WO2013166342A2 - Composition de soin de la peau en émulsion huile-dans-eau - Google Patents

Composition de soin de la peau en émulsion huile-dans-eau Download PDF

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Publication number
WO2013166342A2
WO2013166342A2 PCT/US2013/039354 US2013039354W WO2013166342A2 WO 2013166342 A2 WO2013166342 A2 WO 2013166342A2 US 2013039354 W US2013039354 W US 2013039354W WO 2013166342 A2 WO2013166342 A2 WO 2013166342A2
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Prior art keywords
composition
weight
skin
oil
present
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PCT/US2013/039354
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English (en)
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WO2013166342A3 (fr
Inventor
Suryamani ROUT
Naohisa Yoshimi
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The Procter & Gamble Company
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Priority to CN201380023132.XA priority Critical patent/CN104302360A/zh
Priority to EP13721885.5A priority patent/EP2844352A2/fr
Priority to JP2015510468A priority patent/JP2015515500A/ja
Publication of WO2013166342A2 publication Critical patent/WO2013166342A2/fr
Publication of WO2013166342A3 publication Critical patent/WO2013166342A3/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/062—Oil-in-water emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone

Definitions

  • the present invention relates to an oil-in-water emulsion skin care composition.
  • the present invention also relates to a skin care method comprising applying the composition.
  • Occlusive agents such as hydrocarbon oils
  • Such high occlusivity is desired as it enhances the penetration into the skin of skin care actives contained in the skin care products.
  • occlusive agents form a film on the skin and therefore prevent moisture evaporation from the skin, resulting in an enhanced absorption of skin care actives, particularly water soluble actives, into the skin.
  • occlusive agents renders skin care products to have a negative skin sensory, e.g., a greasy, sticky feeling, and is thus disliked by users.
  • users prefer skin care products that provide a pleasing skin sensory, like a fresh feel or lower draginess after application.
  • Volatile oils such as low viscosity cyclic silicone oils are commonly used in skin care products to deliver a fresh feel on contact with the skin due to their quick evaporation after being applied onto the skin.
  • volatile oils typically leads to a significant decrease in occlusivity due to a diluted level of occlusive agents and thus a poor penetration of skin care actives.
  • An alternative approach is to use oil-in-water emulsions that contain no or limited amounts of occlusive agents.
  • Such oil-in-water emulsions have a better skin sensory than water-in-oil emulsions that typically contain a high amount of occlusive agents.
  • the incorporation of no or limited amounts of occlusive agents leads to a poor penetration of skin care actives, as mentioned previously.
  • the present invention relates to an oil-in-water emulsion skin care composition, comprising: from about 3% to about 25%, by weight of the composition, of a hydrocarbon oil or a mixture thereof, from about 2% to about 15%, by weight of the composition, of silicone particles or a mixture thereof, from about 0.1% to about 5%, by weight of the composition, of an emulsifier or a mixture thereof, and from about 30% to about 90%, by weight of the composition, of water.
  • the present invention relates to an oil-in-water emulsion skin care composition, comprising: from about 3% to about 25%, by weight of the composition, of a hydrocarbon oil or a mixture thereof, from about 2% to about 15%, by weight of the composition, of silicone particles or a mixture thereof, from about 0.1% to about 5%, by weight of the composition, of an emulsifier or a mixture thereof, from about 2% to about 15%, by weight of the composition, of a silicone oil or a mixture thereof, and from about 30% to about 90%, by weight of the composition, of water.
  • the present invention relates to an oil-in-water emulsion skin care composition, comprising from about 5% to about 15%, by weight of the composition, of a hydrocarbon oil or a mixture thereof, from about 3% to about 10%, by weight of the composition, of silicone particles or a mixture thereof, from about 0.3% to about 1.5%, by weight of the composition, of an emulsifier or a mixture thereof, from about 3% to about 10%, by weight of the composition, of a silicone oil or a mixture thereof, and from about 30% to about 88%, by weight of the composition, of water.
  • the present invention relates to an oil-in-water emulsion skin care composition, comprising: from about 7% to about 10%, by weight of the composition, of a hydrocarbon oil or a mixture thereof, from about 3% to about 5%, by weight of the composition, of silicone particles or a mixture thereof, from about 0.5% to about 1%, by weight of the composition, of an emulsifier or a mixture thereof, from about 3% to about 5%, by weight of the composition, of a silicone oil or a mixture thereof, and from about 50% to about 85%, by weight of the composition, of water.
  • the present invention further relates to a skin care method comprising applying the composition onto skin.
  • skin care product means a product that is used to treat or care for, or somehow moisturize, improve, or clean the skin.
  • the skin care products include, but are not limited to skin moisturizers, skin cleansers, skin treatment emulsions, skin toners, skin remedial products, skin exfoliants, shaving creams, skin masks, and the like.
  • skin care composition means a composition that constitutes the main part of a skin care product.
  • the skin care composition generally comprises skin care actives, which deliver the function of treating, moisturizing, improving, or cleaning the skin.
  • oil-in-water emulsion refers to an emulsion, in which oil is the dispersed liquid and an aqueous solution is the continuous phase.
  • water-in-oil emulsion refers to an emulsion when water is the dispersed phase in the continuous oil phase.
  • occlusivity refers to covering the skin with a film and thus preventing moisture evaporation from the skin.
  • occlusive agent means a material that delivers the function of occlusivity when incorporated in a skin care product.
  • the occlusive agents typically have relatively high occlusivity.
  • skin sensory refers to the user perception for a skin care product that how the user feels about the product.
  • criteria of fresh feel and draginess are used to characterize the skin sensory.
  • non- volatile means a material that exhibits a vapor pressure of no more than 0.2 mm Hg at 25 °C at one atmosphere and/or a material that has a boiling point at one atmosphere of at least 300°C.
  • volatile refers to all materials that are not “non- volatile” as defined herein.
  • the articles including “a” and “an” when used in a claim are understood to mean one or more of what is claimed or described.
  • the terms “comprise”, “comprises”, “comprising”, “include”, “includes”, “including”, “contain”, “contains”, and “containing” are meant to be non-limiting, i.e., other steps and other ingredients which do not affect the end of result can be added.
  • the above terms encompass the terms “consisting of and “consisting essentially of”.
  • the oil-in-water emulsion skin care composition of the present invention comprises from about 3% to about 25%, by weight of the composition, of a hydrocarbon oil or a mixture thereof, from about 2% to about 15%, by weight of the composition, of silicone particles or a mixture thereof, from about 0.1% to about 5%, by weight of the composition, of an emulsifier or a mixture thereof, from about 30% to about 90%, by weight of the composition, of water, and optionally an additional ingredient or a mixture thereof.
  • the composition herein comprises from about 5% to about 15%, by weight of the composition, of the hydrocarbon oil or a mixture thereof, from about 3% to about 10%, by weight of the composition, of the silicone particles or a mixture thereof, from about 0.3% to about 1.5%, by weight of the composition, of the emulsifier or a mixture thereof, from about 30% to about 90%, by weight of the composition, of water, and optionally an additional ingredient or a mixture thereof.
  • the composition comprises from about 7% to about 10%, by weight of the composition, of the hydrocarbon oil or a mixture thereof, from about 3% to about 5%, by weight of the composition, of the silicone particles or a mixture thereof, from about 0.5% to about 1%, by weight of the composition, of the emulsifier or a mixture thereof, from about 50% to about 85%, by weight of the composition, of water, and optionally an additional ingredient or a mixture thereof.
  • the composition herein comprises an additional ingredient or a mixture thereof.
  • the additional ingredient is selected from the group consisting of a silicone oil, a skin care active, and mixtures thereof.
  • composition herein comprises one or more adjunct ingredients.
  • the oil-in-water emulsion skin care composition of the present invention comprises a hydrocarbon oil or a mixture thereof in an amount of from about 3% to about 25%, by weight of the composition.
  • the hydrocarbon oil is present in the composition in an amount of from about 5% to about 15%, more preferably from about 7% to about 10%, by weight of the composition.
  • hydrocarbon oils include: petrolatum, mineral oil, micro- crystalline wax, polyalkene, paraffin, cerasin, ozokerite, polyethylene, perhydrosqualene, poly alpha olefin, hydrogenated polyisobutene, and mixtures thereof.
  • the most preferred example of the hydrocarbon oils is petrolatum (e.g., Perfecta ® Petrolatum available from Sonneborn, Inc).
  • the hydrocarbon oils herein function as an occlusive agent in the composition. They are solid or semisolid at normal temperatures (25°C). When applied onto skin, they form a film on the skin, prevent water from being vaporized from the skin, and therefore retain water at the surface of the skin. Thus, the dissolved state of skin care actives, particularly water soluble agents, is kept, and the absorption thereof into the skin is enhanced.
  • oil-in-water emulsions that contain limited amounts of occlusive agents, e.g., less than 25% of hydrocarbon oils, typically are aesthetically more appealing to users due to formulating oil-soluble actives and water-soluble actives in the same composition as well as decreased greasiness and heaviness.
  • the oil-in-water emulsion skin care composition of the present invention comprises silicone particles or a mixture thereof in an amount of from about 2% to about 15%, by weight of the composition.
  • the silicone particles are present in the composition in an amount of from about 3% to about 10%, more preferably from about 3% to about 5%, by weight of the composition.
  • the silicone particles suitable for use herein are selected from the group consisting of silicone resin particles, silicone rubber particles, and mixtures thereof.
  • the silicone particles are selected from the group consisting of spherical silicone resin particles, spherical silicone rubber particles, and mixtures thereof.
  • the silicone particles are a mixture of silicone resin particles and silicone rubber particles.
  • the silicone particles herein are silicone resin particles. More preferably, the silicone particles are spherical silicone resin particles. Even more preferably, the silicone particles have an average particle size of from about 0.01 ⁇ to about 5 ⁇ , preferably from about 0.1 ⁇ to about 4 ⁇ , more preferably from about 1 ⁇ to about 3 ⁇ , even more preferably of being about 2 ⁇ .
  • the silicone particles are polymethylsilsesquioxane (e.g., KMP-590 available from Shin-Etsu Chemical).
  • the applicant has surprisingly found that a combination of the silicone particles with a hydrocarbon oil in an oil-in-water emulsion skin care composition, within specific levels, achieves a pleasing skin sensory without much affecting occlusivity.
  • a combination namely, from about 2% to about 15%, by weight of the composition, of the silicone particles and from about 3% to about 25%, by weight of the composition, of the hydrocarbon oil, achieves a pleasing skin sensory, particularly an improved fresh feel and decreased draginess, as well as relatively high occlusivity.
  • the oil-in-water emulsion skin care composition of the present invention comprises an emulsifier or a mixture thereof in an amount of from about 0.1% to about 5%, by weight of the composition.
  • the emulsifier is present in the composition in an amount of from about 0.1% to about 2%, more preferably from about 0.3% to about 1.5%, even more preferably from about 0.5% to about 1%, by weight of the composition.
  • the emulsifier herein generally helps disperse and suspend the discontinuous phase within the continuous phase in the oil-in-water emulsion.
  • emulsifiers include: hydrophobically-modified crosslinked polyacrylate polymers and copolymers, polyacrylamide polymers and copolymers, and poly aery loyldimethyl taurates. More preferred examples of the emulsifiers include: acrylates/C 10-30 alkyl acrylate crosspolymer having tradenames PemulenTM TR-1, PemulenTM TR-2 (all available from Lubrizol); acrylates/steareth-20 methacrylate copolymer with tradename ACRYSOLTM 22 (from Rohm and Hass); polyacrylamide with tradename SEPIGEL 305 (from Seppic).
  • the emulsifier used herein is acrylates/C 10-30 alkyl acrylate crosspolymer (e.g., PemulenTM TR-2 available from Lubrizol) present in an amount of from about 0.3% to about 1.5%, preferably from about 0.5% to about 1%, more preferably of being about 0.5%, by weight of the composition.
  • Silicone Oil e.g., PemulenTM TR-2 available from Lubrizol
  • the oil-in-water emulsion skin care composition of the present invention may include a silicone oil or a mixture thereof as an additional ingredient. Suitable levels of the silicone oil herein are in the range of from about 2% to about 15%, preferably from about 3% to about 10%, more preferably from about 3% to about 5%, by weight of the composition.
  • the silicone oils herein can be selected from any silicone oils well known in the art.
  • the silicone oils are disclosed in U.S. Patent 4,781,917 issued to Luebbe et al. on Nov. 1, 1988, herein incorporated by reference in its entirety.
  • the silicone oil herein is selected from the group consisting of a volatile silicone oil, a non-volatile silicone oil, and mixtures thereof.
  • the silicone oil herein is a volatile silicone oil. More preferably, the silicone oil herein is selected from the group consisting of a linear volatile silicone oil, a cyclic volatile silicone oil, and mixtures thereof. Linear volatile silicone oils generally have a viscosity of less than 5 centistokes at 25°C, whereas the cyclic silicone oils have viscosities of less than 10 centistokes at 25°C. Additionally, a description of various silicone materials is found in Todd et al., "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, 91:27- 32 (1976), herein incorporated by reference in its entirety.
  • the silicone oil herein is selected from the group consisting of volatile silicone oils c a:
  • n is from 3 to 7; linear volatile silicones corresponding to the formula:
  • volatile silicone oils include cyclomethicones of varying viscosities, e.g., Dow Corning ® 200, Dow Corning ® 244, Dow Corning ® 245, Dow Corning ® 344, and Dow Corning ® 345, XIAMETER ® PMX-0245 (all available from Dow Corning); SF-1204 and SF-1202 (all available from Momentive), GE 7207 and 7158 (all available from General Electric Co.); SWS-03314 (available from SWS Silicones); and KF-995 (available from Shin-Etsu Chemical).
  • Dow Corning ® 200 Dow Corning ® 244, Dow Corning ® 245, Dow Corning ® 344, and Dow Corning ® 345
  • XIAMETER ® PMX-0245 all available from Dow Corning
  • SF-1204 and SF-1202 all available from Momentive
  • GE 7207 and 7158 all available from General Electric Co.
  • SWS-03314 available from SWS Silicones
  • Preferred examples of the liner volatile silicone oils include KF-96A-lcs, KF-96L-1.5cs, KF-96L-2cs, KF-96A-5cs (all available from Shin-Etsu Chemical).
  • Preferred examples of the branched volatile silicone oils include TMF-1.5 (available from Shin-Etsu Chemical).
  • the most preferred example of the silicone oil is cyclopentasiloxane (e.g., SF-1202 available from Momentive).
  • Silicone oils particularly volatile silicone oils, have been used in skin care compositions to deliver a fresh feel.
  • the incorporation of such volatile silicone oils typically leads to a significant decrease in occlusivity and thus a poor penetration of skin care actives.
  • the applicant has surprisingly found that when combining the silicone oil with the hydrocarbon oil and silicone particles in an oil-in-water emulsion skin care composition, within specific levels, an excellent skin sensory is achieved without compromising occlusivity significantly.
  • such a combination namely, from about 3% to about 25%, by weight of the composition, of the hydrocarbon oil, from about 2% to about 15%, by weight of the composition, of the silicone particles, and from about 2% to about 15%, by weight of the composition, of the silicone oil, achieves an excellent skin sensory, particularly a substantially improved fresh feel and decreased draginess, without compromising occlusivity significantly.
  • a skin care active or a mixture thereof may be present in the oil-in-water emulsion skin care composition of the present invention as an additional ingredient and/or in a preparation that is applied onto skin prior to applying the composition of the present invention.
  • the skin care actives are present in the preparation that is applied onto skin prior to applying the composition of the present invention.
  • the skin care actives are present in the composition of the present invention.
  • the skin care actives for use herein can be any skin care actives that deliver the function of treating, moisturizing, improving, or cleaning the skin.
  • the skin care actives herein can be classified by the benefit they provide or by their postulated mode of action.
  • the skin care actives herein in some instances provide more than one benefit or operate via more than one mode of action. Therefore, classifications herein are made for the sake of convenience and are not intended to limit the skin care actives to that particular application or applications listed.
  • the skin care actives herein are selected from the group consisting of a vitamin B3 compound, a whitening agent, a peptide, a sugar amine, a skin conditioning agent, a sunscreen agent, and mixtures thereof.
  • Vitamin B3 compound such as niacinamide is a preferred skin care active for use herein.
  • the vitamin B3 compound When used in the present composition or the preparation that is applied onto skin prior to applying the present composition, the vitamin B3 compound is present from about 0.1% to about 30%, preferably from about 1% to about 20%, more preferably from about 2% to about 10%, by weight of the composition or the preparation.
  • vitamin B3 com ound means a compound having the formula:
  • R is - CONH 2 (i.e., niacinamide), - COOH (i.e., nicotinic acid) or - CH 2 OH (i.e., nicotinyl alcohol); derivatives thereof; and salts of any of the foregoing.
  • exemplary derivatives of the foregoing vitamin B3 compounds include nicotinic acid esters, including non-vasodilating esters of nicotinic acid (e.g., tocopheryl nicotinate), nicotinyl amino acids, nicotinyl alcohol esters of carboxylic acids, nicotinic acid N-oxide and niacinamide N-oxide.
  • a whitening agent may be included in the present composition and/or the preparation that is applied onto skin prior to applying the present composition.
  • the term "whitening agent" refers to active ingredients that not only alter the appearance of the skin, but further improve hyperpigmentation as compared to pre-treatment.
  • the whitening agent is present from about 0.1% to about 10%, preferably from about 0.2% to about 5%, by weight of the composition or the preparation.
  • the whitening agent herein is selected from the group consisting of ascorbic acid compound, azelaic acid, butyl hydroxy anisole, gallic acid and its derivatives, hydroquinoine, kojic acid, arbutin, mulberry extract, undecylenoyl phenylalanine, cetyl pyridinium chloride, glycyrrhizic acid, tetrahydrocurcumin, and mixtures thereof.
  • Preferred examples of the whitening agent are ascorbic acid compounds having the formula:
  • V and W are independently -OH; R 1 is - CH(OH)-CH 2 OH; and salts thereof.
  • the ascorbic acid compound herein is an ascorbic acid salt or derivative thereof, such as the non-toxic alkali metal, alkaline earth metal, and ammonium salts well known in the art including, but not limited to, the sodium, potassium, lithium, calcium, magnesium, barium, ammonium and protamine salts which are prepared by methods well known in the art.
  • Peptides including but not limited to, di-, tri-, tetra-, and pentapeptides and derivatives thereof, may be included in the present composition and/or the preparation that is applied onto skin prior to applying the present composition.
  • peptides refers to both the naturally occurring peptides and synthesized peptides. Also useful herein are naturally occurring and commercially available compositions that contain peptides.
  • a peptide When used in the present composition or the preparation that is applied onto skin prior to applying the present composition, a peptide is present in amounts that are safe and effective, preferably from about lxl0 ⁇ 6 % to about 10%, more preferably from about lxl0 "6 % to about 0.1%, even more preferably from about lxl0 "5 % to about 0.01%, by weight of the composition or the preparation.
  • a sugar amine may be included in the present composition and/or the preparation that is applied onto skin prior to applying the present composition.
  • sugar amine refers to an amine derivative of a six-carbon sugar.
  • Preferred examples of the sugar amine herein include glucosamine, N-acetyl glucosamine, mannosamine, N-acetyl mannosamine, galactosamine, N-acetyl galactosamine.
  • a more preferred example of the sugar amine is glucosamine. Additionally, combinations of two or more sugar amines may be used.
  • the sugar amine herein is present from about 0.001% to about 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 5%, by weight of the composition or the preparation.
  • a skin conditioning agent may be included in the present composition and/or the preparation that is applied onto skin prior to applying the present composition.
  • a skin conditioning agent is selected from the group consisting of humectants, exfoliants, emollients, and mixtures thereof.
  • Humectants are polyhydric alcohols intended for moisturizing, reducing scaling and stimulating removal of built-up scale from the skin.
  • Typical polyhydric alcohols include polyalkylene glycols and more preferably alkylene polyols and their derivatives.
  • Preferred examples of the humectants are propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1,3-butylene glycol, 1,2,6-hexanetriol, ethoxylated glycerin, propoxylated glycerin and mixtures thereof.
  • the most preferred humectant is glycerin.
  • Exfoliants may be selected from the group consisting of C2-C30 alpha-hydroxycarboxylic acids, beta-hydroxycarboxylic acids, salts of these acids, and mixtures thereof.
  • Preferred examples of the exfoliants are glycolic, lactic and salicylic acids and their ammonium salts.
  • Emollients may be selected from the group consisting of hydrocarbons, fatty acids, fatty alcohols, esters, and mixtures thereof.
  • the skin-condition agent is present from about 1% to about 60%, preferably from about 2% to about 50%, more preferably from about 5% to about 40%, by weight of the composition or the preparation.
  • a sunscreen agent may be included in the present composition and/or the preparation that is applied onto skin prior to applying the present composition.
  • sunscreen agent refers to those that generally prevent excessive scaling and texture changes of the stratum corneum by exposure of ultraviolet light.
  • sunscreen agents include octyl methoxylcinnamate, octyl salicylate, octocrylene, avobenzone, homosalate, octyl triazone, and mixtures thereof.
  • Other conventional Sunscreen agents are also useful herein.
  • Such agents include, for example, butylmethoxydibenzoyl- methane, 2-hydroxy-4-methoxybenzo-phenone, 2-phenylbenzimidazole-5-sulfonic acid, octyldimethyl-p-aminobenzoic acid, 2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p- aminobenzoic acid, oxybenzone, 4-isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4- methylbenzylidene) camphor.
  • the sunscreen agent When used in the present composition or the preparation that is applied onto skin prior to applying the present composition, the sunscreen agent is present from about 0.1% to about 20%, preferably from about 0.5% to about 10%, more preferably from about 1% to about 5%, by weight of the composition or the preparation. Exact amounts will vary depending upon the sunscreen agent chosen and the desired Sun Protection Factor (SPF). SPF is a commonly used measure of photoprotection of a sunscreen against erythema. See Federal Register, Vol. 43, No. 166, pp. 38206-38269, August 25, 1978.
  • SPF Sun Protection Factor
  • adjunct ingredients may be incorporated into the composition of the present invention.
  • the adjunct ingredients herein are selected from the group consisting of skin appearance modifying actives; anti-acne actives; oil-soluble vitamin compounds, terpene alcohols, phytosterol, beta-hydroxy acids such as salicylic acid, and derivatives thereof; chelators; flavonoid compounds; anti-inflammatory agents; anti-cellulite agents; desquamation actives; anti-oxidant/radical scavengers; tanning actives; skin soothing or skin healing actives such as panthenoic acid derivatives (including panthenol, dexpanthenol, ethyl panthenol), aloe vera, allantoin, bisabolol, and dipotassium glycyrrhizinate; antimicrobial or antifungal actives; and mixtures thereof.
  • the oil-in-water emulsion skin care composition of the present invention is generally prepared by conventional methods such as are known in the art of making skin care compositions. Such methods typically involve mixing of the ingredients in one or more steps to a relatively uniform state, with or without heating, cooling, application of vacuum, and the like.
  • Non-limiting examples of the product form can be a gel, emulsion, lotion, cream, ointment, solution, liquid, etc.
  • composition herein may be prepared by the following steps:
  • step b) mixing the combination obtained in step a) with water at 70°C - 75 °C by applying a shear of 1000 rpm to 3000 rpm; and c) homogenizing the combination obtained in step b) in a homogenizer at 8000 rpm to 12000 rpm for 8 minutes to 12 minutes, thus reducing the particle size of the combination and forming an oil-in-water emulsion composition,
  • the hydrocarbon oil is present in an amount of from about 3% to about 25%
  • the silicone particles are present in an amount of from about 2% to about 15%
  • the surfactant is present in an amount of from about 0.1% to about 5%
  • water is present in an amount of from about 30% to about 90%, by weight of the composition.
  • the composition herein is prepared by the following steps: a) heating a combination of a hydrocarbon oil and silicone particles at 70°C - 75 °C, and then mixing the combination with an emulsifier by applying a shear of from 1000 rpm to 3000 rpm;
  • step b) mixing the combination obtained in step a) with water at 70°C - 75 °C by applying a shear of 1000 rpm to 3000 rpm;
  • step b) homogenizing the combination obtained in step b) in a homogenizer at 8000 rpm to 12000 rpm for 8 minutes to 12 minutes, thus reducing the particle size of the combination;
  • step d) once the temperature of the combination obtained in step c) is below 35 °C, adding a silicone oil into the combination and mixing, and then homogenizing the mixture in the homogenizer at 8000 rpm to 12000 rpm for 8 minutes to 12 minutes, thus forming an oil-in-water emulsion composition,
  • the hydrocarbon oil is present in an amount of from about 3% to about 25%
  • the silicone particles are present in an amount of from about 2% to about 15%
  • the surfactant is present in an amount of from about 0.1% to about 5%
  • the silicone oil is present in an amount of from about 2% to about 15%
  • water is present in an amount of from about 30% to about 90%, by weight of the composition.
  • the composition herein is prepared by the following steps: a) heating a combination of a hydrocarbon oil and silicone particles at 70°C - 75 °C, and then mixing the combination with an emulsifier by applying a shear of from 1000 rpm to 3000 rpm;
  • step b) mixing the combination obtained in step a) with water at 70°C - 75 °C by applying a shear of 1000 rpm to 3000 rpm; c) homogenizing the combination obtained in step b) in a homogenizer at 8000 rpm to 12000 rpm for 8 minutes to 12 minutes, thus reducing the particle size of the combination and forming an oil-in-water emulsion;
  • step d) once the temperature of the combination obtained in step c) is below 35 °C, adding a silicone oil and a vitamin B3 compound into the combination and mixing, and then homogenizing the mixture in the homogenizer at 8000 rpm to 12000 rpm for 8 minutes to 12 minutes, thus forming an oil-in-water emulsion composition,
  • the hydrocarbon oil is present in an amount of from about 3% to about 25%
  • the silicone particles are present in an amount of from about 2% to about 15%
  • the surfactant is present in an amount of from about 0.1% to about 5%
  • the silicone oil is present in an amount of from about 2% to about 15%
  • the vitamin B3 compound is present in an amount of from about 1% to about 20%
  • water is present in an amount of from about 30% to about 90%, by weight of the composition.
  • the skin care method of the present invention comprises applying an oil-in-water emulsion skin care composition onto skin, wherein the composition comprises from about 3% to about 25%, by weight of the composition, of a hydrocarbon oil or a mixture thereof, from about 2% to about 15%, by weight of the composition, of silicone particles or a mixture thereof, from about 0.1% to about 5%, by weight of the composition, of an emulsifier or a mixture thereof; from about 30% to about 90%, by weight of the composition, of water, and optionally an additional ingredient or a mixture thereof.
  • the skin care method herein is a multiple-step method, e.g., a two-step method.
  • the term "multiple- step” refers to requiring separate steps of applying two or more compositions onto skin in a particular sequence.
  • the skin care method comprises the steps of a) applying a preparation comprising a skin care active onto skin; and b) applying the composition of the present invention onto skin.
  • the skin care active herein is selected from the group consisting of a vitamin B3 compound, a whitening agent, a peptide, a sugar amine, a skin conditioning agent, a sunscreen agent, and mixtures thereof.
  • the skin care method herein is a one-step method.
  • the term "one-step” refers to applying a single composition onto skin, without requiring separate steps of applying two or more compositions onto skin in a particular sequence.
  • the skin care method comprises applying a composition onto skin, wherein the composition comprises from about 3% to about 25%, by weight of the composition, of a hydrocarbon oil or a mixture thereof, from about 2% to about 15%, by weight of the composition, of silicone particles or a mixture thereof, from about 0.1% to about 5%, by weight of the composition, of an emulsifier or a mixture thereof, from about 30% to about 90%, by weight of the composition, of water, and a skin care active or a mixture thereof.
  • the skin care active is selected from the group consisting of a vitamin B3 compound, a whitening agent, a peptide, a sugar amine, a skin conditioning agent, a sunscreen agent, and mixtures thereof.
  • the multiple-step skin care method is generally considered more effective for skin care actives to penetrate into the skin, even though it is more time-consuming than the one-step method.
  • the multiple-step method comprises the steps of applying a first composition comprising skin care actives onto the skin and then applying a second composition that contains occlusive agents and has high occlusivity onto the skin, thus ensuring a sufficient penetration of the skin care actives into the skin.
  • the applicant has surprisingly found that the oil-in-water emulsion skin care composition, which comprises from about 3% to about 25%, by weight of the composition, of a hydrocarbon oil or a mixture thereof, from about 2% to about 15%, by weight of the composition, of silicone particles or a mixture thereof, from about 0.1% to about 5%, by weight of the composition, of an emulsifier or a mixture thereof, from about 30% to about 90%, by weight of the composition, of water or a mixture thereof, and a skin care active or a mixture thereof, provides a relatively high occlusivity and therefore an enhanced penetration into the skin of the skin care active contained in the composition, without requiring a separate step of applying other compositions.
  • the method uses a standardized stainless-steel testing chamber into which a collagen film
  • the cup (Naturin COFFI J) is placed as semi-permeable membrane.
  • the cup is filled Calcium chloride (10 g), and the material (0.535g) to be tested is coated to on the rough surface of the membrane.
  • the testing chamber is closed and placed in a temperature-controlled room initially at 25 °C /60%RH room for 1 hour and then at 40°C /75%RH room for 24 hours. After the testing period the weight of the cup is measured. The weight of the cup is also measured after the removal of Chloride. The absorption of water vapor by the CaCl 2 is used for the calculation of occlusivity.
  • Occlusivity (%) 100 - ( (amount of total cup weight - amount of the cup w/o CaCl 2 ) -10 (Original CaCl 2 ) * 10.0)
  • test product A total number of 10 qualified panelists have participated in the study.
  • 0.1 ml of test product and the Baseline were applied on forearms.
  • the attributes of test product versus the Baseline were evaluated with dipolar scales (from -3 to +3). "0" indicates to be no difference compared with control.
  • the results are the mean value of 10 volunteers participated in the study.
  • “Fresh feel” refers to the attribute that is not sticky and referred as a positive attribute.
  • a positive value of the fresh feel means a better fresh feel than the Baseline, and a greater absolute value thereof means a more significant difference versus the Baseline.
  • Draginess refers to the resistance that the product creates while being applied onto the skin. A negative value of the draginess means better draginess than the Baseline, and a greater absolute value thereof means a more significant difference versus the Baseline.
  • Examples herein are meant to exemplify the present invention but are not used to limit or otherwise define the scope of the present invention.
  • Examples 1A - II are examples according to the present inventions, and Examples 2A - 2D are comparative examples.
  • Example 1A - II Formulations of oil-in-water emulsion skin care compositions
  • compositions comprising the listed ingredients in the listed proportions (weight %).
  • PemulenTM TR-2 d 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% niacinamide 0 5% 0 0 5% 0 0 0 0 0
  • KMP-590 is polymethylsilsesquioxane available from Shin-Etsu Chemical
  • c SF-1202 is cyclopentasiloxane available from Momentive
  • PemulenTM T -2 is acrylates/ClO-30 alkyl acrylate crosspolymer available from Lubrizol
  • Example 1A The composition of Example 1A is prepared by the following steps:
  • step b) mixing the combination obtained in step a) with water at 70°C by applying a shear of
  • step b) homogenizing the combination obtained in step b) in TK Robomics Homogenizer at 10000 rpm for 10 minutes, thus reducing the particle size of the combination and forming an oil-in- water emulsion composition
  • PemulenTM TR-2 is present in an amount of 0.5%
  • water is present in an amount of 84.5%, by weight of the composition.
  • Example IB The composition of Example IB is prepared by the following steps:
  • step b) mixing the combination obtained in step a) with water at 70°C by applying a shear of 2000 rpm;
  • step b) homogenizing the combination obtained in step b) in TK Robomics Homogenizer at
  • step c) once the temperature of the combination obtained in step c) is below 35°C, adding niacinamide into the combination and mixing, and then homogenizing the mixture in TK Robomics Homogenizer at 10000 rpm for 10 minutes, thus forming an oil-in-water emulsion composition
  • Example 1C The composition of Example 1C is prepared by the same steps as in Example 1A, except for the following: Perfecta® Petrolatum is present in an amount of 15%, and water is present in an amount of 77%, by weight of the composition.
  • Example ID The composition of Example ID is prepared by the following steps:
  • step b) mixing the combination obtained in step a) with water at 70°C by applying a shear of 2000 rpm;
  • step c) homogenizing the combination obtained in step b) in TK Robomics Homogenizer at 10000 rpm for 10 minutes, thus reducing the particle size of the combination; and d) once the temperature of the combination obtained in step c) is below 35°C, adding SF- 1202 into the combination and mixing, and then homogenizing the mixture in TK Robomics Homogenizer at 10000 rpm for 10 minutes, thus forming an oil-in-water emulsion composition,
  • Example IE The composition of Example IE is prepared by the following steps:
  • step b) mixing the combination obtained in step a) with water at 70°C by applying a shear of 2000 rpm;
  • step c) homogenizing the combination obtained in step b) in TK Robomics Homogenizer at 10000 rpm for 10 minutes, thus reducing the particle size of the combination; and d) once the temperature of the combination obtained in step c) is below 35°C, adding SF- 1202 and niacinamide into the combination and mixing, and then homogenizing the mixture in TK Robomics Homogenizer at 10000 rpm for 10 minutes, thus forming an oil-in- water emulsion composition,
  • Example IF The composition of Example IF is prepared by the same steps as in Example ID, except for the following: Perfecta® Petrolatum is present in an amount of 20%, KMP-590 is present in an amount of 10%, PemulenTM TR-2 is present in an amount of 0.5%, SF-1202 is present in an amount of 10%, and water is present in an amount of 59.5%, by weight of the composition.
  • Example 1G The composition of Example 1G is prepared by the same steps as in Example ID, except for the following: Perfecta® Petrolatum is present in an amount of 15%, KMP-590 is present in an amount of 7.5%, PemulenTM TR-2 is present in an amount of 0.5%, SF-1202 is present in an amount of 7.5%, and water is present in an amount of 69.5%, by weight of the composition. Preparation of the composition of Example 1H
  • Example 1H The composition of Example 1H is prepared by the same steps as in Example ID, except for the following: Perfecta® Petrolatum is present in an amount of 15%, KMP-590 is present in an amount of 5%, PemulenTM TR-2 is present in an amount of 0.5%, SF-1202 is present in an amount of 5%, and water is present in an amount of 74.5%, by weight of the composition.
  • Example II The composition of Example II is prepared by the same steps as in Example ID, except for the following: Perfecta® Petrolatum is present in an amount of 5%, KMP-590 is present in an amount of 5%, PemulenTM TR-2 is present in an amount of 0.5%, SF-1202 is present in an amount of 5%, and water is present in an amount of 84.5%, by weight of the composition.
  • Comparative Example 2 A - 2D Comparative Formulations of oil-in-water emulsion skin care compositions The following comparative compositions are made comprising the listed ingredients in the listed proportions (weight %).
  • PemulenTMTR-2 d 0.5% 0.5% 0.5% 0.5% 0.5%
  • KMP-590 is polymethylsilsesquioxane available from Shin-Etsu Chemical
  • c SF-1202 is cyclopentasiloxane available from Momentive
  • PemulenTM T -2 is acrylates/ClO-30 alkyl acrylate crosspolymer available from Lubrizol
  • Example 2A The composition of Example 2A is prepared by the following steps:
  • step b) mixing the combination obtained in step a) with water at 70°C by applying a shear of 2000 rpm;
  • step b) homogenizing the combination obtained in step b) in TK Robomics Homogenizer at
  • Example 2B The composition of Example 2B is prepared by the following steps:
  • step b) mixing the combination obtained in step a) with water at 70°C by applying a shear of 2000 rpm; c) homogenizing the combination obtained in step b) in TK Robomics Homogenizer at 10000 rpm for 10 minutes, thus reducing the particle size of the combination; and d) once the temperature of the combination obtained in step c) is below 35°C, adding SF- 1202 into the combination and mixing, and then homogenizing the mixture in TK Robomics Homogenizer at 10000 rpm for 10 minutes, thus forming an oil-in-water emulsion composition,
  • Example 2C The composition of Example 2C is prepared by the following steps:
  • step f) mixing the combination obtained in step a) with water at 70°C by applying a shear of
  • step b) homogenizing the combination obtained in step b) in TK Robomics Homogenizer at 10000 rpm for 10 minutes, thus reducing the particle size of the combination; and h) once the temperature of the combination obtained in step c) is below 35°C, adding SF- 1202 into the combination and mixing, and then homogenizing the mixture in TK
  • Example 2D The composition of Example 2D is prepared by the same steps as in Example 2C, except for the following: Perfecta® Petrolatum is present in an amount of 2%, KMP-590 is present in an amount of 1.5%, PemulenTM TR-2 is present in an amount of 0.5%, SF-1202 is present in an amount of 1.5%, and water is present in an amount of 94.5%, by weight of the composition. Comparative Data of Examples 1 and 2
  • the occlusivity is measured according to the method for determining of occlusivity for skin care compositions as described herein above. It's worth noting that, an occlusivity value as low as 70% does not lead to a good penetration of niacinamide into the skin.
  • Example 2A is taken as the Baseline for generating the data of fresh feel and draginess.
  • Example 1A the oil-in-water emulsion skin care compositions according to the present invention
  • Examples 1C, ID, IF, 1G, 1H, and II demonstrate a pleasing skin sensory without much affecting occlusivity
  • the comparative compositions that are out of the scope of the present invention show either a negative skin sensory or relatively low occlusivity.
  • Example 1A demonstrates a much higher value of occlusivity (88.2%) than Example 2B (75.1%), even though the amount of silicone particles in Example 1A is the same as that of silicone oils in Example 2B.
  • Example 2C demonstrates a quite negative skin sensory, namely, a low value of fresh feel (-0.2) and a high value of draginess (0.5) even though it has a quite high value of occlusivity (96.5%).
  • Example IF achieves a value of occlusivity (95.6%) almost as high as Example 2C as well as a positive skin sensory, namely, a value of fresh feel at 0.3 and a value of draginess at - 0.4.
  • Example 2D demonstrates a quite low value of occlusivity (70.5%) and a skin sensory close to the Baseline.
  • Example II leads to an excellent skin sensory, namely, a value of fresh feel at 0.9 and a value of draginess at -1.1, whereas the value of occlusivity thereof (78.0%) is not too low.

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Abstract

L'invention concerne une composition de soin de la peau en émulsion huile-dans-eau, laquelle comprend d'environ 3 % à environ 25 %, en poids de la composition, d'une huile hydrocarbonée ou un mélange d'huiles hydrocarbonnés, d'environ 2 % à environ 15 %, en poids de la composition, de particules de silicone ou un mélange de celles-ci, d'environ 0,1 % à environ 5 %, d'un émulsifiant ou un mélange d'émulsifiants, et d'environ 30 % à environ 90 %, en poids de la composition, d'eau. La composition fournit une sensation de peau plaisante sans beaucoup affecter le caractère occlusif.
PCT/US2013/039354 2012-05-03 2013-05-03 Composition de soin de la peau en émulsion huile-dans-eau WO2013166342A2 (fr)

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CN201380023132.XA CN104302360A (zh) 2012-05-03 2013-05-03 水包油乳液皮肤护理组合物
EP13721885.5A EP2844352A2 (fr) 2012-05-03 2013-05-03 Composition de soin de la peau en émulsion huile-dans-eau
JP2015510468A JP2015515500A (ja) 2012-05-03 2013-05-03 水中油型エマルションスキンケア組成物

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105916557A (zh) * 2014-01-14 2016-08-31 宝洁公司 包含硅氧烷微粒和非挥发性油的涂饰组合物
US9931285B2 (en) 2014-01-14 2018-04-03 The Procter & Gamble Company Multi-step product for improving the appearance and feel of human skin
US10206859B2 (en) 2014-07-29 2019-02-19 The Procter & Gamble Company Cosmetic composition
US10512595B2 (en) 2014-01-14 2019-12-24 The Procter & Gamble Company Multi-step product for improving the appearance and feel of human skin

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3334403B1 (fr) 2015-08-10 2021-03-31 Mary Kay, Inc. Compositions topiques
CN113271913B (zh) * 2018-12-18 2024-04-02 宝洁公司 具有增加的蒸气释放的个人护理组合物

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4781917A (en) 1987-06-26 1988-11-01 The Proctor & Gamble Company Antiperspirant gel stick

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MXPA02011623A (es) * 2000-05-23 2003-03-27 Procter & Gamble Composiciones humectantes y con filtro solar para el cuidado de la piel que comprenden material organico en particulas.
US20030113357A1 (en) * 2000-05-23 2003-06-19 The Procter & Gamble Company Skin Care Compositions
JP4993508B2 (ja) * 2008-07-16 2012-08-08 信越化学工業株式会社 皮膜形成性重合体を含む化粧料
US20130272995A1 (en) * 2012-04-12 2013-10-17 Mamoru Hagiwara Cosmetic product containing film-forming polymer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4781917A (en) 1987-06-26 1988-11-01 The Proctor & Gamble Company Antiperspirant gel stick

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FEDERAL REGISTER, vol. 43, no. 166, 25 August 1978 (1978-08-25), pages 38206 - 38269
TODD ET AL.: "Volatile Silicone Fluids for Cosmetics", COSMETICS AND TOILETRIES, vol. 91, 1976, pages 27 - 32

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105916557A (zh) * 2014-01-14 2016-08-31 宝洁公司 包含硅氧烷微粒和非挥发性油的涂饰组合物
US9446265B2 (en) 2014-01-14 2016-09-20 The Procter & Gamble Company Cosmetic composition
US9931285B2 (en) 2014-01-14 2018-04-03 The Procter & Gamble Company Multi-step product for improving the appearance and feel of human skin
US10512595B2 (en) 2014-01-14 2019-12-24 The Procter & Gamble Company Multi-step product for improving the appearance and feel of human skin
US10206859B2 (en) 2014-07-29 2019-02-19 The Procter & Gamble Company Cosmetic composition

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