPF is a measure of how much solar Not all antioxidants that boost UVA protection provide the energy (UV radiation ) is required to produce sunburn on same degree ofboosting . Therefore , the increase in UVAPPD protected skin (i.e. , in the presence of sunscreen ) relative to PF provided by the cosmetic compositions of the present the amount of solar energy required to produce sunburn on disclosure can vary depending on the antioxidant ( s ) included unprotected skin . As the SPF value increases, sunburn 30 in the compositions. Non - limiting examples of antioxidants protection increases. There is a popular misconception that that boost UVA protection include polydatin , phloretin , SPF relates to time of solar exposure . For example , many resveratrol, ferulic acid , their derivatives, and mixtures consumers believe that , if they normally get sunburn in one thereof. hour, then an SPF 15 sunscreen allows them to stay in the The degree of increase (boost ) in UVA protection pro sun 15 hours (i.e. , 15 times longer ) without getting sunburn . 35 thevided UVAPPD by each PF of of these cosmetic antioxidants compositions can vary comprising and therefore them This is not true because SPF is not directly related to time may vary . of solar exposure but to amount of solar exposure. Although A cosmetic composition comprising polydatin may pro solar energy amount is related to solar exposure time, there vide an increase in UVAPPDPF of at least 150 % relative to are other factors that impact the amount of solar energy . For 40 an otherwise identical cosmetic composition without poly example , the intensity of the solar energy impacts the datin . In some instances, a cosmetic composition comprising amount. polydatin may provide an increase in UVAPPD PF of at least To characterize protection from UVA radiation , the PPD 150 , 160 , 170 , 180 , 190 , 200 % , relative to an otherwise (Persistent Pigment Darkening ) method , which measures the identical cosmetic composition without polydatin . A maxi color of the skin observed 2 to 4 hours after exposure of the 45 mum percent increase in UVAPPD PF when the cosmetic skin to UVA radiation , is used . This method was adopted in composition includes polydatin may be 230 , 250 , 270 , or 1996 by the Japanese Cosmetic Industry Association ( ICIA ) 300 % ( e.g., the percent increase by be from at least 150 % to as the official test procedure for the UVA labelling of 300 % , relative to an otherwise identical cosmetic composi products and is commonly used in industry, especially in tion without polydatin ) . Europe and the United States. See JAPAN COSMETIC INDUSTRY 50 A cosmetic composition comprising phloretin may pro ASSOCIATION TECHNICAL BULLETIN ,Measurement Standards for UVA Protection Efficacy . Issued Nov. 21 , 1995 and effective vide an increase in UVAPPDPF of at least 50 % relative to an of Jan. 1 , 1996 ), which is incorporated herein by reference otherwise identical cosmetic composition without phloretin . in its entirety . In some instances, a cosmetic composition comprising phlo The UVA protection factor based on Persistent Pigment retin may provide an increase in UVAPPD PF of at least 55 , Darkening (PPD ) is designated as “UV - Apps PF ” and is 55 metic60 , 65 , composition 70, or 75 % withoutrelative phloretinto an otherwise . A maximum identical percent cos expressed mathematically by the ratio of the dose of UVA increase in UVAPPD PF when the cosmetic composition radiation necessary to reach the pigmentation threshold with includes phloretin may be 75 , 80 , 85 , 90 , 95, or 100 % ( e.g., the UV screening agent (MPPDP ) to the dose of UVA the percent increase by be from at least 50 % to 100 % , radiation necessary to reach the pigmentation threshold 60 relative to an otherwise identical cosmetic composition without UV screening agent (MPPD.np ), as shown below . without phloretin ). MPPDP A cosmetic composition comprising resveratrol may pro UVAppd PF = MPPDnp vide an increase in UVAPPD PF of at least 40 % relative to an otherwise identical cosmetic composition without resvera The methods of the present disclosure provide broad 65 trol . In some instances , a cosmetic composition comprising spectrum photo -protection to skin by topically applying to resveratrol may provide an increase in UVAPPD PF of at the skin a cosmetic composition comprising : least 45 or 50 % relative to an otherwise identical cosmetic US 10,729,633 B2 5 6 composition without resveratrol. A maximum percent disclosure have an SPF of at least 5. The SPF however, can increase in UVAPPD PF when the cosmetic composition vary as needed . The type and amount of UVB filters can be includes resveratrol may be 50 , 55 , 60 , or 65 % ( e.g., the varied to obtain a desired level of SPF . In some instances, the percent increase by be from at least 40 to 65 % , relative to an SPF of the cosmetic composition is at least 10 , 20 , 25 , 30 , otherwise identical cosmetic composition without resvera 5 35 , 40 , 45 , 50 , 55 , 60 , 65 , 70 , 75 , 80 , 85 , 90 , 95 , 100 , 125 , trol) . 150 , 175 , or 200. The maximum SPF of the cosmetic A cosmetic composition comprising ferulic acid may composition may be 100 , 125 , 150 , 175 , 200 , 250 , or 300 . provide an increase in UVAPPD PF of at least 30 % relative Accordingly , the cosmetic compositions of the present dis to an otherwise identical cosmetic composition without closure can have an SPF of about 5 to about 250 , about 50 ferulic acid . In some instances , a cosmetic composition 10 to about 200 , about 5 to about 150 , about 5 to about 125 , comprising ferulic acid may provide an increase in UVAPPD about 5 to about 100 , about 5 to about 75 , about 10 to about PF of at least 32 , 35 , or 37 % relative to an otherwise 250 , about 10 to about 200 , about 10 to about 150 , about 10 identical cosmetic composition without ferulic acid . A maxi to about 125 , about 10 to about 100 , about 15 to about 250 , mum percent increase in UVAPPD PF when the cosmetic about 15 to about 200 , about 15 to about 150 , about 15 to composition includes resveratrol may be 37, 40 , or 45 % 15 about 125, or about 15 to about 100. In some cases, the SPF ( e.g. , the percent increase by be from at least 30 to 45 % , of the cosmetic composition is about 5 to about 150 , about relative to an otherwise identical cosmetic composition 10 to about 125 , about 15 to about 100 , or about 30 to about without ferulic acid ) . 75 . The total amount of antioxidant( s ) that boost UVA photo The ratio of UVAPPD PF to SPF (UVAPPD PF :SPF ) can protection in the cosmetic compositions can vary but is 20 vary but in some instances is about 1 : 1 to about 1:20 . For typically about 0.01 to about 10 wt. % , based on the total instance , for a ratio of about 1 : 1 , if the UVA ,PPDI PF of the weight of the cosmetic composition . Similarly , the total sunscreen composition is about 10 , the SPF would also be amount of antioxidant( s ) can be about 0.01 to about 5 wt. % , about 10. For a ratio of about 1:20 , if the UVAPPD PF of the about 0.01 to about 4 wt. % , about 0.01 to about 3 wt. % , sunscreen composition is about 10 , the SPF would be about about 0.01 to about 2 wt. % , about 0.1 to about 10 wt. % , 25 200. The ratio ofUVAPPD PF to SPF (UVAPPD PF :SPF )may about 0.1 to about 5 wt. % , about 0.1 to about 4 wt. % , about also be about 1 : 1 to about 1:15 , about 1 : 1 to about 1:12 ; 0.1 to about 3 wt. % , about 0.1 to about 2 wt. % , or about about 1 : 1 to about 1:10 , about 1 : 1 to about 1 : 8 , or about 1 : 1 0.1 o about 1 wt. % , based on the total weight of the to about 1 : 5 . cosmetic composition . The cosmetic compositions of the present disclosure The UVAPPD PF of the cosmetic composition is typically 30 include at least one antioxidant that boosts photo -protection at least 4. Skin properly treated with a cosmetic composition from UVA radiation . Therefore, these antioxidants can be having a UVAPPd PF of 4 means that it takes about 4 times combined with UVA filters , for example organic UVA filters , longer for the skin to darken ( i.e., to reach a threshold level to boost (increase ) the UVA photo -protection provided by of pigment darkening ) compared to skin without treatment the UVA filters . UVA filters are categorized as either UVA1 with the cosmetic composition . In some cases, the UVA PPD, 35 orUVA 2 filters depending on the range of UVA radiation for PF of the cosmetic composition is at least 5 , 6 , 7 , 8, 9 , 10 , which they provide protection . UVA1 filters cover a range of 11, 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19, 20, or higher. The cosmetic 340 nm to 400 nm . UVA2 filters cover a range of 320 nm to composition may have a maximum UVAPPD PF 20, 25, or 340 nm . The only organic UVA1 filter approved for use in 30. Based on the UVAPPD PF , the cosmetic compositions can the United States by the US Food and Drug Administration be characterized based on their “ PA " value, another common 40 (FDA ) is avobenzone . Organic filters that provide protection system used to characterize the degree of UVA protection from UVA2 radiation include dioxybenzone, oxybenzone , provided by a sunscreen . The term “ PA ” designates “ Pro sulisobenzone, ecamsule , and meradimate , but these filters tection Grade of UVA ” and this characterization method , also provide protection from UVB radiation . One or more which was originally developed in Japan , is widely used UVA1 and / or UVA2 filters may optionally be included in the worldwide. It is based on PPD (Persistent Pigment Darken- 45 cosmetic compositions. ing ) at 2-4 hours of UVA exposure. The term “ PA ” is The total amount of UVA filters (both UVA1 and UVA2 ) followed by one or more “ + ” symbols (plus signs ). More in the cosmetic compositions may vary but is typically from plus signs represent greater protection from UVA rays . none (zero ) to about 20 wt. % , based on the total weight of A cosmetic composition designated as “ PA + ” means that the cosmetic composition . If UVA filter (s ) are present in the the cosmetic composition has a UV PPD PF of from 2 to 4 ; 50 cosmetic composition , the total amount of UVA filters may A cosmetic composition designated as “ PA ++ ” means that be in an amount greater than zero to about 20 wt. % , based the cosmetic composition has a UV PPD PF of from above 4 on the total weight of the cosmetic composition . In some to 8 ; cases, the total amount of UVA filters in the cosmetic A cosmetic composition designated as “ PA +++ ” means compositions is from about 0.01 to about 20 wt. % , about that the cosmetic composition has a UV PPD PF of from 55 0.01 to about 15 wt. % , about 0.01 to about 10 wt. % , about above 8 to 16 ; and 0.01 to about 8 wt. % , about 0.01 to about 6 wt. % , about A cosmetic composition designated as “ PA ++++” means 0.01 to about 5 wt. % , about 0.1 to about 20 wt. % , about 0.1 that the cosmetic composition has a UVPPPD PF of greater to about 15 wt. % , about 0.1 to about 10 wt. % , about 0.1 to than 16 . about 8 wt. % , about 0.1 to about 6 wt. % , about 0.1 to about The cosmetic compositions of the present disclosure can 60 5 wt. % , about 1 to about 20 wt. % , about 1 to about 15 wt. have a Protection Grade of UVA (PA ) of PA + , of PA ++, of % , about 1 to about 10 wt. % , about 1 to about 8 wt. % , about PA +++ , or of PA ++++ . 1 to about 6 wt. % , or about 1 to about 5 wt. % , based on the The cosmetic compositions of the present disclosure total weight of the cosmetic composition . provide broad spectrum photo -protection to skin and there The cosmetic compositions include at least one organic fore provide protection from both UVA and UVB radiation . 65 UVB filter . In some instances it is preferable to includemore Sun Protection Factor (SPF ) is a measure of UVB protec than one organic UVB filter, for example , at least 2 , 3 , 4 , or tion . Typically , the cosmetic compositions of the present 5 UVB filters .Non - limiting examples of UVB filters include US 10,729,633 B2 7 8 a para - aminobenzoic acid derivative , a salicylic derivative , 1 : 2 to about 1 : 8 , about 1 : 3 to about 1:20 , about 1 : 3 to about a cinnamic derivative, a benzophenone or an aminobenzo 1:15 , about 1 : 3 to about 1:10 , about 1 : 3 to about 1 : 8 . phenone , an anthranillic derivative , a B, B -diphenylacrylate In some instances, the cosmetic compositions of the derivative , a benzylidenecamphor derivative, a phenylben present disclosure may include avobenzone , a UVA1 filter . zimidazole derivative , a benzotriazole derivative , a triazine 5 When the cosmetic compositions include avobenzone, the derivative , a bisresorcinyl triazine, an imidazoline deriva total amount of avobenzone to the total amount of UVB tive , a benzalmalonate derivative, a 4,4 -diarylbutadiene filters in the cosmetic composition may be about 1: 1 to about derivative, a benzoxazole derivative, a merocyanine, malo 1:20 . In some cases, the ratio of avobenzone to the total nitrile or a malonate diphenyl butadiene derivative , a chal amount of UVB filters is about 1 : 1 to about 1:15 , about 1 : 1 cone, and mixtures thereof. 10 to about 1:10 , about 1: 1 to about 1 :8 , about 1 : 2 to about 1:20 , In some instances, at least one UVB filter may be selected about 1 : 2 to about 1:15 , about 1 : 2 to about 1:10 , about 1 : 2 from the group consisting of methylene bis -benzotriazolyl to about 1 : 8 , about 1 : 3 to about 1:20 , about 1 : 3 to about 1:15 , tetramethylphenol ( Tinosorb M ) , diethylamino hydroxyben about 1 :3 to about 1:10 , about 1: 3 to about 1 :8 . zoyl hexyl benzoate , ethylhexyl salicylate , ethylhexyl The antioxidant (s ) that boost photo - protection from UVA methoxycinnamate , isoamyl methoxycinnamate , polysili 15 radiation and the UV filters are combined in a cosmetically cone- 15 , menthyl anthranilate , ethylhexyl dimethyl PABA , acceptable carrier to form the cosmetic compositions of the aminobenzoic acid (PABA ) , cinoxate , dioxybenzone, ecam present disclosure . sule (Mexoryl SX ), ensulizole ( phenylbenzimiazole sulfonic The cosmetically acceptable carrier allows the anti acid ), homosalate , meradimate (menthyl anhranilate ), octoc- 20 oxidant( s ) and UVB filter( s ) to be combined and applied to rylene , octinoxate ( octyl methoxycinnamate ), octisalate (oc skin in a form that is appropriate for application to skin , in tyl salicylate ), oxybenzone , padimate 0 , sulisobenzone, tro particular , human skin . Perhaps the most common cosmeti lamine salicylate , and a mixture thereof. cally acceptable carrier is water, and in some instances, the The cosmetic compositions of the present disclosure may cosmetically acceptable carrier for the cosmetic composi optionally include one or more inorganic UV filters that 25 tions of the present disclosure is water (but is not required provide protection from UVA and /or UVB radiation . In to be water ). Non - limiting examples of cosmetically accept some instances, however, the cosmetic compositions of the able carriers other than water include glycerin , C1-4 alcohols , present disclosure are free or essentially free of inorganic organic solvents , fatty alcohols , fatty ethers , fatty esters , UVA and / or inorganic UVB filters . polyols , glycols , vegetable oils , mineral oils , liposomes, A more exhaustive but non - limiting list of UV filters that 30 laminar lipid materials , water , or a mixture thereof. Non may be included in the cosmetic compositions is provided limiting examples of organic solvents include mono - alco later , under the heading " UV Filters . " hols and polyols such as ethyl alcohol, isopropyl alcohol, The total amount of UVB filters in the cosmetic compo propyl alcohol, benzyl alcohol, and phenylethyl alcohol, or sitions of the present disclosure can vary and will depend on glycols or glycol ethers such as, for example , monomethyl, the desired SPF for the cosmetic composition . Higher 35 monoethyl and monobutyl ethers of ethylene glycol, pro amounts of UVB filters typically provide higher SPFs. In pylene glycol or ethers thereof such as , for example , some instances, the total amount of UVB filters in the monomethyl ether of propylene glycol, butylene glycol, sunscreen compositions may be about 0.1 to about 40 wt. % , hexylene glycol, dipropylene glycol as well as alkyl ethers based on the total weight of the cosmetic composition . The of diethylene glycol, for example monoethyl ether or total amount of UVB filters may be about 0.1 to about 35 wt. 40 monobutyl ether of diethylene glycol. Other suitable % , about 0.1 to about 30 wt. % , about 0.1 to about 25 wt. % , examples of organic solvents are ethylene glycol, propylene about 0.1 to about 20 wt. % , about 0.1 to about 15 wt. % , glycol, butylene glycol, hexylene glycol, propane diol, and about 0.1 to about 10 wt. % , about 1 to about 40 wt. % , about glycerin . The organic solvents can be volatile or non -volatile 1 to about 35 wt. % , about 1 to about 30 wt. % , about 1 to compounds. In some cases the cosmetic compositions of the about 25 wt. % , about 1 to about 20 wt. % , about 1 to about 45 present disclosure include, as a cosmetically acceptable 15 wt. % , about 1 to about 10 wt. % , about 5 to about 40 wt. carrier, at least water. % , about 5 to about 35 wt. % , about 5 to about 30 wt. % , The total amount of cosmetically acceptable carrier in the about 5 to about 25 wt. % , about 5 to about 20 wt. % , about cosmetic compositions can vary but is typically about 40 to 5 to about 15 wt. % , or about 5 to about 10 wt. % , based on about 90 wt. % , based on the total weight of the cosmetic the total weight of the cosmetic composition . 50 composition . In some cases , the total amount of cosmetically The inventors discovered that antioxidants that boost acceptable carrier is about 40 to about 85 wt. % , about 40 to photo -protection from UVA radiation synergistically interact about 80 wt. % , about 45 to about 90 wt. % , about 45 to with organic UV filters to significantly increase the UVA about 85 wt. % , about 45 to about 80 wt. % , about 50 to protection provided by a cosmetic composition comprising about 90 wt. % , about 50 to about 85 wt. % , or about 50 to the antioxidant( s ) and the organic UV filter ( s ) . This allows 55 about 80 wt. % , based on the total weight of the cosmetic for lower amounts of UVA filters to be used while obtaining composition . the same or higher degree of protection from UVA radiation , In some cases , the cosmetic compositions of the present and therefore changes the ratio of the total amount of organic disclosure include at least water as a cosmetically acceptable UVA filter ( s ) to the total amount of UVB filter ( s ) (UVA carrier. The total amount of water in the cosmetic compo Filters: UVB Filters ) needed in a cosmetic composition for 60 sition can vary but is typically about 35 to about 95 wt. % , attaining broad spectrum photo - protection . In some based on the total weight of the cosmetic composition . In instances the ratio of the total amount of UVA filters to the some cases , the total amount of water is about 35 to about total amount of UVB filters is about 1 : 1 to about 1:20 . In 90 wt. % , about 35 to about 85 wt. % , about 35 to about 80 some cases , the ratio of the total amount of UVA filters to the wt. % , about 40 to about 85 wt. % , about 40 to about 80 wt. total amount of UVB filters is about 1 : 1 to about 1:15 , about 65 % , about 45 to about 90 wt. % , about 45 to about 85 wt. % , 1 : 1 to about 1:10 , about 1 : 1 to about 1 :8 , about 1 :2 to about about 45 to about 80 wt. % , about 50 to about 90 wt. % , 1:20 , about 1 : 2 to about 1:15 , about 1 :2 to about 1:10 , about about 50 to about 85 wt. % , about 50 to about 80 wt. % , US 10,729,633 B2 9 10 about 60 to about 90 wt. % , about 60 to about 85 wt. % , or tion . In some instances, the total amount of the one or more about 60 to about 80 wt. % , based on the total weight of the water- soluble solvents may be about 0.1 to about 40 wt. % , cosmetic composition . about 0.1 to about 30 wt. % , about 0.1 to about 20 wt. % , The cosmetic compositions of the present disclosure may about 0.1 to about 10 wt. % , about 0.1 to about 5 wt. % , include at least one water -soluble solvent. The term " water 5 about 1 to about 50 wt. % , about 1 to about 40 wt. % , about soluble solvent” is interchangeable with the term “ water 1 to about 30 wt. % , about 1 to about 20 wt. % , about 1 to miscible solvent” and means a compound that at 25 ° C. and about 15 wt. % , about 1 to about 10 wt. % , or about 1 to at atmospheric pressure ( 760 mmHg) has a solubility of at about 5 wt. % , based on the total weight of the cosmetic least 70 % in water. In some cases, the water - soluble solvent composition . has a solubility of at least 80 % , 90 % , or 95 % in water at 25 ° 10 Solubilizing agents are compounds that help solubilize C. and at atmospheric pressure ( 760 mmHg ) . Non - limiting the antioxidant( s ) and / or the UV filters in the cosmetic examples of water- soluble solvents include , for example , compositions. A particularly useful but non - limiting glycerin , alcohols ( for example , C1-8 or C -4 alcohols ) , example of a solubilizing agent is a hydrotrope. Hydrotropes organic solvents , polyols , glycols , and a mixture thereof. (or hydrotropic agents ) are a diverse class of typically Non -limiting examples of organic solvents includemono- 15 water - soluble compounds that may be characterized by an alcohols and polyols such as ethyl alcohol, isopropyl alco amphiphilic molecular structure and an ability to dramati hol, propyl alcohol, benzyl alcohol, and phenylethyl alcohol, cally increase the solubility of poorly soluble organic mol or glycols or glycol ethers such as , for example , monom ecules in water . Many hydrotropes have an aromatic struc ethyl, monoethyl and monobutyl ethers of ethylene glycol, ture with an ionic moiety , while some of them are linear propylene glycol or ethers thereof such as , for example , 20 alkyl chains. Although hydrotropes can resemble surfactants monomethyl ether of propylene glycol, butylene glycol , and have the ability to reduce surface tension , their small hexylene glycol, dipropylene glycol as well as alkyl ethers hydrophobic units and relatively shorter alkyl chains distin of diethylene glycol, for example monoethyl ether or guish them as a separate class of amphiphiles . Consequently monobutyl ether of diethylene glycol . Other suitable their hydrophobicity is not sufficient enough to create well examples of organic solvents are ethylene glycol , propylene 25 organized self -associated structures , such as micelles , even glycol, butylene glycol, hexylene glycol, propane diol, and with a high concentration . glycerin . The organic solvents can be volatile or non -volatile Non - limiting examples of hydrotopes include sodium compounds . 1,3 -benzenedisulfonate , sodium benzoate , sodium 4 -pyri Further non - limiting examples of water - soluble solvents dinecarboxylate , sodium salicylate , sodium benzene sul include alkanols (polyhydric alcohols such as glycols and 30 fonate , caffeine, sodium p - toluene sulfonate , sodium butyl polyols) such as glycerin , 1,2,6 -hexanetriol , trimethylolpro monoglycolsulfate , 4 - aminobenzoic acid HCl, sodium pane, ethylene glycol, propylene glycol, diethylene glycol, cumene sulfonate , N ,N -diethylnicotinamide , N -picolylnico butylene glycol, hexylene glycol, triethylene glycol, tetra tinamide, N - allylnicotinamide, 2 -methacryloyloxyethyl ethylene glycol, pentaethylene glycol, dipropylene glycol, phosphorylcholine, resorcinol, butylurea , pyrogallol, N -pi 1,3 -butanediol , 2,3 -butanediol , 1,4 -butanediol , 3 -methyl - 1 , 35 colylacetamide 3.5 , procaine HCl, proline HCl, nicotina 3 -butanediol , 1,5 -pentanediol , tetraethylene glycol, 1,6 mide, pyridine, 3 -picolylamine , sodium ibuprofen , sodium hexanediol, 2 -methyl - 2,4 - pentanediol, polyethylene glycol, xylenesulfonate , ethyl carbamate , pyridoxal hydrochloride, 1,2,4 -butanetriol , 1,2,6 -hexanetriol , 2 -butene - 1,4 - diol, sodium benzoate , 2 -pyrrolidone , ethylurea, N ,N - dimethyl 2 - ethyl- 1,3 - hexanediol, 2 -methyl - 2,4 -pentanediol , (caprylyl acetamide , N -methylacetamide , and isoniazid . Additional glycol) , 1,2 -hexanediol , 1,2 -pentanediol , and 4 -methyl - 1,2- 40 examples of hydrotopes that may be used can be found in pentanediol ; alkyl alcohols having 1 to 4 carbon atoms such Lee J. et al. , " Hydrotropic Solubilization of Paclitaxel: as ethanol, methanol, butanol, propanol, and isopropanol; Analysis of Chemical Structures for Hydrotropic Property ” , glycol ethers such as ethylene glycol monomethyl ether, PHARMACEUTICAL RESEARCH , Vol. 20 , No. 7 , 2003; and Lee S. ethylene glycol monoethyl ether, ethylene glycol monobutyl et al. , “ Hydrotropic Polymers : Synthesis and Characteriza ether , ethylene glycol monomethyl ether acetate , diethylene 45 tion of Polymers Containing Picolylnicotinamide Moieties " , glycol monomethyl ether, diethylene glycol monoethyl MACROMOLECULES , 36 , 2248-2255 , 2003 , which are incorpo ether, diethylene glycol mono - n -propyl ether, ethylene gly rated herein by reference in their entirety . In some cases , col mono -iso -propyl ether, diethylene glycolmono - iso -pro particularly useful hydrotropes include nicotinamide ( niaci pyl ether , ethylene glycol mono - n -butyl ether , ethylene namide ), caffeine, sodium PCA , sodium salicylate , urea , and glycol mono -t - butyl ether , diethylene glycol mono -t -butyl 50 dihydroxyethyl urea , in particular , nicotinamide (niacina ether , 1 -methyl - 1 -methoxybutanol , propylene glycol mide ) and /or caffeine . A combination of two or more , three monomethyl ether, propylene glycol monoethyl ether , pro or more , or four or more hydrotopes may also be used in the pylene glycol mono - t -butyl ether, propylene glycol mono cosmetic compositions . n -propyl ether , propylene glycol mono -iso -propyl ether, The total amount of solubilizing agent( s ) in the cosmetic dipropylene glycol monomethyl ether, dipropylene glycol 55 compositions of the present disclosure , if present ,may vary monoethyl ether , dipropylene glycol mono -n -propyl ether, but are typically in an amount of about 0.01 to about 20 wt. and dipropylene glycol mono - iso -propyl ether; 2 -pyrroli % , based on the total weight of the cosmetic composition . done , N -methyl - 2 -pyrrolidone , 1,3 -dimethyl - 2 - imidazolidi The total amount of solubilizing agent( s ) may be in an none, formamide, acetamide, dimethyl sulfoxide, sorbit, amount of about 0.01 to about 15 wt. % , about 0.01 to about sorbitan , acetine , diacetine , triacetine, sulfolane , and a mix- 60 10 wt. % , about 0.01 to about 8 wt. % , about 0.1 to about 20 ture thereof. wt. % , about 0.1 to about 15 wt. % , about 0.1 to about 10 wt. In some cases, the water- soluble solvent may be selected % , about 0.1 to about 8 wt. % , about 0.5 to about 20 wt. % , from the group consisting of one or more glycols , C1-4 about 0.5 to about 15 wt. % , about 0.5 to about 10 wt. % , alcohols , glycerin , and a mixture thereof. about 0.5 to about 8 wt. % , about 1 to about 20 wt. % , about The total amount water- soluble solvent( s ) in the cosmetic 65 1 to about 15 wt. % , about 1 to about 10 wt. % , or about 1 composition may vary but is typically about 0.1 to about 50 to about 8 wt. % , based on the total weight of the cosmetic wt. % , based on the total weight of the cosmetic composi composition . US 10,729,633 B2 11 12 The cosmetic compositions of the present disclosure may The total amount of silicone compound ( s) in the cosmetic include at least one emulsifier . Many emulsifiers are known compositions can vary but is typically about 0.1 to about in the art and may be used , including , amphoteric , anionic , 20 wt. % , based on the total weight of the cosmetic com cationic , and nonionic emulsifiers. In some instances, it is position . In some cases, the total amount of silicone com useful to include at least one nonionic emulsifier . Non - 5 pound (s ) is about 0.1 to about 15 wt. % , about 0.1 to about limiting examples of nonionic emulsifiers include polyol 12 wt. % , about 0.1 to about 10 wt. % , about 0.1 to about 8 esters , a glycerol ethers, oxyethylenated and /or oxypropyl wt. % , about 0.1 to about 5 wt. % , about 0.5 to about 20 wt. enated ethers , ethylene glycol polymers , and mixtures % , about 0.5 to about 15 wt. % , about 0.5 to about 10 wt. % , about 0.5 to about 8 wt. % , about 0.5 to about 5 wt. % , about thereof. For example , in some cases the emulsifier includes 10 1 to about 20 wt. % , about 1 to about 15 wt. % , about 1 to a mixture of a polyol ester and an ethylene glycol polymer, about 10 wt. % , about 1 to about 8 wt. % , or about 1 to about for example , a mixture of glyceryl stearate and PEG - 100 5 wt. % , based on the total weight of the cosmetic compo stearate. In some instances, an oxyalkylenated organosilox sition . ane emulsifier is included . Non - limiting examples include At least one fatty compound may be included in the dimethicone /PEG - 10 /15 crosspolymer, PEG - 15 lauryl dime 15 cosmetic compositions of the present disclosure. Non - lim thicone crosspolymer , PEG - 15 lauryl dimethicone iting examples of fatty compounds include oils , mineral oil , crosspolymer , PEG - 10 lauryl dimethicone crosspolymer, or fatty alcohols , fatty acids, fatty alcohol derivatives, fatty a mixture thereof. In some instances, the cosmetic compo acid derivatives ( such as alkoxylated fatty acids or polyeth sitions of the present disclosure are in the form of an ylene glycol esters of fatty acids or propylene glycol esters emulsion . For example , a water in oil emulsion , an oil in 20 of fatty acids or butylene glycol esters of fatty acids or esters water emulsion , or a silicone in water emulsion . of neopentyl glycol and fatty acids or polyglycerol/ glycerol Amore exhaustive but non - limiting list of emulsifiers that esters of fatty acids or glycol diesters or diesters of ethylene may be included in the cosmetic compositions is provided glycol and fatty acids or esters of fatty acids and fatty later , under the heading “ Emulsifiers .” alcohols , esters of short chain alcohols and fatty acids ), The total amount of emulsifier (s ) in the cosmetic com- 25 esters of fatty alcohols , hydroxy - substituted fatty acids, positions, when present, may vary but is typically about 0.01 waxes, triglyceride compounds, lanolin , and a mixture to about 10 wt. % , based on the total weight of the compo thereof. In some instances, the at least one fatty compound sition . In some instances, the total amount of the one or more includes one or more fatty alcohols , fatty acids , esters of emulsifiers in the cosmetic compositions is about 0.1 to fatty acids and fatty alcohols ( for example , cetyl palmitate , about 10 wt. % , about 0.1 to about 8 wt. % , about 0.1 to 30 cetyl stearate , myristyl myristate , myristyl stearate , cetyl about 5 wt. % , about 0.5 to about 10 wt. % , about 0.5 to myristate , and stearyl stearate ) . about 8 wt. % , about 0.5 to about 5 wt. % , about 1 to about A more exhaustive but non - limiting list of fatty com 10 wt. % , about 1 to about 8 wt. % , or about 1 to about 5 wt. pounds that may be included in the cosmetic compositions % , based on the total weight of the cosmetic composition . is provided later , under the heading “ Fatty Compounds. " The cosmetic compositions of the present disclosure may 35 The total amount of fatty compound( s ) in the cosmetic include at least one silicone compound (which may also be compositions can vary but is typically about 0.1 to about 30 referred to as silicone oils ) . Non - limiting examples of sili wt. % , based on the total weight of the cosmetic composi cone compounds include polydimethylsiloxanes, polydieth tion . In some cases, the total amount of fatty compound (s ) ylsiloxanes, polydimethylsiloxanes having terminal is about 0.1 to about 25 wt. % , about 0.1 to about 20 wt. % , hydroxyl groups (dimethiconols ), polymethylphenylsilox- 40 0.1 to about 15 wt. % , about 0.1 to about 12 wt. % , about 0.1 anes , phenylmethylsiloxanes , amino functional polydimeth to about 10 wt. % , about 0.1 to about 8 wt. % , about 0.1 to ylsiloxane ( amodimethicone ) , non - ionic dimethicone copo about 5 wt. % , about 0.5 to about 30 wt. % , about 0.5 to lyols , dimethicone copolyol esters, dimethicone copolyol about 25 wt. % , about 0.5 to about 20 wt. % , about 0.5 to quaternium nitrogen containing compounds, dimethicone about 15 wt. % , about 0.5 to about 10 wt. % , about 0.5 to copolyol phosphate esters , and mixtures thereof. More spe- 45 about 8 wt. % , about 0.5 to about 5 wt. % , about 1 to about cific but non - limiting examples of silicone compounds 30 wt. % , about 1 to about 25 wt. % , about 1 to about 20 wt. include dimethicone, cyclomethicone , polysilicone - 11, phe % , about 1 to about 15 wt. % , about 1 to about 10 wt. % , nyl trimethicone , trimethylsilylamodimethicone , and stear about 1 to about 8 wt. % , or about 1 to about 5 wt. % , based oxytrimethylsilane . In some cases, the cosmetic composition on the total weight of the cosmetic composition . includes dimethicone , and optionally one or more additional 50 The cosmetic compositions of the instant disclosure may silicone compounds. include at least one thickening agent. The term “ thickening Other examples of silicone compounds thatmay be men agent” is interchangeable with the terms “ thickener, ” “ gell tioned include volatile linear or cyclic silicone oils , espe ing agent, ” and “ viscosity modifier. ” Non - limiting examples cially those with a viscosity 8 centistokes (8x10 m²/ s ) and of useful thickening agents include cellulose polymers, especially containing from 2 to 7 silicon atoms, these 55 gums, modified or unmodified carboxyvinyl polymers, poly silicones optionally comprising alkyl or alkoxy groups con acrylamides , copolymers of acrylic acid and of acrylamide , taining from 1 to 10 carbon atoms. As volatile silicone oils sodium salts of polyhydroxycarboxylic acids, optionally that may be used in the disclosure , mention may be made crosslinked and /or neutralized 2 -acrylamido - 2 -methylpro especially of octamethylcyclotetrasiloxane, decamethylcy panesulphonic acid polymers and copolymers , polyacrylic clopentasiloxane, dodecamethyl- cyclohexasiloxane , hep- 60 acid / alkyl acrylate , glucans , modified or unmodified tamethylhexyltrisiloxane , heptamethyloctyltrisiloxane , hex starches, silicas , and mixtures thereof. amethyldisiloxane, octamethyltrisiloxane , In some instances , the at least one thickening agent decamethyltetrasiloxane and dodecamethylpentasiloxane , comprises a gum , especially those derived from natural and mixtures thereof. sources . Non- limiting examples of useful gums include A more exhaustive but non - limiting list of silicone com- 65 acacia , agar , algin , alginic acid , ammonium alginate , amy pounds that may be included in the cosmetic compositions lopectin , calcium alginate , calcium carrageenan , carnitine, is provided later , under the heading “ Silicone Compounds. " carrageenan , dextrin , gelatin , gellan gum , guar gum , guar US 10,729,633 B2 13 14 hydroxypropyltrimonium chloride , hectorite , hyaluronic humectant, a moisturizing ingredient, an anti- aging agent , a acid , hydrated silica , hydroxypropyl chitosan , hydroxypro depigmenting agent, an anti -wrinkle agent, an agent that pyl guar, karaya gum , kelp , locust bean gum , natto gum , treats oily skin , and a mixture thereof. In some cases , the one potassium alginate , potassium carrageenan , propylene gly or more skin active ingredients may be adenosine, ascorbic col alginate , sclerotium gum , sodium carboxymethyl dex- 5 acid , 2- [4- ( 2 -hydroxyethyl ) piperazin - 1 -yllethanesulfonic tran , sodium carrageenan , tragacanth gum , xanthan gum , acid (HEPES ) , hyaluronic acid , lanolin , citric acid , malic biosacharide gum , and mixtures thereof. Particularly pre acid, lactic acid , tartaric acid , salicylic acid , vitamin C , a ferred gums include xanthan gum , guar gum , biosaccharide vitamin , a retinoid , retinal , retinoic acid , a carotenoid , an gum , cellulose , acacia gum , seneca gum , sclerotium gum , amino acid , a protein , an enzyme, a coenzyme, or a mixture agarose , gellan gum , and mixtures thereof. A more exhaus- 10 thereof. tive list of useful thickening agents that may be included is The total amount of skin active ingredient( s ) may be from provided later, under the heading “ Thickening Agent. " about 0.001 to about 10 wt. % , based on the total weight of The total amount of thickening agent( s ) in the cosmetic the composition . In some instances, the amount of skin compositions may vary but is typically about 0.01 to about active ingredient( s ) may be from about 0.001 wt. % to about 10 wt. % , based on the total weight of the cosmetic com- 15 9 wt. % , about 8 wt. % , about 7 wt. % , about 6 wt. % , about position . The total amount of the at least one thickening 5 wt. % , about 4 wt. % , about 3 wt. % , or about 2 wt. % . agent may be about 0.01 to about 6 wt. % , about 0.01 to Likewise, in some instances the amount of the skin active about 5 wt. % , about 0.01 to about 3 wt. % , about 0.01 to ingredients may be from about 0.01 wt. % to about 9 wt. % , about 1 wt. % , about 0.1 to about 10 wt. % , about 0.1 to about 8 wt. % , about 7 wt. % , about 6 wt. % , about 5 wt. % , about 6 wt. % , about 0.1 to about 5 wt. % , about 0.1 to about 20 about 4 wt. % , about 3 wt. % , or about 2 wt. % . Additionally , 3 wt. % , or about 0.1 to about 1 wt. % , based on the total the total amount of the skin active ingredients may be from weight of the cosmetic composition . 0.1 wt. % to about 9 wt. % , about 8 wt. % , about 7 wt. % , The cosmetic compositions of the present disclosure may about 6 wt. % , about 5 wt. % , about 4 wt. % , about 3 wt. % , optionally include at least one film - forming polymer . For or about 2 wt. % . Finally , the amount of the skin active instance , non -limiting examples of film - forming polymers 25 ingredients may be from about 0.5 wt. % to about 5 wt. % , include vinyl polymers , polyesters , polyamides , polyureas , about 0.5 wt. % to about 3 wt. % , 0.5 wt. % to about 2 wt. and a mixture thereof. The one or more film - forming poly % , or about 1 wt. % . mers may be polyethyleneimine, polylysine , polyvinyl alco The methods described in the present disclosure include hols , poly (hydroxyethyl (meth )acrylate ), hydroxyalkylcel topically applying the cosmetic compositions described luloses , polyacrylic acid , polyvinylimidazoles , 30 herein to the skin and /or hair. The cosmetic compositions polypropyleneimines, polyallylamines, chitosan , carboxy may be applied once or may be applied repeatedly over a alkylcelluloses, aminoalkylcelluloses, maleic , fumaric and / period of time to ensure that the skin consistently enjoys or itaconic acid or anhydride polymers , polyamidoamines , broad spectrum photoprotection over a period of time. In and a mixture thereof. some instances , the cosmetic compositions of the present The one or more film - forming polymers may be copoly- 35 disclosure are sunscreen compositions, i.e., the composi mers of (meth )acrylic acid and of at least one ester monomer tions are formulated and used specifically for preventing of linear , branched or cyclic (meth ) acrylic acid and / or of at damage to the skin and /or hair by the sun . The cosmetic least one amide monomer of linear , branched or cyclic , compositions may be in a variety of different forms. For mono- or disubstituted (meth )acrylic acid ; (meth )acrylic example , the cosmetic compositions may be a spray, a acid /tert -butyl ( meth ) acrylate and /or isobutyl (meth )acrylate / 40 lotion , a gel , a cream , a stick (or bar ) , or a foam . In some C -C4 alkyl( meth ) acrylate copolymers ; (meth )acrylic acid / cases , it is desirable , especially for sunscreen composition , ethyl acrylate /methyl methacrylate terpolymers and tet for the cosmetic compositions of the present disclosure to be rapolymers ; methyl methacrylate / butyl or ethyl acrylate / in spray form , for example , a pump spray or an aerosol hydroxyethyl or 2 -hydroxypropyl acrylate or methacrylate/ spray . (methacrylic acid tetrapolymers ; copolymers of acrylic acid 45 The cosmetic compositions may be clear or transparent. and of C , -C4 alkyl methacrylate ; terpolymers of vinylpyr The term “ transparent” or “ clear ” means that the composi rolidone, of acrylic acid and of C1-20 alkyl methacrylate ; tion / product allows light to pass through so that objects amphoteric copolymers; vinyl esters of branched acids ; behind can be seen . A transparent material allows light to vinyl esters of benzoic acid ; copolymers of (meth )acrylic pass through , and makes it possible to distinguish alphanu acid and of at least one olefinic monomer; copolymers of 50 meric characters using 5 mm thick samples . A simple vinyl monoacid and /or of allylic monoacid ; and a mixture example of a transparent material is a glass window . One can thereof. In some cases, the one or more film - forming poly see through a glass window . More specifically , term “ trans mers include VP /dimethylaminoethylmethacrylate copoly parent" relates to a material having a maximum light trans mer . mittance value , at a wavelength equal to 500 nm , through a The total amount of the one or more film - forming poly- 55 sample 1 cm thick , of at least 60 % and preferably of at least mers ( other than the one or more latex polymers ) may vary 70 % . but is typically about 0.01 to about 10 wt. % , based on the In some instance , the cosmetic compositions of the instant total weight of the hair - treatment composition . The total disclosure may be opaque or cloudy . The term " opaque" or amount of the one or more film - forming polymers (other “ cloudy” means that the composition/ product that is not than the one or more latex polymers ) may be about 0.01 to 60 transparent. Steam on a window is an example of an opaque about 8 wt. % , about 0.01 to about 6 wt. % , about 0.01 to or cloudy scenario . about 5 wt. % , about 0.1 to about 10 wt. % , about 0.1 to Finally , the instant disclosure relates to methods of using about 8 wt. % , about 0.1 to about 6 wt. % , or about 0.1 to the compositions described herein , for example , in the about 5 wt. % . treatment of skin ( in addition to providing broad spectrum In some instances, the cosmetic compositions of the 65 photo protection to the skin ). For example , the compositions present disclosure include one or more skin active ingredi may be used in methods for : providing anti -aging benefits to ents. For example , the skin active ingredient may be a the skin ; whitening or preventing darkening of skin ; improv US 10,729,633 B2 15 16 ing the appearance of skin ; strengthening skin's natural For W / O emulsions , examples of emulsifiers that may be antioxidant defenses ; diminishing the visible signs of skin mentioned include dimethicone copolyols , such as the mix aging ; and improving skin's radiance and firmness . These ture of cyclomethicone and dimethicone copolyol sold under methods typically entail applying the compositions the trade name DC 5225 C by the company Dow Corning , described herein to the skin . 5 and alkyl dimethicone copolyols such as the lauryl dime More exhaustive but non - limiting lists of components thicone copolyol sold under the name Dow Corning 5200 useful in the instant compositions disclosed herein are Formulation Aid by the company Dow Corning , and the presented below . cetyl dimethicone copolyol sold under the name Abil EM UV Filters 90TM by the company Goldschmidt. UV filters are well known in the art for their use in 10 For O / W emulsions , examples of emulsifiers that may be stopping UV radiation . For example , the UV filter may be mentioned include nonionic emulsifiers such as oxyalky one or more organic UV filters and /or one or more inorganic lenated (more particularly polyoxyethylenated ) fatty acid UV filters . Non - limiting examples of UV filters include: esters of glycerol; oxyalkylenated fatty acid esters of sorbi i. Sparingly soluble UV filters (not appreciably soluble in tan ; oxyalkylenated ( oxyethylenated and / or oxypropyl either water or oil) such as Methylene Bis -Benzotriaz 15 enated ) fatty acid esters; oxyalkylenated ( oxyethylenated olyl Tetramethylbutylphenol, Tris- Biphenyl Triazine , and / or oxypropylenated ) fatty alcohol ethers ; sugar esters Methanone, 1,1' - (1,4 -piperazinediyl ) bis [ 1- [ 2-[ 4- ( di such as sucrose stearate ; and mixtures thereof. ethylamino )-2 -hydroxybenzoyl ] phen -yl ) - and mixtures In some instance , the one or more emulsifiers include an thereof. 20 oganosiloxane emulsifier, including crosslinked organosi ii . Oil soluble organic UV filters (at least partially soluble loxane emulsifiers . For example , the compositions may in oil or organic solvent) , such as Bis - Ethylhexyloxy comprise one or more crosslinked organosiloxane emulsifier phenol Methoxyphenyl Triazine, Butyl Methoxydiben selected from the group consisting of dimethicone/ dimethi zoylmethane (BMBM ), Oxybenzone , Sulisobenzone, cone PEG /PPG 15 crosspolymer, dimethicone PEG - 10 Diethylhexyl Butamido Triazone (DBT ) , Drometrizole 25 crosspolymer , dimethicone PEG - 10/ 15 crosspolymer, dime Trisiloxane, Ethylhexyl Methoxycinnamate (EHMC ) , thicone PEG - 15 crosspolymer, dimethicone polyglycerin - 3 Ethylhexyl Salicylate ( EHS) , Ethylhexyl Triazone crosspolymer , dimethicone PPG - 20 crosspolymer , dimethi (EHT ) , Homosalate , Isoamyl p -Methoxycinnamate , conol/ methylsilanol / silicate crosspolymer , dimethiconol/ 4 -Methylbenzylidene Camphor , Octocrylene ( OCR ) , silicate crosspolymer, lauryl dimethicone PEG - 15 Polysilicone - 15 , and Diethylamino Hydroxy Benzoyl 30 crosspolymer , lauryl dimethicone polyglycerin - 3 crosspoly Hexyl Benzoate (DHHB ) ; mer , PEG - 8 dimethicone polysorbate - 20 crosspolymer , iii . Inorganic UV filters such as titanium oxide and zinc PEG - 10 dimethicone/ vinyl dimethicone crosspolymer , side, iron ide, zirconium oxide and cerium oxide ; PEG - 10 lauryl dimethicone crosspolymer, PEG - 15/ lauryl and dimethicone crosspolymer , PEG -15 laurylpolydimethylsi iv . Water soluble UV filters such as Phenylbenzimidazole 35 loxyethyl crosspolymer . Sulfonic Acid (PBSA ), Sulisobenzone - sodium salt, In another embodiment, the compositions include one or Benzydilene Camphor Sulfonic Acid , Camphor Ben more linear organosiloxane emulsifier selected from the zalkonium Methosulfate , Cinoxate , Disodium Phenyl group consisting of cyclotetrasiloxane ( and ) cyclopentasi Dibenzylmidazole Tetrasulfonate , Terephthalylidene loxane (and ) PEG /PPG -18 dimethicone, cyclopentasiloxane Dicamphor Sulfonic Acid , PABA , and PEG - 25 PABA . 40 (and ) PEG /PPG - 18 / 18 dimethicone; PEG /PPG - 18 /18 dime In some instances, the UV filter is one or more of: a thicone ; lauryl PEG /PPG - 18 / 18 methicone; cetyl PEG /PPG para - aminobenzoic acid derivative , a salicylic derivative , a 14/14 dimethicone ; bis -cetyl PEG /PPG - 14 / 14 dimethicone ; cinnamic derivative, a benzophenone or an aminobenzophe cetyl PEG /PPG - 10 / 1 dimethicone ; PEG - 11 methyl ether none , an anthranillic derivative, a B , ß - diphenylacrylate dimethicone; PEG /PPG - 20 /22 butyl ether dimethicone ; derivative , a benzylidenecamphor derivative, a phenylben- 45 PEG - 9 dimethicone ; PEG -3 dimethicone; PEG - 9 methyl zimidazole derivative, a benzotriazole derivative , a triazine ether dimethicone, PEG - 10 dimethicone ; lauryl PEG - 9 derivative , a bisresorcinyl triazine, an imidazoline deriva polydimethylsiloxyethyl dimethicone. tive, a benzalmalonate derivative, a 4,4 -diarylbutadiene Usable oxyalkylenated organosiloxane emulsifier include derivative , a benzoxazole derivative, a merocyanine, malo the following : nitrile or a malonate diphenyl butadiene derivative, a chal- 50 An oxyalkylenated organosiloxane emulsifier having the cone, or a mixture thereof. general formula: Suitable UV filters can include broad -spectrum UV filters that protect against both UVA and UVB radiation , or UV filters that protect against UVA or UVB radiation . In some CH3 CH3 ??3 CH3 CH3 instances, the one or more UV filters may be methylene 55 H3C — Si Si Si - CH3 bis - benzotriazolyl tetramethylphenol, diethylamino | hydroxybenzoyl hexyl benzoate , coated or uncoated zinc CH3 (CH2 ) (CH2 ) 3 CH3 CH3 oxide , ethylhexyl methoxycinnamate , isoamyl methoxycin | namate , homosalate ethyl hexyl salicilate , octocrylene, poly CH3 silicone- 15, butyl methoxydibenzoylmethane, menthyl 60 anthranilate , and ethylhexyl dimethyl PABA . PE Emulsifiers Emulsifiers are well known in the art and include ampho wherein p is 0-40 ( the range including all numbers teric , anionic , cationic or nonionic emulsifiers , used alone or between and subranges such as 2 , 3 , 4 , 13 , 14, 15 , 16 , 17 , 18 , as a mixture , and optionally with a co -emulsifier . The 65 etc. ), and PE is ( C2H40.6C3H60 )6 - H wherein a is emulsifiers are chosen in an appropriate manner according to 0-25 , b is 0-25 with the proviso that both a and b cannot be the emulsion to be obtained . O simultaneously , x , y , and z are each independently ranging US 10,729,633 B2 17 18 from 0 to 1 million with the proviso that x and y cannot be Dimethicone PEG - 7 Undecylenate ; Lauryl Dimethicone O simultaneously . In some cases, x , y , z , a , and b are such that PEG - 10 Phosphate ; Isopolyglyceryl- 3 Dimethicone ; Isopo the molecular weight of the polymer ranges from about lyglyceryl - 3 Dimethiconol; Isostearyl Carboxyldecyl PEG - 8 5,000 to about 500,000 , from about 10,000 to 100,000 , or is Dimethicone; LaurylMethicone PEG - 10 Phosphate ; Lauryl about 50,000 , and the polymer is generically referred to as 5 PEG - 8 Dimethicone ; Lauryl PEG - 10 Methyl Ether Dime dimethicone copolyol. In some instances , p is such that the thicone ; Lauryl PEG /PPG - 18 / 18 Methicone ; PEG - 6 Methyl long chain alkyl is cetyl or lauryl, and the compound is Ether Dimethicone ; PEG - 7 Methyl Ether Dimethicone ; PEG - 9 Methyl Ether Dimethicone; PEG - 10 Methyl Ether called , generically , cetyl dimethicone copolyol or lauryl Dimethicone; PEG - 11 Methyl Ether Dimethicone; PEG - 11 berdimethicone of repeating copolyol ethylene respectively oxide or .propylene In some cases oxide the units num in 10 Methyl Ether Dimethicone; PEG -32 Methyl Ether Dimethi the polymer are also specified , such as a dimethicone cone ; PEG - PEG /PPG - 28 /21 Acetate Dimethicone; PEG / copolyol that is also referred to as PEG - 15/ PPG - 10 dime PPG - 22 / 22 Butyl Ether Dimethicone , PEG /PPG - 23 /23 thicone, which refers to a dimethicone having substituents Butyl Ether Dimethicone ; PEG /PPG - 24 / 18 Butyl Ether containing 15 ethylene glycol units and 10 propylene glycol 15 Dimethicone ;; PEGPEG / PPG - 6 3 / 11 10 DimethiconeDimethicone ; PEG /PPG PPG - 84 / 1214 units on the siloxane backbone. It is also possible for one or Dimethicone ; PEG / PPG - 12 / 16 Dimethicone; PEG /PPG - 12 / more of the methyl groups in the above general structure to 18 Dimethicone; PEG / PPG - 14 /4 Dimethicone ; PEG /PPG be substituted with a longer chain alkyl ( e.g. ethyl, propyl, 15/5 Dimethicone ; PEG /PPG - 15 / 15 Dimethicone ; PEG / butyl, etc. ) or ether , such as methyl ether , ethyl ether , propyl PPG - 16 / 2 Dimethicone ; PEG /PPG - 16 / 8 Dimethicone ; PEG / ether , butyl ether, and the like . 20 PPG - 17 / 18 Dimethicone; PEG /PPG - 18 / 12 Dimethicone ; An oxyalkylenated organosiloxane emulsifier having the PEG / PPG - 19 / 19 Dimethicone; PEG / PPG - 20 / 6 Dimethi general formula : cone ; PEG /PPG - 20 / 15 Dimethicone; PEG / PPG -20 /20 Dimethicone ; PEG / PPG - 20 / 29 Dimethicone ; PEG /PPG -22 / 23 Dimethicone ; PEG /PPG - 22 /24 Dimethicone ; PEG /PPG CH3 CH3 CH3 25 25/25 Dimethicone , PEG / PPG -27 /27 Dimethicone ; PEG / OSI ( H3C ) 3 Si Si PPG -30 / 10 Dimethicone; PEG /PPG - 10 / 3 Oleyl Ether 1 | Dimethicone ; PEG - 8 trisiloxane ; Polyglyceryl- 3 Polydim CH3 (CH2 )n ( CH2) n ethylsiloxyethyl Dimethicone; PPG - 12 Butyl Ether Dime H | thicone; Silicone Quaternium - 17 ; TEA -Dimethicone PEG - 7 CH3( SiO )CH3 O 30 Phosphate ; or mixtures thereof. Si( CH3 ) 3 PE y Further examples of commercial linear organosiloxane emulsifiers are those sold by Dow Corning under the trade CH3 name Dow Corning 3225C Formulation Aid having the -Si( CH3) 3 CTFA name cyclotetrasiloxane ( and ) cyclopentasiloxane 35 (and ) PEG /PPG - 18 dimethicone ; or 5225C Formulation Aid , (CH2 ) n Z having the CTFA name cyclopentasiloxane (and ) PEG /PPG 18/18 dimethicone ; or Dow Corning 190 Surfactant having CH3 the CTFA name PEG /PPG - 18 / 18 dimethicone; or Dow Corning 193 Fluid , Dow Corning 5200 having the CTFA wherein each n is independently 0-100 with the proviso 40 name lauryl PEG / PPG - 18/ 18 methicone; or Abil EM 90 that there must be at least one PE radical. In some instances, having the CTFA name cetyl PEG /PPG - 14 / 14 dimethicone where each n independently ranges from about 2 to 30 , and sold by Goldschmidt; or Abil EM 97 having the CTFA name PE ( C2H4O4C3H 0 ).- H wherein a is 0-25 , b is bis - cetyl PEG / PPG - 14/ 14 dimethicone sold by Gold 0-25 with the proviso that both a and b cannot simultane schmidt; or Abil WE 09 having the CTFA name cetyl ously be 0 ; and wherein w , x , y , and z are each independently 45 PEG /PPG - 10 / 1 dimethicone in a mixture also containing 0 to 1,000,000 with the proviso that there is at least one PE . polyglyceryl- 4 isostearate and hexyl laurate ; or KF - 6011 In some embodiments the organosiloxane emulsifier is lau sold by Shin - Etsu Silicones having the CTFA name PEG - 11 ryl PEG - 9 Polydimethylsiloxyethyl Dimethicone . Oxyalky methyl ether dimethicone ; KF -6012 sold by Shin - Etsu Sili lenated organosiloxane emulsifiers disclosed in U.S. Pat. cones having the CTFA name PEG /PPG -20 /22 butyl ether No. 9,095,543 are useful in the instant compositions. U.S. 50 dimethicone ; or KF- 6013 sold by Shin - Etsu Silicones hav Pat . No. 9,095,543 is incorporated herein by reference in its ing the CTFA name PEG - 9 dimethicone; or KF -6015 sold by entirety . Shin -Etsu Silicones having the CTFA name PEG - 3 dime Further examples of organosiloxane emulsifiers include thicone ; or KF -6016 sold by Shin - Etsu Silicones having the those having C.T.F.A. names Bis - Butyldimethicone CTFA name PEG - 9 methyl ether dimethicone; or KF -6017 Polyglyceryl- 3 ; Bis - PEG /PPG - 14 / 14 Dimethicone ; Bis -bu- 55 sold by Shin - Etsu Silicones having the CTFA name PEG - 10 tyldimethicone Polyglyceryl- 3 ; Bis - isobutyl PEG /PPG - 10 / 7 dimethicone ; or KF -6038 sold by Shin -Etsu Silicones hav Dimethicone copolymer ; Bis -PEG /PPG - 18 /6 Dimethicone; ing the CTFA name lauryl PEG - 9 polydimethylsiloxyethyl Bis -PEG /PPG - 20 /20 Dimethicone ; Bis -PEG /PPG - 16 / 16 dimethicone . PEG /PPG - 16 / 16 Dimethicone ; Bis ( PPG - 7 Undeceneth -21 Also suitable are various types of fully or partially cross Dimethicone ; Cetyl Dimethicone PEG - 7 Acetate ; Cetyl 60 linked oxyalkylenated organosiloxane emulsifiers . They PEG - 8 Dimethicone ; Cetyl PEG /PPG - 15/ 16 Butyl Ether may be elastomeric or non -elastomeric . They are sometimes Dimethicone , Cetyl PEG / PPG -15 / 15 Butyl Ether Dimethi referred to as “ emulsifying elastomers” because of they have cone ; Cetyl PEG /PPG - 7 / 3 Dimethicone ; Cetyl PEG /PPG both elastomeric and emulsifying properties. 10/1 Dimethicone; Dimethicone PEG - 15 Acetate ; Dimethi Polyoxyalkylenated silicone elastomers that may be used cone PEG - 7 Cocoate ; Dimethicone PEG - 7 Phosphate ; 65 in at least one embodiment include those sold by Shin -Etsu Dimethicone PEG - 10 Phosphate ; Dimethicone PEG /PPG Silicones under the names KSG -21 , KSG -20 , KSG -30 , 7/4 Phosphate ; Dimethicone PEG /PPG - 12 / 4 Phosphate ; KSG -31 , KSG -32 , KSG -33 ; KSG - 210 which is dimethi US 10,729,633 B2 19 20 cone/ PEG -10 / 15 crosspolymer dispersed in dimethicone ; Non - limiting examples of hydrocarbons include linear or KSG - 310 which is PEG - 15 lauryl dimethicone crosspoly branched , optionally cyclic C. -C16 alkanes; hexane, unde mer; KSG -320 which is PEG - 15 lauryl dimethicone cane, dodecane , tridecane, and isoparaffins, for instance crosspolymer dispersed in isododecane; KSG -330 ( the for isohexadecane , isododecane and isodecane. Additionally , mer dispersed in triethylhexanoin ), KSG -340 which is a 5 the linear or branched hydrocarbonsmay be composed only mixture of PEG - 10 lauryl dimethicone crosspolymer and of carbon and hydrogen atoms of mineral, plant, animal or PEG - 15 lauryl dimethicone crosspolymer . synthetic origin with more than 16 carbon atoms, such as Also suitable are polyglycerolated silicone elastomers volatile or non -volatile liquid paraffins , petroleum jelly , include dimethicone /polyglycerin - 3 crosspolymer dispersed liquid petroleum jelly , polydecenes , hydrogenated poly in dimethicone; or lauryl dimethicone/ polyglycerin - 3 10 isobutene, and squalane . crosspolymer dispersed in a variety of solvent such as The fatty alcohols that can be used may be liquid at 25 ° isododecane , dimethicone, triethylhexanoin , sold under the C., 1 atm , or may even be solid . They may even be Shin - Etsu tradenames KSG - 810 , KSG - 820 , KSG - 830 , or glycerolated and /or oxyalkylenated , and may include from 8 KSG - 840 . Also suitable are silicones sold by Dow Corning to 30 carbon atoms. They may be saturated or unsaturated . under the tradenames 9010 and DC9011 . 15 The fatty alcohols useful herein include those having from Further examples of crosslinked organosiloxane emulsi about 10 to about 30 carbon atoms, from about 12 to about fiers include, but are not limited to Dimethicone/ dimethi 22 carbon atoms, and from about 16 to about 22 carbon cone PEG / PPG 15 crosspolymer ; Dimethicone PEG - 10 atoms . These fatty alcohols can be straight or branched chain crosspolymer ; Dimethicone PEG - 10 /15 Crosspolymer ; alcohols and can be saturated or unsaturated . Nonlimiting Dimethicone PEG - 15 Crosspolymer ; Dimethicone 20 examples of fatty alcohols include decyl alcohol, undecyl Polyglycerin - 3 Crosspolymer; Dimethicone PPG - 20 alcohol, dodecyl, myristyl, cetyl alcohol, stearyl alcohol, Crosspolymer; Dimethiconol /Methylsilanol / Silicate isostearyl alcohol, isocetyl alcohol, behenyl alcohol, lina Crosspolymer, Dimethiconol/ Silicate Crosspolymer, Lauryl lool, oleyl alcohol, cholesterol, cis4 - t- butylcyclohexanol , Dimethicone PEG - 15 Crosspolymer; Lauryl Dimethicone myricyl alcohol and a mixture thereof. In some cases, the Polyglycerin - 3 Crosspolymer ; PEG - 8 Dimethicone Polysor- 25 fatty alcohols are those selected from the group consisting of bate -20 Crosspolymer; PEG - 10 Dimethicone /Vinyl Dime cetyl alcohol , stearyl alcohol, isostearyl alcohol, oleyl alco thicone Crosspolymer , PEG - 10 Lauryl Dimethicone hol, isotridecyl alcohol, and a mixture thereof. Crosspolymer, PEG - 15 / Lauryl Dimethicone Crosspolymer , The saturated liquid fatty alcohols may be branched . They and PEG - 15 Laurylpolydimethylsiloxyethyl Crosspolymer . can optionally comprise , in their structure , at least one Fatty Compounds 30 aromatic or non -aromatic ring , but are preferably acyclic . The hair conditioning compositions may also include at Non - limiting examples of liquid saturated fatty alcohols least one fatty compound. A " fatty compound” is an organic include octyldodecanol, isostearyl alcohol, and 2 -hexylde compound that is not soluble in water at normal temperature canol. (25 ° C.) and at atmospheric pressure (750 mmHg) ( solubil The unsaturated liquid fatty alcohols include in their ity below 10 % ) . In some instances , the solubility in water 35 structure at least one double or triple bond and preferably may be below 5 % , below 1 % , or below 0.1 % ). Moreover, one or more double bonds. When several double bonds are fatty compounds are generally soluble in one or more present, there are preferably 2 or 3 of them and they can be organic solvents under the same conditions of temperature conjugated or non -conjugated . These unsaturated fatty alco and pressure , for example organic solvents such as chloro hols can be linear or branched . They can optionally include form , ethanol, benzene or decamethylcyclopentasiloxane. 40 in their structure at least one aromatic or non - aromatic ring Non -limiting examples of fatty compounds include oils , but they are preferably acyclic . Among liquid unsaturated mineral oil, fatty alcohols , fatty acids, fatty alcohol deriva fatty alcohols , oleyl alcohol, linoleyl alcohol, linolenyl tives , fatty acid derivatives ( such as alkoxylated fatty acids alcohol and undecylenyl alcohol can be cited . or polyethylene glycol esters of fatty acids or propylene Non -limiting examples of solid fatty alcohols include glycol esters of fatty acids or butylene glycol esters of fatty 45 linear or branched , saturated or unsaturated alcohols con acids or esters of neopentyl glycol and fatty acids or taining from 8 to 30 carbon atoms, for example , myristic polyglycerol/ glycerol esters of fatty acids or glycol diesters alcohol, cetyl alcohol , stearyl alcohol and their mixture , or diesters of ethylene glycol and fatty acids or esters of fatty cetylstearyl alcohol. acids and fatty alcohols , esters of short chain alcohols and Non -limiting examples of liquid fatty esters include esters fatty acids) , esters of fatty alcohols , hydroxy - substituted 50 from a C6- C32 fatty acid and / or a C6 -C32 fatty alcohol, and fatty acids, waxes , triglyceride compounds, lanolin , and a are liquid at 25 ° C., 1 atm . These esters may be liquid esters mixture thereof. In some instances , the at least one fatty of saturated or unsaturated , linear or branched C -C26 ali compound includes one or more fatty alcohols , fatty acids , phatic mono or polyacids and of saturated or unsaturated , esters of fatty acids, and /or esters of fatty alcohols ( for linear or branched C , -C25 aliphatic mono or polyalcohols , example , cetyl palmitate , cetyl stearate , myristyl myristate , 55 the total number of carbon atoms in the esters being greater myristyl stearate , cetyl myristate , and stearyl stearate (a than or equal to 10. In some cases, for the esters of mixture of which is referred to as “ cetyl esters ” ) ) . monoalcohols , at least one of the alcohol or the acid from Fatty compounds include hydrocarbons , fatty alcohols , which the esters of the invention result is branched . Among fatty alcohol derivatives, fatty acids, fatty acid derivatives , the monoesters of monoacids and of monoalcohols, mention fatty esters , fatty ethers , oils , waxes , etc. The fatty com- 60 may be made of ethyl palmitate , isopropyl palmitate , alkyl pounds may be liquid or solid at room temperature and at myristates such as isopropyl myristate or ethyl myristate , atmospheric pressure (25º C., 1 atm ). Non - limiting isocetyl stearate , 2 - ethylhexyl isononanoate , isononyl examples of the fatty alcohols , fatty acids, fatty alcohol isononanoate , isodecyl neopentanoate and isostearyl neo derivatives , and fatty acid derivatives are found in Interna pentanoate . tional Cosmetic Ingredient Dictionary , Sixteenth Edition , 65 In some cases , it is particularly useful to include cetyl 2016 , which is incorporated by reference herein in its esters in the hair conditioning compositions. Cetyl Esters is entirety. a mixture of the following esters of saturated fatty acids and US 10,729,633 B2 21 22 fatty alcohols : cetyl palmitate , cetyl stearate , myristyl As oils of plant origin or synthetic triglycerides that may myristate , myristyl stearate , cetyl myristate , and stearyl be used in the composition of the invention as liquid fatty stearate . esters , the following can be cited , for example , triglyceride Fatty alcohol derivatives include alkyl ethers of fatty oils of plant or synthetic origin , such as liquid fatty acid alcohols , alkoxylated fatty alcohols, alkyl ethers of alkoxy- 5 triglycerides containing from 6 to 30 carbon atoms, for lated fatty alcohols , esters of fatty alcohols and a mixture instance heptanoic or octanoic acid triglycerides , or alter thereof. Nonlimiting examples of fatty alcohol derivatives natively , for example , sunflower oil, corn oil, soybean oil , include materials such asmethyl stearyl ether; 2 -ethylhexyl marrow oil , grapeseed oil, sesame seed oil , hazelnut oil, dodecyl ether ; stearyl acetate ; cetyl propionate ; the ceteth apricot oil, macadamia oil , arara oil, castor oil , avocado oil , series of compounds such as ceteth - 1 through ceteth -45 , 10 olive oil, rapeseed oil, coconut oil , wheatgerm oil, sweet which are ethylene glycol ethers of cetyl alcohol, wherein almond oil , apricot oil, safflower oil, candlenut oil , coconut the numeric designation indicates the number of ethylene oil, camellina oil, tamanu oil, babassu oil and pracaxi oil , glycol moieties present; the steareth series of compounds caprylic /capric acid triglycerides , jojoba oil, and shea butter such as steareth - 1 through 10 , which are ethylene glycol oil . ethers of steareth alcohol, wherein the numeric designation 15 The solid fatty acid esters and / or fatty alcohol esters that indicates the number of ethylene glycol moieties present; may be mentioned include solid esters obtained from C7 -C26 ceteareth 1 through ceteareth - 10 , which are the ethylene fatty acids and from C9 - C25 fatty alcohols. Among these glycol ethers of ceteareth alcohol, i.e. a mixture of fatty esters , mention may be made of octyldodecyl behenate , alcohols containing predominantly cetyl and stearyl alcohol, 20 isocetyl behenate, cetyl lactate, stearyl octanoate , octyl octanoate , cetyl octanoate , decyl oleate , myristyl stearate , wherein the numeric designation indicates the number of octyl palmitate , octyl pelargonate , octyl stearate , alkyl ethylene glycol moieties present; C , -C30 alkyl ethers of the myristates such as cetyl myristate , myristyl myristate or ceteth , steareth , and ceteareth compounds just described ; stearyl myristate, and hexyl stearate . polyoxyethylene ethers of branched alcohols such as octyl The liquid fatty ethers may be chosen from liquid dialkyl dodecyl alcohol, dodecylpentadecyl alcohol, hexyldecyl 25 ethers such as dicaprylyl ether. The non - liquid fatty ethers alcohol, and isostearyl alcohol; polyoxyethylene ethers of may also be chosen from dialkyl ethers and in particular behenyl alcohol; PPG ethers such as PPG - 9 - steareth - 3 , dicetyl ether and distearyl ether , alone or as a mixture. PPG - 11 stearyl ether, PPG8- ceteth - 1 , and PPG - 10 cetyl Non - limiting examples of waxes include carnauba wax , ether ; and a mixture thereof. candelilla wax , esparto wax , paraffin wax , ozokerite , plant Esters of C4- C22 dicarboxylic or tricarboxylic acids and of 30 waxes such as olive tree wax , rice wax , hydrogenated jojoba C , -C22 alcohols and esters ofmonocarboxylic , dicarboxylic wax or absolute flower waxes , such as the blackcurrant or tricarboxylic acids and of C4 -C26 dihydroxy, trihydroxy , blossom essential wax sold by Bertin (France ), or animal tetrahydroxy or pentahydroxy non -sugar alcohols may also waxes such as beeswaxes or modified beeswaxes ( cerabel be Mentionused . may be made in particular of diethyl sebacate; 35 lina) , and ceramides. Non - limiting examples of ceramides diisopropyl sebacate ; diisopropyl adipate ; di- n - propyl adi include N - linoleyldihydrosphingosine, N -oleyldihy pate ; triisopropyl citrate ; glyceryl trilactate ; glyceryl trioc drosphingosine , N -palmityldihydrosphingosine , N - stearyl tanoate ; neopentyl glycol diheptanoate ; and diethylene gly dihydrosphingosine or N -behenyldihydrosphingosine , or col diisononanoate . mixtures of these compounds . Mention may also be made of sugar esters and diesters of 40 Non -limiting olyglycerol esters of fatty acids include Co- C30 and preferably C12 -C22 fatty acids . The term “ sugar ” those of the following formula : means oxygen- bearing hydrocarbon -based compounds con taining several alcohol functions , with or without aldehyde or ketone functions , and which comprise at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccha- 45 OR rides or polysaccharides . Examples of suitable sugars that R1— ( OCH2 - CH - CH2O )n - R3 may be mentioned include saccharose, glucose , galactose , ribose , fucose , maltose , fructose , mannose, arabinose, wherein the average value of n is about 3 and R ' , R2 and xylose and lactose, and derivatives thereof, especially alkyl R3 each may independently be a fatty acid moiety or derivatives , such as methyl derivatives, for instance meth- 50 hydrogen , provided that at least one of R ', R2, and R3 is a ylglucose . The sugar esters of fatty acids may be chosen in fatty acid moiety . For instance , R ' , R2 and R may be particular from the group comprising the esters or mixtures saturated or unsaturated , straight or branched , and have a of esters of sugars described previously and of linear or length of C1 -C40 , C1- C30 , C1- C25 , or C - C20 , C1 -C ., or branched , saturated or unsaturated Co- C30 and preferably C - C10 . For example , nonionic polyglycerol esters of fatty C12 - C22 fatty acids . If they are unsaturated , these com- 55 acids include polyglyceryl- 5 laurate , pounds may comprise one to three conjugated or non The fatty acid derivatives are defined herein to include conjugated carbon - carbon double bonds. The esters accord fatty acid esters of the fatty alcohols as defined above , fatty ing to this variantmay also be chosen from mono-, di- , tri acid esters of the fatty alcohol derivatives as defined above and tetraesters , and polyesters , and mixtures thereof. These when such fatty alcohol derivatives have an esterifiable esters may be, for example, oleates , laurates , palmitates, 60 hydroxyl group , fatty acid esters of alcohols other than the myristates , behenates , cocoates, stearates, linoleates, lino fatty alcohols and the fatty alcohol derivatives described lenates, caprates and arachidonates , and mixtures thereof, above, hydroxy - substituted fatty acids, and a mixture such as, in particular, oleopalmitate , oleostearate or palmi thereof. Nonlimiting examples of fatty acid derivatives tostearate mixed esters . More particularly , use is made of include ricinoleic acid , glycerol monostearate , 12 -hydroxy monoesters and diesters and in particular of sucrose , glucose 65 stearic acid , ethyl stearate , cetyl stearate , cetyl palmitate , or methylglucose mono- or dioleates, stearates, behenates , polyoxyethylene cetyl ether stearate , polyoxyethylene oleopalmitates , linoleates , linolenates or oleostearates . stearyl ether stearate , polyoxyethylene lauryl ether stearate , US 10,729,633 B2 23 24 ethyleneglycol monostearate , polyoxyethylene monostear plied products are often mixtures of fatty alcohols having ate , polyoxyethylene distearate , propyleneglycol monoste alkyl chain length distribution in which the main alkyl chain arate , propyleneglycol distearate , trimethylolpropane dis is cetyl, stearyl or behenyl group . In the present application , tearate , sorbitan stearate , polyglyceryl stearate , dimethyl more preferred fatty alcohols are cetyl alcohol , stearyl sebacate , PEG -15 cocoate , PPG -15 stearate , glyceryl 5 alcohol and mixtures thereof. monostearate , glyceryl distearate, glyceryl tristearate , PEG - 8 laurate , PPG - 2 isostearate , PPG - 9 laurate , and a Implementation of the present disclosure is provided by mixture thereof. Preferred for use herein are glycerol monos way of the following examples . The examples serve to tearate , 12 -hydroxy stearic acid , and a mixture thereof. illustrate the technology without being limiting in nature . In some cases , the one or more fatty compounds may be 10 one or more high melting point fatty compounds. A high melting point fatty compound is a fatty compound having a EXAMPLES melting point of 25 ° C. Even higher melting point fatty compounds may also be used , for example , fatty compounds Example 1 having a melting point of 40 ° C. or higher, 45 ° C. or higher, 15 50 ° C. or higher . The high melting point fatty compound may be selected from the group consisting of fatty alcohols , Sunscreen Formulations of SPF 30 A B C D E INCI US Antioxidants PHLORETIN 0.5 POLYDATIN 0.5 FERULIC ACID 0.5 RESVERATROL 0.5 BAICALIN 0.5 UVA Filter AVOBENZONE 3 3 3 3 3 3 UVB Filter HOMOSALATE 5 5 5 5 5 5 ETHYLHEXYL SALICYLATE 5 5 5 5 5 5 OCTOCRYLENE 7 7 7 7 7 7 Fatty DICAPRYLYL CARBONATE , 3.6 3.6 3.6 3.6 3.6 3.6 Compound CETYL ALCOHOL , MYRISTIC ACID , PALMITIC ACID , AND /OR STEARIC ACID Nonionic PEG - 100 STEARATE 3 3 3 3 3 3 Emulsifier AND /OR GLYCERYL STEARATE Solubilizing CAFFEINE AND /OR 5 5 5 5 5 5 Agent NIACINAMIDE Silicone DIMETHICONE AND /OR 3 3 3 3 3 3 Compound DIMETHICONE / VINYL DIMETHICONE CROSSPOLYMER Filler SILICA 3 ??? 3 3 3 ??? Water Soluble CAPRYLYL GLYCOL 3.3 3.3 3.3 3.3 3.3 3.3 Solvent AND /OR GLYCERIN Thickening AMMONIUM 0.9 0.9 0.9 0.9 0.9 0.9 Agent POLYACRYLOYLDIMETHYL TAURATE AND /OR XANTHAN GUM Miscellaneous Preservative (s ), chelating s3 53 53 53 s3 < 3 agent( s ) , Vitamin ( s ) , etc. Water WATER QS QS QS QS QS QS

50 fatty acids, fatty alcohol derivatives, fatty acid derivatives, Example 2 and mixtures thereof. Non - limiting examples of the high melting point compounds are found in International Cos In Vivo PPD metic Ingredient Dictionary, Fifteenth Edition , 2014 , which is incorporated herein by reference in its entirety . The fatty 55 Sunscreen formulation A (of Example 1 ) , which does not alcohols useful herein are those having from about 14 to include any antioxidants , was compared with sunscreen about 30 carbon atoms, preferably from about 16 to about 22 formulations B and C , which include 0.5 wt. % of the carbon atoms. These fatty alcohols are saturated and can be antioxidants baicalin and polydatin , respectively. The degree straight or branched chain alcohols . Non -limiting examples 60 of UVA protection provided by each of the formulations was ofhigh melting point fatty compounds include fatty alcohols determined in terms of UVPPPD PF . Based on these results , such as, for example , cetyl alcohol (having a melting point the formulations were assigned a “ PA " value , which repre of about 56 ° C. ), stearyl alcohol (having a melting point of sents the protection grade ofUVA . PA values are commmonly about 58-59 ° C.) , behenyl alcohol (having a melting point of used to simplify the results of UV PPDPF testing . It ranges about 71 ° C.) , and mixtures thereof. These compounds are 65 from PA + to PA ++++, wherein : known to have the abovemelting point. However, they often PA + is sunscreen with a UV PPD PF from 2 to 4 ; have lower melting points when supplied, since such sup PA ++ is a sunscreen with UV PPD, PF from above 4 to 8 ; US 10,729,633 B2 25 26 PA +++ is a sunscreen with a UV PPD PF from above 8 to 16 ; and Sunscreen Formulation UV PPD PF PA Value PA ++++ is a sunscreen with a UV PPD PF of greater than Formulation A (no antioxidants ) 8 PA ++ 16 . Formulation D ( 0.5 wt. % ferulic acid ) 11 PA +++ The UV PPD PF for each of sunscreen formulations A , B , 5 Formulation E ( 0.5 wt. % resveratrol ) 12.2 PA +++ and C was determined according to ISO 24442 , which was Formulation F (0.5 wt. % phloretin ) 14 PA +++ adopted by the Japan Cosmetic Industry Association in 2012 for characterization of UVA protection and is incorporated The data show that sunscreen formulation D , containing herein by reference in its entirety . The area of the back ferulic acid , exhibited an improvement in both UV PPD PF between the scapula line and the waste is utilized for testing 10 and PA Value (more than 37 % improvement in UV PPDPF ) . using a light Source such as a 150 watt Xenon Arc Solar Formulation E , containing resveratrol, exhibited an even Simulator equipped with an Ultraviolet (UV ) reflecting greater improvement in UV PPD PF (more than a 52 % dichroic mirror, 3 mm thick Schott WG - 335 filter together improvement in UV PPD PF ). Formulation F , containing with a 1 mm thick Schott UG - 11 filter to produce simulation 15 phloretin , exhibited the greatest degree of improvement in of the UVA solar spectrum . UVA radiation can be monitored UV PPD PF ( 75 % improvement in UV PPD PF ) . It was not continuously during exposure using a Model DCS - 1 Sun known that antioxidants could provide UVA protection . burn UV Meter /Dose Controller System (Solar Light Co.) , Therefore , the improvement in UV PPD PF and PA values for formerly known as the Robertson -Berger Sunburn meter ferulic acid , resveratrol , and phloretin was unexpected and ( R - B meter ) . The threshold dose for PPD in unprotected skin 20 surprising . Moreover, the extent to which these antioxidants is determined over the mid to lowed back by administering improved the UV PF and PA value is particularly sig series of exposures in 25 % dose increments of UVA radia nificant and surprisingPPD . tion in geometric progression . The minimum PPD dose (MPPD ) is the smallest UVA dose required to persist for Example 4 more than 2 hours after exposure . A minimum of 5 expo- 25 sures are made . The MPPD of unprotected skin is deter Antioxidant Activity mined under standardized lighting conditions 2 to 4 hours after exposures. Persistent pigmentation on each sub site is In tubo antioxidant testing was carried out to determine graded and themean UVA Protection Factor (UVAnd PF ) of the antioxidant profile of antioxidants that boost UVA photo the sample , when at least 5 subjects tested is reported . 30 protection . The testing results are summarized below and graphically ORAC presented in FIG . 1. The Oxygen Radical Absorbance Capacity (ORAC ) assay is one of most commonly used methods to evaluate the capacity of antioxidants against ROS (reactive oxygen spe Sunscreen Formulation UV PPD PF PA Value 35 cies ), specific for peroxyl which is one of themost important Formulation A ( no antioxidants ) 8 PA ++ free radicals present in the human skin environment. The Formulation B (0.5 wt. % baicalin ) 8.8 PA +++ ORAC assay measures the oxidative degradation of the Formulation C (0.5 wt. % polydatin ) 17 PA ++++ fluorescent probe ( fluorescein ) after being mixed with free 1.7 radical generators such as azo - initiator compounds (2,2' SPFTree Formulation( 0.5 wt % polydatin ) 40 Azobis ( 2- amidinopropane ) dihydrochloride, AAPH ) . Azo The data show that sunscreen formulation B , containing initiators produce the peroxyl radical by heating , which baicalin , exhibited a slight improvement in both UVPPPD PF damages the fluorescent molecule , resulting in the loss of and PA Value (about 10 % improvement in UV PPDPF ) . fluorescence . Antioxidants protect the fluorescent molecule Formulation C , containing polydatin , exhibited an much from the oxidative degeneration . By quantifying the decay more pronounced improvement in UV PPD, PF and PA Value 45 of fluorescence using a fluorometer , the degree of protection (more than a 200 % improvement in UV PPD PF ). It was not is determined comparing with a standard control antioxidant known that certain antioxidants could boost UVA protection Trolox . The result is expressed in mol equivalent of Trolox of sunscreens. Therefore , the significant improvement in per gram of sample (i.e. , umol TE /g ) . Equipment that can UV PPD PF and PA values for polydatin was unexpected and automatically measure and calculate the capacity is com surprising . Clearly it is not from the antioxidant itself (PPD 50 mercially available , such as the VarioSkan flash microplate value of 0.5 % polydatin in formula without UV filters is only reader from Thermo Scientific . To test samples for ORAC , 1.7 ) but from a synergistic interaction with UV filters . compounds are dissolved into water -based NaH2PO4 buffer. HORAC Example 3 The HORAC assay is another common method to exam 55 ine antioxidant activity . It is specific for hydroxyl radicals . In Vivo PPD The Varioskan Flash is employed for the quantification of the capacity of an antioxidant to avert the hydroxyl radical. The ability of other antioxidants to boost UVA protection The hydroxyl radical, generated from hydrogen peroxide was investigated in the same manner described above in and Cobalt ( II ) fluoride, will quench a fluorescent probe by Example 2. Sunscreen formulation A (of Example 1) , which 60 a hydrogen atom transfer reaction . In the presence of an does not include any antioxidants , was compared with antioxidant, however, the molecule will chelate the Co ( II) , sunscreen formulations D , E , and F , which include 0.5 wt. % preventing the generation of the hydroxyl radical and ini of the antioxidants ferulic acid , resveratrol, and phloretin , tially block or prevent the quenching of the probe , causing respectively . The degree of UVA protection provided by a delay in the fluorescence decay profile . The area under the each of the formulationswas determined as described above 65 fluorescence decay curves for samples with and without the in Example 2. The results are summarized below and presence of an antioxidantmolecule are compared to that of graphically presented in FIG . 2 . a standard reference material and the hydroxyl radical US 10,729,633 B2 27 28 averting capacity is determined . By quantifying the decay of The term “ volatile ” , as used herein ,means having a flash fluorescence using a fluorometer , the degree of protection is point of less than about 100 ° C. determined by comparison with a standard control antioxi The term “ non - volatile ” , as used herein , means having a dant Gallic Acid ( standard reference material ) . The result is flash point of greater than about 100 ° C. expressed in umol equivalent of Gallic Acid per gram of 5 The term “ substituted ,” as used herein , means comprising sample ( i.e., umol GAE / g ) . Equipment that can automati one or more substituents . Non - limiting examples of sub cally measure and calculate the capacity is commercially stituents include atoms, such as oxygen atoms and nitrogen available, such as the VarioSkan flash microplate reader atoms, as well as functional groups, such as hydroxyl from Thermo Scientific . To test samples by using HORAC , groups, ether groups, alkoxy groups , acyloxyalkyl groups , compounds are dissolved into water -based NaH2PO4 buffer. 10 oxyalkylene groups, polyoxyalkylene groups, carboxylic SORAC acid groups , amine groups , acylamino groups, amide groups, The Superoxide Radical Absorbance Capacity ( SORAC ) halogen containing groups, ester groups, thiol groups, sul assay is an in tubo method to determine the relative capacity phonate groups, thiosulphate groups , siloxane groups , and of an antioxidant to dismutate the superoxide anion . The polysiloxane groups. The substituent( s ) may be further sub Varioskan Flash is employed to measure the superoxide 15 stituted . dismutase -catalyzed dismutation of the superoxide anion in The term “ polymers , " as defined herein , include homopo the presence of the absorbance probe, water- soluble tetra lymers and includes copolymers formed from at least two zolium salt (WST - 1 ). WST- Formazan is produced when different types of monomers. WST- 1 is oxidized by superoxide anion that is generated by 20 The cosmetic methods and compositions of the present the mixture of xanthine and xanthine oxidase . One unit of disclosure can comprise , consist of, or consist essentially of SOD activity is defined as the quantity of antioxidant to the essential elements and limitations of the disclosure obtain 50 % inhibition of the rate of reduction of WST- 1 . The described herein , as well as any additional or optional final SORAC value is expressed as one unit of SOD activity ingredients , components , or limitations described herein or per milligram of dry weight of antioxidant material at 50 % 25 otherwise useful. Additionally any component that is posi inhibition (Unit /mg ) . tively set forth in the present disclosure can be negatively The results for baicalin (negative example ), polydatin , excluded from the methods and compositions of the present disclosure , and in particular from the claims of the present phloretin , resveratrol, and ferulic acid are shown below . disclosure . In particular, the methods and compositions of 30 the present disclosure can be free or essentially free of any ORAC -peroxyl HORAC -hydroxyl SORAC -superoxide component that is positively set forth in the present disclo Antioxidants (umol TE / g ) (umol GAE/ g ) ( U mg/ ) sure . Baicalin Medium Weak Medium Other than in the operating examples , or where otherwise Polydatin Strong Strong None indicated , all numbers expressing quantities of ingredients Phloretin Strong Medium None 35 and /or reaction conditions can be modified , if desired , with Resveartrol Strong Strong None Ferulic acid Strong Strong Weak the term “ about, ” meaning within +/- 5 % of the indicated None No detectable No detectable No detectable value number . value value All percentages , parts and ratios herein are based upon the Weak < 4500 < 2600 200 total weight of the compositions of the present disclosure , Medium 4500-10000 2600-10000 200-1000 40 unless otherwise indicated . Strong > 10000 > 10000 > 1000 As used herein , all ranges provided are meant to include every specific range within , and combination of sub ranges The in tubo antioxidant data above , when compared with between , the given ranges . Thus, a range from 1-5, includes the PPD data from Examples 2 and 3 , suggests that antioxi specifically 1 , 2 , 3 , 4 and 5 , as well as sub ranges such as 2-5 , dants having strong ORAC ( above mol TE / g ) are effective 45 3-5 , 2-3, 2-4 , 1-4 , etc. in boosting the UVA photoprotection of cosmetic composi The terms “ a ," " an , ” and “ the ” are understood to encom tions . Similarly , stronger HORAC ( 2600-10000 umolGAE / pass the plural as well as the singular . Thus, the term “ a g ) was associated with better boosting ability . The role of mixture thereof” is synonymous with “mixtures thereof. ” SORAC however, exhibited the opposite trend . The antioxi Throughout the disclosure , the term “ a mixture thereof ” may dants having less SORAC ( less than 200 U /mg ) exhibited a 50 be used following a list of elements as shown in the boosting effect on UVA photo -protection . Baicalin , having following example where letters A - F represent the elements : the highest SORAC , did not boost UVA photo -protection . " one or more elements selected from the group consisting of The fact that certain antioxidants have any boosting effect on A , B , C , D , E , F , and a mixture thereof. " The term , " a UVA photo - protection is itself surprising and unexpected . It mixture thereof' ' does not require that the mixture include all is further surprising and unexpected to find that the ORAC , 55 of A , B , C , D , E , and F ( although all of A , B , C , D , E , and HORAC , and SORAC of the antioxidants appears to relate F may be included ). Rather , it indicates that a mixture of any to the antioxidants ' boosting effect on UVA photo -protec two or more of A , B , C , D , E , and F can be included . In other tion . words, it is equivalent to the phrase " one or more elements The term “ broad spectrum photo protection ” means pro selected from the group consisting of A , B , C , D , E , F , and tection from both UVA radiation and UVB radiation . 60 a mixture of any two or more of A , B , C , D , E , and F.” “ At least one ” as used herein is synonymous with “ one or Likewise , the term " a salt thereof" also relates to " salts more ” and includes individual components as well as mix thereof. " Thus, where the disclosure refers to “ an element tures /combinations . selected from the group consisting of A , B , C , D , E , F , a salt The term “ treat ” ( and its grammatical variations) as used thereof, and a mixture thereof, ” it indicates that that one or herein refers to the application of the cosmetic compositions 65 more of A , B , C , D , and F may be included , one or more of of the present disclosure onto the surface of the body, and in a salt of A , a salt of B , a salt of C , a salt of D , a salt of E , particular the skin and /or hair of the body. and a salt of F may be include , or a mixture of any two of US 10,729,633 B2 29 30 A , B , C , D , E , F , a salt of A , a salt of B , a salt of C , a salt 6. The method of claim 1 , wherein the at least one of D , a salt of E , and a salt of F may be included . antioxidant that boosts photo - protection from UVA radiation Some of the various categories of components identified is ferulic acid and the cosmetic composition provides an may overlap . In such cases where overlap may exist and the increase in UVAPPD PF of at least 30 % relative to an composition includes both components ( or the composition 5 otherwise identical cosmetic composition without the anti includes more than two components that overlap ), an over oxidant( s ) of (a ). lapping compound does not represent more than one com ponent. For example , a fatty acid may be characterized as 7. The method of claim 1 , wherein the cosmetic compo both a nonionic surfactant and a fatty compound . If a sition comprises from 1 to about 35 wt. % of at least one particular method or composition includes both a nonionic 10 organic UV filter, based on the total weight of the cosmetic surfactant and a fatty compound , a single fatty acid will composition . serve as only the nonionic surfactant or as only the fatty 8. The method of claim 1 , wherein the total amount of compound (the single fatty acid does not serve as both the antioxidant( s ) of ( a ) is from about 0.01 to about 5 wt. % , nonionic surfactant and the fatty compound ) . based on the total weight of the cosmetic composition . All publications , patents , and patent applications cited in 15 9. The method of claim 1 , wherein the at least one organic the present disclosure are herein incorporated by reference , UV filter of (b ) is selected from the group consisting of and for any and all purposes , as if each individual publica selected from the group consisting of a para -aminobenzoic tion , patent, or patent application were specifically and acid derivative , a salicylic derivative , a cinnamic derivative , individually indicated to be incorporated by reference . In the a benzophenone or an aminobenzophenone, an anthranillic event of an inconsistency between the present disclosure and 20 derivative , a B , B - diphenylacrylate derivative , a benzyliden any publications, patents , or patent applications incorpo ecamphor derivative , a phenylbenzimidazole derivative, a rated herein by reference , the present disclosure controls . benzotriazole derivative , a triazine derivative , a bisresorci The invention claimed is : nyl triazine , an imidazoline derivative , a benzalmalonate 1. A method for providing broad spectrum photo -protec derivative , a 4,4 - diarylbutadiene derivative, a benzoxazole tion to skin , the method comprising topically applying to the 25 derivative , a merocyanine ,malonitrile or a malonate diphe skin a cosmetic composition comprising: nyl butadiene derivative , a chalcone , and a mixture thereof . ( a ) at least one antioxidant that boosts photo -protection 10. The method of claim 1 , wherein the cosmetic com from UVA radiation , the at least one antioxidant hav position comprises at least two organic UVB filters . ing : 11. The method of claim 1 , wherein the cosmetic com i. an Oxygen Radical Absorbance Capacity (ORAC ) of 30 position is essentially free of inorganic UV filters . at least 10,000 umol TE / g ; and ii. a Hydroxyl Radical Absorbance Capacity ( HORAC ) 12. The method of claim 1 , wherein the total amount of of at least 2,600 umol GAE / g ; organic UV filter ( s ) of ( b ) is from about 1 to about 40 wt. % , (b ) at least one organic UV filter ; and based on the total weight of the cosmetic composition . ( c ) a cosmetically acceptable carrier; 35 13. The method of claim 1 , wherein the cosmetically wherein the cosmetic composition provides an increase acceptable carrier comprises water. in UVAPPD PF of at least 30 % relative to an other 14. The method of claim 13, wherein the cosmetically wise identical cosmetic composition without the acceptable carrier further comprises at least one water antioxidant( s ) of ( a ) ; soluble solvent . wherein the at least one antioxidant that boosts photo- 40 15. The method of claim 1 , wherein the cosmetic com protection from UVA radiation is selected from the position comprises from about 40 to about 90 wt. % of the group consisting of polydatin , phloretin , resveratrol, cosmetically acceptable carrier , based on the total weight of ferulic acid , their derivatives, and a mixture thereof; the cosmetic composition . and 16. The method of claim 1 , wherein the cosmetic com the cosmetic composition is free of baicalin . 45 position further comprises : 2. The method of claim 1, wherein the at least one at least one solubilizing agent. antioxidant that boosts photo -protection from UVA radiation 17. The method of claim 1 , wherein the cosmetic com has a Superoxide Radical Absorbance Capacity (SORAC ) of position further comprises : less than 200 U /mg . at least one emulsifier . 3. The method of claim 1, wherein the at least one 50 18. The method of claim 1 , wherein the cosmetic com antioxidant that boosts photo -protection from UVA radiation position further comprises : is polydatin and the cosmetic composition provides an at least one silicone compound . increase in UVAPPD PF of at least 150 % relative to an 19. A method for providing broad spectrum photo - pro otherwise identical cosmetic composition without the anti tection to skin , the method comprising topically applying to oxidant( s ) of ( a ) . 55 4. The method of claim 1 , wherein the at least one the skin a cosmetic composition comprising: antioxidant thatboosts photo -protection from UVA radiation ( a ) from about 0.01 to about 5 wt. % , based on the total is phloretin and the cosmetic composition provides an weight of the cosmetic composition , of at least one increase in UVAPPD PF of at least 50 % relative to an antioxidant that boosts photo - protection from UVA otherwise identical cosmetic composition without the anti- 60 radiation selected from the group consisting of poly oxidant( s ) of ( a ) . datin , phloretin , resveratrol, ferulic acid , their deriva 5. The method of claim 1 , wherein the at least one tives, and a mixture thereof: antioxidant that boosts photo -protection from UVA radiation ( b ) from about 1 to about 40 wt. % , based on the total is resveratrol and the cosmetic composition provides an weight of the cosmetic composition , of at least one increase in UVAPPD PF of at least 40 % relative to an 65 organic UV filter, and otherwise identical cosmetic composition without the anti (c ) a cosmetically acceptable carrier comprising water and oxidant( s ) of ( a ). at least one water - soluble solvent or solubilizing agent ; US 10,729,633 B2 31 32 wherein the cosmetic composition provides an increase in UVAPPD PF of at least 30 % relative to an other wise identical cosmetic composition without the antioxidant ( s ) of (a ), and the cosmetic composition is free of baicalin . 5