Sprayable sunscreen composition

Abstract

To provide a sunscreen composition.SOLUTION: The present invention provides an anhydrous, sprayable sunscreen composition comprising one or more oil soluble UV filters and a combination of film formers comprising at least one copolymer of trimethylolpropane, adipic acid, neopentyl glycol and hexanediol and at least one acrylates / octylacrylamide copolymer having a molecular weight of at least 50 kDA measured using dynamic light scattering.SELECTED DRAWING: None

Description

Background Art

[0001] In particular, it is well known that long-term exposure to ultraviolet (UV) rays from the sun can cause light-induced skin diseases and the formation of erythema, and may increase the risk of skin cancer such as melanoma. Exposure to ultraviolet rays also promotes skin aging such as loss of skin elasticity and the appearance of wrinkles. For these reasons, sunscreen compositions are commonly used to provide protection from sunlight. Sprayable sunscreen compositions are a popular product form due to the convenience of their application.

[0002] Recently, there has been increased scrutiny of the use of oxybenzone as a UV filter in sunscreen compositions, and consumer demand for oxybenzone-free sunscreens has been growing. However, removing oxybenzone from sunscreen formulations presents challenges in maintaining an acceptable SPF.

[0003] Film formers are typically used in sunscreen compositions to provide a more uniform distribution of UV filters in the composition and spreading of the composition on the skin, thereby increasing effectiveness and SPF. A wide variety of film formers, including polyesters and acrylate copolymers, are available and are used in commercial sunscreen compositions. For example, U.S. Patent No. 9,149,664 relates to a sunscreen composition comprising one or more sunscreen agents, one or more film-forming polymers, and heat-treated xanthan gum. This patent discloses many synthetic water-dispersible film-forming polymers that can be used, including DERMACRYL 79, an acrylate / octylacrylamide copolymer, LEXFILM SUN, a polyester-7; a copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol (and) neopentyl glycol diheptanoate, and LEXFILM SPRAY, a polyester-10; a copolymer of hexanediol, neopentyl glycol, adipic acid, and pyromellitic dianhydride (and) propylene glycol dibenzoate. However, the use of a specific combination of film formers, including at least one copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol and at least one acrylate / octylacrylamide copolymer, is neither taught nor suggested.

[0004] It has been found that a combination of film formers comprising at least one copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol and at least one acrylate / octylacrylamide copolymer having a molecular weight of at least 50 kDa as measured using dynamic light scattering can be used to prepare a sprayable anhydrous sunscreen composition that provides surprisingly high SPF and may further contain substantially or completely no oxybenzone. SUMMARY OF THE INVENTION MEANS FOR SOLVING THE PROBLEM

[0005] The present invention provides a sunscreen composition comprising a combination of one or more oil-soluble UV filters, at least one copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol, and at least one acrylate / octylacrylamide copolymer having a molecular weight of at least 50 kDa as measured by dynamic light scattering, the composition being anhydrous and sprayable.

Embodiments for Carrying Out the Invention

[0006] Unless otherwise specified, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All publications, patent applications, patents, and other references mentioned herein are hereby incorporated by reference in their entirety.

[0007] Where appropriate, chemical substances are designated by their INCI names. Further information, including definitions, suppliers, and trade names, can be found in the appropriate INCI monographs in the International Cosmetic Ingredient Dictionary and Handbook, 16th Edition, published by the Personal Care Products Council, Washington D.C. It is also available via the Personal Care Products Council's On-Line INFOBASE (http: / / online.personalcarecouncl.org / jsp / Home.jsp).

[0008] As used herein, "applied topically" means spraying, rubbing, applying, or spreading directly onto the skin or scalp, for example, by using the hands or an applicator such as a wipe, roller, or spray.

[0009] When used in the present invention, "cosmetic" specifically refers to a beautifying substance or formulation that, when related to the appearance of tissues or skin, maintains, restores, provides, adorns, or enhances a physically beautiful appearance, or appears to increase beauty or youthfulness.

[0010] As used herein, "sunblock composition" refers to a formulation (e.g., lotion, spray, gel, or other topical product) that absorbs and / or reflects some of the sun's ultraviolet (UV) rays and thereby helps protect against the negative effects of sun exposure, such as sunburn, premature aging, etc.

[0011] When used in the present invention, "cosmetically effective amount" means an amount of a physiologically active compound or composition that is sufficient to treat one or more conditions but low enough to avoid severe side effects. The cosmetically effective amount of a compound or composition will vary depending on the condition being treated, the age and health of the end user, the severity of the condition being treated / prevented, the duration of the treatment, the nature of other treatments, the particular compound or product / composition being used, the cosmetically acceptable carrier being utilized, and similar factors.

[0012] When used in the present invention, "cosmetically acceptable" means that the components described by this term are suitable for use in contact with tissues (e.g., skin) without undue toxicity, inadaptability, instability, irritation, allergic reaction, etc.

[0013] When used in the present invention, "cosmetically acceptable active agent" is a compound (synthetic or natural) that has a cosmetic or therapeutic effect on the skin.

[0014] When used in the present invention, "treating or treat" refers to alleviating, reducing, preventing, improving, or eliminating the presence or symptoms of a condition or disorder.

[0015] As used herein, "phase stability" means maintaining interfacial stability and / or suspension stability, or both, at each of 25°C, 40°C, and 50°C for at least two weeks. "Interfacial stability" refers to the stability against coalescence and coarsening of the discontinuous phase in a composition having two or more phases. "Suspension stability" refers to the stability against creaming and / or sedimentation of the discontinuous phase suspended in the continuous phase, such as a solid.

[0016] As used herein, "substantially free of" means that the component referred to is not added directly and intentionally to the formulation. Preferably, "substantially free of" means containing less than about 1% of the component. More preferably, "substantially free of" means containing less than about 0.5% of the component. Even more preferably, "substantially free of" means containing less than about 0.1% by weight of the component. The composition may not contain the component completely, i.e., it may not contain the component at all.

[0017] Unless otherwise stated, percentages or concentrations refer to weight percentages or weight concentrations (i.e., %(W / W)). Unless otherwise specified, all ranges include both endpoints; for example, "4 to 9" includes both endpoints 4 and 9.

[0018] UV filter The composition includes one or more oil-soluble UV filters.

[0019] As used herein, "organic UV filter" means an organic molecule capable of absorbing UV light, including (i) an aromatic compound conjugated with a carbonyl moiety substituted at the ortho or para position of an aromatic ring and (ii) a polymer made of an organic chromophore bonded to a polymer chain, both of which block or absorb ultraviolet (UV) light.

[0020] Conventional organic UV filters are aromatic low-molecular substances with a molecular weight value of <900 g / mol. Examples of non-polymeric organic UV filters include methoxycinnamate derivatives (such as octyl methoxycinnamate and isoamyl methoxycinnamate), camphor derivatives (such as 4-methylbenzylidene camphor, camphor benzalkonium methosulfate, and terephthalylidene dicamphor sulfonic acid), salicylic acid derivatives (such as octyl salicylate, ethylhexyl salicylate, homosalate), benzophenone derivatives (such as dioxybenzone and oxybenzone), benzoic acid derivatives (such as aminobenzoic acid and octyldimethyl para-aminobenzoic acid), octocrylene and other β,β-diphenyl acrylates, dioctyl butamidotriazone, octyltriazone, avobenzone (butyl methoxydibenzoylmethane), menthyl anthranilate, triazone derivatives (such as ethylhexyltriazone (Uvinul® T150)), diethylhexyl butamidotriazone (UVASorb® HEB), bis-ethylhexyloxyphenol methoxyphenyltriazine (Tinosorb® S), benzoate derivatives (such as diethylamino hydroxybenzoyl hexyl benzoate (Uvinul® A Plus)), benzotriazole derivatives (such as drometrizole trisiloxane (Mexoryl® XL)), methylene bis-benzotriazolyl tetramethylbutylphenol (Tinosorb® M), tris-biphenyltriazine, (2-{4-[2-(4-diethylamino-2-hydroxy-benzoyl)-benzoyl]-piperazine-1-carbonyl}-phenyl)-(4-diethylamino-2-hydroxy-phenyl)-methane, merocyanine derivatives, bis(butyl benzoate) diamino triazine aminopropyl siloxane, and bis-ethylhexyloxyphenol methoxyphenyltriazine encapsulated in a polymer matrix, but are not limited thereto.

[0021] Polymeric organic UV filters are polymers made of organic chromophores attached to a polymer chain, such as a polysiloxane chain having an average molecular weight of, for example, >6000 Daltons. Examples of such polysiloxane UV filters include, but are not limited to, Parsol® SLX and Polysilicone-15. These polysiloxanes absorb the UVB (λ max = 312 nm) portion of the spectrum and are typically combined with a UVA filter to achieve broad-spectrum protection.

[0022] The following table lists various commercially available organic UV filters.

[0023]

Table 1-1

[0024]

Table 1-2

[0025] A sunscreen composition may contain at least about 10 wt% of one or more oil-soluble UV filters, based on the total weight of the composition. The composition may contain about 15 to about 35 wt% of one or more oil-soluble UV filters, based on the total weight of the composition. The composition may contain at least about 21 wt% of one or more oil-soluble filters, based on the total weight of the composition, especially when a particularly transparent composition is desired.

[0026] The oil-soluble UV filter may be selected from one or more of homosalate, octisalate, avobenzone, octocrylene.

[0027] The oil-soluble UV filter may be a mixture of homosalate, octisalate, avobenzone, and octocrylene. For example, the sunscreen composition may contain from about 8 to about 15% by weight of homosalate, from about 4 to about 5% by weight of octisalate, from about 2 to about 3% by weight of avobenzone, and from about 7 to about 10% by weight of octocrylene, based on the total weight of the composition.

[0028] The sunscreen composition may not substantially contain oxybenzone. The sunscreen composition may not completely contain oxybenzone.

[0029] The composition may optionally contain one or more UV blockers which are compounds that reflect, absorb, or scatter ultraviolet light. When present in the sunscreen composition, the UV blocker reflects ultraviolet, visible, and infrared light to enhance protection from sunlight. The UV blocker is typically an inorganic metal oxide, examples of which include titanium dioxide, zinc oxide, and certain other transition metal oxides. Such UV blockers are typically solid particles in micronized or nanosized form having a diameter of from about 0.01 μm to about 10 μm.

[0030] Examples include zinc oxide, titanium dioxide, doped zinc oxide, doped titanium dioxide, and other transition metal oxides. The doped metal oxide contains dopants which are trace elements of other metal atoms incorporated within the crystal lattice of the primary metal oxide to change its electrical or optical properties, and may include aluminum, manganese, and iron.

[0031] In another embodiment, the metal oxide includes coated particles. The coating may include, for example, a hydrophobic material such as an alkylsiloxane (e.g., triethoxycaprylylsilane), silicone, or a metal salt of a fatty acid.

[0032] In one embodiment, the metal oxide includes particles having a diameter of from about 0.01 μm to about 10 μm.

[0033] In one embodiment, the inorganic sunscreen may further comprise particulate doped zinc oxide, as referenced in U.S. Patent Nos. 9,144,535, 9,144,536, and International Publication No. WO 2008 / 117017, which are hereby incorporated by reference in their entirety. Such particulate zinc oxide contains a specific dopant at a specific ratio and provides improved performance with respect to absorption in the UVA portion of the electromagnetic spectrum. The particulate zinc oxide contains a cationic moiety, which in turn contains about 99 wt% or more of a zinc moiety. The cationic moiety further contains first and second dopant moieties including metals such as manganese, iron, aluminum, and copper. The first and second dopant moieties may be present in an amount of about 0.1 wt% to about 0.75 wt% of the cationic moiety. The particulate doped zinc oxide may further contain low concentrations of additional metal cations, such as cations of alkali metals, alkaline earth metals, other transition metals, and metals such as gallium, germanium, gallium, indium, tin, antimony, thallium, lead, bismuth, and polonium.

[0034] These doped zinc oxides can be made by various methods, such as reducing an oxide ore using carbon or another suitable reducing agent and then re-oxidizing, for example. Other suitable methods include wet chemical methods. An example of a wet chemical method involves mixing aqueous solutions of various cations and precipitating ZnO by lowering the pH using an acid such as oxalic acid or formic acid. A particularly suitable wet chemical method is the so-called "sol-gel" method.

[0035] SPF The sun protection factor (SPF) can be tested using the following in vitro SPF test method. The baseline transmittance of a PMMA plate (substrate, available from Helioscience (Marseille, France)) is measured for UV absorbance using a calibrated Labsphere® UV-10005 UV transmittance analyzer or a Labsphere® UV-2000S UV transmittance analyzer (Labsphere (North Sutton, N.H., USA)). Then, the test sample is applied to the PMMA plate using an application density of about 1.3 mg / cm 2 and rubbing with the operator's finger to form a uniform thin layer. The sample is dried for 15 minutes and then measured for UV absorbance in the same manner. Using the measured absorbance values, the SPF is calculated as known in the art using the following equation:

[0036] [Equation] (wherein, E(λ) = erythema action spectrum, I(λ) = spectral irradiance received from the UV source, A0(λ) = average monochromatic absorbance of the test product layer before UV exposure, and d(λ) = wavelength step (1 nm)).

[0037] In one embodiment, the composition has an SPF of at least about 15 when measured by the in vitro SPF test method. In another embodiment, the composition has an SPF of at least about 25 when measured by the in vitro SPF test method.

[0038] The composition may contain one or more SPF boosters such as a styrene / acrylate copolymer. A commercially available styrene / acrylate copolymer is Sunsphere Powder manufactured by Dow Chemical.

[0039] Film former A film-forming agent is generally a polymer that, when dissolved in a composition, forms a continuous or semi-continuous film when the composition is spread, for example, on a smooth glass, and enables the evaporation of the liquid vehicle. Thus, the polymer should mainly dry continuously on the glass rather than form a plurality of separate island-like structures. Generally, the film formed by applying a sunscreen composition onto the skin according to the present invention has an average thickness of less than about 100 μm, for example, less than about 50 μm.

[0040] The sunscreen composition comprises a combination of film-forming agents including at least one copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol and at least one acrylate / octylacrylamide copolymer having a molecular weight of at least 50 kDa as measured by dynamic light scattering.

[0041] The composition may comprise a combination of film-forming agents consisting of at least one copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol and at least one acrylate / octylacrylamide copolymer having a molecular weight of at least 50 kDa as measured by dynamic light scattering.

[0042] The composition may comprise a combination of film-forming agents consisting of one copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol and one acrylate / octylacrylamide copolymer having a molecular weight of at least 50 kDa as measured by dynamic light scattering.

[0043] The total amount of the film-forming agent in the composition can range from about 0.25 wt% to about 15 wt% of the total weight of the composition. The total amount of the film-forming agent in the composition can range from about 0.5 wt% to about 10 wt% of the total weight of the composition. The total amount of the film-forming agent in the composition can range from about 1 wt% to about 5 wt% of the total weight of the composition based on the weight of the composition based on the total weight of the composition.

[0044] The weight ratio of the copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol in the composition to the acrylate / octylacrylamide copolymer can range from about 0.50 to about 3.00.

[0045] Acrylate / octylacrylamide copolymer The acrylate / octylacrylamide copolymer is a copolymer of acrylate and octylacrylamide monomers. It has a molecular weight of at least 50 kDa as measured using the dynamic light scattering method. The acrylate / octylacrylamide copolymer can have a molecular weight of at least 60 kDa as measured using the dynamic light scattering method.

[0046] The molecular weight of the acrylate / octylacrylamide copolymer is measured as follows using the dynamic light scattering method (also known as DLS, photon correlation spectroscopy or PCS). DLS is a well-known method for estimating the z-average molecular weight of macromolecules using the measured hydrodynamic radius d r thereof.

[0047] A sample of the solution of the acrylate / octylacrylamide copolymer is prepared by dissolving a minimum of 0.1 - 0.5 wt% of the copolymer in ethanol. The sample is stirred at 1000 rpm for a minimum of 5 minutes in a vortex mixer and then left to stand overnight before analysis. The sample is then transferred to a dust-free disposable acrylic sizing cuvette and sealed.

[0048] Samples were analyzed using a Zetasizer Nano ZS DLS instrument (Malvern Panalytical, Inc., Westborough, MA) operating at 25.0 °C. Samples need to obtain a minimum count rate of 100,000 counts per second (cps) in order to accurately determine the hydrodynamic radius. For samples with a count rate below this minimum value, the sample concentration may be gradually increased until the minimum count rate is achieved. The value d r of the macromolecule is calculated using the Zetasizer Software v7.01 package (Malvern Panalytical, Inc., Westborough, MA) that calculates the Z-average d r . The molecular weight is then estimated by combining with the calibration curve in the software for the mass versus size of a particular macromolecular higher-order structure. The copolymer is assumed to be linear in its higher-order structure. The calibration curve of mass versus size for linear polymers is not based off pullulan or linear polysaccharides. The output from the software is the molecular weight (MW) of the linear polymer in kilodaltons (kDa). A suitable acrylate / octylacrylamide copolymer for use in the present invention is DERMACRYL 79 commercially available from Nouryon. DERMACRYL 79 has a molecular weight of 65.5 kDa as measured using dynamic light scattering.

[0049] The amount of acrylate / octylacrylamide copolymer in the composition can range from about 0.50 to about 3.25 weight percent based on the total weight of the composition.

[0050] Polyester A copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol is also known as Polyester 7. The copolymer can be solubilized in a solvent. The solvent may be neopentyl glycol diheptanoate.

[0051] Examples of suitable copolymers of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol include LEXFILM SUN, commercially available from INOLEX (Philadelphia, PA).

[0052] The amount of the copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol in the composition can range from about 0.25 to about 2.5 weight percent based on the total weight of the composition. The amount of the copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol in the composition can range from 0.35 to about 1.75 weight percent based on the total weight of the composition.

[0053] Alcohol The sunscreen composition is anhydrous. The composition may be substantially free of water. The composition may be completely free of water.

[0054] The sunscreen composition includes one or more alcohols that can function as a solvent for other components in the composition.

[0055] The alcohol can be selected from, for example, propylene glycol, 1,3 - propanediol, butylene glycol, polyethylene glycol, polypropylene glycol, glycerol, 1,2,4 - butanetriol, sorbitol esters, 1,2,6 - hexanetriol, ethanol, isopropanol, and mixtures thereof.

[0056] In one embodiment, the organic solvent is ethanol.

[0057] The composition can include from about 30 to about 79 weight percent alcohol based on the total weight of the composition. In a preferred embodiment, the composition can include from about 50 to about 79 weight percent alcohol based on the total weight of the composition.

[0058] Topical application composition The composition can be prepared using mixing and blending methods well-known in the sunscreen and cosmetics fields.

[0059] The composition can contain a "cosmetically acceptable carrier for topical application", i.e., a carrier for topical use that contains other ingredients dispersed or dissolved therein and has acceptable properties to be safe for topical use, and can be combined with a carrier for topical use.

[0060] The cosmetically acceptable carrier for topical application can optionally contain a variety of additional oil-soluble materials and / or oil-dispersible materials conventionally used in compositions for use on the skin at concentrations established in the art. For example, surfactants, emulsifiers, nacreous or opacifying agents, thickeners, skin softeners, conditioners, moisturizers, chelating agents, scrubbing agents, preservatives, pH adjusters, and additives that improve the appearance, feel, or fragrance of the composition, such as colorants, fragrances, tactile modifiers, etc. may be included.

[0061] The composition can optionally contain additional film-forming agents, such as natural polymers such as polysaccharides or proteins, and synthetic polymers such as other polyesters, polyacrylates, polyurethanes, vinyl polymers, polysulfonates, polyureas, polyoxazolines, etc. Specific examples include acrylate / dimethicone acrylate copolymer (commercially available as X-22-8247D from Shin-Etsu Chemical Co., Ltd.); hydrogenated dimer dilinoleoyl / dimethyl carbonate copolymer (commercially available as COSMEDIA DC from BASF Corp.); copolymer of vinyl pyrrolidone and long-chain α-olefin (commercially available as GANEX V220 from Ashland Specialty Ingredients, etc.); vinyl pyrrolidone / tricontanyl copolymer (similarly commercially available as GANEX WP660 from Ashland).

[0062] Suitable skin softeners include mineral oil, petrolatum, vegetable oils (such as triglycerides like caprylic / capric triglyceride), waxes and mixtures of other fatty acid esters (including esters (such as isopropyl palmitate, isopropyl myristate, diisopropyl adipate, dibutyl adipate, dicaprylyl carbonate, C12-C15 alkyl benzoate), but not limited to these), silicone oils such as dimethicone, and alkanes such as isohexadecane.

[0063] In one embodiment, the composition may be substantially free of silicone.

[0064] In certain embodiments, the composition comprises a pigment suitable for providing color or hiding power. The pigment may be suitable for use in color cosmetic products, such as compositions for application to hair, nails, and / or skin, particularly the face. Examples of color cosmetic compositions include, but are not limited to, foundations, concealers, primers, blushes, mascaras, eyeshadows, eyeliners, lipsticks, nail enamels, and colored moisturizers. Pigments suitable for providing color or hiding power may consist of iron oxides (including red and yellow iron oxides), titanium dioxide, ultramarine, and pigments of chromium or chromium hydroxide, and mixtures thereof. The pigment may be a lake pigment precipitated on an inert binder such as an insoluble salt, and may be an organic dye such as azo, indigoid, triphenylmethane, anthraquinone, and xanthine dyes, such as those referred to as D&C and FD&C blue, brown, green, orange, red, yellow, etc. Examples of lake pigments include Red #6, Red #7, Yellow #5, Violet #2, and Blue #1. The pigment may be an interference pigment. Examples of interference pigments include those containing mica substrates, bismuth oxychloride substrates, and silica substrates, such as mica / bismuth oxychloride / iron oxide pigments commercially available from BASF as CHROMALITE pigments, titanium dioxide and / or iron oxide coated on mica such as those commercially available from BASF as FLAMENCO pigments, mica / titanium dioxide / iron oxide pigments including KTZ pigments commercially available from Kobo products, BASF's CELLINI pearl pigments, and silicate-containing pigments such as BASF's REFLECKS pigments.

[0065] In one embodiment, the composition comprises a humectant such as butylene glycol or glycerin. The composition may comprise, for example, at least about 1.0 wt% of the humectant.

[0066] The composition may further contain one or more other cosmetically acceptable active agents, such as, for example, anti-acne agents, sebum regulators, antibacterial agents, anti-inflammatory agents, anti-fungal agents, anti-parasitic agents, topical analgesics, antioxidants, keratolytic agents, moisturizers, nutrients, vitamins, energy boosters, antiperspirants, skin astringents, deodorant agents, stabilizers, anti-skin hardening agents, and agents for skin conditioning.

[0067] The amount of the other cosmetically active agent may range from about 0.001 wt% to about 20 wt% of the composition, such as, for example, from about 0.005 wt% to about 10 wt% of the composition, such as, for example, from about 0.01 wt% to about 5 wt% of the composition, and the like.

[0068] Cosmetically acceptable active agents may be selected from, for example, D-panthenol, carotenoids, ceramides, polyunsaturated fatty acids, essential fatty acids, enzymes such as laccase, enzyme inhibitors, minerals, steroids such as hydrocortisone, 2-dimethylaminoethanol, copper salts such as copper chloride; peptides such as aldirelin, shin-ake, and those containing copper; coenzyme Q10, amino acids such as proline, vitamins, lactobionic acid, acetyl coenzyme A, niacin, riboflavin, thiamine, ribose, electron carriers such as NADH and FADH2, natural extracts such as aloe vera, Artemisia princeps, Avena sativa, dill, blackberry, ginger, Picia anomala, and chicory, resorcinols such as 4-hexylresorcinol, curcuminoids, sugar amines such as N-acetylglucosamine, and derivatives thereof and mixtures thereof.

[0069] Examples of vitamins include, but are not limited to, different forms of vitamin A, vitamin B group (such as, for example, vitamin B3, vitamin B5, and vitamin B12), vitamin C, vitamin K, and vitamin E, such as, for example, α, β, γ, or δ tocopherol, or mixtures and derivatives thereof.

[0070] Examples of antioxidants include, but are not limited to, water-soluble antioxidants such as sulfhydryl compounds and their derivatives (e.g., sodium metabisulfite and N-acetyl-cysteine), lipoic acid and dihydrolipoic acid, resveratrol, lactoferrin, and ascorbic acid and ascorbic acid derivatives (e.g., ascorbyl palmitate and ascorbyl polypeptide). Suitable oil-soluble antioxidants for use in the compositions of the present invention include, but are not limited to, butylated hydroxytoluene, retinoids (e.g., retinol and retinyl palmitate), tocopherols (e.g., tocopherol acetate), tocotrienols, and ubiquinone. Natural extracts containing antioxidants suitable for use in the compositions of the present invention include, but are not limited to, extracts containing flavonoids and isoflavonoids and their derivatives (e.g., genistein and daidzein), extracts containing resveratrol, etc. Examples of such natural extracts include grape seeds, green tea, pine bark, and propolis.

[0071] Sprayability The compositions of the present invention are sprayable. As used herein, "sprayable" means that when manually actuated or actuated through pressurized release from a dispensing mechanism such as a bottle or aerosol can equipped with a pump spray nozzle, the composition is uniformly distributed over an area of a defined shape (e.g., circle, ring) and size, creating a reproducible spray pattern. The composition can be sprayable without the use of a propellant, i.e., in a non-aerosol form.

[0072] The present invention is further illustrated by the following non-limiting examples.

Examples

[0073] The following Compositions 1-5 according to the present invention and Comparative Compositions A-D were prepared using the components shown in Table 1 below.

[0074]

Table 2

[0075] Furthermore, each composition contained one or more of the following film formers: (i) Polyester-7: A copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol (and) neopentyl glycol diheptanoate (LEXFILM SUN), (ii) Polyester-10: A copolymer of hexanediol, neopentyl glycol, adipic acid, and pyromellitic dianhydride (and) propylene glycol dibenzoate (LEXFILM SPRAY), (iii) An acrylate / octylacrylamide copolymer (DERMACRYL 79) having a molecular weight of 65.5 kDa measured using dynamic light scattering, (iv) An acrylate / octylacrylamide copolymer (Amphomer 4961) having a molecular weight of 41.1 kDa measured using dynamic light scattering.

[0076] The compositions were prepared as follows.

[0077] Homosalate, octisalate, and octocrylene were added to the main container and mixed at 300 rpm until homogeneous. While continuing the mixing, dicaprylyl carbonate, polyester-7 or polyester-10 (when in use), and denatured alcohol were added and mixed until homogeneous. Next, tocopheryl acetate and fragrance were added and mixing was continued. Avobenzone was added slowly, dissolved completely, and mixed until clear. When using the acrylate / octylacrylamide copolymer, as a final step, it was sprinkled slowly while mixing continuously. Mixing was continued until completely dissolved and clear.

[0078] The in vitro SPF of each composition was measured using the in vitro SPF test method described above.

[0079] The results are shown in Table 2.

[0080]

Table 3

[0081] Surprisingly, Compositions 1 to 5 containing a combination of a copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol and an acrylate / octylacrylamide copolymer having a molecular weight of at least 50 kDa measured using dynamic light scattering as a film-forming agent exhibited an SPF value of 44.57 or higher. In contrast, Compositions C and D containing only one of these film-forming agents but not both provided SPF values of 28.93 and 15.28, respectively.

[0082] Furthermore, Composition A containing a copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol and an acrylate / octylacrylamide copolymer (Amphomer 4961) having a molecular weight of only 41.1 kDa measured using dynamic light scattering provided only 28.05 SPF.

[0083] Similarly, Composition B containing a copolymer of hexanediol, neopentyl glycol, adipic acid, and pyromellitic dianhydride and an acrylate / octylacrylamide copolymer having a molecular weight of at least 50 kDa measured using dynamic light scattering provided only 24.48 SPF.

[0084] 〔Embodiment〕 (1) A sunscreen composition comprising one or more oil-soluble UV filters and a combination of a film-forming agent comprising at least one copolymer of at least one of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol and at least one acrylate / octylacrylamide copolymer having a molecular weight of at least 50 kDa measured using dynamic light scattering, the composition being anhydrous and sprayable. (2) The composition according to embodiment 1, wherein the UV filter is selected from the group consisting of homosalate, octisalate, avobenzone, octocrylene, and mixtures thereof. (3) The composition according to embodiment 1, wherein the copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol is solubilized in neopentyl glycol diheptanoate. (4) The composition according to embodiment 1, wherein the weight ratio of the copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol to the acrylate / octylacrylamide copolymer is from about 0.5 to about 3.0. (5) The composition according to embodiment 1, further comprising at least about 30% by weight of ethanol.

[0085] (6) The composition according to embodiment 1, substantially free of oxybenzone. (7) The composition according to embodiment 1, substantially free of silicone. (8) The composition according to embodiment 1, wherein the combination of film formers comprises a copolymer of trimethylolpropane, adipic acid, neopentyl glycol, and hexanediol solubilized in neopentyl glycol diheptanoate and an acrylate / octylacrylamide copolymer having a molecular weight of at least 50 kDa measured using dynamic light scattering. (9) The composition according to embodiment 1, comprising at least about 21% by weight of an oil-soluble UV filter based on the total weight of the composition.

Claims

**Claim 1**: A sunscreen composition, which is anhydrous and sprayable, comprising: (i) one or more oil-soluble UV filters; (ii) a combination of film formers including (ii-1) at least one copolymer containing monomer units derived from trimethylolpropane, monomer units derived from adipic acid, monomer units derived from neopentyl glycol, and monomer units derived from hexanediol, and (ii-2) at least one acrylate / octylacrylamide copolymer having a molecular weight of at least 60 kDa measured using the dynamic light scattering method, and substantially free of oxybenzone. **Claim 2** The composition according to claim 1, wherein the one or more oil-soluble UV filters in (i) are selected from the group consisting of homosalate, octisalate, avobenzone, octocrylene, and mixtures thereof. **Claim 3** The composition according to claim 1, wherein the at least one copolymer in (ii-1) is solubilized in neopentyl glycol diheptanoate. **Claim 4**: The composition according to claim 1, wherein the weight ratio of the at least one copolymer in (ii-1) to the at least one acrylate / octylacrylamide copolymer in (ii-2) is 0.5 to 3.

0. **Claim 5** The composition according to claim 1, further comprising at least 30% by weight of ethanol. **Claim 6** The composition according to claim 1, completely free of oxybenzone. **Claim 7** The composition according to claim 1, substantially free of silicone. **Claim 8** The composition according to claim 1, wherein the combination of film formers in (ii) consists of the at least one copolymer in (ii-1) solubilized in neopentyl glycol diheptanoate and the at least one acrylate / octylacrylamide copolymer in (ii-2). **Claim 9** The composition according to claim 1, comprising at least 21% by weight of the one or more oil-soluble UV filters based on the total weight of the composition.

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