Mineral sunscreens containing zinc oxide and titanium dioxide

Abstract

To provide a sunscreen composition.SOLUTION: The present invention provides a sunscreen composition comprising (i) TiO2, (ii) ZnO, (iii) triacontanyl PVP, and (iv) a VP / hexadecene copolymer, wherein the composition is an oil-in-water emulsion that is substantially free of low molecular weight organic UV absorbers, wherein the ratio of (iii): (iv) is less than 1, and wherein the composition provides an in vitro SPF of at least 25 as measured by the in vitro SPF test method. The compositions are surprisingly low in viscosity and provide high SPF.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention provides a sunscreen composition comprising (i) TiO, (ii) ZnO, (iii) triacontanyl PVP, and (iv) VP / hexadecene copolymer, wherein the composition is an oil-in-water emulsion substantially free of low molecular weight organic UV absorbers, wherein the weight ratio of (iii):(iv) is less than 1, and the composition provides an in vitro SPF of at least 25 as measured by an In Vitro SPF Test Method. The composition has a surprisingly low viscosity and provides a high SPF. [Background technology]

[0002] It is well known that long-term exposure to ultraviolet light, such as from sunlight, can result in the formation of photodermatological disorders and erythema, and can increase the risk of skin cancers such as melanoma. Exposure to ultraviolet light also accelerates skin aging, such as loss of skin elasticity and the development of wrinkles.

[0003] For these reasons, sunscreen compositions are commonly used to provide sun protection, and various sunscreen compositions are commercially available.Many contain organic UV absorbers such as octocrylene, homosalate, avobenzone, oxybenzone, octyl salicylate, and cinnamates.Although these UV filters are effective in absorbing ultraviolet rays, in order to provide a sunscreen composition with a high SPF, a large amount is often required.Because they are organic compounds, consumers may be concerned about the possibility of them penetrating the skin, especially when used in large amounts.

[0004] Alternatively, mineral-based sunscreens are also commercially available. These typically contain TiO2, ZnO, or both. For example, AVEENO Calm+Restore Daily Moisturizer Mineral Sunscreen SPF 30, available from Johnson & Johnson Consumer Inc., contains 5.8% by weight of TiO2, 12.5% ​​by weight of ZnO, 1.5% by weight of triacontanyl PVP, and 1% by weight of VP / hexadecene copolymer.

[0005] Commonly assigned U.S. Patent Application No. 18 / 136,456, filed April 19, 2023, relates to an anhydrous sunscreen composition containing TiO2 and ZnO. The anhydrous composition is preferably sprayable and includes: (a) at least about 15 wt. % of a combination of TiO2 and ZnO, based on the total weight of the sunscreen composition, wherein the weight ratio of ZnO to TiO2 in the composition is about 0.5 to about 1.5; (b) at least about 50 wt. % of a carrier oil, based on the total weight of the sunscreen composition, the carrier oil comprising at least 50 wt. % of sunflower (helianthus annuus) seed oil; (c) about 10 wt. % to about 20 wt. % of a combination of isododecane and diisopropyl adipate, based on the total weight of the sunscreen composition; and (d) about 2 wt. % to about 6 wt. % of a film-forming agent, based on the total weight of the sunscreen composition, comprising triacontanyl PVP. The '456 application discloses the optional use of a combination of triacontanyl PVP and VP / hexadecene copolymer; in one embodiment, the composition comprises about 2.5% to about 3.2% by weight of triacontanyl PVP and about 2.5% by weight of VP / hexadecene copolymer. Example F of the '456 application is a comparative anhydrous composition containing 15% by weight of TiO, 10% by weight of ZnO, 1.5% by weight of triacontanyl PVP, and 2.5% by weight of VP / hexadecene copolymer. Example F was unstable, exhibiting precipitation at room temperature.

[0006] Typically, mineral-only sunscreens cannot provide the highest SPF values ​​without increasing the amount of mineral UV active ingredients to high levels, which requires high viscosity formulations to suspend the UV blockers, i.e., TiO2 and ZnO. For example, there are very few low viscosity liquid SPF 70 mineral sunscreens on the market today that also have desirable aesthetics.

[0007] Applicants have discovered high SPF oil-in-water emulsions containing only mineral UV active ingredients that also contain triacontanyl PVP and VP / hexadecene copolymer, where the weight ratio of triacontanyl PVP to VP / hexadecene copolymer is less than 1. These compositions advantageously provide in vitro SPF values ​​of at least about 25 and in vivo SPF values ​​of at least 50, preferably at least 70. As emulsions, they also have excellent liquid aesthetics as a result of their surprisingly low viscosity. Summary of the Invention [Means for solving the problem]

[0008] The present invention provides a sunscreen composition comprising (i) TiO2, (ii) ZnO, (iii) triacontanyl PVP, and (iv) VP / hexadecene copolymer, wherein the composition is an oil-in-water emulsion substantially free of low molecular weight organic UV absorbers, wherein the weight ratio of (iii):(iv) is less than 1, and the composition provides an in vitro SPF of at least 25 as measured by an In Vitro SPF Test Method. DETAILED DESCRIPTION OF THE INVENTION

[0009] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference.

[0010] As used herein, "topically apply" means to apply or massage directly onto the skin or scalp, for example, with the hands or with an applicator such as a wipe, roller, or spray.

[0011] As used herein, "cosmetic," particularly as it relates to the appearance of tissue or skin, refers to a beautifying substance or preparation that maintains, restores, imparts, embellishes, or enhances the appearance of physical beauty or youthfulness.

[0012] As used herein, "sunscreen composition" means a formulation (e.g., a lotion, spray, gel, or other topical product) that absorbs and / or reflects a portion of the sun's ultraviolet (UV) radiation, thereby helping to protect against the negative effects of sun exposure, such as sunburn, premature aging, etc.

[0013] As used herein, a "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 serious 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 treatment, the nature of other treatments, the particular compound or product / composition used, the cosmetically acceptable carrier utilized, and similar factors.

[0014] As used herein, "cosmetically acceptable" means that the ingredient it describes is suitable for use in contact with tissue (e.g., skin) without undue toxicity, incompatibility, instability, irritation, allergic reaction, etc.

[0015] As used herein, a "cosmetically acceptable active agent" is a compound (synthetic or natural) that has a cosmetic or therapeutic effect on the skin.

[0016] As used herein, "treat or treating" refers to the alleviation, reduction, prevention, amelioration, or elimination of the presence or symptoms of a condition or disorder.

[0017] As used herein, "substantially free" means that the referenced ingredient is not directly or intentionally added. Preferably, "substantially free" means containing less than about 1% by weight. More preferably, "substantially free" means containing less than about 0.5% by weight. Even more preferably, "substantially free" means containing less than about 0.1% by weight. The sunscreen composition may be completely free of an ingredient, i.e., may not contain any ingredient at all.

[0018] As used herein, a "UV absorber" refers to an active ingredient whose specific function is to absorb radiation in a certain portion of the ultraviolet spectrum (290 nm to 400 nm), e.g., an active ingredient having a saturation of at least about 1000 mol % for at least one wavelength within the ultraviolet spectrum as defined above. -1 cm -1 UV absorbers are distinguished from compounds with other functions that may also absorb ultraviolet light, including, for example, approved sun filters.

[0019] As used herein, "UV blocker" means a compound that reflects or scatters ultraviolet light.

[0020] As used herein, "phase stable" means that the aqueous and oil phases of the emulsion do not appreciably separate for at least two weeks at room temperature.

[0021] Unless otherwise indicated, percentages or concentrations refer to weight percentages or concentrations based on the total weight of the composition (i.e., %(W / W)). Unless otherwise specified, all ranges are inclusive of their endpoints, for example, "4 to 9" includes the endpoints 4 and 9.

[0022] Mineral UV active ingredients The sunscreen compositions of the present invention contain mineral UV active ingredients, specifically a combination of titanium dioxide (TiO2) and zinc oxide (ZnO).

[0023] The composition comprises about 9.0 wt % to about 32.0 wt % of the combination of TiO2 and ZnO, based on the total weight of the composition. Preferably, the composition comprises about 12.0 wt % to about 28.0 wt % of the combination of TiO2 and ZnO, based on the total weight of the composition.

[0024] For example, the composition may include about 23% by weight of a combination of TiO2 and ZnO, based on the total weight of the sunscreen composition.

[0025] The weight ratio of zinc oxide to titanium dioxide in the composition ranges from about 3:1 to about 1:1.

[0026] In one embodiment, the composition comprises about 6.64 wt. % TiO 2 and about 14.4 wt. % ZnO.

[0027] Examples of titanium dioxide that can be used are titanium dioxide, aluminum hydroxide, stearic acid sold under the trade name MICRO TITANIUM DIOXIDE MT-100TV by Tayca Corporation.

[0028] An example of a zinc oxide that can be used is zinc oxide, triethoxycaprylylsilane sold under the trade name Micro Zinc Oxide MZX-304OTS by Tayca Corporation.

[0029] Preferably, the composition is substantially free of UV absorbers. In particular, the composition may be substantially free of low molecular weight organic UV absorbers. As used herein, "low molecular weight organic UV absorbers" refers to UV absorbers that are organic molecules, typically aromatic compounds, that are conjugated with carbonyl moieties substituted at the ortho- or para-positions of aromatic rings, and have a molecular weight of less than 900 g / mol.

[0030] Preferably, the composition is completely free of low molecular weight organic UV absorbers.

[0031] Examples of low molecular weight organic UV absorbers include methoxycinnamate derivatives (such as octyl methoxycinnamate and isoamyl methoxycinnamate), camphor derivatives (such as 4-methylbenzylidene camphor, camphor benzalkonium methosulfate, and terephthalylidene dicamphorsulfonic acid), salicylic acid derivatives (such as octyl salicylate, ethylhexyl salicylate, and homosalate), benzone derivatives (such as dioxybenzone and oxybenzone), benzoic acid derivatives (such as aminobenzoic acid and octyldimethyl paraaminobenzoate), octocrylene, and and other β,β-diphenylacrylates, dioctyl butamido triazone, octyl triazone, avobenzone (butyl methoxydibenzoylmethane), menthyl anthranilate, triazone derivatives (such as ethylhexyl triazone (Uvinul® T150)), diethylhexyl butamido triazone (UVASorb® HEB), bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb® S), benzoate derivatives (diethylamino hydroxybenzoyl hexyl benzoate (Uvinul® A) Plus, etc.), benzotriazole derivatives (such as drometrizole trisiloxane (Mexoryl® XL), methylene bis-benzotriazolyl tetramethylbutylphenol (Tinosorb® M), tris-biphenyl triazine, (2-{4-[2-(4-diethylamino-2-hydroxy-benzoyl)-benzoyl]-piperazine-1-carbonyl}-phenyl)-(4-diethylamino-2-hydroxy-phenyl)-methanone, merocyanine derivatives, bis(butyl benzoate)diaminotriazine aminopropyl siloxane, and bis-ethylhexyloxyphenol methoxyphenyl triazine encapsulated in a polymer matrix.

[0032] The composition may, in certain embodiments, be free of polymeric organic UV absorbers. As used herein, "polymeric organic UV absorber" refers to a polymeric compound comprising organic chromophores attached to a polymer chain. For example, the polymer chain may be a polysiloxane having an average molecular weight, for example, greater than 6000 Daltons. Examples of such polysiloxane UV absorbers include, but are not limited to, Parsol® SLX and Polysilicone-15, available from DSM. These polysiloxanes are suitable for absorbing UV light in the UVB (λ) region of the spectrum. max = 312 nm) and are typically combined with UVA filters to achieve broad spectrum protection.

[0033] Alternatively, the composition may contain one or more polymeric organic UV absorbers, which, due to their relatively high molecular weight, are considered to be substantially non-absorbent to the skin.

[0034] Film-forming agents The composition also contains two film-forming agents, Triacontanyl PVP (a polymer with tricontanyl povidone or 2-pyrrolidinone, 1-ethenyl-, 1-triacontene) and VP / Hexadecene Copolymer (a vinylpyrrolidone / hexadecene copolymer).

[0035] The composition typically contains from about 0.5% to about 2.25% by weight of triacontanyl PVP, preferably from about 0.8% to about 1.5% by weight of triacontanyl PVP.

[0036] The composition typically contains from about 0.5% to about 3% by weight of VP / hexadecene copolymer, preferably from about 1% to about 2.5% by weight of VP / hexadecene copolymer.

[0037] Importantly, in order to achieve a high SPF value for the composition, the weight ratio of triacontanyl PVP to VP / hexadecene copolymer must be less than 1. For example, the weight ratio of triacontanyl PVP to VP / hexadecene copolymer may be about 0.5.

[0038] In one embodiment, the composition comprises about 1% by weight of triacontanyl PVP and about 2% by weight of VP / hexadecene copolymer.

[0039] Triacontanyl PVP (tricontanyl povidone or a polymer having 2-pyrrolidinone, 1-ethenyl-, 1-triacontene) is commercially available, for example, from ISP Freetown Fine Chemicals Inc. under the trade name Antaron™ WP-660 polymer.

[0040] VP / hexadecene copolymers are commercially available, for example, from ISP Freetown Fine Chemicals Inc. under the trade name Antaron™ V216 polymer.

[0041] SPF The sun protection factor (SPF) of a composition 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 Labsphere® UV-2000S UV Transmittance Analyzer (Labsphere, North Sutton, NH, USA). A test sample is then applied to the PMMA plate by rubbing with the operator's finger into a thin, even layer, using an application density of approximately 0.75 mg / cm2. The sample is allowed to dry for 15 minutes and then measured for UV absorbance using the same method. The absorbance measurement is used to calculate the SPF as known in the art using the following equation:

[0042]

number

[0043] In one embodiment, the composition has an SPF, as measured by the in vitro SPF test method, of at least about 25. In another embodiment, the composition has an SPF, as measured by the in vitro SPF test method, of at least about 30.

[0044] Shear Viscosity Test Method The composition advantageously has a low shear viscosity. Shear viscosity is measured by the following method: An appropriate amount of sample is loaded into an Anton Paar MCR302 rheometer equipped with a double-walled Couette geometry. The temperature is maintained at 25°C with a Peltier 5 element, and the shear rate is ramped from 1,000 to 0.1 s-1 using the default steady-state criteria in the rheometer control software RheoCompass.

[0045] The composition is preferably 1 s -1 It has a shear viscosity of less than 32 Pa·s.

[0046] Topical Compositions The sunscreen compositions can be used by topical application to a mammal, for example, by placing, wiping, or spreading the composition directly onto the skin, hair, or nails of a mammal, particularly a human.

[0047] The sunscreen composition is in the form of an oil-in-water emulsion containing a continuous aqueous phase and a discontinuous oil phase dispersed within the continuous aqueous phase. The composition is preferably phase stable.

[0048] The oil phase may be present in the form of discrete droplets or units having an average diameter of, for example, about 1 μm to about 1000 μm, such as about 1 μm to about 100 μm.

[0049] The weight percent of the aqueous phase in the composition may range from about 27.1% to about 85.95%, such as, for example, from about 40% to about 50%.

[0050] Sunscreen composition can be prepared by using the mixing and blending method well known in the field of sunscreen and cosmetics.Typically, sunscreen composition is prepared by preparing an oil phase that contains oil-soluble and oil-miscible ingredients, such as caprylic / capric triglyceride, ethylhexyl methoxycrylene, dimethicone, polyhydroxystearic acid, titanium dioxide, aluminum hydroxide, stearic acid, zinc oxide, triethoxycaprylylsilane, cetearyl olivate, sorbitan olivate, calcium sodium borosilicate, steareth-21, triacontanyl PVP and butyloctyl salicylate, and by mixing water with water-soluble or water-miscible ingredients, such as xanthan gum, disodium EDTA, sodium chloride, chlorphenesin, caprylyl glycol, phenoxyethanol, ethylhexylglycerin, glycerin and tocopheryl acetate to prepare an aqueous phase. The oil and water phases may then be mixed sufficiently to disperse the oil phase substantially uniformly throughout the water phase, such that the water phase is continuous and the oil phase is discontinuous.

[0051] Applicants have found that optimal dispersion of TiO2 in the composition promotes a high SPF. To increase dispersion of TiO2, it is added at room temperature (i.e., without heating) before adding ZnO.

[0052] The composition can be combined with a "cosmetically acceptable topical carrier," i.e., a carrier for topical use that can contain other ingredients dispersed or dissolved therein and that has acceptable properties that make it safe for topical use.

[0053] The composition may optionally contain a wide variety of additional oil-soluble and / or water-soluble materials, at concentrations established in the art, conventionally used in compositions for skin use, such as surfactants, pearlescent or opacifying agents, thickeners, emollients, conditioning agents, moisturizers, chelating agents, exfoliating agents, and additives that improve the appearance, feel, or scent of the cleansing composition, such as colorants, fragrances, preservatives, pH adjusters, etc., provided they do not interfere with the high SPF and low viscosity of the composition.

[0054] In one embodiment, the composition is substantially free or free of waxes, structurants, and fatty alcohols.

[0055] Water-soluble or water-dispersible polymers may be added to the composition. Water-dispersible polymers are typically composed of water-insoluble polymers that are finely divided and dispersed in a water carrier, possibly using a surfactant dispersing aid. Water-dispersible polymers can form films and improve the water resistance of the composition. Examples of water-soluble polymers include Polyaldo® 10-1-L (polyglyceryl-10 laurate) available from Lonza. Examples of water-dispersible polymers include water-dispersible polyurethanes such as Baycusan® C1000 (polyurethane-34) available from Bayer, Dow Corning® 2501 (bis-PEG-18 methyl ether dimethyl silane) available from Dow Corning, Eastman AQTM38S (polyester-5) available from Eastman Chemical, and Intelimer® 8600 (C8-22 alkyl acrylate / methacrylic acid crosspolymer) available from Air Products.

[0056] The sunscreen composition may contain certain additional film formers, provided they do not interfere with the SPF and low viscosity of the composition. Acceptable additional film formers include polyethylene with a molecular weight of 400, available from New Phase Technologies as Performalene® 400. Another suitable film former is polyethylene 2000 (molecular weight 2000), available from New Phase Technologies as Performalene®. Another suitable film former is a synthetic wax available from New Phase Technologies as Performa® V-825. Other typical film-formers include acrylates / acrylamide copolymers, acrylate copolymers, acrylates / C12-C22 alkyl methacrylate copolymers, polyethylene, waxes, VP / dimethiconyl acrylate / polycarbamyl polyglycol ester, butylated PVP, PVP / hexadecene copolymer, octadecene / MA copolymer, PVP / eicosene copolymer, tricontanyl PVP, rapeseed oil / treacle forsythia seed oil copolymer, decamethylcyclopentasiloxane (and) trimethylsiloxysilicate, dimethicone; acrylates / dimethicone copolymer, and mixtures thereof. In some cases, the film-former is an acrylates / C12-C22 alkyl methacrylate copolymer sold under the trade name Allianz™ OPT by Ashland.

[0057] Suitable emollients for use in the compositions include mineral oil, petrolatum, vegetable oils (e.g., triglycerides such as caprylic / capric triglyceride, sunflower (Helianthus Annuus) seed oil), waxes and other mixtures of fatty esters (including, but not limited to, esters of glycerol (e.g., isopropyl palmitate, isopropyl myristate, diisopropyl adipate, dicaprylyl carbonate, C12-15 alkyl benzoates, isononyl isononanoate, neopentyl glycol diheptonoate, neopentyl glycol dibenzoate, butyloctyl salicylate, ethylhexyl methoxycrylene)), hydrocarbons (e.g., isododecane, isohexadecane, squalane), ethers (e.g., PPG-15 stearyl ether, dicaprylyl ether), and silicone oils (such as dimethicone). In certain embodiments, it is a mixture of a triglyceride (eg, caprylic / capric triglyceride) and an ester of a glycol (eg, isopropyl myristate).

[0058] The sunscreen composition may include one or more emulsifiers. In one embodiment, the sunscreen composition includes steareth-21. Preferably, the sunscreen composition includes steareth-21, cetearyl-olivate, and sorbitan-olivate. The ingredients cetearyl-olivate and sorbitan-olivate are commercially available from Hallstar as Olivem 1000.

[0059] Examples of suitable solvents include propylene glycol, polyethylene glycol, polypropylene glycol, glycerol, 1,2,4-butanetriol, sorbitol esters, 1,2,6-hexanetriol, ethanol, and mixtures thereof.

[0060] In certain embodiments, the composition includes a pigment suitable for providing color or hiding power. The pigment may be suitable for use in color cosmetics, including compositions for application to hair, nails, and / or skin, particularly the face. Color cosmetic compositions include, but are not limited to, foundation, concealer, primer, blush, mascara, eye shadow, eyeliner, lipstick, nail polish, and tinted moisturizers. Pigments suitable for providing color or hiding power may be composed of iron oxides (including red and yellow iron oxides), titanium dioxide, ultramarine, and chromium or chromium hydroxide pigments, and mixtures thereof. The pigment may be a lake pigment precipitated on an inert binder, such as an insoluble salt, for example, 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, and yellow. Examples of lake pigments include Red #6, Red #7, Yellow #5, Violet #2, and Blue #1. The pigment can be an interference pigment.Examples of interference pigments include those containing mica substrate, bismuth oxychloride substrate and silica substrate, for example, the mica / bismuth oxychloride / iron oxide pigment commercially available as CHROMALITE pigment (BASF), titanium dioxide and / or iron oxide coated on mica, such as those commercially available as FLAMENCO pigment (BASF), mica / titanium dioxide / iron oxide pigment, including commercially available KTZ pigment (Kobo products), CELLINI pearl pigment (BASF), and borosilicate-containing pigment, such as REFLECKS pigment (BASF).

[0061] In one embodiment, the sunscreen composition includes a moisturizer. Examples of moisturizers include, but are not limited to, glycerin, pentylene glycol, and butylene glycol. In another embodiment, the sunscreen composition includes at least 3% by weight of glycerin. For example, the sunscreen composition may include about 5% by weight of glycerin.

[0062] In another embodiment, the sunscreen composition has a pH of about 7.0 to about 8.9. The sunscreen composition may have a pH of about 8.0.

[0063] In a further embodiment, the sunscreen composition comprises hyaluronic acid, hi another embodiment, the sunscreen composition comprises at least 0.01% by weight of hyaluronic acid.

[0064] The compositions may further comprise one or more other cosmetically acceptable active agents including, for example, anti-acne agents, shine control agents, antibacterial agents, anti-inflammatory agents, antifungal agents, antiparasitic agents, topical analgesics, antioxidants, keratolytic agents, moisturizers, nutrients, vitamins, energy boosters, antiperspirants, skin astringents, deodorants, stabilizers, skin anti-hardening agents, and skin conditioning agents.

[0065] The amount of other cosmetic active agents may range from about 0.001% to about 20% by weight of the composition, for example, from about 0.005% to about 10% by weight of the composition, such as from about 0.01% to about 5% by weight of the composition.

[0066] 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 argireline, syn-ake, acetyl dipeptide-31 amide and those containing copper), coenzyme Q10, amino acids such as proline, vitamins, lactobionic acid, acetyl coenzyme A, niacin, riboflavin, thiamine, ribose, electron transporters such as NADH and FADH2, natural extracts (such as aloe vera, feverfew, oat, dill, blackberry, paulownia, Picia anomala, and chicory), resorcinols such as 4-hexylresorcinol, curcuminoids, sugar amines such as N-acetylglucosamine, and derivatives thereof and mixtures thereof.

[0067] Examples of vitamins and their derivatives include, but are not limited to, vitamin A, B vitamins (such as vitamin B3, niacinamide, vitamin B5, and vitamin B12), vitamin C, vitamin K, and different forms of vitamin E (such as alpha, beta, gamma, or delta tocopherol), or mixtures and derivatives thereof.

[0068] 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 polypeptides). 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. Suitable natural extracts containing antioxidants 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 seed, green tea, pine bark, propolis, and ginger (Zingiber Officinale) root extract.

[0069] In one embodiment, the composition includes one or both of tocopherol and feverfew extract (eg, feverfew (Chrysanthemum Parthenium) flower / leaf / stem juice).

[0070] In one embodiment, the composition comprises phenoxyethanol, chlorphenesin, ethylhexylglycerin, and caprylyl glycol. This particular combination of preservatives surprisingly increases the shelf life of the composition according to the present invention. Preferably, the composition comprises about 0.6% by weight of phenoxyethanol, about 0.27% by weight of chlorphenesin, about 0.5% by weight of ethylhexylglycerin, and about 0.25% by weight of caprylyl glycol.

[0071] The present invention is further illustrated by the following non-limiting examples. [Example]

[0072] A series of TiO2 / ZnO sunscreen compositions without low molecular weight UV absorbers were made using the ingredients shown in Table 1. Compositions 3, 6, and 8-19 were in accordance with the present invention, and compositions 1, 2, 4, 5, and 7 were comparative examples. Composition 1 was AVEENO Calm+Restore Daily Moisturizer Mineral Sunscreen SPF 30, commercially available from Johnson & Johnson Consumer Inc.

[0073] All compositions were water-in-oil emulsions. They were generally prepared by mixing the oil and water phases sufficiently to disperse the oil phase substantially uniformly in the water phase, thereby making the water phase the continuous phase and the oil phase the discontinuous phase. The oil phase ingredients were caprylic / capric triglyceride, ethylhexyl methoxycrylene, dimethicone, polyhydroxystearic acid, titanium dioxide, aluminum hydroxide, stearic acid, zinc oxide, triethoxycaprylylsilane, cetearyl olivate, sorbitan olivate, calcium sodium borosilicate, steareth-21, triacontanyl PVP, and butyloctyl salicylate. The water phase ingredients were water, xanthan gum, disodium EDTA, sodium chloride, chlorphenesin, caprylyl glycol, phenoxyethanol, ethylhexylglycerin, glycerin, and tocopheryl acetate.

[0074] The compositions were tested for in vitro SPF using the in vitro SPF test method described above, and the results are shown in Tables 1, 2, and 3.

[0075] The shear viscosity of some compositions was also measured using the Shear Viscosity Test Method and the results are shown in the Table.

[0076] The results show that only compositions according to the present invention containing TiO, ZnO, triacontanyl PVP, and VP / hexadecene copolymer, where the weight ratio of triacontanyl PVP to VP / hexadecene copolymer was less than 1, provided SPF readings of at least 25 as measured by the in vitro SPF test method. Furthermore, all of these compositions had shear viscosities less than 32 Pa s and exhibited a desirable, light skin feel.

[0077] [Table 1]

[0078] [Table 2]

[0079] [Table 3] [Example]

[0080] Compositions 1 and 3 were tested in vivo for SPF using the methodology described in the US FDA OTC monograph for sunscreens (US Food and Drug Administration Over-the-Counter Monograph M020: Sunscreen Drug Products for Over-the-Counter Human Use (posted September 24, 2021) Final Executive Order (OTC000006), effective upon enactment of the Coronavirus Aid, Relief, and Economic Security Act (CARES Act), Public Law 116-136, March 27, 2020).

[0081] Composition 3 according to the present invention provided an in vivo SPF of 70, while Composition 1 provided an in vivo SPF of only 33. These results confirm the unexpectedly high photoprotective activity of compositions according to the present invention containing triacontanyl PVP and VP / hexadecene copolymer, where the weight ratio of triacontanyl PVP to VP / hexadecene copolymer is less than 1. Compositions 1 and 3 both contained triacontanyl PVP and VP / hexadecene copolymer. However, the weight ratio of the film-forming agent in Composition 1 was 1.5, and the weight ratio of the film-forming agent in Composition 3 was 0.5.

[0082] [Embodiment] (1) A sunscreen composition comprising (i) TiO2, (ii) ZnO, (iii) triacontanyl PVP, and (iv) VP / hexadecene copolymer, said composition being an oil-in-water emulsion substantially free of low molecular weight organic UV absorbers, wherein the weight ratio of (iii):(iv) is less than 1, and said composition provides an in vitro SPF of at least 25 as measured by an In Vitro SPF Test Method. (2) The sunscreen composition of claim 1, comprising less than 25% by weight of a combination of titanium dioxide and zinc oxide, based on the total weight of the sunscreen composition. (3) The sunscreen composition of embodiment 1, comprising about 8% by weight of TiO2 and about 15% by weight of ZnO. (4) The sunscreen composition of embodiment 1, wherein the weight ratio of (iii):(iv) is less than 0.60. (5) The sunscreen composition of embodiment 1, wherein the weight ratio of (iii):(iv) is about 0.50.

[0083] (6) The sunscreen composition of embodiment 1, further comprising about 5% by weight of glycerin. (7) The sunscreen composition of embodiment 1, further comprising steareth-21, cetearyl-olivate, and sorbitan-olivate. (8) 1 s at 25°C -1 2. The sunscreen composition of embodiment 1, having a shear viscosity of less than 32 Pa.s at 100°C. (9) The sunscreen composition of embodiment 1, further comprising phenoxyethanol, chlorphenesin, ethylhexylglycerin, and caprylyl glycol.

Claims

1. (i) TiO ２ 1. A sunscreen composition comprising: (ii) ZnO; (iii) triacontanyl PVP; and (iv) VP / hexadecene copolymer, said composition being an oil-in-water emulsion substantially free of low molecular weight organic UV absorbers; wherein the weight ratio of (iii):(iv) is less than 1; and said composition provides an in vitro SPF of at least 25 as measured by an in vitro SPF test method.

2. 10. The sunscreen composition of claim 1, comprising less than 25% by weight of a combination of titanium dioxide and zinc oxide, based on the total weight of the sunscreen composition.

3. Approximately 8% by weight of TiO ２ and about 15% by weight of ZnO.

4. 10. The sunscreen composition of claim 1, wherein the weight ratio of (iii):(iv) is less than 0.

60.

5. 10. The sunscreen composition of claim 1, wherein the weight ratio of (iii):(iv) is about 0.

50.

6. 10. The sunscreen composition of claim 1, further comprising about 5% by weight of glycerin.

7. 10. The sunscreen composition of claim 1, further comprising steareth-21, cetearyl-olivate, and sorbitan-olivate.

8. 1s at 25°C －１ 10. The sunscreen composition of claim 1, having a shear viscosity of less than 32 Pa.s at 100°C.

9. 10. The sunscreen composition of claim 1, further comprising phenoxyethanol, chlorphenesin, ethylhexylglycerin, and caprylyl glycol.

Images