WO2018124287A1 - Oil-in-water emulsion composition - Google Patents

Oil-in-water emulsion composition Download PDF

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Publication number
WO2018124287A1
WO2018124287A1 PCT/JP2017/047295 JP2017047295W WO2018124287A1 WO 2018124287 A1 WO2018124287 A1 WO 2018124287A1 JP 2017047295 W JP2017047295 W JP 2017047295W WO 2018124287 A1 WO2018124287 A1 WO 2018124287A1
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Prior art keywords
mass
oil
component
less
emulsion composition
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PCT/JP2017/047295
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French (fr)
Japanese (ja)
Inventor
浩一 岸田
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花王株式会社
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Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to KR1020197013598A priority Critical patent/KR20190101359A/en
Priority to CN201780080690.8A priority patent/CN110114053A/en
Publication of WO2018124287A1 publication Critical patent/WO2018124287A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/062Oil-in-water emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29Titanium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39Derivatives containing from 2 to 10 oxyalkylene groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/55Phosphorus compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/55Phosphorus compounds
    • A61K8/553Phospholipids, e.g. lecithin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

  • the present invention relates to an oil-in-water emulsion composition.
  • metal oxide powder such as zinc oxide and titanium oxide, which are ultraviolet scattering agents
  • metal oxide powder such as zinc oxide and titanium oxide, which are ultraviolet scattering agents
  • an ultraviolet scattering agent (hydrophobized metal oxide powder) is prepared using polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether whose carbon chain length and number of moles of ethylene oxide added are within a certain range.
  • a stably formulated sunscreen cosmetic is disclosed. These sunscreen cosmetics have excellent low-temperature stability by forming the soft layered structure (multi-lamellar vesicle structure) by the presence of the compound at the interface between the aqueous phase and the oil phase, elongation on the skin, The stickiness is also good, the sticky feeling and squeaky feeling are suppressed, and the moisturizing effect is also high.
  • Patent Document 1 JP 2006-8796 JP (Patent Document 2) JP 2005-272389 JP (Patent Document 3) JP 2014-114274 JP
  • the present invention includes the following components (A) to (D), wherein the mass ratio [(A) / (B)] of component (A) to component (B) is 0.06 or more and 18 or less
  • An emulsified composition is provided.
  • (A) Polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether having an alkyl group or alkenyl group having 20 to 24 carbon atoms and an average addition mole number of ethylene oxide of 1.5 to 4
  • B Phospholipid
  • C Hydrophobized powder
  • D Water
  • Patent Document 3 there is room for improvement in the stability of the composition, such as partial emulsification failure at high temperatures, and a decrease in viscosity when high shear force is applied.
  • the present invention relates to an oil-in-water emulsion composition that stably contains a hydrophobized powder, is excellent in stability of an emulsification system when stored at high temperature or when shearing force is applied, and is excellent in use feeling such as freshness. .
  • the present inventor formulated a hydrophobized powder by using a specific polyoxyethylene alkyl ether or the like used in the technique described in Patent Document 3 and a phospholipid in a specific ratio.
  • the present invention was completed by finding that the oil-in-water emulsion composition thus obtained can be greatly improved in stability at high temperatures and resistance to shearing force (hereinafter referred to as “shear resistance”).
  • the polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether of component (A) used in the present invention has an alkyl group or an alkenyl group having 20 to 24 carbon atoms and an average added mole number of ethylene oxide of 1.5 to 4 Is.
  • the alkyl group or alkenyl group of component (A) may be linear or branched, and is preferably a linear or branched alkyl group, more preferably from the viewpoint of forming a lamellar structure at the oil phase interface. It is a linear alkyl group.
  • the number of carbon atoms of the alkyl group or alkenyl group is 20 or more, preferably 21 or more, from the viewpoint of forming a lamellar structure at the oil phase interface and improving high temperature stability (emulsification stability) and shear resistance.
  • the alkyl group or alkenyl group preferably has 22 carbon atoms, and among them, an alkyl group having 22 carbon atoms (that is, a behenyl group) is more preferable.
  • the average number of moles of ethylene oxide added in component (A) is 1.5 or more from the viewpoint of lowering the crystallinity and facilitating dissolution in the oil phase. From the viewpoint of improving (emulsion stability) and shear resistance, it is 4 or less, preferably 3 or less, more preferably 2.5 or less.
  • the generally available polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether is a mixture having a very wide distribution centering on a desired degree of polymerization in terms of the number of moles of ethylene oxide added. It is important that the number is within the above range.
  • examples include ether, polyoxyethylene (4) behenyl ether, polyoxyethylene (2) carnerville ether, polyoxyethylene (3) carnerville ether, polyoxyethylene (4) carnerville ether, and preferably polyoxyethylene (2) Behenyl ether, polyoxyethylene (3) behenyl ether, polyoxyethylene (4) behenyl ether are mentioned.
  • the average added mole number of the polyoxyethylene alkyl ether to be used is in the above range, it is possible to use other than those exemplified polyoxyethylene alkyl ether in combination.
  • the content of component (A) in the oil-in-water emulsion composition of the present invention is preferably from the viewpoint of facilitating the formation of a lamellar structure at the oil phase interface, improving the shear resistance, and improving the fresh feeling of use.
  • 0.05% by mass or more more preferably 0.10% by mass or more, further preferably 0.12% by mass or more, more preferably 0.16% by mass or more, further preferably 0.5% by mass or more, further preferably 0.8% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, further preferably 1.82% by mass or less, still more preferably 1.5% by mass or less, and further preferably 1.2% by mass or less.
  • component (A) is preferably 0.05 to 5% by mass, more preferably 0.10 to 3% by mass, still more preferably 0.12 to 2% by mass, still more preferably 0.16 to 1.82% by mass, and still more preferably Is 0.5 to 1.5 mass%, more preferably 0.8 to 1.2 mass%.
  • the phosphatidylcholine content is 60% by mass or more, and further 62% by mass or more from the viewpoint of improving high-temperature stability and shear resistance, suppressing stickiness, accustoming to the skin, and improving makeup. In addition, it is preferably 65% by mass or more. Moreover, what has a phosphatidylcholine content of 98 mass% or less is preferable.
  • phospholipid components other than phosphatidylcholine include phosphatidic acid, phosphatidylserine, phosphatidylethanolamine, phosphatidylinositol, and phosphatidylglycerol.
  • the phospholipid used in the present invention may be a natural product extracted and purified from animals or plants, or may be chemically synthesized, or may be subjected to processing such as hydrogenation or hydroxylation.
  • a natural product lecithin which is an extract / purified product from soybean or egg yolk is preferable from the viewpoint of improving stability over time and reducing skin irritation, and more preferably hydrogenated or hydroxylated.
  • soybean hydrogenated lecithin and egg yolk lecithin hydrogenated are preferably mentioned.
  • the content of phosphatidylcholine in the phospholipid can be analyzed by a method using thin layer chromatography (TLC), high performance liquid chromatography (HPLC), Iatroscan (manufactured by Yatron).
  • TLC thin layer chromatography
  • HPLC high performance liquid chromatography
  • Iatroscan manufactured by Yatron
  • a method of analyzing phospholipids with a post densitometer is mentioned. In addition to the above method, any method may be used as long as it can measure and calculate the content and content of phosphatidylcholine contained in the phospholipid.
  • Phospholipids containing 60% by mass or more of phosphatidylcholine include Coatsome NC-21 (hydrogenated soybean lecithin; manufactured by NOF Corporation), Resinol S-10E, Resinol S-10EX (hydrogenated soybean lecithin; Nikko Chemicals) And Phospholipid PCSH70 (hydrogenated soybean lecithin; manufactured by Nippon Seika Co., Ltd.).
  • the content of the component (B) in the oil-in-water emulsion composition of the present invention is preferably 0.05% by mass or more, more preferably 0.10% by mass or more from the viewpoint of improving high-temperature stability, shear resistance, and usability. More preferably, it is 0.12% by mass or more, more preferably 0.16% by mass or more, further preferably 0.5% by mass or more, further preferably 0.8% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass.
  • it is further preferably 2% by mass or less, more preferably 1.82% by mass or less, further preferably 1.5% by mass or less, and further preferably 1.2% by mass or less.
  • component (B) is preferably 0.05 to 5% by mass, more preferably 0.10 to 3% by mass, still more preferably 0.12 to 2% by mass, still more preferably 0.16 to 1.82% by mass, and still more preferably Is 0.5 to 1.5 mass%, more preferably 0.8 to 1.2 mass%.
  • the total content of component (A) and component (B) in the oil-in-water emulsion composition of the present invention is preferably 0.5% by mass or more, more preferably 1.2% by mass, from the viewpoint of improving high-temperature stability and shear resistance. % Or more, more preferably 1.8% by mass or more, and from the viewpoint of improving freshness, it is preferably 6% by mass or less, more preferably 3.5% by mass or less, and still more preferably 2.5% by mass or less.
  • the specific total content range of component (A) and component (B) is preferably 0.5 to 6% by mass, more preferably 1.2 to 3.5% by mass, and still more preferably 1.8 to 2.5% by mass.
  • the content ratio [(A) / (B)] of the component (A) to the component (B) is preferably 0.06 or more, more preferably 0.08 or more, from the viewpoint of improving high-temperature stability and shear resistance. Preferably, it is 0.10 or more, more preferably 0.5 or more, and from the viewpoint of obtaining a fresh feeling of use, it is preferably 18 or less, more preferably 14 or less, still more preferably 10 or less, and even more preferably 3 or less.
  • the content ratio [(A) / (B)] of the component (A) to the specific component (B) is preferably 0.06 to 18, more preferably 0.08 to 14, still more preferably 0.10 to 10, more preferably 0.5-3.
  • zinc oxide powder for example, FINEX-25, FINEX-50, FINEX-75 (manufactured by Sakai Chemical), MZ500 series, MZ700 series (manufactured by Teika), ZnO-350 (manufactured by Sumitomo Osaka Cement Co., Ltd.), etc. are commercially available.
  • titanium oxide powder TTO-55 series, TTO-51 series (Ishihara Sangyo Co., Ltd.), JR series, JA series (Taika Co., Ltd.), etc. are commercially available.
  • As the iron oxide powder LL-100P, R-516P, BL-100P (manufactured by Titanium Industry Co., Ltd.) and the like are commercially available.
  • the cerium oxide includes high purity cerium sold by Nikki or Seimi Chemical.
  • the average particle size of the powder used for the hydrophobized powder of component (C) is from the emulsified particle size of the oil-in-water emulsion composition from the viewpoint of improving emulsification stability by including the hydrophobized powder in the oil phase.
  • the specific average particle diameter is preferably 0.01 to 28 ⁇ m, more preferably 0.012 to 23 ⁇ m, and still more preferably 0.015 to 18 ⁇ m.
  • Hydrophobic treatment using methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer, hydrophobic treatment using silane compound or silazane compound, hydrophobization treatment using titanate coupling agent and acylamino acid metal salt 1 type or 2 types or more of hydrophobizing treatments selected from the hydrophobizing treatments used are preferable, hydrophobizing treatment using methylhydrogenpolysiloxane, hydrophobizing treatment using silane compound or silazane compound, titanate coupling Hydrophobic treatment using an agent and hydrophobic treatment using an acylamino acid metal salt One or more hydrophobic treatment is more preferable.
  • the powder is at least one of a silicone compound (excluding a silane compound) made of an organopolysiloxane and a silicone resin.
  • a silicone compound excluding a silane compound
  • An example is a method of coating a powder with silicon oxide by coating in a non-gas phase state with at least a seed and then firing at a temperature of 600 to 950 ° C. in an oxygen-containing atmosphere.
  • the silane compound or silazane compound is preferably a silane compound or silazane compound having an alkyl group or fluoroalkyl group having 1 to 20 carbon atoms and having reactivity with an inorganic oxide.
  • a silane compound represented by the general formula (3) can be used.
  • R 2 to R 7 each independently represents a linear or branched alkyl group or fluoroalkyl group having 1 to 20 carbon atoms.
  • silane compounds include hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, octyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, and the like. It is done. Of these, octyltriethoxysilane and octyltrimethoxysilane are preferred. As the silazane compound, hexamethyldisilazane is preferable.
  • the silane compound or silazane compound is characterized in that it is easy to treat uniformly, is easy to supply and is inexpensive in cost, and cosmetics formulated with powders hydrophobized with these compounds have characteristics such as dispersibility. Since it is excellent, it is preferable.
  • the silane compound or silazane compound and powder are mixed in an organic solvent such as n-hexane, cyclohexane or lower alcohol, and finely pulverized in some cases.
  • organic solvent such as n-hexane, cyclohexane or lower alcohol
  • finely pulverized in some cases.
  • the method include a method in which the surface is removed by heating or reduced pressure, and a chemical reaction is preferably performed on the surface of the powder by a reactive group of the silane compound or silazane compound, such as a heat treatment at 80 to 250 ° C.
  • JP-A-2007-326902 there is a method in which a powder is coated with a specific polysiloxane compound, and then an alkylalkoxysilane is hydrophobized in water.
  • the titanate coupling agent When mixing the powder with the titanate coupling agent, it is preferable to add a small amount of an aqueous solution of metal chloride such as zinc chloride or aluminum chloride, thereby causing the reaction to occur rapidly and uniformly over the entire surface of the powder. be able to.
  • metal chloride such as zinc chloride or aluminum chloride
  • N-hexanoyl aspartic acid (glutamic acid)
  • glutamic acid means both N-hexanoyl aspartic acid and N-hexanoyl glutamic acid.
  • metal salt include sodium salt, potassium salt, calcium salt, magnesium salt and the like.
  • the coating amount of the hydrophobizing agent on the powder is based on the total amount of powder used from the viewpoint that the surface of the powder is uniformly coated with the surface treating agent and the hydrophobizing agent does not aggregate or precipitate on the powder surface.
  • the amount is preferably 1% by mass or more, more preferably 1.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less.
  • the specific coating amount is preferably 1 to 10% by mass, more preferably 1.5 to 5% by mass.
  • Liquid organic ultraviolet absorbers include 2-methoxyhexyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, isopropyl dimethoxycinnamate and diisopropyl cinnamate ester, methyl bis (trimethyl trimethoxycinnamate) From the group consisting of (siloxy) silylisopentyl, paradimethylamino acid amyl benzoate, paradimethylamino acid 2-ethylhexyl benzoate, ethylene glycol salicylate, 2-ethylhexyl salicylate, benzyl salicylate, homomenthyl salicylate, octocrylene, dimethicodiethylbenzalmalonate
  • the 1 type (s) or 2 or more types selected can be mentioned.
  • paramethoxycinnamate 2-ethylhexyl, salicylate 2-ethylhexyl, salicylate homomenthyl, octocrylene and dimethicodiethylbenzalmalonate It is preferable that 1 type or 2 or more types selected from these are included, and it is more preferable that 1 type or 2 or more types selected from 2-ethylhexyl paramethoxycinnamate, octocrylene, and dimethicodiethylbenzalmalonate are included. It is more preferable to contain 2-ethylhexyl paramethoxycinnamate.
  • the content of the component (E) in the oil-in-water emulsion composition of the present invention is preferably 5% by mass or more from the viewpoint of improving a fresh feeling of use and improving the emulsified state, high temperature stability and low temperature stability. More preferably, it is 8 mass% or more, More preferably, it is 10 mass% or more, Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 18 mass% or less.
  • the specific content range of component (E) is preferably 5 to 25% by mass, more preferably 8 to 20% by mass, still more preferably 10 to 20% by mass, and further preferably 10 to 18% by mass.
  • component (F) include dimethoxybenzylidenedioxoimidazolidinepropionic acid 2-ethylhexyl, diethylaminohydroxybenzoylbenzoic acid hexyl ester, 2,4-bis [[4- (2-ethylhexyloxy) -2-hydroxy]- Phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine and 4- One type or two or more types selected from the group consisting of tert-butyl-4′-methoxydibenzoylmethane can be mentioned.
  • components (F) are generally commercially available, soft shade DH (dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl; manufactured by Ajinomoto Co., Inc.), ubinal Aplus (2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid Acid hexyl ester; manufactured by BASF), Tinosorb S (2,4-bis [[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl] -6- (4-methoxyphenyl) -1,3, 5-triazine (manufactured by BASF), ubinal T-150 (2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine), parasol 1789 (4-tert- Butyl-4'-methoxydibenzoylmethane; manufactured by Roche).
  • the content of the component (F) in the oil-in-water emulsion composition of the present invention is preferably 0.5% by mass or more, more preferably 1% by mass from the viewpoint of improving the UV protection effect, high temperature stability and shear resistance. More preferably, it is 1.5% by mass or more, preferably 10% by mass or less, more preferably 7.5% by mass or less, and still more preferably 5% by mass or less.
  • the specific content range of component (F) is preferably 0.5 to 10% by mass, more preferably 0.5 to 7.5% by mass, and still more preferably 0.5 to 5% by mass.
  • the cationic polymer examples include hydroxyethyl cellulose (polyquaternium-10) having a chloride O- [2-hydroxy-3- (trimethylammonio) propyl] group, vinylpyrrolidone-dimethylaminomethylethyl methacrylate copolymer Examples thereof include diethyl diethyl sulfate (polyquaternium-11), methylvinylimidazolium chloride / vinylpyrrolidone copolymer, and the like.
  • anionic polymer examples include carboxyvinyl polymer, carboxymethyl cellulose, carrageenan, xanthan gum, polystyrene sulfonate, agar, gatch gum, caraya gum, pectin, alginate salt, acrylic acid / alkyl methacrylate copolymer, (acrylic acid (Na / acryloyldimethyltaurine Na) copolymer, polyacrylamide, (acryloyldimethyltaurine ammonium / VP) copolymer, (acryloyldimethyltaurine ammonium methacrylate, Behenes-25) crosspolymer, (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, ( Acrylamide / ammonium acrylate) copolymer, (Na acrylate / acryloyl dimethyl taurine / dimethyl acrylamide) Ross polymer, polyacrylate-13, polyacrylate
  • amphoteric polymer or the bipolar polymer include octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer, polyquaternium-47, polyquaternium-43 and the like.
  • water-soluble polymers can be used alone or in appropriate combination of two or more.
  • carboxyvinyl polymer acrylic acid / alkyl methacrylate copolymer, xanthan gum, hydroxypropyl methylcellulose, polyacrylamide, (Na acrylate / acryloyldimethyl) It preferably contains at least one selected from taurine Na) copolymer, (acryloyldimethyltauronium ammonium / VP) copolymer and hyaluronic acid or alkali metal salts thereof, polyacrylamide, (Na acrylate / acryloyldimethyltaurine Na) copolymer, More preferably, it contains one or more selected from (acryloyldimethyltaurate ammonium / VP) copolymer and xanthan gum.
  • the content of the component (H) in the oil-in-water emulsion composition of the present invention is not particularly limited, but it has a refreshed feeling of use, good elongation at the time of application, and water / sweat resistance is improved. Therefore, it is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 12% by mass or less. It is.
  • the specific content range of component (H) is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and still more preferably 5 to 12% by mass.
  • the average emulsified particle size of the oil-in-water emulsion composition of the present invention is preferably 1 ⁇ m or more, preferably 30 ⁇ m or less, preferably 25 ⁇ m or less from the viewpoint of improving emulsification stability, improving the fresh feeling of use, and uniform coating properties. More preferred is 20 ⁇ m or less. Specifically, it is preferably 1 to 30 ⁇ m, more preferably 1 to 25 ⁇ m, still more preferably 1 to 20 ⁇ m.
  • the average particle size of the emulsified particles can be obtained from the number-based average value by repeatedly measuring the particle size of 20 arbitrary particles in an arbitrary field of view in the micrograph.
  • oil-in-water emulsion composition of the present invention in addition to the above components, various surfactants, oily components, silicone compounds, high-grade compounds usually incorporated in cosmetics, as long as the effects of the present invention are not impaired.
  • Various raw materials usually used in cosmetics such as perfumes and extracts of various animals and plants can be contained.
  • each of these agents is not limited to the use as each agent, diverted as other uses according to the purpose, for example, using an antiperspirant as a fragrance, or as a combination with other uses, for example, It can be used as an effect as an antiperspirant and a fragrance.
  • the oil-in-water emulsified cosmetic of the present invention can contain a surfactant for the purpose of adjusting the emulsion stability.
  • the surfactant is not particularly limited, and includes nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, natural surfactants, polyether-modified silicones, siloxane derivatives, and the like. Any of a silicone-containing surfactant, a surfactant containing a perfluoroalkyl group, and the like can be used, and one or more of these can be used.
  • the emulsion stability is good without using the above-mentioned surfactant together, and when a large amount of the surfactant is blended, a sticky feeling derived from the surfactant may occur. Therefore, the preferable content is preferably 3% by mass or less, more preferably 1.5% by mass or less, and still more preferably 0.5% by mass or less with respect to the total amount of the oil-in-water emulsion composition. As a specific range, 0 to 3% by mass is preferable, 0 to 1.5% by mass is more preferable, and 0 to 0.5% by mass is still more preferable.
  • the oil-in-water emulsified composition of the present invention is a skin external preparation of the type that is retained on the skin (including the scalp) without being washed away, and more preferably the skin excluding the scalp, more preferably from the viewpoint of excellent moisture occlusive effect.
  • sunscreen applications in particular, sunscreens, suntans, cosmetic base cosmetics, foundations having ultraviolet protective ability, and the like.
  • the dosage form of the oil-in-water emulsion composition of the present invention can be applied to liquids, emulsions, creams, pastes, solids, multilayers, etc., and also to sheet agents, spray agents, and mousse agents. Applicable.
  • the oil-in-water emulsion composition of the present invention can be produced by a predetermined procedure depending on the form.
  • the oil-in-water emulsion composition of the present invention can be produced by a method including a step of mixing together various components including components (A) to (D) and optionally components (E) to (I). .
  • the method for producing the oil-in-water emulsion composition of the present invention includes: An oil phase containing component (A), component (B), component (C), optionally component (E), component (F) and other oil-soluble optional components, preferably at 50 to 90 ° C., more preferably Is a step 1a of heating and stirring at 55 to 85 ° C .;
  • the aqueous phase containing component (D), optionally component (G), component (I), component (H) and other water-soluble optional components is preferably 50 to 90 ° C., more preferably 55 to 85 ° C.
  • Step 3a may be included in which the preparation of Step 1a and the preparation of Step 2a are mixed and emulsified.
  • step 3a the preparation of step 2a is cooled to 15-40 ° C., preferably 20-30 ° C. and the preparation of step 1a is maintained above 40 ° C., preferably 50-70 ° C. While stirring the product, it is preferable to add the preparation of Step 1a and uniformly stir and mix to emulsify. Thereby, at the same time when the oil phase is introduced into the aqueous phase, the component (A) can easily form a lamellar structure at the interface of the oil phase, and a stable oil-in-water emulsion composition can be obtained.
  • the oil phase containing component (A) and component (B), and optionally component (E), component (F) and other oil-soluble optional components is preferably 50 to 90 ° C., more preferably 55 to 85 ° C.
  • Step 1b of heating and stirring at Step 2b for uniformly dispersing component (C) Add the preparation of step 2b to the preparation of step 1b, and heat and stir preferably at 50 to 90 ° C., more preferably 55 to 85 ° C.
  • Step (3b) component (D) if necessary, component (G), component Step 4b of heating and stirring the aqueous phase containing (I), component (H) and other water-soluble optional components, preferably at 50 to 90 ° C., more preferably 55 to 85 ° C .; Step 5b may be included to mix and emulsify the preparation of Step 3b and the preparation of Step 4b.
  • step 3b the preparation of step 4b is cooled to 15-40 ° C., preferably 20-30 ° C., and the preparation of step 3b is maintained above 40 ° C., preferably 50-70 ° C. While stirring the product, it is preferable to add the preparation of Step 3b and uniformly stir and mix to emulsify. Thereby, at the same time when the oil phase is introduced into the aqueous phase, the component (A) can easily form a lamellar structure at the interface of the oil phase, and a stable oil-in-water emulsion composition can be obtained.
  • Oil-in-water emulsification comprising the following components (A) to (D), wherein the mass ratio of component (A) to component (B) [(A) / (B)] is 0.06 or more and 18 or less Composition.
  • B Phospholipid
  • C Hydrophobized powder
  • Water Water
  • the content of the component (A) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, further preferably 0.12% by mass or more, further preferably 0.16% by mass or more, and further preferably 0.5% by mass or more. More preferably, it is 0.8% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, further preferably 1.82% by mass or less, and further preferably 1.5% by mass or less.
  • the oil-in-water emulsion composition according to any one of ⁇ 1> to ⁇ 4>, more preferably 1.2% by mass or less.
  • the phosphatidylcholine content in the phospholipid of component (B) is preferably 60% by mass or more, more preferably 62% by mass or more, still more preferably 65% by mass or more, and 98% by mass or less.
  • ⁇ 7> The oil-in-water emulsion composition according to any one of ⁇ 1> to ⁇ 6>, wherein the component (B) is preferably selected from soybean lecithin hydrogenated product and egg yolk lecithin hydrogenated product.
  • the content of component (B) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, further preferably 0.12% by mass or more, further preferably 0.16% by mass or more, and further preferably 0.5% by mass or more. More preferably, it is 0.8% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, still more preferably 1.82% by mass or less, and further preferably 1.5% by mass.
  • the oil-in-water emulsion composition according to any one of ⁇ 1> to ⁇ 7>, further preferably 1.2% by mass or less.
  • the total content of component (A) and component (B) is preferably 0.5% by mass or more, more preferably 1.2% by mass or more, still more preferably 1.8% by mass or more, and preferably 6% by mass.
  • the mass ratio [(A) / (B)] of the component (A) to the component (B) is preferably 0.06 or more, more preferably 0.08 or more, further preferably 0.10 or more, more preferably 0.5 or more.
  • the powder used for the hydrophobized powder of component (C) is preferably one or more selected from zinc oxide, titanium oxide, cerium oxide, iron oxide, and chromium oxide.
  • the oil-in-water emulsion composition according to any one of the above.
  • the average particle size of the powder used for the hydrophobized powder of component (C) is preferably 0.01 ⁇ m or more, more preferably 0.012 ⁇ m or more, still more preferably 0.015 ⁇ m or more, and preferably 28 ⁇ m or less.
  • Hydrophobizing treatment to powder preferably fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanate coupling agent treatment, oil agent treatment, acylamino acid metal salt treatment, poly
  • fluorine compound treatment silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanate coupling agent treatment, oil agent treatment, acylamino acid metal salt treatment, poly
  • acrylic acid treatment, metal soap treatment, crystalline cellulose treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, silane compound treatment, and silazane compound treatment more preferably, silicone or silicone resin is used.
  • Hydrophobic treatment using methylhydrogenpolysiloxane or methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer represented by the following general formula (1) hydrophobization using silane compound or silazane compound Treatment, using titanate coupling agent
  • hydrophobic treatment and hydrophobic treatment using acylamino acid metal salt more preferably hydrophobic treatment using methylhydrogenpolysiloxane, hydrophobization using silane compound or silazane compound Any one of ⁇ 1> to ⁇ 12> selected from a treatment, a hydrophobic treatment using a titanate coupling agent, and a hydrophobic treatment using an acylamino acid metal salt
  • An oil-in-water emulsion composition An oil-in-water emulsion composition.
  • the coating amount of the hydrophobizing agent on the powder is preferably 1% by mass or more, more preferably 1.5% by mass or more, and preferably 10% by mass or less, based on the total amount of powder used.
  • the content of the component (C) is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 20%.
  • the water content is preferably 40% by mass or more, more preferably 45% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less.
  • the oil-in-water emulsion composition according to any one of the above.
  • the oil-in-water emulsion composition according to any one of ⁇ 1> to ⁇ 16>, further comprising a liquid oil as the component (E).
  • Component (E) is a liquid oil containing one or more selected from 2-ethylhexyl paramethoxycinnamate, 2-ethylhexyl salicylate, homomenthyl salicylate, octocrylene and dimethicodiethylbenzalmalonate
  • 2-ethylhexyl paramethoxycinnamate 2-ethylhexyl salicylate
  • homomenthyl salicylate homomenthyl salicylate
  • octocrylene dimethicodiethylbenzalmalonate
  • the content of component (E) is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, and preferably 25% by mass or less, more preferably 20% or less.
  • the mass ratio of the liquid organic ultraviolet absorber in the total component (E) is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.6 or more, and even more preferably 0.7 or more ⁇ 17> to The oil-in-water emulsion composition according to any one of ⁇ 20>.
  • the oil-in-water emulsion composition according to any one of ⁇ 1> to ⁇ 21>, further comprising an ultraviolet absorbent that is solid at 25 ° C. as component (F).
  • the content of the component (F) is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and preferably 10% by mass or less, more preferably 7.5%.
  • Component (G) is preferably carboxyvinyl polymer, acrylic acid / alkyl methacrylate copolymer, xanthan gum, hydroxypropyl methylcellulose, polyacrylamide, (Na acrylate / acryloyl dimethyl taurine Na) copolymer, (acryloyl dimethyl taurine) Ammonium / VP) copolymer and one or more selected from hyaluronic acid or alkali metal salts thereof, more preferably polyacrylamide, (Na acrylate / acryloyl dimethyl taurine Na) copolymer, (acryloyl dimethyl taurate ammonium / ⁇ VP>
  • the oil-in-water emulsion composition according to ⁇ 24> comprising at least one selected from copolymers and xanthan gum.
  • the content of component (G) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 4% by mass or less, more preferably 2% by mass. % Or less, More preferably, it is 1.5 mass% or less,
  • the content of component (H) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass. % Or less, more preferably 12% by mass or less,
  • component (I) preferably contains one or more selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin and diglycerin More preferably, the oil-in-water emulsion composition according to ⁇ 29>, which is a polyhydric alcohol containing one or more selected from propylene glycol, dipropylene glycol, 1,3-butylene glycol and glycerin .
  • the content of component (I) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 12% by mass or less, more preferably 8% by mass. % Or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less, ⁇ 29> or ⁇ 30>.
  • the average emulsion particle size of the oil-in-water emulsion composition is preferably 1 ⁇ m or more, preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, and even more preferably 20 ⁇ m or less, any one of ⁇ 1> to ⁇ 31> 2.
  • Examples 1 to 13 and Comparative Examples 1 to 11 Oil-in-water emulsion compositions were prepared according to the formulations shown in Tables 1-5.
  • Step a Components 1 to 9 and components 16 to 20 are uniformly mixed, heated to 80 ° C. and dissolved.
  • Step b Disperse components 10 to 15 uniformly.
  • Step c The step b preparation is added to the step a preparation, mixed uniformly, heated to 80 ° C. and dispersed.
  • Step d Ingredients 21 to 30 are heated and dissolved at 40 ° C., naturally cooled to 25 ° C. and then uniformly mixed.
  • Step e While stirring the preparation of Step d, add the preparation of Step c, and uniformly stir and mix with a homomixer.
  • the component (C) used in the examples will be described below.
  • -ASI-treated titanium oxide manufactured by Daito Kasei
  • Titanium oxide substantially spherical, average particle size 0.2 ⁇ m
  • ⁇ ASI processing talc 98% by mass of talc (plate, average particle size 15 ⁇ m, average thickness 0.25 ⁇ m) coated with 1.5% by mass of isopropyl triisostearoyl titanate, 0.42% by mass of sodium lauroyl aspartate, 0.08% by mass of zinc chloride .
  • OTS-treated titanium oxide A slurry consisting of 97 parts by mass of titanium oxide powder (substantially spherical, average particle size 0.2 ⁇ m), 3 parts by mass of octyltriethoxysilane, and toluene was prepared, and a bead mill (Dynomill manufactured by Shinmaru Enterprises Co., Ltd.) was used. Using this, pulverization and crushing were performed. Subsequently, toluene was distilled off by heating under reduced pressure, and then heat-treated at 150 ° C. for 4 hours using a blast airflow dryer to obtain octyltriethoxysilane-treated titanium oxide powder.
  • -OTS-treated flaky zinc oxide flaky zinc oxide particles (average particle size 0.3 ⁇ m, average particle thickness 0.032 ⁇ m, plate ratio 9, iron element content 0.01 mol%) 97 parts by mass and octyltriethoxysilane 3 parts by mass
  • a slurry made of toluene was prepared and pulverized and crushed using a bead mill (Dynomill manufactured by Shinmaru Enterprises Co., Ltd.).
  • toluene was distilled off by heating under reduced pressure, followed by heat treatment at 150 ° C. for 4 hours using an air blast dryer to obtain octyltriethoxysilane-treated flaky zinc oxide powder.
  • a slurry consisting of 97 parts by mass of fine zinc oxide powder (substantially spherical, average particle size 0.017 ⁇ m), 3 parts by mass of methyl hydrogen polysiloxane (KF-99P, manufactured by Shin-Etsu Chemical Co., Ltd.) and isopropyl alcohol is prepared. After thoroughly stirring and pulverizing, the solvent was removed by heating under reduced pressure, and heat treatment was performed in air at 160 ° C. for 4 hours to obtain methylhydrogenpolysiloxane surface-treated fine particle zinc oxide powder.
  • Viscosity change rate is less than 0.8
  • UV protection evaluation The sample was uniformly coated on a PMMA plate at a coating amount of 1.3 mg / cm 2 and dried. Then, using SPF analyzer (UV-2000S; manufactured by Labsphere), SPF value was measured (in vitro) and evaluated based on the following evaluation criteria.
  • SPF value is 40 or more
  • B SPF value is 30 or more and less than 40
  • C SPF value is 20 or more and less than 30
  • X SPF value is less than 20
  • Nikkor BB-2 manufactured by Nippon Surfactant * 2: Nikkor BB-5, manufactured by Nippon Surfactant * 3: Nikkor BC-2, manufactured by Nippon Surfactant * 4: Nikkor BS-2, manufactured by Nippon Surfactant * 5: Nikkor BL-2 manufactured by Nippon Surfactant * 6: Phospholipid PCSH70, manufactured by Nippon Seika Co., Ltd., phosphatidylcholine content 70% by mass or more * 7: COATSOME NC-21, NOF Corporation, phosphatidylcholine content 90% by mass or more * 8: Sphingolipid E, manufactured by Kao Corporation * 9: Yubinar T-150, manufactured by BASF * 10: Yubinar A PLUS GURANULAR, manufactured by BASF * 11: Yubinar MC80, manufactured by BASF * 12: Saracos 913, manufactured by Nisshin Oillio Group * 13: Silicone FK96-6cs, manufactured by Shin-Etsu Chemical
  • Formulation example 1 oil-in-water makeup base) Content (mass%) Behenez-2 (* 1) 1.0 Hydrogenated lecithin (* 6) 1.0 ASI-treated titanium oxide 10.5 ASI-treated iron oxide 1.05 ASI processing talc 0.8 2-Ethylhexyl paramethoxycinnamate (* 11) 5.0 2- (4-Diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester (* 10) 2.0 2,4-Bis [[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (* 16) 0.5 2,4,6-Tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine (* 9) 2.0 Isononyl isononanoate (* 12) 3.0 Diisopropyl sebacate 2.0 Dimethi
  • Formulation example 2 oil-in-water sunscreen) Content (mass%) Behenez-2 (* 1) 0.5 Hydrogenated lecithin (* 6) 1.5 OTS-treated flaky zinc oxide 2.5 SI-treated zinc oxide 7.5 Polysilicone-15 (* 22) 1.0 2- (4-Diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester (* 10) 1.5 2,4-Bis [[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (* 16) 1.5 2,4,6-Tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine (* 9) 2.0 Neopentyl glycol dicaprate 2.5 Diisopropyl sebacate 5.0 Alkyl benzoate (C12-15) 2.5 Dimethicone (* 13) 1.0 Stearyl glycy

Abstract

An oil-in-water emulsion composition which contains the following components (A)-(D) and in which the content mass ratio [(A)/(B)] of component (A) with respect to component (B) is 0.06-18. (A) Polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether in which the number of carbon atoms of the alkyl group or alkenyl group is 20-24 and the average number of added mol of ethylene oxide is 1.5-4; (B) a phospholipid; (C) a hydrophobically treated powder; and (D) water.

Description

水中油型乳化組成物Oil-in-water emulsion composition
 本発明は、水中油型乳化組成物に関する。 The present invention relates to an oil-in-water emulsion composition.
 近年、日常生活における日焼け対策の重要性が指摘されてきており、紫外線に対する防御効果を有する化粧料においても、さっぱりとした使用感で連用使用しやすい、水中油型乳化型の日焼け止め化粧料が開発されてきている。これらの水中油型乳化化粧料には、紫外線防御効果を高めるため、紫外線散乱剤(疎水化処理金属酸化物粉末)が配合されている(特許文献1、2参照)。 In recent years, the importance of sunburn countermeasures in daily life has been pointed out, and even in cosmetics that have a protective effect against ultraviolet rays, an oil-in-water emulsion type sunscreen cosmetic that is easy to use continuously with a refreshing feeling of use It has been developed. In these oil-in-water emulsified cosmetics, an ultraviolet scattering agent (hydrophobized metal oxide powder) is blended in order to enhance the ultraviolet protection effect (see Patent Documents 1 and 2).
 しかしながら、紫外線散乱剤である酸化亜鉛、酸化チタン等の金属酸化物粉末を多く配合すると、経時で粉末の凝集、沈降等が生じるばかりでなく、粘度低下、乳化分離、析出などの経時安定性が低下するという問題があった。 However, when a large amount of metal oxide powder such as zinc oxide and titanium oxide, which are ultraviolet scattering agents, is blended, not only powder aggregation and sedimentation occur over time, but also stability over time such as viscosity reduction, emulsification separation and precipitation. There was a problem of lowering.
 これに対し、特許文献3では、炭素鎖長とエチレンオキシド付加モル数が一定範囲内にあるポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルケニルエーテルを用いて紫外線散乱剤(疎水化処理金属酸化物粉末)を安定配合した日焼け止め化粧料が開示されている。これらの日焼け止め化粧料は、前記化合物が水相と油相の界面に存在して柔らかい層状の構造体(マルチラメラベシクル構造)を形成することで低温安定性に優れ、皮膚上での伸び、つきも良好で、べたつき感やきしみ感が抑えられ、更には保湿効果も高いものである。 On the other hand, in Patent Document 3, an ultraviolet scattering agent (hydrophobized metal oxide powder) is prepared using polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether whose carbon chain length and number of moles of ethylene oxide added are within a certain range. A stably formulated sunscreen cosmetic is disclosed. These sunscreen cosmetics have excellent low-temperature stability by forming the soft layered structure (multi-lamellar vesicle structure) by the presence of the compound at the interface between the aqueous phase and the oil phase, elongation on the skin, The stickiness is also good, the sticky feeling and squeaky feeling are suppressed, and the moisturizing effect is also high.
    (特許文献1)特開2006-8796号公報
    (特許文献2)特開2005-272389号公報
    (特許文献3)特開2014-114274号公報
(Patent Document 1) JP 2006-8796 JP (Patent Document 2) JP 2005-272389 JP (Patent Document 3) JP 2014-114274 JP
 本発明は、下記成分(A)~(D)を含有し、成分(B)に対する成分(A)の含有質量比〔(A)/(B)〕が、0.06以上18以下である水中油型乳化組成物を提供するものである。
 (A) アルキル基又はアルケニル基の炭素数が20以上24以下で、エチレンオキサイドの平均付加モル数が1.5以上4以下であるポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルケニルエーテル
 (B) リン脂質
 (C) 疎水化処理粉末
 (D) 水
The present invention includes the following components (A) to (D), wherein the mass ratio [(A) / (B)] of component (A) to component (B) is 0.06 or more and 18 or less An emulsified composition is provided.
(A) Polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether having an alkyl group or alkenyl group having 20 to 24 carbon atoms and an average addition mole number of ethylene oxide of 1.5 to 4 (B) Phospholipid (C ) Hydrophobized powder (D) Water
発明の詳細な説明Detailed Description of the Invention
 特許文献3に記載の技術では、高温時に部分的な乳化不良の発生や、高いせん断力がかかると粘度低下が生じる場合があるなど組成物の安定性に改善の余地があった。 In the technique described in Patent Document 3, there is room for improvement in the stability of the composition, such as partial emulsification failure at high temperatures, and a decrease in viscosity when high shear force is applied.
 したがって本発明は、疎水化処理粉末を安定に含有し、高温保存時やせん断力をかけた際の乳化系の安定性に優れ、みずみずしさなどの使用感にも優れる水中油型乳化組成物に関する。 Therefore, the present invention relates to an oil-in-water emulsion composition that stably contains a hydrophobized powder, is excellent in stability of an emulsification system when stored at high temperature or when shearing force is applied, and is excellent in use feeling such as freshness. .
 本発明者は種々の検討を行った結果、特許文献3に記載の技術で用いられている特定のポリオキシエチレンアルキルエーテル等とリン脂質を特定比で併用することで、疎水化処理粉末を配合した水中油型乳化組成物の高温安定性とせん断力に対する耐性(以下、「せん断耐性」という)を大きく改善できることを見出し、本発明を完成させた。 As a result of various studies, the present inventor formulated a hydrophobized powder by using a specific polyoxyethylene alkyl ether or the like used in the technique described in Patent Document 3 and a phospholipid in a specific ratio. The present invention was completed by finding that the oil-in-water emulsion composition thus obtained can be greatly improved in stability at high temperatures and resistance to shearing force (hereinafter referred to as “shear resistance”).
〔成分(A):炭素鎖長・EO付加モル数が特定範囲のポリオキシエチレンアルキル(又はアルケニル)エーテル〕
 本発明に用いる成分(A)のポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルケニルエーテルは、アルキル基又はアルケニル基の炭素数が20以上24以下で、エチレンオキサイドの平均付加モル数が1.5以上4以下のものである。
[Component (A): Polyoxyethylene alkyl (or alkenyl) ether having a specific range of carbon chain length / EO addition moles]
The polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether of component (A) used in the present invention has an alkyl group or an alkenyl group having 20 to 24 carbon atoms and an average added mole number of ethylene oxide of 1.5 to 4 Is.
 成分(A)が有するアルキル基又はアルケニル基は、直鎖でも分岐鎖でもよく、油相界面でラメラ構造体を形成する観点から、好ましくは直鎖又は分岐鎖のアルキル基であり、より好ましくは直鎖のアルキル基である。アルキル基又はアルケニル基の炭素数は、油相界面でラメラ構造体を形成し、高温安定性(乳化安定性)、せん断耐性を向上させる観点から、20以上であって、好ましくは21以上であり、また、油相に安定に溶解する観点から、24以下であって、好ましくは23以下である。これらの観点から、アルキル基又はアルケニル基の炭素数が22であることが更に好ましく、なかでも炭素数22のアルキル基(すなわちベヘニル基)が好ましい。 The alkyl group or alkenyl group of component (A) may be linear or branched, and is preferably a linear or branched alkyl group, more preferably from the viewpoint of forming a lamellar structure at the oil phase interface. It is a linear alkyl group. The number of carbon atoms of the alkyl group or alkenyl group is 20 or more, preferably 21 or more, from the viewpoint of forming a lamellar structure at the oil phase interface and improving high temperature stability (emulsification stability) and shear resistance. Moreover, from the viewpoint of stably dissolving in the oil phase, it is 24 or less, preferably 23 or less. From these viewpoints, the alkyl group or alkenyl group preferably has 22 carbon atoms, and among them, an alkyl group having 22 carbon atoms (that is, a behenyl group) is more preferable.
 成分(A)におけるエチレンオキサイドの平均付加モル数は、結晶性を低くし、油相に溶解しやすくする観点から1.5以上であり、また、油相界面にて構造体を形成し、高温安定性(乳化安定性)、せん断耐性を向上させる観点から、4以下であって、好ましくは3以下、更に好ましくは2.5以下である。一般的に入手可能なポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルケニルエーテルは、エチレンオキシドの付加モル数に関しては、所望の重合度を中心として極めて幅広く分布した混合物であるが、本発明においては平均付加モル数が上記範囲内であることが重要である。 The average number of moles of ethylene oxide added in component (A) is 1.5 or more from the viewpoint of lowering the crystallinity and facilitating dissolution in the oil phase. From the viewpoint of improving (emulsion stability) and shear resistance, it is 4 or less, preferably 3 or less, more preferably 2.5 or less. The generally available polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether is a mixture having a very wide distribution centering on a desired degree of polymerization in terms of the number of moles of ethylene oxide added. It is important that the number is within the above range.
 成分(A)としては、ポリオキシエチレン(2)アラキルエーテル、ポリオキシエチレン(3)アラキルエーテル、ポリオキシエチレン(4)アラキルエーテル、ポリオキシエチレン(2)ベヘニルエーテル、ポリオキシエチレン(3)ベヘニルエーテル、ポリオキシエチレン(4)ベヘニルエーテル、ポリオキシエチレン(2)カルナービルエーテル、ポリオキシエチレン(3)カルナービルエーテル、ポリオキシエチレン(4)カルナービルエーテル等が挙げられ、好ましくはポリオキシエチレン(2)ベヘニルエーテル、ポリオキシエチレン(3)ベヘニルエーテル、ポリオキシエチレン(4)ベヘニルエーテルが挙げられる。なお、使用するポリオキシエチレンアルキルエーテルの平均付加モル数が上記範囲内であれば、これら例示されたポリオキシエチレンアルキルエーテル以外のものを併用することも可能である。 As component (A), polyoxyethylene (2) aralkyl ether, polyoxyethylene (3) aralkyl ether, polyoxyethylene (4) aralkyl ether, polyoxyethylene (2) behenyl ether, polyoxyethylene (3) behenyl Examples include ether, polyoxyethylene (4) behenyl ether, polyoxyethylene (2) carnerville ether, polyoxyethylene (3) carnerville ether, polyoxyethylene (4) carnerville ether, and preferably polyoxyethylene (2) Behenyl ether, polyoxyethylene (3) behenyl ether, polyoxyethylene (4) behenyl ether are mentioned. In addition, as long as the average added mole number of the polyoxyethylene alkyl ether to be used is in the above range, it is possible to use other than those exemplified polyoxyethylene alkyl ether in combination.
 本発明の水中油型乳化組成物中における成分(A)の含有量は、油相界面でラメラ構造体を形成しやすくし、せん断耐性を向上させ、みずみずしい使用感を向上させる観点から、好ましくは0.05質量%以上、より好ましくは0.10質量%以上、更に好ましくは0.12質量%以上、更に好ましくは0.16質量%以上、更に好ましくは0.5質量%以上、更に好ましくは0.8質量%以上であり、また好ましくは5質量%以下、より好ましくは3質量%以下、更に好ましくは2質量%以下、更に好ましくは1.82質量%以下、更に好ましくは1.5質量%以下、更に好ましくは1.2質量%以下である。成分(A)の具体的な含有量範囲は、好ましくは0.05~5質量%、より好ましくは0.10~3質量%、更に好ましくは0.12~2質量%、更に好ましくは0.16~1.82質量%、更に好ましくは0.5~1.5質量%、さらに好ましくは0.8~1.2質量%である。 The content of component (A) in the oil-in-water emulsion composition of the present invention is preferably from the viewpoint of facilitating the formation of a lamellar structure at the oil phase interface, improving the shear resistance, and improving the fresh feeling of use. 0.05% by mass or more, more preferably 0.10% by mass or more, further preferably 0.12% by mass or more, more preferably 0.16% by mass or more, further preferably 0.5% by mass or more, further preferably 0.8% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, further preferably 1.82% by mass or less, still more preferably 1.5% by mass or less, and further preferably 1.2% by mass or less. The specific content range of component (A) is preferably 0.05 to 5% by mass, more preferably 0.10 to 3% by mass, still more preferably 0.12 to 2% by mass, still more preferably 0.16 to 1.82% by mass, and still more preferably Is 0.5 to 1.5 mass%, more preferably 0.8 to 1.2 mass%.
〔成分(B):リン脂質〕
 成分(B)のリン脂質としては、高温安定性、せん断耐性を向上させ、べたつきを抑制し、肌馴染み、化粧のりを向上させる観点より、ホスファチジルコリン含量が60質量%以上、更には62質量%以上、更には65質量%以上であるものが好ましい。また、ホスファチジルコリン含量が98質量%以下であるものが好ましい。ホスファチジルコリン以外のリン脂質成分としては、ホスファチジン酸、ホスファチジルセリン、ホスファチジルエタノールアミン、ホスファチジルイノシトール、ホスファチジルグリセロール等が挙げられる。
[Component (B): Phospholipid]
As the phospholipid of component (B), the phosphatidylcholine content is 60% by mass or more, and further 62% by mass or more from the viewpoint of improving high-temperature stability and shear resistance, suppressing stickiness, accustoming to the skin, and improving makeup. In addition, it is preferably 65% by mass or more. Moreover, what has a phosphatidylcholine content of 98 mass% or less is preferable. Examples of phospholipid components other than phosphatidylcholine include phosphatidic acid, phosphatidylserine, phosphatidylethanolamine, phosphatidylinositol, and phosphatidylglycerol.
 本発明に用いられるリン脂質は、動植物から抽出、精製した天然物であっても、化学合成したものであってもよく、水素添加、水酸化処理などの加工を施したものであってもよい。天然物としては、経時安定性を向上させ、皮膚刺激を低減させる観点から、大豆又は卵黄等からの抽出・精製物であるレシチンが好ましく、水素添加又は水酸化処理されたものがより好ましい。 The phospholipid used in the present invention may be a natural product extracted and purified from animals or plants, or may be chemically synthesized, or may be subjected to processing such as hydrogenation or hydroxylation. . As a natural product, lecithin which is an extract / purified product from soybean or egg yolk is preferable from the viewpoint of improving stability over time and reducing skin irritation, and more preferably hydrogenated or hydroxylated.
 具体的には、大豆レシチン水素添加物、卵黄レシチン水素添加物が好適に挙げられる。 Specifically, soybean hydrogenated lecithin and egg yolk lecithin hydrogenated are preferably mentioned.
 リン脂質中のホスファチジルコリンの含有率は、薄層クロマトグラフィー(TLC)や高速液体クロマトフラフィー(HPLC)、イアトロスキャン(ヤトロン社製)等を用いた方法で分析することができる。例えば、特開2001-186898号公報に記載されるリン脂質が含まれる有機溶媒をTLCにスポットしてクロロホルム:メタノール:酢酸=65:25:10で展開し、50質量%硫酸エタノールを噴霧、加熱後デンシトメーターでリン脂質を分析する方法が挙げられる。前記方法以外でも、リン脂質中に含まれるホフファチジルコリンの含有量、含有率を測定、算出できる方法であれば、いずれの方法でもよい。 The content of phosphatidylcholine in the phospholipid can be analyzed by a method using thin layer chromatography (TLC), high performance liquid chromatography (HPLC), Iatroscan (manufactured by Yatron). For example, an organic solvent containing phospholipids described in JP-A-2001-186898 is spotted on TLC, developed in chloroform: methanol: acetic acid = 65: 25: 10, sprayed with 50% by mass of ethanol sulfate, and heated. A method of analyzing phospholipids with a post densitometer is mentioned. In addition to the above method, any method may be used as long as it can measure and calculate the content and content of phosphatidylcholine contained in the phospholipid.
 ホスファチジルコリンを60質量%以上含有しているリン脂質としては、コートソームNC-21(水素添加大豆レシチン;日油社製)、レシノールS-10E、レシノールS-10EX(水素添加大豆レシチン;日光ケミカルズ社製)、Phospholipid PCSH70(水素添加大豆レシチン;日本精化社製)等を挙げることができる。 Phospholipids containing 60% by mass or more of phosphatidylcholine include Coatsome NC-21 (hydrogenated soybean lecithin; manufactured by NOF Corporation), Resinol S-10E, Resinol S-10EX (hydrogenated soybean lecithin; Nikko Chemicals) And Phospholipid PCSH70 (hydrogenated soybean lecithin; manufactured by Nippon Seika Co., Ltd.).
 本発明の水中油型乳化組成物中における成分(B)の含有量は、高温安定性、せん断耐性、及び使用感を向上させる観点から、好ましくは0.05質量%以上、より好ましくは0.10質量%以上、更に好ましくは0.12質量%以上、更に好ましくは0.16質量%以上、更に好ましくは0.5質量%以上、更に好ましくは0.8質量%以上であり、また、好ましくは5質量%以下、より好ましくは3質量%以下、更に好ましくは2質量%以下、更に好ましくは1.82質量%以下、更に好ましくは1.5質量%以下、更に好ましくは1.2質量%以下である。成分(B)の具体的な含有量範囲は、好ましくは0.05~5質量%、より好ましくは0.10~3質量%、更に好ましくは0.12~2質量%、更に好ましくは0.16~1.82質量%、更に好ましくは0.5~1.5質量%、さらに好ましくは0.8~1.2質量%である。 The content of the component (B) in the oil-in-water emulsion composition of the present invention is preferably 0.05% by mass or more, more preferably 0.10% by mass or more from the viewpoint of improving high-temperature stability, shear resistance, and usability. More preferably, it is 0.12% by mass or more, more preferably 0.16% by mass or more, further preferably 0.5% by mass or more, further preferably 0.8% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass. Hereinafter, it is further preferably 2% by mass or less, more preferably 1.82% by mass or less, further preferably 1.5% by mass or less, and further preferably 1.2% by mass or less. The specific content range of component (B) is preferably 0.05 to 5% by mass, more preferably 0.10 to 3% by mass, still more preferably 0.12 to 2% by mass, still more preferably 0.16 to 1.82% by mass, and still more preferably Is 0.5 to 1.5 mass%, more preferably 0.8 to 1.2 mass%.
 本発明の水中油型乳化組成物中における成分(A)及び成分(B)の合計含有量は、高温安定性及びせん断耐性を向上させる観点から、好ましくは0.5質量%以上、より好ましくは1.2質量%以上、更に好ましくは1.8質量%以上であり、また、みずみずしさの向上の観点から、好ましくは6質量%以下、より好ましくは3.5質量%以下、更に好ましくは2.5質量%以下である。成分(A)及び成分(B)の具体的な合計含有量範囲は、好ましくは0.5~6質量%、より好ましくは1.2~3.5質量%、更に好ましくは1.8~2.5質量%である。 The total content of component (A) and component (B) in the oil-in-water emulsion composition of the present invention is preferably 0.5% by mass or more, more preferably 1.2% by mass, from the viewpoint of improving high-temperature stability and shear resistance. % Or more, more preferably 1.8% by mass or more, and from the viewpoint of improving freshness, it is preferably 6% by mass or less, more preferably 3.5% by mass or less, and still more preferably 2.5% by mass or less. The specific total content range of component (A) and component (B) is preferably 0.5 to 6% by mass, more preferably 1.2 to 3.5% by mass, and still more preferably 1.8 to 2.5% by mass.
 また、成分(B)に対する成分(A)の含有質量比[(A)/(B)]は、高温安定性及びせん断耐性を向上させる観点から、好ましくは0.06以上、より好ましくは0.08以上、更に好ましくは0.10以上、更に好ましくは0.5以上であり、また、みずみずしい使用感を得る観点から、好ましくは18以下、より好ましくは14以下、更に好ましくは10以下、更に好ましくは3以下である。具体的な成分(B)に対する成分(A)の含有質量比[(A)/(B)]は、好ましくは0.06~18、より好ましくは0.08~14、更に好ましくは0.10~10、更に好ましくは0.5~3である。 In addition, the content ratio [(A) / (B)] of the component (A) to the component (B) is preferably 0.06 or more, more preferably 0.08 or more, from the viewpoint of improving high-temperature stability and shear resistance. Preferably, it is 0.10 or more, more preferably 0.5 or more, and from the viewpoint of obtaining a fresh feeling of use, it is preferably 18 or less, more preferably 14 or less, still more preferably 10 or less, and even more preferably 3 or less. The content ratio [(A) / (B)] of the component (A) to the specific component (B) is preferably 0.06 to 18, more preferably 0.08 to 14, still more preferably 0.10 to 10, more preferably 0.5-3.
〔成分(C):疎水化処理粉末〕
 成分(C)の疎水化処理粉末に用いる粉末としては、医薬品、化粧品、食品分野で利用されているものであれば特に制限されず、酸化亜鉛、酸化チタン、酸化セリウム、酸化鉄、酸化クロム、カーボンブラック、チタンブラック、ベントナイト、カオリン、マイカ、セリサイト、タルク、グンジョウ、グンジョウピンク、赤色202号、赤色220号、赤色226号、青色404号、黄色401号、ポリエチレン粉末、ポリスチレン粉末、ポリメチルメタクリレート粉末、ナイロン粉末、シリコーン粉末、セルロース粉末等が挙げられるが、乳化安定性、紫外線防御効果を向上させる観点から、金属酸化物粉末が好ましく、酸化亜鉛、酸化チタン、酸化セリウム、酸化鉄及び酸化クロムから選択される1種以上を含むことがより好ましく、酸化亜鉛、酸化チタン及び酸化鉄から選択される1種以上を含むことが更に好ましい。特に肌色補正用途に用いる場合には、肌色に近い発色に調整可能な酸化鉄を用いることが好ましく、日焼け止め用途に用いる場合には、紫外線散乱効果の高い、酸化亜鉛、酸化チタン及び酸化セリウムから選択される1種以上を用いることが好ましく、これらを併用することで肌色補正及び日焼け止め効果を両立させることもできる。
[Component (C): Hydrophobized powder]
The powder used for the hydrophobized powder of component (C) is not particularly limited as long as it is used in the pharmaceutical, cosmetic and food fields, zinc oxide, titanium oxide, cerium oxide, iron oxide, chromium oxide, Carbon Black, Titanium Black, Bentonite, Kaolin, Mica, Sericite, Talc, Gunjo, Gunjo Pink, Red 202, Red 220, Red 226, Blue 404, Yellow 401, Polyethylene powder, Polystyrene powder, Poly Examples include methyl methacrylate powder, nylon powder, silicone powder, and cellulose powder. From the viewpoint of improving emulsification stability and UV protection effect, metal oxide powder is preferable, and zinc oxide, titanium oxide, cerium oxide, iron oxide, and the like. More preferably, it contains at least one selected from chromium oxide, zinc oxide, titanium oxide and acid It is further preferred to include one or more selected from iron. In particular, when used for skin color correction, it is preferable to use iron oxide that can be adjusted to a color close to skin color, and when used for sunscreen, it has a high ultraviolet light scattering effect, from zinc oxide, titanium oxide, and cerium oxide. It is preferable to use one or more selected ones, and by using these together, it is possible to achieve both skin color correction and sunscreen effects.
 酸化亜鉛粉末としては、例えばFINEX-25、FINEX-50、FINEX-75(堺化学社製)、MZ500シリーズ、MZ700シリーズ(テイカ社製)、ZnO-350(住友大阪セメント社製)等が市販されている。酸化チタン粉末としては、TTO-55シリーズ、TTO-51シリーズ(石原産業社製)、JRシリーズ、JAシリーズ(テイカ社製)などが市販されている。酸化鉄粉末としては、LL-100P、R-516P、BL-100P(チタン工業社製)等が市販されている。また、酸化セリウムとしては、ニッキ社又はセイミケミカル社から販売される高純度セリウムが含まれる。 As zinc oxide powder, for example, FINEX-25, FINEX-50, FINEX-75 (manufactured by Sakai Chemical), MZ500 series, MZ700 series (manufactured by Teika), ZnO-350 (manufactured by Sumitomo Osaka Cement Co., Ltd.), etc. are commercially available. ing. As titanium oxide powder, TTO-55 series, TTO-51 series (Ishihara Sangyo Co., Ltd.), JR series, JA series (Taika Co., Ltd.), etc. are commercially available. As the iron oxide powder, LL-100P, R-516P, BL-100P (manufactured by Titanium Industry Co., Ltd.) and the like are commercially available. The cerium oxide includes high purity cerium sold by Nikki or Seimi Chemical.
 成分(C)の疎水化処理粉末に用いる粉末の平均粒子径は、疎水化処理粉末を油相内に包含させて乳化安定性を向上させる観点から、水中油型乳化組成物の乳化粒子径よりも小さいことが望ましく、好ましくは28μm以下、より好ましくは23μm以下、更に好ましくは18μm以下であり、また、粉末の凝集性を抑制する観点から、好ましくは0.01μm以上、より好ましくは0.012μm以上、更に好ましくは0.015μm以上である。具体的な平均粒子径としては、好ましくは0.01~28μm、より好ましくは0.012~23μm、更に好ましくは0.015~18μmである。本発明の水中油型乳化組成物においては、着色顔料レベルの大きさの粉末を油相内に内包させる場合において、より効果を発揮する。なお、平均粒子径の測定は、透過電子顕微鏡写真中、任意の視野の任意の粉末20個についての粒子径の相加平均により求めた。尚、棒状、紡錘状、針状、薄片状、不定形状等の球状以外の粉末に対しては、長軸の相加平均を平均粒子径とみなした。 The average particle size of the powder used for the hydrophobized powder of component (C) is from the emulsified particle size of the oil-in-water emulsion composition from the viewpoint of improving emulsification stability by including the hydrophobized powder in the oil phase. Is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and preferably from 0.01 μm or more, more preferably 0.012 μm or more, from the viewpoint of suppressing powder agglomeration, More preferably, it is 0.015 μm or more. The specific average particle diameter is preferably 0.01 to 28 μm, more preferably 0.012 to 23 μm, and still more preferably 0.015 to 18 μm. The oil-in-water emulsion composition of the present invention is more effective when a powder having a color pigment level is encapsulated in the oil phase. The average particle size was measured by arithmetic average of the particle sizes of 20 arbitrary powders in an arbitrary field of view in a transmission electron micrograph. For powders other than a spherical shape such as a rod shape, a spindle shape, a needle shape, a flake shape, and an indefinite shape, the arithmetic average of the major axes was regarded as the average particle diameter.
 本発明で用いる粉末の形状としては、球状、棒状、紡錘状、針状、薄片状、不定形状等が挙げられるが、平均粒子径が前記範囲にあれば任意の形状のものを使用することができる。 Examples of the shape of the powder used in the present invention include a spherical shape, a rod shape, a spindle shape, a needle shape, a flake shape, and an indeterminate shape, but any shape having an average particle diameter in the above range may be used. it can.
 前記粉末への疎水化処理としては、特に限定されず、種々の疎水化処理、例えば、フッ素化合物処理、シリコーン処理、シリコーン樹脂処理、ペンダント処理、シランカップリング剤処理、チタネート系カップリング剤処理、油剤処理、アシルアミノ酸金属塩処理、ポリアクリル酸処理、金属石鹸処理、結晶セルロース処理、無機化合物処理、プラズマ処理、メカノケミカル処理、シラン化合物処理、シラザン化合物処理等を用いることができる。 The hydrophobizing treatment to the powder is not particularly limited, and various hydrophobizing treatments such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanate coupling agent treatment, Oil agent treatment, acylamino acid metal salt treatment, polyacrylic acid treatment, metal soap treatment, crystalline cellulose treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, silane compound treatment, silazane compound treatment and the like can be used.
 これらのうち、粉末の分散性を向上させ、高温安定性及び低温安定性を向上させる観点から、シリコーン又はシリコーン樹脂を用いた疎水化処理、メチルハイドロジェンポリシロキサン又は下記一般式(1)で表されるメチルハイドロジェンポリシロキサン・ジメチルポリシロキサン共重合体を用いた疎水化処理、シラン化合物又はシラザン化合物を用いた疎水化処理、チタネート系カップリング剤を用いた疎水化処理及びアシルアミノ酸金属塩を用いた疎水化処理から選択される1種又は2種以上の疎水化処理が好ましく、メチルハイドロジェンポリシロキサンを用いた疎水化処理、シラン化合物又はシラザン化合物を用いた疎水化処理、チタネート系カップリング剤を用いた疎水化処理及びアシルアミノ酸金属塩を用いた疎水化処理から選択される1種又は2種以上の疎水化処理がより好ましい。 Among these, from the viewpoint of improving the dispersibility of the powder and improving the high temperature stability and the low temperature stability, hydrophobic treatment using silicone or silicone resin, methyl hydrogen polysiloxane or the following general formula (1) Hydrophobic treatment using methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer, hydrophobic treatment using silane compound or silazane compound, hydrophobization treatment using titanate coupling agent and acylamino acid metal salt 1 type or 2 types or more of hydrophobizing treatments selected from the hydrophobizing treatments used are preferable, hydrophobizing treatment using methylhydrogenpolysiloxane, hydrophobizing treatment using silane compound or silazane compound, titanate coupling Hydrophobic treatment using an agent and hydrophobic treatment using an acylamino acid metal salt One or more hydrophobic treatment is more preferable.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
 前記シリコーン又はシリコーン樹脂を用いた疎水化処理としては、特許第3187440号公報に記載されるように、粉末をオルガノポリシロキサン類及びシリコーン樹脂よりなるシリコーン化合物(ただし、シラン化合物を除く)の少なくとも1種以上で非気相状態で被覆した後、酸素含有雰囲気中で600~950℃の温度で焼成することにより、酸化珪素で粉末を被覆する方法が挙げられる。 As the hydrophobizing treatment using the silicone or the silicone resin, as described in Japanese Patent No. 3187440, the powder is at least one of a silicone compound (excluding a silane compound) made of an organopolysiloxane and a silicone resin. An example is a method of coating a powder with silicon oxide by coating in a non-gas phase state with at least a seed and then firing at a temperature of 600 to 950 ° C. in an oxygen-containing atmosphere.
 前記シラン化合物又はシラザン化合物としては、炭素数1~20のアルキル基又はフルオロアルキル基を有し、無機酸化物と反応性を有するシラン化合物又はシラザン化合物が好ましく、具体的には下記一般式(2)で示されるシラン化合物又は一般式(3)で示されるシラザン化合物が挙げられ、これらを1種又は2種以上用いることができる。 The silane compound or silazane compound is preferably a silane compound or silazane compound having an alkyl group or fluoroalkyl group having 1 to 20 carbon atoms and having reactivity with an inorganic oxide. Specifically, the following general formula (2 ) Or a silazane compound represented by the general formula (3), and one or more of these can be used.
  RR1 nSiX3-n    (2) RR 1 n SiX 3-n (2)
(nは0又は1の整数であり、Rは炭素数1~20の直鎖又は分岐鎖のアルキル基又はフルオロアルキル基を示し、R1は炭素数1~6のアルキル基を示し、Xはハロゲン原子又はアルコキシ基を示す。) (N is an integer of 0 or 1, R is a linear or branched alkyl group or fluoroalkyl group having 1 to 20 carbon atoms, R 1 is an alkyl group having 1 to 6 carbon atoms, and X is Represents a halogen atom or an alkoxy group.)
  R234SiNHSiR567     (3) R 2 R 3 R 4 SiNHSiR 5 R 6 R 7 (3)
(R2~R7は、それぞれ独立して、炭素数1~20の直鎖又は分岐鎖のアルキル基又はフルオロアルキル基を示す。) (R 2 to R 7 each independently represents a linear or branched alkyl group or fluoroalkyl group having 1 to 20 carbon atoms.)
 具体的なシラン化合物としては、ヘキシルトリメトキシシラン、オクチルトリメトキシシラン、デシルトリメトキシシラン、オクタデシルトリメトキシシラン、オクチルトリエトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘプタデカフルオロデシルトリメトキシシラン等が挙げられる。これらのうちオクチルトリエトキシシラン、オクチルトリメトキシシランが好ましい。シラザン化合物としては、ヘキサメチルジシラザンが好ましい。当該シラン化合物又はシラザン化合物は均一に処理しやすく、かつ供給が容易でコスト的に安価である特長があり、更にこれらの化合物で疎水化処理した粉末を配合した化粧料は分散性等の特性が優れているので好ましい。 Specific silane compounds include hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, octyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, and the like. It is done. Of these, octyltriethoxysilane and octyltrimethoxysilane are preferred. As the silazane compound, hexamethyldisilazane is preferable. The silane compound or silazane compound is characterized in that it is easy to treat uniformly, is easy to supply and is inexpensive in cost, and cosmetics formulated with powders hydrophobized with these compounds have characteristics such as dispersibility. Since it is excellent, it is preferable.
 前記シラン化合物又はシラザン化合物を用いた疎水化処理としては、n-ヘキサン、シクロヘキサン、低級アルコール等の有機溶媒中でシラン化合物又はシラザン化合物と粉末を混合し、場合により微粉砕した後、有機溶媒を加熱や減圧により除去し、好ましくは80~250℃で加熱処理する方法等で、シラン化合物又はシラザン化合物の反応性基により粉末の表面で化学反応させる方法が挙げられる。 As the hydrophobization treatment using the silane compound or silazane compound, the silane compound or silazane compound and powder are mixed in an organic solvent such as n-hexane, cyclohexane or lower alcohol, and finely pulverized in some cases. Examples of the method include a method in which the surface is removed by heating or reduced pressure, and a chemical reaction is preferably performed on the surface of the powder by a reactive group of the silane compound or silazane compound, such as a heat treatment at 80 to 250 ° C.
 また、特開2007-326902号公報に記載されるように、粉末を特定のポリシロキサン化合物で被覆処理した後に、アルキルアルコキシシランを水中にて疎水化処理する方法も挙げられる。 In addition, as described in JP-A-2007-326902, there is a method in which a powder is coated with a specific polysiloxane compound, and then an alkylalkoxysilane is hydrophobized in water.
 前記チタネート系カップリング剤を用いた疎水化処理としては、特開平1-131282号公報に記載されるように、粉末水分散液中にイソプロピルトリイソステアロイルチタネート、イソプロピルトリス(ジオクチルパイロフォスフェート)チタネート、イソプロピルトリ(N-アミノエチル-アミノエチル)チタネート、イソプロピルトリデシルベンゼンスルホニルチタネート等のチタン酸塩を加え、高速攪拌して混合し、場合により水洗、乾燥処理する方法、粉末にチタネート系カップリング剤を噴霧し、高せん断攪拌して混合し、場合により粉砕処理する方法が挙げられる。粉末とチタネート系カップリング剤を混合する際に、塩化亜鉛、塩化アルミニウム等の金属塩化物の水溶液を微量添加することが好ましく、これにより、粉末の表面全体で反応を速やかにかつ均一に起こさせることができる。 As the hydrophobizing treatment using the titanate coupling agent, as described in JP-A-1-131282, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate in an aqueous powder dispersion is used. , Titanate such as isopropyltri (N-aminoethyl-aminoethyl) titanate, isopropyltridecylbenzenesulfonyl titanate, etc., stirring at high speed and mixing, optionally washing with water and drying, titanate coupling to powder Examples of the method include spraying the agent, mixing with high shear stirring, and optionally pulverizing. When mixing the powder with the titanate coupling agent, it is preferable to add a small amount of an aqueous solution of metal chloride such as zinc chloride or aluminum chloride, thereby causing the reaction to occur rapidly and uniformly over the entire surface of the powder. be able to.
 前記アシルアミノ酸金属塩を用いた疎水化処理としては、水、アルコール類(エタノール、イソプロピルアルコール、イソブタノール等)、極性溶剤(アセトン、酢酸エチル、酢酸ブチル等)等の溶媒又は種々の混合溶媒にN-アシルアミノ酸金属塩を溶解又は分散させ、その溶液を粉末と攪拌混合した後、溶剤を除去する方法が挙げられる。 Hydrophobing treatment using the acylamino acid metal salt may be carried out with a solvent such as water, alcohols (ethanol, isopropyl alcohol, isobutanol, etc.), polar solvents (acetone, ethyl acetate, butyl acetate, etc.) or various mixed solvents. An example is a method in which the N-acylamino acid metal salt is dissolved or dispersed, the solution is stirred and mixed with the powder, and then the solvent is removed.
 N-アシルアミノ酸金属塩としては、N-ヘキサノイルアスパラギン酸(グルタミン酸)、N-オレイリルアスパラギン酸(グルタミン酸)、N-ラウロイルアスパラギン酸(グルタミン酸)、N-ミリストイルアスパラギン酸(グルタミン酸)、N-パルミトイルアスパラギン酸(グルタミン酸)、N-ステアロイルアスパラギン酸(グルタミン酸)、N-リノレノイルアスパラギン酸(グルタミン酸)等の金属塩等が挙げられる。なお、上記「N-ヘキサノイルアスパラギン酸(グルタミン酸)」等の表記は、N-ヘキサノイルアスパラギン酸とN-ヘキサノイルグルタミン酸の両方の併記を意味する。金属塩としては、ナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩等が挙げられる。 N-acylamino acid metal salts include N-hexanoyl aspartic acid (glutamic acid), N-oleyl aspartic acid (glutamic acid), N-lauroyl aspartic acid (glutamic acid), N-myristoyl aspartic acid (glutamic acid), N-palmitoyl Examples thereof include metal salts such as aspartic acid (glutamic acid), N-stearoyl aspartic acid (glutamic acid), and N-linolenoyl aspartic acid (glutamic acid). Note that the notation such as “N-hexanoyl aspartic acid (glutamic acid)” means both N-hexanoyl aspartic acid and N-hexanoyl glutamic acid. Examples of the metal salt include sodium salt, potassium salt, calcium salt, magnesium salt and the like.
 粉末への疎水化処理剤の被覆量は、粉末表面に表面処理剤が均一に被覆され、粉末表面で疎水化処理剤が凝集や析出することがない観点から、用いられる粉末の総量に対して、好ましくは1質量%以上、より好ましくは1.5質量%以上であり、また好ましくは10質量%以下、より好ましくは5質量%以下である。具体的な被覆量は、好ましくは1~10質量%、より好ましくは1.5~5質量%である。 The coating amount of the hydrophobizing agent on the powder is based on the total amount of powder used from the viewpoint that the surface of the powder is uniformly coated with the surface treating agent and the hydrophobizing agent does not aggregate or precipitate on the powder surface. The amount is preferably 1% by mass or more, more preferably 1.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less. The specific coating amount is preferably 1 to 10% by mass, more preferably 1.5 to 5% by mass.
 本発明の水中油型乳化組成物中における成分(C)の含有量は、紫外線防御効果及び乳化安定性を向上させる観点から、好ましくは0.1質量%以上、より好ましくは1質量%以上、更に好ましくは5質量%以上であり、また、好ましくは30質量%以下、より好ましくは20質量%以下、更に好ましくは15質量%以下である。成分(C)の具体的な範囲は、好ましくは0.1~30質量%、より好ましくは1~20質量%、更に好ましくは5~15質量%である。 The content of component (C) in the oil-in-water emulsion composition of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably, from the viewpoint of improving the UV protection effect and emulsion stability. Is 5% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. The specific range of component (C) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 5 to 15% by mass.
〔成分(D):水〕
 本発明の水中油型乳化組成物中における水の含有量は、みずみずしい感触を向上させ、高温安定性、せん断耐性に優れた水中油型乳化組成物を形成する点から、好ましくは40質量%以上、より好ましくは45質量%以上であり、また好ましくは80質量%以下、より好ましくは75質量%以下である。水の具体的な含有量範囲は、好ましくは40~80質量%、より好ましくは45~75質量%である。
[Component (D): Water]
The water content in the oil-in-water emulsion composition of the present invention is preferably 40% by mass or more from the viewpoint of improving the fresh feel and forming an oil-in-water emulsion composition excellent in high temperature stability and shear resistance. More preferably, it is 45% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less. The specific content range of water is preferably 40 to 80% by mass, more preferably 45 to 75% by mass.
〔成分(E):液状油〕
 成分(E)の液状油は、1013.25hPa下、25℃で流動性を有する油剤であり、これには、液状の有機紫外線吸収剤、及び通常の化粧料に用いられる油剤が含まれる。本発明においては、紫外線防御効果を高めるため、液状の有機紫外線吸収剤を含有することが好ましい。
[Component (E): Liquid oil]
The liquid oil of component (E) is an oil having fluidity at 25 ° C. under 1013.25 hPa, and this includes liquid organic ultraviolet absorbers and oils used in ordinary cosmetics. In the present invention, in order to enhance the ultraviolet protection effect, it is preferable to contain a liquid organic ultraviolet absorber.
 液状の有機紫外線吸収剤としては、パラメトキシケイ皮酸2-エチルヘキシル、パラメトキシケイ皮酸2-エトキシエチル、パラメトキシケイ皮酸イソプロピル・ジイソプロピルケイ皮酸エステル混合物、トリメトキシケイ皮酸メチルビス(トリメチルシロキシ)シリルイソペンチル、パラジメチルアミノ酸安息香酸アミル、パラジメチルアミノ酸安息香酸2-エチルヘキシル、サリチル酸エチレングリコール、サリチル酸2-エチルヘキシル、サリチル酸ベンジル、サリチル酸ホモメンチル、オクトクリレン、ジメチコジエチルベンザルマロネートからなる群から選択される1種又は2種以上を挙げることができる。これらのうち、紫外線防御効果、乳化状態、高温安定性及び低温安定性を向上させる観点から、パラメトキシケイ皮酸2-エチルヘキシル、サリチル酸2-エチルヘキシル、サリチル酸ホモメンチル、オクトクリレン及びジメチコジエチルベンザルマロネートから選択される1種又は2種以上を含むことが好ましく、パラメトキシケイ皮酸2-エチルヘキシル、オクトクリレン及びジメチコジエチルベンザルマロネートから選択される1種又は2種以上を含むことがより好ましく、パラメトキシケイ皮酸2-エチルヘキシルを含むことが更に好ましい。 Liquid organic ultraviolet absorbers include 2-methoxyhexyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, isopropyl dimethoxycinnamate and diisopropyl cinnamate ester, methyl bis (trimethyl trimethoxycinnamate) From the group consisting of (siloxy) silylisopentyl, paradimethylamino acid amyl benzoate, paradimethylamino acid 2-ethylhexyl benzoate, ethylene glycol salicylate, 2-ethylhexyl salicylate, benzyl salicylate, homomenthyl salicylate, octocrylene, dimethicodiethylbenzalmalonate The 1 type (s) or 2 or more types selected can be mentioned. Among these, from the viewpoint of improving UV protection effect, emulsified state, high temperature stability and low temperature stability, paramethoxycinnamate 2-ethylhexyl, salicylate 2-ethylhexyl, salicylate homomenthyl, octocrylene and dimethicodiethylbenzalmalonate It is preferable that 1 type or 2 or more types selected from these are included, and it is more preferable that 1 type or 2 or more types selected from 2-ethylhexyl paramethoxycinnamate, octocrylene, and dimethicodiethylbenzalmalonate are included. It is more preferable to contain 2-ethylhexyl paramethoxycinnamate.
 液状油中に含まれる前記有機紫外線吸収剤以外の油剤としては、1013.25hPa下、25℃の環境下において液状であれば特に限定されない。具体的には、α-オレフィンオリゴマー、流動イソパラフィン、流動パラフィン、スクワラン等の炭化水素油;トリオクタン酸グリセリル、アボカド油、オリーブ油、ゴマ油、コメヌカ油、サフラワー油、ダイズ油、トウモロコシ油、ナタネ油、ヒマシ油、綿実油、ミンク油等のトリグリセリド;オレイン酸、イソステアリン酸等の脂肪酸;ミリスチン酸イソプロピル、ミリスチン酸ブチル、パルミチン酸イソプロピル、オレイン酸エチル、リノール酸エチル、リノール酸イソプロピル、カプリル酸セチル、ラウリン酸ヘキシル、ミリスチン酸デシル、オレイン酸デシル、オレイン酸オレイル、ラウリン酸イソステアリル、ミリスチン酸イソトリデシル、ミリスチン酸イソセチル、ミリスチン酸イソステアリル、ミリスチン酸オクチルドデシル、パルミチン酸オクチル、パルミチン酸イソセチル、パルミチン酸イソステアリル、ジオレイン酸プロピレングリコール、オレイン酸イソデシル、イソステアリン酸イソプロピル、2-エチルヘキサン酸セチル、2-エチルヘキサン酸ステアリル、ジカプリン酸プロピレングリコール、ジオレイン酸プロピレングリコール、トリ2-エチルヘキサン酸グリセリル、トリ(カプリル・カプリン酸)グリセリル、イソノナン酸イソノニル、セバシン酸ジイソプロピル、イソステアリン酸プロピレングリコール等のエステル油;2-オクチルドデカノール、イソステアリルアルコール、オレイルアルコール等の分岐又は不飽和の高級アルコール;ジメチルポリシロキサンなどを挙げることができる。これらのうち、好ましくはミリスチン酸オクチルドデシル、ミリスチン酸イソセチル、2-エチルヘキサン酸セチル、トリ2-エチルヘキサン酸グリセリル、トリ(カプリル・カプリン酸)グリセリル、イソノナン酸イソノニル、セバシン酸ジイソプロピル、イソステアリン酸プロピレングリコール、ジカプリン酸ネオペンチルグリコール、イソヘキサデカン、スクワラン及び水添ポリイソブテンから選択される1種又は2種以上である。 The oil agent other than the organic ultraviolet absorber contained in the liquid oil is not particularly limited as long as it is liquid in an environment of 1013.25 hPa and 25 ° C. Specifically, hydrocarbon oils such as α-olefin oligomer, liquid isoparaffin, liquid paraffin, squalane; glyceryl trioctanoate, avocado oil, olive oil, sesame oil, rice bran oil, safflower oil, soybean oil, corn oil, rapeseed oil, Triglycerides such as castor oil, cottonseed oil, mink oil; fatty acids such as oleic acid and isostearic acid; isopropyl myristate, butyl myristate, isopropyl palmitate, ethyl oleate, ethyl linoleate, isopropyl linoleate, cetyl caprylate, lauric acid Hexyl, decyl myristate, decyl oleate, oleyl oleate, isostearyl laurate, isotridecyl myristate, isocetyl myristate, isostearyl myristate, octyldodecyl myristate Octyl palmitate, isocetyl palmitate, isostearyl palmitate, propylene glycol dioleate, isodecyl oleate, isopropyl isostearate, cetyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, propylene glycol dicaprate, propylene glycol dioleate, Ester oils such as glyceryl tri-2-ethylhexanoate, glyceryl tri (capryl / caprate), isononyl isononanoate, diisopropyl sebacate, propylene glycol isostearate; branched or 2-octyldodecanol, isostearyl alcohol, oleyl alcohol, etc. Examples thereof include unsaturated higher alcohols; dimethylpolysiloxane. Of these, octyldodecyl myristate, isocetyl myristate, cetyl 2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, glyceryl tri (capryl-caprate), isononyl isononanoate, diisopropyl sebacate, propylene isostearate One or more selected from glycol, neopentyl glycol dicaprate, isohexadecane, squalane and hydrogenated polyisobutene.
 本発明の水中油型乳化組成物中における成分(E)の含有量は、みずみずしい使用感を向上させ、乳化状態、高温安定性及び低温安定性を向上させる観点から、好ましくは5質量%以上、より好ましくは8質量%以上、更に好ましくは10質量%以上であり、また好ましくは25質量以下%以下、より好ましくは20質量%以下、更に好ましくは18質量%以下である。成分(E)の具体的な含有量範囲は、好ましくは5~25質量%、より好ましくは8~20質量%、更に好ましくは10~20質量%、更に好ましくは10~18質量%である。 The content of the component (E) in the oil-in-water emulsion composition of the present invention is preferably 5% by mass or more from the viewpoint of improving a fresh feeling of use and improving the emulsified state, high temperature stability and low temperature stability. More preferably, it is 8 mass% or more, More preferably, it is 10 mass% or more, Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 18 mass% or less. The specific content range of component (E) is preferably 5 to 25% by mass, more preferably 8 to 20% by mass, still more preferably 10 to 20% by mass, and further preferably 10 to 18% by mass.
 また、液状油含有量を低減しつつ、みずみずしい使用感を向上させ、高温安定性、紫外線防御効果を向上させる観点から、全成分(E)中における液状の有機紫外線吸収剤の含有質量比は、0.3以上であることが好ましく、0.5以上であることがより好ましく、0.6以上が更に好ましく、0.7以上が更に好ましい。 In addition, from the viewpoint of improving the fresh feeling of use while reducing the liquid oil content, and improving the high temperature stability and the UV protection effect, the content ratio of the liquid organic UV absorber in the total component (E) is: It is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.6 or more, and even more preferably 0.7 or more.
〔成分(F):25℃で固体状の紫外線吸収剤〕
 本発明の水中油型乳化組成物は、紫外線防御効果を高めるため、更に成分(F)として、25℃で固体状の紫外線吸収剤を含有することが好ましい。本発明で用いる25℃で固体状の紫外線吸収剤としては、化粧料、医薬部外品、医薬品に配合され得るものであれば特に限定されない。
[Component (F): UV absorber solid at 25 ° C]
The oil-in-water emulsion composition of the present invention preferably further contains a UV absorber solid at 25 ° C. as component (F) in order to enhance the UV protection effect. The ultraviolet absorber solid at 25 ° C. used in the present invention is not particularly limited as long as it can be blended in cosmetics, quasi drugs, and pharmaceuticals.
 成分(F)の具体例として、ジメトキシベンジリデンジオキソイミダゾリジンプロピオン酸2-エチルヘキシル、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシルエステル、2,4-ビス[[4-(2-エチルヘキシルオキシ)-2-ヒドロキシ]-フェニル]-6-(4-メトキシフェニル)-1,3,5-トリアジン、2,4,6-トリス[4-(2-エチルヘキシルオキシカルボニル)アニリノ]-1,3,5-トリアジン及び4-tert-ブチル-4'-メトキシジベンゾイルメタンからなる群から選択される1種又は2種以上を挙げることができる。 Specific examples of component (F) include dimethoxybenzylidenedioxoimidazolidinepropionic acid 2-ethylhexyl, diethylaminohydroxybenzoylbenzoic acid hexyl ester, 2,4-bis [[4- (2-ethylhexyloxy) -2-hydroxy]- Phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine and 4- One type or two or more types selected from the group consisting of tert-butyl-4′-methoxydibenzoylmethane can be mentioned.
 これらのうち、紫外線防御効果、高温安定性及びせん断耐性を向上させる観点から、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシルエステル、2,4-ビス[[4-(2-エチルヘキシルオキシ)-2-ヒドロキシ]-フェニル]-6-(4-メトキシフェニル)-1,3,5-トリアジン及び2,4,6-トリス[4-(2-エチルヘキシルオキシカルボニル)アニリノ]-1,3,5-トリアジンからなる群から選択される1種又は2種以上を好ましく用いることができる。 Among these, diethylaminohydroxybenzoyl benzoic acid hexyl ester, 2,4-bis [[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl, from the viewpoint of improving UV protection effect, high temperature stability and shear resistance ] -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine One or two or more selected can be preferably used.
 これら成分(F)は、一般に市販されており、ソフトシェードDH(ジメトキシベンジリデンジオキソイミダゾリジンプロピオン酸2-エチルヘキシル;味の素社製)、ユビナールAplus(2-(4-ジエチルアミノ-2-ヒドロキシベンゾイル)安息香酸へキシルエステル;BASF社製)、チノソーブS(2,4-ビス[[4-(2-エチルヘキシルオキシ)-2-ヒドロキシ]-フェニル]-6-(4-メトキシフェニル)-1,3,5-トリアジン;BASF社製)、ユビナールT-150(2,4,6-トリス[4-(2-エチルヘキシルオキシカルボニル)アニリノ]-1,3,5-トリアジン)、パラソル1789(4-tert-ブチル-4'-メトキシジベンゾイルメタン;ロッシュ社製)等を挙げることができる。 These components (F) are generally commercially available, soft shade DH (dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl; manufactured by Ajinomoto Co., Inc.), ubinal Aplus (2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid Acid hexyl ester; manufactured by BASF), Tinosorb S (2,4-bis [[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl] -6- (4-methoxyphenyl) -1,3, 5-triazine (manufactured by BASF), ubinal T-150 (2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine), parasol 1789 (4-tert- Butyl-4'-methoxydibenzoylmethane; manufactured by Roche).
 本発明の水中油型乳化組成物中における成分(F)の含有量は、紫外線防御能効果、高温安定性及びせん断耐性を向上させる観点から、好ましくは0.5質量%以上、より好ましくは1質量%以上、更に好ましくは1.5質量%以上であり、また、好ましくは10質量%以下、より好ましくは7.5質量%以下、更に好ましくは5質量%以下である。成分(F)の具体的な含有量範囲は、好ましくは0.5~10質量%、より好ましくは0.5~7.5質量%、更に好ましくは0.5~5質量%である。 The content of the component (F) in the oil-in-water emulsion composition of the present invention is preferably 0.5% by mass or more, more preferably 1% by mass from the viewpoint of improving the UV protection effect, high temperature stability and shear resistance. More preferably, it is 1.5% by mass or more, preferably 10% by mass or less, more preferably 7.5% by mass or less, and still more preferably 5% by mass or less. The specific content range of component (F) is preferably 0.5 to 10% by mass, more preferably 0.5 to 7.5% by mass, and still more preferably 0.5 to 5% by mass.
〔成分(G):水溶性高分子〕
 本発明の水中油型乳化組成物は、水相の分散安定性を高め、高温及び低温安定性を向上させるため、更に成分(G)として、水溶性高分子を含有することが好ましい。本発明で用いる水溶性高分子としては、水溶性のカチオン性高分子、アニオン性高分子、非イオン性高分子、及び両性高分子又は双極性高分子が挙げられる。
[Component (G): Water-soluble polymer]
The oil-in-water emulsion composition of the present invention preferably further contains a water-soluble polymer as component (G) in order to increase the dispersion stability of the aqueous phase and improve the high temperature and low temperature stability. Examples of the water-soluble polymer used in the present invention include a water-soluble cationic polymer, an anionic polymer, a nonionic polymer, and an amphoteric polymer or a bipolar polymer.
 カチオン性高分子としては、具体的には、塩化O-[2-ヒドロキシ-3-(トリメチルアンモニオ)プロピル]基を有するヒドロキシエチルセルロース(ポリクオタニウム-10)、ビニルピロリドン-ジメチルアミノメチルエチルメタクリレート共重合体ジエチル硫酸塩(ポリクオタニウム-11)、塩化メチルビニルイミダゾリウム・ビニルピロリドン共重合体等が挙げられる。 Specific examples of the cationic polymer include hydroxyethyl cellulose (polyquaternium-10) having a chloride O- [2-hydroxy-3- (trimethylammonio) propyl] group, vinylpyrrolidone-dimethylaminomethylethyl methacrylate copolymer Examples thereof include diethyl diethyl sulfate (polyquaternium-11), methylvinylimidazolium chloride / vinylpyrrolidone copolymer, and the like.
 アニオン性高分子としては、具体的には、カルボキシビニルポリマー、カルボキシメチルセルロース、カラゲーナン、キサンタンガム、ポリスチレンスルホネート、寒天、ガッチガム、カラヤガム、ペクチン、アルギネート塩、アクリル酸・メタクリル酸アルキル共重合体、(アクリル酸Na/アクリロイルジメチルタウリンNa)コポリマー、ポリアクリルアミド、(アクリロイルジメチルタウリンアンモニウム/VP)コポリマー、(アクリロイルジメチルタウリンアンモニウムメタクリル酸ベヘネス-25)クロスポリマー、(アクリル酸ヒドロキシエチル/アクリロイルジメチルタウリンNa)コポリマー、(アクリルアミド/アクリル酸アンモニウム)コポリマー、(アクリル酸Na/アクリロイルジメチルタウリン/ジメチルアクリルアミド)クロスポリマー、ポリアクリレート-13、ポリアクリレートクロスポリマー-6、ポリ(アクリル酸)のアルカリ金属塩、ヒアルロン酸又はそのアルカリ金属塩が挙げられる。 Specific examples of the anionic polymer include carboxyvinyl polymer, carboxymethyl cellulose, carrageenan, xanthan gum, polystyrene sulfonate, agar, gatch gum, caraya gum, pectin, alginate salt, acrylic acid / alkyl methacrylate copolymer, (acrylic acid (Na / acryloyldimethyltaurine Na) copolymer, polyacrylamide, (acryloyldimethyltaurine ammonium / VP) copolymer, (acryloyldimethyltaurine ammonium methacrylate, Behenes-25) crosspolymer, (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, ( Acrylamide / ammonium acrylate) copolymer, (Na acrylate / acryloyl dimethyl taurine / dimethyl acrylamide) Ross polymer, polyacrylate-13, polyacrylate crosspolymer-6, alkali metal salt of poly (acrylic acid), hyaluronic acid or an alkali metal salt thereof.
 非イオン性高分子としては、具体的には、セルロースエーテル(ヒドロキシブチルメチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、エチルヒドロキシエチルセルロース、ヒドロキシエチルセルロース等)、プロピレングリコールアルギネート、ポリ(エチレンオキシド)、ポリビニルアルコール、ポリビニルピロリドン、ヒドロキシプロピルグアーゴム、ローカストビーンゴム、アミロース、ヒドロキシエチルアミロース、澱粉及び澱粉誘導体並びにこれらの混合物が挙げられる。 Specific examples of the nonionic polymer include cellulose ether (hydroxybutylmethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxyethylcellulose, etc.), propylene glycol alginate, poly (ethylene oxide), polyvinyl alcohol, polyvinyl Examples include pyrrolidone, hydroxypropyl guar gum, locust bean gum, amylose, hydroxyethyl amylose, starch and starch derivatives, and mixtures thereof.
 両性高分子又は双極性高分子としては、具体的には、オクチルアクリルアミド/アクリレート/ブチルアミノエチルメタクリレートコポリマー、ポリクオタニウム-47、ポリクオタニウム-43等が挙げられる。 Specific examples of the amphoteric polymer or the bipolar polymer include octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer, polyquaternium-47, polyquaternium-43 and the like.
 これらの水溶性高分子は、単独で又は2種以上を適宜組み合わせて使用することができる。乳化安定性を向上させ、様々な剤形へ応用のしやすくする観点から、カルボキシビニルポリマー、アクリル酸・メタクリル酸アルキル共重合体、キサンタンガム、ヒドロキシプロピルメチルセルロース、ポリアクリルアミド、(アクリル酸Na/アクリロイルジメチルタウリンNa)コポリマー、(アクリロイルジメチルタウリンアンモニウム/VP)コポリマー及びヒアルロン酸又はそのアルカリ金属塩から選択される1種以上を含むことが好ましく、ポリアクリルアミド、(アクリル酸Na/アクリロイルジメチルタウリンNa)コポリマー、(アクリロイルジメチルタウリンアンモニウム/VP)コポリマー及びキサンタンガムから選択される1種以上を含むことがより好ましい。 These water-soluble polymers can be used alone or in appropriate combination of two or more. From the viewpoint of improving emulsion stability and facilitating application to various dosage forms, carboxyvinyl polymer, acrylic acid / alkyl methacrylate copolymer, xanthan gum, hydroxypropyl methylcellulose, polyacrylamide, (Na acrylate / acryloyldimethyl) It preferably contains at least one selected from taurine Na) copolymer, (acryloyldimethyltauronium ammonium / VP) copolymer and hyaluronic acid or alkali metal salts thereof, polyacrylamide, (Na acrylate / acryloyldimethyltaurine Na) copolymer, More preferably, it contains one or more selected from (acryloyldimethyltaurate ammonium / VP) copolymer and xanthan gum.
 本発明の水中油型乳化組成物中における成分(G)の含有量は、前記の観点から、好ましくは0.01質量%以上、より好ましくは0.05質量%以上、更に好ましくは0.1質量%以上であり、また好ましくは4質量%以下、より好ましくは2質量%以下、更に好ましくは1.5質量%以下である。成分(G)の具体的な含有量範囲は、好ましくは0.01~4質量%、より好ましくは0.05~2質量%、更に好ましくは0.1~1.5質量%である。 From the above viewpoint, the content of the component (G) in the oil-in-water emulsion composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. Further, it is preferably 4% by mass or less, more preferably 2% by mass or less, and further preferably 1.5% by mass or less. The specific content range of component (G) is preferably 0.01 to 4% by mass, more preferably 0.05 to 2% by mass, and still more preferably 0.1 to 1.5% by mass.
〔成分(H):炭素数1~3の飽和1価アルコール〕
 本発明の水中油型乳化組成物は、さっぱりとした使用感、塗布時の伸びの良さ、耐水・耐汗性を高める点から、更に成分(H)として、炭素数1~3の飽和1価アルコールを含有することが好ましい。成分(H)としては、メチルアルコール、エチルアルコール、プロピルアルコール、イソプロピルアルコールが挙げられ、単独で又は2種以上を適宜組み合わせて使用することができる。このうち、前記の観点から、エチルアルコール及びイソプロピルアルコールから選択される1種又は2種を含むことが好ましく、エチルアルコールを含むことがより好ましい。
[Component (H): C1-C3 saturated monohydric alcohol]
The oil-in-water emulsified composition of the present invention is a monovalent saturated monovalent having 1 to 3 carbon atoms as a component (H) from the viewpoint of a refreshing feeling of use, good elongation at the time of application, and water / sweat resistance. It is preferable to contain alcohol. Examples of the component (H) include methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol, which can be used alone or in appropriate combination of two or more. Among these, from the above viewpoint, it is preferable to include one or two selected from ethyl alcohol and isopropyl alcohol, and it is more preferable to include ethyl alcohol.
 本発明の水中油型乳化組成物中における成分(H)の含有量は、特に限定されるものではないが、さっぱりとした使用感、塗布時の伸びの良さ、耐水・耐汗性を高める点から、好ましくは1質量%以上、より好ましくは3質量%以上、更に好ましくは5質量%以上であり、また好ましくは20質量%以下、より好ましくは15質量%以下、更に好ましくは12質量%以下である。成分(H)の具体的な含有量範囲は、好ましくは1~20質量%、より好ましくは3~15質量%、更に好ましくは5~12質量%である。 The content of the component (H) in the oil-in-water emulsion composition of the present invention is not particularly limited, but it has a refreshed feeling of use, good elongation at the time of application, and water / sweat resistance is improved. Therefore, it is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 12% by mass or less. It is. The specific content range of component (H) is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and still more preferably 5 to 12% by mass.
〔成分(I):多価アルコール〕
 本発明の水中油型乳化組成物は、塗布後の保湿性、塗布時の伸びの良さを向上させるため、更に成分(I)として、多価アルコールを含有することが好ましい。成分(I)としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール(平均分子量650未満が好ましい)、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール(平均分子量650未満が好ましい)、イソプレングリコール、1,3-ブチレングリコール等のグリコール類;グリセリン、ジグリセリン、ポリグリセリン等のグリセリン類が挙げられ、単独で又は2種以上を適宜組み合わせて使用することができる。
[Component (I): Polyhydric alcohol]
The oil-in-water emulsion composition of the present invention preferably further contains a polyhydric alcohol as component (I) in order to improve the moisture retention after coating and the good elongation during coating. Examples of the component (I) include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (average molecular weight is preferably less than 650), propylene glycol, dipropylene glycol, polypropylene glycol (average molecular weight is preferably less than 650), isoprene glycol, Glycerols such as 1,3-butylene glycol; glycerins such as glycerin, diglycerin, and polyglycerin can be used, and these can be used alone or in combination of two or more.
 このうち、前記の観点から、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、1,3-ブチレングリコール、グリセリン及びジグリセリンから選択される1種又は2種以上を含有することが好ましく、プロピレングリコール、ジプロピレングリコール、1,3-ブチレングリコール及びグリセリンから選択される1種又は2種以上を含むことがより好ましい。 Among these, from the above viewpoint, it is preferable to contain one or more selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin and diglycerin, More preferably, it contains one or more selected from dipropylene glycol, 1,3-butylene glycol and glycerin.
 本発明の水中油型乳化組成物中における成分(I)の含有量は、保湿性、塗布時の伸びの良さを高める点から、好ましくは0.1質量%以上、より好ましくは0.5質量%以上、更に好ましくは1質量%以上であり、また好ましくは12質量%以下、より好ましくは8質量%以下、更に好ましくは5質量%以下、更に好ましくは3質量%以下である。具体的な含有量範囲は、好ましくは0.1~12質量%、より好ましくは0.5~8質量%、更に好ましくは1~5質量%、更に好ましくは1~3質量%である。 The content of the component (I) in the oil-in-water emulsion composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 0.5% by mass or more from the viewpoint of improving the moisturizing property and good elongation during application. The amount is preferably 1% by mass or more, more preferably 12% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, and further preferably 3% by mass or less. The specific content range is preferably 0.1 to 12% by mass, more preferably 0.5 to 8% by mass, still more preferably 1 to 5% by mass, and still more preferably 1 to 3% by mass.
 本発明の水中油型乳化組成物の平均乳化粒子径は、乳化安定性を向上させ、みずみずしい使用感、均一塗布性を向上させる観点から、1μm以上が好ましく、また30μm以下が好ましく、25μm以下がより好ましく、20μm以下が更に好ましい。具体的には、1~30μmが好ましく、1~25μmがより好ましく、1~20μmが更に好ましい。なお、乳化粒子の平均粒子径は、顕微鏡写真中の任意の視野の任意の粒子20個についての粒径を繰り返し測定し、個数基準平均値より求めることができる。 The average emulsified particle size of the oil-in-water emulsion composition of the present invention is preferably 1 μm or more, preferably 30 μm or less, preferably 25 μm or less from the viewpoint of improving emulsification stability, improving the fresh feeling of use, and uniform coating properties. More preferred is 20 μm or less. Specifically, it is preferably 1 to 30 μm, more preferably 1 to 25 μm, still more preferably 1 to 20 μm. The average particle size of the emulsified particles can be obtained from the number-based average value by repeatedly measuring the particle size of 20 arbitrary particles in an arbitrary field of view in the micrograph.
〔その他の任意成分〕
 本発明の水中油型乳化組成物には、以上の成分以外に、本発明の効果を損なわない範囲であれば、通常化粧料に配合される各種の界面活性剤、油性成分、シリコーン化合物、高級アルコール、フッ素化合物、樹脂、増粘剤、防菌防腐剤、保湿剤、塩類、溶媒、酸化防止剤、キレート剤、中和剤、pH調整剤、昆虫忌避剤、生理活性成分、制汗剤、香料、各種動植物の抽出液等の通常化粧料に用いられる各種の原料を含有することができる。なお、これらの各剤は、各剤としての用途に限られず、目的に応じて他の用途としての転用、例えば、制汗剤を香料として使用したり、他の用途との兼用として、例えば、制汗剤と香料としての効果を奏するものとして使用することができる。
[Other optional ingredients]
In the oil-in-water emulsion composition of the present invention, in addition to the above components, various surfactants, oily components, silicone compounds, high-grade compounds usually incorporated in cosmetics, as long as the effects of the present invention are not impaired. Alcohol, fluorine compound, resin, thickener, antibacterial preservative, moisturizer, salt, solvent, antioxidant, chelating agent, neutralizer, pH adjuster, insect repellent, bioactive ingredient, antiperspirant, Various raw materials usually used in cosmetics such as perfumes and extracts of various animals and plants can be contained. In addition, each of these agents is not limited to the use as each agent, diverted as other uses according to the purpose, for example, using an antiperspirant as a fragrance, or as a combination with other uses, for example, It can be used as an effect as an antiperspirant and a fragrance.
 本発明の水中油型乳化化粧料には、乳化安定性を調整する目的で、界面活性剤を含有させることができる。界面活性剤としては、特に制限されず、非イオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、天然系界面活性剤、ポリエーテル変性シリコーン、シロキサン誘導体等のシリコーン含有界面活性剤、パーフルオロアルキル基を含有する界面活性剤等のいずれでも用いることができ、これらを1種又は2種以上用いることができる。 The oil-in-water emulsified cosmetic of the present invention can contain a surfactant for the purpose of adjusting the emulsion stability. The surfactant is not particularly limited, and includes nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, natural surfactants, polyether-modified silicones, siloxane derivatives, and the like. Any of a silicone-containing surfactant, a surfactant containing a perfluoroalkyl group, and the like can be used, and one or more of these can be used.
 これらの界面活性剤のうち、非イオン性界面活性剤、ポリエーテル変性シリコーン、シリコーン含有界面活性剤が好ましく、具体的には、モノイソソテアリン酸ソルビタン、ジメチコンコポリオール、ポリオキシエチレン硬化ヒマシ油(40EO)、ポリオキシエチレンヒマシ油(40EO)、モノラウリン酸ポリオキシエチレンソルビタン(20EO)、モノステアリン酸ポリオキシエチレン(20EO)、オレイン酸ポリオキシエチレンソルビタン(20EO)、ポリオキシエチレン(7)ラウリルエーテル、PEG-7トリメチロールプロパンヤシ油アルキルエーテル等が挙げられる。 Of these surfactants, nonionic surfactants, polyether-modified silicones, and silicone-containing surfactants are preferred. Specifically, sorbitan monoisosotearate, dimethicone copolyol, polyoxyethylene hydrogenated castor oil (40EO), polyoxyethylene castor oil (40EO), polyoxyethylene sorbitan monolaurate (20EO), polyoxyethylene monostearate (20EO), polyoxyethylene sorbitan oleate (20EO), polyoxyethylene (7) lauryl And ether, PEG-7 trimethylolpropane coconut oil alkyl ether, and the like.
 本発明の水中油型乳化化粧料では、上記界面活性剤を併用しなくとも乳化安定性が良好であり、多量に界面活性剤を配合すると、界面活性剤に由来するべたつき感が生じてしまうことがあるため、好ましい含有量は水中油型乳化組成物総量に対して、3質量%以下が好ましく、1.5質量%以下がより好ましく、0.5質量%以下が更に好ましい。具体的な範囲として記載すると0~3質量%が好ましく、0~1.5質量%がより好ましく、0~0.5質量%が更に好ましい。 In the oil-in-water emulsified cosmetic of the present invention, the emulsion stability is good without using the above-mentioned surfactant together, and when a large amount of the surfactant is blended, a sticky feeling derived from the surfactant may occur. Therefore, the preferable content is preferably 3% by mass or less, more preferably 1.5% by mass or less, and still more preferably 0.5% by mass or less with respect to the total amount of the oil-in-water emulsion composition. As a specific range, 0 to 3% by mass is preferable, 0 to 1.5% by mass is more preferable, and 0 to 0.5% by mass is still more preferable.
〔用途〕
 本発明の水中油型乳化組成物の用途としては、特に制限がなく、化粧料、医薬品、医薬部外品等に好適に用いることができる。本発明の水中油型乳化組成物は、水分の閉塞効果に優れる点から、洗い流さず、皮膚(頭皮を含む)に保持するタイプの皮膚外用剤として、皮膚、好ましくは頭皮を除く皮膚、より好ましくは顔、身体、手足等のいずれかに塗布することにより、使用することができる。また、紫外線吸収剤又は紫外線散乱剤を含有しても安定性に優れる点から、日焼け止め用途、特にサンスクリーン、サンタン、化粧下地化粧料、紫外線防御能を有するファンデーション等に適用するのが好ましい。
[Use]
There is no restriction | limiting in particular as an application of the oil-in-water type emulsion composition of this invention, It can use suitably for cosmetics, a pharmaceutical, a quasi-drug, etc. The oil-in-water emulsified composition of the present invention is a skin external preparation of the type that is retained on the skin (including the scalp) without being washed away, and more preferably the skin excluding the scalp, more preferably from the viewpoint of excellent moisture occlusive effect. Can be used by applying to any of the face, body, limbs and the like. Moreover, since it is excellent in stability even if it contains an ultraviolet absorber or an ultraviolet scattering agent, it is preferably applied to sunscreen applications, in particular, sunscreens, suntans, cosmetic base cosmetics, foundations having ultraviolet protective ability, and the like.
〔剤型〕
 本発明の水中油型乳化組成物の剤形としては、液状、乳液状、クリーム状、ペースト状、固形状、多層状等に適用が可能であり、更にシート剤、スプレー剤、ムース剤にも適用できる。
(Drug type)
The dosage form of the oil-in-water emulsion composition of the present invention can be applied to liquids, emulsions, creams, pastes, solids, multilayers, etc., and also to sheet agents, spray agents, and mousse agents. Applicable.
〔製造方法〕
 本発明の水中油型乳化組成物は、形態に応じて所定の手順により製造することができる。例えば、本発明の水中油型乳化組成物は、成分(A)~(D)、必要により成分(E)~(I)を含む各種成分を共に混合する工程を含む方法により製造することができる。具体的には、本発明の水中油型乳化組成物の製造方法は、
 成分(A)、成分(B)、成分(C)、必要により成分(E)、成分(F)及びその他の油溶性の任意成分を含む油相を、好ましくは50~90℃で、より好ましくは55~85℃で加熱撹拌する工程1aと、
 成分(D)、必要により成分(G)、成分(I)、成分(H)及びその他の水溶性の任意成分を含む水相を、好ましくは50~90℃で、より好ましくは55~85℃で加熱撹拌する工程2aと、
 工程1aの調製物と工程2aの調製物とを混合し、乳化させる工程3aを含むことができる。
〔Production method〕
The oil-in-water emulsion composition of the present invention can be produced by a predetermined procedure depending on the form. For example, the oil-in-water emulsion composition of the present invention can be produced by a method including a step of mixing together various components including components (A) to (D) and optionally components (E) to (I). . Specifically, the method for producing the oil-in-water emulsion composition of the present invention includes:
An oil phase containing component (A), component (B), component (C), optionally component (E), component (F) and other oil-soluble optional components, preferably at 50 to 90 ° C., more preferably Is a step 1a of heating and stirring at 55 to 85 ° C .;
The aqueous phase containing component (D), optionally component (G), component (I), component (H) and other water-soluble optional components is preferably 50 to 90 ° C., more preferably 55 to 85 ° C. And heating and stirring in step 2a,
Step 3a may be included in which the preparation of Step 1a and the preparation of Step 2a are mixed and emulsified.
 工程3aにおいては、工程2aの調製物を15~40℃、好ましくは20~30℃に冷却し、工程1aの調製物を40℃超、好ましくは50~70℃に維持し、工程2aの調製物を攪拌しながら、工程1aの調製物を加え、均一に攪拌混合して乳化させることが好ましい。これにより、油相の水相への投入と同時に成分(A)が油相界面でラメラ構造を形成しやすくなり、安定な水中油型乳化組成物を得ることができる。 In step 3a, the preparation of step 2a is cooled to 15-40 ° C., preferably 20-30 ° C. and the preparation of step 1a is maintained above 40 ° C., preferably 50-70 ° C. While stirring the product, it is preferable to add the preparation of Step 1a and uniformly stir and mix to emulsify. Thereby, at the same time when the oil phase is introduced into the aqueous phase, the component (A) can easily form a lamellar structure at the interface of the oil phase, and a stable oil-in-water emulsion composition can be obtained.
 また、成分(C)の油相への分散性を向上させるために、油相に添加する前に予め成分(C)を分散させる工程を含むことが好ましい。具体的には、
 成分(A)及び成分(B)、必要により成分(E)、成分(F)及びその他の油溶性の任意成分を含む油相を、好ましくは50~90℃で、より好ましくは55~85℃で加熱撹拌する工程1bと、
成分(C)を均一に分散する工程2bと、
 工程1bの調製物に工程2bの調製物を添加し、好ましくは50~90℃で、より好ましくは55~85℃で加熱撹拌する工程3bと
 成分(D)、必要により成分(G)、成分(I)、成分(H)及びその他の水溶性の任意成分を含む水相を、好ましくは50~90℃で、より好ましくは55~85℃で加熱撹拌する工程4bと、
 工程3bの調製物と工程4bの調製物とを混合し、乳化させる工程5bを含むことができる。
In order to improve the dispersibility of the component (C) in the oil phase, it is preferable to include a step of dispersing the component (C) in advance before adding the component (C) to the oil phase. In particular,
The oil phase containing component (A) and component (B), and optionally component (E), component (F) and other oil-soluble optional components, is preferably 50 to 90 ° C., more preferably 55 to 85 ° C. Step 1b of heating and stirring at
Step 2b for uniformly dispersing component (C);
Add the preparation of step 2b to the preparation of step 1b, and heat and stir preferably at 50 to 90 ° C., more preferably 55 to 85 ° C. and step (3b), component (D) if necessary, component (G), component Step 4b of heating and stirring the aqueous phase containing (I), component (H) and other water-soluble optional components, preferably at 50 to 90 ° C., more preferably 55 to 85 ° C .;
Step 5b may be included to mix and emulsify the preparation of Step 3b and the preparation of Step 4b.
 工程3bにおいては、工程4bの調製物を15~40℃、好ましくは20~30℃に冷却し、工程3bの調製物を40℃超、好ましくは50~70℃に維持し、工程4bの調製物を攪拌しながら、工程3bの調製物を加え、均一に攪拌混合して乳化させることが好ましい。これにより、油相の水相への投入と同時に成分(A)が油相界面でラメラ構造を形成しやすくなり、安定な水中油型乳化組成物を得ることができる。 In step 3b, the preparation of step 4b is cooled to 15-40 ° C., preferably 20-30 ° C., and the preparation of step 3b is maintained above 40 ° C., preferably 50-70 ° C. While stirring the product, it is preferable to add the preparation of Step 3b and uniformly stir and mix to emulsify. Thereby, at the same time when the oil phase is introduced into the aqueous phase, the component (A) can easily form a lamellar structure at the interface of the oil phase, and a stable oil-in-water emulsion composition can be obtained.
 以上述べた実施形態に関し、以下に本発明の好ましい態様を更に開示する。 With respect to the embodiments described above, preferred embodiments of the present invention will be further disclosed below.
<1> 下記成分(A)~(D)を含有し、成分(B)に対する成分(A)の含有質量比〔(A)/(B)〕が、0.06以上18以下である水中油型乳化組成物。
 (A) アルキル基又はアルケニル基の炭素数が20以上24以下で、エチレンオキサイドの平均付加モル数が1.5以上4以下であるポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルケニルエーテル
 (B) リン脂質
 (C) 疎水化処理粉末
 (D) 水
<1> Oil-in-water emulsification comprising the following components (A) to (D), wherein the mass ratio of component (A) to component (B) [(A) / (B)] is 0.06 or more and 18 or less Composition.
(A) Polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether having an alkyl group or alkenyl group having 20 to 24 carbon atoms and an average addition mole number of ethylene oxide of 1.5 to 4 (B) Phospholipid (C ) Hydrophobized powder (D) Water
<2> 成分(A)が有するアルキル基又はアルケニル基が、好ましくは直鎖又は分岐鎖のアルキル基であり、より好ましくは直鎖のアルキル基である<1>に記載の水中油型乳化組成物。 <2> The oil-in-water emulsion composition according to <1>, wherein the alkyl group or alkenyl group of component (A) is preferably a linear or branched alkyl group, more preferably a linear alkyl group. object.
<3> 成分(A)におけるアルキル基又はアルケニル基の炭素数が、好ましくは21以上23以下であり、より好ましくは22である<1>又は<2>に記載の水中油型乳化組成物。 <3> The oil-in-water emulsion composition according to <1> or <2>, wherein the carbon number of the alkyl group or alkenyl group in the component (A) is preferably 21 or more and 23 or less, more preferably 22.
<4> 成分(A)におけるエチレンオキサイドの平均付加モル数が、好ましくは3以下、更に好ましくは2.5以下である<1>~<3>のいずれか1項に記載の水中油型乳化組成物。 <4> The oil-in-water emulsion composition according to any one of <1> to <3>, wherein the average added mole number of ethylene oxide in component (A) is preferably 3 or less, more preferably 2.5 or less. .
<5> 成分(A)の含有量が、好ましくは0.05質量%以上、より好ましくは0.10質量%以上、更に好ましくは0.12質量%以上、更に好ましくは0.16質量%以上、更に好ましくは0.5質量%以上、更に好ましくは0.8質量%以上であり、また好ましくは5質量%以下、より好ましくは3質量%以下、更に好ましくは2質量%以下、更に好ましくは1.82質量%以下、更に好ましくは1.5質量%以下、更に好ましくは1.2質量%以下である<1>~<4>のいずれか1項に記載の水中油型乳化組成物。 <5> The content of the component (A) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, further preferably 0.12% by mass or more, further preferably 0.16% by mass or more, and further preferably 0.5% by mass or more. More preferably, it is 0.8% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, further preferably 1.82% by mass or less, and further preferably 1.5% by mass or less. The oil-in-water emulsion composition according to any one of <1> to <4>, more preferably 1.2% by mass or less.
<6> 成分(B)のリン脂質におけるホスファチジルコリン含量が、好ましくは60質量%以上、より好ましくは62質量%以上、更に好ましくは65質量%以上であり、また、98質量%以下である<1>~<5>のいずれか1項に記載の水中油型乳化組成物。 <6> The phosphatidylcholine content in the phospholipid of component (B) is preferably 60% by mass or more, more preferably 62% by mass or more, still more preferably 65% by mass or more, and 98% by mass or less. The oil-in-water emulsion composition according to any one of> to <5>.
<7> 成分(B)が、好ましくは大豆レシチン水素添加物及び卵黄レシチン水素添加物から選ばれるものである<1>~<6>のいずれか1項に記載の水中油型乳化組成物。 <7> The oil-in-water emulsion composition according to any one of <1> to <6>, wherein the component (B) is preferably selected from soybean lecithin hydrogenated product and egg yolk lecithin hydrogenated product.
<8> 成分(B)の含有量が、好ましくは0.05質量%以上、より好ましくは0.10質量%以上、更に好ましくは0.12質量%以上、更に好ましくは0.16質量%以上、更に好ましくは0.5質量%以上、更に好ましくは0.8質量%以上であり、また、好ましくは5質量%以下、より好ましくは3質量%以下、更に好ましくは2質量%以下、更に好ましくは1.82質量%以下、更に好ましくは1.5質量%以下、更に好ましくは1.2質量%以下である<1>~<7>のいずれか1項に記載の水中油型乳化組成物。 <8> The content of component (B) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, further preferably 0.12% by mass or more, further preferably 0.16% by mass or more, and further preferably 0.5% by mass or more. More preferably, it is 0.8% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, still more preferably 1.82% by mass or less, and further preferably 1.5% by mass. The oil-in-water emulsion composition according to any one of <1> to <7>, further preferably 1.2% by mass or less.
<9> 成分(A)及び成分(B)の合計含有量が、好ましくは0.5質量%以上、より好ましくは1.2質量%以上、更に好ましくは1.8質量%以上であり、また、好ましくは6質量%以下、より好ましくは3.5質量%以下、更に好ましくは2.5質量%以下である<1>~<8>のいずれか1項に記載の水中油型乳化組成物。 <9> The total content of component (A) and component (B) is preferably 0.5% by mass or more, more preferably 1.2% by mass or more, still more preferably 1.8% by mass or more, and preferably 6% by mass. The oil-in-water emulsion composition according to any one of <1> to <8>, more preferably 3.5% by mass or less, and still more preferably 2.5% by mass or less.
<10> 成分(B)に対する成分(A)の含有質量比[(A)/(B)]が、好ましくは0.06以上、より好ましくは0.08以上、更に好ましくは0.10以上、更に好ましくは0.5以上であり、また、好ましくは18以下、より好ましくは14以下、更に好ましくは10以下、更に好ましくは3以下である<1>~<9>のいずれか1項に記載の水中油型乳化組成物。 <10> The mass ratio [(A) / (B)] of the component (A) to the component (B) is preferably 0.06 or more, more preferably 0.08 or more, further preferably 0.10 or more, more preferably 0.5 or more. The oil-in-water emulsion composition according to any one of <1> to <9>, which is preferably 18 or less, more preferably 14 or less, still more preferably 10 or less, and still more preferably 3 or less.
<11> 成分(C)の疎水化処理粉末に用いる粉末が、好ましくは酸化亜鉛、酸化チタン、酸化セリウム、酸化鉄及び酸化クロムから選択される1種以上である<1>~<10>のいずれか1項に記載の水中油型乳化組成物。 <11> The powder used for the hydrophobized powder of component (C) is preferably one or more selected from zinc oxide, titanium oxide, cerium oxide, iron oxide, and chromium oxide. <1> to <10> The oil-in-water emulsion composition according to any one of the above.
<12> 成分(C)の疎水化処理粉末に用いる粉末の平均粒子径が、好ましくは0.01μm以上、より好ましくは0.012μm以上、更に好ましくは0.015μm以上であり、また、好ましくは28μm以下、より好ましくは23μm以下、更に好ましくは18μm以下である<1>~<11>のいずれか1項に記載の水中油型乳化組成物。 <12> The average particle size of the powder used for the hydrophobized powder of component (C) is preferably 0.01 μm or more, more preferably 0.012 μm or more, still more preferably 0.015 μm or more, and preferably 28 μm or less. The oil-in-water emulsion composition according to any one of <1> to <11>, which is more preferably 23 μm or less, and still more preferably 18 μm or less.
<13> 粉末への疎水化処理が、好ましくはフッ素化合物処理、シリコーン処理、シリコーン樹脂処理、ペンダント処理、シランカップリング剤処理、チタネート系カップリング剤処理、油剤処理、アシルアミノ酸金属塩処理、ポリアクリル酸処理、金属石鹸処理、結晶セルロース処理、無機化合物処理、プラズマ処理、メカノケミカル処理、シラン化合物処理、シラザン化合物処理から選ばれる1種又は2種以上、より好ましくは、シリコーン又はシリコーン樹脂を用いた疎水化処理、メチルハイドロジェンポリシロキサン又は下記一般式(1)で表されるメチルハイドロジェンポリシロキサン・ジメチルポリシロキサン共重合体を用いた疎水化処理、シラン化合物又はシラザン化合物を用いた疎水化処理、チタネート系カップリング剤を用いた疎水化処理及びアシルアミノ酸金属塩を用いた疎水化処理から選択される1種又は2種以上、更に好ましくはメチルハイドロジェンポリシロキサンを用いた疎水化処理、シラン化合物又はシラザン化合物を用いた疎水化処理、チタネート系カップリング剤を用いた疎水化処理及びアシルアミノ酸金属塩を用いた疎水化処理から選択される1種又は2種以上である<1>~<12>のいずれか1項に記載の水中油型乳化組成物。 <13> Hydrophobizing treatment to powder, preferably fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanate coupling agent treatment, oil agent treatment, acylamino acid metal salt treatment, poly One or more selected from acrylic acid treatment, metal soap treatment, crystalline cellulose treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, silane compound treatment, and silazane compound treatment, more preferably, silicone or silicone resin is used. Hydrophobic treatment using methylhydrogenpolysiloxane or methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer represented by the following general formula (1), hydrophobization using silane compound or silazane compound Treatment, using titanate coupling agent One or more selected from hydrophobic treatment and hydrophobic treatment using acylamino acid metal salt, more preferably hydrophobic treatment using methylhydrogenpolysiloxane, hydrophobization using silane compound or silazane compound Any one of <1> to <12> selected from a treatment, a hydrophobic treatment using a titanate coupling agent, and a hydrophobic treatment using an acylamino acid metal salt An oil-in-water emulsion composition.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
<14> 粉末への疎水化処理剤の被覆量が、用いられる粉末の総量に対して、好ましくは1質量%以上、より好ましくは1.5質量%以上であり、また好ましくは10質量%以下、より好ましくは5質量%以下である<1>~<13>のいずれか1項に記載の水中油型乳化組成物。 <14> The coating amount of the hydrophobizing agent on the powder is preferably 1% by mass or more, more preferably 1.5% by mass or more, and preferably 10% by mass or less, based on the total amount of powder used. The oil-in-water emulsion composition according to any one of <1> to <13>, which is preferably 5% by mass or less.
<15> 成分(C)の含有量が、好ましくは0.1質量%以上、より好ましくは1質量%以上、更に好ましくは5質量%以上であり、また、好ましくは30質量%以下、より好ましくは20質量%以下、更に好ましくは15質量%以下である<1>~<14>のいずれか1項に記載の水中油型乳化組成物。 <15> The content of the component (C) is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 20%. The oil-in-water emulsion composition according to any one of <1> to <14>, which is not more than mass%, more preferably not more than 15 mass%.
<16> 水の含有量が、好ましくは40質量%以上、より好ましくは45質量%以上であり、また好ましくは80質量%以下、より好ましくは75質量%以下である<1>~<15>のいずれか1項に記載の水中油型乳化組成物。 <16> The water content is preferably 40% by mass or more, more preferably 45% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less. <1> to <15> The oil-in-water emulsion composition according to any one of the above.
<17> 好ましくは、更に、成分(E)として液状油を含有する<1>~<16>のいずれか1項に記載の水中油型乳化組成物。 <17> Preferably, the oil-in-water emulsion composition according to any one of <1> to <16>, further comprising a liquid oil as the component (E).
<18> 成分(E)の液状油が、好ましくは1013.25hPa下、25℃で流動性を有する油剤である<17>に記載の水中油型乳化組成物。 <18> The oil-in-water emulsion composition according to <17>, wherein the liquid oil of component (E) is an oil agent having fluidity at 25 ° C., preferably under 1013.25 hPa.
<19> 成分(E)が、パラメトキシケイ皮酸2-エチルヘキシル、サリチル酸2-エチルヘキシル、サリチル酸ホモメンチル、オクトクリレン及びジメチコジエチルベンザルマロネートから選択される1種又は2種以上を含む液状油である<17>又は<18>に記載の水中油型乳化組成物。 <19> Component (E) is a liquid oil containing one or more selected from 2-ethylhexyl paramethoxycinnamate, 2-ethylhexyl salicylate, homomenthyl salicylate, octocrylene and dimethicodiethylbenzalmalonate The oil-in-water emulsion composition according to <17> or <18>.
<20> 成分(E)の含有量が、好ましくは5質量%以上、より好ましくは8質量%以上、更に好ましくは10質量%以上であり、また好ましくは25質量以下%以下、より好ましくは20質量%以下、更に好ましくは18質量%以下である<17>~<19>のいずれか1項に記載の水中油型乳化組成物。 <20> The content of component (E) is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, and preferably 25% by mass or less, more preferably 20% or less. The oil-in-water emulsion composition according to any one of <17> to <19>, which is not more than mass%, more preferably not more than 18 mass%.
<21> 全成分(E)中における液状の有機紫外線吸収剤の含有質量比が、好ましくは0.3以上、より好ましくは0.5以上、更に好ましくは0.6以上、更に好ましくは0.7以上である<17>~<20>のいずれか1項に記載の水中油型乳化組成物。 <21> The mass ratio of the liquid organic ultraviolet absorber in the total component (E) is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.6 or more, and even more preferably 0.7 or more <17> to The oil-in-water emulsion composition according to any one of <20>.
<22> 好ましくは、更に、成分(F)として25℃で固体状の紫外線吸収剤を含有する<1>~<21>のいずれか1項に記載の水中油型乳化組成物。 <22> Preferably, the oil-in-water emulsion composition according to any one of <1> to <21>, further comprising an ultraviolet absorbent that is solid at 25 ° C. as component (F).
<23> 成分(F)の含有量が、好ましくは0.5質量%以上、より好ましくは1質量%以上、更に好ましくは1.5質量%以上であり、また、好ましくは10質量%以下、より好ましくは7.5質量%以下、更に好ましくは5質量%以下である<1>~<22>のいずれか1項に記載の水中油型乳化組成物。 <23> The content of the component (F) is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and preferably 10% by mass or less, more preferably 7.5%. The oil-in-water emulsion composition according to any one of <1> to <22>, which is not more than mass%, more preferably not more than 5 mass%.
<24> 好ましくは、更に、成分(G)として、水溶性高分子を含有する<1>~<23>のいずれか1項に記載の水中油型乳化組成物。 <24> The oil-in-water emulsion composition according to any one of <1> to <23>, preferably further containing a water-soluble polymer as component (G).
<25> 成分(G)が、好ましくはカルボキシビニルポリマー、アクリル酸・メタクリル酸アルキル共重合体、キサンタンガム、ヒドロキシプロピルメチルセルロース、ポリアクリルアミド、(アクリル酸Na/アクリロイルジメチルタウリンNa)コポリマー、(アクリロイルジメチルタウリンアンモニウム/VP)コポリマー及びヒアルロン酸又はそのアルカリ金属塩から選択される1種以上を含むものであり、より好ましくはポリアクリルアミド、(アクリル酸Na/アクリロイルジメチルタウリンNa)コポリマー、(アクリロイルジメチルタウリンアンモニウム/VP)コポリマー及びキサンタンガムから選択される1種以上を含むものである<24>に記載の水中油型乳化組成物。 <25> Component (G) is preferably carboxyvinyl polymer, acrylic acid / alkyl methacrylate copolymer, xanthan gum, hydroxypropyl methylcellulose, polyacrylamide, (Na acrylate / acryloyl dimethyl taurine Na) copolymer, (acryloyl dimethyl taurine) Ammonium / VP) copolymer and one or more selected from hyaluronic acid or alkali metal salts thereof, more preferably polyacrylamide, (Na acrylate / acryloyl dimethyl taurine Na) copolymer, (acryloyl dimethyl taurate ammonium / <VP> The oil-in-water emulsion composition according to <24>, comprising at least one selected from copolymers and xanthan gum.
<26> 成分(G)の含有量が、好ましくは0.01質量%以上、より好ましくは0.05質量%以上、更に好ましくは0.1質量%以上であり、また好ましくは4質量%以下、より好ましくは2質量%以下、更に好ましくは1.5質量%以下である<24>又は<25>に記載の水中油型乳化組成物。 <26> The content of component (G) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 4% by mass or less, more preferably 2% by mass. % Or less, More preferably, it is 1.5 mass% or less, The oil-in-water emulsion composition as described in <24> or <25>.
<27> 更に成分(H)として、好ましくは炭素数1~3の飽和1価アルコールを含有する<1>~<26>のいずれか1項に記載の水中油型乳化組成物。 <27> The oil-in-water emulsion composition according to any one of <1> to <26>, further comprising a saturated monohydric alcohol having 1 to 3 carbon atoms as component (H).
<28> 成分(H)の含有量が、好ましくは1質量%以上、より好ましくは3質量%以上、更に好ましくは5質量%以上であり、また好ましくは20質量%以下、より好ましくは15質量%以下、更に好ましくは12質量%以下である<27>に記載の水中油型乳化組成物。 <28> The content of component (H) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass. % Or less, more preferably 12% by mass or less, The oil-in-water emulsion composition according to <27>.
<29> 更に成分(I)として、好ましくは多価アルコールを含有する<1>~<28>のいずれか1項に記載の水中油型乳化組成物。 <29> The oil-in-water emulsion composition according to any one of <1> to <28>, further containing a polyhydric alcohol as component (I).
<30> 成分(I)が、好ましくはエチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、1,3-ブチレングリコール、グリセリン及びジグリセリンから選択される1種又は2種以上を含有する多価アルコールであり、より好ましくはプロピレングリコール、ジプロピレングリコール、1,3-ブチレングリコール及びグリセリンから選択される1種又は2種以上を含む多価アルコールである<29>に記載の水中油型乳化組成物。 <30> Polyhydric alcohol in which component (I) preferably contains one or more selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin and diglycerin More preferably, the oil-in-water emulsion composition according to <29>, which is a polyhydric alcohol containing one or more selected from propylene glycol, dipropylene glycol, 1,3-butylene glycol and glycerin .
<31> 成分(I)の含有量が、好ましくは0.1質量%以上、より好ましくは0.5質量%以上、更に好ましくは1質量%以上であり、また好ましくは12質量%以下、より好ましくは8質量%以下、更に好ましくは5質量%以下、更に好ましくは3質量%以下である<29>又は<30>に記載の水中油型乳化組成物。 <31> The content of component (I) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 12% by mass or less, more preferably 8% by mass. % Or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less, <29> or <30>.
<32> 水中油型乳化組成物の平均乳化粒子径が、好ましくは1μm以上、また好ましくは30μm以下、より好ましくは25μm以下、更に好ましくは20μm以下である<1>~<31>のいずれか1項に記載の水中油型乳化組成物。 <32> The average emulsion particle size of the oil-in-water emulsion composition is preferably 1 μm or more, preferably 30 μm or less, more preferably 25 μm or less, and even more preferably 20 μm or less, any one of <1> to <31> 2. The oil-in-water emulsion composition according to item 1.
<33> <1>~<32>のいずれか1項に記載の水中油型乳化組成物の皮膚外用剤としての使用。 <33> Use of the oil-in-water emulsion composition according to any one of <1> to <32> as a skin external preparation.
実施例1~13、比較例1~11
 表1~5に示す処方に従い、水中油型乳化組成物を調製した。
(製造方法)
工程a:成分1~9、成分16~20を均一に混合し、80℃に加熱し、溶解させる。
工程b:成分10~15を均一に分散させる。
工程c:工程aの調製物に工程bの調製物を加え、均一に混合させ、80℃に加熱し、分散させる。
工程d:成分21~30を40℃で加熱溶解し、25℃まで自然冷却後、均一に混合する。
工程e:工程dの調製物を攪拌しながら工程cの調製物を加え、ホモミキサーで均一に攪拌混合する。
Examples 1 to 13 and Comparative Examples 1 to 11
Oil-in-water emulsion compositions were prepared according to the formulations shown in Tables 1-5.
(Production method)
Step a: Components 1 to 9 and components 16 to 20 are uniformly mixed, heated to 80 ° C. and dissolved.
Step b: Disperse components 10 to 15 uniformly.
Step c: The step b preparation is added to the step a preparation, mixed uniformly, heated to 80 ° C. and dispersed.
Step d: Ingredients 21 to 30 are heated and dissolved at 40 ° C., naturally cooled to 25 ° C. and then uniformly mixed.
Step e: While stirring the preparation of Step d, add the preparation of Step c, and uniformly stir and mix with a homomixer.
 実施例で用いた成分(C)につき、以下に説明する。
・ASI処理酸化チタン(大東化成社製)
 酸化チタン(略球状、平均粒子径0.2μm)98質量%に対し、イソプロピルトリイソステアロイルチタネート1.5質量%、ラウロイルアスパラギン酸ナトリウム0.42質量%、塩化亜鉛0.08質量%で被覆処理したもの。
The component (C) used in the examples will be described below.
-ASI-treated titanium oxide (manufactured by Daito Kasei)
Titanium oxide (substantially spherical, average particle size 0.2 μm) 98% by mass coated with 1.5% by mass of isopropyltriisostearoyl titanate, 0.42% by mass of sodium lauroyl aspartate, and 0.08% by mass of zinc chloride.
・ASI処理酸化鉄(大東化成社製)
 酸化鉄(針状、平均粒子径(長さ)0.9μm、平均幅0.08μm)98質量%に対し、イソプロピルトリイソステアロイルチタネート1.5質量%、ラウロイルアスパラギン酸ナトリウム0.42質量%、塩化亜鉛0.08質量%で被覆処理したもの。
・ ASI-treated iron oxide (manufactured by Daito Kasei)
Iron oxide (needle, average particle size (length) 0.9μm, average width 0.08μm) 98% by mass, isopropyl triisostearoyl titanate 1.5% by mass, sodium lauroyl aspartate 0.42% by mass, zinc chloride 0.08% by mass Coated.
・ASI処理タルク(大東化成社製)
 タルク(板状、平均粒子径15μm、平均厚さ0.25μm)98質量%に対して、イソプロピルトリイソステアロイルチタネート1.5質量%、ラウロイルアスパラギン酸ナトリウム0.42質量%、塩化亜鉛0.08質量%で被覆処理したもの。
・ ASI processing talc (manufactured by Daito Kasei)
98% by mass of talc (plate, average particle size 15μm, average thickness 0.25μm) coated with 1.5% by mass of isopropyl triisostearoyl titanate, 0.42% by mass of sodium lauroyl aspartate, 0.08% by mass of zinc chloride .
・OTS処理酸化チタン
 酸化チタン粉末(略球状、平均粒子径0.2μm)97質量部とオクチルトリエトキシシラン3質量部と、トルエンからなるスラリーを作成し、ビーズミル(シンマルエンタープライゼス社製ダイノミル)を用いて粉砕・解砕を行った。次いで、トルエンを減圧下に加熱留去した後、送風気流型乾燥機を用いて150℃にて4時間加熱処理し、オクチルトリエトキシシラン処理酸化チタン粉末を得た。
・ OTS-treated titanium oxide A slurry consisting of 97 parts by mass of titanium oxide powder (substantially spherical, average particle size 0.2 μm), 3 parts by mass of octyltriethoxysilane, and toluene was prepared, and a bead mill (Dynomill manufactured by Shinmaru Enterprises Co., Ltd.) was used. Using this, pulverization and crushing were performed. Subsequently, toluene was distilled off by heating under reduced pressure, and then heat-treated at 150 ° C. for 4 hours using a blast airflow dryer to obtain octyltriethoxysilane-treated titanium oxide powder.
・OTS処理薄片状酸化亜鉛
 薄片状酸化亜鉛粒子(平均粒子径0.3μm、平均粒子厚さ0.032μm、板状比9、鉄元素含有量0.01mol%)97質量部とオクチルトリエトキシシラン3質量部と、トルエンからなるスラリーを作成し、ビーズミル(シンマルエンタープライゼス社製ダイノミル)を用いて粉砕・解砕を行った。次いで、トルエンを減圧下に加熱留去した後、送風気流型乾燥機を用いて150℃にて4時間加熱処理し、オクチルトリエトキシシラン処理薄片状酸化亜鉛粉末を得た。
-OTS-treated flaky zinc oxide flaky zinc oxide particles (average particle size 0.3μm, average particle thickness 0.032μm, plate ratio 9, iron element content 0.01 mol%) 97 parts by mass and octyltriethoxysilane 3 parts by mass Then, a slurry made of toluene was prepared and pulverized and crushed using a bead mill (Dynomill manufactured by Shinmaru Enterprises Co., Ltd.). Subsequently, toluene was distilled off by heating under reduced pressure, followed by heat treatment at 150 ° C. for 4 hours using an air blast dryer to obtain octyltriethoxysilane-treated flaky zinc oxide powder.
・OTS処理酸化鉄
 酸化鉄粉末(針状、平均粒子径(長さ)0.9μm、平均幅0.08μm)97質量部とオクチルトリエトキシシラン3質量部と、トルエンからなるスラリーを作成し、ビーズミル(シンマルエンタープライゼス社製ダイノミル)を用いて粉砕・解砕を行った。次いで、トルエンを減圧下に加熱留去した後、送風気流型乾燥機を用いて150℃にて4時間加熱処理し、オクチルトリエトキシシラン処理微粒子酸化鉄粉末を得た。
・ OTS treated iron oxide Iron oxide powder (needle, average particle size (length) 0.9μm, average width 0.08μm) 97 parts by mass, octyltriethoxysilane 3 parts by mass, and a slurry made of toluene, bead mill ( Crushing and crushing were performed using a Shinmaru Enterprises Dynomill). Subsequently, toluene was distilled off by heating under reduced pressure, followed by heat treatment at 150 ° C. for 4 hours using an air blast dryer to obtain octyltriethoxysilane-treated fine particle iron oxide powder.
・SI処理酸化亜鉛
 微粒子酸化亜鉛粉末(略球状、平均粒子径0.017μm)97質量部とメチルハイドロジェンポリシロキサン(KF-99P、信越化学工業社製)3質量部とイソプロピルアルコールからなるスラリーを作成し、よく攪拌・粉砕した後、溶媒を減圧下に加熱留去し、空気中160℃で4時間加熱処理を行い、メチルハイドロジェンポリシロキサン表面処理微粒子酸化亜鉛粉末を得た。
・ SI-treated zinc oxide A slurry consisting of 97 parts by mass of fine zinc oxide powder (substantially spherical, average particle size 0.017 μm), 3 parts by mass of methyl hydrogen polysiloxane (KF-99P, manufactured by Shin-Etsu Chemical Co., Ltd.) and isopropyl alcohol is prepared. After thoroughly stirring and pulverizing, the solvent was removed by heating under reduced pressure, and heat treatment was performed in air at 160 ° C. for 4 hours to obtain methylhydrogenpolysiloxane surface-treated fine particle zinc oxide powder.
 表1~5に示す水中油型乳化組成物(試料)について、以下の方法及び基準に従って各種評価を行い、結果を表1~5に併せて示した。 The oil-in-water emulsion compositions (samples) shown in Tables 1 to 5 were subjected to various evaluations according to the following methods and standards, and the results are also shown in Tables 1 to 5.
〔乳化安定性(高温安定性)評価〕
 試料をガラス瓶に入れ、それぞれの試料を60℃の恒温槽に1ヶ月間静置保管した。製造直後の状態を基準として、1ヶ月後の外観変化について、目視及び顕微鏡観察(測定倍率100倍)により下記基準に基づいて判定した。
[Emulsification stability (high temperature stability) evaluation]
Samples were placed in glass bottles, and each sample was stored in a constant temperature bath at 60 ° C. for 1 month. Based on the state immediately after production, the appearance change after one month was judged based on the following criteria by visual observation and microscopic observation (measurement magnification: 100 times).
(判定基準)
 A:目視による観察及び顕微鏡による観察のいずれにおいても外観変化が認められない。
 B:目視による観察では外観変化が認められなかったが、顕微鏡による観察では全体的に乳化粒子の合一が認められた。
 X:目視による観察で外観変化(分離、クリーミング等)が認められた。
(Criteria)
A: Appearance change is not recognized in any of observation by visual observation and observation by a microscope.
B: Appearance change was not recognized by visual observation, but coalescence of emulsified particles was observed as a whole by microscopic observation.
X: Appearance change (separation, creaming, etc.) was observed by visual observation.
〔せん断耐性評価〕
 レオメーター(Physica MCR301;Anton Paar社製)を用いて以下の条件で試料にせん断を加え、下記粘度変化率を測定した。また、合わせてせん断を加える前後の試料の顕微鏡観察(測定倍率100倍)を行い、外観観察を合わせて行った。これらの結果から、以下の判定基準に基づき、評価を行った。

測定条件:定常流測定モード、せん断速度:17(1/s)、プレート:PP25、測定時間:300秒(測定間隔15秒)、測定温度25℃

粘度変化率=(測定開始300秒時のせん断粘度)/(測定開始15秒時のせん断粘度)
[Shear resistance evaluation]
Using a rheometer (Physica MCR301; manufactured by Anton Paar), the sample was sheared under the following conditions, and the following viscosity change rate was measured. In addition, the sample was observed with a microscope (measurement magnification: 100 times) before and after applying shear, and the appearance was also observed. From these results, evaluation was performed based on the following criteria.

Measurement conditions: steady flow measurement mode, shear rate: 17 (1 / s), plate: PP25, measurement time: 300 seconds (measurement interval 15 seconds), measurement temperature 25 ° C

Viscosity change rate = (shear viscosity at the start of measurement 300 seconds) / (shear viscosity at the start of measurement 15 seconds)
(判定基準)
 A:粘度変化率が0.8以上で、顕微鏡による観察で乳化粒子の合一が認められない。
 B:粘度変化率が0.8以上で、顕微鏡による観察で乳化粒子の合一が認められた。
 X:粘度変化率が0.8未満
(Criteria)
A: The viscosity change rate is 0.8 or more, and coalescence of emulsified particles is not observed by observation with a microscope.
B: Viscosity change rate was 0.8 or more, and coalescence of emulsified particles was observed by microscopic observation.
X: Viscosity change rate is less than 0.8
〔使用感評価(官能評価)〕
 専門パネラー10名に試料を使用してもらい、塗布後にみずみずしさを感じると回答した人数により、評価を行った。
[Usage evaluation (sensory evaluation)]
The evaluation was performed by the number of respondents who asked 10 professional panelists to use samples and felt fresh after application.
〔紫外線防御能評価〕
 試料をPMMAプレート上に1.3mg/cm2の塗布量で均一に塗布し、乾燥させた。その後、SPFアナライザー(UV-2000S;Labsphere社製)を用いて、(in vitro)SPF値を測定し、以下の評価基準に基づき評価を行った。
[UV protection evaluation]
The sample was uniformly coated on a PMMA plate at a coating amount of 1.3 mg / cm 2 and dried. Then, using SPF analyzer (UV-2000S; manufactured by Labsphere), SPF value was measured (in vitro) and evaluated based on the following evaluation criteria.
(評価基準)
 A:SPF値が40以上
 B:SPF値が30以上40未満
 C:SPF値が20以上30未満
 X:SPF値が20未満
(Evaluation criteria)
A: SPF value is 40 or more B: SPF value is 30 or more and less than 40 C: SPF value is 20 or more and less than 30 X: SPF value is less than 20
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
*1:ニッコール BB-2、日本サーファクタント工業社製
*2:ニッコール BB-5、日本サーファクタント工業社製
*3:ニッコール BC-2、日本サーファクタント工業社製
*4:ニッコール BS-2、日本サーファクタント工業社製
*5:ニッコール BL-2、日本サーファクタント工業社製
*6:Phospholipid PCSH70、日本精化社製、ホスファチジルコリン含量70質量%以上
*7:COATSOME NC-21、日油社製、ホスファチジルコリン含量90質量%以上
*8:スフィンゴリピッド E、花王社製
*9:ユビナール T-150、BASF社製
*10:ユビナール A PLUS GURANULAR、BASF社製
*11:ユビナール MC80、BASF社製
*12:サラコス913、日清オイリオグループ社製
*13:シリコーン FK96-6cs、信越化学工業社製
*14:SIMULGEL EG(純分換算値)、SEPPIC社製
*15:エコーガム、DSP五協フード&ケミカル社製
* 1: Nikkor BB-2, manufactured by Nippon Surfactant
* 2: Nikkor BB-5, manufactured by Nippon Surfactant
* 3: Nikkor BC-2, manufactured by Nippon Surfactant
* 4: Nikkor BS-2, manufactured by Nippon Surfactant
* 5: Nikkor BL-2 manufactured by Nippon Surfactant
* 6: Phospholipid PCSH70, manufactured by Nippon Seika Co., Ltd., phosphatidylcholine content 70% by mass or more
* 7: COATSOME NC-21, NOF Corporation, phosphatidylcholine content 90% by mass or more
* 8: Sphingolipid E, manufactured by Kao Corporation
* 9: Yubinar T-150, manufactured by BASF
* 10: Yubinar A PLUS GURANULAR, manufactured by BASF
* 11: Yubinar MC80, manufactured by BASF
* 12: Saracos 913, manufactured by Nisshin Oillio Group
* 13: Silicone FK96-6cs, manufactured by Shin-Etsu Chemical Co., Ltd.
* 14: SIMULGEL EG (Pure value), manufactured by SEPPIC
* 15: Echo Gum, DSP Gokyo Food & Chemical
 以下、本発明の処方例を示す。いずれも実施例と同等の効果を奏するものである。 Hereafter, the prescription example of this invention is shown. Both have the same effects as the embodiment.
処方例1 (水中油型化粧下地)
                          含有量(質量%)
 ベヘネス-2(*1)                     1.0
 水添レシチン(*6)                    1.0
 ASI処理酸化チタン                    10.5
 ASI処理酸化鉄                       1.05
 ASI処理タルク                       0.8
 パラメトキシケイ皮酸2-エチルヘキシル(*11)        5.0
 2-(4-ジエチルアミノ-2-ヒドロキシベンゾイル)安息香酸へキシルエステル(*10)
                              2.0
 2,4-ビス[[4-(2-エチルヘキシルオキシ)-2-ヒドロキシ]-フェニル]-6-(4-メトキシフェニル)-1,3,5-トリアジン(*16)               0.5
 2,4,6-トリス[4-(2-エチルヘキシルオキシカルボニル)アニリノ]-1,3,5-トリアジン(*9)                              2.0
 イソノナン酸イソノニル(*12)               3.0
 セバシン酸ジイソプロピル                 2.0
 ジメチコン(*13)                     0.5
 EDTA-2Na                         0.02
 グリセリン                        0.5
 エタノール                        10.0
 海藻抽出物(*17)                     0.1
 加水分解コラーゲン(*18)                 0.1
 ローヤルゼリーエキス(*19)                0.1
 ハトムギ種子エキス(*20)                 0.1
 (アクリル酸Na/アクリロイルジメチルタウリンNa)コポリマー(*14)
                                                            0.86
 1,3-ブチレングリコール                  1.0
 ヒアルロン酸Na(*21)                   0.01
 キサンタンガム(*15)                   0.1
 イソヘキサデカン                     0.52
 ポリソルベート80                     0.17
 オレイン酸ソルビタン                   0.06
 精製水                          残量
Formulation example 1 (oil-in-water makeup base)
Content (mass%)
Behenez-2 (* 1) 1.0
Hydrogenated lecithin (* 6) 1.0
ASI-treated titanium oxide 10.5
ASI-treated iron oxide 1.05
ASI processing talc 0.8
2-Ethylhexyl paramethoxycinnamate (* 11) 5.0
2- (4-Diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester (* 10)
2.0
2,4-Bis [[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (* 16) 0.5
2,4,6-Tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine (* 9) 2.0
Isononyl isononanoate (* 12) 3.0
Diisopropyl sebacate 2.0
Dimethicone (* 13) 0.5
EDTA-2Na 0.02
Glycerin 0.5
Ethanol 10.0
Seaweed extract (* 17) 0.1
Hydrolyzed collagen (* 18) 0.1
Royal Jelly Extract (* 19) 0.1
Pearl seed extract (* 20) 0.1
(Na acrylate / acryloyl dimethyl taurine Na) copolymer (* 14)
0.86
1,3-butylene glycol 1.0
Hyaluronic acid Na (* 21) 0.01
Xanthan gum (* 15) 0.1
Isohexadecane 0.52
Polysorbate 80 0.17
Sorbitan oleate 0.06
Purified water remaining
*16:BASF社製:チノソーブS
*17:丸善製薬社製:海藻エキスM
*18:成和化成社製:プロモイスWU-32R
*19:一丸ファルコス社製:ローヤルゼリーエキス
*20:丸善製薬社製:ヨクイニン抽出液BG-S
*21:キッコーマンバイオケミファ社製:ヒアルロン酸FCH-SU
* 16: Made by BASF: Chinosorb S
* 17: Maruzen Pharmaceutical Co., Ltd .: Seaweed Extract M
* 18: Seiwa Kasei Co., Ltd .: Promois WU-32R
* 19: Made by Ichimaru Falcos: Royal Jelly Extract
* 20: Made by Maruzen Pharmaceutical Co., Ltd .: Yokuinin extract BG-S
* 21: Kikkoman Biochemifa Corporation: Hyaluronic acid FCH-SU
処方例2 (水中油型サンスクリーン)
                          含有量(質量%)
 ベヘネス-2(*1)                     0.5
 水添レシチン(*6)                    1.5
 OTS処理薄片状酸化亜鉛                   2.5
 SI処理酸化亜鉛                      7.5
 ポリシリコーン-15(*22)                 1.0
 2-(4-ジエチルアミノ-2-ヒドロキシベンゾイル)安息香酸へキシルエステル
(*10)                                                    1.5
 2,4-ビス[[4-(2-エチルヘキシルオキシ)-2-ヒドロキシ]-フェニル]-6-(4-メトキシフェニル)-1,3,5-トリアジン(*16)              1.5
 2,4,6-トリス[4-(2-エチルヘキシルオキシカルボニル)アニリノ]-1,3,5-トリアジン(*9)                                2.0
 ジカプリン酸ネオペンチルグリコール            2.5
 セバシン酸ジイソプロピル                 5.0
 安息香酸アルキル(C12-15)                2.5
 ジメチコン(*13)                     1.0
 グリチルレチン酸ステアリル(*23)             0.1
 EDTA-2Na                         0.02
 グリセリン                        3.0
 DPG                                                       2.0
 エタノール                        5.0
 フェノキシエタノール                   0.3
 クロルフェネシン                     0.2
 オトギリソウ花/葉/茎エキス(*24)            0.1
 オリーブ葉エキス(*25)                  0.1
 (アクリル酸Na/アクリロイルジメチルタウリンNa)コポリマー(*14)
                                                            0.83
 イソヘキサデカン                     0.5
 ポリソルベート80                     0.17
 オレイン酸ソルビタン                   0.06
 1,3-ブチレングリコール                  2.0
 キサンタンガム(*15)                   0.1
 精製水                          残量
Formulation example 2 (oil-in-water sunscreen)
Content (mass%)
Behenez-2 (* 1) 0.5
Hydrogenated lecithin (* 6) 1.5
OTS-treated flaky zinc oxide 2.5
SI-treated zinc oxide 7.5
Polysilicone-15 (* 22) 1.0
2- (4-Diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester (* 10) 1.5
2,4-Bis [[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (* 16) 1.5
2,4,6-Tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine (* 9) 2.0
Neopentyl glycol dicaprate 2.5
Diisopropyl sebacate 5.0
Alkyl benzoate (C12-15) 2.5
Dimethicone (* 13) 1.0
Stearyl glycyrrhetinate (* 23) 0.1
EDTA-2Na 0.02
Glycerin 3.0
DPG 2.0
Ethanol 5.0
Phenoxyethanol 0.3
Chlorphenesin 0.2
Hypericum flower / leaf / stem extract (* 24) 0.1
Olive leaf extract (* 25) 0.1
(Na acrylate / acryloyl dimethyl taurine Na) copolymer (* 14)
0.83
Isohexadecane 0.5
Polysorbate 80 0.17
Sorbitan oleate 0.06
1,3-butylene glycol 2.0
Xanthan gum (* 15) 0.1
Purified water remaining
*22:DSM Nutritional Products社製:パルソールSLX
*23:丸善製薬社製:シーオーグレチノール
*24:一丸ファルコス社製:ファルコレックス オトギリソウ B
*25:丸善製薬社製:オリーブ葉抽出液BG
* 22: DSM Nutritional Products: Pulsol SLX
* 23: Maruzen Pharmaceutical Co., Ltd .: Sea Augretinol
* 24: Made by Ichimaru Falcos: Falco Rex Hypericum B
* 25: Maruzen Pharmaceutical Co., Ltd .: Olive leaf extract BG

Claims (6)

  1.  下記成分(A)~(D)を含有し、成分(B)に対する成分(A)の含有質量比〔(A)/(B)〕が、0.06以上18以下である水中油型乳化組成物。
     (A) アルキル基又はアルケニル基の炭素数が20以上24以下で、エチレンオキサイドの平均付加モル数が1.5以上4以下であるポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルケニルエーテル
     (B) リン脂質
     (C) 疎水化処理粉末
     (D) 水
    An oil-in-water emulsion composition comprising the following components (A) to (D), wherein the mass ratio [(A) / (B)] of component (A) to component (B) is 0.06 or more and 18 or less.
    (A) Polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether having an alkyl group or alkenyl group having 20 to 24 carbon atoms and an average addition mole number of ethylene oxide of 1.5 to 4 (B) Phospholipid (C ) Hydrophobized powder (D) Water
  2.  成分(A)及び成分(B)の合計含有量が、0.5質量%以上6質量%以下である請求項1に記載の水中油型乳化組成物。 The oil-in-water emulsion composition according to claim 1, wherein the total content of the component (A) and the component (B) is from 0.5% by mass to 6% by mass.
  3.  更に、成分(E)として液状油を含有する請求項1又は2に記載の水中油型乳化組成物。 Furthermore, the oil-in-water emulsion composition according to claim 1 or 2, further comprising liquid oil as component (E).
  4.  前記成分(E)が、パラメトキシケイ皮酸2-エチルヘキシル、サリチル酸2-エチルヘキシル、サリチル酸ホモメンチル、オクトクリレン及びジメチコジエチルベンザルマロネートから選択される1種又は2種以上を含む液状油である請求項3に記載の水中油型乳化組成物。 The component (E) is a liquid oil containing one or more selected from 2-ethylhexyl paramethoxycinnamate, 2-ethylhexyl salicylate, homomenthyl salicylate, octocrylene, and dimethicodiethylbenzalmalonate. Item 4. The oil-in-water emulsion composition according to Item 3.
  5.  更に、成分(F)として25℃で固体状の紫外線吸収剤を含有する請求項1~4のいずれか1項に記載の水中油型乳化組成物。 The oil-in-water emulsion composition according to any one of claims 1 to 4, further comprising an ultraviolet absorber that is solid at 25 ° C as component (F).
  6.  請求項1~5のいずれか1項に記載の水中油型乳化組成物の皮膚外用剤としての使用。 Use of the oil-in-water emulsion composition according to any one of claims 1 to 5 as a skin external preparation.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108524309A (en) * 2018-07-17 2018-09-14 赵宏伟 A kind of sun care preparations and preparation method with water proofing property
WO2020128556A1 (en) * 2018-12-19 2020-06-25 L V M H Recherche Oil-in-water emulsified cosmetic with ultraviolet ray-protecting effect
CN115397520A (en) * 2020-03-26 2022-11-25 花王株式会社 Oil-in-water type emulsion cosmetic

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7275939B2 (en) * 2018-09-28 2023-05-18 住友大阪セメント株式会社 Method for producing surface-treated metal oxide particles
JP7308085B2 (en) * 2019-06-28 2023-07-13 花王株式会社 Oil-in-water emulsified cosmetic
JP2021138621A (en) * 2020-03-02 2021-09-16 花王株式会社 Oil-in-water-type emulsified cosmetic material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010229067A (en) * 2009-03-26 2010-10-14 Kose Corp Emulsified cosmetic
JP2012250916A (en) * 2011-05-31 2012-12-20 Nippon Zettoc Co Ltd Oil-in-water type emulsified cosmetic
JP2013209303A (en) * 2012-03-30 2013-10-10 Kose Corp Treated powder for cosmetic and cosmetic blended therewith
JP2014114274A (en) * 2012-11-14 2014-06-26 Kao Corp Oil-in-water type emulsified composition
JP2014240382A (en) * 2013-05-15 2014-12-25 株式会社コーセー Emulsion cosmetic preparation
JP2016084330A (en) * 2014-10-28 2016-05-19 富士フイルム株式会社 Sunscreen cosmetic

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005272389A (en) 2004-03-25 2005-10-06 Kose Corp Oil-in-water type emulsifying cosmetic
JP4401875B2 (en) 2004-06-24 2010-01-20 株式会社資生堂 Oil-in-water emulsion composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010229067A (en) * 2009-03-26 2010-10-14 Kose Corp Emulsified cosmetic
JP2012250916A (en) * 2011-05-31 2012-12-20 Nippon Zettoc Co Ltd Oil-in-water type emulsified cosmetic
JP2013209303A (en) * 2012-03-30 2013-10-10 Kose Corp Treated powder for cosmetic and cosmetic blended therewith
JP2014114274A (en) * 2012-11-14 2014-06-26 Kao Corp Oil-in-water type emulsified composition
JP2014240382A (en) * 2013-05-15 2014-12-25 株式会社コーセー Emulsion cosmetic preparation
JP2016084330A (en) * 2014-10-28 2016-05-19 富士フイルム株式会社 Sunscreen cosmetic

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108524309A (en) * 2018-07-17 2018-09-14 赵宏伟 A kind of sun care preparations and preparation method with water proofing property
WO2020128556A1 (en) * 2018-12-19 2020-06-25 L V M H Recherche Oil-in-water emulsified cosmetic with ultraviolet ray-protecting effect
CN115397520A (en) * 2020-03-26 2022-11-25 花王株式会社 Oil-in-water type emulsion cosmetic

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