CA3011986C - Hydrophobic topical compositions - Google Patents

Abstract

An anhydrous topical composition provides a water repellent surface. The anhydrous topical composition has at least one film former with surface tension lower than 35 dynes/cm, at least one particle having a hydrophobic surface or a hydrophobic surface treatment, and a volatile topical carrier.

Description

HYDROPHOBIC TOPICAL COMPOSITIONS AND METHODS FOR PRODUCING SAME CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application Serial Number 62/281854, filed on January 22, 2016, the contents of which are incorporated herein for reference in its entirety. BACKGROUND OF THE INVENTION

[0002] Field of the Invention

[0003] The invention involves chemical compositions capable of repelling water. Specifically, the invention involves chemical compositions, safe for application to human skin, capable of repelling water by imparting hydrophobic or superhydrophobic characteristics into topical formulae.

[0004] Description of Related Art

[0005] Water repellency or durability is one of key performance characteristics in certain topical compositions including long-wearing color cosmetics and water resistant sunscreens. Conventional technologies in cosmetics and sunscreens have focused on staying power on skin, such as long-lasting skin adhesion or water resistance of cosmetic actives. Many film formers have been used to enhance the durability of cosmetic and other topical compositions on human skin. Typically, when a topical composition is exposed to water, such as through sweating or swimming, the water starts to wet the composition surface. A wet surface ultimately results in a lack of durability in a topical composition. This lack of durability is caused by a loss of topical actives due to any re-emulsification process.

[0006] Past compositions attempted to create water resistant surfaces, whereas hydrophobic or superhydrophobic technology creates a water repellent surface. A water repellent surface creates a physical interaction with water molecules, so that water will bead up and roll off the topical surface without wetting the surface. Water repel lency not only provides a desirable dry feel on skin but also creates a visual cue for formula durability on skin.

[0007] Hydrophobicity is measured by the water contact angle. The water contact angle on a surface is the angleof the leading edge of a water droplet bn the surface as measured from the center of the interface between the droplet and the surface. A surface with acontact angle of 180 degrees means that water sits on the surface as a perfect sphere. Hydrophobic surfaces, when measured, have a contact angle between 90 degrees and150 degrees. Superhydrophobic surfaces, when measured, have a contact angle between 150 degrees and180degrees.

[0008] A superhydrophobic surface can cause water to roll off the surface leaving little or no residue. Hydrophobicsurfaces aredesirable inmany arts for varied uses and arecreated through varying means. For example, a superhydrophobic surface can be created on polytetrafluoroethylene (PTFE) with a picosecond laser for use on underwater materials (Shang et al, "Nanostructured Superhydrophobic Surfaces," 40 J. Mater. Scl 3587 (2005)). Carbon nanotubules alsocan achieve a superhydrophobic surface through deoxygenation of a chemical treatment(Uu^ah,"Superhydrophobic Carbon NanotubeForests," 3 NANOLetters1701(2003); U.S. Patent Neu 9,115,424). Additionally, acid absorbed onto aluminum coated in polyethyleneimine (PEI) can create a superhydrophobic surface (Ren et al., "Preparation and 2CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 Characterization of an Ultrahydrophobic Surface Based on a Stearic Add Seif-Assembled Monolayer over F^lyethyleneimine ThinFilms/' 546 SurfaceScsence 64 (2003)],

[0009] Film formers are known to be used in topical compositions to create water resistant barriers. Film formers are durable water resistant polymers that have wide use in industrial processes. Whenapplied to a surface, film formers act as a barrier between the surface and any outside matter,such as water. Film formers are commercially available in manydifferent forms. Emulsion-based film formers are typically water-in-oil or watdr-ln-silicone emulsions. The use of such emulsions relies on the water evaporating and leaving the oilor the silicone in contact with the skin to produce a water resistant layer. However, the use of emulsion-based film formers creates unpleasant aesthetics on the skin, such as an oily appearance and a greasy feet The resulting film is not water repellent and leaves an unnatural appearance on theskin.

[0010] Anhydrous film formers typically include organic solvents, such as amalcphol. Such film formers can also produce a tacky feeling on human skin and other undesirable aesthetics when introducedto water. Representative patentsregardingsuch waterresistant topicalcompositions are set forth below inTable1.

[0011] TABLE1 1 U55,985,297 Anhydrous and water-resistant cosmetic compositions 2 US 5,925,337 Waterproofcompositions for coveringthe dygta^ies,and process for the preparation thereof 3 US4,795,631 Water based lip color comprising an alkali soluble filmforming agent 384378923 [0012J used in topical do not reach a desirable level of hydrophobicity that imparts durability. Ideally, a topical composition has a ^rhydtepMc syrface-tM^at^ water contactanglecf W$^or'i|to& TabM belowshowsthat most filmformers atane canbarely achieve a water contact anglegreater than IWdegrees/Whlleitisdesirabletoachieveasurface^ water is 130 degrees or greater. It should also be notedthat uponincorporation into atopical composiildh ^uch cdnta<ahglesaredifficult to maintain. 10013] TABLE'2 Polymer Name CASW. Mfr Tension (dynes/cm) withWater ft Polyvinyl alcohol (PVOH) 25213-24-5 37 51 l^ton™fi(pd^^ 25038-54-4 43.9 62.6 Polyethylenee«de(P^ 25322-68-3 43 63 ltetem«^mdifcac^^ $01144-7 37.$' W' Polystyrene^ 9003-53-6 34 87.4 Polybutadiehe 900347-2 29.3 96 Pblyethyten<0>E] 02-884 31> 96 PolydimethyisllbXane (POMS) 9016-00-6 20d 1071 i^raffto^ 24.8 108.9 Polytetrafluoroethylene (PTFE) 9002-84-0 19.4 $091 Polyisobutylene(PB,butyl wblw) 27 112.1 4 Date Re^ue/Date Received 2023-06-20GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0014] Despite the many advances in water resistant topical compositions, there Is still a need for a water repellent topical composition that provides pleasant and desirable aesthetics for consumers. SUMMARY OF THE INVENTION (0015] in a first aspect, the present invention is directed to an anhydrous topical composition comprising at least one film former having a surface tension lower than 35 dyhes/cm selected from the groupconsisting of glycol ester crosspolymers, silicones, resins and derivatives thereof, and olefinicpolymers andcrosspolymers, said at least one film former is presentinan amount of 5% to 10% by weight based on a total weight of said anhydrous topical composition; particles comprisinghydrophobic-treatedsilica,fumedsilica,polytetrafluoroethylene,polyurethane,silica silylate, polymethylsilsesquioxane, hydrophobic-treated calcium silicate, hydrophobic-treated cellulose, hydrophobic-treated polymethylmethacrylate, hydrophobic-treated zinc oxide, hydrophobic-treated titanium dioxide, or combinations thereof, said particles present in an amount of 1.5% to 10% by weight based on the total weight of said anhydrous topical composition; a volatile topical carrier present in an amount of 30% to 60% by weight based on the total weight of said anhydrous topical composition; and an active agent selected from the group consistingof a sunscreen active agent, an insect repellent, a colorant, and combinations thereof; wherein said anhydrous topical composition has an initial water contact angle greater than 90 degrees.

[0016] The active agent may comprise a therapeutic amount of at least one sunscreen active agent selected from the group consisting of an ultraviolet A long-wave sunscreen active agent, 5GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 an ultraviolet 3 shortwave sunscreen active agents a full spectrum sunscreen active agent, an encapsulated UV filter, and combinations thereof. The active agent may also comprise a therapeutic amount of at least one insect repellent selected from the group consisting of N,N diethybm-toluamlde, ethyl butylacetylaminopropionate, hydroxyethyl isobutyl piperidine carboxylate, oil of citronella, soy bean oil, lemon grass oil, geranium/geraniol oil, neem oil, natural essentialoils,p-menthane-3,8-diol,and mixturesthereof. Alternatively,the active agent comprises at least one colorant selected from the group consisting of an organicpigment or dye, an inorganic pigment or dye, and mixtures thereof. [00171 Preferably, the anhydrous topical composition has an initial water contact angle greater than120degrees. More preferably,the anhydroustopical composition has a water contact angle greater than 60degrees after 40 minutes.

[0018] In another aspect, the present Invention is also directed to an anhydrous sunscreen composition comprising a sunscreen active agent comprising avobenzone, terephthalylidene dicamphor sulfonic acid, b&-disulizole disodlum, disodium phenyl dibenzimidazole tetrasulfonate, dlethylamino hydroxybenzoyl hexylbenzoate, bfs-diethylamind hydroxybenzoyl benzoate, bfs-benzpxazolylphenyl ethylhexylamino triazine, octocrylene, octinoxate, octisalate, homosalate, ehsulizote, ethylhexyl triazohe, enzacamene, amiloxate, diethylhexyi butamido triazine, benzylidene malonate polysiloxane, padimate-O, trolamine salicylate, cinoxate, paminobenzoic acid, oxybenzone, meradimate, titanium dioxide, zinc oxide, bfs-octrizole, bemotrizinol, drometrizole trisiloxane, sulisobenzone, dioxybenzone, encapsulated UV filters, or combinations thereof; at least one film former having asurface tension lower then 35 dynes/cm 6GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 wherein the filmformer is selected from the group consisting of a polymer, awax, an ester, a resin, a rosin, a silicone, a silicone resin, and a fluorinated silicone; particles comprising hydrophobic-treated silica, fumed silica, polytetrafluoroethylene, polyurethane, silica silylate, polymethylsilsesquioxane, hydrophobic-treated calcium silicate, hydrophobic-treated cellulose, hydrophobic-treated polymethylmethacrylate, hydrophobic-treated zinc oxide, hydrophobictreated titanium dioxide, or combinations thereof; and a volatile topical carrier; wherein said anhydroussunscreen compositionhas aninitial water contact angle greater than90degrees and a water contact angle of at least 60 degrees after 40 minutes. Preferably, the anhydrous sunscreen composition has an initial water contact angle greater than 100 degrees and a water contact angle of at least 60 degrees after 80 minutes.

[0019] In yet another aspect, the present invention is directed to an anhydrous topical composition comprising at least one film former having a surface tension lower than 35 dynes/cm; hydrophobic particles comprising hydrophobic-treated silica; fumed silica, polytetrafluoroethylene, polyurethane, silica silylate, polymethylsilsesquioxane, hydrophobictreated calcium silicate, hydrophobic-treated cellulose, hydrophobic-treated polymethylmethacrylate, hydrophobic-treatedzinc oxide,hydrophobic-treatedtrtanium dioxide, or combinations thereof; and a volatile topical carrier; wherein said composition has an initial water contact angle greater than 90 degrees. [0020J Preferably, the anhydrous topical composition further includes an active agent comprising sunscreen active agents; insect repellents; colorants; amino acids; moisturizers; pH adjusters; perfumes; essential oils; essential fatty acids; sphingolipids; antioxidants; chelating 7GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 agents;emollients;humectants;moisturizers;minerals;keratolytics;retmoids;hormones;alpha¬ keto acids; anti-mycobacterial agents; anti-fungal agents; anti-mlcrobials; anti-virals;analgesics; anti-allergenic agents; Hl or HZ antihistamines; anti-inflammatory agents; anti-irritants; antineoplastics; immune system boosting agents; immune system suppressing agents; anti-acne agents; anesthetics; antiseptics; skin cooling compounds; skin warming; compounds; skin protectants; skin penetration enhancers; exfoliants; lubricants; depigmenting agents; hypopigmenting agents; pharmaceutical agents; photostabiRzing agents; plant extracts; absorbents; salicylic acid; alpha and beta hydroxy acids; vitamins including vitamins A, C, and E; retinol and its derivatives; or combinationsthereof.

[0021] Most preferably, the active agent comprises a sunscreen active agent selected from the group consisting of avobenzone, terephthalylidene dicamphor sulfonic acid, b/s^disulizote disodium, disodium phenyl dibenzimidazole tetrasulfonate, diethylaminp hydroxybenzoyl hexylbenzoate, bfs-dieth^amino hydroxybenzoyl benzoate, b/s-benzoxazolylphenyl ethylhexylaminotriazine, octocrylene,octinoxate, octisalate, homosalate, ensulizole, ethylhexyl triazone, enzacamene, amiloxate, diethylhexyl butamido triazine, benzylidene malonate polysiloxane, padimate~O, trolamine salicylate, cinoxate, p-aminobenzoic -acid, oxybenzone, meradimate, titanium dioxide, zinc oxide, b&octrizole, bemotrizinol, drbmdtri:^ trisiloxane, sulisobenzone, dioxybenzone, encapsulated UV filters, and combinations thereof. Alternatively, the active agent comprises at least one insect repellentbeing a member selectedfromthegroup consistingof N,Ndtethyl-m-toluamide, ethyl butylacetylaminopropionate, hydroxyethyl isobutyl 884378923 piperidine carfeoxyiate,oilofcitronella,soy bean oMtlemonirassoil^eranlu^ oilnatural essential oiis,p-menthane-3,8-dH andmixtures thereof. [0022] the ant0W;t^^ has an' than 100 degrees, and more preferably,an initial water contact anglegreater than150 degrees. More preferably, the anhydrous topical composition hasawater contact angle greater than 60 degrees after 40 minutes, and most preferably, a water contact angle greater than go degrees after 80minPtes. {OO23J Preferably,the atleast one filmformer is presentinan amount of 0,5%to.20%by weight based wa and ^selectedto glycol ester crosspolymers, silicones,: resins and derivatives thereof, and olefinic polymers and Preferably, thfe^m^-iarW^W amount of 0.$* to 15% hy Weight based on at^ weight of said composition. Preferably, the volatile topical carrteris present m an amount of to80%by weight based on a toMweight pf-said^rnposlfionand is selected from the group consisting of a volatile hydrocarbon, a volatile silicone fluid, ethanol, and combinationsthereof,

[0024] The inventive compositions may be one of a lotion, a cream, an emulsion, a get a sOensi^^^ or apinyin 9 Date Re^ue/Date Received 2023-06-2084378923 [0024a] In one embodiment, the present invention is directed to an anhydrous topical composition comprising: at least one film former comprising a silicone having a surface tension lower than 35 dynes/cm, wherein the silicone comprises C24-28 alkyldimethylsiloxy trimethylsiloxysilicate, trifluoropropyldimethylsiloxy/trimethylsiloxy silsesquioxane, or combinations thereof, and wherein the at least one film former is present in an amount of 0.5% to 10% by weight based on a total weight of said anhydrous topical composition; hydrophobic particles comprising silica silylate and polymethylsilsesquioxane, wherein the polymethylsilsesquioxane is present in an amount greater than 0.5% based on the total weight of said anhydroustopical composition, and wherein the particles are present in an amount of up to 10% by weight based on the total weight of said anhydrous topical composition; a volatile topical carrier present in an amount of 10% to 80% by weight based on the total weight of said anhydroustopical composition; and a sunscreen active agent selected from the group consisting of an organic sunscreen active agent. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1illustrates a measurement of a water contact angle for Example 9 at 138.2 degrees measured with a Kruss Drop Shape Analysis System DSA 100. 9a Date Re?ue/Date Received 2023-06-20GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0026] Figure 2illustrates another measurement of a water contact angle for Example 18 at 155 degrees measured with a Kruss Drop Shape Analysis System DSA 100.

[0027] Figure 3 are photographic images of the initial water contact angles of commercially available sunscreens and inventive compositions, and the water contact angles after one (1) minute.

[0028] Figure 4 are photographic images of sunscreen coated Vitro-Skin* after blue water droplets are dripped onto the surface after one (1) second.

[0029] Figure 5 are photographic images of sunscreen coated Vitro-Skin*: after blue water droplets are dripped onto the surface after one (1) minute.

[0030] Figure S are photographic images of sunscreen coated PMMA plates;after blue water droplets are dripped ontothe surface.

[0031] Figure 7 is a graph comparing the water contact angles of inventive compositions and commercially available sunscreensover a time period ofInitial contact up to eighty (80) minutes. DETAILED DESCRIPTION OF THE INVENTION

[0032] The embodiments of the present disclosure can comprise, consist of, and consist essentially of the features and/or steps described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein or would otherwise be appreciated by one of skill in the art. ft is to be understood that all concentrations disclosed herein are by weight percent based on a total weight of the composition unless otherwise indicated. Any numerical range recited herein is intended to include ail sub-ranges subsumed therein, and such ranges are understood to include each and every number and/or fraction 10GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 betweenthe statedrange lower and upper values. For example, a range of about 0.5% and15% by weight of hydrophobic particles would expressly include all intermediate values of 0.6, 0.7, 0.8, all the way up to and including 14.7, 14.7, 14.9 and 15% by weight of hydrophobic particles. The same appliesto all other composition ranges set forth herein. Where appropriate, the INO (International Nomenclature of Cosmetic Ingredients) name of ingredieots/components is provided.

[0033] Given the broad applicability of the teachings of the present specification, it is not possible todiscuss each and every use and application of the present inventionand certainly not in any detail. Rather, the following specification, while mentioning a number of specific teachings, is primarily focused on general topical compositions, such as sunscreens, make-up, and insect repellents,though these teachingsare applicable toanynumber of cosmetic, skincare, health and beauty aid products including,but not limited to, personal cleansingproducts such as soaps, shampoos, gels, fragrances, as well as food, household cleaning, sanitizing, odor control products, etc. {0034] The present inventionprovides an anhydrous topical composition havingat least one film former withsurface tensionlower than 35 dynes/cm, at leastoneparticle having a hydrophobic surface or hydrophobic surface treatment, and a Volatile topical carrier. Unexpectedly, the anhydrous topical composition has an initial water contact angle greater than 60 degrees, preferably greater than 90 degrees, and most preferably greater than100 degrees, and wherein the contact angle of the composition can be maintained for an extended period of time greater than forty (40) minutes or longer, preferably for eighty (80) minutes or longer Embodiments of 11GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 the invention include one or more active agents that are added to the anhydrous topical composition toprovide a desirable dermatological effect. Desirable active agents may include a sunscreen active agent, an insect repellent active agent, a colorant, a fragranceor combinations of these active agents. These and other embodiments of the anhydrous topicalcomposition can be produced either in spray form, anhydrous lotion form, or other forms known in the pharmaceuticalcosmetic,and similar arts. Anhydrous isconsideredtobe lessthan1%by weight water based on a total weight of the composition.

[0035] It hasbeep foundthat usinga layer of hydrophobic particles alongwith$him former with a surface tension lower than 35 dynes/cm produces a water repellent surface in a topical composition. The hydrophobic particles increase the surface roughness of anyapplied layer and are added to the topical composition to create a micro-roughness on the skin. The advantage of adding particles 1$ that the micro-roughness increases the hydrophobicity of the topical composition by creating hydrophobic peaks to support and repel water droplets white still producing an overall desirable smoothness to the surface of the topical composition. However, pockets are formed In the particle layer where water can move freely through. A film former with a surface tension lower than 35 dynes/cm used in connection with a hydrophobic particle laypr covers these pockets in the particle layer, and together the film former and particle layer create a water repellent surface when formulated into a topical composition.

[0036] Filmformers useful intheinventive compositions musthavea surface tensionlower than 35 dynes/cm. Such preferred film formers can be, but are hot limited to, glycol ester crosspolymers, silicones, resins and derivatives thereof, and olefinic polymers and 12GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 crosspolymers, andcombinations thereof. Glycol esters having a surface tensiontower than 35 dynes/cm may include, without limitation, adipic add/diglyco! crosspolymer (LEXOREZ* 100), trimethyipentanedioi/adipic acid/glycerin crosspolymer (LEXOREZ 200), polyester-7 (and) neopentyl glycol diheptanoate (LEXF1LM® Sun), polyester-10 (and) propylene glycol dibenzoate (LEXFILM Spray),arid combinations thereof. Preferred silicones havinga surface area lower than 35 dynes/cm may include, without limitation, ethanol (and) crotonic acid/vinyi isoalkyl esters/vinyl acetate/b/s-vinyidimethicone crosspolymer (BELSIL® P1101), acrylates/dimethicone copolymer (KR-550), trimethylslloxysilicate (MQ resin), Cz-w® alkyldimethylsitoxy tnmethylstloxysilicate (GRANRESIN MQI-2450, GRANRESIN MQC-2450), polymethyisilseRwoxane/tn^^^ (GRANRESIN MQJ-T50, GRANRESIN MQC-T50), polymethylsilseTOOxane (GRANRESIN PMSCMD, GRANRESIN PMSQ-FLUID, GRANRESiN PMSQ- €§), perfluorononyl dimethieone (PECOSIL® FSH-1500), perfluorononyl dimethieone (PECOSIL FSH-300), Trifluprppropyldimethylsitoxy/Trimethylsiloxy Silsesquioxane (and) Dimethlcone (SILFORM® FR-5), Trifluoropropyldimethylsiloxy/Tfimethylsiloxy Silsesquioxane (and) Dimethlcone (SILFORM FR-10) or any combinations thereof. Resins may include, without limitations, its rosin derivatives, and abietic acid derivatives such as methyl dihydroabietate (MERISTANT® 1011). Olefinic polymers useful as film formers havinga surface tension lower than 35 dynes/cm mayinclude hydrogenated polycyclopentadiene (and) isododecane (KOBOGUARD® 5400 IDD). 13GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0037] A filmfarmer with a surfacetensionlower than 35 dynes/cmtypically comprises between 0.5%and 20% by weight of the composition. A preferredrange ofthe filmformer is between 5% and 10% by weight of the composition.

[0038] Particles useful in the present invention can be a hydrophobic-treated silica or fumed silica, a polytetrafluoroethylene, a polyurethane, a silica silylate, a polymeth^lsesquioxane, a hydrophobic-treated calcium silicate, a hydrophobic-treated cellulose, a hydrophobic-treated PMMA, a hydrophobic-treated zinc oxide, a hydrophobic-treated titanium dioxide, arid combinations thereof. Such surface treated particles are sold under the trade names EA-2Q9, FLO-BEADS* SE-3107A, BPD-800, BPD-500, BPD-500T, BPA-500, MSP-822, BPA^OOX, MSP-930, MSP-825, TR-1, TR-2, POMP900, SP-10, SP-500, DAIAMID* MSP-100, DAJAM1D MSP-BIO, DAIAMID MSP-S, Ct-2080, ECOBEADS* D-l, ECOBEADS D-5, DIASPHERE* KS-500, DIASPHERE KS- 1000, MST-203, MST-547, TOSPEARL* MSA, TOSPEARL 2000B, TOSPEARL 3OO0A, TOSPEARL 150KA, TOSPEARL 1110A, TOSPEARL 120A, SESQ-ML5, SESQ-MH5, SESQ-Whltel, SESQ-CL3, SESQ-CH1, MSS-500, MSS-500W, MSS-500/N, MSS-500/7N, MSS-500/H, MSS-500/3, MSS- 500/3N, MSS-5OO/3H, MSS-500/3H4, MSS-500/20N, SILICA SHELLS, FLORITE* R; FLORITE PS-10, CELLULOBEADS D-S, CELLULOBEADS D-10, CELLULOBEADS D-30, CELLULOBEADS D-SO, CELLULOBEADS USE, CELLULOBEADS D-10(R-33P), CELLULOBEADS D-W-33P|,; CELL D-10(UB-33), CELLULOBEADS D-W(Ti-33), CAB-O-SIL* TS-530, CAB-O-SIL TS-61Q, CAB-O-SIL TS- 710, CAB-O-SIL TS-720, AEROSIL* R 972, AEROSIL R974, AEROSIL R 104, AEROSIL R 106, AEROSIL R 202, AEROSIL R 208, AEROSIL R 805, AEROSIL R 812, AEROSIL R 812 S, AEROSIL R 816, AEROSIL R 7200, AEROSILR 8200, AEROSILR 9200, AEROSiL R 711, AEROSIL RY 50, AEROSILNY 50, AEROSIL 14GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 NY 50 L, AEROSILRY 200, AEROSIL RY 200 S, AEROSIL RX 50, AEROSIL MAX 50, AEROSIL* RX 200, AEROSIL RX 300, AEROSIL R 504, AEROSIL NX 90 S, AEROSIL NX 90 0, AEROSIL RY 300, AEROSIL REA 90, AEROSIL REA 200, AEROSIL RY 51, AEROSIL NA 50 Y, AEROSIL RA 200 HS, AEROSIL NA 50 H, AEROSIL RA 200 H, AEROSIL NA130K, AEROSIL NA 200 Y, AEROSIL NX 130, AEROSIL RY 200 L, R 709, AEROSIL R 976 S, AEROSIL R 972 Pharma, HDK® H13L, HDK H15, HDK H17, HDK H18, HDK H20,HDK H2000,HDK N20,HDKN20 NUTRITION,HDK N20 PHARMA, HDK N20D,HDK N20P, HDK N20ST, HDK S13,HDKT30, HDK T30P, HDK T40, HDK T40 NUTRITION, HDK V15, HDK VISA, HDK V15D, and combinations thereof. [00391 The particles may have a particle .size' of about 0.1to about 50 microns; preferably, a particle size of about 0,1toabout 30 microns, and most preferably aparticle sizeof about 0.2 to about 20 microns.

[0040] The particles typically comprise between 0.5% and 15% by weight of the composition. A preferred rangebfthe particles Is between 1.5%and 10% by weightof the composition.

[0041] The volatiletopical carrier usefulin the present inventioncanbe either polar or non-polar and can be,but is not limitedto,ethanol, isododecane,volatile hydrocarbons such as isobutane, or volatile silicones such as cyclopentasiloxane dislioxane,and combinations thereof.

[0042] For the non-polar, volatile topical carriers, a noh-polar, volatile oil tends to impart highly desirable aesthetic properties to the compositions of the present invention. Consequently, the non-polar,volatile oils are preferably utilizedat a fairly high level of commercialproducts. Non¬ polar, volatile oils particularly useful in the present invention include a member selected from the group consisting of silicone oils,hydrocarbons, and mixtures thereof. The non-polar, volatile 1584378923 oils useful inthe present invention can be either saturated or unsaturated, have an aliphatic character and be straight or branched chained or contain alicyclic or aromatic rings. Examples of preferred: ncfe^olar^oletfe h^ttocar^ns lh^ud» CttHCb (e^, PERMETHY^^A which is available from Prospers© Inc.),isodecane,andthe C?-C* through Cir Ci5isoparaffifis(suchas the iSOPAR^Series availablefrom Exxon™ ChemicafeCorp.). (0043] Highly preferred examples of proprietary commercial volatile silicone fluids include cydomWcph^ ofvarying viscosities*;^^ Dow™ doming2&D, Dow Cording 2^4, Corning 245, Dow Corning 344, and Dow Coming 345, (commercially available from. Dow Coming Corporation's^ Sllfepne Fluids (commercially available fromAnXMto GE 7207 and 7158 (commercially available from General Electric Co.); and SWS-03314 SeriesW£.).: Ad&tionaliy, lii^ri^coh^^ boused, including, but not limited to, dimethicones havinga viscosity of about 0.65 centistokes to about 2.dcentistokes

[0044] For the polar, volatile topical earners, two different categories are desirable. The first category is'the useM ethanol alon< The second category.: Is a .mixBra of dthahd with isodadecane or linear dsmethicones. (0045) The y^atllpctoplc^ Carrier' typf^H^ between 10%to 80% byiyeight of the ppmpce^om Apreferred tangoedthe volatile topical carrier Isbetween 30% of the composition. Desirable polar, volatiIe topical carriers that include ethan<<or ethanolin combinationwithi&dode&heor dimethicones/typic^ comprise 10% to60%byweight of the 30% td,50% by weight of the cdWpoipbn, Ddsfr^Me non-polar, 16 Date Re^ue/Date Received 2023-06-20GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 volatile topical carriers typically comprise 10% to 80% by weight of the composition, most preferably 30% fo60% by weight of the composition.

[0046] The anhydrous topical composition can provide the foundation or basecompositions for numerousalternativeembodiments. Alternative embodimentsmayinclude a lotion,a cream,an emulsion, a gel, a suspension, an aerosol, and a powder. Desirable alternative:embodiments further includeahactive agent toprovide a desiredtherapeutic functiontotheanhydroustopical composition, Desirable active agents may be selected from a group consisting of a sunscreen active agent, an insect repellent, a colorant, a fragrance, a pharmaceutical active agent, and combinations thereof present In a sufficient amount to provide their desired effect. Colorants, fragrances, and other dermatological or pharmaceutical active agents can be present in concentrations according totheir respective arts.

[0047] One embodiment of the invention provides a sunscreen. This "sunscreen topical composition" isan anhydrous topical composition having at least one sunscreenactive agent.

[0048] One or more sunscreen active agents, that can be used in the present invention, are capable of attenuating all or part of the harmful effects of ultraviolet ("UV") radiation. In addition, the sunscreen active agents must be non-toxic and non-irritating when applied to the skin. Sunscreenactive agents are, typically, categorized into four groups, as follows.

[0049] A first group of sunscreen active agents includes ultraviolet A long-wave or "UVA" sunscreen active agents. UVA sunscreen active agents, for example, include a member selected from the group consisting of avobenzone, terephthaiylidene dicamphor sulfonic acid, blsdisulizote dispdium, disodium phenyl dibenzimidazole tetrasuffonate, diethylamino 1784378923 hydroxyten^ hexylbenzoate, te*dlethyiamino hydroxybenzoyl benzoate, benzoxazoMphehy! ethylhexyla^ triazIne, and combinationsthereof (0050] A second:group of sunscreen, actlvd:^r^'lndW.fe or "UVB" sunscreen active agents, WB sunscreen active agents, for example,include a member selected from 'the group ^misting of octafrylene, octinoxate, oaisalate, homosaW,- #n$uliz<M ethylhexyl triazone, enzacamene, amiloxate, dtethylhexyl butamido triazin®, benzylidene matondte p^sfloxane, >adifo^^Oj. tfofomlnr salicylate, cfooxate, p^mlrfotfonzblc a<^> derivatives thereof,and combinationsthereof. (0051] A thlMgroupof sunsereenjctiw^ active"agentsfombsorbboth UVA andUVBradiation. These full spectrum UV active agents include a member selected from tHpgfoWcph^lng^formfopik d^behfone,'Wad|mat< titanium dfofode,,^^ bisoctrizote, bemotrizinoi, drometrizole trisiloxane, sulisobenzpne, dioxybenzone, and combinations thereof. Ifofthdr,$urfape'treafod/fc ortifonlum diemfoes induing, but not limited to, foeproprietary commercial products, Zano™10 Plus and UV-Titan M2S2, can be usedwafull spectrumwhscre&n'activeag^.

[0052] The fourth group of sunscreen active agents include encapsulated W filters. gpc^psplaW uv fitters 'include fopmber ifoJectpd ffom' the gi^fop rfopslstiM bf AvoCap (encapsulatedAyobenzone 60%payload and 15% Of Octocrylene), QmcCap (encapsulated Octyl MMhowcimamate,. 60%: payload), OxyCap (encapsulated Oxyberwone, 47%? payload and Q&Pcr^ene5O%VHomCap^ 60% payload), OctiCap, (ehcapsulated 18 Date Re^ue/Date Received 2023-06-2084378923 telsalMe6(S%payfoadV^ 70%payload). (0053] The s«Mebpf one or more sumpr^'i^^^ for usafo-a sunscreen of the invention, is made in accordance with the desired objectives for the final product. For Wmpte»fcoiW^ desiwfuilSpectrum ofUV pfofoctiodfofossertte riskpfWWand accelerated skinagingfrom prolongedsunexposure. Some consumersdesirea limitedexposure ofUV hidiatetoddduifoppmefonnhgeffects from sunexposure, while mlhimlidn^ rl&^pf burning.

[0054] Anoi^embodiment of theIwentlcw anInsectrepellent. This "insect repellent topicalcomposition" is an anhydrous topicalcompositionhavingat least one insectrepellent,

[0055] Desirable insect repellents include, but are not limited to, a member selected from the group consisting of N,N diethyl-m-tolupmide (DRETh ethyl butylacetylaminopropionate (IR3535 by Merck™ Oa;); hydroxyethyi^obutylpipelineearbo^tejpH of citronella, soybeanoil, lemon grass oil, gemmum/geraniol oil, neem oil and other natural essential oils,j^erahane^^ or any::mixture thereof. Preferred. ^pellint active^ agents'.may include COX/ ethyl butylacetylaminopropionate, p-menthane-l.S-diol, and oil of dtronella. Further, a fragrance is often $dd$d'WW Cdr^slt^s. [0056]The insect repellent desirably comprises between 1% to 20% by weight pf the composition, Apreferred range;of insect repellent 'is between 5% to 10% by weight of the composition. 19 Date Re^ue/Date Received 2023-06-20GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0057] Another embodiment of the invention provides a colorant. This "co!orant topical composition" is art anhydrous topical composition having at least one colorant

[0058] Desirable colorants can be an organic or an inorganic pigment or dye. Colorants that can be used in the present compositions include, but are not limited to, proprietary commercial products seiectedfrom the group consisting of O&C Red No. 3, D&C Red No. 6/D&C Red No. 7, D&C Red No. 8,D&C Red No. 9, D&C Red No. 21, D&C Red No. 22,D&C Red No.27» D&C Red No. 28, D&C Red No, 30, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, FD&CRed No, 40, D&C Yellow NO. 5, FD&C:Yellow No. 5, FD&C Yellow No. 6, D&C Yellow No. 10,D&C Green No. 3, D&C Green No.5, D&COrange No. 5,FD&C Blue No.1,annatto, copper powder, bismuth oxychloride, guanine, bronze powder, iron oxides, caramel, manganese violet, carmine, mica, titanium dioxide-coated mica, carotene, titanium dioxide, zinc oxide, self-tanning compounds such as dihydroxyacetone (DHA) and erythruloses, and any combinations thereof. Further, the colorant can be an encapsulated pigment or colorant. Including, but not limited to, amember selected from the group consisting of TagraCap 1, RedCap 1, Black Cap 1, YellowCap1, WhiteCap 1, BlueCap 1, MicaCap1,TagraCap 3,RedCap 3, Black Cap3,YellowCap 3, BrownCap 3,TagraCap 5, RedCap 5, Black Cap 5, YellowCap 5, BlueCap 5, Red7Cap, CarbonCap, CameleonCaps, and combinations thereof.

[0059] The colorant desirably comprises between 0.5% and 10% by weight df the composition. A preferred range of colorant is between 0.5% and 5% by weight of the composition.

[0060] Alternativeembodiments may comprise other therapeutic or cosmetic active agents such but not limitedto, amino acids; moisturizers; pH adjusters; perfumes; essential oils; essential 20GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 fatty acids; sphingolipids; antioxidants; chelating agents; emollients; humectants; moisturizers; minerals; keratolytics; retinoids; hormones; alpha-keto acids; anti-mycobact<rial agents; anti¬ fungal agents; anti-mlcrobials; anti-virals; analgesics; anti-allergenic agents; Hl or H2 antihistamines; anti-inflammatory agents; anti-irritants; anti-neopiastics; immune system boosting agents; immune system suppressing agents; anti-acne agents; anesthetics; antiseptics; skincoolingcompounds;skinwarmingcompounds;skinprotectants;skinpenetrationenhancers; exfoiiants; lubricants; depigmenting agents; hypopigmenting agents; pharmaceutical agents; photostabilizing agents; plant extracts; absorbents; salicylic acid; alpha and beta hydroxy acids; vitamins including vitamins A, C, and E; retinol and its derivatives; or any combination of the foregoing. It should be appreciated and understood that thislist is not limiting* and that various other active ingredients may be usedin the present sunscreen formulations. (0061] Further embodiments of the invention can comprise other topical compositions for human, veterinarian, horticultural, and other coated substrates. Desirableembodiments include combinations of two or more of the already listed embodiments. For example, another embodiment of;an anhydrous topical composition comprises an anhydrous topical composition having at least one film former having a surface tension lower than 35 dynes/cm, at least one particle, a volatile topical carrier, a colorant, and a sunscreen active agent, wherein the anhydrous topical composition has an initial water contact angle greater than 60 degrees, preferably greater than 90 degrees, and preferably greater than 100 degrees. Another embodiment of an anhydrous topical composition comprises an anhydrous topical composition having at least one film former having a surface tension lower than 35 dynes/cm, at least one 21CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 hydrophobic particle, a volatile topicalcarrier, aninsect repellent,and a sunscreen active, where the anhydrous topicalcompositionmaintains a water contact angle greater than60degrees after 40 minutes.

[0062] Preparing the anhydrous topical composition can be performed using a mufti-phase approach mixingtwo or more phases together that are known to one of ordinary skill in the art. A phase can contain a certain set of components that are mixed together beforebeingcombined with another phase. The order of mixing the phases is determined by the compositions of the particular phasesbeingmixedineach process step and the desiredfinal product(e.g., a lotion,a cream, an aerosol,etc.)

[0063] The following processes illustrate exemplary methods for producing the invention. Variations of th^ processes and other processes can be used for producing; the anhydrous topicalcomposition.

[0064] Compounds in a Phase A may be mixed together at room temperature, with or without heat, with propeller mixing to ensure all components are homogenous. Compounds in a Phase B may bemixedtogether in a separate container, one at a time,until a component is completely dissolved. The Phase B mixture is then homogenized for three minutes at4000RPM. Phase B is then added Into Phase A. Compounds in a Phase C may be mixed together in another separate container, and subsequently homogenized for four minutes at 4000 RPM. ThePhase C mixture isthen added tothe Phase A and B mixture with mixing,

[0065] Alternatively, two or more phases are miscible with one another such that each phase is mixed together or one or more components are dissolved in another component to forma neat 22CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 solution. This process can produce lotion, a cream, a solution, ora volatile liquid. For example only, compounds In a Phase A may be mixed together at room temperature with a propeller mixing. Compounds In a Phase B may be mixed together In a separate container,one at a time, until all components are completely dissolved. The Phase 8 mixture is then homogenized then added into Phase A.

[0066] Once the twoor more phases of the composition areproperly mixed together to produce a final composition,depending on individual embodiments, a PMMA plate (Le^an HOB plate sold by HelioScreen Labs) is coated with 2 mg/cm2 of the inventive composition:. This coating thickness is recommendedby the UnitedStatesFood andDrugAdministrationasanoptimal dose for sunscreen application,and this concentration is used hereinfor consistency* (0067) A contact angle/surface tension or "drop shape” analyzer Is used to measure the water contact angle of a composition. Figure 1illustrates an initial water contact angle of 130.9 degrees, which was achieved by an embodiment of the present invention. Example 9. A water drop10 is formedon a composition surface 12 placed on a drop shape analyzer1, The angle 15 of the water drop 10 measured at the composition surface 12 is the "water contact angle" for the sample of composition being measured. Figure 2 illustrates a water contact angle of 155.00 degrees, which Was achieved by another embodiment of the present invention. Example 18. A water drop 20 isformed on another composition surface 22 placed on a dropshape analyzer 1. The angle 25 of the water drop 20 measured at the composition surface 22 is the "water contact angle" for the Sample of composition beingmeasured. 23GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0068] EXAMPLES [00691 The following examples illustrate a representative sampling of Hie many possible embodiments of the anhydrous topical composition. A brief description of the compounds included in the composition, the process used In preparing the composition, and the resulting water contact angle of the composition are included for each embodiment. These examples are provided in orderto demonstrate the many possible anhydrous topical compounds covered by the present invention and not as alimitation on the scope of the present invention. All examples disclosed hereinused a Kruss Orop Shape Analysis System OSA 100 to measure the initial and subsequent water contact angles of the anhydrous topical composition and its various embodiments onthe specified surfaces. The initial water contact angles of Examples1to 23 are shown below. Aneedle with a diameter of 1,8mm was used to form the water droplets. Unless otherwise stated, each composition was coated onto a HD6 PMMA plate from Helioscreen Labs at a thickness of 2 mg/cm2 and kept at 30X for 20 minutes to evaporate any solvent and form a continuous film on the plate. The percentage by weight of each component included In the exemplary composition is shown below in each phase. 2484378923 25 [0070]

[0071] Example1illuslrates an embodiment of theinvention that is a sunscreen. Phase Material Name <by Weight PHASE A Trifluoropropyldimethylsiloxy/ 8.00 Trimethylsiloxy Sifeesquioxane (and) Dimethicone (SILFORM FR-5) Isododecane 5.00 Ethanol 15.00 Silica dimethyl silylate (HDK H18) 2.00 Silica dimethicone silylate (CAB-O-SIL TS-720) 2.00 PHASES Ethanol 4s3o~ Trihydroxystearin (THIXCIN™R) 1.50 PHASE Isododecane 15.00 Polyhydroxystearic acid (DISPERSUN DSP-0L1OO) 0.30 Titanium Dioxide (And) Alumina (And) 3.50 Dimethicone (UV-Titan M262) Zinc Oxide and Triethoxycaprylylsilane 4.00 (Zano10 Plus) TOTAL 100.00 WATER CONTACT ANGLE: 145.7 Date Recue/Date Received 2023-06-20CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 (0072] Example 2 illustrates an embodiment of the invention that is a sunscreen. Phase Material Name %by Weight PHASE A Trifluoropropyldimethylsiloxy/ 8.00 Trimethylsiloxy Siisesqutoane (and) Dimethlcone (SILFORM FR-5) Cyclic methylsiloxane (Dow ComingD5&D6) 5.00 Isododecane 8.00 Ethanol 10.00 Homosaiate 2.00 Octisaiate 3.00 Silica dimethyl silylate (HDK H18) 1.00 Silica dlmethicone dilylate (CAB-O-SIL* TS-720) 3.00 Silica (MSS-500/20N) 4.00 PHASE B Ethanol 34.20 Trihydroxystearin (THIXCiN R) 1.50 PHASE c Isododecane 15.00 Polyhydroxystearic acid (DISPERSUN DSP-OL100) 030 Zinc Oxide and Triethoxycaprylylsilane (Zano 10Plus) 5.00 TOTAL 100.00 WATER CONTACT ANGLE: 106.4 26CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 (0073] Example 3illustrates an embodiment of the invention that is a sunscreen. Phase Material Name %by Weight PHASE A Trifiuoropropyidimethyhiloxy/ 8.00 Trimethylsiloxy Siisesquioxane (and) Dimethicone (SILFORM FR-5) Cyclic methylsiloxane (Dow Coming D5&D6) 5.00 Isododecane 8.00 Ethanol 10.00 Homosaiate 2.00 Octisaiate 3.00 Silica dimethyl silylate (HDK H18) 1.00 Silica Dimethicone Silylate (CAB-O-SIL TS-720) 3.00 Marshmallow Powder (HDI/Trimethylol Hexyllactone 4.00 Crosspolymer (and) Polymethyl Methacrylate) PHASE B Ethanol 34.20 Trihydroxystearin (THIXCIN R) 1.50 PHASE C Isodddecane 15.00 Polyhydroxystearic acid (DISPERSUN DSP-OL100) 0.30 Zinc Oxide and Triethoxycaprylylsilane (Zano 10 Plus) 5.00 TOTAL 100.00 WATER C0IMTACTAN6LE: 103.0 degrees 27CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0074] Exampie 4illustrates an embodimentsthe invention that is a sunscreen. Phase Material Name %by Weight PHASE A Trifluoropropyldimethylsiloxy/ 8.00 Trimethylsiloxy Siisesquioxane (and) Dimethlcone (SILFORM FR-5) Cyclopentasiloxane/Cydohexasiloxane (Dow Corning D5&D6) 5.00 Isododecane 8.00 Ethanol 10.00 Homosaiate 2.00 Octisaiate 3.00 Silica dimethyl silylate (HOK H18) 1.00 Silica siiylate (CAB-O-SILTS-610) 3.00 Cellulose (CEUULOBEADS) 0-50 4.00 PHASE B Ethanol 34.20 Trihydroxystearin (THIXCIN R) 1.50 PHASE c Isododecane 15.00 Polyhydroxystearic acid (DISPERSUN DSP-OL100) 030 Zinc Oxide and Triethoxycaprylylsilane (Zano 10Plus) 5.00 TOTAL 100.00 WATER CONTACT ANGLE: 107.1 28CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 (0075] Example 5 illustrates an embodiment of the invention that is a sunscreen. Phase Material Name %by Weight PHASE A Trifluoropropyldimethylsiloxy/ 8.00 Trimethylsiloxy Silsesqutoane (and) Dimethlcone (SILFORM FR-5) isododecane 8.00 Ethanol 15.00 Silicadimethyl silylate (HOK H18) 1.00 Silica dlmethlcone silylate (CA8-0-SIL TS-720) 3.00 Silica (MSS-5OO/2ON) 4.00 PHASE B Ethanol 36.70 Trihydroxystearin (THIXCIN R) 1.50 PHASE C Isododecane 15.00 Potyhydroxystearlc acid (Dispersun DSPOL100) 0.30 Titanium Dioxide (And) Alumina (And) DimethicOne (UV-Titan 3.50 M262) Zinc Oxide and Triethoxycaprylylsilane (Zano 10Plus) 4.00 TOTAL 100.00 WATER CONTACT ANGLE; 130.6 29CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0076] Example6illustrates an embodiment of the invention that is a sunscreen. Phase Material Name %by Weight PHASE A Trifiuoropropyidimethylsiloxy/ 8.00 Trimethylsiloxy Siisesqutoane (and) Dimethlcone (SILFORM FR-5) Perfluorononyl Dimethicone (PECOSIL FSH-300) 3.00 isododecane 8.00 Ethanol 15.00 Homosaiate 2.00 Octisaiate 3.00 Silica dimethyl silylate (HOK H18) 1.00 Silica dlmethieone silylate (CAB-O-SIL TS-720) 3.00 Silica (MSS-500/20N) 4.00 PHASE B Ethanol 30.70 Trihydroxystearin (THIXCIN R) 2.00 PHASE C isododecane 15.00 Polyhydroxystearic acid (DISPERSUN DSP-OL100) 0.30 Zinc Oxide and Triethoxycaprylylsiiane (ZANO 10 Plus) 5.00 TOTAL 100.00 WATER CONTACT ANGLE: 104.1 30CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 (0077] Example7illustrates an embodiment of the invention that is a sunscreen. Phase Material Name %by Weight PHASE A Trifluoropropyldimethylsiloxy/ 8.00 Trimethylsiloxy Siisesqutoane (and) Dimethicone (SILFORM FR-5) Cyelppentasiloxane and dimethicone/ vinyl dImethicone cross 5.00 polymer and perfluorononyl dimethicone (SILMER G162F) Isododecane 8.00 Ethanol 15.0) Homosalate 2.00 Ck^salate 3.00 Silica dimethyl silylate (HDK H18) 1.00 Silicadimethicone silylate (CAB-O-SILTS-720) 3.00 Silica.tM55^»/20N( <0& PHASE B Ethanol 28.70 Trihydroxystearin (THIXCIN R) 2.00 PHASE C Isodddecane 15.00 Polyhydroxystearic acid (DISPERSUN DSP-OL100) 0.30 Zinc Oxide and Triethoxycaprylylsilane (Zano 10 Plus) 5.00 TOTAL 100.00 WATER CONTACT ANOLE*. 102.7 31GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0078] Example 8 illustrates an embodiment of the invention that is a sunscreen. Phase Material (INC! Name) %by Weight PHASE A TriRuoropropyldimethylsnox 8.00 Trimethyisiloxy Silsesquioxane (and) Dimethicone (SILFORM FR-5) Isbdbdecane 8.00 Ethanol 15.00 HomosaIate 2.00 Octisalate 3.00 CaM5 Alkyldimethylsilyl Polypropylsilsesquioxene 2.00 (Dow Corning SW-8005 Resin Wax) Silica dimethyl silylate (HPK H18) 1.00 ~ Silica dimethicone silylate (CAB^O-SILTS-720) 3.00 PHASE 8 Ethanol 35.70 2.m PHASE C fsodddecane 15.00 Polyhydroxystearic acid (DISPERSUN DSP-OL100) 0.30 Zinc Oxide and Triethoxycaprylylsilane (Zano 10 Plus) 5.00 100.00 TOTAL WATER CONTACT ANGLE: 101.8 32CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0079] Exampie9Illustrates an embodimentof theinvention that is a sunscreenwitha colorant. Phase PHASEA Material (INCI Name) % Trifluoropropyldimethy1stloxy/ Trimethylsiloxy Siisesquloxane (and) Dlmethlcone (SILFORM FR-5) by Weight 8.00 Isododecane 8.00 Ethanol Silicadimethyl silylate (HDK H18) 15.00 1.00 jutCa Girneinicotw SHy?8w l ) $ Hn Silica (MSS-5OO/2ON) 3>W 4.00 Synthetic fluorphlogopite (and) titanium dioxide (and) iron oxides (and) tin oxide (SYNCRYSTAL* ivory Pigment) 1.00 PHASE B Ethanoi 35.20 Trihydroxystearin (THiXCIN R) 2.00 PHASE C Isododecane 15.00 Polyhydroxystearic add (DISPERSUN DSP-0L1OO) 0.30 Titanium Dioxide (And) Alumina (And) Dlmethlcone 3.50 (UV-TitanM262) Zinc Oxide and Triethoxycapryiylsiiane (Zano 10Pius) 4.00 TOTAL 100.00 WATER CONTACT ANOLE: 138.2 33GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0080] Example 10illustrates an embodiment of the invention that is a sunscreen composition. Phase Material (INCI Name! %by Weight PHASE A Alcohol (and) Crotonic Acid/Vinyl Cs-i? Isoalkyl Esters/VA/Bis-; 8.00 Vihyldimethicone Ethanol 15.00 Homosalate 5.00 Silica Dimethicone Silylate (CAB-O-SiL TS-720) 4.00 PHASE 8 Ethanol 68.00 TOTAL 100.00 WATER CONTACT ANGLE: 102.6

[0081] Exampleilillustrates anembodiment of the invention that is a sunscreen composition. Phase Material (INCI Name) %by Weight PHASE A Alcohol (and) Crotonic Acid/Vinyl Ca^i? isoalkyl Esters/VA/Bis- 8.00 Vlnyldlmethicone Ethanol 15.00 Octisalate S.00 Silica Dimethicone Silylate (CAB-O-SIL TS-720) 4.00 PHASE B Ethanol 68.00 TOTAL 100.00 WATER CONTACT ANGLE: 109.7 3484378923 35

[0082] Example12 illustrates an embodiment of theinvention that is a sunscreen composition. Phase Material(INCI Name) %by Weight PHASE A Alcohol (and) Crotonlc Acid/Vinyl Cw Isoalkyi Esters/VA/Bls- 8.00 Vihyldimethicone Crosspolymer (BELSIL™ P1101) Ethanol 15.00 Octylcrylene 5.00 Silica dlmethiew 4.00 PHASE B Ethanol 68.00 TOTAL 100.00 WATER CONTACT ANGLE: 110.0

[0083] Example13 illustrates anembodiment of theinvention that is a sunscreen. Phase Material Name %by Weight PHASE A Alcohol (and) Crotonlc Acid/Vinyl Cs-i2 Isoalkyl Esters/VA/Bls- 8.00 VmyldimethiconeCrosspolymer (BELSIL P1101) Ethanol 15.00 Silica dimethicone silylate (CAB O SILTS 720) 4.00 PHASE B Ethanol 66.00 Trihydroxystearin (THiXCIN R) 2.00 PHASE C Zinc Oxide and Triethoxycaprylylsilane (Zano10 Plus) 5.00 TOTAL 100.00 WATER CONTACT ANGLE: 136.2 Date Recue/Date Received 2023-06-20GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0084] Example14illustrates anembodiment of the invention that is a sunscreen. Phase Material Name %by Weight PHASE A Alcohol (and) Crotonic Acid/Vinyl Cs-i? Isoalkyl Esters/VA/Bis-; 8.00 Vihyldimethicone Ethanol 15.00 Avobenzone 3.00 Silica dimethicone silylate 4.00 PHASE 8 Ethanol 68.00 Trihydroxystearin (THIXCIN R) 2.00 TOTAL 100.00 WATER CONTACT ANGLE; 142.1

[0085] Example15illustrates anembodiment of the invention thatis a sunscreen. Phase Material Name >by Weight PHASE A Alcohol (and) Crotonic Acid/Vinyl Cs-n isoalkyl Esters/VA/Bi$- 8.00 Vinyldimethfcone Crosspotymer (BELSIL P1101) Ethanol 15.00 Oxybenzone 6.00 Silicadimethicone silylate (CAB-O-SILTS-720) 4.00 PHASE B Ethariol 65.00 Trlbydroxystearin (THIXCIN R) 2.00 TOTAL 100.00 WATER CONTACT ANGLE; 117.3 36CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0086] Example16illustrates anembodiment of the invention that is a sunscreen. Phase Material Name %by Weight PHASE A Alcohol (and) Crotonic Acid/Vinyl Cs-n Isoalkyl Esters/VA/Bls-; 8.00 Vihyldimethlcone Crosspolymer (BELSIL P1101) Ethanol 15.00 Avobenzone 3.00 Oxybenzone 6.00 Silica dimethicone silylate (CAB-O-SIL TS-720) 4.00 PHASE B Ethanol 62.00 Trihydroxystearin (THIXCtN R) 2.00 TOTAL 100.00 WATER CONTACTANGLE: 124.2

[0087] Example17Illustrates anembodiment of theInvention that is a topical composition. Phase PHASE A Material (INCI Name) %by Weight Alcohol (and) Crotonic Acid/Vinyl Ca-ia Isoalkyl Esters/VA/Bis- 8.00 Vinyldimethicohe Ethanol 67.7 Silica Dimethicone Silylate (CAB-O-SILTS-720) 4.00 Synthetic fluorphlogopite (and) titanium dioxide (and) iron 1.00 oxides (and) tin oxide (SYNCRYSTAL Ivory Pigment) Phase B Isododecane 15.00 Polyhydroxystearlc acid (DiSPERSUN DSP-OL100) 0.30 ZineOxide and Triethoxycaprylylsilane (Zano 10 Plus) 5.00 TOTAL WATER COf 100.00 iTACT ANGLE: 126.8 37CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475

[0088] Example18illustrates anembodiment of the invention that is a topicaldelivery system. Phase Material (INCI Name) %by Weight PHASE A Alcohol (and) Crotonic Acid/Vinyl Cs-n isoalkyl Esters/VA/Bis-; 8,00 Vihyldimethicone Ethanol 15.00 Silica dlmethicone silylate (CAB-O-SIL TS-720) 4.00 PHASE B Ethanol 71.00 Trihydroxystearin (THIXCIN R) 2.00 TOTAL 100.00 WATER CONTACT ANGLE: 155.0 [00891 Example19Illustrates an embodiment of the Invention that is a topicaldelivery system. Phase Material Name S by Weight PHASE A Alcohol (and) Crotonic Acid/Vinyl Cms Isoalkyl Esters/VA/Bis- 8.00 Vinyldlmethicone Perfluorononyl Dimethicone (PECOSIL FSH-300) 3.00 Ethanol 15.00 Silica dimethicone silylate (CAB-O-S!LTS-720) 4.00 Polymethyisilsesquioxane (And) Perfluorooctyl Triethoxysilane 2.00 (MST-547-FS) PHASE B Ethanol 68.00 TOTAL 100.00 WATER CONTACT ANGLE: 137.5 38GA 03011986 2018-07-19

[0090] Example 20illustrates anembodiment of the invention that is a topicaldelivery system. Phase Material Name %by Weight PHASE A Alcohol (and) Crotonic Acid/Vinyl Cs-n isoalkyl Esters/VA/Bis-; 8,00 Vihyldimethicone Ethanol 15.00 Silica dlmethicone silylate (CAB-O-SIL TS-720) 4.00 PHASE B Ethanol 73.00 TOTAL 100.00 WATER CONTACT ANGLE: 155.9

[0091] Example 21illustrates anembodiment of the invention that is a topicaldelivery system. Phase Material Name by Weight PHASE A Alcohol (and) Crotonic Acid/Vinyl Cg-u Isoalkyl Esters/VA/Bis- 8.00 Vinyidimethieone Perfiuorononyl Dimethlcone (PECOSIL FSH-300) 3.00 Ethanol 15.00 Silica dimethlcone silylatd (CAB-O-5IL TS-720) 4.00 PHASE B Ethanol 68.00 Trihydroxystearin (THIXCIN R) 2.00 TOTAL 100.00 WATER CONTACT ANGLE: 130^5 39CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 (0092] Example 12.Illustrates anembodiment of the invention that is a sunscreen. PHASE C Fragrance 0.30 TOTAL 100.00 WATER CONTACT ANGLE: 95.9 Phase PHASEA Material Name Avobenzone %by Weight 3.00 Octocryiene Homosalate Octisalate Phenethyl Benzoate Propylparaben Caoxs Alkyl Methicone (and) Olefin 3.00 5.50 4.50 8.00 0.18 2.00 PHASE B Triflupropropyldimethylsiloxy/Trimethylsiloxy Silsesquioxane (and) Dimethicone Perfluorononyi Dimethicone 8.00 3.00 Isododecane Disitexane Tryhydroxysteann CmsAlkylBenzoate (and) Stearalkpnium Hectorite (and) Propylene Carbonate 30.00 17.82 2.50 1.50 Silica Dimethicone Silylate Potymethylsilsesquioxane (and) Perfluorooctyl Triethoxysilane 6.00 2.00 Capiyiyl Methicone (and) PEG-12 Dimethicone/PPG-20 Crosspoh/mer 2.70 40GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 (0093] Example 23illustrates anembodiment of the invention that is a sunscreen. Phase Material Name %by Weight PHASE A Oxybenzone 3.00 Octocrylene 2.00 HomosaIate 2.00 Octisalate 2.00 Dilsooroovl Adtoate 2.00 Ethylhexyl Methoxycrylene 3.00 Cans Alkyl Methicpne andCios Olefin 2.00 Propylparaben 0.18 PHASE 8 TrimethylsiloxysiHcate 2.00 PerfluorononylDimethicone 3.00 Isododecane 15.00 Disiloxane 24.95 Trihydroxystearin 4.00 Cu^s Alkyl Benzoate (and) Steamikcmium Hectorite 1.500 (and) Propylene Carbonate Silica Dimethicone Silylate 4.00 Isododecane (and) Dimethicone/Bis-lsobutyl PPG- 20 6,57 Crosspolymer PHASE C Isododecane 15,00 Polyhydroxystearic acid 0.400 Zine Oxide (and) Triethoxycaprylylsilane 7.00 PHASE D Fragrance 0,30 TOTAL 100.00 WATER CONTACT ANGLE: 104.9 4184378923 (0094) Representative of the unexpected results of the inventive compositions, are the initial water contactangles of the inventive compositions Examples 9 and 18,and after one (1) minute, in comparison with commercially available sunscreen compositions are presented shown in Figure 3 and tabled in Table 3 below. (0095) Table 3 Name BANANA BOAT™ Sport Lotion SPF30 Initial Contact Angle 30.0 Contact Angie after 1minute 11.3 NEUTROGENA™ Beach Defense Lotion 20.0 5.5 i<>rr3v COPPERTONE™ Sport Lotion SPF30 60.1 20.3 (2016) Example 9 138.2 133.3 Example 18 155.0 155.0 [0096} It was observed that the commercial sunscreen lotion products all had relatively low contact anglesto start, and, after one (1) minute, the contact angles quickly decreased due to the water re-emulsification process of these oil-in-water emulsion products. Contrast this with the inventive compositionsof Examples 9 and18 wherein the contact angles didnot significantly decrease thereby exhibiting a continuing water repellent effect.

[0097] Figure 4 shows photographic images of VITRO-SKIN coated with commercially available sunscreen compositions and the inventive composition of Example 13 applied at a thickness of 2 mg/cm2. The WRO-SKIN was tilted at a thirty-degree angle (30’). Droplets of water, dyed blue to better show distinction, was dropped onto the top of the VITRQ-SKIN plates ahd the image taken after one (1) second. On the inventive composition, the water droplet quicWyrolls to the 42 Date Recue/Date Received 2023-06-20GA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 bottom of the surface without remainingonthe V1TR0-SKIN sample (as it doeswith the BANANA BOAT Sport Spray SPF 50 and NEUTROGENA Beach Defense Spray SPF 70) or trailing a tail (as seen inthe COPPERTONE Wet N Clear Spray SPF 45). In Figure 5, the photographic images show the path of water droplets one (1) minute after application on the treated VITRO-SKIN of Figure 4. Except for theinventive composition, the water droplets remain on thesurface.

[0098] Figure 6are photographic images showingthe same unexpected effects of the inventive compositions of Examples 1and 2 when the water droplets are applied ontoPMMA plates, coated with the sunscreen compositions, as specified, and tilted at 30 degrees: Water droplets applied onto the PMMA plates coated with the inventive compositions of Examples 1and 2 readily bead up and roll off the plate. The initial contact angles of Examples1and 2 are greater than 90 degrees,nameiy 145.7 degrees and 106.4 degrees, respectively whereas the initial contact angle of the BANANA BOAT Sport Lotion SPF 50 is 17.5 degrees, and the initial contact angle for the COPPERTONE Sport AccuSpray SPF 50 is 69.0 degrees.

[0099] Figure 7 shows a graphic representation of the water contact angles overtime from time 0 at the onset ofapplication of the water dropletsto at least 80 minutes, which is the time limit for determining water resistance in accordance with the 2011U.S. Food & Drug Administration (FDA) FinalMonograph for Water Resistance. The Water contact angles greater than 60 degrees created on the treated surfaces, are considered non-wettable surfaces; the water droplets do not tail or wet the treated surface. Unexpectedly, over time, the water contact angles of the exemplary compositions. Examples 22 and 23 are maintained such that the Water repellency Is not significantly diminished. Contrast thisto the commercially available sunscreencompositions, 43CA 03011986 2018-07-19 WO 2017/127771 PCT/US2017/014475 BANANA BOAT Sport Lotion SPF 50, COPPERTONE Sport AccuSpray SPF 50, and NEUTROGENA Beach Defense Lotion SPF 30, where the contact angles decrease significantly over a very short periodof time. th20minutes or less,theinitialwater contactangleshavefallenbelow60 degrees wettingthe surface of the plate.

[0100] The compositions of the present inventionprovide a water repellent finish when topically applied to a keratinous surface such as mammalian skin as determined by a water contact angle greater than 60 degrees, preferably greater than 90 degrees, and most preferably greater than 100 degrees. This water repellency effect has been shown to be maintainedover a period of at least80 minutes. {0101] While the present disclosure has been particularly described, in conjunction with specific preferred embodiments,it is evident that many alternatives, modifications andvariationswill be apparent to those skilled in the art In light of the foregoing description. It is therefore contemplated that the appended claims will embrace any such alternatives* modifications and variations as failing within the true scope and spirit of the present disclosure.:

Claims (20)

1. CLAIMS: 1. An anhydrous topical composition comprising: at least one film former comprising a silicone having a surface tension lower than 35 dynes/cm, wherein the silicone comprises C24-28 alkyldimethylsiloxy trimethylsiloxysilicate, trifluoropropyldimethylsiloxy/trimethylsiloxy silsesquioxane, or combinations thereof, and wherein the at least one film former is present in an amount of 0.5% to 10% by weight based on a total weight of said anhydrous topical composition; hydrophobic particles comprising silica silylate and polymethylsilsesquioxane, wherein the polymethylsilsesquioxane is present in an amount greater than 0.5% based on the total weight of said anhydrous topical composition, and wherein the particles are present in an amount of up to 10% by weight based on the total weight of said anhydrous topical composition; a volatile topical carrier present in an amount of 10% to 80% by weight based on the total weight of said anhydrous topical composition; and a sunscreen active agent selected from the group consisting of an organic sunscreen active agent.
2. 2. The anhydrous topical composition of claim 1 wherein the organic sunscreen active agent is selected from the group consisting of an organic ultraviolet A long-wave sunscreen active agent, an organic ultraviolet B shortwave sunscreen active agent, an organic full spectrum sunscreen active agent, an encapsulated organic UV filter, or combinations thereof.
3. 3. The anhydrous topical composition of claim 1 further comprising a therapeutic amount of at least one insect repellent selected from the group consisting of N,N diethyl-m-toluamide, ethyl butylacetylaminopropionate, hydroxyethyl isobutyl piperidine carboxylate, oil of citronella, soy bean oil, lemon grass oil, geranium/geraniol oil, neem oil, natural essential oils, p-menthane- 3,8-diol, or combinations thereof.
4. 4. The anhydrous topical composition of claim 1 comprising at least one colorant selected from the group consisting of an organic pigment or dye, an inorganic pigment or dye, and mixtures thereof. Date Reçue/Date Received 2024-01-1584378923 46
5. 5. The anhydrous topical composition of claim 1 wherein said anhydrous topical composition has an initial water contact angle greater than 90 degrees.
6. 6. The anhydrous topical composition of claim 1 wherein said anhydrous topical composition is free of colorants.
7. 7. The anhydrous topical composition of claim 1 wherein: the sunscreen active agent comprises avobenzone and further comprises terephthalylidene dicamphor sulfonic acid, bis-disulizole disodium, disodium phenyl dibenzimidazole tetrasulfonate, diethylamino hydroxybenzoyl hexylbenzoate, bis-diethylamino hydroxybenzoyl benzoate, bis-benzoxazolylphenyl ethylhexylamino triazine, octocrylene, octinoxate, octisalate, homosalate, ensulizole, ethylhexyl triazone, enzacamene, amiloxate, diethylhexyl butamido triazine, benzylidene malonate polysiloxane, padimate-O, trolamine salicylate, cinoxate, p-aminobenzoic acid, oxybenzone, meradimate, bis-octrizole, bemotrizinol, drometrizole trisiloxane, sulisobenzone, dioxybenzone, or combinations thereof; and the at least one film former further comprises a wax, an ester, a resin, a rosin, or combinations thereof.
8. 8. The anhydrous topical composition of claim 1 further including amino acids, moisturizers, pH adjusters, perfumes, essential oils, essential fatty acids, sphingolipids, antioxidants, chelating agents, emollients, humectants, minerals, keratolytics, retinoids, hormones, alpha-keto acids, anti-mycobacterial agents, anti-fungal agents, anti-microbials, anti-virals, analgesics, antiallergenic agents, H1 or H2 antihistamines, anti-inflammatory agents, anti-irritants, antineoplastics, immune system boosting agents, immune system suppressing agents, anti-acne agents, anesthetics, antiseptics, skin cooling compounds, skin warming compounds, skin protectants, skin penetration enhancers, exfoliants, lubricants, depigmenting agents, hypopigmenting agents, pharmaceutical agents, photostabilizing agents, plant extracts, absorbents, salicylic acid, alpha and beta hydroxy acids, vitamins, retinol, or combinations thereof. Date Reçue/Date Received 2024-01-1584378923 47
9. 9. The anhydrous topical composition of claim 8 wherein the organic sunscreen active agent comprises avobenzone, terephthalylidene dicamphor sulfonic acid, bis-disulizole disodium, disodium phenyl dibenzimidazole tetrasulfonate, diethylamino hydroxybenzoyl hexylbenzoate, bis-diethylamino hydroxybenzoyl benzoate, bis-benzoxazolylphenyl ethylhexylamino triazine, octocrylene, octinoxate, octisalate, homosalate, ensulizole, ethylhexyl triazone, enzacamene, amiloxate, diethylhexyl butamido triazine, benzylidene malonate polysiloxane, padimate-O, trolamine salicylate, cinoxate, p-aminobenzoic acid, oxybenzone, meradimate, bis-octrizole, bemotrizinol, drometrizole trisiloxane, sulisobenzone, dioxybenzone, or combinations thereof.
10. 10. The anhydrous topical composition of claim 1 wherein said composition has an initial water contact angle greater than 100 degrees or 150 degrees.
11. 11. The anhydrous topical composition of claim 1 wherein said composition has a water contact angle greater than 60 degrees after 40 minutes or after 80 minutes.
12. 12. The anhydrous topical composition of claim 1 wherein said volatile topical carrier is present in an amount of 30% to 60% by weight based on a total weight of said composition.
13. 13. The anhydrous topical composition of claim 1 wherein said composition is one of a lotion, a cream, an emulsion, a gel, a suspension, an aerosol, or a powder.
14. 14. The anhydrous topical composition of claim 1 wherein the silicone comprises isododecane and C24-28 alkyldimethylsiloxy trimethylsiloxysilicate, cyclopentasiloxane and C24-28 alkyldimethylsiloxy trimethylsiloxysilicate, trifluoropropyldimethylsiloxy/trimethylsiloxy silsesquioxane and dimethicone, or combinations thereof.
15. 15. The anhydrous topical composition of claim 14 wherein the polymethylsilsesquioxane comprises polymethylsilsesquioxane and perfluorooctyl triethoxysilane.
16. 16. The anhydrous topical composition of claim 15 wherein the silica silylate comprises silica dimethicone silylate, silica dimethyl silylate, or combinations thereof. Date Reçue/Date Received 2024-01-1584378923 48
17. 17. The anhydrous topical composition of claim 1 wherein the volatile topical carrier is nonpolar or polar.
18. 18. The anhydrous topical composition of claim 1 wherein the volatile topical carrier comprises ethanol, isododecane, volatile hydrocarbons, volatile silicones, or combinations thereof.
19. 19. The anhydrous topical composition of claim 1 wherein said particles further comprise polytetrafluoroethylene.
20. 20. The anhydrous topical composition of claim 1 wherein the polymethylsilsesquioxane is present in an amount greater than 1.0% by weight based on the total weight of said anhydrous topical composition, and wherein the hydrophobic particles are present in an amount of 5% to 10% by weight based on the total weight of said anhydrous topical composition.