WO2017188319A1 - Produit cosmétique en émulsion de type huile-dans-eau - Google Patents

Produit cosmétique en émulsion de type huile-dans-eau Download PDF

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Publication number
WO2017188319A1
WO2017188319A1 PCT/JP2017/016561 JP2017016561W WO2017188319A1 WO 2017188319 A1 WO2017188319 A1 WO 2017188319A1 JP 2017016561 W JP2017016561 W JP 2017016561W WO 2017188319 A1 WO2017188319 A1 WO 2017188319A1
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Prior art keywords
oil
water
cosmetic
oil phase
mass
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PCT/JP2017/016561
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English (en)
Japanese (ja)
Inventor
崇広 香取
悟史 八巻
太一 原田
崇志 松田
百合香 渡辺
佳保里 石田
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株式会社 資生堂
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Application filed by 株式会社 資生堂 filed Critical 株式会社 資生堂
Priority to JP2018514666A priority Critical patent/JP7088830B2/ja
Priority to CN201780025626.XA priority patent/CN109069357B/zh
Priority to KR1020187033440A priority patent/KR102415538B1/ko
Publication of WO2017188319A1 publication Critical patent/WO2017188319A1/fr
Priority to HK19100450.2A priority patent/HK1258070A1/zh

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    • 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
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • 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
    • A61K8/60—Sugars; Derivatives thereof
    • 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
    • A61K8/73—Polysaccharides
    • 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
    • A61K8/73—Polysaccharides
    • A61K8/732—Starch; Amylose; Amylopectin; Derivatives thereof
    • 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
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier 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
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

  • the present invention relates to an oil-in-water emulsified cosmetic. More specifically, it is an oil-in-water emulsified cosmetic containing a powder in the inner aqueous phase, which is superior in water resistance and improves the UV protection effect etc. immediately after application by contact with water or sweat.
  • the present invention relates to an oil-in-water emulsified cosmetic having no characteristics.
  • UV care cosmetics a type of UV care cosmetics, contain UV absorbers and UV scattering agents to block UVA and UVB from reaching the skin and protect the skin from UV damage.
  • Protect Non-Patent Document 1. Recently, it is considered that it is important to protect the skin from ultraviolet rays in daily life as well as the harsh UV conditions in outdoor activities such as summer swimming and swimming in the sea and winter skiing. Cosmetics having an ultraviolet protection effect are desired.
  • Patent Document 1 As the dosage form of sunscreen cosmetics, many preparations in an emulsified form are used, and the instability of emulsification sometimes leads to a decrease in UV protection ability.
  • Patent Document 1 it is described that storage stability is improved by blending free fatty acids having 14 to 24 carbon atoms, and a decrease in UV protection ability due to long-term storage is suppressed.
  • sunscreen cosmetics applied to the skin come into contact with water or sweat, UV absorbers or UV scattering agents will flow out from the applied cosmetics, and UV rays It was thought that it was inevitable that the protective effect would decline.
  • Oil-in-water emulsions are widely used as sunscreen cosmetics because they provide a fresh feeling to use.
  • oil-in-water emulsified cosmetics are often inferior in water resistance as compared to water-in-oil type, and the UV protection ability is likely to decrease due to the outflow of UV absorbers and UV scattering agents.
  • oil-in-water emulsified cosmetics containing a powder such as an ultraviolet scattering agent in the inner oil phase are known to be particularly inferior in water resistance, and increasing the amount of powder to obtain a high UV protection ability, There is also a problem that it is necessary to add a large amount of the oil as the dispersion medium, and as a result, a sticky feeling is given.
  • Patent Document 2 In oil-in-water emulsified cosmetics, attempts have been made to improve water resistance by blending a film agent (Patent Document 2).
  • cosmetics applied to the skin are exposed to various moisture from inside and outside the coating, such as moisture from the outside environment such as sweat and seawater secreted from the skin, resins and coatings for imparting water resistance It was difficult to completely prevent the ultraviolet absorber and the ultraviolet scattering agent from flowing out even when the agent was blended in a high amount.
  • the present invention does not reduce the UV protection effect due to contact with water, sweat, etc. Based on finding the phenomenon for the first time.
  • the oil-in-water emulsified cosmetic targeted by the present invention has an unprecedented novel and innovative characteristic that the UV protection effect and the like are improved by contact with moisture.
  • the present inventors have formulated an oil-phase thickener in an oil-in-water emulsified cosmetic in which a powder is blended in the inner oil phase, and further increases the oil phase.
  • the ratio of the total amount of the viscous agent and the hydrophobized powder to the amount of the non-volatile oil within a specific range, the water resistance and stability are improved, and the above new and innovative properties Has been found to achieve the present invention.
  • the present invention (A) UV absorber, (B) oil phase thickener, (C) Hydrophobized powder, (D) a nonionic surfactant and / or a core-corona type microgel, and (E) a non-volatile liquid oil (including the (A) ultraviolet absorber), (E) The ratio ([(B) + (C)] / (E)) of the total blending amount of (B) oil phase thickener and (C) hydrophobized powder to the blending amount of the non-volatile liquid oil.
  • the present invention provides an oil-in-water emulsified cosmetic characterized by being 0.2 to 20.
  • the ultraviolet protection effect after contact with water, sweat, or the like is remarkably improved as compared with that immediately after the cosmetic is applied to the skin.
  • the oil-in-water emulsified cosmetic according to the present invention has the conventional common sense that the UV protection effect and the like is improved by contact with moisture and the like, which has been the cause of the effect deterioration in the conventional oil-in-water emulsified cosmetic.
  • the cosmetic coating film is made uniform by contact with water, the optical properties of the skin to which the cosmetic is applied become close to the bare skin, and the aesthetic effect that the sense of transparency is increased and the skin feels beautiful is also exhibited.
  • the oil-in-water emulsified cosmetic composition of the present invention is excellent in stability, and the water resistance of the cosmetic coating film is improved without adding a coating agent or the like. Therefore, there is no film feeling, the elongation at the time of use (when applied) is good, and it can be easily removed with a general-purpose cleaning agent or soap. That is, the present invention can provide an oil-in-water emulsified cosmetic that is excellent in usability and detergency in addition to the unique UV protection effect and aesthetic effect.
  • the oil-in-water emulsified cosmetic of the present invention comprises (A) an ultraviolet absorber, (B) an oil phase thickener, (C) a hydrophobized powder, (D) a nonionic surfactant, and / or Alternatively, it contains a core-corona type microgel and (E) a non-volatile liquid oil.
  • the oil-in-water emulsified sunscreen cosmetic that is one embodiment of the present invention will be described in detail below as an example.
  • A Ultraviolet Absorber
  • component A Ultraviolet absorber blended in the oil-in-water emulsion cosmetic according to the present invention is conventionally used in sunscreen cosmetics. It can be set as at least 1 type selected from the ultraviolet absorber mix
  • the ultraviolet absorber (component A) used in the present invention is not particularly limited, but specific examples thereof include 2-ethylhexyl paramethoxycinnamate, 2,4-bis- ⁇ [4- (2- Ethylhexyloxy) -2-hydroxy] -phenyl ⁇ -6- (4-methoxyphenyl) 1,3,5-triazine, octocrylene, dimethicodiethylbenzalmalonate, polysilicon-15, t-butylmethoxydibenzoylmethane , Ethylhexyltriazone, diethylaminohydroxybenzoyl hexyl benzoate, bisethylhexyloxyphenol methoxyphenyltriazine, oxybenzone-3, methylenebisbenzotriazolyltetramethylbutylphenol, phenylbenzimidazole sulfonic acid, homosalate, ethyl salicylate It may include organic
  • the blending amount of the ultraviolet absorber (component A) in the oil-in-water emulsion cosmetic of the present invention is 1% by mass or more, more preferably 1 to 40% by mass with respect to the total amount of the cosmetic in the case of sunscreen cosmetics. More preferably, it is 2 to 30% by mass.
  • the ultraviolet absorbent (component A) in the present invention also constitutes a part (or all) of the non-volatile liquid oil (component E).
  • UV protection can be secured with a UV scattering agent that is stably maintained in the inner oil phase by adding a non-volatile liquid oil other than the UV absorber, It is also possible to make it less than 6 mass%, for example, 5 mass% or less, 3 mass% or less, or 2 mass% or less.
  • Oil phase thickener (B) An oil phase thickener (hereinafter sometimes simply referred to as “component B”) is a substance that can adjust the viscosity of the oil phase. Esters, sucrose fatty acid esters, solid or semi-solid hydrocarbon oils, organically modified clay minerals, fatty acids or salts thereof are preferred, and two or more selected from these are particularly preferred.
  • the dextrin fatty acid ester is an ester of dextrin or reduced dextrin and a higher fatty acid, and can be used without particular limitation as long as it is generally used in cosmetics. It is preferable to use dextrin or reduced dextrin having an average sugar polymerization degree of 3 to 100.
  • the constituent fatty acid of the dextrin fatty acid ester it is preferable to use a saturated fatty acid having 8 to 22 carbon atoms. Specific examples include dextrin palmitate, dextrin oleate, dextrin stearate, dextrin myristate, dextrin (palmitic acid / 2-ethylhexanoic acid), and the like.
  • sucrose fatty acid ester a linear or branched fatty acid saturated or unsaturated fatty acid having 12 to 22 carbon atoms can be preferably used. Specifically, sucrose caprylate, sucrose caprate, sucrose laurate, sucrose myristic ester, sucrose palmitate, sucrose stearate, sucrose oleate, sucrose elca An acid ester etc. can be mentioned.
  • the solid or semi-solid hydrocarbon oil is a solid or semi-solid hydrocarbon at normal temperature (25 ° C.).
  • Specific examples include petrolatum, hydrogenated palm oil, hydrogenated castor oil (castor wax), and palm kernel-cured oil. , Hydrogenated peanut oil, hydrogenated peanut (peanut) oil, hydrogenated rapeseed seed oil, hydrogenated camellia oil, hydrogenated soybean oil, hydrogenated olive oil, hydrogenated macadamia nut oil, hydrogenated sunflower oil, hydrogenated wheat germ oil, Examples thereof include hydrogenated rice germ oil, hydrogenated rice nutka oil, hydrogenated cottonseed oil, hydrogenated avocado oil, and waxes.
  • the organically modified clay mineral is a kind of colloidal hydrous aluminum silicate having a three-layer structure, and is representative of a clay mineral represented by the following general formula (1) modified with a quaternary ammonium salt type cationic surfactant.
  • dimethyl distearyl ammonium hectorite diseardimonium hectorite
  • dimethyl alkyl ammonium hectorite benzyl dimethyl stearyl ammonium hectorite
  • distearyl dimethyl ammonium chloride-treated aluminum magnesium silicate and the like.
  • Benton 27 benzyldimethylstearylammonium chloride-treated hectorite: manufactured by Elementis Japan
  • Benton 38 disearyldimethylammonium chloride-treated hectorite: manufactured by Elementis Japan
  • the fatty acid can be used at room temperature, and examples thereof include myristic acid, palmitic acid, stearic acid, and behenic acid.
  • Examples of fatty acid salts include calcium salts, magnesium salts and aluminum salts of these fatty acids.
  • the powder in the present invention (hereinafter, also simply referred to as “component C”) is a powder blended as an ultraviolet scattering agent, a usable powder, and a coloring material in conventional sunscreen cosmetics and the like.
  • the ultraviolet light scattering agent is not particularly limited, but is preferably a fine metal oxide such as zinc oxide, titanium oxide, iron oxide, cerium oxide, Examples thereof include powders of tungsten oxide, etc.
  • Examples of usable powders and coloring materials include talc and titanium mica.
  • the surface hydrophobizing agent those generally used in the cosmetics field, for example, dimethicone, silicone such as alkyl-modified silicone, alkoxysilane such as octyltriethoxysilane, dextrin fatty acid ester such as dextrin palmitate, stearic acid, etc. Fatty acid, silica and the like can be used.
  • an ultraviolet scatterer whose surface has been hydrophobized with alkoxysilane such as octyltriethoxysilane or silica is particularly preferable.
  • Nonionic surfactant and / or core-corona type microgel (D) Nonionic surfactant and / or core-corona type microgel (D1) Nonionic surfactant
  • component D1 The nonionic surfactant in the present invention (hereinafter sometimes referred to as “component D1”) is:
  • One or more kinds selected from nonionic surfactants conventionally used in oil-in-water emulsified cosmetics may be used, and among them, those having an HLB of 6 or more are preferably used.
  • the nonionic surfactant used in the present invention particularly preferably contains polyoxyethylene hydrogenated castor oil in terms of the stability of the preparation and the effect of improving the absorbance by contact with moisture.
  • polyoxyethylene hydrogenated castor oil include PEG-10 hydrogenated castor oil, PEG-20 hydrogenated castor oil, PEG-25 hydrogenated castor oil, PEG-30 hydrogenated castor oil, and PEG-40 hydrogenated castor oil. Oil, PEG-50 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-80 hydrogenated castor oil, PEG-100 hydrogenated castor oil, and the like.
  • polyoxyethylene hydrogenated castor oil is not included, it is preferable to use a nonionic surfactant having an HLB of 8 or more, preferably 10 or more, more preferably 12 or more.
  • the blending amount of the (D1) nonionic surfactant is 0.1 to 10% by mass, preferably 0.5 to 5% by mass, more preferably 0.8 to 3%, based on the total amount of the cosmetic. % By mass. If the amount of component D1 is less than 0.1% by mass, sufficient stability is difficult to obtain, and if it exceeds 10% by mass, it may not be preferable in terms of usability. Moreover, it is preferable to mix
  • component D2 Core-corona-type microgel
  • component D2 is a gel in which a hydrophilic group (corona) is partially provided on the surface of a hydrophobic core. Fine particles.
  • component D2 both a crosslinked type and a non-crosslinked type can be used.
  • core-corona type microgels As particularly preferred core-corona type microgels, as shown below, (acrylates / methoxy methacrylate PGE) crosspolymer [crosslinked core-corona type microgel] and acrylamide-based core-corona type microgel [non-crosslinked type core-corona type] Microgel] is exemplified.
  • cross-linked core-corona-type microgel [(Acrylates / Methoxy methacrylate PGE-90) crosspolymer]]
  • the cross-linked core-corona microgel according to this embodiment can be obtained by radical polymerization of monomers represented by the following formulas (1) to (3) under specific conditions.
  • R 1 is an alkyl group having 1 to 3 carbon atoms, and n is a number of 8 to 200.
  • X is H or CH 3 .
  • polyethylene oxide macromonomer represented by the formula (1) for example, a commercially available product commercially available from Aldrich, or a commercially available product such as BLEMMER (registered trademark) available from NOF Corporation may be used.
  • Examples of such a macromonomer include Blemmer (registered trademark) PME-400, Blemmer (registered trademark) PME-1000, and Blemmer (registered trademark) PME-4000 manufactured by NOF Corporation.
  • R 2 is an alkyl group having 1 to 3 carbon atoms.
  • R 3 is an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.
  • hydrophobic monomer represented by the formula (2) for example, a commercially available product commercially available from Aldrich or Tokyo Kasei can be used.
  • hydrophobic monomer of the formula (2) examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, Decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, etc. Can be mentioned. In particular, it is preferable to use methyl methacrylate, butyl methacrylate, or octyl methacrylate.
  • These hydrophobic monomers are general-purpose raw materials and can be easily obtained as general industrial raw materials.
  • R 4 and R 5 each independently represents an alkyl group having 1 to 3 carbon atoms, and m is a number from 0 to 2.
  • the crosslinkable monomer represented by the formula (3) can be obtained as a commercial product or an industrial raw material.
  • This crosslinkable monomer is preferably hydrophobic.
  • the value of m is preferably 0-2.
  • EGDMA ethylene glycol dimethacrylate
  • Blemmer registered trademark
  • the crosslinked core-corona type microgel according to this embodiment is obtained by radical polymerization of the above monomer under the following conditions (a1) to (e1).
  • A1 The molar ratio represented by the charged molar amount of the polyethylene oxide macromonomer / the charged molar amount of the hydrophobic monomer is 1:10 to 1: 250.
  • B1 The charge amount of the crosslinkable monomer is 0.1 to 1.5% by mass with respect to the charge amount of the hydrophobic monomer.
  • the hydrophobic monomer represented by the formula (2) has a monomer composition in which one or more methacrylic acid derivatives having an alkyl group having 1 to 8 carbon atoms are mixed.
  • the charged amount of the crosslinkable monomer with respect to the charged amount of the hydrophobic monomer is defined as “crosslinking density (mass%)”.
  • the crosslinking density of the core-corona type microgel used in the present invention is such that the amount of the crosslinkable monomer charged is 0.1 to 1.5% by mass with respect to the amount of the hydrophobic monomer charged according to the condition (b1). Must.
  • the charged molar amount is preferably 1:10 to 1: 200, more preferably 1:25 to 1: 100.
  • the molar amount of the hydrophobic monomer is less than 10 times the molar amount of the polyethylene oxide macromonomer, the polymer to be polymerized becomes water-soluble and no core-corona microgel is formed.
  • ⁇ Condition (b1) By copolymerizing the crosslinkable monomer, it is possible to polymerize the microgel in which the hydrophobic polymer in the core portion is crosslinked.
  • the charge amount of the crosslinkable monomer is less than 0.1% by mass of the charge amount of the hydrophobic monomer, the crosslink density is low, and the microgel collapses when swollen.
  • the charged amount exceeds 1.5% by mass, aggregation of microgel particles occurs, and suitable microgel particles having a narrow particle size distribution cannot be polymerized.
  • the amount of the crosslinkable monomer charged is preferably 0.2 to 1.0, more preferably 0.2 to 0.8, and most preferably 0.2 to 0.5% by mass.
  • the hydrophobic monomer represented by the formula (2) needs to have a monomer composition in which one or more methacrylic acid derivatives having an alkyl group having 1 to 8 carbon atoms are mixed. If the number of carbon atoms is 0 (a monomer having no terminal ester bond), the monomer may be too hydrophilic to perform emulsion polymerization well. On the other hand, when the number of carbon atoms is 9 or more, there may be a steric hindrance during polymerization, and a crosslinked structure may not be successfully constructed.
  • the polymerization solvent needs to be a mixed solvent of water-organic solvent.
  • the organic solvent ethanol, propanol, butanol, polyol and the like can be used.
  • dissolve is preferable.
  • the polyol used in the present invention needs to be dipropylene glycol, 1,3-butylene glycol, or isoprene glycol. It is possible to manufacture industrially, that is, when considering using the polymerization solution as a raw material as it is without requiring a purification step such as dialysis, the solvent mixed with water is ethanol, propanol, butanol, etc. when applied to the skin It is preferably an polyol that can be blended into cosmetics for general purposes, not an organic solvent in which irritation is a concern.
  • the mixing ratio of the organic solvent is 10 to 90 volume ratio.
  • the solubility of the hydrophobic monomer is extremely low, the polymerization proceeds in the form of monomer droplets to form a huge mass, and no microgel is formed.
  • the mixing ratio of the organic solvent exceeds 90 volume ratio, an emulsion of a hydrophobic monomer due to hydrophobic interaction is not generated, emulsion polymerization does not proceed, and a microgel cannot be obtained.
  • Core-corona type microgel obtained by using polyol as an organic solvent is a water-polyol mixed solvent as a polymerization solvent and does not contain ethanol. Obtainable.
  • polymerization initiator used in the polymerization system a commercially available polymerization initiator used for usual water-soluble thermal radical polymerization can be used. In this polymerization system, even if the polymerization is carried out without strictly controlling the stirring conditions, it is possible to obtain a polymer having a very narrow particle size distribution.
  • Non-crosslinked core-corona microgel [acrylamide core-corona]
  • the non-crosslinked core-corona microgel suitably used in the present invention is a dispersion of core-corona microparticles obtained by radical polymerization of monomers represented by the following formulas (4) to (6) under specific conditions. It is a liquid.
  • R 1 is an alkyl group having 1 to 3 carbon atoms, and n (molecular weight of the polyethylene oxide portion) is a number of 8 to 200.
  • X is H or CH 3 .
  • the polyethylene oxide macromonomer represented by the above formula (4) is preferably an acrylic acid derivative or a methacrylic acid derivative.
  • a commercial product commercially available from Aldrich or a commercial product such as Bremer (registered trademark) marketed by NOF Corporation may be used.
  • R 2 represents an alkyl group having 1 to 3 carbon atoms
  • R 3 represents a substituent containing an alkyl group having 1 to 12 carbon atoms.
  • the hydrophobic monomer represented by the above formula (5) is preferably an acrylic acid derivative or a methacrylic acid derivative (also referred to as “acrylate derivative monomer”), for example, methyl acrylate, ethyl acrylate, acrylic acid monomer.
  • Pill butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, pill methacrylate, butyl methacrylate, Pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, and the like can be used.
  • methyl methacrylate also known as methyl methacrylate
  • butyl methacrylate also known as butyl methacrylate
  • octyl methacrylate are particularly suitable.
  • These hydrophobic monomers are general-purpose raw materials and can be easily obtained as general industrial raw materials. For example, you may use the commercial item marketed from Aldrich or Tokyo Kasei.
  • R 4 represents H or an alkyl group having 1 to 3 carbon atoms
  • R 5 and R 6 represent H or a substituent containing an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms.
  • the hydrophobic monomer represented by the above formula (6) is preferably an acrylamide derivative or a methacrylamide derivative (also referred to as “acrylamide derivative monomer”).
  • acrylamide derivative monomer also referred to as “acrylamide derivative monomer”.
  • t-butyl acrylamide, N, N-dimethylacrylamide, N- [3- (dimethylamino) propyl] acrylamide, t-butyl methacrylamide, octyl acrylamide, octyl methacrylamide, octadecyl acrylamide and the like can be suitably used.
  • t-butylacrylamide, N, N-dimethylacrylamide, and N- [3- (dimethylamino) propyl acrylamide] acrylamide are particularly preferable.
  • These hydrophobic monomers are available as commercial products or industrial raw materials.
  • the copolymer constituting the core-corona type microparticles according to the present invention comprises a macromonomer represented by the above formula (4) by any radical polymerization method according to the following conditions (a2) to (d2): One or two or more selected from the hydrophobic monomers represented by the above formulas (5) and (6) are copolymerized.
  • A2 The molar ratio represented by the charged molar amount of the polyethylene oxide macromonomer / (the acrylate derivative monomer and / or acrylamide derivative monomer) is 1:10 to 1: 250.
  • the macromonomer represented by the above formula (4) is an acrylic acid derivative or a methacrylic acid derivative having a polyethylene glycol group having a repeating unit of 8 to 200
  • the acrylate derivative monomer represented by the above formula (5) is an acrylic acid derivative or a methacrylic acid derivative having a substituent containing an alkyl group having 1 to 12 carbon atoms
  • the acrylamide derivative monomer represented by the above formula (6) is an acrylamide derivative or a methacrylamide derivative having a substituent containing an alkyl group having 1 to 12 carbon atoms
  • the polymerization solvent is a water-alcohol mixed solvent, and the alcohol is one or more selected from ethanol, dipropylene glycol, 1,3-butylene glycol, and isoprene glycol.
  • the charged molar amount is preferably 1:10 to 1: 200, more preferably 1:25 to 1: 100.
  • the molar amount of the hydrophobic monomer is less than 10 times the molar amount of the polyethylene oxide macromonomer, the polymer to be polymerized becomes water-soluble and does not form core-corona type particles.
  • the condition (b2) includes the following three conditions (b2-1) to (b2-3).
  • the macromonomer represented by the formula (4) is an acrylic acid derivative or a methacrylic acid derivative having a polyethylene glycol group having 8 to 200 repeating units. When the repeating unit is 7 or less, particles stably dispersed in the solvent may not be obtained, and when it exceeds 200, the particles may be made fine and unstable when blended in a cosmetic.
  • the acrylate derivative monomer represented by the formula (5) is an acrylic acid derivative or a methacrylic acid derivative having a substituent containing an alkyl group having 1 to 12 carbon atoms.
  • the acrylamide derivative monomer represented by the formula (6) is an acrylamide derivative or a methacrylamide derivative having a substituent containing an alkyl group having 1 to 18 carbon atoms.
  • the hydrophobic monomer according to this embodiment has a monomer composition in which one or more selected from the acrylate derivative monomer represented by the above formula (5) and the acrylamide derivative monomer represented by the formula (6) are mixed. It is necessary.
  • hydrophobic monomers methacrylate and butyl methacrylate, or methacrylate, t-butylacrylamide, N, N-dimethylacrylamide, and N- [3- (dimethylamino) propyl] acrylamide] are used. It is particularly preferable to use four types. In the combination of these hydrophobic monomers, it is further preferable to use methoxypolyethylene glycol monometalate as a macromonomer.
  • the polymerization solvent needs to be a water-alcohol mixed solvent.
  • alcohol what can melt
  • the mixing ratio of alcohol is lower than 10 volume ratio, the dissolving ability of the hydrophobic monomer becomes extremely low, and microparticles may not be generated.
  • the mixing ratio of the alcohol exceeds 90 volume ratio, an emulsion of a hydrophobic monomer due to hydrophobic interaction may not be generated, and emulsion polymerization may not proceed, resulting in failure to obtain Mikuguchi particles.
  • the core-corona type microgel preferably used in the present invention is a microgel stabilized with a polyethylene oxide chain which is a nonionic polymer, and its dispersion stability in water has acid resistance and salt resistance. I can expect.
  • the hydrophilic macromonomer and the hydrophobic monomer are ordered in the solvent, the particle diameter is almost constant, and the core part is crosslinked or non-crosslinked core-corona type polymer microgel. Is considered to generate.
  • the blending amount of the core-corona type microgel in the cosmetic of the present invention is usually preferably 0.01 to 10% by mass (pure) with respect to the total amount of the cosmetic. If the blending amount is less than 0.01% by mass (pure content), it may be difficult to obtain a stable cosmetic. When the blending amount exceeds 10% by mass (pure content), it may not be preferable from the viewpoint of stability in long-term storage under high temperature conditions, or the feeling of use may be inferior.
  • the above-mentioned core-corona type microgel has a structure in which an oil phase component and an aqueous phase component are emulsified and the core-corona type microgel emulsifier is adsorbed onto oil droplets of the oil phase component dispersed in the aqueous phase component. Having an oil-in-water emulsion composition.
  • the core-corona type microgel emulsifier as described above is excellent in emulsifying power, and when used as an emulsifier, it becomes an oil-in-water type emulsified composition having extremely excellent stability.
  • the core-corona type microgel can obtain sufficient strength against the behavior of the hydrophobic powder having a large specific gravity present in the oil phase.
  • Non-volatile liquid oil content The oil-in-water emulsified cosmetic of the present invention contains (E) a non-volatile liquid oil content.
  • “Non-volatile liquid oil” in the present specification indicates no volatility at normal temperature (25 ° C.) and normal pressure (1 atm (9.8 ⁇ 10 4 Pa)) (for example, the boiling point at normal pressure is (It includes oils of about 200 ° C or higher), fluid oil at normal temperature and pressure, and non-solid liquid oil.
  • the non-volatile liquid oil in the present invention includes an oily ultraviolet absorber corresponding to the component A. Therefore, the present invention includes (1) an embodiment in which the non-volatile liquid oil component (component E) contains a non-volatile liquid oil component other than the ultraviolet absorber, and (2) an embodiment in which component E consists of only the ultraviolet absorber. .
  • the non-volatile liquid oil other than the ultraviolet absorber contained in Component E includes, for example, hydrocarbon oil, vegetable oil, ester oil, high molecular weight polyoxyalkylene glycol, and silicone oil.
  • palm oil linseed oil, camellia oil, macadamia nut oil, corn oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, kyounin oil, cinnamon oil, jojoba oil, grape oil, almond oil, Rapeseed oil, sesame oil, sunflower oil, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, tea seed oil, evening primrose oil, egg yolk oil, liver oil, triglycerin, glyceryl trioctanoate, triisopalmitin Liquid fats and oils such as glyceryl acid; octanoic acid esters such as cetyl octanoate, isooctanoic acid esters such as glyceryl tri-2-ethylhexanoate and pentaerythritol tetra-2-ethylhexanoate, and lauric
  • the cosmetic of the present invention is an oil-in-water emulsified cosmetic, and contains powder in the inner oil phase.
  • a powder-in-oil-in-water emulsion if the viscosity of the inner oil phase is large, it tends to be difficult to obtain a stable emulsion.
  • the total amount of (B) oil phase thickener and (C) hydrophobized powder constituting the inner oil phase and (E) non-volatile liquid oil (including (A) ultraviolet absorber) By setting the ratio ([B + C / E]) to the blending amount within a predetermined range, a stable emulsion can be obtained, and there is a unique effect of improving the ultraviolet protection ability by contact with moisture.
  • the total amount of (B) oil phase thickener and (C) hydrophobized powder is preferably 7.5 to 40% by mass based on the total amount of cosmetics.
  • components usually used in cosmetics can be blended as optional components as long as the effects of the present invention are not impaired.
  • optional components include volatile oils, and volatile oils that can be blended in the present invention include volatile hydrocarbon oils and volatile silicone oils, and lower alcohols such as ethanol.
  • volatile hydrocarbon oil content is not particularly limited as long as it is a hydrocarbon oil having volatility at room temperature (25 ° C.) conventionally used in cosmetics and the like. Specific examples include isododecane, isohexadecane, hydrogenated polyisobutene and the like.
  • Volatile silicone oils include silicone oils that are volatile at room temperature (25 ° C.), such as volatile linear silicone oils (volatile dimethicone) and volatile cyclic rings that have been used in cosmetics and the like. Silicone oil (volatile cyclomethicone) is included. As volatile dimethicone, low-viscosity dimethylpolysiloxane such as decamethyltetrasiloxane can be used, and commercially available products include KF-96L-1.5cs and KF-96L-2cs (both manufactured by Shin-Etsu Chemical Co., Ltd.). ) And the like. Examples of volatile cyclomethicone include decamethylcyclopentasiloxane (D5).
  • blending the coating agent it is possible to further enhance the resistance to (A) the ultraviolet absorber and (C) the spilling of the hydrophobic treatment powder and the rub-off caused by clothes.
  • the blending amount is preferably within a range in which the film feeling (usability) and the cleaning property are not deteriorated.
  • the coating agent is not particularly limited as long as it is usually used in cosmetics. Specifically, polyvinylpyrrolidone (PVP), PVP / dimethylaminoethyl methacrylic acid copolymer, PVP / eicosene copolymer, PVP / PVP coatings such as / methacrylic acid / methacrylic acid copolymer, PVP / hexadecene copolymer, PVP / VA copolymer, PVP / vinyl acetate / itaconic acid copolymer, styrene / PVP copolymer; acrylic Ethyl acrylate / acrylic amide / acrylic acid copolymer, ethyl acrylate / butyl acrylate copolymer, ethyl acrylate / ethyl methacrylate copolymer, ethyl acrylate / methacrylic acid copolymer, ethy
  • ingredients usually used in cosmetics such as whitening agents, moisturizers, antioxidants, oily active agents, surfactants, aqueous phase thickeners, usable powders (hydrophobized ones) ), Coloring materials, aqueous activators and the like.
  • ⁇ Usable powders and color materials which are optional components, can be those usually blended in makeup cosmetics such as pigments and pearl pigments.
  • inorganic white pigments titanium dioxide, zinc oxide
  • inorganic red pigments iron oxide (bengara), iron titanate
  • inorganic brown pigments ⁇ -iron oxide
  • inorganic yellow pigments Yellow iron oxide, ocher
  • inorganic black pigment black iron oxide, carbon, low-order titanium oxide
  • inorganic purple pigment mango violet, cobalt violet
  • inorganic green pigment chromium oxide, chromium hydroxide, titanic acid) Cobalt
  • inorganic blue pigments ultraviolet, bitumen
  • pearl pigments titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil
  • metal powder pigments Alluminum powder, copper powder
  • organic pigment red 202, red 205, red 220,
  • the oil-in-water emulsified cosmetic of the present invention can be produced according to a conventional method.
  • an aqueous phase thickener is optionally dissolved in an aqueous component (including a nonionic surfactant and / or a core-corona type microgel), and a surface activity is partially applied to the oily component in which the oil phase thickener is dissolved.
  • It can be prepared by adding an agent to dissolve or disperse the UV scattering agent, adding it to the aqueous component, emulsifying with a homomixer, etc., and finally adding the remaining oil component and powder and stirring and mixing ( When stirring, a shearing force may optionally be added).
  • the oil-in-water emulsified cosmetic composition of the present invention can be preferably used as, for example, a sunscreen cream, a sunscreen emulsion, a sunscreen lotion, a foundation imparted with a sunscreen effect, a makeup base and the like.
  • sunscreen cosmetics As mentioned above, although the aspect of sunscreen cosmetics was demonstrated, this invention is not limited to this aspect.
  • a pearl agent, a colorant (pigment), etc. based on the cosmetic of the present invention, the characteristics (transparency, color developability, unevenness correction effect, etc.) change by contact with moisture.
  • the cosmetic in such an embodiment has a novel property that the makeup effect and the skin care effect are improved by contact with sweat or moisture.
  • This characteristic is that (A) a sunscreen cosmetic containing 1% by mass or more of an ultraviolet absorber also contains (A) a cosmetic that contains less than 1% by mass of the ultraviolet absorber or a cosmetic that does not contain an ultraviolet absorber. (See Table 4 and formulation examples 5 and 6).
  • the present invention (A1) 1% by mass or less of an ultraviolet absorber, (B) oil phase thickener, (C) Hydrophobized powder, (D) a nonionic surfactant and / or a core-corona type microgel, and (E) a non-volatile liquid oil (including the (A) ultraviolet absorber), (E) The ratio ([(B) + (C)] / (E)) of the total blending amount of (B) oil phase thickener and (C) hydrophobized powder to the blending amount of the non-volatile liquid oil.
  • An embodiment of an oil-in-water emulsified cosmetic that is 0.2 to 20 is also included.
  • the components (A) to (E) are the same as those described for the sunscreen cosmetic.
  • the blending amount of the (A) ultraviolet absorber may be less than 1% by mass, for example, 0.5% by mass or less, 0.3% by mass or less, or 0.1% by mass or less, and does not include the ultraviolet absorber. Also good.
  • the oil-in-water emulsified cosmetic of the present invention is characterized in that the cosmetic coating film (film thickness) is uniformized by contact with moisture.
  • the present inventors are the result that the distribution (density) of the UV absorber in the direction perpendicular to the skin in the cosmetic coating film on the skin is made uniform over the entire coating film. , Bears that UV protection is improved. This phenomenon is not limited to ultraviolet absorbers, and is thought to contribute to the uniformity of the distribution of the various components incorporated.
  • the optical characteristics (diffuse reflection light and internal reflection light) of the decorative coating film are close to the bare skin, and the aesthetic effect that the transparent feeling is increased and it feels beautiful. Play.
  • Oil-in-water emulsified sunscreen cosmetics having the compositions listed in Tables 1 to 4 below were prepared according to the method described in Paragraph 0078. For each sample, the emulsion stability and the change in absorbance before and after the water bath were measured.
  • Abs -log (T / To) T: Transmittance of sample, To: Transmittance when uncoated The measured plate was sufficiently immersed in water having a hardness of 50 to 500 and stirred in water as it was for 30 minutes (300 rpm with a 3-1 motor). Thereafter, the sample was dried for about 15 to 30 minutes until water droplets on the surface disappeared, the absorbance was measured again, and the Abs change rate (the following formula) was calculated as an effect of improving UV protection ability from the Abs integrated value before and after the water bath.
  • Absorbance change rate before and after water bath (%) (Absorbance integrated value after bathing) / (Absorbance integrated value before bathing) ⁇ 100 In the present invention, it is defined that the UV protection effect is improved when the absorbance change rate exceeds 100%.
  • a cross-linked core-corona type microgel ((acrylates / methoxymethacrylic acid methoxy-PEG-90) crosspolymer) or non-crosslinked type Examples 12 to 15 using a core-corona type microgel (acrylamide-based core corona) were excellent in emulsification stability, the absorbance change rate before and after the water bath exceeded 100%, and further excellent in water resistance.
  • the surface treatment agent of the hydrophobized powder was changed to silicone (dimethicone), alkoxysilane (octyltriethoxysilane), dextrin fatty acid ester such as dextrin palmitate, fatty acid such as stearic acid, and silica. It was also confirmed that the effects of the present invention can be obtained.
  • a water-in-oil emulsified cosmetic with the formulation shown in Table 5 below was prepared in the same manner as in the other examples.
  • the sweat (water bath) test was implemented to the panel of 10 persons on the following conditions. After applying the sample of each example, whether the skin after spending 60 minutes in an environment of 30 ° C. and 80% humidity is more transparent and clearer than before the sweat (water bath) test (actual feeling) Presence or absence).
  • the results of the sweat (water bath) test were ranked according to the following criteria. A: 8 or more out of 10 people feel B: 5 to 7 out of 10 people feel C: 4 or less out of 10 people feel

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Abstract

La présente invention a trait à un produit cosmétique en émulsion de type huile-dans-eau qui comporte une poudre dans sa phase huile interne, le produit cosmétique en émulsion de type huile-dans-eau présentant une résistance améliorée à l'eau et des caractéristiques de pénétration sans précédent telles que les effets protecteurs contre le rayonnement ultraviolet augmentant davantage après que le produit cosmétique entre en contact avec de l'eau, de la sueur, etc. que immédiatement après l'application, ainsi qu'une sensation excellente lors de l'application et une excellente aptitude au lavage. La présente invention porte sur un produit cosmétique en émulsion de type huile-dans-eau qui comporte (A) un agent d'absorption du rayonnement ultraviolet, (B) un épaississant de phase huile, (C) une poudre de traitement d'hydrophobisation, (D) un tensioactif non ionique et/ou un microgel type cœur-couronne, et (E) une teneur en huile non volatile (comprenant l'agent d'absorption du rayonnement ultraviolet (A)), et qui est caractérisée en ce que le rapport de la quantité combinée de (B) l'épaississant de la phase huile et (C) la poudre de traitement d'hydrophobisation à la quantité de (E) la teneur en huile non volatile ([(B) + (C)]/(E)) est de 0,2 à 20.
PCT/JP2017/016561 2016-04-28 2017-04-26 Produit cosmétique en émulsion de type huile-dans-eau WO2017188319A1 (fr)

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KR1020187033440A KR102415538B1 (ko) 2016-04-28 2017-04-26 수중 유형 유화 화장료
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WO2018180179A1 (fr) * 2017-03-29 2018-10-04 株式会社 資生堂 Produit cosmétique de type huile dans l'eau
JP2021031475A (ja) * 2019-08-29 2021-03-01 ポーラ化成工業株式会社 水中油型乳化組成物
WO2021090740A1 (fr) * 2019-11-08 2021-05-14 株式会社資生堂 Composition d'huile dans l'eau
JPWO2020075666A1 (ja) * 2018-10-09 2021-10-07 株式会社 資生堂 油中水型乳化組成物
WO2023094847A1 (fr) * 2021-11-29 2023-06-01 Lvmh Recherche Produit cosmétique eau-dans-huile

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WO2023211211A1 (fr) * 2022-04-29 2023-11-02 주식회사 엘지생활건강 Composition cosmétique sans effet blanc sur la peau permettant de bloquer des rayons ultraviolets
CN115006311B (zh) * 2022-07-06 2024-03-26 浙江宜格企业管理集团有限公司 一种透明双相防晒组合物及其制备方法

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JP2018168087A (ja) * 2017-03-29 2018-11-01 株式会社 資生堂 水中油型化粧料
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JPWO2017188319A1 (ja) 2019-02-28
CN109069357B (zh) 2022-08-30
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