(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2017/048706 Al 23 March 2017 (23.03.2017) P O P C T

(51) International Patent Classification: AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, A61Q 17/04 (2006.01) A61K 8/35 (2006.01) BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, A61K 8/81 (2006.01) DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, (21) International Application Number: KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, PCT/US20 16/05 1505 MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, (22) International Filing Date: OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, 13 September 2016 (13.09.201 6) SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, (25) Filing Language: English ZW. (26) Publication Language: English 4 Designated States (unless otherwise indicated, for every (30) Priority Data: kind of regional protection available): ARIPO (BW, GH, 62/218,032 14 September 2015 (14.09.2015) US GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, (71) Applicant: EDGEWELL PERSONAL CARE TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, BRANDS, LLC [US/US]; 1350 Timberlake Manor Park DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, way, Chesterfield, Missouri 63017 (US). LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, (72) Inventors: SANOGUEIRA, James; 4 Kimmissy Court, GW, KM, ML, MR, NE, SN, TD, TG). Wesley Hills, New Jersey 10901 (US). WIENER, Glenn; 18 River Ridge Trail, Ormond Beach, Florida 32174 (US). Published: ZHENG, Tao; 124 Burda Lane, New City, New York — with international search report (Art. 21(3)) 10956 (US). — before the expiration of the time limit for amending the (74) Agent: MA, Shirley S.; 6 Research Drive, Shelton, Con claims and to be republished in the event of receipt of necticut 06484 (US). amendments (Rule 48.2(h)) (81) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM,

o 00 (54) Title: COMPOSITIONS WITH IMPROVED WATER RESISTANCE OF UVA SUNSCREEN ACTIVE AGENTS (57) Abstract: Sunscreen compositions, products and methods that include at least one UVA sunscreen active agent, at least one o UVB sunscreen active agent, and one or more water insoluble film forming polymers. The compositions, products and methods may further include one or more active or inactive cosmetic ingredients. The water insoluble film forming polymers synergistically affect the UVA and UVB sunscreen active agents, in particularly the UVA sunscreen active agents by significantly enhancing the water resistance of the UVA sunscreen active agents after water exposure as determined by the SPF and UVAPF values measured before and after water exposure. SU NSCREEN COM POSITIONS WITH IM PROVED WATER RESISTANCE O F UVA SU NSCREEN ACTIVE AGENTS

Background Of The Invention

1. Field of the Invention

The invention is directed t o sunscreen compositions, and in particular, sunscreen compositions, products and methods having polymeric additives that improve water resistance of UVA actives contained therein.

2. Description of Related Art

Numerous are currently available for protecting keratinous substrates such as skin and hair from (UV) solar radiation falling within both the UVB region (between 290nm t o

320 nm wavelengths) and the UVA region (between 320nm and 400nm wavelengths). Protection from

UVA radiation is measured as a Protection Factor - UVA or PFA. Protection from UVB radiation is measured as a Sun Protection Factor or SPF. For instance, UVB radiation is absorbed by the epidermis layer causing erythema and cellular mutations, all of which damage the skin and underlying tissue.

UVA radiation is even more damaging as it reaches deeper into the dermis layer. As such, UVA radiation may suppress immune functions, lead t o loss of skin elasticity, promote premature signs of aging, as well as other undesirable health effects.

Currently available sunscreens can protect against both UVB and UVA radiation. However, water exposure and other adverse conditions such as sweat, can lead t o diminished protection as the sunscreen can wash off the skin. Sunscreen manufacturers provide the consumer with a water resistance rating that is dictated by the 2011 U.S. Food & Drug Administration (FDA) Final Rule for

Water Resistance wherein a sunscreen composition must meet the critical wavelength of 370 nm.

However, the critical wavelength protocol does not take into account the efficacy of the sunscreen composition after exposure t o real life conditions of water, sweat, salt water or pool water. Under the adverse conditions of water, salt, and/or chemicals, the sunscreen composition can lose its efficacy and provide limited or no protection t o the consumer. Yet even though the critical wavelength is met,

SPF is primarily a measure of protection against UVB radiation only. As such, a loss in protection against UVA radiation after a period of water immersion is not accounted for in efficacy testing.

The SPF of a sunscreen composition is determined by measuring the minimal erythema response on human skin treated with a sunscreen composition and untreated human skin on a single human subject. From these two measurements, the SPF is the ratio of the energy required t o generate erythema on treated skin as compared to the energy required t o generate erythema on untreated skin. While erythema is produced on human skin exposed to both UVB and UVA rays, UVB rays play a much greater role in their effect on skin. The erythemal action spectrum reveals that 99% of erythemal action resides in the UVB region and only 1 % in the UVA region.

The marker used to measure UVA Protection Factor (UVAPF) is referred to as Persistent

Pigment Darkening (PPD), which implements use of UVA rays only. PPD is based on the skin's response to the amount of UVA that enters the viable epidermis. One such test measures sunscreen-protected

PPD skin to the unprotected PPD skin after exposure to UVA. However, these tests do not measure water resistance of UVA sunscreens.

Again, whether or not a sunscreen is deemed water resistant is based on the 2011 FDA Final

Rule for water resistance. By relying on testing in which 99% of the effective energy dosage comes from UVB rays, and only 1% coming from UVA rays, currently available sunscreens incorrectly imply that both UVB and UVA protectants are "water resistant" to the same degree. As such, loss in protection against UVA radiation after a period of water immersion is not accounted for in sunscreens.

To overcome these deficiencies in the prior art, the present invention provides products, methods and sunscreen compositions with an increase in water resistance, namely, an increase in the water resistance of the UVA sunscreen active agents.

Summary of the Invention

Bearing in mind the problems and deficiencies of the prior art, it is therefore an object of the present invention to provide sunscreen compositions, products, and methods thereof having broad spectrum of water resistance protection across both the UVB and UVA bands of the UV spectrum.

It is another object of the present invention t o provide a sunscreen composition comprising: one or more UVA sunscreen active agents; one or more water insoluble film forming polymers, wherein the one or more water insoluble film forming polymers increase water resistance of the one or more

UVA sunscreen active agents such that the level of retention of UVAPF values after water exposure, as determined by UVAPF values measured before and after water exposure, is greater than at least

60%, preferably greater than at least 70%, and most preferably greater than at least 80%.

The one or more UVA sunscreen active agents may comprise ; terephthalylidene dicamphor sulfonic acid; /'s-disulizole disodium; disodium phenyl dibenzimidazole tetrasulfonate; diethylamino hydroxybenzoyl hexylbenzoate; /'s-diethylamino hydroxybenzoyl benzoate; bis- benzoxazolylphenyl ethylhexylamino triazine, or combinations thereof. The sunscreen composition may further include one or more UVB sunscreen active agents comprising ; octinoxate; octisalate; ; ; ; ; ; diethylhexyl butamido triazine; benzylidene malonate polysiloxane; padimate-O; ; ; p-aminobenzoic acid and derivatives thereof; or combinations thereof. The sunscreen composition may also include one or more sunscreen active agents that absorb both UVA and UVB radiation such as, for example, ; meradimate; ; ; /'s-octrizole; ; ; ; ; or combinations thereof.

The one or more water insoluble film forming polymers may comprise monomers, copolymers, cross polymers and terpolymers of organo-silicone hybrids, biopolymers, acrylate, abietic acid derivatives, polyolefins, silicone resins, vinyl acetates, maleates, alkyl esters, long chain and short chain carboxylic acids, or combinations thereof. The one or more water insoluble film forming polymers may be present in a non-aqueous solvent. The non-aqueous solvent may comprise an alcohol, ether, fatty acid, silicone fluid, ester, hydrocarbon, fluorinated hydrocarbon, or combinations thereof. The one or more water insoluble film forming polymers may be present in an aqueous emulsion.

Preferably, the one or more water insoluble film forming polymers comprises of a terpolymer of vinyl acetate, mono-n-butyl maleate and isobornyl acrylate. Preferably, the terpolymer of vinyl acetate, mono-n-butyl maleate and isobornyl acrylate is dissolved in ethanol.

Preferably, the one or more water insoluble film forming polymers comprises of a silicone-

' organic hybrid material of crotonic acid/vinyl C8 -i2 isoalkyl esters/VA/b/ s-vinyldimethicone

crosspolymer. Preferably, the crotonic acid/vinyl C8 -i2 isoalkyl esters/VA/b/s-vinyldimethicone crosspolymer is dissolved in ethanol.

Preferably, the one or more water insoluble film forming polymers comprises of a biopolymer of shellac. Preferably, the shellac is dissolved in ethanol.

Preferably, the one or more water insoluble film forming polymers comprises of at least two water insoluble film forming polymers selected from the group consisting of trimethylsiloxysilicate, isododecane (and) acrylate/dimethicone copolymer, and acrylates/dimethicone copolymer (and) cyclopentasiloxane. Preferably, the at least two water insoluble film forming polymers are dissolved in one or both of isododecane and isohexadecane. Preferably, the one or more water insoluble film forming polymers comprises of at least two water insoluble film forming polymers selected from the group consisting of methyl dihydroabietate, trimethylsiloxysilicate, hydrogenated polycyclopentadiene (and) isododecane, acrylates/dimethicone copolymer (and) cyclopentasiloxane, and combinations thereof. Preferably, the at least two water insoluble film forming polymers are dissolved in one or more solvents selected from the group consisting of isododecane, isohexadecane, disiloxane and diisopropyl adipate.

The sunscreen composition may further include one or more active or inactive cosmetic ingredients comprising of cosmetically acceptable carriers; oils; sterols; amino acids; moisturizers; powders; colorants; pigments; dyes; p H adjusters; perfumes; essential oils; cosmetic active ingredients; vitamins; essential fatty acids; sphingolipids; self-tanning compounds; fillers; emulsifying agents; antioxidants; surfactants; additional film formers; chelating agents; gelling agents; thickeners; emollients; humectants; moisturizers; minerals; viscosity and/or rheology modifiers; keratolytics; retinoids; hormonal compounds; alpha-keto acids; anti-mycobacterial agents; ant i fungal agents; anti-microbials; anti-virals; analgesics; anti-allergenic agents; HI or H2 antihistamines; anti-inflammatory agents; anti-irritants; anti-neoplastics; immune system boosting agents; immune system suppressing agents; anti-acne agents; anesthetics; antiseptics; insect repellents; skin cooling compounds; skin protectants; skin penetration enhancers; exfoliants; lubricants; fragrances; colorants; staining agents; depigmenting agents; hypopigmenting agents; preservatives; stabilizers; pharmaceutical agents; photostabilizing agents; spherical powders; one or more fragrances; plant extracts; absorbents; salicylic acid; alpha and beta hydroxy acids; vitamins; retinol and its derivatives; or any combination of the foregoing.

It is still yet another object of the invention t o provide a sunscreen composition comprising: one or more UVA sunscreen active agents; one or more water insoluble film forming polymers comprising of monomers, copolymers, cross polymers and terpolymers of organo-silicone hybrids, biopolymers, acrylate, abietic acid derivatives, polyolefins, silicone resins, vinyl acetates, maleates, alkyl esters, long chain and short chain carboxylic acids, or combinations thereof; and one or more solvents comprising C2-10 alcohol, ether, fatty acid, silicone fluid, ester, hydrocarbon, fluorinated hydrocarbon, wherein said one or more water insoluble film forming polymers increase water resistance of said one or more UVA sunscreen active agents such that retention of UVAPF values after water exposure, as determined by UVAPF values measured before and after water exposure, is greater than at least 70%. Preferably, in one embodiment, the one or more water insoluble film forming polymers is present in an amount of up to 6 wt. % and the one or more solvents comprises ethanol.

Preferably, in an alcohol-free embodiment, the one or more water insoluble film forming polymers is present in an amount of up t o 6 wt. % and the one or more solvents comprises isododecane, isohexadecane, disiloxane, diisopropyl adipate, or a combination thereof.

It is another object of the present invention to provide a sunscreen composition comprising: one or more UVA sunscreen active agents; one or more UVB sunscreen active agents; one or more water insoluble film forming polymers, wherein the one or more water insoluble film forming polymers increase water resistance of the one or more UVA sunscreen active agents such that the level of retention of UVAPF values after water exposure, as determined by UVAPF values measured before and after water exposure, is greater than at least 60%.

It is yet another object of the present invention to provide a consumer packaged product comprising a sunscreen composition as disclosed herein.

It is still yet another object of the present invention to provide a method of absorbing ultraviolet radiation on a keratinous substrate comprising applying a sunscreen composition according to the embodiments disclosed herein t o a keratinous substrate and subjecting the keratinous substrate to ultraviolet radiation.

Description of the Preferred Embodiment(s)

The embodiments of the present invention 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. It is to be understood that all concentrations disclosed herein are by weight percent (wt.

%.) based on a total weight of the composition unless otherwise indicated. Where appropriate, the

INCI (International Nomenclature of Cosmetic Ingredients) name of ingredients/components is used.

A wide variety of sunscreen compositions contain both UVA active agents and UVB active agents.

When these sunscreens are exposed to water it has been found that the UVA active agents wash off faster than their UVB counterparts. Some UVA active agents are water soluble such that upon exposure t o water and/or sweat, they are washed away completely thereby exposing the user t o harmful UVA rays. Upon exposure to water and/or sweat, the efficacy of both the UVB and UVA active agents in the sunscreen compositions is depleted, unless there is re-application of the sunscreen composition. It has further been found that over user wear time, the UVA active agents and their corresponding protection from UVA radiation are lost at a higher rate and amount as compared to the

UVB active agents therein. As such, using only the SPF as a measure of water resistance is insufficient to measure the level of protection from UVA radiation.

Table I is a list of sunscreen UVB and UVA active agents and their corresponding degrees of lipophilicity, measured as relative polarities (water (log P)).

Table I

Relative Lipophilicity of Sunscreen Chemicals Based Upon Their Calculated Pa ci i Coefi cient s Between Octa. l and a

Log P CT nam Other names °C

Glyceryl MBA ,2,3-PrOpanetrioi, -(4 - ni en ate) . 02 B 2 p benon S is . t e - 1.5 PAB p- m o benzoic acid 0.74 Benzop e ne xyb z ne 2, Cinoxate tho ye yl et b xy e i arr t 2, 5 Bet zQph i n - Oxyber i n 2.63 Ethyl di yd oxypr py BA Ethyl-4-bis(2-hydroxypropyl-amioobefti;oate) 2.84 Amy dimethyl PABA Amyl dimethyl PABA 4 .5 Butylmethoxy iben¾ylme ha e Butylmethoxy d ben ylro t a e 4.86 Mer t y a th a late M nt y -a n ber ate 5.05 cty salicylate 2 t ylh yi salicylate 5,30 o os ate .Ho T me thy salicylate 5.61 Octyl ech xy ci a Ethy h y -p-tne h xy c nna 5.65 Octocrylene Octyl cya dip enylacrylat 5.69 Octyl dimethyl PABA 2-Echylhexyl-p-dimethyl a nobe at .08

(See J. Soc. Cosmetic Chem., 38, 209-221, Table V (July/August 1987).)

The data is listed in decreasing order of polarity (i.e., increasing log P values), and shows that the lipophilicity of sunscreens increase from water soluble (log P< 1) to oil-soluble (log P > 1). The table shows UVA active agents, e.g., avobenzone (butylmethoxy dibenzoylmethane), having lower polarities than their counterpart UVB active agents, e.g., octocrylene. Based on these polarities, UVA active agents tend t o be more water soluble than UVB active agents. For instance, the polarities based on log P values show that avobenzone is more easily washed off than octocrylene such that upon exposure t o water over time, the level of protection from UV radiation decreases at a faster rate for the UVA active agents in comparison with UVB active agents as shown below in the schematic. water

In accordance with the various embodiments of the invention, sunscreen compositions, products, and methods are provided that unexpectedly increase water resistance of UVA active agents. In one or more embodiments, sunscreen compositions are provided having improved water resistance with greater retention of both UVB active agents and UVA active agents after exposure to water and/or sweat. The various sunscreen compositions of the invention include at least one or more polymer additives that synergistically affect the UVA active agents present in the compositions to unexpectedly retain a desirable level of protection against UVA radiation after exposure to water and/or sweat.

The present invention includes one or more polymeric additives in combination with various sunscreen UVB and UVA active agents to provide a sunscreen composition that has enhanced water resistance, and preferably enhanced water resistance of the UVA active agent, after water exposure.

In one or more embodiments, the polymer additive is a water insoluble film forming polymer. The various water insoluble film forming polymers suitable for use in the present invention provide the resultant sunscreen composition with preferably greater than 60% retention, more preferably greater than 70% retention, and most preferably greater than 80% retention of the UVAPF levels after water exposure.

The sunscreen compositions of the invention may include various sunscreen active agents.

Suitable sunscreen actives that may be used in sunscreen compositions of the invention include, but are not limited to, one or more of the following: p-aminobenzoic acid (PABA) and derivatives thereof; avobenzone (also known as butylmethoxy dibenzoylmethane); 2,4-dihydroxybenzophenone; 2,2',4,4'- tetrahydroxybenzophenone; oxybenzone; sulisobenzone; sulisobenzone sodium; 2,2'-dihydroxy-4,4'- dimethoxybenzophenone; 5-chloro-2-hydroxybenzophenone; dioxybenzone; sodium 2,2'-dihydroxy-

4,4'-dimethoxybenzophenone-5,5'-disulfonate; 2-hydroxy-4-methoxy-4'-methyl-benzophenone; octabenzone; ethyl dihydroxypropyl-p-aminobenzoate; glyceryl-p-aminobenzoate; homosalate; methyl anthranilate; octocrylene; octyl dimethyl-p-aminobenzoate; isoamyl-p-methoxycinnamate; ; ; triethanolamine salicylate; 3-(4-methylbenzylidene) camphor; enzacamene; phenylbenzimidazole sulfonic acid; methylene /'s-benzotriazolyl tetramethylbutyl phenol; 4-isopropyldibenzoylmethane; octisalate; /'s-ethylhexyloxyphenol methoxyphenyl triazine; 4-isopropyl-dibenzoylmethane; metal oxides such as zinc oxide or titanium dioxide; terephthalylidene dicamphor sulfonic acid (also known as ); drometrizole trisiloxane; diethylhexylbutamido triazone; ethylhexyl triazone; cinoxate; ensulizole; /'s-disulizole disodium; diethylamino hydroxybenzoyl hexylbenzoate; or combinations thereof. It should be appreciated and understood that the present sunscreen compositions may include one or more other known ingredients suitable for use in absorbing, scattering and/or deflecting UVA and UVB radiation on a keratinous substrate.

Preferred sunscreen active agents that absorb and provide protection in the UVB spectrum include, but are not limited to, octocrylene; octinoxate; octisalate; homosalate; ensulizole; ethylhexyl triazone; enzacamene; amiloxate; diethylhexyl butamido triazine; benzylidene malonate polysiloxane; padimate-O; trolamine salicylate; cinoxate; PABA; or combinations thereof.

Preferred sunscreen active agents that absorb and provide protection in the UVA spectrum include, but are not limited to, avobenzone; terephthalylidene dicamphor sulfonic acid; /'s-disulizole disodium; disodium phenyl dibenzimidazole tetrasulfonate; diethylamino hydroxybenzoyl hexylbenzoate; /'s-diethylamino hydroxybenzoyl benzoate; b/s-benzoxazolylphenyl ethylhexylamino triazine, or combinations thereof.

Preferred sunscreen active agents that absorb and provide both broad UVA and UVB protection include, but are not limited to, oxybenzone; meradimate; titanium dioxide; zinc oxide; bis- octrizole; bemotrizinol; drometrizole trisiloxane; sulisobenzone; dioxybenzone, or combinations thereof.

The various sunscreen active agents of the instant sunscreen formulations may be present in an amount of about 0.01 wt. % t o about 40.0 wt. %, based on a total weight of the sunscreen composition. The individual weight percentage amounts and types of sunscreen active agents of the instant compositions will vary depending upon the desired sun protection factor (SPF) and the UVA

Protection Factor (UVAPF). The higher the SPF and UVAPF,the greater the total amount of sunscreen active agents. The one or more sunscreen active agents may be present in an amount of about 3.0 wt. % t o about 30.0 wt. % t o achieve a SPF of about 15 t o about 200 and more, based on a total weight of the sunscreen composition. The one or more additional sunscreen agents may be present in an amount of about 3.0 wt. % t o about 25.0 wt. %, based on a total weight of the sunscreen composition, for a lower SPF.

The sunscreen compositions further include at least one or more polymer additives that enhance the water resistance of the sunscreen composition and, in particular, the UVA active agents after exposure t o water. The one or more polymer additives have a synergistic effect on the sunscreen active agents, particularly on the UVA active agents, enhancing the water resistance during water activity or sweat. The one or more polymer additives suitable for use in the invention provide high retention rates of UVAPF values of greater than at least 60%, more preferably greater than at least 70%, and most preferably greater than at least 80%, after water exposure as determined by

UVAPF values measured before and after water exposure.

The one or more polymer additives comprise water insoluble film forming polymers. The water insoluble film forming polymers comprise, but are not limited to, monomers, copolymers, cross polymers and/or terpolymers of organo-silicone hybrids, silicone resins, biopolymers, acrylates, abietic acid derivatives, polyolefins, vinyl acetates, maleates, alkyl esters, long chain and short chain carboxylic acids, and combinations thereof.

Exemplary of the water insoluble film forming polymers as a terpolymer is vinyl acetate

(VA)/butyl maleate/isobornyl acrylate copolymer commercially available as ADVANTAGE™ Plus from

Ashland Inc., Covington, Kentucky, as a 50% ethanolic solution. Exemplary of an organo-silicone hybrid is ethanol (and) crotonic acid/vinyl C - isoalkyl esters/VA/b/ 's-vinyldimethicone crosspolymer commercially available as BELSIL® P1101 available from Wacker Chemie AG, Laramie, Wyoming.

Exemplary of biopolymers is shellac commercially available as POLY-SOLEIL® from Mantrose-Haeuser

Co., Inc., Westport, Connecticut. Exemplary acrylate copolymers useful as water insoluble film forming polymers are isododecane (and) acrylate/dimethicone copolymer such as, KP 550, or acrylates/dimethicone copolymer (and) cyclopentasiloxane such as KP 545, both commercially available from Shin-Etsu Chemical Co., Ltd., Japan. An exemplary abietic acid derivative is methyl dihydroabietate, such as M ERISTANT® 101L commercially available from Essential Ingredients,

Lawrenceville, Georgia. Exemplary of a polyolefinic water insoluble film forming polymer useful in the present invention is hydrogenated polycyclopentadiene (and) isododecane commercially available as

KOBOGUARD® 5400 IDD available from Kobo Products, Inc., South Plainfield, New Jersey, sold as an isododecane solution. Exemplary of a silicone resin useful in the present invention is MQ Solid Resin commercially available from Dow Corning Corporation, Midland, Michigan.

The water insoluble film forming polymers may be provided in amounts ranging from 0.2 wt.

% t o about 15 wt. %, of the total weight of the sunscreen composition, preferably from about 1.0 wt.

% to about 10 wt. %, and most preferably from about 1.5 wt. % t o about 6.0 wt. % (of the total weight of the sunscreen composition). While the water insoluble film forming polymers are known film formers, it is unexpected that the addition of these polymeric additives to a sunscreen composition would enhance water resistance of both UVB and UVA active agents, and significantly maximize the water resistance of UVA active agents such that the level of retention of the UVAPF values after water exposure is greater than at least 60%.

In preparing the sunscreen compositions of the present invention, the water insoluble film forming polymers are provided in solution in one phase, and added to another phase containing the sunscreen active agents. These water insoluble film forming polymers are preferably dissolved or suspended in a non-aqueous solvent although sunscreen compositions utilizing emulsions involving aqueous phases are also contemplated herein. Such non-aqueous solvents include, but are not limited to, C t o Cio alcohols, ethers, fatty acids, silicone fluids, esters, hydrocarbons, and fluorinated hydrocarbons. Some of the commercially available water insoluble film forming polymers are sold as a solution in a non-aqueous solvent, for example, ADVANTAGE Plus, KOBOG UARD, and others disclosed herein.

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 3 wt. % VA/butyl maleate/isobornyl acrylate copolymer and the solvent is ethanol.

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 3 wt. % crotonic

' acid/vinyl C8 -i2 isoalkyl esters/VA/b/ s-vinyldimethicone crosspolymer and the solvent is ethanol.

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 1.5 wt. % shellac and the solvent is ethanol.

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 3 wt. % trimethylsiloxysilicate, 3 wt. % isododecane (and) acrylate/dimethicone copolymer and the solvents are isododecane and isohexadecane.

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 0.5 wt. % trimethylsiloxysilicate, 0.2 wt. % acrylate/dimethicone copolymer (and) cyclopentasiloxane and the solvent is isododecane.

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 3 wt. % trimethylsiloxysilicate, 3 wt. % acrylate/dimethicone copolymer (and) cyclopentasiloxane and the solvents are isododecane and isohexadecane.

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 3 wt. % trimethylsiloxysilicate, 3 wt. % acrylate/dimethicone copolymer (and) cyclopentasiloxane and the solvents are isododecane, isohexadecane, and disiloxane.

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 2 wt. % trimethylsiloxysilicate, 1 wt. % methyl dihydroabietate and the solvents are isododecane, isohexadecane, and disiloxane.

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 2 wt. % trimethylsiloxysilicate, 1 wt. % methyl dihydroabietate and the solvents are isododecane, diisopropyl adipate, and disiloxane

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 2 wt. % polycyclopentadiene (and) isododecane and the solvents further include isohexadecane and disiloxane.

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 2 wt. % methyl dihydroabietate and the solvents are isododecane, isohexadecane and disiloxane. ln some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 4 wt. % polycyclopentadiene (and) isododecane and the solvents further include isohexadecane and disiloxane.

In some embodiments, the sunscreen composition includes sunscreen active agents, and a synergistic combination of a water insoluble film forming polymer comprising 4 wt. % methyl dihydroabietate and the solvents are isododecane, isohexadecane and disiloxane.

While the invention has been described in relation to two phases of the resultant sunscreen compositions (i.e., Phase A and Phase B), it should be appreciated and understood that multiple phases of compositions may be prepared and ultimately mixed to provide the various sunscreen compositions of the invention having improved UVA water resistance. In accordance with one or more embodiments, the ingredients or constituents of a first phase containing the sunscreen active agents, with or without other cosmetic ingredients, are provided into a vessel and mixed under temperatures of about 70°C to 75°C until a uniform or clear solution is rendered. This solution is cooled to a temperature of about 30°C with continuous mixing. In a separate vessel, the water-insoluble polymeric additives are dissolved in a solvent and mixed at a temperature of about 30°C until a homogeneous water insoluble polymer additive second phase solution is rendered. The first and second phases may then be mixed together until a homogenous solution is obtained. Optionally, preservatives, such as phenoxyethanol as an example only, may be added to the sunscreen formulation, and the composition cooled, preferably to room temperature. Adjustments t o the pH of the final sunscreen composition may also be made at this time.

The sunscreen composition may further include one or more active or inactive cosmetic ingredients, such as, but not limited to, cosmetically acceptable carriers; oils; sterols; amino acids; moisturizers; powders; colorants (including pigments and/or dyes); p H adjusters; perfumes; essential oils; cosmetic active ingredients; vitamins; essential fatty acids; sphingolipids; self-tanning compounds such as dihydroxyacetone (DHA) and erythruloses; fillers; emulsifying agents; antioxidants; surfactants; additional film formers; chelating agents; gelling agents; thickeners; emollients; humectants; moisturizers; minerals; viscosity and/or rheology modifiers; keratolytics; retinoids; hormonal compounds; alpha-keto acids; anti-mycobacterial agents; anti-fungal agents; anti- microbials; anti-virals; analgesics; anti-allergenic agents; HI or H2 antihistamines; anti-inflammatory agents; anti-irritants; anti-neoplastics; immune system boosting agents; immune system suppressing agents; anti-acne agents; anesthetics; antiseptics; insect repellents; skin cooling compounds; skin protectants; skin penetration enhancers; exfoliants; lubricants; fragrances; colorants; staining agents; depigmenting agents; hypopigmenting agents; preservatives; stabilizers; pharmaceutical agents; photostabilizing agents; spherical powders; one or more fragrances; 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 this list is not limiting, and that various other active or inactive ingredients may be used in the present sunscreen formulations.

Testing was performed on the sunscreen compositions of the invention. In vitro water resistance testing was performed on compositions of the invention and the results analyzed using both high performance liquid chromatography (HPLC) and spectroscopic analysis, as well as in vivo water resistance using the methodology disclosed in the 2011 FDA Final Rule for Water Resistance t o show the improved water resistance of the inventive compositions. In the spectroscopic analysis, absorbance retention rates across both the UVB and UVA regions were obtained using an ultraviolet spectrophotometer (Ultraviolet Transmittance Analyzer Model UV-2000 available from Labsphere

Inc., North Sutton, New Hampshire) and presented in the below tables. In the spectroscopic analysis, an amount of the sunscreen compositions was uniformly applied t o VITRO-SKI N , commercially available from IMS, Inc., Portland, Maine, by finger with a pre-saturated finger cot. The coated plate was air-dried (e.g., for about 15 minutes) and then placed inside the ultraviolet spectrophotometer.

Spectral absorbance measurements were taken at four randomly selected points. The readings were recorded by the spectrophotometer and the calculation of the SPF value was made based on the following equation:

I Ε ( ) Ι ( λ Χ

_

with the use of built-in software: UV-2000 application Version 1.1.0.0, wherein Ε(λ) is the erythemal action spectrum, Ι(λ) is the spectral irradiance received from the UV source, and Αο(λ) is the mean monochromatic absorbance of the test product layer before UV exposure, and λ is the wavelength step (1 nm). Averages of the four readings are shown in the below tables as the percent of UVB absorbance retention based on the measured SPF before and after water exposure.

Based on the ultraviolet spectrophotometer analysis and readings, the UVAPF in vitro water resistance was measured, and UVA absorbance retention percentage was obtained using measurements before water immersion and after water immersion in accordance with the 2011 FDA

Final Rule for Very Water Resistance (VWR) based on eighty minutes of submersion. The UVA absorbance retention percentage was calculated based on the following equation:

Concentration of UV active agents on a substrate as determined by HPLC was also performed on samples of the inventive compositions. Test samples were applied in duplicate onto a substrate followed by water immersion of one substrate containing sample over one or more timed intervals.

The test sample was extracted from both the immersed substrate and the un-immersed substrate and

HPLC assay was conducted on the diluent from each substrate. The difference in before and after measurements provides the amount of each UV active agent lost due to water exposure. The in vitro

HPLC sunscreen retention percentages of the following active agents: octocrylene, avobenzone, octisalate and homosalate, after water exposure are discussed below.

Sunscreen compositions of the invention were also tested using in vivo methods t o show the enhanced retention rates of the UVB and UVA active agents in the inventive compositions after water exposure. Table II below shows in vivo water resistance retention percentages across both the UVB and UVA spectrum for Examples 1 to 3. These in vivo water resistance tests confirm that the water insoluble film forming polymers suitable in the present invention provide enhanced water resistance of the sunscreen composition, and significantly maximized the water resistance of UVA active agents wherein greater than at least 60%, more preferably greater than at least 70%, and most preferably greater than at least 80%, UVA active agents are retained on the substrate surface after water exposure, or even after exposure to sweat.

Various sunscreen formulations in accordance with the invention are set forth in the following examples. It should be appreciated and understood that these formulations may be modified and/or added t o with various constituents at different concentrations while still falling within the scope of the invention. EXAM PLES

In all examples, the inventive compositions contained the following sunscreen active agents: homosalate (10 wt. %), octocrylene (6 wt. %), octisalate (5 wt. %), avobenzone (3 wt. %); and the following cosmetic ingredients: caprylyl glycol (0.70 wt. %), tocopheryl acetate (0.01 wt. %), and aloe barbadensis leaf extract (and) mineral oil (0.01 wt. %), all based on a total weight of the sunscreen composition.

Examples 1 t o 3 are inventive anhydrous formulations wherein the water insoluble film forming polymers are dissolved in an alcohol. These examples were formulated as aerosols. The first phase included the UVA and UVB components as well as the above mentioned cosmetic ingredients.

The first phase constituents were provided into a beaker neat, heated t o about 70°C t o 75°C with mixing until a clear solution was obtained. The solution was then allowed t o cool t o a temperature of about 30°C with continuous mixing.

The second phase constituents included at least one of the following water insoluble film

forming polymers: VA/butyl maleate/isobornyl acrylate copolymer; crotonic acid/vinyl C8 -i2 isoalkyl esters/VA/b/ 's-vinyldimethicone crosspolymer, or shellac. These water insoluble film forming polymers were combined with an alcohol solvent, in particular, ethanol. The water insoluble film forming polymer and alcohol solvent were provided into and mixed in a separate beaker at a temperature of about 30°C until a homogeneous solution was obtained. The two phases were combined until a clear solution was obtained.

Referring t o Table II below, different alcohol-based sunscreen compositions were tested for

UVB and UVA retention rates. These results show the enhanced UVB and UVA retention rates due to use of the water insoluble film forming polymer additives in one or more embodiments of alcohol based sunscreen compositions of the invention. Table II: Alcohol Based Sunscreen Compositions

*commercially available as ADVANTAG E Plus Commercially available as BELSI L P1101 Commercially available as POLY-SOLEIL The in vitro water resistance test results analyzed by UV spectrophotometer, and the in vivo water resistance test results of Examples 1 to 3 are shown in Table II. While these results show that selected water insoluble film forming polymers may show more retention of UVB and UVA in one test method as compared to another, the unexpected advantage is that all three water insoluble film forming polymers show enhanced water resistance of both UVB and UVA active agents in one test method or the other, and importantly, a significant enhancement (e.g., preferably at least 60% or greater retention) in water resistance of UVA active agents not found in conventional sunscreen formulations. For example, while the in vitro water resistance data of Example 1 shows a modest retention of UVA absorbance, the in vivo test data shows a significant retention of UVA absorbance that was not predicted by the in vitro data. In vivo test results in Examples 2 and 3 show the retention of UVAPF on par with SPF not found in conventional sunscreen compositions due t o the addition of the water insoluble film forming polymers.

HPLC results show the effects of the individual water insoluble film forming polymers of

Examples 1 t o 3 on different UVB and UVA active agents. Examples 2 and 3 show a broader spectrum coverage with enhanced water resistance of different UVB and UVA active agents after water exposure. For instance, the HPLC results show that Examples 2 and 3 retain the UVA active avobenzone t o a significantly greater extent as compared to Example 1, which is most similar t o commercially available sunscreen compositions.

In other examples of the present invention, alcohol-free compositions were made in accordance with the various embodiments of the invention. Examples 4 to 13 shown in Table III show different alcohol-free compositions having the following sunscreen actives agents: 10% homosalate,

5% octisalate, 6% octocrylene, and 3% avobenzone, with avobenzone providing the bulk of protection against UVA radiation. Like that of the alcohol based formulations, these compositions may also be made using one or more phases, with a first phase including one or more UVA and UVB active agents and other cosmetic active or inactive ingredients and a second phase containing one or more of the water insoluble film forming polymers. These examples may include one, two, or possibly more, water insoluble film forming polymers dissolved in one or more, preferably at least two, organic solvents t o provide a water insoluble film forming polymers second phase that is combined with the sunscreen active agent phase to render the present sunscreen formulations having enhanced UVB and/or UVA water resistance. Tabl : Alcohol-Free Sunscreen Formulations Exan 4 5 6 7 8 9 10 11 12 13

Polyi ' polycyclopenta methyl polycyclopenta methyl Addi trimethylsi- trimethylsi- trimethylsi- trimethylsi- trimethylsi- trimethylsi- -diene (and) dihydro -diene (and) dihydro # : loxysilicate loxysilicate loxysilicate loxysilicate loxysilicate loxysilicate isododecane abietate isododecane abietate

3 wt. % 0.5 wt. % 3 wt. % 3 wt. % 2 wt. % 2 wt. % 2 wt. % 2 wt. % 4 wt. % 4 wt. %

acrylate/ acrylate/ acrylate/ isododecane dimethicone dimethicone dimethicone (and) copolymer copolymer copolymer Polymer acrylate/ (and) (and) (and) methyl methyl Additive# dimethicone cyclopenta- cyclopenta- cyclopenta- dihydro dihydro 2 copolymer siloxane^ siloxane siloxane abietate abietate 3 wt. % 0.2 wt. % 3 wt. % 3 wt. % 1 wt. % l wt. % - - - -

49.3 wt. % 20 wt. % Solvent #1 49.3 wt. % IDD 74.6% IDD IDD 20 wt. % IDD 20 wt. % IDD 20 wt. % IDD 42 wt. % IDD 42 wt. % IDD 20 wt. % IDD IDD

20 wt. % 20 wt. % Solvent #2 20 wt. % IHD - 20 wt. % IHD 20 wt. % IHD 20 wt. % IHD D I A 19 wt. % IHD 19 wt. % IHD 20 wt. % IH D IHD

12.3 wt. % 31.3 wt. Solvent #3 - - - 29.3 wt. % DS 32.3 wt. % DS 32.3 wt. % DS 12.3 wt. % DS DS 31.3 wt. % DS DS

IDD = isododecane; IH D = isohexadecane; DS = disiloxane; DIPA = diisopropyl adipate Table continued

Commercially available as MQ-1600 Solid Resin Commercially available as KOBOGUARD 5400 IDD Commercially available as M ERISTANT 101L Commercially available as KP 550 Commercially available as KP 545 ln vitro water resistance tests were analyzed using a UV spectrophotometer on Examples 4 to

13 and presented in Table II I above. These results show the retention percent of both the UVB absorbance and UVA absorbance of the sunscreen compositions of Examples 4 to 13. Each of the exemplary sunscreen compositions in Examples 4 to 9 exhibit high retention rates of greater than at least 60%, more preferably greater than at least 70%, and most preferably greater than at least 80%, of the UVA and UVB absorbance after water exposure measured using the UV spectrophotometer. A synergistic effect of more than one water insoluble film forming polymers with one or more solvents is also evident noting the high retention of UVA active agents after water exposure.

Examples 7 to 9 include one or more water-insoluble film forming polymers in combination with at least three different solvents t o render the sunscreen compositions of the invention. Thus, one of ordinary skill in the art can appreciate that in some embodiments, more than two water- insoluble film forming polymers may be combined with more, or less, than three different solvents.

Examples 7 to 9 provide enhanced water resistance of both the UVB and UVA active agents.

Examples 10 t o 13 include one water-insoluble polymeric additive in combination with at least three different solvents. These results illustrate the preference in one or more embodiments of the invention in utilizing combinations of water-insoluble polymeric additives when using combinations of solvents.

Commercial sunscreen compositions were evaluated as shown in Table IIA. The UVA sunscreen active agents are shown to wash off the skin after water immersion at much higher rates than those found in the inventive compositions disclosed herein.

Table IIA - Comparative Data

CT = Clearly Sheer SPF 50+ BB1 = Banana Boat Clear Spray SPF 50 It has been found that the various sunscreen compositions of the present invention are more robust after water exposure providing consumers with lasting UVA protection and UVB protection.

The synergistic effects of the various water-insoluble film forming polymers (either singularly or in combinations of two or more) suitable for use in the invention with UVB and UVA sunscreen active agents provides increased water resistance of such active agents when exposed to water and/or sweat. One of skill in the art will understand how to formulate the inventive sunscreen compositions into suitable consumer packaged products.

In accordance with the various embodiments, the inventive sunscreen compositions may be formulated as continuous aerosol sprays, such as the alcohol-based aerosol sprays in Examples 1 to 3, oil-in-water (O/W) or water-in-oil (W/O) emulsions, anhydrous topical formulations, lotions, creams, sprays, etc., as show in Examples 4 to 13. It has unexpectedly been found that the water insoluble film forming polymers suitable for use in the invention provide sunscreen compositions having improved water resistance of both UVB and UVA active agents, with significant water resistance enhancement of the UVA active agents. UVA active agents are retained on a keratinous substrate to at least 60% or greater retention after exposure to water and/or sweat. As such, the sunscreen compositions of the invention decrease the loss of UVA active agents on the skin, and thereby increase protection from UV radiation between 320nm and 400nm wavelengths, after water wash, water immersion, swimming, sweating, and the like.

While the present invention has been particularly described, in conjunction with a specific preferred embodiment, it is evident that many alternatives, modifications and variations will 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 falling within the true scope and spirit of the present invention.

Thus, having described the invention, what is claimed is: Claims

What is claimed is:

1. A sunscreen composition comprising:

one or more UVA sunscreen active agents;

one or more water insoluble film forming polymers, wherein said one or more water insoluble film forming polymers increase water resistance of said one or more UVA sunscreen active agents such that retention of UVAPF values after water exposure, as determined by UVAPF values measured before and after water exposure, is greater than at least 60%.

2. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming polymers increase water resistance of said one or more UVA sunscreen active agents such that the level of retention of UVAPF values after water exposure as determined by UVAPF values measures before and after water exposure is greater than at least 70%.

3. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming polymers increase water resistance of said one or more UVA sunscreen active agents such that the level of retention of UVAPF values after water exposure as determined by UVAPF values measures before and after water exposure is greater than at least 80%.

4. The sunscreen composition of claim 1 wherein said one or more UVA sunscreen active agents comprise avobenzone; terephthalylidene dicamphor sulfonic acid; /'s-disulizole disodium; disodium phenyl dibenzimidazole tetrasulfonate; diethylamino hydroxybenzoyl hexylbenzoate; bis- diethylamino hydroxybenzoyl benzoate; /'s-benzoxazolylphenyl ethylhexylamino triazine, or combinations thereof.

5. The sunscreen composition of claim 1 further including one or more UVB sunscreen active agents.

6. The sunscreen composition of claim 5 wherein said one or more UVB sunscreen active agents comprise octocrylene; octinoxate; octisalate; homosalate; ensulizole; ethylhexyl triazone; enzacamene; amiloxate; diethylhexyl butamido triazine; benzylidene malonate polysiloxane; padimate-O; trolamine salicylate; cinoxate; p-aminobenzoic acid and derivatives thereof; or combinations thereof. 7. The sunscreen composition of claim 1 wherein said sunscreen composition includes one or more sunscreen active agents that absorb both UVA and UVB radiation.

8. The sunscreen composition of claim 7 wherein said one or more sunscreen actives comprise oxybenzone; meradimate; titanium dioxide; zinc oxide; /'s-octrizole; bemotrizinol; drometrizole trisiloxane; sulisobenzone; dioxybenzone; or combinations thereof.

9. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming polymers is present in an amount of about 0.2 wt. %to about 15 wt. %.

10. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming polymers is present in an amount of about 1.5 wt. %to about 6 wt. %.

11. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming polymers comprise monomers, copolymers, cross polymers and terpolymers of organo-silicone hybrids, biopolymers, acrylate, abietic acid derivatives, polyolefins, silicone resins, vinyl acetates, maleates, alkyl esters, long chain and short chain carboxylic acids, or combinations thereof.

12. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming polymers are present in a non-aqueous solvent.

13. The sunscreen composition of claim 12 wherein said non-aqueous solvent comprises an alcohol, ether, fatty acid, silicone fluid, ester, hydrocarbon, fluorinated hydrocarbon, or combinations thereof.

14. The sunscreen composition of claim 13 wherein said non-aqueous solvent comprises a C2-10 alcohol.

15. The sunscreen composition of claim 13 wherein said non-aqueous solvent comprises isododecane, isohexadecane, disiloxane, diisopropyl adipate, and combinations thereof.

16. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming polymers are present in an aqueous emulsion.

17. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming polymers comprise a terpolymer of vinyl acetate, mono-n-butyl maleate and isobornyl acrylate. 18. The sunscreen composition of claim 17 wherein said terpolymer of vinyl acetate, mono-n- butyl maleate and isobornyl acrylate is dissolved in ethanol.

19. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming

' polymers comprise a silicone-organic hybrid material of crotonic acid/vinyl C8 -i2 isoalkyl esters/VA/b/ s- vinyldimethicone crosspolymer.

20. The sunscreen composition of claim 19 wherein said crotonic acid/vinyl C8 -i2 isoalkyl esters/VA/b/ 's-vinyldimethicone crosspolymer is dissolved in ethanol.

21. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming polymers comprise a biopolymer of shellac.

22. The sunscreen composition of claim 21 wherein said biopolymer of shellac is dissolved in ethanol.

23. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming polymers comprise at least two water insoluble film forming polymers selected from the group consisting of trimethylsiloxysilicate, isododecane (and) acrylate /dimethicone copolymer, and acrylates/dimethicone copolymer (and) cyclopentasiloxane.

24. The sunscreen composition of claim 23 wherein said at least two water insoluble film forming polymers are dissolved in one or both of isododecane and isohexadecane.

25. The sunscreen composition of claim 1 wherein said one or more water insoluble film forming polymers comprise at least two water insoluble film forming polymers selected from the group consisting of methyl dihydroabietate, trimethylsiloxysilicate, hydrogenated polycyclopentadiene (and) isododecane, acrylates/dimethicone copolymer (and) cyclopentasiloxane, and combinations thereof.

26. The sunscreen composition of claim 25 wherein said at least two water insoluble film forming polymers are dissolved in one or more of solvents selected from the group consisting of isododecane, isohexadecane, disiloxane and diisopropyl adipate.

27. The sunscreen composition of claim 1 wherein said sunscreen composition includes sunscreen active agents comprising said one or more UVA sunscreen active agents in combination with one or more UVB sunscreen active agents, said sunscreen active agents present in an amount of about 0.01 wt. % to about 40.0 wt. %, based on a total weight of the sunscreen composition.

28. The sunscreen composition of claim 27 wherein said sunscreen active agents are present in an amount of about 3.0 wt. % to about 30.0 wt. %.

29. The sunscreen composition of claim 1 wherein said sunscreen composition further includes one or more active or inactive cosmetic ingredients.

30. The sunscreen composition of claim 29 wherein said one or more active or inactive cosmetic ingredients comprise cosmetically acceptable carriers; oils; sterols; amino acids; moisturizers; powders; colorants; pigments; dyes; pH adjusters; perfumes; essential oils; cosmetic active ingredients; vitamins; essential fatty acids; sphingolipids; self-tanning compounds; fillers; emulsifying agents; antioxidants; surfactants; additional film formers; chelating agents; gelling agents; thickeners; emollients; humectants; moisturizers; minerals; viscosity and/or rheology modifiers; keratolytics; retinoids; hormonal compounds; alpha-keto acids; anti-mycobacterial agents; anti-fungal agents; ant i microbials; anti-virals; analgesics; anti-allergenic agents; HI or H2 antihistamines; anti-inflammatory agents; anti-irritants; anti-neoplastics; immune system boosting agents; immune system suppressing agents; anti-acne agents; anesthetics; antiseptics; insect repellents; skin cooling compounds; skin protectants; skin penetration enhancers; exfoliants; lubricants; fragrances; colorants; staining agents; depigmenting agents; hypopigmenting agents; preservatives; stabilizers; pharmaceutical agents; photostabilizing agents; spherical powders; one or more fragrances; plant extracts; absorbents; salicylic acid; alpha and beta hydroxy acids; vitamins; retinol and its derivatives; or any combination of the foregoing.

31. A sunscreen composition comprising:

one or more UVA sunscreen active agents;

one or more water insoluble film forming polymers comprising of monomers, copolymers,

cross polymers and terpolymers of organo-silicone hybrids, biopolymers, acrylate, abietic acid

derivatives, polyolefins, silicone resins, vinyl acetates, maleates, alkyl esters, long chain and

short chain carboxylic acids, or combinations thereof; and

one or more solvents comprising C2-10 alcohol, ether, fatty acid, silicone fluid, ester,

hydrocarbon, fluorinated hydrocarbon, wherein said one or more water insoluble film forming polymers increase water resistance of said one or more UVA sunscreen active agents such that retention of UVAPF values after water exposure, as determined by UVAPF values measured before and after water exposure, is greater than at least 70%.

32. The sunscreen composition of claim 31 wherein said one or more water insoluble film forming polymers is present in an amount of up to 10 wt. % and said one or more solvents comprises ethanol.

33. The sunscreen composition of claim 31 wherein said one or more water insoluble film forming polymers is present in an amount of up t o 6 wt. % and said one or more solvents comprises ethanol.

34. The sunscreen composition of claim 31 wherein said one or more water insoluble film forming polymers is present in an amount of up to 10 wt. % and said one or more solvents comprises isododecane, isohexadecane, disiloxane, diisopropyl adipate, or a combination thereof.

35. The sunscreen composition of claim 31 wherein said one or more water insoluble film forming polymers is present in an amount of up t o 6 wt. % and said one or more solvents comprises isododecane, isohexadecane, disiloxane, diisopropyl adipate, or a combination thereof.

36. A sunscreen composition comprising:

one or more UVA sunscreen active agents including avobenzone;

one or more UVB sunscreen active agents;

one or more water insoluble film forming polymers present in an amount of up t o about 10 wt. % based on a total weight of said sunscreen composition, wherein said one or more water insoluble film forming polymers increase water resistance of said one or more UVA sunscreen active agents such that retention of UVAPF values after water exposure, as determined by UVAPF values measured before and after water exposure, is greater than at least 60%.

37. A consumer packaged product comprising a sunscreen composition of claim 1.

38. A consumer packaged product comprising a sunscreen composition of claim 31.

39. A consumer packaged product comprising a sunscreen composition of claim 32.

40. A consumer packaged product comprising a sunscreen composition of claim 34 that is alcohol- free. 41. A consumer packaged product comprising a sunscreen composition of claim 36.

42. A method of absorbing ultraviolet radiation on a keratinous substrate comprising applying a sunscreen composition according t o claim 1 to a keratinous substrate and subjecting the keratinous substrate t o ultraviolet radiation.

43. A method of absorbing ultraviolet radiation on a keratinous substrate comprising applying a sunscreen composition according to claim 31 to a keratinous substrate and subjecting the keratinous substrate t o ultraviolet radiation.

44. A method of absorbing ultraviolet radiation on a keratinous substrate comprising applying a sunscreen composition according to claim 32 to a keratinous substrate and subjecting the keratinous substrate t o ultraviolet radiation.

45. A method of absorbing ultraviolet radiation on a keratinous substrate comprising applying an alcohol-free sunscreen composition according to claim 34 t o a keratinous substrate and subjecting the keratinous substrate to ultraviolet radiation.

46. A method of absorbing ultraviolet radiation on a keratinous substrate comprising applying a sunscreen composition according to claim 36 to a keratinous substrate and subjecting the keratinous substrate t o ultraviolet radiation. International application No PCT/US2016/051505

A. CLASSIFICATION O F SUBJECT MATTER INV. A61Q17/04 A61K8/81 A61K8/35 ADD.

According to International Patent Classification (IPC) or to both national classification and IPC

B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols A61Q A61K

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal , WPI Data, CHEM ABS Data

C. DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

WO 2011/097448 Al (ISP INVESTMENTS INC 1-18, [US] ; BARRETT CHRISTINE M [US] ; FARES HANI 27-46 [US] ; G) 11 August 2011 (2011-08-11) the whole document

DONALD PRETTYPAUL , HANI FARES: 1-18, "Mi croscopi c eval uati on of polymeri c f i l m 27-46 properties of anhydrous sunscreen composi t i ons and thei r rel ati on t o absorption and water resi stance" , JOURNAL OF COSMETIC SCI ENCE, vol . 63, no. 3 , May 2012 (2012-05) , June 2012 (2012-06) , pages 213-221 , XP002763286, the whole document

/ -

X Further documents are listed in the continuation of Box C. See patent family annex.

* Special categories of cited documents : "T" later document published after the international filing date or priority date and not in conflict with the application but cited to understand "A" document defining the general state of the art which is not considered the principle or theory underlying the invention to be of particular relevance "E" earlier application or patent but published on or after the international "X" document of particular relevance; the claimed invention cannot be filing date considered novel or cannot be considered to involve an inventive "L" document which may throw doubts on priority claim(s) orwhich is step when the document is taken alone cited to establish the publication date of another citation or other " document of particular relevance; the claimed invention cannot be special reason (as specified) considered to involve an inventive step when the document is "O" document referring to a n oral disclosure, use, exhibition or other combined with one or more other such documents, such combination means being obvious to a person skilled in the art "P" document published prior to the international filing date but later than the priority date claimed "&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

4 November 2016 18/01/2017

Name and mailing address of the ISA/ Authorized officer European Patent Office, P.B. 5818 Patentlaan 2 NL - 2280 HV Rijswijk Tel. (+31-70) 340-2040, Fax: (+31-70) 340-3016 Nopper, Agathe International application No PCT/US2016/051505

C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

Ol ga V.Dueva-Koganov, Mi chael Russel l , 1-18, Steven Mi cceri and Artyom Duev: 27-46 " Eval uati ng Sunscreen Spray Polymers" , HAPPI

5 March 2012 (2012-03-05) , page 8PP, XP002763287, Retri eved from the Internet: URL: http : //www. happi . com/contents/vi ew_onl i ne-excl usi ves/2012-03-05/eval uati ng-sunsc reen- spray-polymers [retri eved on 2016-10-19] the whole document

US 2014/170090 Al (THAGGARD HOLLY E [US] ) 1-18, 19 June 2014 (2014-06-19) 27-46 paragraphs [0023] , [0025] , [0033] , [0105] ; c l aims 1, 18,20; exampl es 1-3

0 2012/078961 Al (ISP INVEST INS [US] ; 1-18, FARES HANI [US] ; PRETTYPAUL DONALD [US] ) 27-46 14 June 2012 (2012-06-14) paragraphs [0001] , [0014] , [0016] , [0033] ; exampl es 1,4-5; tables 2 , 5

W0 2012/149355 Al (ISP INVESTMENTS INC 1-18, [US] ; FARES HANI [US] ; PRETTYPAUL DONALD 27-46 [US] ; KEN) 1 November 2012 (2012-11-01) exampl es 1-11 ; tables 2-13 International application No. PCT/US2016/051505 INTERNATIONAL SEARCH REPORT

Box No. II Observations where certain claims were found unsearchable (Continuation of item 2 of first sheet)

This international search report has not been established in respect of certain claims under Article (2)(a) for the following reasons:

□ Claims Nos.: because they relate to subject matter not required to be searched by this Authority, namely:

claims NOB.: 1-46 (parti al 1y ) because they relate to parts of the international application that do not comply with the prescribed requirements to such an extent that no meaningful international search can be carried out, specifically: FURTHER INFORMATION sheet PCT/ISA/21Q

□ Claims Nos.: because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4(a).

Box No. Ill Observations where unity of invention is lacking (Continuation of item 3 of first sheet)

This International Searching Authority found multiple inventions in this international application, as follows:

see addi tional sheet

1. 1 As all required additional search fees were timely paid by the applicant, this international search report covers all searchable ' claims.

2 . I I As all searchable claims could be searched without effort justifying an additional fees, this Authority did not invite payment of additional fees.

As only some of the required additional search fees were timely paid by the applicant, this international search report covers ' ' only those claims for which fees were paid, specifically claims Nos. :

No required additional search fees were timely paid by the applicant. Consequently, this international search report is restricted to the invention first mentioned in the claims; it is covered by claims Nos.: 1-18, 27-46

Remark on Protest The additional search fees were accompanied by the applicant's protest and, where applicable, the ' ' payment of a protest fee. The additional search fees were accompanied by the applicant's protest but the applicable protest ' ' fee was not paid within the time limit specified in the invitation.

I INo protest accompanied the payment of additional search fees.

Form PCT/ISA/21 0 (continuation of first sheet (2)) (April 2005) International Application No. PCTY US2Q16/ Q515Q5

FURTHER INFORMATION CONTINUED FROM PCT/ISA/ 210

Continuati on of Box 11.

Cl aims Nos. : l-46(partial ly)

Analysi s of the content of the independent claims :

Independent cl aims 1,31,36-46 are not clear and/or conci se wi thin the meaning of Arti cle 6 PCT for the fol lowing reasons: The water insol uble f i l m formi ng polymers are defi ned by the fol lowing feature " said one or more water insol uble f i l m forming polymers increase water resi stance of said one or more UVA sunscreen active agents such that the retenti on of UVAPF val ues after water exposure, as determined by UVAPF val ues measured before and after water exposure, i s greater than at least 60% or 70%" . However, thi s feature defi nes a desi red functi on of the water insol ubl e f i l m formi ng polymers , contrary t o the requi rements of clari t y of Arti cle 6 PCT, because thi s resul t-to-be-achieved type of defi ni t i on does not al low the scope of the claim t o be ascertained. The fact that any compound could be screened does not overcome thi s objection, as the ski l led person would not have knowledge beforehand as t o whether i t would fal l wi thi n the scope claimed. Undue experimentati on would be requi red t o screen al l possibl e compounds randomly. Claim 1 i s i n dependent claim 4 l imi ted t o certain speci f i c UVA sunscreen acti ve agents; the same i n cl aim 36. However, i n the l i st of speci f i c UVA sunscreen active agents gi ven i n claim 4 , two compounds are the same (bi s-di sul zole di sodi um and di sodi u phenyl di benzimidazol e tetrasul fonate) and one i s structural l y not possible (bi s-benzoxazoylylphenyl ethyl hexyl ami no triazine) .Thi s inconsi stency leads t o doubt concerning the matter for whi ch protection i s sought, thereby renderi ng the aforementioned cl aims unclear, Arti cl e 6 PCT. Claim 3 1 and i t s dependent cl aims are not l imi ted t o speci f i c UVA sunscreen acti ve agents, but t o the choi ce of water insol uble f i lms forming polymers and the presence of solvents . The water i nsol uble f i l m forming polymers are selected from "monomers, copolymers, cross polymers and terpolymers of organo-si 1i cone hybrids, bi opolymers, acryl ate, abieti c acid and derivatives, polyolefins , si l i cone resins, vi nyl acetates, maleates, al kyl esters, long chain and short chain carboxyl i c acids , or combinations thereof" . However, thi s defini tion engl obes so many options and/or possible al ternati ves that claim 3 1 and i t s dependent cl aims as a whole are not i n compl iance wi t h the provi sions of clari t y and conci seness of Arti cle 6 PCT. The term " water insol uble " al so leads t o a l ack of clari t y (Arti cle 6 PCT) due t o the absence of further techni cal informations (temperature, presence of other sol utes, pressi on. . ) . The non-compl iance wi t h the substanti ve provi sions of Arti cl e 6 PCT i s t o such an extent, that the search has t o be l imi ted t o UVA sunscreen acti ve agents and water insol ubl e f i l m formi ng polymers whi ch are clearly defi ned i n the claims and whi ch al so appear t o be cl early supported by the descripti on (see pages 15-21) , namely: - one or more UVA sunscreen agent selected at l east from Avobenzone (cl aims 4,36) International Application No. PCTV US2Q16/ Q515Q5

FURTHER INFORMATION CONTINUED FROM PCT/ISA/ 210

and, - a water insol uble f i l m forming polymer selected ei ther from a terpolymer of vinyl acetate/mono-n-butyl maleate/i sobornyl (cl aim 17) , a si i cone-organi c hybri d materi al of crotoni c acid/vinyl C8-12 i soal kyl esters/VA/bi s-vinyldimethi cone crosspolymer (claim 19) , or a biopolymer of shel lac (cl aim 21) .

The appl i cant ' s attention i s drawn t o the fact that cl aims rel ating t o inventions i n respect of whi ch no international search report has been establ i shed need not be the subject of an international prel iminary examination (Rule 66. 1(e) PCT) . The appl i cant i s advi sed that the EPO pol i cy when acting as an Internati onal Prel imi nary Examini ng Authori t y i s normal l y not t o carry out a prel iminary examination on matter whi ch has not been searched. Thi s i s the case i rrespecti ve of whether or not the cl aims are amended fol lowi ng recei pt of the search report or during any Chapter I I procedure. I f the appl i cati on proceeds into the regional phase before the EPO, the appl i cant i s reminded that a search may be carried out during examination before the EPO (see EPO Gui del i nes C-IV, 7.2) , should the problems whi ch led t o the Arti cle 17(2) declaration be overcome. International Application No. PCTY US2Q16/ Q515Q5

FURTHER INFORMATION CONTINUED FROM PCT/ISA/ 210

Thi s International Searching Authori t y found mul tiple (groups of) i nventions i n thi s international appl i cation , as fol l ows :

1. claims: 1-18, 27-46

Sunscreen composi tion compri sing one or more UVA sunscreen active agent and one or more water insol uble f i l m forming polymer i ncl uding at least a terpolymer of vi nyl acetate/ mono-n-butyl maleate/i sobornyl acetate. A consumer packaged containing the sunscreen composi tion . A method of absorbi ng UV radiation on a keratinous substrate using the sunscreen composi t i on.

2. claims: 1-16, 19 , 20, 27-46

Sunscreen composi tion compri sing one or more UVA sunscreen active agent and one or more water insol uble f i l m forming polymer i ncl uding at least a si l i cone-organi c hybrid material of crotoni c acid/vinyl C8-12 i soal kyl esters/VA/bi s-vinyldimethi cone crosspolymer.A consumer packaged containi ng the sunscreen composi tion. A method of absorbing UV radi ation on a keratinous substrate using the sunscreen composi tion.

3. claims: 1-16, 2 1 , 22 , 27-46

Sunscreen composi tion compri sing one or more UVA sunscreen active agent and one or more water insol uble f i l m forming polymer i ncl uding at least a biopolymer of shel lac. A consumer packaged containing the sunscreen composi tion. A method of absorbi ng UV radiation on a keratinous substrate using the sunscreen composi t i on.

4. claims: 1-16, 23 , 24, 27-46

Sunscreen composi tion compri sing one or more UVA sunscreen active agent incl uding at least avobenzone and at least two water insol uble f i l m forming polymers sel ected from the group of trimethyl si l oxysi 1i cate, i sododecane(and) acryl ate/dimethi cone copolymer, and acryl ates/dimethi cone copolymer (and) cyclopentasi l oxane.A consumer packaged containing the sunscreen composi tion . A method of absorbi ng UV radiation on a keratinous substrate using the sunscreen composi t i on.

5. claims: 1-16, 25-46

Sunscreen composi tion compri sing one or more UVA sunscreen active agent incl uding at least avobenzone and at least two water insol uble f l m forming polymers sel ected from the group of methyl di hydroabietate, trimethyl si oxysi 1i cate, International Application No. PCTV US2Q16/ Q515Q5

FURTHER INFORMATION CONTINUED FROM PCT/ISA/ 210

hydrogenated polycycl opent adiene (and) i sododecane,acryl ates/dimethi cone copolymer (and) cyclopentasi l oxane, and combi nati ons thereof. A consumer packaged containi ng the sunscreen composi tion. A method of absorbing UV radi ation on a keratinous substrate using the sunscreen composi tion.

ims: 1-46

Sunscreen composi tion compri sing one or more UVA sunscreen active agent and one or more water insol uble f i l m forming polymers A consumer packaged containi ng the sunscreen composi t i on. A method of absorbing UV radiati on on a keratinous substrate using the sunscreen composi tion . International application No Information on patent family members PCT/US2016/051505

Patent document Publication Patent family Publication cited in search report date member(s) date

WO 2011097448 A l 11-08-2011 AU 2011212859 A l 23-08-2012 CA 2788691 A l 11-08-2011 CN 102781404 A 14-11-2012 EP 2531168 A l 12-12-2012 P 5814265 B2 17-11-2015 P 2013518898 A 23-05-2013 KR 20120112849 A 11-10-2012 US 2013243703 A l 19-09-2013 WO 2011097448 A l 11-08-2011

US 2014170090 A l 19-06-2014 NONE

WO 2012078961 A l 14-06-2012 US 2013309185 A l 21-11-2013 WO 2012078961 A l 14-06-2012

W0 2012149355 A l 01-11-2012 AU 2012249453 A l 31-10-2013 BR 112013027893 A2 23-08-2016 CA 2834Q35 A l 01-11-2012 CN 103596542 A 19-02-2014 EP 2701670 A l 05-03-2014 P 2014513105 A 29-05-2014 KR 2014Q023989 A 27-02-2014 US 2014030198 A l 30-01-2014 W0 2012149355 A l 01-11-2012