WO2023201023A1 - Sprayable-skin formulations - Google Patents

Sprayable-skin formulations Download PDF

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Publication number
WO2023201023A1
WO2023201023A1 PCT/US2023/018612 US2023018612W WO2023201023A1 WO 2023201023 A1 WO2023201023 A1 WO 2023201023A1 US 2023018612 W US2023018612 W US 2023018612W WO 2023201023 A1 WO2023201023 A1 WO 2023201023A1
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WO
WIPO (PCT)
Prior art keywords
formulation
skin
sprayable
water
film
Prior art date
Application number
PCT/US2023/018612
Other languages
French (fr)
Inventor
Henry Fong
Albert Hirschon
Georgina Hum
Original Assignee
Sri International
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sri International filed Critical Sri International
Publication of WO2023201023A1 publication Critical patent/WO2023201023A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/046Aerosols; Foams
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241Containing particulates characterized by their shape and/or structure
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87Polyurethanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60Particulates further characterized by their structure or composition
    • A61K2800/61Surface treated
    • A61K2800/62Coated
    • A61K2800/624Coated by macromolecular compounds

Definitions

  • Skin formulations can be used for a variety of cosmetic and other purposes.
  • skin formulations can provide ultraviolet (UV) sun protection, a barrier between the skin and other cosmetic products, and color correction and/or blemish coverage.
  • UV ultraviolet
  • skin formulation can be difficult to apply, must be reapplied throughout the day or are otherwise not durable, are allergenic, cannot be applied consistently or to the entire intended skin surface area, and/or are not sufficiently elastic to move with skin movement, among other limitations.
  • the present invention is directed to overcoming the above-mentioned challenges and others related to skin formulations, such as for cosmetics.
  • Various aspects of the present disclosure are directed to a sprayable-skin formulation comprising a polyurethane polymer solution, a water-dispersible polymer solution, an ultraviolet (UV) protecting agent, a particle coating agent, and a water- miscible solvent.
  • UV ultraviolet
  • the sprayable-skin formulation is sprayable and configured to cure and form an elastic and UV protecting film.
  • the water-miscible solvent is selected from: water, ethanol, and a combination thereof.
  • ethanol is configured to increase evaporabihty of the sprayable-skin formulation in response to application of the sprayable-skin formulation.
  • the polyurethane polymer solution is a dispersion comprising one of a di cyclohexylmethane diisocyanate copolymer and a hexamethylene diisocyanate copolymer.
  • the water-dispersible polymer solution is an emulsion comprising an acrylates/polytrimethylsiloxymethacrylate copolymer and laureth-1 phosphate polymer.
  • the sprayable-skin formulation comprises: about 45 weight percent (wt%) to about 85 wt% of the polyurethane polymer solution based on the total weight of the sprayable-skin formulation, and about 5 wt% to about 15 wt% of the water-dispersible polymer solution based on the total weight of the sprayable-skin formulation. In some aspects, the sprayable-skin formulation comprises: about 0.
  • the polyurethane polymer solution comprises a water-based polyurethane dispersion formed of: about 30 wt% to about 40 wt% polyurethane based on the total weight of the water-based polyurethane dispersion, and a balance of water and surfactants.
  • the UV protecting agent comprises inorganic particles configured to absorb UV radiation and the particle coating agent is configured to coat the inorganic particles and disperse the inorganic particles in the formulation.
  • the inorganic particles have a diameter less than 100 nanometers.
  • the particle coating agent is selected from polyethylene glycol (PEG)- 12 dimethicone, dimethicon PEG-8 Laurate, and a combination thereof.
  • the UV protecting agent is selected from: zinc oxide, titanium dioxide, and a combination thereof.
  • the UV protecting agent is a broadband UV absorbing agent formed of a combination of different types of inorganic particles configured to absorb UVA and UVB light in a range of about 280 nanometers to about 400 nanometers.
  • the sprayable-skin formulation further comprises at least one of: a color pigment mixture, a pigment coating agent for particles of the color pigment mixture, an antioxidant and metal chelate, a functional filler, and a UV protection booster.
  • kits for forming a sprayable-skin formulation comprising: about 45 wt% to about 85 wt% of a polyurethane polymer dispersion based on the total weight of the formulation, about 5 wt% to about 15 wt% of a water-dispersible polymer emulsion based on the total weight of the formulation, about 0.5 wt% to about 15 wt% of an UV protecting agent based on the total weight of the formulation, about 0.5 wt% to about 15 wt% of a particle coating agent based on the total weight of the formulation, and a balance of a water- miscible solvent.
  • the sprayable-skin formulation is sprayable as an aerosol and configured to cure and form an elastic and UV protecting film on skin within about 1 minute to about 5 minutes after spraying.
  • the water-miscible solvent is selected from: about 1 wt % to about 10 wt% of ethanol based on the total weight of the formulation, about 5 wt% to about 20 wt% of water based on the total weight of the formulation, and a combination thereof.
  • the kit further comprises about 0.01 wt% to about 2 wt% of color pigments based on the total weight of the formulation, and about 0.01 wt% to about 2 wt% of pigment coating agent based on the total weight of the formulation.
  • the kit comprises a ratio of the polyurethane polymer dispersion to the water-dispersible polymer emulsion of between about 5: 1 and about 10:1.
  • the kit further comprises at least one of: about 0.01 wt% to about 0.5 wt% of an antioxidant and metal chelate based on the total weight of the formulation, about 0.01 wt% to about 10 wt% of a functional filler based on the total weight of the formulation, and about 0.01 wt% to about 5 wt% of a UV protection booster based on the total weight of the formulation.
  • the kit further comprises an aerosol container with the sprayable-skin formulation in the form of one of an emulsion and a suspension containing the polyurethane polymer dispersion, the water-dispersible polymer emulsion, the UV protecting agent, the particle coating agent, and water.
  • Various aspects of the present disclosure are directed to method of applying a sprayable-skin formulation to skin. Then method comprises spraying a layer of sprayable-skin formulation to skin, the sprayable-skin formulation comprising: a polyurethane polymer dispersion, a water-dispersible polymer emulsion, a UV protecting agent, a particle coating agent, and a water-miscible solvent. The method further comprises drying, via exposure to air, the layer to form an elastic and UV protecting film on the skin.
  • the film is durable such that the film is cohesive and configured to remain intact on the skin in response to contact, and the method further comprises removing the film by at least one of peeling the film and applying water to the film.
  • the method further comprises applying a layer of other cosmetics on top of film, wherein the sprayable-skin formulation comprises: about 45 wt% to about 85 wt% of the polyurethane polymer dispersion based on the total weight of the sprayable-skin formulation, about 5 wt% to about 15 wt% of the water- dispersible polymer emulsion based on the total weight of the sprayable-skin formulation, about 0.
  • the film comprises about 5 wt% to about 20 wt% of the UV protecting agent based on the total weight of the film and is configured to provide at least Sun Protection Factor (SPF) 15.
  • SPF Sun Protection Factor
  • the film is between about 5 microns and about 80 microns and substantially uniform in thickness.
  • FIGs. 1A-1B illustrate example sprayable-skin formulations, in accordance with the present disclosure.
  • FIG. 2 illustrates an example kit for forming a sprayable-skin formulation, in accordance with the present disclosure.
  • FIG. 3 illustrates an example method of applying a sprayable-skin formulation, in accordance with the present disclosure.
  • FIG. 4 illustrates example pre-mixtures, in accordance with the present disclosure.
  • FIGs. 5A-5B illustrate example films formed from a polyurethane polymer formulation, in accordance with the present disclosure.
  • FIGs. 6A-6C illustrate example films formed from modified polyurethane polymer formulations, in accordance with the present disclosure.
  • FIGs. 7A-7B illustrate example films formed from hybrid polymer formulations, in accordance with the present disclosure.
  • FIG. 8 is a graph illustrating the assessed breathability of the hybrid polymer formulation, in accordance with the present disclosure.
  • FIGs. 9A-9D are images of resulting films formed using the hybrid polymer formulation of Candidate A, in accordance with the present disclosure.
  • FIG. 10 is an image of a film formed using the modified polyurethane polymer formulation of Candidate B, in accordance with the present disclosure.
  • FIGs. 11 A-l IB are images of a film formed using the hybrid polymer formulation of Candidate A with titanium dioxde added, in accordance with the present disclosure.
  • FIGs. 12A-12B are images of a film formed using the hybrid polymer formulation of Candidate A with an iron oxide colorant added, in accordance with the present disclosure.
  • FIGs. 13A-13D are graphs showing the storage stability results, in accordance with the present disclosure.
  • FIG. 14 is an image of different polymer formulations having the different color mixtures from Table 20, in accordance with the present disclosure.
  • FIGs. 15A-15B are images of films formed from hybrid polymer formulations with UV protecting agents, in accordance with the disclosure.
  • FIG. 16 is a graph showing example transmissions of different candidates, in accordance with the present disclosure.
  • FIG. 17 is a graph illustrating the UV-vis transmission for films formed of the polymer formulations illustrated by Table 19 in accordance with the present disclosure.
  • FIGs. 18A-18B illustrate example absorbance of films formed of polymer formulations, in accordance with the present disclosure.
  • Various products such as skin formulations, may be used for cosmetics and other purposes.
  • cosmetic users apply cosmetic products directly to the skin, which can lead to allergic reactions.
  • the cosmetics may wear off over the day and have to reapplied, which can be burdensome for the users and cause extra use of the product.
  • reapplication of the cosmetics and sunblocks throughout the day is often necessary to maintain the desired appearance and function.
  • removal of cosmetics from the skin can be difficult, requiring copious amounts of w ater, soap, and/or other cleaning products.
  • Some cosmetic products include a polymer film for the face that reduces the appearance of winkles under the eye.
  • such polymer film products must be applied by hand and use a precious metal (platinum) within the formulation. Furthemiore, the polymer film can often only be applied to a small area, such as under the eye.
  • Embodiments in accordance with the present disclosure are directed to a sprayable-skin formulations, kits, pre-mixtures, and methods associated therewith that can be used to form or involve forming a uniform and durable film.
  • the film can be formed on skin of the user and may be referred to as an artificial skin.
  • the sprayable- skin formulation can act as a durable barrier between the user’s skin and cosmetics, can be applied to the whole face and/or other skin area on the body and as a continuous and uniform film, and can be easily removed.
  • the sprayable-skin formulation can be sprayed onto the skin and allowed to dry to form the film that provides ultraviolet (UV) sun protection.
  • UV ultraviolet
  • the sprayable-skin formulation can contain UV protecting agents and can also contain colorants (e.g., color pigments such as iron oxides) to create color, similar to a cosmetic foundation formulation.
  • the sprayable-skin formulation can be applied to the skin through an aerosolizing, handheld spray applicator and dries on the skin to form the cohesive and elastic film.
  • the formed film can be sufficiently durable to last throughout the day without reapphcation and such that cosmetics can be applied on top of the dried film.
  • the dried film e.g., artificial skin
  • the film product (e.g., artificial skin) is a polymer formulation consisting primarily of polyurethane and water-dispersible polymers in a water-based solution (e.g., in water with optional additives, such as ethanol).
  • a water-based solution e.g., in water with optional additives, such as ethanol.
  • additives can be incorporated into the formulation to create properties such as UV protection, color, improved spray-ability (e.g., aerosolizing ability), and long-term storage stability (e.g., preservatives).
  • the polymer formulation is comprised of the polyurethane and water-dispersible polymer solutions in an amount of at least 50 weight percent of the total weight of the polymer formulation, and additives of inorganic UV protecting agents and coating agents, with the polymer formulation being sprayable or having aerosolizing ability'.
  • the disclosed approach involves a water-based polymer formulation consisting of polyurethane and silicone acrylate polymers and other additives for UV sun protection, color, improved spray-ability (e.g., aerosolizing ability), long-term storage stability (e.g., preservatives), among others.
  • the following are example properties or characteristics of the spray able-skin formulation and the resulting film formed on skin.
  • the formulation can be sprayed as an aerosol onto the skin, avoiding more laborious application methods that require use of a hand or finger, brush, or similar methods. Spraying the formulation can also provide better application uniformity. Additionally, the formulation can dry within minutes and form a cohesive and elastic film that is thin (e.g., less than 80 microns) and provides comfortable, long-lasting wear.
  • the film can be transparent, translucent, or opaque with color in different embodiments. In some embodiments, the film can function as a foundation layer on the skin.
  • the film is sufficiently durable that other cosmetics can be applied on top of it by brush, puff, or hand/fingers without damaging the film.
  • the artificial skin can contain UV protecting (sunblock) agents such as zinc oxide, titanium dioxide, or other UV protecting agents. Since these agents are incorporated within the film, the agents can have greater lifetimes, reducing the need to reapply new sunscreen. As another example property, since the film is elastic, it can be removed easily and without requiring copious amounts of water, soap, and/or other cleaning agents. The film can be peeled when dry, with water, or removed by gentle application of a moist towel/tissue, or other cleaning products.
  • the formulation may contain any or all of the following ingredients: polyurethane polymer dispersed in solution (e.g., Baycusan® C 1001, Baycusan® C 1004), a silicon acrylate emulsion (e.g.
  • sprayable-skin formulation includes and/or refers to a formulation which is sprayable onto skin of a user.
  • a polyurethane polymer solution includes and/or refers to a solution that contains an amount of a polyurethane polymer.
  • a polymer includes and/or refers to a substance or other material containing chains of multiple monomer units.
  • a water-dispersible polymer solution includes and/or refers to a solution that contains a polymer that disperses in water.
  • a UV protecting agent includes and/or refers to an element and/or compound, such as particles, which provide protection from UV radiation.
  • a particle coating agent includes and/or refers to an element and/or compound that coats the UV protecting agent, and which can aid in dispersibility of the UV protecting agent in water.
  • a solution includes and/or refers to a mixture of two or more substances, such as a homogeneous mixture of two or more substances (e.g., polymer and solvent) in relative amounts.
  • a solute is the substance dissolved in another mixture, referred to as the solvent.
  • the solvent can dissolve the solute, resulting in the solution.
  • a solvent includes and/or refers to a substance that dissolves a solute.
  • a formulation includes and/or refers to a combination of substances, such as a solution in the form of an emulsion or suspension.
  • an additive includes and/or refers to an element and/or compound added to the formulation to effect a desired change in property of the formulation and/or resulting film, such as the rate of evaporation, adding fragrance, and/or stability.
  • a color pigment mixture includes and/or refers to a mixture of at least one type of color substance (e.g., a color pigment).
  • the color pigments include substances exhibiting color that may be insoluble in water.
  • a pigment coating agent includes and/or refers to an element and/or compound that coats the particles of the color pigment, and which can aid in dispersibility of the color pigments in water.
  • An antioxidant and metal chelate includes and/or refers to a compound containing a ligand bounded to a central metal atom, and which can exhibit antioxidant properties.
  • a functional filler includes and/or refers to a substance or other compound which adjusts sensorial and/or optical properties and/or application behavior of the formulation.
  • a UV protection booster includes and/or refers to an additive and/or mixture of additives that reflects UV light and can increase UV protection.
  • FIGs. 1A-1B illustrate example sprayable-skin formulations, in accordance with the present disclosure.
  • the example sprayable-skin formulation 100, 101 can be used to form an elastic film on skin of a user.
  • the elastic protecting film may be cosmetic.
  • the user can include a human or other organism having skin.
  • the sprayable-skin formulation 100 includes a polyurethane polymer solution 102.
  • the polyurethane polymer solution 102 can assist with forming of the film, which can be referred to as providing filmformability to the sprayable-skin formulation 100.
  • the polyurethane polymer solution 102 is a dispersion comprising a di cyclohexylmethane diisocyanate copolymer or a hexamethylene diisocyanate copolymer.
  • the polyurethane polymer solution 102 comprises a water-based polyurethane dispersion formed of about 30 weight percent (wt%) to about 40 wt% polyurethane based on the total weight of the polyurethane polymer solution 102, and a balance of water and, optionally, surfactants.
  • Some specific example polyurethane polymer solutions include Baycusan® C 1001 or Baycusan® C 1004.
  • the sprayable-skin formulation 100 includes about 45 wt% to about 85 wt% of the polyurethane polymer solution 102 based on the total weight of the sprayable-skin formulation 100.
  • the polyurethane polymer solution 102 is between about 50 wt% and about 80 wt% based on the total weight of the spray able-skm formulation 100.
  • the polyurethane polymer solution 102 is between about 60 wt% and about 80 wt%, about 65 wt% and about 80 wt%, about 70 wt% and about 80 wt%, about 75 wt% and about 80 wt%, about 60 wt% and about 75 wt%, about 60 wt% and about 70 wt%, about 65 wt% and about 80 wt%, or about 65 wt% and about 75 wt% based on the total weight of the sprayable- skin formulation 100, among other ranges.
  • the spray able-skin formulation 100 further includes a water-dispersible polymer solution 104.
  • the water-dispersible polymer solution 104 can provide at least one of strength and film-formability to the sprayable-skin formulation 100 and/or the resulting film, as further described herein.
  • the water-dispersible polymer solution 104 comprises a silicon acrylate polymer in solution, which is sometimes herein referred to as “a silicon acrylate polymer solution”.
  • the water-dispersible polymer solution 104 is an emulsion comprising an acrylates/polytrimethylsiloxymethacrylate copolymer and laureth-1 phosphate polymer.
  • the water-dispersible polymer solution 104 comprises a waterbased silicon acrylate emulsion formed of about 30 wt% to about 40 wt% silicon acrylate polymer based on the total weight of the water-dispersible polymer solution 104, and a balance of water and, optionally, surfactants.
  • a water-dispersible polymer solution 104 include, but not limited to, DOWSILTM FA 410, PEG-40, among other water-dispersible polymers, including emulsions.
  • the sprayable-skin formulation 100 includes about 5 wt% to about 15 wt% of the water-dispersible polymer solution 104 based on the total weight of the water-dispersible polymer solution 104.
  • the water- dispersible polymer solution 104 can be between about 5.2 wt% and about 12 wt%, about 5.4 wt% and about 10 wt%, or about 5.6 wt% and about 8 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges.
  • the sprayable-skin formulation 100 includes a ratio of the polyurethane polymer solution 102 and the water-dispersible polymer solution 104 of between about 5: 1 and about 10: 1.
  • the ratio can be between about 6: 1 and about 10: 1, about 7: 1 and about 10:1, about 8: 1 and about 10: 1, about 9: 1 and about 10: 1, about 5: 1 and about 9: 1, about 5: 1 and about 8: 1, about 5: 1 and about 7: 1, about 5 : 1 and about 6 : 1 , or about 6 : 1 and about 8:1, among other ranges.
  • the ratio can be about 10: 1, about 9: 1, about 8: 1, about 7: 1, about 6: 1, or about 5: 1.
  • the combination of polyurethane polymer solution 102 and the water-dispersible polymer solution 104 can provide elasticity and result in fonnation of a cohesive film, as further described below.
  • the sprayable-skin formulation 100 can further include a UV protecting agent 106.
  • Example UV protecting agents 106 include minerals (e.g., zinc oxide, titanium dioxide) and organic chemical compounds. Some specific example UV protecting agents 106 include zinc oxide, titanium dioxide, aminobenzoic acid (PABA), Avobenzone, Cinoxate, Dioxybenzone, ecamsule, homosalate.
  • PABA aminobenzoic acid
  • Avobenzone Cinoxate
  • Dioxybenzone Dioxybenzone
  • ecamsule homosalate.
  • the UV protecting agent 106 can include inorganic particles configured to absorb UV radiation.
  • the inorganic particles can include minerals, such as zinc oxide and/or titanium dioxide.
  • the UV protecting agent 106 is a broadband UV absorbing agent formed of a combination of different types of inorganic particles configured to absorb UVA and UVB light in a range of about 280 nanometers (nm) to about 400 nm.
  • the UV protecting agent 106 can include a combination of zinc oxide and titanium dioxide, or one of zinc oxide and titanium dioxide.
  • the UV protecting agent 106 in addition to providing UV protection, the UV protecting agent 106 can provide color.
  • the UV protecting agent 106 can additionally be an antibacterial and antiinflammatory, such as for treating acne.
  • zinc oxide is antibacterial and anti-inflammatory .
  • the UV protecting agents 106 are mineral-based, such as zinc oxide or titanium dioxide.
  • Mineral-based UV protecting agents can serve as a shield against UV radiation and sit on the surface of the skin.
  • the mineral-based UV protecting agents can reflect sunlight away from the skin, do not absorb into the skin, provide UV protection as soon as applied, provide color to hide skin blemishes, are not chemical based, and have other properties, such as being antibacterial and anti-inflammatory.
  • the mineral-based UV protecting agent can provide a white color
  • the skin-sprayable formulation 100 can include other color pigments to correct the white coloration, as further described below.
  • embodiments are not so limited and can include other types of UV protecting agents 106.
  • the inorganic particles can have a diameter less than 100 nm. Inorganic particles with a diameter of 100 nm or less may absorb higher levels of UV radiation than particles that are larger than 100 nm.
  • the UV protecting agent 106 includes inorganic particles of zinc oxide, titanium dioxide, or a combination of zinc oxide and titanium dioxide. Zinc oxide can provide protection from UVB light and titanium dioxide can provide protection from UVA light.
  • Example inorganic particles of zinc oxide include a combination of zinc oxide and triethoxy caprylyl silane, such as Zano® 10 plus.
  • Example inorganic particles of titanium dioxide can include a combination of titanium dioxide, aluminum hydroxide, and hydrogen dimethicone or a combination of titanium dioxide and hydrogen dimethicone, such as Avo TiO2, STR-100-LP TiO2, Kobo A35 TiO2, and others.
  • the inorganic particles include Zano® 10 plus and/or Kobo A35.
  • a diameter of the particle e.g., for UV protecting agents, functional fillers, and others refers to the diameter of a single spherical particle, or the average diameter of non-spherical particles.
  • the diameter or average diameter of the particles may be measured using a volume based size distribution analytical chemical analysis. The size of the particles may be measured by using a static light scattering technique, such as laser diffraction.
  • the sprayable-skin formulation 100 includes between about 0 wt% and 10 wt% of the UV protecting agents 106. In some embodiments, the amount of UV protective agents is between about 0.1 wt% to about 10 wt% based on the total weight of the sprayable-skin formulation 100.
  • the amount of UV protective agent 106 is between about 0 wt% and about 6 wt%, about 0 wt% and about 4 wt%, about 1 wt% and about 10 wt%, about 2 wt% and about 10 wt%, about 3 wt% and about 10 wt%, about 4 wt% and about 10 wt%, about 5 wt% and about 10 wt%, about 6 wt% and about 10 wt%, about 8 wt% and about 10 wt%, about 1 wt% and about 8 wt%, about 1 wt% and about 8 wt%, about 1 wt% and about 6 wt%, about 1 wt% and about 4 wt%, about 1 wt% and about 2 wt%, about 2 wt% and about 8 wt%, about 4 wt% and about 8 wt%, or about 6 wt% and about 18 wt% based on the
  • the sprayable-skin formulation 100 can further include a particle coating agent 108.
  • the particle coating agent 108 is configured to coat the UV protecting agent 106 and to aid in dispersibility of inorganics (e.g., the UV protecting agent 106) in the sprayable-skin formulation 100, which is aqueous.
  • the particle coating agent 108 can coat the inorganic particles and disperse the inorganic particles in the formulation 100.
  • the particle coating agent 108 includes polyethylene glycol (PEG)-12 dimethicone, dimethicon PEG-8 Laurate, or a combination thereof.
  • the sprayable-skin formulation 100 can include about 0.5 wt% to about 15 wt% of the particle coating agent 108 based on the total weight of the sprayable-skin formulation 100.
  • the amount of particle coating agent 108 is between about 1 wt% and about 15 wt%, about 2 wt% and about 15 wt%, about 5 wt% and about 15 wt%, about 10 wt% and about 15 wt%, about 0.5 wt% and about 10 wt%, about 0.5 wt% and about 5 wt%, about 0.5 wt% and about 2 wt%, about 0.5 wt% and about 1 wt%, about 1 wt% and about 10 wt%, about 2 wt% and about 10 wt%, about 5 wt% and about 10 wt%, or about 10 wt% and about 15 wt% based on the total weight of the sprayable-s
  • the particle coating agent 108 can include an ethoxylated poly dimethylsiloxane.
  • the amount of ethoxylated poly dimethylsiloxane is between about 0 wt% and about 3 wt%, about 0 wt% and about 2.5 wt%, about 0 wt% and about 2.0 wt%, about 0 wt% and about 1.5 wt%, about 0 wt% and about 1 wt%, about 0.10 wt% and about 3 wt%, about 0.10 wt% and about 2.5 wt%, about 0.10 wt% and about 2 wt%, about 0.10 wt% and about 1.5 wt%, about 0.
  • ethoxylated poly dimethylsiloxane includes PEG-12 dimethicone, such as Silsurf® D212-CG.
  • the particle coating agent 108 can include a lubricant.
  • the amount of lubricant is between about 0.5 wt% and about 12 wt%, about 1 wt% and about 10 wt%, about 0.5 wt% and about 10 wt%, about 0.5 wt% and about 5 wt%, about 0.5 wt% and about 3 wt%, about 0.5 wt% and about 1 wt%, about 1 wt% and about 15 wt%, about 5 wt% and about 15 wt%, about 8 wt% and about 15 wt%, about 10 wt% and about 15 wt%, about 2 wt% and about 10 wt%, about 5 wt% and about 10 wt%, or about 5 wt% and about 8 wt% based on the total weight of the spray able-skin formulation 100, among other range
  • the particle coating agent 108 can include the ethoxylated poly dimethylsiloxane and the lubricant.
  • the particle coating agent 108 can include a combination of PEG- 12 dimethicon and dimethicon PEG-8 Laurate.
  • the sprayable-skm formulation 100 can be water-based and further includes a water-miscible solvent 112.
  • water-miscible solvents include water, ethanol, and water and ethanol, among others that are miscible in water.
  • the water-miscible solvent 112 can assist with evaporation and/or be in the form of an emulsifier to incorporate additives and to enhance SPF values or other cosmetic components.
  • the water-miscible solvent 112 can provide or increase evaporability of the spray able-skin formulation 100 in response to application thereof.
  • the sprayable-skin formulation 100 includes a water-miscible solvent 112 of water and ethanol. The combination of water and ethanol can provide viscosity, sprayability, and evaporation properties.
  • the sprayable-skin formulation 100 includes about 5 wt% to about 30 wt% of water-miscible solvent 112 based on the total weight of the sprayable-skin formulation 100.
  • the amount of water-miscible solvent 112 is between about 5 wt% and about 25 wt%, about 5 wt% and about 20 wt%, about 5 wt% and about 15 wt%, about 5 wt% and about 10 wt%, about 10 wt% and about 30 wt%, about 15 wt% and about 30 wt%, about 20 wt% and about 30 wt%, about 25 wt% and about 30 wt%, about 10 wt% and about 25 wt%, about 10 wt% and about 20 wt%, or about 15 wt% and about 20 wt% based on the total weight of the spray able- skin formulation 100, among other ranges.
  • the water-miscible solvent 112 includes water.
  • the amount of water is between about 2 wt% and 20 wt%, about 2 wt% and about 18 wt%, about 2 wt% and about 16 wt%, about 4 wt% and about 14 wt%, about 5 wt% and about 18 wt%, about 5 wt% and about 15 wt%, about 5 wt% and about 10 wt%, about 10 wt% and about 20 wt%, about 10 wt% and about 15 wt%, or about 10 wt% and about 12 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges.
  • the above listed amounts of water are referring to additional water added to the sprayable-skin formulation 100 as a solvent and does not include the wt% of water in the polyurethane polymer solution 102 and the water-dispersible polymer solution 104.
  • the water-miscible solvent 112 includes ethanol.
  • the sprayable-skin formulation 100 includes about 1 wt% to about 10 wt% of ethanol, based on the total weight of the sprayable-skin formulation 100.
  • the amount of ethanol is between about 1 wt% and about 8 wt%, about 1 wt% and about 5 wt%, about 1 wt% and about 2 wt%, about 2 wt% and about 10 wt%, about 5 wt% and about 10 wt%, about 8 wt% and about 10 wt%, about 2 wt% and about 8 wt%, about 5 wt% and about 8 wt%, or about 5 wt% and about 6 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges.
  • the sprayable-skin formulation 100 includes ethanol in an amount between about 0 wt% and about 10 wt%, about 0 wt% and about 8 wt%, or about 1 wt% and about 6 wt%, among other ranges.
  • the water-miscible solvent 112 includes water and ethanol in any of the above provided ranges and combinations.
  • the sprayable-skin formulation 100 includes between about 2 wt% and 20 wt% water and about 1 wt% and about 10 wt% ethanol based on the total weight of the sprayable-skin formulation 100.
  • the sprayable-skin formulation 100 includes between about 5 wt% and 20 wt% water and about 1 wt% and about 10 wt% ethanol, about 5 wt% and 15 wt% water and about 1 wt% and about 10 wt% ethanol, about 5 wt% and 10 wt% water and about 1 wt% and about 10 wt% ethanol, about 10 wt% and 20 wt% water and about 1 wt% and about 10 wt% ethanol, about 15 wt% and 20 wt% water and about 1 wt% and about 10 wt% ethanol, about 5 wt% and 20 wt% water and about 5 wt% and about 10 wt% ethanol, about 5 wt% and 20 wt% water and about 8 wt% and about 10 wt% ethanol, about 5 wt% and 20 wt% water and about 1 wt% and about 5 wt% ethanol,
  • the spray able-skin formulation 100 further includes additional components.
  • the sprayable- skin formulation can include a color pigment mixture, a pigment coating agent for particles of the color pigment mixture, an antioxidant and metal chelate, a functional filler, and/or a UV protection booster, among other additives or ingredients.
  • additional additives can be added to enhance UV protection or other cosmetics.
  • the color pigment mixture can include a mixture of iron oxide or other colorants and which are configured to provide a visible color to the resulting film, similar to a foundation or concealer.
  • the color pigment mixture can assist with hiding skin imperfections, such as blemishes, discolored skin, birthmarks, scars, and other imperfections.
  • Example color pigment mixtures include different ratios of yellow, red, and/or black iron oxide particles, such as Cl 77492, Cl 77491, and Cl 77499.
  • the sprayable-skin formulation 100 includes between about 0.01 wt% and about 2 wt% of color pigments based on the total weight of the sprayable-skin formulation 100.
  • Each of the different pigments can be present in an amount between about 0 wt% and about 4 wt%, about 0 wt% and about 2 wt%, or about 0 wt% and about 1 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges.
  • Examples are not so limited and can include other colorants such as Bismuth Oxychloride, D&C colorants, FD&C colorants. Chromium Hydroxide, Chromium Oxide, Mica, Ultramarines, Talc, and Luminescent Zine Sulfide, among others.
  • the pigment coating agent can coat the particles of the color pigment mixture such that the particles are dispersed in solution.
  • the particles of the color pigment mixture can be pre-coated with the pigment coating agent.
  • the sprayable-skin formulation 100 includes between about 0.01 wt% and about 2 wt% of pigment coating agent based on the total weight of the sprayable-skin formulation 100. In some embodiments, the amount of the pigment coating agent is between about 0.
  • 1 wt% and about 2 wt% about 0.5 wt% and about 2 wt%, about 1 wt% and about 2 wt%, about 1.5 wt% and about 2 wt%, about 0.01 wt% and about 1.5 wt%, 0.01 wt% and about 1.0 wt%, about 0.01 wt% and about .05 wt%, about 0.01 wt% and about 0. 1 wt%, about 0.1 wt% and about 1.5 wt%, or about 1.0 wt% and about 1.5 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges.
  • the pigment coating agent includes a hydrogen dimethicone, such as Pecosil® SH-25L.
  • the amount of hydrogen dimethicone is between about 0 wt% and about 1.5 wt%. In some embodiments, the amount of hydrogen dimethicone is between about 0 wt% and about 1 wt%.
  • the antioxidant and metal chelate may act as a stabilizer.
  • An example antioxidant and metal chelate includes sodium phylate, such as Greengard.
  • the sprayable-skin formulation 100 includes between about 0.01 wt% to about 0.5 wt% of an antioxidant and metal chelate based on the total weight of the sprayable-skin formulation 100.
  • the amount of antioxidant and metal chelate is between about 0 wt% and about 0.4 wt%, about 0 wt% and about 0.3% wt%, about 0.
  • the antioxidant and metal chelate may additionally assist with dispersing particles.
  • the spray able-skin formulation 100 contains one or more functional fillers, sometimes referred to as cosmetic fillers.
  • the functional fillers can scatter light to hide skin imperfections, such as blemishes.
  • Example functional fillers include silica, titanium dioxide, iron oxide, illite, cellulose particles, amino acids or amino acid derivatives, and combinations thereof.
  • Some specific example functional fillers include RonaFlair® Flawless, RonaFlair® Satin, Amihope® LL, and Amihope® OL.
  • the spray able-skin formulation 100 can include between about 0.01 wt% to about 10 wt% of the functional filler based on the total weight of the sprayable-skin formulation 100.
  • the amount of the functional filler may be between about 0.01 wt% and about 8 wt%, about 0.01 wt% and about 6 wt%, about 0.01 wt% and about 4 wt%, about 0.01 wt% and about 2 wt%, about 0.01 wt% and about 1 wt%, about 0.1 wt% and about 10 wt%, about 1 wt% and about 10 wt%, about 2 wt% and about 10 wt%, about 4 wt% and about 10 wt%, about 6 wt% and about 10 wt%, about 8 wt% and about 10 wt%, about 0.1 wt% and about 8 wt%, about 1 wt% and about 6 wt%, or about 2
  • the functional filler includes one or more of RonaFlair® Flawless, RonaFlair® Satin, Amihope® LL, and Amihope® OL. In some embodiments, the functional filler includes two or more of RonaFlair® Flawless, RonaFlair® Satin, Amihope® LL, and Amihope® OL.
  • RonaFlair® Flawless is formed of silica, titanium dioxide (Cl 77891) and iron oxide (Cl 77491). More particularly, Ronaflair® Flawless is a peach colored powder including silica microspheres coated with titanium dioxide and iron oxide. In some embodiments, the particle size (e.g., the microspheres) distribution of RonaFlair® Flawless in the 80% range is about 1.0 micron (pm) to about 25.0 pm and the average particle size is about 4 pm to about 8 pm.
  • RonaFlair® Satin is a naturally sourced functional filler based on kaolin and mica. In various embodiments, RonaFlair® Satin is formed of particles of illite. In some embodiments, the particle distribution of RonaFlair® Satin in the 80% range is less than about 25 pm [0084]
  • Amihope® is an amino-acid derivative made from L-Lysine and a fatly acid, formed of fiat and hexagonal shaped particles. The structure of the amino-acid derivative can include: wherein R is Cl 1H23 for Amihope® LL or C7H15 for Amihope® OL. The particles can have a mean particle size of about 20 pm to about 30 pm.
  • the amount of each functional filler can be between about 0 wt% and about 10 wt%, about 0 wt% and about 8 wt%, about 0 wt% and about 6 wt%, or about 0 wt% and about 4 wt% based on the total weight of the sprayable-skin formulation 100. In embodiments where the sprayable-skin formulation 100 contains more than one functional filler, the amount of each functional filler can be the same or different.
  • the sprayable-skin formulation 100 includes a UV protection booster.
  • the UV protection booster can include polymer particles that scatter light for the inorganics.
  • Example UV protection boosters include a styrene/acrylates copolymer and Pongamia Pinnata seed extract, such as SunspheresTM, Assure+, and others.
  • the sprayable-skin formulation 100 can include about 0.01 wt% to about 5 wt% of the UV protection booster based on the total weight of the sprayable-skin formulation 100.
  • the amount of UV protection booster is between about 0 wt% and about 5 wt%, about 0 wt% and about 4 wt%, about 0 wt% and about 3 wt%, about 0.01 wt% and about 4 wt%, about 0.01 wt% and about 3 wt%, about 0.01 wt% and about 2 wt%, about 0.01 wt% and about 1 wt%, about 0.1 wt% and about 5 wt%, 1 wt% and about 5 wt%, 2 wt% and about 5 wt%, 3 wt% and about 5 wt%, 4 wt% and about 5 wt%, 1 wt% and about 4 wt%, 2 wt% and about 4 wt%, or 2 wt% and about 3 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges.
  • FIG. IB illustrates an example implementation of the sprayable-skin formulation 100 of FIG. 1A.
  • the example sprayable-skin formulation 101 includes a polyurethane polymer dispersion 103, a water-dispersible polymer emulsion 105, a UV protecting agent 106, a particle coating agent 108, water-miscible solvent 112, and one or more of an additive 110, color pigment mixture 114, pigment coating agent 116, an antioxidant and metal chelate 118, a functional filler 120, and a UV protection booster 122, as previously described in connection with FIG. 1A and shown by the common numbering.
  • FIG. 1A illustrates an example implementation of the sprayable-skin formulation 100 of FIG. 1A.
  • the example sprayable-skin formulation 101 includes a polyurethane polymer dispersion 103, a water-dispersible polymer emulsion 105, a UV protecting agent 106, a particle coating agent 108, water-miscible solvent 112, and one or more of
  • the water-miscible solvent 112 includes water 113 and/or ethanol 115.
  • the functionalities, example wt%, and properties of the common components are not repeated for ease of reference.
  • the sprayable-skm formulation 100, 101 of FIGs. 1A-1B which include polyurethane and water-dispersible polymer solutions in a high concentration of at least 50 wt% and additives of inorganic UV protecting agents and a particle coating agent, are sprayable and configured to cure to form a film.
  • the sprayable-skin formulation 100, 101 can be sprayed onto skin and allowed to dry to form an elastic and UV protecting film.
  • the sprayable-skin formulation 100, 101 can cure and form the film, after spraying on a skin surface, within about 1 minute to about 5 minutes.
  • the resulting film can be durable such that other cosmetics can be applied on top of the film, and the film may last the entire day without reapplication.
  • the film is elastic such that the film moves with the skin and can be removed via peeling and/or with water.
  • the film provides UV protection and color correction and/or hiding of imperfections, among other features described above.
  • embodiments can include a formulation including a combination of the above components, which is used for a different purposes.
  • An example embodiment includes a sprayable formulation, which can be spread onto surfaces other than skin.
  • the formulation may be applied using techniques other than spraying.
  • a skin or other surface coating formulation may be applied using other techniques.
  • the example formulation may include at least the polyurethane polymer solution 102, the water-dispersible polymer solution 104, and water-miscible solvent 112.
  • the formulation additionally includes the UV protecting agent 106 and the particle coating agent 108, and optionally the UV protection booster 122. In some embodiments, the formulation additionally includes the color pigment mixture 114, the pigment coating agent 116, and optionally one or more of the antioxidant and metal chelate 118 and the functional filler 120. In some embodiments, the formulation additionally includes different combinations of the UV protecting agent 106, the particle coating agent 108, the UV protection booster 122, color pigment mixture 114, the pigment coating agent 116, the antioxidant and metal chelate 118, and the functional filler 120.
  • FIG. 2 illustrates an example kit for forming a sprayable-skin formulation, in accordance with the present disclosure.
  • the kit 230 can include or be used to form the sprayable-skin formulation(s) 100, 101 illustrated by FIGs. 1A-1B. [0091] As shown by FIG. 1A-1B.
  • the kit 230 for forming the sprayable-skin formulation includes: (i) about 45 wt% to about 85 wt% of a polyurethane polymer dispersion 103 based on the total weight of the formulation, (ti) about 5 wt% to about 15 wt% of a water-dispersible polymer emulsion 105 based on the total weight of the formulation, (iii) about 0.5 wt% to about 15 wt% of a UV protecting agent 106 based on the total weight of the formulation, (iv) about 0.5 wt% to about 15 wt% of a particle coating agent 108 based on the total weight of the formulation, and (v) a balance of water- miscible solvent 112.
  • the ratio of the polyurethane polymer dispersion 103 to the water-dispersible polymer emulsion 105 is between about 5: 1 and about 10: 1.
  • the kit 230 may include various different optional components, including but not limited to an additive 110, color pigments 114, a pigment coating agent 116, antioxidant and metal chelate 118, a functional filler 120, and UV protection booster 122, as previously described in connection with FIGs. 1A-1B.
  • the water-miscible solvent 112 includes about 1 wt% to about 10 wt% of ethanol based on the total weight of the formulation. In some embodiments, the water-miscible solvent 112 includes water and ethanol, such as about 1 wt % to about 10 wt% of ethanol and about 5 wt% to about 20 wt% of water. In some embodiments, the water-miscible solvent 112 includes water, such as about 1 wt% to about 20 wt% and without ethanol.
  • the kit 230 further includes about 0.01 wt% to about 2 wt% of color pigments 114 based on the total weight of the fonnulation and about 0.01 wt% to about 2 wt% of a pigment coating agent 116 based on the total weight of the formulation.
  • the kit 230 further includes: (i) about 0.01 wt% to about 0.5 wt% of an antioxidant and metal chelate 118 based on the total weight of the formulation, (ii) about 0.01 wt% to about 10 wt% of a functional filler 120 based on the total weight of the formulation, and/or (lii) about 0.01 wt% to about 5 wt% of a UV protection booster 122 based on the total weight of the formulation.
  • the formulation is sprayable as an aerosol and configured to cure and form an elastic and UV protecting film on skin within about 1 minute to about 5 minutes after spraying.
  • the kit 230 may further include an aerosol container 232 configured to contain the sprayable-skin formulation in the form of one of an emulsion and a suspension including the polyurethane polymer dispersion 103, the water-dispersible polymer emulsion 105, the UV protecting agent 106, the particle coating agent 108, and water-miscible solvent 112, among the other optional components.
  • FIG. 3 illustrates an example method of applying a sprayable-skin formulation, in accordance with the present disclosure.
  • the method 340 can be implemented using the sprayable-skin formulation(s) 100, 101 ofFIGs. 1 A- IB and/or the kit 230 of FIG. 2.
  • the method 340 can include using a sprayable-skin formulation, including the wt% ranges, as described above.
  • the method 340 includes spraying a layer of sprayable-skin formulation to skin.
  • the sprayable-skin formulation can include polyurethane polymer dispersion, a water-dispersible polymer emulsion, UV protecting agent, a particle coating agent, and water-miscible solvent, among the other optional components as previously described.
  • the method 340 includes dry ing, via exposure to air, the layer to form an elastic and UV protecting film on the skin.
  • the film is durable such that the film is cohesive and configured to remain intact on the skin in response to contact.
  • the method 340 further comprises removing the film by at least one of peeling the film and applying water to the film.
  • the film comprises about 5 wt% to about 20 wt% of the UV protecting agent based on the total weight of the film.
  • the film can provide Sun Protection Factor (SPF) of at least 15, such as between about SPF 15 and SPF 50.
  • SPF Sun Protection Factor
  • the resulting film can have a thickness of between about 5 microns and about 80 microns.
  • the film may additionally be at least substantially uniform in thickness, such as varying less than 5%.
  • the firm can be durable such that a layer of other cosmetics may be applied on top of the film.
  • the method 340 can further include applying the layer of other cosmetics on top of the film.
  • Embodiments are not limited to the method 340 of FIG. 3 and may include other methodologies and/or be used to form a kit, such as the kit 230 of FIG. 2.
  • Various embodiments are directed to methods of forming the sprayable-skin formulation and/or kit, such as methods of forming the formulation as an emulsion or a suspension.
  • the following is an example method of forming a sprayable-skin formulation as an emulsion.
  • the polymers e.g., polyurethane polymer solution and water-dispersible polymer solution
  • other components that are soluble in oil are dissolved in the solvent to form an oil phase.
  • the components that are soluble in water are dissolved in water to form an aqueous phase.
  • the oil phase and aqueous phase are blended to form an emulsion, and optionally an emulsifying agent is added.
  • the following is an example method of forming a sprayable-skin formulation as a suspension.
  • the components which are water soluble are dissolved in water, including ionic or non-ionic surfactants, thickening agents, viscosity modifiers, wetting agents, and buffering agents.
  • the stabilizers can prevent the formation of a cake or sediment upon storage.
  • the polymer is dissolved or dispersed in solvent. The two solutions are blended along with UV protecting agents, with the solids added slowly to avoid formation of agglomerate and form a suspension.
  • Embodiments are not limited the above described methods of forming the sprayable-skin formulation, and methods can include variations thereof.
  • Embodiments are not limited to the specifically illustrated sprayable-skin formulation 100, 101 of FIGs. 1 A-1B and/or kit illustrated by FIG. 2, and may include different combinations of the features described therein.
  • a kit may be formed of the components illustrated by any of FIGs. 1A-1B.
  • the sprayable- skin formulation may be formed of the wt% of components as illustrated by FIG. 2.
  • Some embodiments are directed to pre-mixtures which may be used to form the formulations and/or kits described herein, and/or to perform any methods described herein.
  • the pre-mixtures can include a polymer mixture, a silicone mixture, and a pigment mixture, among others.
  • FIG. 4 illustrates example pre-mixtures, in accordance with the present disclosure.
  • the pre-mixtures 450 include a polymer mixture 452, a silicone mixture 454, and/or a pigment mixture 456, among others.
  • each of the premixtures 450 can be separately formed and packaged.
  • the polymer mixture 452 includes the polyurethane polymer dispersion 403 and the water-dispersible polymer emulsion 405, as previously described in connection with FIGs. 1A-1B.
  • the silicone mixture 454 can include a first particle coating agent 408-1 and a second particle coating agent 408-2.
  • the first particle coating agent 408-1 can include PEG-12 dimethicone
  • the second particle coating agent 408-2 can include dimethicon PEG-8 Laurate, although embodiments are not so limited.
  • the silicone mixture 454 further includes the UV protecting agent 406.
  • the particles of the UV protecting agent 406 may be pre-coated with the first particle coating agent 408-1 and the second particle coating agent 408-2 in the silicone mixture 454.
  • the pigment mixture 456 includes a first color pigment 414-1, a second color pigment 414-2, and a third color pigment 414-3 or combinations thereof, such as iron oxide yellow, iron oxide red, and/or iron oxide black.
  • the pigment mixture 456 further includes the pigment coating agent 416 that coat the color pigments 414-1, 414-2, 414-3 in the pigment mixture 456.
  • a polymer mixture was prepared.
  • the polymer mixture included Baycusan® C 1001(90 parts by wt.) mixed with DOWSILTM FA 4103 (10 parts by wt.).
  • the silicone mixture was also be prepared.
  • the silicon mixture was Silsurf® D212-CG (1 part by wt.) mixed with Silwax® WS-L (9 parts by wt.).
  • the pigment mixture was also pre-prepared.
  • the mixture is by weight iron oxide yellow (74.29 parts), iron oxide red (18.57 parts), and iron oxide black (7. 14 parts).
  • 34.5 mg of the pigment mixture was placed in a microcentrifuge tube and around 0.5 rnL of hydrogen dimethicone was added. The mixture was vortexed for 5 minutes, centrifuged, and washed 3 times with ethanol to remove the non-coated hydrogen dimethicone and the mix was allowed to dry.
  • the coating on inorganics with dimethicone in a commercial setting may be conducted with a blender and only a trace of silicone.
  • the UV protecting agents are coated with the silicone mixture.
  • ten parts of Zano® 10 plus was mixed with eleven parts of the silicone mixture in a mixer.
  • the formulation contained one part by volume stabilizing solution (sodium phytate GreenGuard) and nine-part by volume water.
  • the skin formulation consisted of the following: 69.75 wt% Baycusan® C 1001, 7.75 wt% DOWSILTM FA 4103, 0.43 wt% Silsurf® D212, 3.87 wt% SilwaxTM, 2.3 wt% Zano® 10 plus, 0.23 wt% pigment mixture, 0.3 wt% GreenGuard, 1.95 wt% ethanol, 4.5 wt% RonaFlair® Flawless, 1.25 wt% RonaFlair® Satin, and 7.6 wt7% water based on the total weight of the formulation.
  • the formulation procedure was:
  • the iron oxide was then added and the vial containing the oxide was rinsed out into the mixing vessel with the ethanol (0.295 g), water (0.7455 mL), and sodium phytate GreenGuard solution with water (0.45 rnL).
  • TiO2 particles and ZnO particles particle size impacts the amount of UV protection, with particles of a diameter of 100 nm or less having higher levels of protection (absorbance) than larger particles.
  • the particles with 100 nm diameter or less also have lower whitening effects than the larger particles.
  • siloxane polymer was assessed for forming the sprayble-skin formulation.
  • Two different polysiloxane film formers were assessed that cure into an elastic film without the application of a catalyst (e.g., without silicone monomers).
  • Siloxane film formers were used in place of silicon monomers (e.g., vinyl- and hydrogen-terminated silicone).
  • the two siloxane film formers tests were Trimethylsiloxysilicate and Cyclopentasiloxane (Shin-Etsu X-21-5250, herein sometimes referred to as “5250”) having a viscosity of 60 mm 2 /s and Trimethylsilioxysilicate and Isododecane (Shin-Etsu X-21-5595, herein sometimes referred to as “5595”) having a viscosity of 35 mm 2 /s.
  • the two siloxane film formers were mixed at different ratios to adjust the film properties, with 5595 being a hard film former and 5250 being a mild film former. Table 2 illustrates the results:
  • the films tackiness may not be suitable for artificial skin.
  • Baycusan® C 1001 was slightly more elastic than Baycusan® C 1004, but both satisfied qualitative elasticity requirements for an artificial skin film.
  • these polymer formulations were modified through the addition of various solvents and viscosity modifiers.
  • modification of the Baycusan® C 1004 formulation with PEG-40, a humectant and viscosity modifier was successful for producing a spray-able polymer formulation and elastic film.
  • modification of the Baycusan® C 1001 formulations with similar additives proved unsuccessful.
  • Baycusan® C 1001 was modified using an acrylate modifier to create a hybrid polyurethane-acrylate polymer.
  • Baycusan® C 1001 is a safe cosmetic ingredient that is a co-polymer based on hexamethylene diisocyanate, and has a viscosity of ⁇ 1000 mPa-s and a % solids of 32%.
  • the structure of hexamethylene diisocyanate is illustrated below:
  • Baycusan® C 1004 is a safe cosmetic ingredient that is a co-polymer based on dicyclohexylmethane diisocyanate, and has a viscosity of ⁇ 500 mPa-s and a % solids of 41%.
  • the structure of dicyclohexylmethane diisocyanate is illustrated below:
  • FIGs. 5A-5B illustrate example films formed from a polyurethane polymer formulation, in accordance with the present disclosure.
  • Baycusan® C 1001 was cast neat (100%) and as ethanol diluted formulation onto a glass slide. The polymer was allowed to dry for around 1.5 hours, with the drying time depending on the film thickness as well as the substate used. The dried film was transparent and had mnimal blemishes/inhomogeneity. The film thickness was 0.32 mm.
  • Baycusan® C 1001 cures into a transparent film. The film was additionally stretched without breaking, thus showing that the Baycusan® C 1001 formed an elastic film.
  • FIGs. 6A-6C illustrate example films formed from modified polyurethane polymer formulations, in accordance with the present disclosure.
  • Baycusan® C 1001 and Baycusan® C 1004 were modified for providing sprayability and/or elasticity.
  • Baycusan® C 1001 was thinned out with a cream to form formulation 1 and formulation 2.
  • the cream was a mask cream which was used to thin out Baycusan® C 1001 to provide sprayability.
  • Formulation 1 may be too thick to spray and was further modified to remove cream forming agents, pH modifier and Ultrez 20.
  • Ultrez 20 was replaced with Atroflex AVC, which has a thickening effect that is more controlable.
  • a drop casting solution yeilded an elastic, transparent film.
  • spray attempt clogged the top loading airbrush (Badger 100) which was believed to be due to fast water evaporation upon aerosolization.
  • FIG. 6A illustrates a resulting film formed by drop casted Baycusan® C 1001 Cream (formulation 1) which was cured in 2 hours, was 0.04 mm thick and was peelable to remove in multiple pieces.
  • Table 5 summarizes formulations 1 and 2.
  • FIGs. 6B-6C illustrate resulting films formed using modified Baycusan® C 1004.
  • Baycusan® C 1004 was identifed as not being sufficiently elastic for artificial skin and was modifed using PEG-40 to improve elasticty.
  • PEG-40 is a water and oil soluable emusifier, emollient, and surfactant.
  • FIG. 6B illustrates a film formed from Baycusan® C 1004-PEG-40 (39: 1 ratio)
  • FIG. 6C illustrate a film formed of Baycusan® C 1004-PEG-40 (116: 1 ratio) after curing for 24 hours (FIG. 6B).
  • the 39: 1 ratio is a viscous solution and resulted in an uneven and inhomgenous film.
  • the 116:1 ratio was a low viscous solution and resulted in an even relatively homogous film (FIG. 6C).
  • the experimetnts illustrated that Baycusan® can be adjusted from an elastic film to an
  • Some embodiments were directed to assessing the breathability (e.g., water vapor transmission rate) of a sprayed-on film of Baycusan® C lOOl-DOWSILTM FA 4103 (90: 10 ratio) formulation.
  • the results indicate that the polymer film is highly breathable and will not restrict water transmission from skin.
  • DOWSILTM FA 4103 is a silicone acrylate emulsion which is safe cosmetic ingredient that is a 30% oil-in-water emulsion. The water-dispersible emulsion allows for the formulation with Baycusan® based polyurethanes. DOWSILTM FA 4103 is water and sebum repellent, resistant to abrasion, has skin tightening properties, and feels smooth on the skin. Table 7 below provides example hybrid formulations:
  • FIGs. 7A-7B illustrate example films formed from hybrid polymer formulations, in accordance with the present disclosure.
  • FIG. 7A is formulation 4 and FIG. 7B is formulations 6 and 7, showing the resulting films are transparent and elastic.
  • FIG. 8 is a graph illustrating the assessed breathability of the hybrid polymer formulation, in accordance with the present disclosure.
  • Some embodiments were directed to assessing the breathability of the hybrid Baycusan® C 1001-DOWSILTM FA 4103 (90: 10 ratio). More particularly, water-vapor vapor transport rate (WVTR) assessment was conducted on sprayed film of hybrid Baycusan® C 1001-DOWSILTM FA 4103 (90:10 ratio). WVTR was measured on Mocon Permatran-W instrument Model 1/50.
  • WVTR water-vapor vapor transport rate
  • the measurement procedures were as follows: (i) hybrid polymer was sprayed and dried on a porous polypropylene substrate (25 pm thick, 5 cm 2 area), (ii) hybrid polymer thickness: 50 - 76 pm, and (iii) WVTR temperature: 37.8 degrees C.
  • the hybrid film was dried on a porous support substrate (polypropylene, 25 pm), and measured. The value appeared to be at the saturation limit of the instrument, and the actual WVTR may be even higher.
  • Polyderm PPI-CO-200 is a thermoplastic polyurethane elastomer (BIS-PEG-15 Dimethicone/Isophorone diisocyanate (IPDI) Copolymer) that forms a transparent and cohesive film, and is hydrophobic.
  • NuLastic Silk-E is a silicone elastomer (Polysilicone 23) that is a film modifier, e.g. eliminates stickiness. Table 8 illustrates the resulting hybrid formulations and films.
  • the hybrid Polyderm-NuLastic polymer formulation resulted in biphasic formulation and may be used for artificial skin.
  • Various embodimetns were directed to determining spray-ability of the different example polymers, evaluating films of the polymers, and identifying the diluent and polymer combination that gives a continuous and peel-able film.
  • the hybrid polymer was also spray tested in the Mineral Air airbrush (YA- MAN’s) successfully.
  • the polymer was sprayed onto leather.
  • prolonged spraying was required. No clogging was observed in the Mineral Air during the spray test, but the system clogged after sitting for a few minutes.
  • FIGs. 9A-9D are images of resulting films formed using the hybrid polymer formulation of Candidate A, in accordance with the present disclosure. More particularly, FIGs. 9A-9B are images of a film formed by spraying Baycusan® C 1001 (FIG. 9A) and after peeling the film (FIG. 9B). The film was sprayed onto leather using the Badger 250 airbrush and allowed to dry for 1-2 hours.
  • FIG. 9A illustrates the film after drying and FIG.
  • FIGs. 9B illustrates the film after attempted to peel.
  • the film was around 110 microns thick and broke when attempting to peel, was elastic, and not tacky.
  • FIGs. 9C-9D are images of a film formed by spraying Baycusan® C 1001-DOWSILTM FA 4103 (FIG. 9C) and after peeling the film (FIG. 9D).
  • the Baycusan® C 1001- DOWSILTM FA 4103 formulation was sprayed onto leather for 20 seconds using the Badger 250 airbrush and allowed to dry for around 30 minutes.
  • the formulation increased viscosity and prevent dripping, and after setting, the film was transparent and nearly invisible to the eye.
  • the film was around 100 microns thick, transparent, intact, and the leather patter was apparent on the film after peeling, as shown by FIG. 9D, demonstrating good setting behavior.
  • Candidate A was sprayed using Mineral Air sprayer onto leather and green food coloring ( ⁇ 10 volume percent) was added to the polymer formulation for visualization purposes.
  • the Mineral Air sprayer sprays a finer mist and smaller droplets than the Badger 250 airbrush and requires a longer spray time (around 1 minute) than the Badger 250 (around 20 seconds).
  • the polymer appears to be dry after 1 hour and a coherent, transparent film developed. The film was left on the leather for two days at room temperature and was peeled from the leather. After peeling, the thickness was measured to be 10-40 microns thick, and the film was elastic.
  • FIG. 10 is an image of a film formed using the modified polyurethane polymer formulation of Candidate B, in accordance with the present disclosure. More particularly, FIG. 10 is an image of a film formed by spraying Baycusan® C 1004-PEG- 40 (116: 1 ratio) sprayed onto leather using the Badger 250 sprayer. The polymer formulation was sprayed and allowed to dry for 6 hours, and was inconspicuous and transparent on the leather. The film was removed from the leather in a single piece after 48 hours and was intact.
  • Various embodiments were directed to assessing different UV protecting agents and colorants, such as minerals and iron oxide colorants.
  • titanium-oxide, zinc-oxide, and a colorant (iron oxide) were added into the hybrid polymer Baycusan® C 1001-DOWSILTM FA 4103 (Candidate A) to demonstrate that UV-reflecting agents and colorants can be added to the polymers without affecting elasticity of the film.
  • FIGs. 11A-1 IB are images of a film formed using the hybrid polymer formulation of Candidate A with titanium dioxde added, in accordance with the present disclosure.
  • the polymer forms the illustrated film, and the solid titanium content is around 5 wt% with respect to the solid film.
  • the polymer formulation is around 32 wt% polymer solution and around 68 wt% water.
  • the resulting film was elastic and was removable from the glass, as shown by FIG. 1 IB.
  • Such embodiments illustrate that titanium diocide can be loaded in the film and the film retains elasticity.
  • zinc-oxide was used to create a suspension.
  • Kobo ZnO-B was used having a primary particle size of 90 nm and which is a safe cosmetic ingredient.
  • the suspension was unstable in water but stable at 15% loading in Baycusan® C 1004.
  • a high level (1 wt%) of red iron oxide particles was added into the hybrid polymer formulation (Candidate A). This is a high loading level, and a bright red film was expected.
  • the iron oxide-hybrid polymer formulation was drop casted onto a glass slide and dried at room temperature. Upon drying, an opaque, red film developed. The film was easily removed from the glass. Notably, the elasticity of the artificial skin film was maintained. This demonstrates that the hybrid polymer is capable of supporting high levels of particle-based colorants such as iron oxide.
  • the total level of colorants in the artificial skin product may be lower. Furthermore, to produce natural looking colors that mimic skin tones, combination of multiple colorants may be used.
  • different colorants were assessed which included surface treated and non-treat colorants.
  • An example surface treated colorant was iron oxide red (Shin Etsu, KTP-09R), which is a silicon/alkyl treated iron oxide (or Iron Oxide, Triethoxysilylethyl Poly dimethylsiloxy ethyl Hexyl Dimethicone).
  • Non-treated colorants include iron oxide red (Cl 77491, Making Cosmetics, average particle size 0.56 pm) and iron oxide yellow (Cl 77421, Making Cosmetics, average particle size 2.93 pm).
  • FIGs. 12A-12B are images of a film formed using the hybrid polymer formulation of Candidate A with an iron oxide colorant added, in accordance with the present disclosure.
  • about 1 wt% iron oxide red was added to the hybrid polymer formulation, drop casted on glass and dried for a day. After water evaporates, the hybrid polymer formulation forms a film having a solid iron oxide content of about 3 wt% of the total weight of the film, as shown by FIG. 12 A.
  • the polymer formulation is around 32 wt% polymer solution and around 68 wt% water.
  • the resulting film was elastic and was removable from the glass, as shown by FIG. 12B.
  • Such embodiments illustrate that iron oxides can be added to the solution while maintaining film elasticity.
  • Some specific embodiments were directed to generating and assessing a polymer formulation including Candidate A with TiCb and ZnO particles to provide UV protection as well as with iron oxide pigment particles to imbue the polymer with color.
  • Three different color formulations were created as a preliminary demonstration of the incorporation of color into the artificial skm/film. These mineral UV protection and color pigment particles did not affect the spray-ability of the polymer formulation.
  • the polymer formulation demonstrated the ability to spray the colored artificial skin polymer formulations onto skin.
  • the polymer formulation dries on the skin within 2 minutes and the material sets into a uniform film on the skin, and the color imparts a natural look similar to foundation.
  • the polymer formulation was sprayed using a nozzle diameter of between 0.43-0.45 mm, however embodiments are not so limited.
  • the storage stability of the polymer formulations were assessed.
  • the storage stability testing was conducted in temperature-controlled environments at temperatures: 5 degrees C, 20 degrees C, 40 degrees C, and 50 degrees C. Note that standard stability tests are conducted at 12 weeks for 5 degrees C, 20 degrees C, and 40 degrees C; while 50 degrees C was used for accelerated aging test for 4 weeks. Aging tests were conducted for 13 weeks at 5 degrees C, 20 degrees C, 40 degrees C, and 50 degrees C and with polymers in polypropylene and glass containers.
  • Candidate A polymer formulation spray-ability does not appear to be significantly affected by mass loss, and the polymer formulation effectively forms a film after spray from both the Badger and Mineral Air sprayers.
  • the polymer formulation does not spray as well after storage, and the polymer immediately clogs the sprayer (Mineral Air and Badger) on each attempt.
  • the increase in clogging indicates that Candidate B may be slightly coalescing in solution or coalescing quickly in the sprayer, leading to quicker precipitation within the sprayer.
  • Candidate B poly mer (Baycusan® C 1004) is much more cross-linked than Candidate A (Baycusan® C 1001), which may negatively affect spray. [00152] FIGs.
  • FIG. 13A-13D are graphs showing the storage stability results, in accordance with the present disclosure.
  • FIG. 13A and FIG. 13B show Candidate A samples in a polypropylene bottle (FIG. 13 A) and a glass bottle (FIG. 13B). Both Candidate A samples exhibit increased mass loss with increasing temperature, but low overall loss ( ⁇ 4%), with a 3-month storage test complete for polypropylene samples, and solutions visually appear unchanged in all samples. Tables 11-12 summarize the results for Candidate A.
  • FIG. 13C and FIG. 13D show Candidate B-l samples in a propylene bottle (FIG. 13C) and a glass bottle (FIG. 13D). Both Candidate B-l samples exhibit increased mass loss with increasing temperature, but low overall loss ( ⁇ 3%), and solutions visually appear unchanged in all samples. Tables 13-14 summarize the results for Candidate B-l.
  • Candidate A 9: 1 Baycusan® C 100EDOWSILTM FA 4103 polymer formulations were developed The four variations include: (i) A-2-uvl: contains TiCh and ZnO, (ii) A-2-cl : contains TiCh and ZnO, as well as iron oxide color mix #1 at half the concentration of A-2-c3, (iii) A-2-c2: TiCh and ZnO and color mix #1.
  • Table 18 includes the ingredients used in the example formulations:
  • the formulations in Table 16 each provide UV protection and the formulas with a A-2-c# provide UV protection and color foundations.
  • each of the formulation in Table 16 were sprayed using a Mineral Air spray and with minimal clogging.
  • A-2-c l contains half the amount of color pigments than A-2-c2 and A-2-c3. Decreasing the pigments by half appears to maintain adequate color and improves the mineral suspension.
  • a benefit of lower colorant amount is that the polymer can be applied in a thicker coat to enhance elasticity while maintaining proper color appearance.
  • iron oxide color pigments were mixed to generate different colors, with white TiCh added to the formualtion for color balance.
  • iron oxide particles were coated with dimethicone/methicone copolymer (Pecosil SH-25L) prior to use to prevent suspension in the formulation. Three colors were chosen to mimic (not exact match) Mineral Air foundation samples provided. Additional colors may be created by adjusting the iron oxide and TiCh ratios. Table 17 is a summary of the different mixtures:
  • FIG. 14 is an image of different polymer formulations having the different color mixtures from Table 17, in accordance with the present disclosure.
  • the polymer formulations were previously described by Table 16.
  • Various embodiments were directed to reducing mineral ( TiCb. ZnO, and iron oxides) settling.
  • Methods to reduce setting include mixing during formulation preparation required in order to disperse solids: (1) zinc oxide was premixed with silicones to prepare a ZnO paste for better dispersion was added first to the solution of Baycusan® C 1001/DOWSILTM FA 4103, (2) vortex mixing was applied at each stage of the solution preparation, (3) for large samples (>20 mL), resonant acoustic mixing (RAM) was used as the last mixing step, and (4) for commercial scale samples, homogenizing mixers can be used. In some embodiments, increase to solution viscosity led to significant sprayer clogging.
  • silicone coatings on iron oxide and ZnO minerals reduced rate of settling (e.g., MKR-1 T1O2 pre-coated by the supplier with low amount of hydrogen dimethicone).
  • reducing TiO2 and iron oxide content significantly reduced rate of settling, and the color appearance did not appear to be compromised.
  • Some embodiments were directed to spray testing the different polymer formulations from Table 16 using a Badger airbrush sprayer and Mineral Air.
  • Candidate A and Candidate B both exhibited sprayability with Badger, with Candidate A being less prone to cloggined with Mineral Air than Candidate B.
  • the polymer formulationss were sprayed with Badger 105 airbrush at 10 psi for 10-15 seconds using a raster motion (e.g., alternative between left-right and updown), at an airbrush distance from the skin of about 7.5 cm, and for a patch size of 3.8 cm x 3.8 cm. The patches were monitored for five minutes for dry ness and tack, and peeled off the skin after five minutes.
  • Candidate A-2-c2 sprayed with Mineral Air resulted in a more uniform film, sprayed on skin in 15 seconds, and once dried, was warn for over four hours to test durability and ease of removal with water. Table 18 summarizes the spray and peel results:
  • the resulting film thickness should be ⁇ 80 microns. Some embodiments were directed to measuring the thickness of the film. In a specific embodiments, a Candidate A-2-c2 film onto a glass slide using Mineral Air.
  • UV transmission is a measure of the proportion of light that travels through the substrate (artificial skin), with:
  • UV absorbance i.e., both are UV absorbers.
  • U V protection a goal can be low transmission ⁇ 400 nm (U V range).
  • Broad spectrum UV is defined as providing UV-A and -B protection.
  • FDA defines it as having a critical wavelength > 370 nm and UVA protection factor > 4.
  • the critical wavelength (X c ) is where the area under the absorbance spectrum for the irradiated product from 290 nm to Xc is 90% of the integral of the absorbance spectrum from 290 nm to 400 nm.
  • FIGs. 15A-15B are images of films formed from hybrid polymer formulations with UV protecting agents, in accordance with the disclosure. As previously described, embodiments included adding UV protecting agents (TiCh and ZnO) into Candidate A and Candidate B-l. The polymer solutions were mixed with 5.9 wt% UV protecting agents and casted onto glass slides. When dried, the film had 1 wt% UV protecting agents.
  • FIG. 15A is images of films formed from Candidate A
  • FIG. 15B is images of films formed from Candidate B-l. More particularly, FIG.
  • FIG. 15A shows a first film 2101 formed from Candidate A only, a second film 2105 formed from Candidate A with TiO2, and a third film 2107 formed from Candidate A with ZnO.
  • FIG. 15B shows a fourth film 2109 formed from Candidate B-l only, a fifth film 2113 formed from Candidate B-l with TiO2, and a sixth film 2115 formed from Candidate B-l with ZnO.
  • Candidate B-l dries to inhomogeneous film.
  • ZnO is translucent, whereas UO2 is opaque ⁇ 15 wt% TiO 2 .
  • FIG. 16 is a graph showing example transmissions of different candidates, in accordance with the present disclosure.
  • Candidates A and B are highly transmissive at 300 - 700 nm, with Candidate B having higher transmission.
  • Candidate A transmission decreases significantly at 280 nm (UV-B/-C), while Candidate B decrease around 250 nm (UV-C).
  • the drop in transmission corresponds to the polymers reduced transmission.
  • All TiO2 and ZnO samples do not transmit at ⁇ 400 nm and ⁇ 380 nm, respectively (UV-A and below).
  • Some embodiments were directed to generating different polymer formulations for providing UV protection and assessing the same. Such embodiments involved creating ZnO and UO2 loaded polymer samples. ZnO and TiO2 were loaded to levels equivalent to 15% ZnO and 5% TiO2 in the final, solid polymer film. Table 19 below sumamries different formulations generated:
  • FIG. 17 is a graph illustrating the UV-vis transmission for films formed of the polymer formulations illustrated by Table 19, in accordance with the present disclosure.
  • films loaded with lower levels of TiCh and ZnO exhibited broadband UV protection.
  • ZnO and TiO2 levels were reduced to test for UV absorbing efficiency, including ZnO level: -4.5% (-1.4% in solution), and TiO2 level: -1.5% (-0.5% in solution).
  • the samples were sprayed with around 15% ZnO and around 5% T1O2.
  • the data provides qualitative information on UV protection. As shown, there were low UV transmission below 380 nm for ZnO + TiO2 samples, and the samples likely provide broadband UV protection. Inhomogeneity /cracks in the Baycusan® C 1004 (Candidate B) samples may be causing low levels of UV transmission (5 - 10%)
  • the C36 polymer formulation had an increase of polymer content, decrease of ZnO content, and decrease of RonaFlair® compared to C31 polymer formulation.
  • Spraying of the C36 polymer formulation when sprayed around ten seconds and allowed to dry onto skin resulted in a film without obvious visible distinction between the skin and the film, and scratches and rubs did not remove the polymer film from the skin.
  • moisture and pressure was applied to remove C36 from the skin surface.
  • Table 21 provides example total UV protecting content: Table 21
  • C44 was formulated to add TiCh added to improve SPF and reduced RonaFlair® content.
  • the example formulations have slightly lower mineral content.
  • commercial spray sunscreens have >12% ZnO (non-nano) for SPF 30.
  • Dried films of C44 has comparable to mineral content (TiCh + ZnO) to wet sunscreen sprays.
  • Expected SPF’s were determined based on manufacturer estimates of TiO2 (nano): 2.7 SPF per % of TiO2 and ZnO (nano): 1.6 SPF per % of ZnO.
  • FIGs. 18A-18B illustrate example absorbance of films formed of polymer formulations, in accordance with the present disclosure. Some embodiments were directed to assessing SPF of the dried films, in accordance with the present disclosure.
  • FIG. 18A illustrates the absorbance of a film formed from C36 polymer formulation before and after irradiation with UVA dose of 1.2 UVAPFo.
  • C36 polymer formulation was applied by hand over a 15 - 18 mg over 23 cm 2 area.
  • Table 22 summarizes the same below:
  • a second layer of film was applied on top of the first layer, allowing for around 10 minutes to dry before the second layer is applied.
  • FIG. 18B illustrates the absorbance of a film formed from C44 polymer formulation before and after irradiation with UVA dose of 1.2 UVAPFo.
  • adding UV absorbing TiCh improves SPF.
  • the polymer formulation was sprayed rather than hand application to improve uniformity.
  • the film had good SPF (SPF > 15), due to absence of TiCh, high critical wavelength (CW > 370 nm), and good UVAPF (UVAPF : SPF ratio > 1/3).
  • Table 23 summarizes the same below:
  • Example embodiments in accordance with the present disclosure are directed to different polymer-based formulations which are sprayable onto skin and dry within 1-5 minutes to form a film that is elastic and durable.
  • the polymer-based and sprayable formulation is formed of polyurethane and water-dispersible polymer solutions in an amount of at least 50 wt% of the total weight of the polymer formulation, and additives of inorganic UV protecting agents and coating agent.
  • the film provides UV protection, color balance and/or correction, is long wearing (e.g., last all day), provides a base layer for other cosmetics, and/or is easily removable via peeling or with the application of water, among other properties.

Abstract

Embodiments are directed to sprayable-skin formulations, kits, and methods associated therewith. An example sprayable-skin formulation comprises a polyurethane polymer solution, a water-dispersible polymer solution, an ultraviolet (UV) protecting agent, particle coating agent, and water-miscible solvent.

Description

SPRAYABLE-SKIN FORMULATIONS
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This PCT Application claims benefit to U.S. Provisional Application No. 63/331,708, filed April 15, 2022, titled “Spray-able Artificial Skin Formulation for Cosmetics”, the entirety of which is incorporated herein by reference.
BACKGROUND
[0002] Skin formulations can be used for a variety of cosmetic and other purposes. For example, skin formulations can provide ultraviolet (UV) sun protection, a barrier between the skin and other cosmetic products, and color correction and/or blemish coverage. In many instances, such skin formulation can be difficult to apply, must be reapplied throughout the day or are otherwise not durable, are allergenic, cannot be applied consistently or to the entire intended skin surface area, and/or are not sufficiently elastic to move with skin movement, among other limitations.
SUMMARY
[0003] The present invention is directed to overcoming the above-mentioned challenges and others related to skin formulations, such as for cosmetics.
[0004] Various aspects of the present disclosure are directed to a sprayable-skin formulation comprising a polyurethane polymer solution, a water-dispersible polymer solution, an ultraviolet (UV) protecting agent, a particle coating agent, and a water- miscible solvent.
[0005] In some aspects, the sprayable-skin formulation is sprayable and configured to cure and form an elastic and UV protecting film.
[0006] In some aspects, the water-miscible solvent is selected from: water, ethanol, and a combination thereof. In some aspects, ethanol is configured to increase evaporabihty of the sprayable-skin formulation in response to application of the sprayable-skin formulation. [0007] In some aspects, the polyurethane polymer solution is a dispersion comprising one of a di cyclohexylmethane diisocyanate copolymer and a hexamethylene diisocyanate copolymer.
[0008] In some aspects, the water-dispersible polymer solution is an emulsion comprising an acrylates/polytrimethylsiloxymethacrylate copolymer and laureth-1 phosphate polymer.
[0009] In some aspects, the sprayable-skin formulation comprises: about 45 weight percent (wt%) to about 85 wt% of the polyurethane polymer solution based on the total weight of the sprayable-skin formulation, and about 5 wt% to about 15 wt% of the water-dispersible polymer solution based on the total weight of the sprayable-skin formulation. In some aspects, the sprayable-skin formulation comprises: about 0. 1
Figure imgf000004_0001
to about 10 wt% of the UV protecting agent based on the total weight of the sprayable-skin formulation, about 0.5 wt% to about 15 wt% of the particle coating agent based on the total weight of the sprayable-skin formulation, and about 5 wt% to about 30 wt% of a water-miscible solvent based on the total weight of the sprayable- skin formulation.
[0010] In some aspects, the polyurethane polymer solution comprises a water-based polyurethane dispersion formed of: about 30 wt% to about 40 wt% polyurethane based on the total weight of the water-based polyurethane dispersion, and a balance of water and surfactants.
[0011] In some aspects, the UV protecting agent comprises inorganic particles configured to absorb UV radiation and the particle coating agent is configured to coat the inorganic particles and disperse the inorganic particles in the formulation. In some aspects, the inorganic particles have a diameter less than 100 nanometers. [0012] In some aspects, the particle coating agent is selected from polyethylene glycol (PEG)- 12 dimethicone, dimethicon PEG-8 Laurate, and a combination thereof.
[0013] In some aspects, the UV protecting agent is selected from: zinc oxide, titanium dioxide, and a combination thereof.
[0014] In some aspects, the UV protecting agent is a broadband UV absorbing agent formed of a combination of different types of inorganic particles configured to absorb UVA and UVB light in a range of about 280 nanometers to about 400 nanometers.
[0015] In some aspects, the sprayable-skin formulation further comprises at least one of: a color pigment mixture, a pigment coating agent for particles of the color pigment mixture, an antioxidant and metal chelate, a functional filler, and a UV protection booster.
[0016] Various aspects of the present disclosure are directed to a kit for forming a sprayable-skin formulation comprising: about 45 wt% to about 85 wt% of a polyurethane polymer dispersion based on the total weight of the formulation, about 5 wt% to about 15 wt% of a water-dispersible polymer emulsion based on the total weight of the formulation, about 0.5 wt% to about 15 wt% of an UV protecting agent based on the total weight of the formulation, about 0.5 wt% to about 15 wt% of a particle coating agent based on the total weight of the formulation, and a balance of a water- miscible solvent.
[0017] In some aspects, the sprayable-skin formulation is sprayable as an aerosol and configured to cure and form an elastic and UV protecting film on skin within about 1 minute to about 5 minutes after spraying.
[0018] In some aspects, the water-miscible solvent is selected from: about 1 wt % to about 10 wt% of ethanol based on the total weight of the formulation, about 5 wt% to about 20 wt% of water based on the total weight of the formulation, and a combination thereof.
[0019] In some aspects, the kit further comprises about 0.01 wt% to about 2 wt% of color pigments based on the total weight of the formulation, and about 0.01 wt% to about 2 wt% of pigment coating agent based on the total weight of the formulation. [0020] In some aspects, the kit comprises a ratio of the polyurethane polymer dispersion to the water-dispersible polymer emulsion of between about 5: 1 and about 10:1.
[0021] In some aspects, the kit further comprises at least one of: about 0.01 wt% to about 0.5 wt% of an antioxidant and metal chelate based on the total weight of the formulation, about 0.01 wt% to about 10 wt% of a functional filler based on the total weight of the formulation, and about 0.01 wt% to about 5 wt% of a UV protection booster based on the total weight of the formulation.
[0022] In some aspects, the kit further comprises an aerosol container with the sprayable-skin formulation in the form of one of an emulsion and a suspension containing the polyurethane polymer dispersion, the water-dispersible polymer emulsion, the UV protecting agent, the particle coating agent, and water.
[0023] Various aspects of the present disclosure are directed to method of applying a sprayable-skin formulation to skin. Then method comprises spraying a layer of sprayable-skin formulation to skin, the sprayable-skin formulation comprising: a polyurethane polymer dispersion, a water-dispersible polymer emulsion, a UV protecting agent, a particle coating agent, and a water-miscible solvent. The method further comprises drying, via exposure to air, the layer to form an elastic and UV protecting film on the skin.
[0024] In some aspects, the film is durable such that the film is cohesive and configured to remain intact on the skin in response to contact, and the method further comprises removing the film by at least one of peeling the film and applying water to the film.
[0025] In some aspects, the method further comprises applying a layer of other cosmetics on top of film, wherein the sprayable-skin formulation comprises: about 45 wt% to about 85 wt% of the polyurethane polymer dispersion based on the total weight of the sprayable-skin formulation, about 5 wt% to about 15 wt% of the water- dispersible polymer emulsion based on the total weight of the sprayable-skin formulation, about 0. 1 wt% to about 10 wt% of the UV protecting agent based on the total weight of the sprayable-skin formulation, about 0.5 wt% to about 15 wt% of the particle coating agent based on the total weight of the sprayable-skin formulation, and a balance of the water-miscible solvent.
[0026] In some aspects, the film comprises about 5 wt% to about 20 wt% of the UV protecting agent based on the total weight of the film and is configured to provide at least Sun Protection Factor (SPF) 15.
[0027] In some aspects, the film is between about 5 microns and about 80 microns and substantially uniform in thickness. BRIEF DESCRIPTION OF THE DRAWINGS
Various example embodiments can be more completely understood in consideration of the following detailed description in connection with the accompanying drawings, in which:
[0028] FIGs. 1A-1B illustrate example sprayable-skin formulations, in accordance with the present disclosure.
[0029] FIG. 2 illustrates an example kit for forming a sprayable-skin formulation, in accordance with the present disclosure.
[0030] FIG. 3 illustrates an example method of applying a sprayable-skin formulation, in accordance with the present disclosure.
[0031] FIG. 4 illustrates example pre-mixtures, in accordance with the present disclosure.
[0032] FIGs. 5A-5B illustrate example films formed from a polyurethane polymer formulation, in accordance with the present disclosure.
[0033] FIGs. 6A-6C illustrate example films formed from modified polyurethane polymer formulations, in accordance with the present disclosure.
[0034] FIGs. 7A-7B illustrate example films formed from hybrid polymer formulations, in accordance with the present disclosure.
[0035] FIG. 8 is a graph illustrating the assessed breathability of the hybrid polymer formulation, in accordance with the present disclosure.
[0036] FIGs. 9A-9D are images of resulting films formed using the hybrid polymer formulation of Candidate A, in accordance with the present disclosure.
[0037] FIG. 10 is an image of a film formed using the modified polyurethane polymer formulation of Candidate B, in accordance with the present disclosure.
[0038] FIGs. 11 A-l IB are images of a film formed using the hybrid polymer formulation of Candidate A with titanium dioxde added, in accordance with the present disclosure.
[0039] FIGs. 12A-12B are images of a film formed using the hybrid polymer formulation of Candidate A with an iron oxide colorant added, in accordance with the present disclosure. [0040] FIGs. 13A-13D are graphs showing the storage stability results, in accordance with the present disclosure.
[0041] FIG. 14 is an image of different polymer formulations having the different color mixtures from Table 20, in accordance with the present disclosure.
[0042] FIGs. 15A-15B are images of films formed from hybrid polymer formulations with UV protecting agents, in accordance with the disclosure.
[0043] FIG. 16 is a graph showing example transmissions of different candidates, in accordance with the present disclosure.
[0044] FIG. 17 is a graph illustrating the UV-vis transmission for films formed of the polymer formulations illustrated by Table 19 in accordance with the present disclosure. [0045] FIGs. 18A-18B illustrate example absorbance of films formed of polymer formulations, in accordance with the present disclosure.
DETAILED DESCRIPTION
[0046] In the following detailed description, reference is made to the accompanying drawings which form a part hereof, and in which is show n by way of illustration specific examples in which the disclosure can be practiced. It is to be understood that other examples can be utilized, and various changes may be made without departing from the scope of the disclosure. The following detailed description, therefore, is not to be taken in a limiting sense, and the scope of the disclosure is defined by the appended claims. It is to be understood that features of the various examples described herein may be combined, in part or whole, with each other, unless specifically noted otherwise.
[0047] Various products, such as skin formulations, may be used for cosmetics and other purposes. In many instances, cosmetic users apply cosmetic products directly to the skin, which can lead to allergic reactions. Furthermore, the cosmetics may wear off over the day and have to reapplied, which can be burdensome for the users and cause extra use of the product. For example, reapplication of the cosmetics and sunblocks throughout the day is often necessary to maintain the desired appearance and function. Additionally, removal of cosmetics from the skin can be difficult, requiring copious amounts of w ater, soap, and/or other cleaning products. Some cosmetic products include a polymer film for the face that reduces the appearance of winkles under the eye. However, such polymer film products must be applied by hand and use a precious metal (platinum) within the formulation. Furthemiore, the polymer film can often only be applied to a small area, such as under the eye.
[0048] Embodiments in accordance with the present disclosure are directed to a sprayable-skin formulations, kits, pre-mixtures, and methods associated therewith that can be used to form or involve forming a uniform and durable film. The film can be formed on skin of the user and may be referred to as an artificial skin. The sprayable- skin formulation can act as a durable barrier between the user’s skin and cosmetics, can be applied to the whole face and/or other skin area on the body and as a continuous and uniform film, and can be easily removed. In some embodiments, the sprayable-skin formulation can be sprayed onto the skin and allowed to dry to form the film that provides ultraviolet (UV) sun protection. For example, the sprayable-skin formulation can contain UV protecting agents and can also contain colorants (e.g., color pigments such as iron oxides) to create color, similar to a cosmetic foundation formulation. The sprayable-skin formulation can be applied to the skin through an aerosolizing, handheld spray applicator and dries on the skin to form the cohesive and elastic film. The formed film can be sufficiently durable to last throughout the day without reapphcation and such that cosmetics can be applied on top of the dried film. The dried film (e.g., artificial skin) can be removed by peeling and/or with small amounts of water or other cleaning products.
[0049] In some embodiments, the film product (e.g., artificial skin) is a polymer formulation consisting primarily of polyurethane and water-dispersible polymers in a water-based solution (e.g., in water with optional additives, such as ethanol). Other additives can be incorporated into the formulation to create properties such as UV protection, color, improved spray-ability (e.g., aerosolizing ability), and long-term storage stability (e.g., preservatives). In various embodiments, somewhat surprisingly, the polymer formulation is comprised of the polyurethane and water-dispersible polymer solutions in an amount of at least 50 weight percent of the total weight of the polymer formulation, and additives of inorganic UV protecting agents and coating agents, with the polymer formulation being sprayable or having aerosolizing ability'. [0050] In some specific embodiments, the disclosed approach involves a water-based polymer formulation consisting of polyurethane and silicone acrylate polymers and other additives for UV sun protection, color, improved spray-ability (e.g., aerosolizing ability), long-term storage stability (e.g., preservatives), among others. The following are example properties or characteristics of the spray able-skin formulation and the resulting film formed on skin. An example property is that the formulation can be sprayed as an aerosol onto the skin, avoiding more laborious application methods that require use of a hand or finger, brush, or similar methods. Spraying the formulation can also provide better application uniformity. Additionally, the formulation can dry within minutes and form a cohesive and elastic film that is thin (e.g., less than 80 microns) and provides comfortable, long-lasting wear. The film can be transparent, translucent, or opaque with color in different embodiments. In some embodiments, the film can function as a foundation layer on the skin. As another example property', the film is sufficiently durable that other cosmetics can be applied on top of it by brush, puff, or hand/fingers without damaging the film. Furthermore, the artificial skin can contain UV protecting (sunblock) agents such as zinc oxide, titanium dioxide, or other UV protecting agents. Since these agents are incorporated within the film, the agents can have greater lifetimes, reducing the need to reapply new sunscreen. As another example property, since the film is elastic, it can be removed easily and without requiring copious amounts of water, soap, and/or other cleaning agents. The film can be peeled when dry, with water, or removed by gentle application of a moist towel/tissue, or other cleaning products.
[0051] Various embodiments demonstrate the successful implementation of the sprayable-skin formulation. In some embodiments, the formulation may contain any or all of the following ingredients: polyurethane polymer dispersed in solution (e.g., Baycusan® C 1001, Baycusan® C 1004), a silicon acrylate emulsion (e.g. aery lates/polytrimethylsiloxy methacrylate copolymer (and) laureth-1 Phosphate (DOWSIL™ FA 4103)), cosmetic grade ethoxylated poly dimethylsiloxane (e.g., Silsurf® D212-CG), lubricant (e.g., PEG-12 dimethicone (Silwax® WS-L)), broadband UV protecting agents (e.g., zinc oxides (Zano® 10 Plus), titanium oxide (e.g., Avo TiCh, STR-100-LP TiCh, Kobo A35 TiCh), pigments (e.g., iron oxide Cl 77491 red, iron oxide Cl 77492 yellow, iron oxide Cl 77499 black), stabilizers (e.g., sodium phytate (e.g., GreenGuard solution)), antimicrobial agents, ethanol, cosmetic fillers (e.g., RonaFlair® Flawless, RonaFlair® Satin, Amihope® Lauroyl Lysine (LL), Amihope® N-Capryloyl Lysine (OL)), hydrogen dimethicone (e.g., Pecosil® SH-25L), UV protection boosters (e.g., styrene/acrylates copolymer (SunSpheres™) or Pongamia Pinnata Seed Extract) water and fragrance. However, embodiments are not so limited and other types of polyurethane polymer solutions, water-dispersible polymer solutions, UV protecting agents, particle coating agents, water-based solvents, and/or additives can be used to form example sprayable-skin formulations.
[0052] As used herein, sprayable-skin formulation includes and/or refers to a formulation which is sprayable onto skin of a user. A polyurethane polymer solution includes and/or refers to a solution that contains an amount of a polyurethane polymer. A polymer includes and/or refers to a substance or other material containing chains of multiple monomer units. A water-dispersible polymer solution includes and/or refers to a solution that contains a polymer that disperses in water. A UV protecting agent includes and/or refers to an element and/or compound, such as particles, which provide protection from UV radiation. A particle coating agent includes and/or refers to an element and/or compound that coats the UV protecting agent, and which can aid in dispersibility of the UV protecting agent in water.
[0053] As used herein, a solution includes and/or refers to a mixture of two or more substances, such as a homogeneous mixture of two or more substances (e.g., polymer and solvent) in relative amounts. In such a mixture, a solute is the substance dissolved in another mixture, referred to as the solvent. The solvent can dissolve the solute, resulting in the solution. A solvent includes and/or refers to a substance that dissolves a solute. A formulation includes and/or refers to a combination of substances, such as a solution in the form of an emulsion or suspension.
[0054] As further used herein, an additive includes and/or refers to an element and/or compound added to the formulation to effect a desired change in property of the formulation and/or resulting film, such as the rate of evaporation, adding fragrance, and/or stability. A color pigment mixture includes and/or refers to a mixture of at least one type of color substance (e.g., a color pigment). The color pigments include substances exhibiting color that may be insoluble in water. A pigment coating agent includes and/or refers to an element and/or compound that coats the particles of the color pigment, and which can aid in dispersibility of the color pigments in water. An antioxidant and metal chelate includes and/or refers to a compound containing a ligand bounded to a central metal atom, and which can exhibit antioxidant properties. A functional filler includes and/or refers to a substance or other compound which adjusts sensorial and/or optical properties and/or application behavior of the formulation. A UV protection booster includes and/or refers to an additive and/or mixture of additives that reflects UV light and can increase UV protection.
[0055] Turning to the figures, FIGs. 1A-1B illustrate example sprayable-skin formulations, in accordance with the present disclosure. The example sprayable-skin formulation 100, 101 can be used to form an elastic film on skin of a user. In various embodiments, the elastic protecting film may be cosmetic. The user can include a human or other organism having skin.
[0056] As shown by FIG. 1A, in some embodiments, the sprayable-skin formulation 100 includes a polyurethane polymer solution 102. The polyurethane polymer solution 102 can assist with forming of the film, which can be referred to as providing filmformability to the sprayable-skin formulation 100. In some embodiments, the polyurethane polymer solution 102 is a dispersion comprising a di cyclohexylmethane diisocyanate copolymer or a hexamethylene diisocyanate copolymer. In some embodiments, the polyurethane polymer solution 102 comprises a water-based polyurethane dispersion formed of about 30 weight percent (wt%) to about 40 wt% polyurethane based on the total weight of the polyurethane polymer solution 102, and a balance of water and, optionally, surfactants. Some specific example polyurethane polymer solutions include Baycusan® C 1001 or Baycusan® C 1004.
[0057] In some embodiments, the sprayable-skin formulation 100 includes about 45 wt% to about 85 wt% of the polyurethane polymer solution 102 based on the total weight of the sprayable-skin formulation 100. In some embodiments, the polyurethane polymer solution 102 is between about 50 wt% and about 80 wt% based on the total weight of the spray able-skm formulation 100. In some embodiments, the polyurethane polymer solution 102 is between about 60 wt% and about 80 wt%, about 65 wt% and about 80 wt%, about 70 wt% and about 80 wt%, about 75 wt% and about 80 wt%, about 60 wt% and about 75 wt%, about 60 wt% and about 70 wt%, about 65 wt% and about 80 wt%, or about 65 wt% and about 75 wt% based on the total weight of the sprayable- skin formulation 100, among other ranges.
[0058] The spray able-skin formulation 100 further includes a water-dispersible polymer solution 104. The water-dispersible polymer solution 104 can provide at least one of strength and film-formability to the sprayable-skin formulation 100 and/or the resulting film, as further described herein. In some embodiments, the water-dispersible polymer solution 104 comprises a silicon acrylate polymer in solution, which is sometimes herein referred to as “a silicon acrylate polymer solution”. In some embodiments, the water-dispersible polymer solution 104 is an emulsion comprising an acrylates/polytrimethylsiloxymethacrylate copolymer and laureth-1 phosphate polymer. In some embodiments, the water-dispersible polymer solution 104 comprises a waterbased silicon acrylate emulsion formed of about 30 wt% to about 40 wt% silicon acrylate polymer based on the total weight of the water-dispersible polymer solution 104, and a balance of water and, optionally, surfactants. Some specific examples of a water-dispersible polymer solution 104 include, but not limited to, DOWSIL™ FA 410, PEG-40, among other water-dispersible polymers, including emulsions.
[0059] In some embodiments, the sprayable-skin formulation 100 includes about 5 wt% to about 15 wt% of the water-dispersible polymer solution 104 based on the total weight of the water-dispersible polymer solution 104. In some embodiments, the water- dispersible polymer solution 104 can be between about 5.2 wt% and about 12 wt%, about 5.4 wt% and about 10 wt%, or about 5.6 wt% and about 8 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges.
[0060] In some embodiments, the sprayable-skin formulation 100 includes a ratio of the polyurethane polymer solution 102 and the water-dispersible polymer solution 104 of between about 5: 1 and about 10: 1. In some embodiments, the ratio can be between about 6: 1 and about 10: 1, about 7: 1 and about 10:1, about 8: 1 and about 10: 1, about 9: 1 and about 10: 1, about 5: 1 and about 9: 1, about 5: 1 and about 8: 1, about 5: 1 and about 7: 1, about 5 : 1 and about 6 : 1 , or about 6 : 1 and about 8:1, among other ranges. In some embodiments, the ratio can be about 10: 1, about 9: 1, about 8: 1, about 7: 1, about 6: 1, or about 5: 1. The combination of polyurethane polymer solution 102 and the water-dispersible polymer solution 104 can provide elasticity and result in fonnation of a cohesive film, as further described below.
[0061] The sprayable-skin formulation 100 can further include a UV protecting agent 106. Example UV protecting agents 106 include minerals (e.g., zinc oxide, titanium dioxide) and organic chemical compounds. Some specific example UV protecting agents 106 include zinc oxide, titanium dioxide, aminobenzoic acid (PABA), Avobenzone, Cinoxate, Dioxybenzone, ecamsule, homosalate. Menthyl amnthranilate, octocrylene, Octyl methoxy cinnamate, Octyl salicylate, oxybenzone, padimate O, Phenylbenzimidazole, Sulisobenzone, trolamine salicylate, calcium doped cerium dioxide nanoparticles, melanin nanospheres, C60-fullerene nanoparticles (e.g., Veil Fullerene™), and natural UV protecting agents, among others.
[0062] In some embodiments, the UV protecting agent 106 can include inorganic particles configured to absorb UV radiation. For example, the inorganic particles can include minerals, such as zinc oxide and/or titanium dioxide. In some examples, the UV protecting agent 106 is a broadband UV absorbing agent formed of a combination of different types of inorganic particles configured to absorb UVA and UVB light in a range of about 280 nanometers (nm) to about 400 nm. For example, the UV protecting agent 106 can include a combination of zinc oxide and titanium dioxide, or one of zinc oxide and titanium dioxide. In some embodiments, in addition to providing UV protection, the UV protecting agent 106 can provide color. In some embodiments, the UV protecting agent 106 can additionally be an antibacterial and antiinflammatory, such as for treating acne. For example, zinc oxide is antibacterial and anti-inflammatory .
[0063] In various embodiments and as described above, the UV protecting agents 106 are mineral-based, such as zinc oxide or titanium dioxide. Mineral-based UV protecting agents can serve as a shield against UV radiation and sit on the surface of the skin. In addition to absorbing UV radiation, the mineral-based UV protecting agents can reflect sunlight away from the skin, do not absorb into the skin, provide UV protection as soon as applied, provide color to hide skin blemishes, are not chemical based, and have other properties, such as being antibacterial and anti-inflammatory. In some embodiments, the mineral-based UV protecting agent can provide a white color, and the skin-sprayable formulation 100 can include other color pigments to correct the white coloration, as further described below. However, embodiments are not so limited and can include other types of UV protecting agents 106.
[0064] In some embodiments, the inorganic particles can have a diameter less than 100 nm. Inorganic particles with a diameter of 100 nm or less may absorb higher levels of UV radiation than particles that are larger than 100 nm. As described above, in some embodiments, the UV protecting agent 106 includes inorganic particles of zinc oxide, titanium dioxide, or a combination of zinc oxide and titanium dioxide. Zinc oxide can provide protection from UVB light and titanium dioxide can provide protection from UVA light. Example inorganic particles of zinc oxide include a combination of zinc oxide and triethoxy caprylyl silane, such as Zano® 10 plus. Example inorganic particles of titanium dioxide can include a combination of titanium dioxide, aluminum hydroxide, and hydrogen dimethicone or a combination of titanium dioxide and hydrogen dimethicone, such as Avo TiO2, STR-100-LP TiO2, Kobo A35 TiO2, and others. In some embodiments, the inorganic particles include Zano® 10 plus and/or Kobo A35. As used herein, a diameter of the particle (e.g., for UV protecting agents, functional fillers, and others) refers to the diameter of a single spherical particle, or the average diameter of non-spherical particles. In some embodiments, the diameter or average diameter of the particles may be measured using a volume based size distribution analytical chemical analysis. The size of the particles may be measured by using a static light scattering technique, such as laser diffraction.
[0065] In some embodiments of the sprayable-skin formulation 100 includes between about 0 wt% and 10 wt% of the UV protecting agents 106. In some embodiments, the amount of UV protective agents is between about 0.1 wt% to about 10 wt% based on the total weight of the sprayable-skin formulation 100. In some embodiments, the amount of UV protective agent 106 is between about 0 wt% and about 6 wt%, about 0 wt% and about 4 wt%, about 1 wt% and about 10 wt%, about 2 wt% and about 10 wt%, about 3 wt% and about 10 wt%, about 4 wt% and about 10 wt%, about 5 wt% and about 10 wt%, about 6 wt% and about 10 wt%, about 8 wt% and about 10 wt%, about 1 wt% and about 8 wt%, about 1 wt% and about 6 wt%, about 1 wt% and about 4 wt%, about 1 wt% and about 2 wt%, about 2 wt% and about 8 wt%, about 4 wt% and about 8 wt%, or about 6 wt% and about 18 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges.
[0066] The sprayable-skin formulation 100 can further include a particle coating agent 108. The particle coating agent 108 is configured to coat the UV protecting agent 106 and to aid in dispersibility of inorganics (e.g., the UV protecting agent 106) in the sprayable-skin formulation 100, which is aqueous. For example, the particle coating agent 108 can coat the inorganic particles and disperse the inorganic particles in the formulation 100. In some embodiments, the particle coating agent 108 includes polyethylene glycol (PEG)-12 dimethicone, dimethicon PEG-8 Laurate, or a combination thereof.
[0067] In some embodiments, the sprayable-skin formulation 100 can include about 0.5 wt% to about 15 wt% of the particle coating agent 108 based on the total weight of the sprayable-skin formulation 100. In some embodiments, the amount of particle coating agent 108 is between about 1 wt% and about 15 wt%, about 2 wt% and about 15 wt%, about 5 wt% and about 15 wt%, about 10 wt% and about 15 wt%, about 0.5 wt% and about 10 wt%, about 0.5 wt% and about 5 wt%, about 0.5 wt% and about 2 wt%, about 0.5 wt% and about 1 wt%, about 1 wt% and about 10 wt%, about 2 wt% and about 10 wt%, about 5 wt% and about 10 wt%, or about 10 wt% and about 15 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges.
[0068] For example, the particle coating agent 108 can include an ethoxylated poly dimethylsiloxane. In some embodiments of the sprayable-skin formulation 100, the amount of ethoxylated poly dimethylsiloxane is between about 0 wt% and about 3 wt%, about 0 wt% and about 2.5 wt%, about 0 wt% and about 2.0 wt%, about 0 wt% and about 1.5 wt%, about 0 wt% and about 1 wt%, about 0.10 wt% and about 3 wt%, about 0.10 wt% and about 2.5 wt%, about 0.10 wt% and about 2 wt%, about 0.10 wt% and about 1.5 wt%, about 0. 10 wt% and about 1 wt%, about 1 wt% and about 3 wt%, about 1.5 wt% and about 3 wt%, about 2 wt% and about 3 wt%, about 2.5 wt% and about 3 wt%, about 1.5 wt% and about 2.5 wt%, about 1 wt% and about 2.5 wt%, or about 1.5 wt% and about 2 wt% based on the total weight of the spray able-skm formulation 100, among other ranges. An example ethoxylated poly dimethylsiloxane includes PEG-12 dimethicone, such as Silsurf® D212-CG.
[0069] In some embodiments, the particle coating agent 108 can include a lubricant. In some embodiments of the spray able-skin formulation 100, the amount of lubricant is between about 0.5 wt% and about 12 wt%, about 1 wt% and about 10 wt%, about 0.5 wt% and about 10 wt%, about 0.5 wt% and about 5 wt%, about 0.5 wt% and about 3 wt%, about 0.5 wt% and about 1 wt%, about 1 wt% and about 15 wt%, about 5 wt% and about 15 wt%, about 8 wt% and about 15 wt%, about 10 wt% and about 15 wt%, about 2 wt% and about 10 wt%, about 5 wt% and about 10 wt%, or about 5 wt% and about 8 wt% based on the total weight of the spray able-skin formulation 100, among other ranges. An example lubricant includes a dimethicon PEG-8 Laurate, such as Silwax® WS-L or other silicone-esters.
[0070] In some embodiments, the particle coating agent 108 can include the ethoxylated poly dimethylsiloxane and the lubricant. For example, the particle coating agent 108 can include a combination of PEG- 12 dimethicon and dimethicon PEG-8 Laurate.
[0071] The sprayable-skm formulation 100 can be water-based and further includes a water-miscible solvent 112. Non-limiting examples of water-miscible solvents include water, ethanol, and water and ethanol, among others that are miscible in water. The water-miscible solvent 112 can assist with evaporation and/or be in the form of an emulsifier to incorporate additives and to enhance SPF values or other cosmetic components. For example, the water-miscible solvent 112 can provide or increase evaporability of the spray able-skin formulation 100 in response to application thereof. In some embodiments, the sprayable-skin formulation 100 includes a water-miscible solvent 112 of water and ethanol. The combination of water and ethanol can provide viscosity, sprayability, and evaporation properties.
[0072] In some embodiments, the sprayable-skin formulation 100 includes about 5 wt% to about 30 wt% of water-miscible solvent 112 based on the total weight of the sprayable-skin formulation 100. In some embodiments, the amount of water-miscible solvent 112 is between about 5 wt% and about 25 wt%, about 5 wt% and about 20 wt%, about 5 wt% and about 15 wt%, about 5 wt% and about 10 wt%, about 10 wt% and about 30 wt%, about 15 wt% and about 30 wt%, about 20 wt% and about 30 wt%, about 25 wt% and about 30 wt%, about 10 wt% and about 25 wt%, about 10 wt% and about 20 wt%, or about 15 wt% and about 20 wt% based on the total weight of the spray able- skin formulation 100, among other ranges.
[0073] In some embodiments, the water-miscible solvent 112 includes water. In some embodiments, the amount of water is between about 2 wt% and 20 wt%, about 2 wt% and about 18 wt%, about 2 wt% and about 16 wt%, about 4 wt% and about 14 wt%, about 5 wt% and about 18 wt%, about 5 wt% and about 15 wt%, about 5 wt% and about 10 wt%, about 10 wt% and about 20 wt%, about 10 wt% and about 15 wt%, or about 10 wt% and about 12 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges. As may be appreciated, the above listed amounts of water are referring to additional water added to the sprayable-skin formulation 100 as a solvent and does not include the wt% of water in the polyurethane polymer solution 102 and the water-dispersible polymer solution 104.
[0074] In some embodiments, the water-miscible solvent 112 includes ethanol. In some embodiments, the sprayable-skin formulation 100 includes about 1 wt% to about 10 wt% of ethanol, based on the total weight of the sprayable-skin formulation 100. In some embodiments, the amount of ethanol is between about 1 wt% and about 8 wt%, about 1 wt% and about 5 wt%, about 1 wt% and about 2 wt%, about 2 wt% and about 10 wt%, about 5 wt% and about 10 wt%, about 8 wt% and about 10 wt%, about 2 wt% and about 8 wt%, about 5 wt% and about 8 wt%, or about 5 wt% and about 6 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges. In some embodiments, the sprayable-skin formulation 100 includes ethanol in an amount between about 0 wt% and about 10 wt%, about 0 wt% and about 8 wt%, or about 1 wt% and about 6 wt%, among other ranges.
[0075] In some embodiments, the water-miscible solvent 112 includes water and ethanol in any of the above provided ranges and combinations. In some embodiments, the sprayable-skin formulation 100 includes between about 2 wt% and 20 wt% water and about 1 wt% and about 10 wt% ethanol based on the total weight of the sprayable-skin formulation 100. In some embodiments, the sprayable-skin formulation 100 includes between about 5 wt% and 20 wt% water and about 1 wt% and about 10 wt% ethanol, about 5 wt% and 15 wt% water and about 1 wt% and about 10 wt% ethanol, about 5 wt% and 10 wt% water and about 1 wt% and about 10 wt% ethanol, about 10 wt% and 20 wt% water and about 1 wt% and about 10 wt% ethanol, about 15 wt% and 20 wt% water and about 1 wt% and about 10 wt% ethanol, about 5 wt% and 20 wt% water and about 5 wt% and about 10 wt% ethanol, about 5 wt% and 20 wt% water and about 8 wt% and about 10 wt% ethanol, about 5 wt% and 20 wt% water and about 1 wt% and about 5 wt% ethanol, about 5 wt% and 15 wt% water and about 5 wt% and about 10 wt% ethanol, about 5 wt% and 10 wt% water and about 5 wt% and about 10 wt% ethanol, or about 5 wt% and 15 wt% water and about 5 wt% and about 8 wt% ethanol based on the total weight of the spray able-skin formulation 100, among other ranges. [0076] In some embodiments, as further illustrated by FIG. IB, the spray able-skin formulation 100 further includes additional components. For example, the sprayable- skin formulation can include a color pigment mixture, a pigment coating agent for particles of the color pigment mixture, an antioxidant and metal chelate, a functional filler, and/or a UV protection booster, among other additives or ingredients. For example, additional additives can be added to enhance UV protection or other cosmetics.
[0077] The color pigment mixture can include a mixture of iron oxide or other colorants and which are configured to provide a visible color to the resulting film, similar to a foundation or concealer. For example, the color pigment mixture can assist with hiding skin imperfections, such as blemishes, discolored skin, birthmarks, scars, and other imperfections. Example color pigment mixtures include different ratios of yellow, red, and/or black iron oxide particles, such as Cl 77492, Cl 77491, and Cl 77499. In some embodiments, the sprayable-skin formulation 100 includes between about 0.01 wt% and about 2 wt% of color pigments based on the total weight of the sprayable-skin formulation 100. Each of the different pigments can be present in an amount between about 0 wt% and about 4 wt%, about 0 wt% and about 2 wt%, or about 0 wt% and about 1 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges. Examples are not so limited and can include other colorants such as Bismuth Oxychloride, D&C colorants, FD&C colorants. Chromium Hydroxide, Chromium Oxide, Mica, Ultramarines, Talc, and Luminescent Zine Sulfide, among others.
[0078] The pigment coating agent can coat the particles of the color pigment mixture such that the particles are dispersed in solution. In some embodiments, the particles of the color pigment mixture can be pre-coated with the pigment coating agent. In some embodiments, the sprayable-skin formulation 100 includes between about 0.01 wt% and about 2 wt% of pigment coating agent based on the total weight of the sprayable-skin formulation 100. In some embodiments, the amount of the pigment coating agent is between about 0. 1 wt% and about 2 wt%, about 0.5 wt% and about 2 wt%, about 1 wt% and about 2 wt%, about 1.5 wt% and about 2 wt%, about 0.01 wt% and about 1.5 wt%, 0.01 wt% and about 1.0 wt%, about 0.01 wt% and about .05 wt%, about 0.01 wt% and about 0. 1 wt%, about 0.1 wt% and about 1.5 wt%, or about 1.0 wt% and about 1.5 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges. In some embodiments, the pigment coating agent includes a hydrogen dimethicone, such as Pecosil® SH-25L. In some embodiments, the amount of hydrogen dimethicone is between about 0 wt% and about 1.5 wt%. In some embodiments, the amount of hydrogen dimethicone is between about 0 wt% and about 1 wt%.
[0079] The antioxidant and metal chelate may act as a stabilizer. An example antioxidant and metal chelate includes sodium phylate, such as Greengard. In some embodiments, the sprayable-skin formulation 100 includes between about 0.01 wt% to about 0.5 wt% of an antioxidant and metal chelate based on the total weight of the sprayable-skin formulation 100. In some embodiments of the skin formulation, the amount of antioxidant and metal chelate is between about 0 wt% and about 0.4 wt%, about 0 wt% and about 0.3% wt%, about 0. 1 wt% and about 0.5 wt%, about 0.2 wt% and about 0.5 wt%, about 0.3 wt% and about 0.5 wt%, about 0.4 wt% and about 0.5 wt%, about 0.01 wt% and about 0.4 wt%, about 0.01 wt% and about 0.3 wt%, about 0.01 wt% and about 0.2 wt%, about 0.01 wt% and about 0.1 wt%, about 0.1 wt% and about 0.4 wt%, or about 0.2 wt% and about 0.3 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges. In some embodiments, the antioxidant and metal chelate may additionally assist with dispersing particles. [0080] In some embodiments, the spray able-skin formulation 100 contains one or more functional fillers, sometimes referred to as cosmetic fillers. The functional fillers can scatter light to hide skin imperfections, such as blemishes. Example functional fillers include silica, titanium dioxide, iron oxide, illite, cellulose particles, amino acids or amino acid derivatives, and combinations thereof. Some specific example functional fillers include RonaFlair® Flawless, RonaFlair® Satin, Amihope® LL, and Amihope® OL. The spray able-skin formulation 100 can include between about 0.01 wt% to about 10 wt% of the functional filler based on the total weight of the sprayable-skin formulation 100. In some embodiments, the amount of the functional filler may be between about 0.01 wt% and about 8 wt%, about 0.01 wt% and about 6 wt%, about 0.01 wt% and about 4 wt%, about 0.01 wt% and about 2 wt%, about 0.01 wt% and about 1 wt%, about 0.1 wt% and about 10 wt%, about 1 wt% and about 10 wt%, about 2 wt% and about 10 wt%, about 4 wt% and about 10 wt%, about 6 wt% and about 10 wt%, about 8 wt% and about 10 wt%, about 0.1 wt% and about 8 wt%, about 1 wt% and about 6 wt%, or about 2 wt% and about 4 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges.
[0081] In some embodiments, the functional filler includes one or more of RonaFlair® Flawless, RonaFlair® Satin, Amihope® LL, and Amihope® OL. In some embodiments, the functional filler includes two or more of RonaFlair® Flawless, RonaFlair® Satin, Amihope® LL, and Amihope® OL.
[0082] RonaFlair® Flawless is formed of silica, titanium dioxide (Cl 77891) and iron oxide (Cl 77491). More particularly, Ronaflair® Flawless is a peach colored powder including silica microspheres coated with titanium dioxide and iron oxide. In some embodiments, the particle size (e.g., the microspheres) distribution of RonaFlair® Flawless in the 80% range is about 1.0 micron (pm) to about 25.0 pm and the average particle size is about 4 pm to about 8 pm.
[0083] RonaFlair® Satin is a naturally sourced functional filler based on kaolin and mica. In various embodiments, RonaFlair® Satin is formed of particles of illite. In some embodiments, the particle distribution of RonaFlair® Satin in the 80% range is less than about 25 pm [0084] Amihope® is an amino-acid derivative made from L-Lysine and a fatly acid, formed of fiat and hexagonal shaped particles. The structure of the amino-acid derivative can include:
Figure imgf000022_0001
wherein R is Cl 1H23 for Amihope® LL or C7H15 for Amihope® OL. The particles can have a mean particle size of about 20 pm to about 30 pm.
[0085] In some embodiments, the amount of each functional filler can be between about 0 wt% and about 10 wt%, about 0 wt% and about 8 wt%, about 0 wt% and about 6 wt%, or about 0 wt% and about 4 wt% based on the total weight of the sprayable-skin formulation 100. In embodiments where the sprayable-skin formulation 100 contains more than one functional filler, the amount of each functional filler can be the same or different.
[0086] In some embodiments, the sprayable-skin formulation 100 includes a UV protection booster. The UV protection booster can include polymer particles that scatter light for the inorganics. Example UV protection boosters include a styrene/acrylates copolymer and Pongamia Pinnata seed extract, such as Sunspheres™, Assure+, and others. In some embodiments, the sprayable-skin formulation 100 can include about 0.01 wt% to about 5 wt% of the UV protection booster based on the total weight of the sprayable-skin formulation 100. In some embodiments, the amount of UV protection booster is between about 0 wt% and about 5 wt%, about 0 wt% and about 4 wt%, about 0 wt% and about 3 wt%, about 0.01 wt% and about 4 wt%, about 0.01 wt% and about 3 wt%, about 0.01 wt% and about 2 wt%, about 0.01 wt% and about 1 wt%, about 0.1 wt% and about 5 wt%, 1 wt% and about 5 wt%, 2 wt% and about 5 wt%, 3 wt% and about 5 wt%, 4 wt% and about 5 wt%, 1 wt% and about 4 wt%, 2 wt% and about 4 wt%, or 2 wt% and about 3 wt% based on the total weight of the sprayable-skin formulation 100, among other ranges.
[0087] FIG. IB illustrates an example implementation of the sprayable-skin formulation 100 of FIG. 1A. The example sprayable-skin formulation 101 includes a polyurethane polymer dispersion 103, a water-dispersible polymer emulsion 105, a UV protecting agent 106, a particle coating agent 108, water-miscible solvent 112, and one or more of an additive 110, color pigment mixture 114, pigment coating agent 116, an antioxidant and metal chelate 118, a functional filler 120, and a UV protection booster 122, as previously described in connection with FIG. 1A and shown by the common numbering. As shown by FIG. IB, in some embodiments, the water-miscible solvent 112 includes water 113 and/or ethanol 115. The functionalities, example wt%, and properties of the common components are not repeated for ease of reference. [0088] In some embodiments, somewhat surprisingly, the sprayable-skm formulation 100, 101 of FIGs. 1A-1B which include polyurethane and water-dispersible polymer solutions in a high concentration of at least 50 wt% and additives of inorganic UV protecting agents and a particle coating agent, are sprayable and configured to cure to form a film. For example, the sprayable-skin formulation 100, 101 can be sprayed onto skin and allowed to dry to form an elastic and UV protecting film. In some embodiments, the sprayable-skin formulation 100, 101 can cure and form the film, after spraying on a skin surface, within about 1 minute to about 5 minutes. The resulting film can be durable such that other cosmetics can be applied on top of the film, and the film may last the entire day without reapplication. Additionally, the film is elastic such that the film moves with the skin and can be removed via peeling and/or with water. In different implementations, the film provides UV protection and color correction and/or hiding of imperfections, among other features described above.
[0089] While the above and below embodiments described a sprayable-skin formulation, which may be used for cosmetics, embodiments are not so limited. For example, embodiments can include a formulation including a combination of the above components, which is used for a different purposes. An example embodiment includes a sprayable formulation, which can be spread onto surfaces other than skin. In other embodiments, the formulation may be applied using techniques other than spraying. For example, a skin or other surface coating formulation may be applied using other techniques. In any of the above alternative embodiments, the example formulation may include at least the polyurethane polymer solution 102, the water-dispersible polymer solution 104, and water-miscible solvent 112. In some embodiments, the formulation additionally includes the UV protecting agent 106 and the particle coating agent 108, and optionally the UV protection booster 122. In some embodiments, the formulation additionally includes the color pigment mixture 114, the pigment coating agent 116, and optionally one or more of the antioxidant and metal chelate 118 and the functional filler 120. In some embodiments, the formulation additionally includes different combinations of the UV protecting agent 106, the particle coating agent 108, the UV protection booster 122, color pigment mixture 114, the pigment coating agent 116, the antioxidant and metal chelate 118, and the functional filler 120.
[0090] FIG. 2 illustrates an example kit for forming a sprayable-skin formulation, in accordance with the present disclosure. In some embodiments, the kit 230 can include or be used to form the sprayable-skin formulation(s) 100, 101 illustrated by FIGs. 1A-1B. [0091] As shown by FIG. 2, the kit 230 for forming the sprayable-skin formulation includes: (i) about 45 wt% to about 85 wt% of a polyurethane polymer dispersion 103 based on the total weight of the formulation, (ti) about 5 wt% to about 15 wt% of a water-dispersible polymer emulsion 105 based on the total weight of the formulation, (iii) about 0.5 wt% to about 15 wt% of a UV protecting agent 106 based on the total weight of the formulation, (iv) about 0.5 wt% to about 15 wt% of a particle coating agent 108 based on the total weight of the formulation, and (v) a balance of water- miscible solvent 112. As previously described, in some embodiments, the ratio of the polyurethane polymer dispersion 103 to the water-dispersible polymer emulsion 105 is between about 5: 1 and about 10: 1.
[0092] The kit 230 may include various different optional components, including but not limited to an additive 110, color pigments 114, a pigment coating agent 116, antioxidant and metal chelate 118, a functional filler 120, and UV protection booster 122, as previously described in connection with FIGs. 1A-1B.
[0093] In some embodiments, the water-miscible solvent 112 includes about 1 wt% to about 10 wt% of ethanol based on the total weight of the formulation. In some embodiments, the water-miscible solvent 112 includes water and ethanol, such as about 1 wt % to about 10 wt% of ethanol and about 5 wt% to about 20 wt% of water. In some embodiments, the water-miscible solvent 112 includes water, such as about 1 wt% to about 20 wt% and without ethanol. [0094] In some embodiments, the kit 230 further includes about 0.01 wt% to about 2 wt% of color pigments 114 based on the total weight of the fonnulation and about 0.01 wt% to about 2 wt% of a pigment coating agent 116 based on the total weight of the formulation.
[0095] In some embodiments, the kit 230 further includes: (i) about 0.01 wt% to about 0.5 wt% of an antioxidant and metal chelate 118 based on the total weight of the formulation, (ii) about 0.01 wt% to about 10 wt% of a functional filler 120 based on the total weight of the formulation, and/or (lii) about 0.01 wt% to about 5 wt% of a UV protection booster 122 based on the total weight of the formulation.
[0096] In some embodiments, the formulation is sprayable as an aerosol and configured to cure and form an elastic and UV protecting film on skin within about 1 minute to about 5 minutes after spraying. In some embodiments, the kit 230 may further include an aerosol container 232 configured to contain the sprayable-skin formulation in the form of one of an emulsion and a suspension including the polyurethane polymer dispersion 103, the water-dispersible polymer emulsion 105, the UV protecting agent 106, the particle coating agent 108, and water-miscible solvent 112, among the other optional components.
[0097] FIG. 3 illustrates an example method of applying a sprayable-skin formulation, in accordance with the present disclosure. In some embodiments, the method 340 can be implemented using the sprayable-skin formulation(s) 100, 101 ofFIGs. 1 A- IB and/or the kit 230 of FIG. 2. For example, the method 340 can include using a sprayable-skin formulation, including the wt% ranges, as described above.
[0098] As shown at 342, the method 340 includes spraying a layer of sprayable-skin formulation to skin. The sprayable-skin formulation can include polyurethane polymer dispersion, a water-dispersible polymer emulsion, UV protecting agent, a particle coating agent, and water-miscible solvent, among the other optional components as previously described. As shown at 344, the method 340 includes dry ing, via exposure to air, the layer to form an elastic and UV protecting film on the skin.
[0099] In some embodiments, the film is durable such that the film is cohesive and configured to remain intact on the skin in response to contact. In some such embodiments, the method 340 further comprises removing the film by at least one of peeling the film and applying water to the film. In various embodiments, the film comprises about 5 wt% to about 20 wt% of the UV protecting agent based on the total weight of the film. For example, the film can provide Sun Protection Factor (SPF) of at least 15, such as between about SPF 15 and SPF 50.
[00100] The resulting film can have a thickness of between about 5 microns and about 80 microns. In some embodiments, the film may additionally be at least substantially uniform in thickness, such as varying less than 5%.
[00101] In some embodiments, the firm can be durable such that a layer of other cosmetics may be applied on top of the film. For example, the method 340 can further include applying the layer of other cosmetics on top of the film.
[00102] Embodiments are not limited to the method 340 of FIG. 3 and may include other methodologies and/or be used to form a kit, such as the kit 230 of FIG. 2. Various embodiments are directed to methods of forming the sprayable-skin formulation and/or kit, such as methods of forming the formulation as an emulsion or a suspension.
[00103] The following is an example method of forming a sprayable-skin formulation as an emulsion. The polymers (e.g., polyurethane polymer solution and water-dispersible polymer solution) and other components that are soluble in oil are dissolved in the solvent to form an oil phase. The components that are soluble in water are dissolved in water to form an aqueous phase. The oil phase and aqueous phase are blended to form an emulsion, and optionally an emulsifying agent is added.
[00104] The following is an example method of forming a sprayable-skin formulation as a suspension. The components which are water soluble are dissolved in water, including ionic or non-ionic surfactants, thickening agents, viscosity modifiers, wetting agents, and buffering agents. The stabilizers can prevent the formation of a cake or sediment upon storage. The polymer is dissolved or dispersed in solvent. The two solutions are blended along with UV protecting agents, with the solids added slowly to avoid formation of agglomerate and form a suspension.
[00105] Embodiments are not limited the above described methods of forming the sprayable-skin formulation, and methods can include variations thereof.
[00106] Embodiments are not limited to the specifically illustrated sprayable-skin formulation 100, 101 of FIGs. 1 A-1B and/or kit illustrated by FIG. 2, and may include different combinations of the features described therein. For example, a kit may be formed of the components illustrated by any of FIGs. 1A-1B. Similar, the sprayable- skin formulation may be formed of the wt% of components as illustrated by FIG. 2. [00107] Some embodiments are directed to pre-mixtures which may be used to form the formulations and/or kits described herein, and/or to perform any methods described herein. The pre-mixtures can include a polymer mixture, a silicone mixture, and a pigment mixture, among others.
[00108] FIG. 4 illustrates example pre-mixtures, in accordance with the present disclosure. The pre-mixtures 450 include a polymer mixture 452, a silicone mixture 454, and/or a pigment mixture 456, among others. In some embodiments, each of the premixtures 450 can be separately formed and packaged.
[00109] In some embodiments, the polymer mixture 452 includes the polyurethane polymer dispersion 403 and the water-dispersible polymer emulsion 405, as previously described in connection with FIGs. 1A-1B. The silicone mixture 454 can include a first particle coating agent 408-1 and a second particle coating agent 408-2. In some embodiments, the first particle coating agent 408-1 can include PEG-12 dimethicone, and the second particle coating agent 408-2 can include dimethicon PEG-8 Laurate, although embodiments are not so limited. In some embodiments, the silicone mixture 454 further includes the UV protecting agent 406. For example, the particles of the UV protecting agent 406 may be pre-coated with the first particle coating agent 408-1 and the second particle coating agent 408-2 in the silicone mixture 454. In some embodiments, the pigment mixture 456 includes a first color pigment 414-1, a second color pigment 414-2, and a third color pigment 414-3 or combinations thereof, such as iron oxide yellow, iron oxide red, and/or iron oxide black. In some embodiments, the pigment mixture 456 further includes the pigment coating agent 416 that coat the color pigments 414-1, 414-2, 414-3 in the pigment mixture 456.
[00110] The various ranges provided herein include the stated range and any value or sub-range within the stated range. Furthermore, when “about” is utilized to describe a value, this includes, refers to, and/or encompasses variations (up to +/- 10%) from the stated value. Wt%, as used herein, includes or refers to a weight of a component as a percent of the total weight of the formulation or solution. [00111] Reference throughout the specification to “examples”, “an example”, “some examples”, and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the example is included in the example described herein, and may or may not be present in other examples. In addition, it is to be understood that the described elements for any embodiment may be combined in any suitable manner in the various embodiments unless the context clearly dictates otherwise.
[00112] In describing and claiming the embodiments disclosed herein, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise.
[00113] Although specific embodiments have been illustrated and described herein, a variety of alternate and/or equivalent implementations may be substituted for the specific embodiments shown and described without departing from the scope of the present disclosure. This application is intended to cover any adaptations or variations of the specific embodiments discussed herein. Therefore, it is intended that this disclosure be limited only by the claims and the equivalents thereof.
EXPERIMENTAL EMBODIMENTS
[00114] A number of experimental embodiments were conducted to generate a sprayable-skin formulation and to characterize properties of the sprayable-skin formulation and the resulting film formed therefrom.
[00115] In some experimental embodiments, for making the sprayable-skin formulation, different pre-mixtures were prepared. In some embodiments, a polymer mixture was prepared. The polymer mixture included Baycusan® C 1001(90 parts by wt.) mixed with DOWSIL™ FA 4103 (10 parts by wt.). In some embodiments of the sprayable-skin formulation, the silicone mixture was also be prepared. In an embodiment, the silicon mixture was Silsurf® D212-CG (1 part by wt.) mixed with Silwax® WS-L (9 parts by wt.). In some embodiments, the pigment mixture was also pre-prepared. In an embodiment of the pigment mixture, the mixture is by weight iron oxide yellow (74.29 parts), iron oxide red (18.57 parts), and iron oxide black (7. 14 parts). In some embodiments of the sprayable-skin formulation, 34.5 mg of the pigment mixture was placed in a microcentrifuge tube and around 0.5 rnL of hydrogen dimethicone was added. The mixture was vortexed for 5 minutes, centrifuged, and washed 3 times with ethanol to remove the non-coated hydrogen dimethicone and the mix was allowed to dry. The coating on inorganics with dimethicone in a commercial setting may be conducted with a blender and only a trace of silicone. In some embodiments, the UV protecting agents are coated with the silicone mixture. In some embodiments, ten parts of Zano® 10 plus was mixed with eleven parts of the silicone mixture in a mixer. In some embodiments, the formulation contained one part by volume stabilizing solution (sodium phytate GreenGuard) and nine-part by volume water.
[00116] In some embodiments, the skin formulation consisted of the following: 69.75 wt% Baycusan® C 1001, 7.75 wt% DOWSIL™ FA 4103, 0.43 wt% Silsurf® D212, 3.87 wt% Silwax™, 2.3 wt% Zano® 10 plus, 0.23 wt% pigment mixture, 0.3 wt% GreenGuard, 1.95 wt% ethanol, 4.5 wt% RonaFlair® Flawless, 1.25 wt% RonaFlair® Satin, and 7.6 wt7% water based on the total weight of the formulation.
[00117] In some embodiments, the formulation procedure was:
1. Mixture containing ten parts of coating of the Zano® 10 with eleven parts silicone mix (Silsurf® D212-CG (1 part by wt.) was mixed with Silwax® WS-L (9 parts by wt.) (0.69 g) was placed into a mixing container.
2. Functional filler (RonaFlair® Flawless, 0.675 g), (RonaFlair® Satin (0.1875 g)), silicone mixture (0.3 g) were then added.
3. The iron oxide was then added and the vial containing the oxide was rinsed out into the mixing vessel with the ethanol (0.295 g), water (0.7455 mL), and sodium phytate GreenGuard solution with water (0.45 rnL).
4. Polymer mixture (11.625 g of 90 parts Baycusan™® C 1001 by wt. and 10 parts by wt. DOWSIL™ FA 4103) was then added to the mixing container which was then mixed to provide the cosmetic mix.
[00118] In some embodiments, skin properties were assessed using various resources. It was noted that the formulation would be beneficial to mimic such properties. Table 1 below provides example skin properties and comments on the film. Table 1
Figure imgf000030_0001
[00119] As may be appreciated, for both TiO2 particles and ZnO particles particle size impacts the amount of UV protection, with particles of a diameter of 100 nm or less having higher levels of protection (absorbance) than larger particles. The particles with 100 nm diameter or less also have lower whitening effects than the larger particles.
[00120] In some experiments, a one-step siloxane polymer was assessed for forming the sprayble-skin formulation. Two different polysiloxane film formers were assessed that cure into an elastic film without the application of a catalyst (e.g., without silicone monomers). Siloxane film formers were used in place of silicon monomers (e.g., vinyl- and hydrogen-terminated silicone). The two siloxane film formers tests were Trimethylsiloxysilicate and Cyclopentasiloxane (Shin-Etsu X-21-5250, herein sometimes referred to as “5250”) having a viscosity of 60 mm2/s and Trimethylsilioxysilicate and Isododecane (Shin-Etsu X-21-5595, herein sometimes referred to as “5595”) having a viscosity of 35 mm2/s. The two siloxane film formers were mixed at different ratios to adjust the film properties, with 5595 being a hard film former and 5250 being a mild film former. Table 2 illustrates the results:
Table 2
Figure imgf000030_0002
Figure imgf000031_0001
Based on the above results, it was confirmed that the film formers maintain film formation but may not provide sufficient elasticity .
[00121] Some experiments were directed to assessing the effect of adding silicone solvents to the siloxane film formers from Table 2. The mixed ratios of siloxane film formers from Table 2 were diluted with cosmetic silicone solvents from Table 3. Table 4 shows the results.
Table 3
Figure imgf000031_0002
Table 4
Figure imgf000031_0003
Figure imgf000032_0001
While the elastic films could be maintained, the films tackiness may not be suitable for artificial skin.
[00122] Various embodiments were directed to examining different polyurethane polymer formulations. Two different polyurethane polymer solutions were assessed: (1) Baycusan® C 1001, and (2) Baycusan® C 1004. Both polymers exhibited good transparency and film forming ability. Baycusan® C 1001 was slightly more elastic than Baycusan® C 1004, but both satisfied qualitative elasticity requirements for an artificial skin film. In some embodiments, these polymer formulations were modified through the addition of various solvents and viscosity modifiers. In some embodiments, modification of the Baycusan® C 1004 formulation with PEG-40, a humectant and viscosity modifier, was successful for producing a spray-able polymer formulation and elastic film. In some embodiments, modification of the Baycusan® C 1001 formulations with similar additives proved unsuccessful. In further embodiments, Baycusan® C 1001 was modified using an acrylate modifier to create a hybrid polyurethane-acrylate polymer.
[00123] Both Baycusan® formulations were supplied as colloidal suspensions in water or ethanol, confirmed to be spray able, allow for suspension of nanoparticles readily coalesces into a continuous film, and the structure allows for internal hydrogen bonding and interaction with Keratin found in the skin. Baycusan® C 1001 is a safe cosmetic ingredient that is a co-polymer based on hexamethylene diisocyanate, and has a viscosity of < 1000 mPa-s and a % solids of 32%. The structure of hexamethylene diisocyanate is illustrated below:
Figure imgf000033_0001
Baycusan® C 1004 is a safe cosmetic ingredient that is a co-polymer based on dicyclohexylmethane diisocyanate, and has a viscosity of < 500 mPa-s and a % solids of 41%. The structure of dicyclohexylmethane diisocyanate is illustrated below:
Figure imgf000033_0002
[00124] FIGs. 5A-5B illustrate example films formed from a polyurethane polymer formulation, in accordance with the present disclosure. In some embodiments, Baycusan® C 1001 was cast neat (100%) and as ethanol diluted formulation onto a glass slide. The polymer was allowed to dry for around 1.5 hours, with the drying time depending on the film thickness as well as the substate used. The dried film was transparent and had mnimal blemishes/inhomogeneity. The film thickness was 0.32 mm. As shown by FIGs. 5A-5B, Baycusan® C 1001 cures into a transparent film. The film was additionally stretched without breaking, thus showing that the Baycusan® C 1001 formed an elastic film.
[00125] FIGs. 6A-6C illustrate example films formed from modified polyurethane polymer formulations, in accordance with the present disclosure. In various embodiments, Baycusan® C 1001 and Baycusan® C 1004 were modified for providing sprayability and/or elasticity.
[00126] In some embodiments, Baycusan® C 1001 was thinned out with a cream to form formulation 1 and formulation 2. The cream was a mask cream which was used to thin out Baycusan® C 1001 to provide sprayability. Formulation 1 may be too thick to spray and was further modified to remove cream forming agents, pH modifier and Ultrez 20. In formaulation 2, Ultrez 20 was replaced with Atroflex AVC, which has a thickening effect that is more controlable. During initial testing, a drop casting solution yeilded an elastic, transparent film. However, spray attempt clogged the top loading airbrush (Badger 100) which was believed to be due to fast water evaporation upon aerosolization. The formulation was sprayed using a bottom loading airbrush (Badger 250). FIG. 6A illustrates a resulting film formed by drop casted Baycusan® C 1001 Cream (formulation 1) which was cured in 2 hours, was 0.04 mm thick and was peelable to remove in multiple pieces. Table 5 below summarizes formulations 1 and 2.
Table 5
Figure imgf000034_0001
Figure imgf000035_0001
Atempted spraying of formulation 2 with airbrush Badger 100 led to clogging but was sprayed with airbrush Badger 250. The results indicated that further modification of Baycusan® C 1001 may be useful. Table 6 below illustrates another generated formulation 3.
Table 6
Figure imgf000035_0002
[00127] FIGs. 6B-6C illustrate resulting films formed using modified Baycusan® C 1004. Baycusan® C 1004 was identifed as not being sufficiently elastic for artificial skin and was modifed using PEG-40 to improve elasticty. PEG-40 is a water and oil soluable emusifier, emollient, and surfactant. FIG. 6B illustrates a film formed from Baycusan® C 1004-PEG-40 (39: 1 ratio) and FIG. 6C illustrate a film formed of Baycusan® C 1004-PEG-40 (116: 1 ratio) after curing for 24 hours (FIG. 6B). The 39: 1 ratio is a viscous solution and resulted in an uneven and inhomgenous film. The 116:1 ratio was a low viscous solution and resulted in an even relatively homogous film (FIG. 6C). The experimetnts illustrated that Baycusan® can be adjusted from an elastic film to an elastic film using PEG-40.
[00128] Various embodiments were directed to examining different hybrid polymer formulations. Two different hybrid polymer formulations were assessed: (1) a hybrid polyurethane-acrylate polymer using Baycusan® C lOOl-DOWSIL™ FA 4103, and (2) hybrid polyurethane-silicone elastomers using the Polyderm-NuLastic polymer systems. The hybrid Baycusan® C lOOl-DOWSIL™ FA 4103 yields good spray, elasticity, and transparency results. The second formulation based on hybrid polyurethane-silicone elastomer has been more challenging.
[00129] Some embodiments were directed to assessing the breathability (e.g., water vapor transmission rate) of a sprayed-on film of Baycusan® C lOOl-DOWSIL™ FA 4103 (90: 10 ratio) formulation. The results indicate that the polymer film is highly breathable and will not restrict water transmission from skin.
[00130] DOWSIL™ FA 4103 is a silicone acrylate emulsion which is safe cosmetic ingredient that is a 30% oil-in-water emulsion. The water-dispersible emulsion allows for the formulation with Baycusan® based polyurethanes. DOWSIL™ FA 4103 is water and sebum repellent, resistant to abrasion, has skin tightening properties, and feels smooth on the skin. Table 7 below provides example hybrid formulations:
Table 7
Figure imgf000036_0001
Figure imgf000037_0001
[00131] FIGs. 7A-7B illustrate example films formed from hybrid polymer formulations, in accordance with the present disclosure. FIG. 7A is formulation 4 and FIG. 7B is formulations 6 and 7, showing the resulting films are transparent and elastic. [00132] FIG. 8 is a graph illustrating the assessed breathability of the hybrid polymer formulation, in accordance with the present disclosure. Some embodiments were directed to assessing the breathability of the hybrid Baycusan® C 1001-DOWSIL™ FA 4103 (90: 10 ratio). More particularly, water-vapor vapor transport rate (WVTR) assessment was conducted on sprayed film of hybrid Baycusan® C 1001-DOWSIL™ FA 4103 (90:10 ratio). WVTR was measured on Mocon Permatran-W instrument Model 1/50. The measurement procedures were as follows: (i) hybrid polymer was sprayed and dried on a porous polypropylene substrate (25 pm thick, 5 cm2 area), (ii) hybrid polymer thickness: 50 - 76 pm, and (iii) WVTR temperature: 37.8 degrees C. The results of the test indicated the film has high WVTR and does not affect hybrid polymer’s WVTR, the hybrid polymer WVTR being lower than Baycusan® C 1004 (manufacuturer reports that small holes in the film may lead to large WVTR), and WVTR is higher than skin, indicating breathability. In such embodiments, the hybrid film was dried on a porous support substrate (polypropylene, 25 pm), and measured. The value appeared to be at the saturation limit of the instrument, and the actual WVTR may be even higher.
[00133] Additional hydrid polymers were tested including Alzo Polyderm and NuLastic. It was believed that the combination of Poly derm PE-PA (polyurethane) and NuLastic Silk (silicone) gave an elastomer when mixed. As Poly derm PE-PA is no longer produced, PPI-CO-200 was tested. Accordingly, embodiments were directed to forming and testing the combination of Polyderm PPI-CO-200 and NuLastic Silk-E to form a hybrid polymer. Polyderm PPI-CO-200 is a thermoplastic polyurethane elastomer (BIS-PEG-15 Dimethicone/Isophorone diisocyanate (IPDI) Copolymer) that forms a transparent and cohesive film, and is hydrophobic. NuLastic Silk-E is a silicone elastomer (Polysilicone 23) that is a film modifier, e.g. eliminates stickiness. Table 8 illustrates the resulting hybrid formulations and films.
Table 8
Figure imgf000038_0001
As shown by Table 8, the hybrid Polyderm-NuLastic polymer formulation resulted in biphasic formulation and may be used for artificial skin. [00134] Various embodimetns were directed to determining spray-ability of the different example polymers, evaluating films of the polymers, and identifying the diluent and polymer combination that gives a continuous and peel-able film.
[00135] Multiple sprayers were assessed and the Badger 250 airbrush was selected based on the assessment for further testing. The different airbrushes included a pump cosmetic sprayer, Luminess Icon stylus, Badger 100 airbrush, and Badger 250 airbrush. [00136] The hybrid Baycusan® C 1001-DOWSIL™ FA 4103 polymer formulation (90: 10 ratio) (Candidate A) was successfully sprayed onto leather. A thin (around 110 pm) artificial skin film developed. After drying, the film removed intact from the substrate, indicating elasticity and mechanical strength.
[00137] The hybrid polymer was also spray tested in the Mineral Air airbrush (YA- MAN’s) successfully. The polymer was sprayed onto leather. In order to deposit enough polymer material onto the substrate, prolonged spraying was required. No clogging was observed in the Mineral Air during the spray test, but the system clogged after sitting for a few minutes.
[00138] The modified polyurethane Baycusan® C 1004-PEG-40 (Candidate B) was successfully sprayed onto leather. A thin (around 100 pm) artificial skin film formed on the leather substrate after drying. The film can also be removed intact from the leather. [00139] FIGs. 9A-9D are images of resulting films formed using the hybrid polymer formulation of Candidate A, in accordance with the present disclosure. More particularly, FIGs. 9A-9B are images of a film formed by spraying Baycusan® C 1001 (FIG. 9A) and after peeling the film (FIG. 9B). The film was sprayed onto leather using the Badger 250 airbrush and allowed to dry for 1-2 hours. FIG. 9A illustrates the film after drying and FIG. 9B illustrates the film after attempted to peel. The film was around 110 microns thick and broke when attempting to peel, was elastic, and not tacky. FIGs. 9C-9D are images of a film formed by spraying Baycusan® C 1001-DOWSIL™ FA 4103 (FIG. 9C) and after peeling the film (FIG. 9D). The Baycusan® C 1001- DOWSIL™ FA 4103 formulation was sprayed onto leather for 20 seconds using the Badger 250 airbrush and allowed to dry for around 30 minutes. The formulation increased viscosity and prevent dripping, and after setting, the film was transparent and nearly invisible to the eye. The film was around 100 microns thick, transparent, intact, and the leather patter was apparent on the film after peeling, as shown by FIG. 9D, demonstrating good setting behavior. The film peeled in one piece, was elastic and non- tacky.
[00140] In some experiments, Candidate A was sprayed using Mineral Air sprayer onto leather and green food coloring (<10 volume percent) was added to the polymer formulation for visualization purposes. The Mineral Air sprayer sprays a finer mist and smaller droplets than the Badger 250 airbrush and requires a longer spray time (around 1 minute) than the Badger 250 (around 20 seconds). The polymer appears to be dry after 1 hour and a coherent, transparent film developed. The film was left on the leather for two days at room temperature and was peeled from the leather. After peeling, the thickness was measured to be 10-40 microns thick, and the film was elastic.
[00141] FIG. 10 is an image of a film formed using the modified polyurethane polymer formulation of Candidate B, in accordance with the present disclosure. More particularly, FIG. 10 is an image of a film formed by spraying Baycusan® C 1004-PEG- 40 (116: 1 ratio) sprayed onto leather using the Badger 250 sprayer. The polymer formulation was sprayed and allowed to dry for 6 hours, and was inconspicuous and transparent on the leather. The film was removed from the leather in a single piece after 48 hours and was intact.
[00142] Various embodiments were directed to assessing different UV protecting agents and colorants, such as minerals and iron oxide colorants. In some embodiments, titanium-oxide, zinc-oxide, and a colorant (iron oxide) were added into the hybrid polymer Baycusan® C 1001-DOWSIL™ FA 4103 (Candidate A) to demonstrate that UV-reflecting agents and colorants can be added to the polymers without affecting elasticity of the film.
[00143] To demonstrate the minerals could be formulated into the artificial skin, titanium dioxide (TiCh) was added into the hybrid polymer. The TiCh loading level was 1.6 wt% in the hybrid polymer formulation, and after drying (water evaporation) the TiCh content was 5 wt% relative to the hybrid polymer. Note that this a high TiCb content. After drop casting on a glass slide, a translucent, white artificial skin film developed. In some embodiments, the T1O2 loading level can be lowered to reduce the white color and increase transparency. [00144] FIGs. 11A-1 IB are images of a film formed using the hybrid polymer formulation of Candidate A with titanium dioxde added, in accordance with the present disclosure. In some emboidments, around 1.6 wt% of titanium dioxide (Eusolex T-AVO (105335 Eusolex® T-AVO)) was added to the hydrid polymer to form the formulation. The formulation was then drop casted onto glass and dried for a day, as shown by FIG.
11 A. After water evaportated, the polymer forms the illustrated film, and the solid titanium content is around 5 wt% with respect to the solid film. The polymer formulation is around 32 wt% polymer solution and around 68 wt% water. The resulting film was elastic and was removable from the glass, as shown by FIG. 1 IB. Such embodiments illustrate that titanium diocide can be loaded in the film and the film retains elasticity.
[00145] In some embodiments, zinc-oxide was used to create a suspension. In particular, Kobo ZnO-B was used having a primary particle size of 90 nm and which is a safe cosmetic ingredient. The suspension was unstable in water but stable at 15% loading in Baycusan® C 1004.
[00146] In some embodiments, to demonstrate that colorants can be formulated into the artificial skin, a high level (1 wt%) of red iron oxide particles was added into the hybrid polymer formulation (Candidate A). This is a high loading level, and a bright red film was expected. The iron oxide-hybrid polymer formulation was drop casted onto a glass slide and dried at room temperature. Upon drying, an opaque, red film developed. The film was easily removed from the glass. Notably, the elasticity of the artificial skin film was maintained. This demonstrates that the hybrid polymer is capable of supporting high levels of particle-based colorants such as iron oxide.
[00147] The total level of colorants in the artificial skin product may be lower. Furthermore, to produce natural looking colors that mimic skin tones, combination of multiple colorants may be used.
[00148] In some embodiments, different colorants were assessed which included surface treated and non-treat colorants. An example surface treated colorant was iron oxide red (Shin Etsu, KTP-09R), which is a silicon/alkyl treated iron oxide (or Iron Oxide, Triethoxysilylethyl Poly dimethylsiloxy ethyl Hexyl Dimethicone). Non-treated colorants include iron oxide red (Cl 77491, Making Cosmetics, average particle size 0.56 pm) and iron oxide yellow (Cl 77421, Making Cosmetics, average particle size 2.93 pm).
[00149] FIGs. 12A-12B are images of a film formed using the hybrid polymer formulation of Candidate A with an iron oxide colorant added, in accordance with the present disclosure. In such embodiments, about 1 wt% iron oxide red was added to the hybrid polymer formulation, drop casted on glass and dried for a day. After water evaporates, the hybrid polymer formulation forms a film having a solid iron oxide content of about 3 wt% of the total weight of the film, as shown by FIG. 12 A. The polymer formulation is around 32 wt% polymer solution and around 68 wt% water. The resulting film was elastic and was removable from the glass, as shown by FIG. 12B. Such embodiments illustrate that iron oxides can be added to the solution while maintaining film elasticity.
[00150] Some specific embodiments were directed to generating and assessing a polymer formulation including Candidate A with TiCb and ZnO particles to provide UV protection as well as with iron oxide pigment particles to imbue the polymer with color. Three different color formulations were created as a preliminary demonstration of the incorporation of color into the artificial skm/film. These mineral UV protection and color pigment particles did not affect the spray-ability of the polymer formulation. In various embodiments, the polymer formulation demonstrated the ability to spray the colored artificial skin polymer formulations onto skin. In some embodiments, the polymer formulation dries on the skin within 2 minutes and the material sets into a uniform film on the skin, and the color imparts a natural look similar to foundation. In some embodiments, the polymer formulation was sprayed using a nozzle diameter of between 0.43-0.45 mm, however embodiments are not so limited.
[00151] In some embodiments, the storage stability of the polymer formulations were assessed. The storage stability testing was conducted in temperature-controlled environments at temperatures: 5 degrees C, 20 degrees C, 40 degrees C, and 50 degrees C. Note that standard stability tests are conducted at 12 weeks for 5 degrees C, 20 degrees C, and 40 degrees C; while 50 degrees C was used for accelerated aging test for 4 weeks. Aging tests were conducted for 13 weeks at 5 degrees C, 20 degrees C, 40 degrees C, and 50 degrees C and with polymers in polypropylene and glass containers.
Table 9 summarizes the candidates:
Table 9
Figure imgf000043_0001
And Table 10 summarizes the storage results:
Table 10
Figure imgf000043_0002
As shown by Table 10, Candidate A polymer formulation spray-ability does not appear to be significantly affected by mass loss, and the polymer formulation effectively forms a film after spray from both the Badger and Mineral Air sprayers. For Candidate B-l, the polymer formulation does not spray as well after storage, and the polymer immediately clogs the sprayer (Mineral Air and Badger) on each attempt. The increase in clogging indicates that Candidate B may be slightly coalescing in solution or coalescing quickly in the sprayer, leading to quicker precipitation within the sprayer. Candidate B poly mer (Baycusan® C 1004) is much more cross-linked than Candidate A (Baycusan® C 1001), which may negatively affect spray. [00152] FIGs. 13A-13D are graphs showing the storage stability results, in accordance with the present disclosure. FIG. 13A and FIG. 13B show Candidate A samples in a polypropylene bottle (FIG. 13 A) and a glass bottle (FIG. 13B). Both Candidate A samples exhibit increased mass loss with increasing temperature, but low overall loss (< 4%), with a 3-month storage test complete for polypropylene samples, and solutions visually appear unchanged in all samples. Tables 11-12 summarize the results for Candidate A.
Table 11 : Candidate A, polypropylene bottle
Figure imgf000044_0001
Table 12: Candidate A, glass bottle
Figure imgf000044_0002
[00153] FIG. 13C and FIG. 13D show Candidate B-l samples in a propylene bottle (FIG. 13C) and a glass bottle (FIG. 13D). Both Candidate B-l samples exhibit increased mass loss with increasing temperature, but low overall loss (< 3%), and solutions visually appear unchanged in all samples. Tables 13-14 summarize the results for Candidate B-l.
Table 13: Candidate B-l, polypropylene bottle
Figure imgf000044_0003
Figure imgf000045_0001
Table 14: Candidate B-l, glass botle
Figure imgf000045_0002
As shown both Candidates A and B-l are stable after 13 weeks storage between 5-50 degrees C, with Candidate A spraying better.
[00154] In some embodiments, four different variations of Candidate A (9: 1 Baycusan® C 100EDOWSIL™ FA 4103) polymer formulations were developed The four variations include: (i) A-2-uvl: contains TiCh and ZnO, (ii) A-2-cl : contains TiCh and ZnO, as well as iron oxide color mix #1 at half the concentration of A-2-c3, (iii) A-2-c2: TiCh and ZnO and color mix #1. Table 18 includes the ingredients used in the example formulations:
Table 15
Figure imgf000045_0003
Figure imgf000046_0001
And Table 16 summarizes the polymer formulations:
Table 16
Figure imgf000046_0002
Figure imgf000047_0001
* In the nomenclature “uv#” and “-c#”, uv = UV protection, C = color, # indicates the iron-oxide mixture or UV absorber mixture. The relative amounts red, yellow, and black iron oxide used are further provided below.
[00155] The formulations in Table 16 each provide UV protection and the formulas with a A-2-c# provide UV protection and color foundations. In some embodiments, each of the formulation in Table 16 were sprayed using a Mineral Air spray and with minimal clogging. A-2-c l contains half the amount of color pigments than A-2-c2 and A-2-c3. Decreasing the pigments by half appears to maintain adequate color and improves the mineral suspension. A benefit of lower colorant amount is that the polymer can be applied in a thicker coat to enhance elasticity while maintaining proper color appearance.
[00156] In some embodiments, different iron oxide color pigments were mixed to generate different colors, with white TiCh added to the formualtion for color balance. In such embodiments, iron oxide particles were coated with dimethicone/methicone copolymer (Pecosil SH-25L) prior to use to prevent suspension in the formulation. Three colors were chosen to mimic (not exact match) Mineral Air foundation samples provided. Additional colors may be created by adjusting the iron oxide and TiCh ratios. Table 17 is a summary of the different mixtures:
Table 17
Figure imgf000047_0002
Figure imgf000048_0001
[00157] FIG. 14 is an image of different polymer formulations having the different color mixtures from Table 17, in accordance with the present disclosure. The polymer formulations were previously described by Table 16.
[00158] Various embodiments were directed to reducing mineral ( TiCb. ZnO, and iron oxides) settling. Methods to reduce setting include mixing during formulation preparation required in order to disperse solids: (1) zinc oxide was premixed with silicones to prepare a ZnO paste for better dispersion was added first to the solution of Baycusan® C 1001/DOWSIL™ FA 4103, (2) vortex mixing was applied at each stage of the solution preparation, (3) for large samples (>20 mL), resonant acoustic mixing (RAM) was used as the last mixing step, and (4) for commercial scale samples, homogenizing mixers can be used. In some embodiments, increase to solution viscosity led to significant sprayer clogging. In some embodiments, silicone coatings on iron oxide and ZnO minerals reduced rate of settling (e.g., MKR-1 T1O2 pre-coated by the supplier with low amount of hydrogen dimethicone). In some embodiments, reducing TiO2 and iron oxide content significantly reduced rate of settling, and the color appearance did not appear to be compromised.
[00159] Some embodiments were directed to spray testing the different polymer formulations from Table 16 using a Badger airbrush sprayer and Mineral Air. Candidate A and Candidate B both exhibited sprayability with Badger, with Candidate A being less prone to cloggined with Mineral Air than Candidate B. In specific embodiments, the polymer formulationss were sprayed with Badger 105 airbrush at 10 psi for 10-15 seconds using a raster motion (e.g., alternative between left-right and updown), at an airbrush distance from the skin of about 7.5 cm, and for a patch size of 3.8 cm x 3.8 cm. The patches were monitored for five minutes for dry ness and tack, and peeled off the skin after five minutes. Canidate A-2-uvl sprayed with Badger and no dripping after 10 seconds of spray and resulted in thin layer on the skin, dried and faintly tacky after 2 minutes, dry and non-tacky after 3 minutes, had slight reflectiveness on skin, could be removed by rubbing due to reduced elasticity and not easily peeled. Candidate A-2-c2 sprayed with Badger and no dripping after 10 seconds, mostly dry and faintly tacky' after 2 minutes, dry and non-tacking after four minute, beige and non-uniform film due poor spray (similar to A-2- and B-4-Zn-Ti samples), could be removed by rubbing due to reduced elasticity and not easily peelabed. Candidate A-2-c2 sprayed with Mineral Air resulted in a more uniform film, sprayed on skin in 15 seconds, and once dried, was warn for over four hours to test durability and ease of removal with water. Table 18 summarizes the spray and peel results:
Table 18
Figure imgf000049_0001
Each film is mostly dry by 2 minutes, and entirely dry by 3 - 4 minutes, were comfortable wear and low tack. ZnO, T1O2, and iron oxides reduced peel-ability, elasticity. Other color samples (A-2-cl and A-2-c3) are anticipated to have similar or identical spray and peel results.
[00160] To provide adequate permeability, the resulting film thickness should be < 80 microns. Some embodiments were directed to measuring the thickness of the film. In a specific embodiments, a Candidate A-2-c2 film onto a glass slide using Mineral Air.
The film was cut/scored to create an internal reference point (thickness = 0). Area A and Area B were measured, resulting in Area A: 8 - 10 micron (avg) and Area B: 5 micron (avg). Spraying on a thicker film may increase elasticity without eliminating permeability.
[00161] Some embodiments were directed to assessing UV transmission. Transmission is a measure of the proportion of light that travels through the substrate (artificial skin), with:
Transmission = 1 - Reflectance - Absorbance.
For TiCh and ZnO, the transmission is determined mostly by absorbance (i.e., both are UV absorbers). For U V protection, a goal can be low transmission < 400 nm (U V range). Broad spectrum UV is defined as providing UV-A and -B protection. FDA defines it as having a critical wavelength > 370 nm and UVA protection factor > 4. The critical wavelength (Xc) is where the area under the absorbance spectrum for the irradiated product from 290 nm to Xc is 90% of the integral of the absorbance spectrum from 290 nm to 400 nm.
[00162] FIGs. 15A-15B are images of films formed from hybrid polymer formulations with UV protecting agents, in accordance with the disclosure. As previously described, embodiments included adding UV protecting agents (TiCh and ZnO) into Candidate A and Candidate B-l. The polymer solutions were mixed with 5.9 wt% UV protecting agents and casted onto glass slides. When dried, the film had 1 wt% UV protecting agents. FIG. 15A is images of films formed from Candidate A and FIG. 15B is images of films formed from Candidate B-l. More particularly, FIG. 15A shows a first film 2101 formed from Candidate A only, a second film 2105 formed from Candidate A with TiO2, and a third film 2107 formed from Candidate A with ZnO. FIG. 15B shows a fourth film 2109 formed from Candidate B-l only, a fifth film 2113 formed from Candidate B-l with TiO2, and a sixth film 2115 formed from Candidate B-l with ZnO. Candidate B-l dries to inhomogeneous film. ZnO is translucent, whereas UO2 is opaque < 15 wt% TiO2.
[00163] FIG. 16 is a graph showing example transmissions of different candidates, in accordance with the present disclosure. As show n. Candidates A and B are highly transmissive at 300 - 700 nm, with Candidate B having higher transmission. Candidate A transmission decreases significantly at 280 nm (UV-B/-C), while Candidate B decrease around 250 nm (UV-C). The drop in transmission corresponds to the polymers reduced transmission. All TiO2 and ZnO samples do not transmit at < 400 nm and < 380 nm, respectively (UV-A and below).
[00164] Some embodiments were directed to generating different polymer formulations for providing UV protection and assessing the same. Such embodiments involved creating ZnO and UO2 loaded polymer samples. ZnO and TiO2 were loaded to levels equivalent to 15% ZnO and 5% TiO2 in the final, solid polymer film. Table 19 below sumamries different formulations generated:
Table 19
Figure imgf000051_0001
*all numbers are wt% based on total weight of the formulation.
[00165] FIG. 17 is a graph illustrating the UV-vis transmission for films formed of the polymer formulations illustrated by Table 19, in accordance with the present disclosure. As shown, films loaded with lower levels of TiCh and ZnO exhibited broadband UV protection. ZnO and TiO2 levels were reduced to test for UV absorbing efficiency, including ZnO level: -4.5% (-1.4% in solution), and TiO2 level: -1.5% (-0.5% in solution). The samples were sprayed with around 15% ZnO and around 5% T1O2. The data provides qualitative information on UV protection. As shown, there were low UV transmission below 380 nm for ZnO + TiO2 samples, and the samples likely provide broadband UV protection. Inhomogeneity /cracks in the Baycusan® C 1004 (Candidate B) samples may be causing low levels of UV transmission (5 - 10%)
[00166] Some embodiments were directed to specific polymer formulations. Table 20 provides specific example and non-limited formulations:
Table 20: Polymer Formulations
Figure imgf000052_0001
As shown, the C36 polymer formulation had an increase of polymer content, decrease of ZnO content, and decrease of RonaFlair® compared to C31 polymer formulation. Spraying of the C36 polymer formulation when sprayed around ten seconds and allowed to dry onto skin, resulted in a film without obvious visible distinction between the skin and the film, and scratches and rubs did not remove the polymer film from the skin. To remove C36 from the skin surface, moisture and pressure was applied. Table 21 provides example total UV protecting content: Table 21
Figure imgf000053_0001
In C36, TiCh was not added to formulation due to the relatively high fraction of RonaFlair® wrinkle concealers, leading to poor SPF. C44 was formulated to add TiCh added to improve SPF and reduced RonaFlair® content. Compared to SPF 30 sunscreen sprays, the example formulations have slightly lower mineral content. For example, commercial spray sunscreens have >12% ZnO (non-nano) for SPF 30. Dried films of C44 has comparable to mineral content (TiCh + ZnO) to wet sunscreen sprays. Expected SPF’s were determined based on manufacturer estimates of TiO2 (nano): 2.7 SPF per % of TiO2 and ZnO (nano): 1.6 SPF per % of ZnO.
[00167] FIGs. 18A-18B illustrate example absorbance of films formed of polymer formulations, in accordance with the present disclosure. Some embodiments were directed to assessing SPF of the dried films, in accordance with the present disclosure. FIG. 18A illustrates the absorbance of a film formed from C36 polymer formulation before and after irradiation with UVA dose of 1.2 UVAPFo. In the embodiments, C36 polymer formulation was applied by hand over a 15 - 18 mg over 23 cm2 area. There was measurable absorbance in UV-A and UV-B wavelengths, and low SPF (SPF less than 15), due to absence of TiCh, high critical wavelength (CW > 370 nm), and good UVAPF (UVAPF : SPF ratio > 1/3). Table 22 summarizes the same below:
Table 22
Figure imgf000053_0002
* the single application was one layer of film applied. For the double application, a second layer of film was applied on top of the first layer, allowing for around 10 minutes to dry before the second layer is applied.
[00168] FIG. 18B illustrates the absorbance of a film formed from C44 polymer formulation before and after irradiation with UVA dose of 1.2 UVAPFo. As shown, adding UV absorbing TiCh improves SPF. To apply the film, the polymer formulation was sprayed rather than hand application to improve uniformity. Four samples each of C44 and Mineral Air (Light Beige) spray-applied to PMMA substrate and tested. The film had good SPF (SPF > 15), due to absence of TiCh, high critical wavelength (CW > 370 nm), and good UVAPF (UVAPF : SPF ratio > 1/3). Table 23 summarizes the same below:
Table 23
Figure imgf000054_0001
[00169] Example embodiments in accordance with the present disclosure are directed to different polymer-based formulations which are sprayable onto skin and dry within 1-5 minutes to form a film that is elastic and durable. The polymer-based and sprayable formulation is formed of polyurethane and water-dispersible polymer solutions in an amount of at least 50 wt% of the total weight of the polymer formulation, and additives of inorganic UV protecting agents and coating agent. In various embodiments, the film provides UV protection, color balance and/or correction, is long wearing (e.g., last all day), provides a base layer for other cosmetics, and/or is easily removable via peeling or with the application of water, among other properties.

Claims

1. A sprayable-skin formulation, comprising: a polyurethane polymer solution; a water-dispersible polymer solution; an ultraviolet (UV) protecting agent; a particle coating agent; and a water-miscible solvent.
2. The formulation of claim 1, wherein the sprayable-skin formulation is spray able and configured to cure and form an elastic and UV protecting film.
3. The formulation of claim 1, wherein the water-miscible solvent is selected from: water, ethanol, and a combination thereof.
4. The formulation of claim 3, wherein the ethanol is configured to increase evaporability of the sprayable-skin formulation in response to application of the sprayable-skin formulation.
5. The formulation of claim 1, wherein the polyurethane polymer solution is a dispersion comprising one of a di cyclohexylmethane dnsocyanate copolymer and a hexamethylene diisocyanate copolymer.
6. The formulation of claim 1, wherein the water-dispersible polymer solution is an emulsion comprising an acrylates/polytrimethylsiloxymethacrylate copolymer and laureth-1 phosphate polymer.
7. The fomiulation of claim 1, wherein the sprayable-skin formulation comprises: about 45 weight percent (wt%) to about 85 wt% of the polyurethane polymer solution based on the total weight of the sprayable-skin formulation; and about 5 wt% to about 15 wt% of the water-dispersible polymer solution based on the total weight of the sprayable-skin formulation.
8. The formulation of claim 7, wherein the sprayable-skin formulation comprises: about 0.1 wt% to about 10 wt% of the UV protecting agent based on the total weight of the sprayable-skin formulation; about 0.5 wt% to about 15 wt% of the particle coating agent based on the total weight of the sprayable-skin formulation; and about 5 wt% to about 30 wt% of a water-miscible solvent based on the total weight of the sprayable-skin formulation.
9. The formulation of claim 1, wherein the polyurethane polymer solution comprises a water-based polyurethane dispersion formed of: about 30 weight percent (wt%) to about 40 wt% polyurethane based on the total weight of the water-based polyurethane dispersion; and a balance of water and surfactants.
10. The formulation of claim 1, wherein the UV protecting agent comprises inorganic particles configured to absorb UV radiation and the particle coating agent is configured to coat the inorganic particles and disperse the inorganic particles in the formulation.
11. The formulation of claim 10, wherein the inorganic particles have a diameter less than 100 nanometers.
12. The formulation of claim 1, wherein the particle coating agent is selected from: polyethylene glycol (PEG)-12 dimethicone, dimethicon PEG-8 Laurate, and a combination thereof.
13. The fonnulation of claim 1, wherein the UV protecting agent is selected from: zinc oxide, titanium dioxide, and a combination thereof.
14. The formulation of claim 1, wherein the UV protecting agent is a broadband UV absorbing agent formed of a combination of different types of inorganic particles configured to absorb UVA and UVB light in a range of about 280 nanometers to about 400 nanometers.
15. The fonnulation of claim 1, wherein the spray able-skin formulation further comprises at least one of: a color pigment mixture; a pigment coating agent for particles of the color pigment mixture: an antioxidant and metal chelate; a functional filler; and a UV protection booster.
16. A kit for forming a spray able-skin formulation, comprising: about 45 weight percent (wt%) to about 85 wt% of a polyurethane polymer dispersion based on the total weight of the formulation; about 5 wt% to about 15 wt% of a water-dispersible polymer emulsion based on the total weight of the formulation; about 0.5 wt% to about 15 wt% of an ultraviolet (UV) protecting agent based on the total weight of the formulation; about 0.5 wt% to about 15 wt% of a particle coating agent based on the total weight of the formulation; and a balance of a water-miscible solvent.
17. The kit of claim 16, wherein the spray able-skin formulation is spray able as an aerosol and configured to cure and form an elastic and UV protecting film on skin within about 1 minute to about 5 minutes after spraying.
18. The kit of claim 16, wherein the water-miscible solvent is selected from: about 1 wt % to about 10 wt% of ethanol based on the total weight of the fonnulation; about 5 wt% to about 20 wt% of water based on the total weight of the formulation; and a combination thereof.
19. The kit of claim 16, wherein the kit further comprises: about 0.01 wt% to about 2 wt% of color pigments based on the total weight of the formulation; and about 0.01 wt% to about 2 wt% of pigment coating agent based on the total weight of the formulation.
20. The kit of claim 16, wherein the kit comprises a ratio of the polyurethane polymer dispersion to the water-dispersible polymer emulsion of between about 5:1 and about 10: 1.
21. The kit of claim 16, wherein the kit further comprises at least one of: about 0.01 wt% to about 0.5 wt% of an antioxidant and metal chelate based on the total weight of the formulation; about 0.01 wt% to about 10 wt% of a functional filler based on the total weight of the formulation; and about 0.01 wt% to about 5 wt% of a UV protection booster based on the total weight of the formulation.
22. The kit of claim 16 wherein the kit further comprises an aerosol container with the sprayable-skin formulation in the form of one of an emulsion and a suspension containing the polyurethane polymer dispersion, the water-dispersible polymer emulsion, the UV protecting agent, the particle coating agent, and water
23. A method of applying a sprayable-skin formulation to skin, comprising: spraying a layer of sprayable-skin formulation to skin, the sprayable-skin formulation compnsing: a polyurethane polymer dispersion; a water-dispersible polymer emulsion; a ultraviolet (UV) protecting agent; a particle coating agent; and a water-miscible solvent; and drying, via exposure to air, the layer to form an elastic and UV protecting film on the skin.
24. The method of claim 23, wherein the film is durable such that the film is cohesive and configured to remain intact on the skin in response to contact, and the method further comprises removing the film by at least one of peeling the film and applying water to the film.
25. The method of claim 23, the method further compnsmg applying a layer of other cosmetics on top of film, wherein the sprayable-skin formulation comprises: about 45 weight percent (wt%) to about 85 wt% of the polyurethane polymer dispersion based on the total weight of the sprayable-skin formulation; about 5 wt% to about 15 wt% of the water-dispersible polymer emulsion based on the total weight of the sprayable-skin formulation; about 0. 1 wt% to about 10 wt% of the UV protecting agent based on the total weight of the sprayable-skin formulation; about 0.5 wt% to about 15 wt% of the particle coating agent based on the total weight of the sprayable-skm formulation; and a balance of the water-miscible solvent.
26. The method of claim 23, wherein the film comprises about 5 weight percent (wt%) to about 20 wt% of the UV protecting agent based on the total weight of the film and is configured to provide at least Sun Protection Factor (SPF) 15.
27. The method of claim 23, wherein the film is between about 5 microns and about 80 microns and substantially uniform in thickness.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100119464A1 (en) * 2008-07-10 2010-05-13 L'oreal Sun protection kit
US20120258055A1 (en) * 2011-04-11 2012-10-11 L'oreal S.A. Mineral sunscreen composition and process for protecting skin from photodamage and aging
US20150342845A1 (en) * 2014-05-29 2015-12-03 Eveready Battery Company Inc. Cosmetic compositions with enhanced color retention for improved skin appearance
US20210330571A1 (en) * 2018-08-15 2021-10-28 Dow Toray Co., Ltd. Oil-in-water type emulsion cosmetics

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100119464A1 (en) * 2008-07-10 2010-05-13 L'oreal Sun protection kit
US20120258055A1 (en) * 2011-04-11 2012-10-11 L'oreal S.A. Mineral sunscreen composition and process for protecting skin from photodamage and aging
US20150342845A1 (en) * 2014-05-29 2015-12-03 Eveready Battery Company Inc. Cosmetic compositions with enhanced color retention for improved skin appearance
US20210330571A1 (en) * 2018-08-15 2021-10-28 Dow Toray Co., Ltd. Oil-in-water type emulsion cosmetics

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