WO2022137636A1 - Oil-in-water type sunscreen cosmetic - Google Patents

Oil-in-water type sunscreen cosmetic Download PDF

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Publication number
WO2022137636A1
WO2022137636A1 PCT/JP2021/029915 JP2021029915W WO2022137636A1 WO 2022137636 A1 WO2022137636 A1 WO 2022137636A1 JP 2021029915 W JP2021029915 W JP 2021029915W WO 2022137636 A1 WO2022137636 A1 WO 2022137636A1
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Prior art keywords
oil
mass
total amount
water
cosmetics
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PCT/JP2021/029915
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French (fr)
Japanese (ja)
Inventor
圭太 西田
堅登 上野
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株式会社 資生堂
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Priority to CN202180079224.4A priority Critical patent/CN116710042A/en
Priority to JP2022571035A priority patent/JPWO2022137636A1/ja
Publication of WO2022137636A1 publication Critical patent/WO2022137636A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/14—Liposomes; Vesicles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

  • the present invention relates to an underwater oil type sunscreen cosmetic having improved vibration stability and water resistance in sunscreen cosmetics.
  • Some amphipathic substances form spherical closures consisting of bilayer membranes (lamella liquid crystals) in the aqueous phase, and such bilayer membrane closures are called vesicles. Vesicles can retain water-soluble components inside the closed body, oil-based components can be retained inside the bilayer membrane, and can be expected to have effects such as improving the stability of the system, so they are the basis of cosmetics. It is used as an agent.
  • vesicles are formed by using a specific polyoxyethylene hydrogenated castor oil derivative as an amphipathic substance, and by containing this as an emulsifier, cosmetics that are not sticky and have a good usability. Is disclosed that was obtained.
  • a silicone-based surfactant can be mentioned as an amphipathic substance forming a vesicle.
  • the vesicle formed by the silicone-based surfactant is preferably used because it has advantages such as a composition having no stickiness and a good usability and being easy to prepare.
  • Patent Document 3 the stability of vesicles was improved by adding a water-soluble low-molecular-weight surfactant to a vesicle-containing aqueous solution previously formed by mixing an aqueous formulation and a silicone-based surfactant. Is described. Further, Patent Document 4 describes that the stability of the vesicle is improved by adding the anionic surfactant after forming the vesicle from the silicone-based surfactant.
  • Patent Document 4 shows that the stability tends to decrease when the oil content is 0.4% by mass or more.
  • Patent Document 5 discloses a technique of dispersing a liquid phase insoluble in water in an outer phase by a vesicle including an inner phase.
  • a vesicle including an inner phase since emulsification by vesicles is unstable and there are restrictions on practical use, the amount of vesicles to be blended tends to be large, and as is generally known, stickiness due to a surfactant forming vesicles is a problem. In some cases.
  • An object of the present invention is to provide an oil-in-water emulsified sunscreen cosmetic having excellent stability and water resistance and high ultraviolet protection.
  • the inventors have used a vesicle formed by a specific silicone-based surfactant in the presence of a specific aqueous component in an oil-in-water emulsified composition as a precursor.
  • a specific silicone-based surfactant in the presence of a specific aqueous component in an oil-in-water emulsified composition as a precursor.
  • nanodisc is a flat plate-shaped lamellar liquid crystal closure whose precursor is a vesicle (lamellar liquid crystal spherical closure) formed by an amphipathic substance, and contains a water-soluble component inside the closure. However, it refers to a substance having an amphipathic group at the edge portion. Nanodiscs exist as precursor vesicles in oil-free compositions, and the vesicles undergo structural changes (hereinafter also referred to as "transfers”) to nanodisks by adding oil and emulsifying.
  • an anionic surfactant and an oil component are added to a vesicle aqueous dispersion obtained by mixing an aqueous component selected from a monohydric alcohol and a divalent alcohol with a polyoxyalkylene-modified silicone to form a vesicle. It is obtained by adding and dispersing while applying a strong stirring force.
  • Nanodiscs exist in a state of being adsorbed on the oil-water interface in an emulsified state, and contribute to emulsification stability.
  • the amphipathic substance forming the vesicle is a silicone-based surfactant
  • the nanodisk of the present invention is also referred to as “silicone nanodisk”.
  • the present invention (A) Aqueous component selected from monohydric alcohols and divalent alcohols, (B) Polyoxyalkylene modified silicone, (C) Oil containing polar oil, (D) An ultraviolet scattering agent having a hydrophobic surface, and (E) Containing anionic surfactant,
  • Aqueous component selected from monohydric alcohols and divalent alcohols,
  • B) Polyoxyalkylene modified silicone (C) Oil containing polar oil, (D) An ultraviolet scattering agent having a hydrophobic surface, and (E) Containing anionic surfactant,
  • the aqueous component (A) is monohydric alcohol alone, it is 1 to 15% by mass with respect to the total amount of cosmetics, and when dihydric alcohol is alone, it is 1 to 20% by mass with respect to the total amount of cosmetics.
  • the total amount is 1 to 45% by mass with respect to the total amount of cosmetics.
  • the ratio of the low molecular weight oil to the total amount of the oil excluding the ultraviolet absorber is 50% or less in terms of mass ratio, which is an oil-in-water sunscreen.
  • the oil-in-water emulsified cosmetic according to the present invention is characterized in that nanodisks made of the (B) polyoxyalkylene-modified silicone are attached to the oil-water interface.
  • the cosmetic according to the present invention becomes an oil-in-water emulsion having a high emulsifying power by the above composition, a large amount of an ultraviolet protective agent (ultraviolet absorber and ultraviolet scattering agent) is blended in the oil phase. Can be done. In addition, vibration stability and water resistance can be improved as compared with the conventional emulsification by vesicles. Therefore, it is possible to realize a cosmetic that is more suitable for carrying. Furthermore, since the silicone nanodisc according to the present invention has sufficient emulsifying power, it is also possible to add a water-soluble agent such as a salt-type whitening agent, which tends to have poor stability when added to the aqueous phase, which is usually the outer phase. It becomes.
  • a water-soluble agent such as a salt-type whitening agent
  • the cosmetic according to the present invention comprises (A) an aqueous component selected from a monohydric alcohol and a divalent alcohol, (B) a polyoxyalkylene-modified silicone, (C) an oil containing polar oil, and (D) a hydrophobic surface. It is characterized by containing an ultraviolet scattering agent having and (E) an anionic surfactant.
  • A an aqueous component selected from a monohydric alcohol and a divalent alcohol
  • B a polyoxyalkylene-modified silicone
  • C an oil containing polar oil
  • D a hydrophobic surface. It is characterized by containing an ultraviolet scattering agent having and (E) an anionic surfactant.
  • the (A) aqueous component (hereinafter, may be simply referred to as "(A) component”) blended in the cosmetic according to the present invention is one or more selected from monohydric alcohol and dihydric alcohol.
  • the monohydric alcohol is not particularly limited as long as it is usually used for cosmetics, and examples thereof include ethyl alcohol (ethanol), normal propyl alcohol, and isopropyl alcohol, and in the present invention, ethyl alcohol is preferable.
  • the divalent alcohol is not particularly limited as long as it is usually used for cosmetics, but examples thereof include 1,3-butylene glycol, dipropylene glycol and the like, and dipropylene glycol is preferable in the present invention.
  • the surface of the spherical vesicles formed by the surfactant is entirely covered with hydrophilic groups, but since nanodiscs have lipophilic groups at the edges, it is difficult to generate nanodisks in water.
  • the solvent effect hydrophilizes the surfactant (polyether-modified silicone in the present invention), resulting in accelerated transfer from spherical vesicles to nanodisks.
  • the blending amount is 1 to 15% by mass with respect to the total amount of cosmetics
  • the divalent alcohol is used alone
  • the blending amount is 1 to 15% by mass with respect to the total amount of cosmetics. It is 1 to 20% by mass.
  • the total blending amount is 1 to 45% by mass, preferably 1 to 35% by mass, based on the total amount of the cosmetics. More preferably, it is preferably blended with the concentration of the monohydric alcohol and the divalent alcohol satisfying the following formula (1) as the upper limit.
  • the blending amount of monohydric alcohol alone, the blending amount of dihydric alcohol alone, and the total blending amount of monohydric alcohol and divalent alcohol is less than 1% by mass, vesicles may not be generated or the structure may be disturbed and emulsification may not be possible. .. Further, when the blending amount of the monohydric alcohol alone exceeds 15% by mass or when the blending amount of the dihydric alcohol alone exceeds 20% by mass, the blending ratio of the monohydric alcohol and the dihydric alcohol is further in the above formula (1).
  • the (B) polyoxyalkylene-modified silicone (hereinafter, may be simply referred to as “component (B)”) blended in the cosmetic according to the present invention has a polysiloxane structure as a hydrophobic group and a polyoxyalkylene as a hydrophilic group. It is a surfactant having a structure, and is preferably a water-soluble silicone-based surfactant in which a part of the methyl group of dimethicone is replaced with polyethylene glycol. Specifically, it is expressed by the following equation (2).
  • R 1 is hydrogen or an alkyl group having 1 to 6 carbon atoms, and may be the same or independently different from each other.
  • At least one of A is the formula (3): -(CH 2 ) a- (C 2 H 4 O) b- (C 3 H 6 O) c-R 2 (3)
  • the other A is a hydrogen or an alkyl group having 1 to 6 carbon atoms, which may be the same or independently different from each other.
  • R 2 in the formula (3) is hydrogen or an alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 6, b is an integer of 0 to 50, c is an integer of 0 to 50, and b + c is at least 5 or more. be.
  • m is an integer of 1 to 200
  • n is an integer of 0 to 50.
  • the (B) polyoxyalkylene-modified silicone of the present invention preferably has an HLB of less than 10 in the HLB calculation according to the Griffin formula.
  • PEG-12 dimethicone in which c is 0 and b is 12 in the above formula (3) is particularly preferable. Further, it is more preferable that PEG-12 dimethicone has an HLB of less than 10.
  • Examples of commercially available products of PEG-12 dimethicone include DOWNSIL TM ES-5373, SH3772M, SH3773M, SH3775M (all manufactured by Dow Toray), IM-22 (manufactured by Wacker Chemical Co., Ltd.) and the like.
  • the blending amount of the component (B) is not particularly limited as long as it can form a vesicle that is a precursor of nanodisks, but is, for example, 0.1 to 5.0% by mass, preferably 0, based on the total amount of cosmetics. .3 to 3.0% by mass, more preferably 0.8 to 2.0% by mass. If the blending amount is less than 0.1% by mass, vesicles may not be sufficiently formed, and if it exceeds 5.0% by mass, the stability of the vesicles may be inferior.
  • the cosmetic according to the present invention contains nanodiscs made of the surfactant of the component (B).
  • Vesicles which are precursors of nanodisks, can be formed by a conventional method. Specifically, a vesicle composed of the component (B) is formed by mixing and stirring (A) the aqueous component and (B) the polyoxyalkylene-modified silicone.
  • a vesicle composed of the component (B) is formed by mixing and stirring (A) the aqueous component and (B) the polyoxyalkylene-modified silicone.
  • water or an aqueous component usually used in cosmetics may be blended in an amount within a range that does not impair the stability of the vesicle.
  • the average particle size of the vesicle is not particularly limited, but is usually about 30 nm to 150 nm.
  • the (C) oil component (hereinafter, may be simply referred to as “(C) component”) blended in the cosmetics according to the present invention refers to an oil content that contains at least polar oil indispensable.
  • the oil content (C) of the present invention contains a low molecular weight oil content
  • the ratio of the low molecular weight oil content to the total amount of the oil content excluding the ultraviolet absorber shall be 50% or less in terms of mass ratio. Needs.
  • Examples of the polar oil blended in the cosmetics according to the present invention include ester oils, particularly ester oils having an IOB value of about 0.1 to 0.6, and oil-soluble and polar ultraviolet absorbers.
  • ester oil having an IOB value of about 0.1 to 0.6 are not limited, but are limited to diisopropyl sebacate, pentaerythrityl tetraethylhexanoate, cetyl ethylhexanate, jojoba oil, and di (phytosteryl / octyl) lauroyl glutamate.
  • oil-soluble and polar UV absorber may be those normally blended in sunscreen cosmetics, and are not particularly limited, but specific examples include ethylhexyl methoxycinnamate, octocrylene, and dimethico.
  • organic UV absorbers such as butylphenol, phenylbenzimidazole sulfonic acid, homosalate, ethylhexyl salicylate, terephthalylidenedicanfursulfonic acid, and drometrizoletrisiloxane.
  • the polar oil used in the present invention one kind or a combination of two or more kinds may be used.
  • the oil (C) of the present invention may further contain one or more selected from hydrocarbon oils and silicone oils.
  • hydrocarbon oil examples include isododecane, isohexadecane, hydrogenated polydecene, isoparaffin, liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalane, petrolatum, microcrystalline wax and the like.
  • silicone oil examples include chain polysiloxane (eg, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.) and cyclic polysiloxane (eg, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethyl, etc.).
  • chain polysiloxane eg, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.
  • cyclic polysiloxane eg, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethyl, etc.
  • Silicone resin forming a three-dimensional network structure, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic Examples include silicones.
  • the ratio of the low molecular weight oil to the total amount of the oil excluding the ultraviolet absorber is set to 50% or less in terms of mass ratio. There must be. This is because if the ratio of the small molecule oil to the total amount of the oil excluding the ultraviolet absorber exceeds 50%, sufficient vibration stability cannot be obtained. Since it is not necessary to add a small molecule oil as an oil in the cosmetic according to the present invention, the lower limit of the ratio of the small molecule oil to the total amount of the oil excluding the ultraviolet absorber is 0%. ..
  • the small molecule oil content refers to an oil content having a volatilization rate at 25 ° C. and a weight change rate of 30% or more per hour.
  • the volatilization rate refers to the value of the rate of change in weight per hour measured under the condition of 25 ° C. by placing a filter paper on a glass petri dish, dropping about 0.2 g of a sample, and using a gravimetric method.
  • Specific examples of the small molecule oil include isododecane, low-viscosity volatile silicone (low-viscosity dimethicone) having an average degree of polymerization of less than 650, and the like.
  • Examples of commercially available small molecule oil products include Creasil ID CG (manufactured by Shima Trading Co., Ltd.) and KF-96L-1.5CS (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the volatilization rate of Creasil ID CG is 90% or more, and the volatilization rate of KF-96L-1.5CS is about 50%.
  • At least polar oil may be included as the oil component (C) of the present invention. Therefore, the cosmetic of the present invention includes an embodiment containing only polar oil as an oil component.
  • the amount of the oil (C) blended in the cosmetic according to the present invention is not particularly limited as long as it is an amount normally used for blending an ultraviolet scattering agent in the oil phase, but for example, with respect to the total amount of the cosmetic. It is mentioned that it is 1 to 40% by mass. (C) If the blending amount of the oil exceeds 40% by mass, the stability and usability tend to decrease.
  • a UV absorber When a UV absorber is blended, it is preferably 1% by mass or more, or 3 to 30% by mass or 5 to 25, based on the total amount of the cosmetic, from the viewpoint of obtaining a sufficient UV protection effect by the UV absorber. It is more preferable to use% by mass.
  • the (D) ultraviolet scattering agent (hereinafter, may be simply referred to as “(D) component”) blended in the cosmetic according to the present invention is not particularly limited, but is appropriately selected from those usually used in cosmetics. be able to. Specific examples include metal oxides such as titanium oxide, zinc oxide, iron oxide, cerium oxide, and tungsten oxide. In the present invention, titanium oxide and zinc oxide are preferable.
  • the (D) ultraviolet scattering agent used in the present invention may be either untreated or hydrophobized as long as the surface of the particles is hydrophobic.
  • Various types of hydrophobizing surface treatments can be used to hydrophobize the surface.
  • Examples of the method for hydrophobizing surface treatment include silicone oils such as methylhydrogenpolysiloxane, dimethylpolysiloxane, and methylphenylpolysiloxane, and methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, and the like.
  • the blending amount of the component (D) is not particularly limited, but is usually 1% by mass or more, for example, 1 to 30% by mass, preferably 1 to 20% by mass with respect to the total amount of the cosmetic. If the blending amount is less than 1% by mass, it is difficult to obtain a sufficient UV protection effect, and if it exceeds 30% by mass, the stability tends to deteriorate. Since the cosmetic according to the present invention has excellent emulsification stability, it is possible to add an ultraviolet scattering agent exceeding 10% by mass.
  • the cosmetic according to the present invention is a powder-type composition in oil in water in which (D) an ultraviolet scattering agent is dispersed in oil droplets as an internal phase.
  • the oil phase is preferably 1 to 50% by mass with respect to the total amount of the cosmetics.
  • the (E) anionic surfactant (hereinafter, may be simply referred to as "(E) component") blended in the cosmetics according to the present invention may be any one usually used for cosmetics, and the above-mentioned ( B) A surfactant other than a silicone-based surfactant such as polyoxyalkylene-modified silicone, which has an anionic hydrophilic group such as a carboxylic acid, a sulfonic acid, and a surfactant having a phosphoric acid structure.
  • the formulation of anionic surfactant stabilizes the nanodisc.
  • an anionic surfactant having a Krafft temperature higher than room temperature.
  • the silicone-based surfactant and the anionic surfactant are likely to mix and interact with each other, which tends to prevent the transfer from the vesicle to the nanodisc. be.
  • a sulfonate-type anionic surfactant is preferable.
  • the sulfonate-type anionic surfactant include sulfosuccinic acid diester salt, alkylallyl sulfonate, alkyl ether sulfonate, sulfosuccinic acid ester salt, acylmethyl taurine salt, acyl taurine salt, potassium cetyl phosphate, and potassium cocoyl glutamate. And so on. Among them, it is preferable to select and use from acylmethyltaurine salt, potassium cetylphosphate and potassium cocoylglutamate.
  • N-acylmethyl taurine salt as the (E) anionic surfactant.
  • the N-acylmethyl taurine salts represented by the following formula (4) the N-stearoyl-N-methyl taurine salt is preferable.
  • the blending amount of the component (E) is preferably 0.01 to 1% by mass, more preferably 0.01 to 0.1% by mass, and 0.01 to 0. It is more preferably 06% by mass. If the blending amount is less than 0.01% by mass, the nanodisk may not be sufficiently stable, and if it exceeds 1% by mass, the vesicle that is the precursor of the nanodisk is solubilized or the formation of the nanodisk is hindered. In some cases. Further, the mixing amount ratio of (B) polyoxyalkylene-modified silicone and (E) anionic surfactant is 1: 0 in terms of mass ratio. It is preferably 01 to 1: 0.06.
  • a whitening agent is added to sunscreen cosmetics, but it is generally known that when a salt-type whitening agent is added to the aqueous phase, which is the outer phase, the stability tends to deteriorate. Since the cosmetic according to the present invention is emulsified by nanodiscs formed of a specific silicone-based surfactant and the emulsifying power is enhanced by limiting the oil content to be blended, a salt-type whitening agent is blended in the aqueous phase. Even so, it has the effect of being excellent in vibration stability.
  • the (F) whitening agent (hereinafter, may be simply referred to as "(F) component”) blended in the cosmetic according to the present invention is not particularly limited as long as it is normally blended in the cosmetic.
  • Specific examples include L-ascorbic acid and its derivatives, tranexamic acid and its derivatives, alkoxysalicylic acid and its derivatives, glycyrrhizic acid and its derivatives, nicotinic acid and its derivatives, and the like.
  • one kind or a combination of two or more kinds of the above-mentioned agents may be blended.
  • L-ascorbic acid monoalkyl esters such as L-ascorbic acid monostearate, L-ascorbic acid monopalmitate, and L-ascorbic acid monoolate; L-ascorbic acid monophosphate ester, L.
  • L-L-ascorbic acid monoesters such as ascorbic acid-2-sulfate ester
  • L-ascorbic acid dialkyl esters such as L-ascorbic acid distearate, L-ascorbic acid dipalmitate, L-ascorbic acid dioleate
  • L-ascorbic acid tri L-ascorbic acid trialkyl esters such as stearate, L-ascorbic acid tripalmitate, L-ascorbic acid triolate
  • L-ascorbic acid triesters such as L-ascorbic acid triphosphate
  • L-ascorbic acid 2 -L-ascorbic acid glucosides such as glucoside can be mentioned.
  • L-ascorbic acid, L-ascorbic acid phosphate ester, L-ascorbic acid-2-sulfate ester, L-ascorbic acid 2-glucoside and salts thereof are preferably used.
  • tranexamic acid Derivatives of tranexamic acid include dimers of tranexamic acid (eg, trans-4- (trans-aminomethylcyclohexanecarbonyl) aminomethylcyclohexanecarboxylic acid, etc.), esters of tranexamic acid and hydroquinone (eg, 4).
  • tranexamic acid and a salt thereof are preferably used.
  • the derivative of alkoxysalicylic acid is one in which the hydrogen atom at any of the 3-position, 4-position or 5-position of salicylic acid is substituted with an alkoxy group, and the alkoxy group as the substituent is preferably a methoxy group, an ethoxy group, or the like. It is any one of a propoxy group, an isopropoxy group, a butoxy group and an isobutoxy group, and more preferably a methoxy group or an ethoxy group.
  • compound names include 3-methoxysalicylic acid, 3-ethoxysalicylic acid, 4-methoxysalicylic acid, 4-ethoxysalicylic acid, 4-propoxysalicylic acid, 4-isopropoxysalicylic acid, 4-butoxysalicylic acid, and 5-methoxysalicylic acid. , 5-ethoxysalicylic acid, 5-propoxysalicylic acid and the like.
  • methoxysalicylic acid and a salt thereof are preferably used.
  • Examples of the derivative of glycyrrhizic acid include salts of glycyrrhizic acid and esters of glycyrrhizic acid and higher alcohols.
  • glycyrrhizic acid and salts thereof are preferably used.
  • the salt of the above-mentioned drug is not particularly limited, and examples thereof include alkali metal salts such as sodium salt, potassium salt and calcium salt, alkaline earth metal salts, ammonium salts, amino acid salts and the like.
  • nicotinic acid and its derivatives examples include nicotinic acid, benzyl nicotinate, nicotinic acid amide, and dl- ⁇ -tocopherol nicotinate. Nicotinamide is preferably used in the present invention.
  • the blending amount of the (F) whitening agent is 0.05 to 10% by mass, preferably 0.1 to 7% by mass, and more preferably 0.5 to 5% by mass with respect to the total amount of the cosmetic. If the blending amount is less than 0.05% by mass, it is difficult to obtain a sufficient medicinal effect, and if it exceeds 10% by mass, the stability and usability tend to deteriorate.
  • the (F) whitening agent of the present invention may be dissolved or dispersed in the aqueous phase together with other aqueous components.
  • the cosmetic according to the present invention may contain one or more (G) dispersants.
  • the dispersant include sorbitan sesquiisostearate, isostearic acid, palmitic acid, polyhydroxystearic acid and the like.
  • sorbitan sesquiisostearate and isostearic acid are exemplified as particularly suitable ones, and one or both of them may be blended.
  • the dispersant is a selective compounding ingredient in the cosmetics of the present invention, and therefore must be blended, but when blended, the effect of the blending is recognized and the dispersant is blended. It is preferable to add the mixture to the extent that no adverse effects such as an excessive amount of the compounding and impairing the usability are observed.
  • the suitable blending amount of the (G) dispersant in the cosmetic according to the present invention is preferably about 0.01 to 1% by mass with respect to the total amount of the cosmetic.
  • the water to be blended in the cosmetic according to the present invention is selected as necessary, such as ion-exchanged water, purified water, tap water, and natural water.
  • the blending amount is the remaining amount (mass% with respect to the total amount of cosmetics) with respect to the sum of the essential ingredient according to the present invention and other optional blending ingredients. Generally, about 30 to 70% by mass is preferable with respect to the total amount of cosmetics.
  • the oil-in-water emulsified cosmetic according to the present invention includes any other additive ingredients usually used for external skin preparations such as cosmetics and pharmaceuticals, as long as the purpose and effect of the present invention are not impaired.
  • cosmetics and pharmaceuticals for example, fats and oils, waxes, higher fatty acids, higher alcohols, oil phase thickeners, surfactants, water-soluble ultraviolet absorbers, pigments, chelating agents, lower alcohols, polyhydric alcohols, pH adjusters, antioxidants, powders.
  • Ingredients, fragrances and the like can be appropriately blended as needed.
  • the present invention is not limited to these examples.
  • (B) polyoxyalkylene-modified silicone is sufficiently mixed with (A) an aqueous component, and then the mixed solution is water containing an aqueous component other than (A) component. It can be produced as a vesicle aqueous dispersion by dropping the mixture into the phase while stirring.
  • the mixed state of the (B) polyoxyalkylene-modified silicone and the (A) aqueous component may be as long as it can be confirmed that the mixed solution is transparent and in a one-phase state. For example, mixing is performed at room temperature to 90 ° C. for 1 to 30 minutes. It can be achieved by doing.
  • vesicle particles having an average particle size of 30 to 150 nm measured by a dynamic light scattering method can be obtained.
  • the vesicle according to the present invention can also be produced in a form in which an oily component is retained inside the bilayer membrane of the vesicle by a conventional method.
  • the vesicle according to the present invention is oil-soluble by adding and mixing an oil-soluble component such as a fragrance in the step of mixing (B) polyoxyalkylene-modified silicone and (A) an aqueous component. It may be produced as a vesicle in which the component is retained in the bilayer membrane of the vesicle.
  • the oil-in-water emulsified cosmetic according to the present invention is emulsified by nanodiscs transferred from vesicles by adding an anionic surfactant and oil to the aqueous phase containing vesicles and dispersing while applying strong stirring force. It was done.
  • the cosmetic of the present invention is stabilized by a three-phase structure of aqueous phase-nanodisc phase-oil phase in which nanodiscs (phases) are attached to oil phases (oil droplets). Therefore, the oil-in-water emulsified cosmetic according to the present invention is characterized in that nanodiscs made of polyoxyalkylene-modified silicone are attached (localized) around the oil-water interface, that is, around the oil droplets made of the oil phase. ..
  • the major axis of the nanodisk is 20 nm to 1000 nm.
  • the three-phase structure of the aqueous phase-nanodisc phase-oil phase in the oil-in-water emulsified cosmetic according to the present invention can be formed by a conventional method. That is, under stirring, polyoxyalkylene-modified silicone was dropped onto an aqueous component to form vesicle particles to obtain a vesicle aqueous dispersion, and an oily component separately mixed and dissolved with an anionic surfactant in this vesicle aqueous dispersion. Is added and dispersed with a strong stirring force, the vesicles are transferred to the nanodisks, forming a three-phase structure of aqueous phase-nanodisk phase-oil phase.
  • Oil droplets composed of oily components are emulsified and dispersed in the aqueous phase, and nanodisks are localized on the surface of the oil droplet particles, so that the emulsification stability is excellent and the feeling of use (freshness, non-stickiness) is also improved.
  • the stirring device used for stirring is not particularly limited, and for example, a homomixer, a disper, or the like can be used.
  • the vesicle particles formed in the aqueous phase can be molded into a sufficiently fine particle size by applying a strong share with the above-mentioned homomixer or the like, and uniformly dispersed in the aqueous phase.
  • the degree of strong share is not particularly limited, but is usually about 5 minutes under the condition of 7,000 to 12,000 rpm by a homomixer.
  • the cosmetic of the present invention is obtained by forming vesicle particles in an aqueous phase, adding an anionic surfactant to the vesicle dispersion, and then adding an oily component to emulsify. Therefore, the method for producing an oil-in-water emulsified cosmetic according to the present invention is obtained by a vesicle forming step of mixing (A) an aqueous component and (B) a polyoxyalkylene-modified silicone to form a vesicle, and a vesicle forming step.
  • aqueous component and (B) a polyoxyalkylene-modified silicone are previously dissolved, and the solution is mixed with the remaining aqueous phase components to disperse the vesicles in the aqueous phase.
  • a liquid may be obtained, or the vesicles are dispersed in the aqueous phase by mixing and stirring (B) the polyoxyalkylene-modified silicone in the aqueous phase containing (A) an aqueous component and an aqueous component other than (A).
  • a vesicle dispersion may be obtained.
  • the cosmetic according to the present invention has a fresh feeling of use peculiar to an oil-in-water emulsion and exhibits an excellent UV protection effect.
  • the nanodisc-containing emulsion according to the present invention can be blended with a large amount of oil that cannot be blended with a normal solubilized product, yet a refreshing feeling of use can be obtained.
  • the cosmetic according to the present invention is suitably used in various dosage forms such as creamy, milky liquid, and liquid.
  • a product form it can be a skin care cosmetic having a sunscreen effect, or a make-up cosmetic such as a foundation or a foundation having a sunscreen effect.
  • the present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.
  • the blending amount is shown in mass% with respect to the system in which the component is blended.
  • Vibration stability 30 ml of the prepared sample was placed in a resin tube, vibrated for 30 minutes under the condition of 10 Hz or higher, and the emulsified separation and powder aggregation state of the sample after standing were visually observed. The evaluation was based on the following criteria. A: No emulsification destruction or powder agglomeration is observed. B: Emulsification destruction and powder agglomeration are rarely seen. C: Emulsification destruction and powder agglomeration are observed. D: Emulsification destruction and powder agglomeration are severely observed.
  • Water resistance measures the UV protection ability of UV protection agents (UV absorbers and UV scattering agents) contained in cosmetics before and after bathing, and the ratio of UV protection ability remaining after bathing (absorbance). By calculating the residual rate), the strength of water resistance was measured. Specifically, the cosmetics (samples) of each example were dropped onto a measurement plate (S plate) (5 x 5 cm V-groove PMMA plate, SPFMASTER-PA01) in an amount of 2 mg / cm 2 and applied with a finger for 60 seconds. Then, the absorbance of the coating film formed after drying for 15 minutes was measured with a U-3500 type self-recording spectrophotometer manufactured by Hitachi, Ltd.
  • S plate 5 x 5 cm V-groove PMMA plate, SPFMASTER-PA01
  • Abs residual rate (%) (Abs integrated value after water bath) / (Abs integrated value before water bath) ⁇ 100 Based on the calculated Abs residual rate, the determination was made according to the following criteria. A: 80% or more remains. B: 60% or more and less than 80% remains. C: Less than 60% remains.
  • KF-96L-1.5CS manufactured by Shin-Etsu Chemical Co., Ltd.
  • Volatilization rate approx. 50%
  • 2: KF-96L-6T manufactured by Shin-Etsu Chemical Co., Ltd.
  • 3: KF-96A-20CS manufactured by Shin-Etsu Chemical Co., Ltd.
  • Table 1 shows cosmetics prepared by changing the amphipathic substance forming the vesicle, (E) anionic surfactant, and (C) oil.
  • Example 1 and Example 2 which are the oil-in-water emulsified cosmetics of the present invention, were both excellent in vibration stability and water resistance.
  • the vibration stability was excellent, but the water resistance was inferior. rice field.
  • polar oil diisopropyl sebacate, cetyl ethylhexanate, ultraviolet absorber
  • silicone oil or hydrocarbon oil is blended in addition to polar oil as an oil component.
  • All of the cosmetics of Examples 8 to 10 had excellent vibration stability and water resistance. As shown in Example 7, it was confirmed that excellent vibration stability and water resistance can be obtained by blending polar oil without containing an ultraviolet absorber.
  • KF-96L-1.5CS manufactured by Shin-Etsu Chemical Co., Ltd.
  • Volatilization rate approx. 50%
  • 2: KF-96L-6T manufactured by Shin-Etsu Chemical Co., Ltd.
  • 3: KF-96A-20CS manufactured by Shin-Etsu Chemical Co., Ltd.
  • Table 2 shows cosmetics prepared by changing the ratio of small molecule oil to the total amount of oil excluding ultraviolet absorbers. Comparison of cosmetics containing isododecane with a volatilization rate of 90% or more, which is a low molecular weight oil, or dimethicone with a volatility rate of about 50%, in which the ratio of these low molecular weight oils to the total amount of oils excluding UV absorbers exceeds 50%. In the cosmetics of Example 5, Comparative Example 6 and Comparative Example 7, the vibration stability was significantly reduced. On the other hand, cosmetics in which the ratio of the small molecule oil content to the total amount of oil excluding the ultraviolet absorber is 50% (Example 12, Example 14, Example 15) and cosmetics in which the ratio is 25% (Example 13, Implementation). All of Examples 16) had sufficient vibration stability.

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Abstract

The purpose of the present invention is to provide an oil-in-water type emulsified sunscreen cosmetic that, as a vesicle-containing oil-in-water type emulsified composition, exhibits an excellent vibration stability and water resistance and possesses a high ultraviolet-blocking capacity. An oil-in-water type emulsified sunscreen cosmetic according to the present invention is characterized by comprising an aqueous component (A) selected from monohydric alcohols and dihydric alcohols, a polyoxyalkylene-modified silicone (B), a polar oil-containing oil fraction (C), an ultraviolet scattering agent (D) having a hydrophobicized surface, and an anionic surfactant (E), wherein when the aqueous component (A) is only a monohydric alcohol, it is 1-15 mass% with reference to the total amount of the cosmetic; when the aqueous component (A) is only a dihydric alcohol, it is 1-20 mass% with reference to the total amount of the cosmetic; and when the aqueous component (A) is a monohydric alcohol/dihydric alcohol combination, it is 1-45 mass% with reference to the total amount of the cosmetic. Another characteristic feature is that, when a low-molecular-weight oil fraction is incorporated as the oil fraction (C), the proportion for the low-molecular-weight oil fraction with reference to the total amount of the oil fraction excluding ultraviolet absorbers, is not more than 50% as the mass ratio.

Description

水中油型日焼け止め化粧料Underwater oil type sunscreen cosmetics
　本発明は、日焼け止め化粧料において、振動安定性および耐水性が向上した水中油型日焼け止め化粧料に関する。 The present invention relates to an underwater oil type sunscreen cosmetic having improved vibration stability and water resistance in sunscreen cosmetics.
　両親媒性物質のなかには、水性相中で二分子膜（ラメラ液晶）からなる球状の閉鎖体を形成するものがあり、このような二分子膜閉鎖体をベシクルという。ベシクルは、閉鎖体内部に水溶性成分を保持可能であり、二分子膜内部には油性成分を保持可能であるとともに、系の安定性が向上するなどの効果が期待できるため、化粧料の基剤として用いられている。 Some amphipathic substances form spherical closures consisting of bilayer membranes (lamella liquid crystals) in the aqueous phase, and such bilayer membrane closures are called vesicles. Vesicles can retain water-soluble components inside the closed body, oil-based components can be retained inside the bilayer membrane, and can be expected to have effects such as improving the stability of the system, so they are the basis of cosmetics. It is used as an agent.
　例えば、特許文献１および特許文献２では、両親媒性物質として特定のポリオキシエチレン硬化ヒマシ油誘導体を用いることによってベシクルが形成され、これを乳化剤として含むことでべたつかず、使用感の良い化粧料が得られたことが開示されている。 For example, in Patent Document 1 and Patent Document 2, vesicles are formed by using a specific polyoxyethylene hydrogenated castor oil derivative as an amphipathic substance, and by containing this as an emulsifier, cosmetics that are not sticky and have a good usability. Is disclosed that was obtained.
　また、ベシクルを形成する両親媒性物質としてシリコーン系界面活性剤が挙げられる。シリコーン系界面活性剤により形成されるベシクルは、べたつきがなく使用感が良い組成物が得られるとともに、調製が容易であるなどの利点があるため、好ましく用いられる。 Further, as an amphipathic substance forming a vesicle, a silicone-based surfactant can be mentioned. The vesicle formed by the silicone-based surfactant is preferably used because it has advantages such as a composition having no stickiness and a good usability and being easy to prepare.
　例えば、特許文献３では、予め水性処方とシリコーン系界面活性剤とを混合して形成したベシクル含有水性溶液中に、水溶性低分子界面活性剤を添加することによってベシクルの安定性が改善したことが記載されている。また、特許文献４では、シリコーン系界面活性剤からベシクルを形成させた後にアニオン性界面活性剤を添加することによってベシクルの安定性が向上したことが記載されている。 For example, in Patent Document 3, the stability of vesicles was improved by adding a water-soluble low-molecular-weight surfactant to a vesicle-containing aqueous solution previously formed by mixing an aqueous formulation and a silicone-based surfactant. Is described. Further, Patent Document 4 describes that the stability of the vesicle is improved by adding the anionic surfactant after forming the vesicle from the silicone-based surfactant.
　しかし、これらシリコーン系界面活性剤から形成させたベシクルは主に油分の配合量が少ない可溶化溶液に用いられており、乳化系組成物に用いられている例はなかった。実際、特許文献４では、油分を０．４質量％以上とすると安定性が低下する傾向であったことが示されている。 However, vesicles formed from these silicone-based surfactants are mainly used in solubilized solutions with a small amount of oil, and there have been no examples of use in emulsified compositions. In fact, Patent Document 4 shows that the stability tends to decrease when the oil content is 0.4% by mass or more.
　特許文献５では、内相を包含するベシクルによって水と溶解しない液相を外相に分散する技術が開示されている。しかしながら、ベシクルによる乳化は不安定であり実用には制約があったため、ベシクルの配合量が多くなる傾向があり、一般的に知られているようにベシクルを形成する界面活性剤によるべたつきなどが課題になる場合があった。 Patent Document 5 discloses a technique of dispersing a liquid phase insoluble in water in an outer phase by a vesicle including an inner phase. However, since emulsification by vesicles is unstable and there are restrictions on practical use, the amount of vesicles to be blended tends to be large, and as is generally known, stickiness due to a surfactant forming vesicles is a problem. In some cases.
国際公開２０１０－０６４６７８号公報International Publication No. 2010-064678 特開２０１１－１９５５０９号公報Japanese Unexamined Patent Publication No. 2011-195509 特開２００８－０２４６８１号公報Japanese Unexamined Patent Publication No. 2008-0246881 特開２０１２－０９２０８４号公報Japanese Unexamined Patent Publication No. 2012-209084 特許第３１３７５９２号公報Japanese Patent No. 3137592
　本発明は、安定性および耐水性に優れ、高い紫外線防御力を有する水中油型乳化日焼け止め化粧料を提供することを目的とする。 An object of the present invention is to provide an oil-in-water emulsified sunscreen cosmetic having excellent stability and water resistance and high ultraviolet protection.
　発明者等は、前記の課題を解決すべく鋭意検討を重ねた結果、水中油型乳化組成物において、特定の水性成分存在下で特定のシリコーン系界面活性剤により形成させたベシクルを前駆体とするシリコーンナノディスクにより乳化するとともに、油相に配合される油分を特定のものに限定することによって振動安定性が著しく向上し、耐水性にも優れることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the inventors have used a vesicle formed by a specific silicone-based surfactant in the presence of a specific aqueous component in an oil-in-water emulsified composition as a precursor. By emulsifying with the silicone nanodiscs and limiting the oil content in the oil phase to a specific one, it has been found that the vibration stability is remarkably improved and the water resistance is also excellent, and the present invention has been completed. ..
　ここで「ナノディスク」とは、両親媒性物質により形成されるベシクル（ラメラ液晶球状閉鎖体）を前駆体とした平板状のラメラ液晶閉鎖体であり、閉鎖体内部に水溶性成分を内包せず、エッジ部分に親油基を有するものをいう。ナノディスクは、油を含まない組成においては前駆体であるベシクルとして存在し、油を添加して乳化を行うことでベシクルがナノディスクに構造変化（以下「転移」ともいう）する。本発明のナノディスクは、１価アルコールおよび２価アルコールから選択される水性成分とポリオキシアルキレン変性シリコーンとを混合してベシクルを形成させたベシクル水分散液に、アニオン性界面活性剤と油分を添加し、強い攪拌力を加えながら分散することによって得られる。ナノディスクは、乳化状態において油水界面に吸着した状態で存在し、乳化安定性に寄与する。本明細書では、ベシクルを形成する両親媒性物質がシリコーン系界面活性剤であるので、本発明のナノディスクを「シリコーンナノディスク」とも指す。 Here, the "nanodisc" is a flat plate-shaped lamellar liquid crystal closure whose precursor is a vesicle (lamellar liquid crystal spherical closure) formed by an amphipathic substance, and contains a water-soluble component inside the closure. However, it refers to a substance having an amphipathic group at the edge portion. Nanodiscs exist as precursor vesicles in oil-free compositions, and the vesicles undergo structural changes (hereinafter also referred to as "transfers") to nanodisks by adding oil and emulsifying. In the nanodisc of the present invention, an anionic surfactant and an oil component are added to a vesicle aqueous dispersion obtained by mixing an aqueous component selected from a monohydric alcohol and a divalent alcohol with a polyoxyalkylene-modified silicone to form a vesicle. It is obtained by adding and dispersing while applying a strong stirring force. Nanodiscs exist in a state of being adsorbed on the oil-water interface in an emulsified state, and contribute to emulsification stability. In the present specification, since the amphipathic substance forming the vesicle is a silicone-based surfactant, the nanodisk of the present invention is also referred to as “silicone nanodisk”.
　すなわち、本発明は、
（Ａ）１価アルコールおよび２価アルコールから選択される水性成分、
（Ｂ）ポリオキシアルキレン変性シリコーン、
（Ｃ）極性油を含む油分、
（Ｄ）疎水化表面を有する紫外線散乱剤、および、
（Ｅ）アニオン性界面活性剤
を含み、
前記（Ａ）水性成分が、１価アルコール単独の場合には化粧料全量に対して１～１５質量％であり、２価アルコール単独の場合には化粧料全量に対して１～２０質量％であり、１価アルコールと２価アルコールとの組み合わせである場合にはその合計量が化粧料全量に対して１～４５質量％であり、
前記（Ｃ）油分として低分子油分を配合する場合には、紫外線吸収剤を除く油分の合計量に対して低分子油分が占める割合が質量比にして５０％以下である、水中油型日焼け止め化粧料を提供する。
　また、本発明に係る水中油型乳化化粧料においては、前記（Ｂ）ポリオキシアルキレン変性シリコーンからなるナノディスクが油水界面に付着していることを特徴とする。 That is, the present invention
(A) Aqueous component selected from monohydric alcohols and divalent alcohols,
(B) Polyoxyalkylene modified silicone,
(C) Oil containing polar oil,
(D) An ultraviolet scattering agent having a hydrophobic surface, and
(E) Containing anionic surfactant,
When the aqueous component (A) is monohydric alcohol alone, it is 1 to 15% by mass with respect to the total amount of cosmetics, and when dihydric alcohol is alone, it is 1 to 20% by mass with respect to the total amount of cosmetics. Yes, in the case of a combination of monohydric alcohol and dihydric alcohol, the total amount is 1 to 45% by mass with respect to the total amount of cosmetics.
When a low molecular weight oil is blended as the oil (C), the ratio of the low molecular weight oil to the total amount of the oil excluding the ultraviolet absorber is 50% or less in terms of mass ratio, which is an oil-in-water sunscreen. Provide cosmetics.
Further, the oil-in-water emulsified cosmetic according to the present invention is characterized in that nanodisks made of the (B) polyoxyalkylene-modified silicone are attached to the oil-water interface.
　本発明に係る化粧料は、上記構成とすることにより、高い乳化力を有する水中油型乳化物となるので、油相中に紫外線防御剤（紫外線吸収剤および紫外線散乱剤）を多く配合することができる。また、従来のベシクルによる乳化に比して振動安定性および耐水性を向上することができる。よって、より携帯に適する化粧料を実現することができる。さらに、本発明によるシリコーンナノディスクは十分な乳化力があるので、通常外相である水相に配合すると安定性が悪くなる傾向がある塩型の美白剤等の水溶性薬剤を配合することも可能となる。 Since the cosmetic according to the present invention becomes an oil-in-water emulsion having a high emulsifying power by the above composition, a large amount of an ultraviolet protective agent (ultraviolet absorber and ultraviolet scattering agent) is blended in the oil phase. Can be done. In addition, vibration stability and water resistance can be improved as compared with the conventional emulsification by vesicles. Therefore, it is possible to realize a cosmetic that is more suitable for carrying. Furthermore, since the silicone nanodisc according to the present invention has sufficient emulsifying power, it is also possible to add a water-soluble agent such as a salt-type whitening agent, which tends to have poor stability when added to the aqueous phase, which is usually the outer phase. It becomes.
　本発明に係る化粧料は、（Ａ）１価アルコールおよび２価アルコールから選択される水性成分、（Ｂ）ポリオキシアルキレン変性シリコーン、（Ｃ）極性油を含む油分、（Ｄ）疎水化表面を有する紫外線散乱剤および、（Ｅ）アニオン性界面活性剤を含むことを特徴とする。以下、本発明の化粧料を構成する各成分について詳述する。 The cosmetic according to the present invention comprises (A) an aqueous component selected from a monohydric alcohol and a divalent alcohol, (B) a polyoxyalkylene-modified silicone, (C) an oil containing polar oil, and (D) a hydrophobic surface. It is characterized by containing an ultraviolet scattering agent having and (E) an anionic surfactant. Hereinafter, each component constituting the cosmetic of the present invention will be described in detail.
＜（Ａ）水性成分＞
　本発明に係る化粧料に配合される（Ａ）水性成分（以下、単に「（Ａ）成分」と称する場合がある）は、１価アルコールおよび２価アルコールから選択される１種または２種以上を指す。
　１価アルコールとしては、化粧料に通常用いられるものであれば特に限定されないが、エチルアルコール（エタノール）、ノルマルプロピルアルコール、イソプロピルアルコール等が挙げられ、本発明においては、エチルアルコールが好ましい。
　２価アルコールとしては、化粧料に通常用いられるものであれば特に限定されないが、１，３－ブチレングリコール、ジプロピレングリコール等が挙げられ、本発明においては、ジプロピレングリコールが好ましい。 <(A) Aqueous component>
The (A) aqueous component (hereinafter, may be simply referred to as "(A) component") blended in the cosmetic according to the present invention is one or more selected from monohydric alcohol and dihydric alcohol. Point to.
The monohydric alcohol is not particularly limited as long as it is usually used for cosmetics, and examples thereof include ethyl alcohol (ethanol), normal propyl alcohol, and isopropyl alcohol, and in the present invention, ethyl alcohol is preferable.
The divalent alcohol is not particularly limited as long as it is usually used for cosmetics, but examples thereof include 1,3-butylene glycol, dipropylene glycol and the like, and dipropylene glycol is preferable in the present invention.
　界面活性剤により形成される球状ベシクルは表面がすべて親水基で覆われているが、ナノディスクはエッジ部分に親油基を有するため、ナノディスクを水中で生成させることは難しい。１価および２価のアルコールが水中に存在すると溶媒効果により界面活性剤（本発明においては、ポリエーテル変性シリコーン）が親水化され、その結果、球状ベシクルからナノディスクへの転移が促進される。 The surface of the spherical vesicles formed by the surfactant is entirely covered with hydrophilic groups, but since nanodiscs have lipophilic groups at the edges, it is difficult to generate nanodisks in water. When monohydric and divalent alcohols are present in water, the solvent effect hydrophilizes the surfactant (polyether-modified silicone in the present invention), resulting in accelerated transfer from spherical vesicles to nanodisks.
　一方、ＰＥＧ－１２ジメチコン等のポリオキシアルキレン変性シリコーンをアルコールに溶解する場合、グリセリン等の３価アルコール、ソルビトール等の多価アルコール等は界面活性剤を親油化してナノディスクへの転移を阻害する傾向があるため、３価以上のアルコールを配合する場合には、１価および２価のアルコールの総量を３価以上の多価アルコールの総量より多くすることが望ましい。 On the other hand, when polyoxyalkylene-modified silicones such as PEG-12 dimethicone are dissolved in alcohols, trihydric alcohols such as glycerin and polyhydric alcohols such as sorbitol make surfactants lipophilic and inhibit transfer to nanodisks. Therefore, when a trihydric or higher alcohol is blended, it is desirable that the total amount of the monohydric and divalent alcohols is larger than the total amount of the trihydric or higher polyhydric alcohols.
　１価アルコールを単独で用いる場合には、その配合量は化粧料全量に対して１～１５質量％であり、２価アルコールを単独で用いる場合には、その配合量は化粧料全量に対して１～２０質量％である。また、１価アルコールと２価アルコールとを組み合わせて用いる場合には、その合計配合量は化粧料全量に対して１～４５質量％であり、好ましくは１～３５質量％である。より好ましくは以下の式（１）を満たす１価アルコールおよび２価アルコールの濃度を上限として配合することが好ましい。
水相中１価アルコール濃度（％）／１５＋水相中２価アルコール濃度（質量％）／２０≦１　　　　　（１） When the monohydric alcohol is used alone, the blending amount is 1 to 15% by mass with respect to the total amount of cosmetics, and when the divalent alcohol is used alone, the blending amount is 1 to 15% by mass with respect to the total amount of cosmetics. It is 1 to 20% by mass. When the monohydric alcohol and the divalent alcohol are used in combination, the total blending amount is 1 to 45% by mass, preferably 1 to 35% by mass, based on the total amount of the cosmetics. More preferably, it is preferably blended with the concentration of the monohydric alcohol and the divalent alcohol satisfying the following formula (1) as the upper limit.
Monohydric alcohol concentration in the aqueous phase (%) / 15 + Divalent alcohol concentration in the aqueous phase (mass%) / 20≤1 (1)
　１価アルコール単独の配合量、２価アルコール単独の配合量、１価アルコールおよび２価アルコールの合計配合量が１質量％未満であるとベシクルが生成しないか構造が乱れて乳化できなくなる場合がある。また、１価アルコール単独の配合量が１５質量％を超える場合や２価アルコール単独の配合量が２０質量％を超える場合、さらに１価アルコールおよび２価アルコールの配合比が上記式（１）の範囲外である場合や上記式（１）の範囲内であっても合計配合量が４５質量％を超えるとベシクル膜が柔軟になりすぎるかベシクルがミセルへ転移してしまい安定化効果が得られない場合がある。 If the blending amount of monohydric alcohol alone, the blending amount of dihydric alcohol alone, and the total blending amount of monohydric alcohol and divalent alcohol is less than 1% by mass, vesicles may not be generated or the structure may be disturbed and emulsification may not be possible. .. Further, when the blending amount of the monohydric alcohol alone exceeds 15% by mass or when the blending amount of the dihydric alcohol alone exceeds 20% by mass, the blending ratio of the monohydric alcohol and the dihydric alcohol is further in the above formula (1). Even if it is out of the range or within the range of the above formula (1), if the total compounding amount exceeds 45% by mass, the vesicle film becomes too flexible or the vesicles are transferred to the micelles, and a stabilizing effect can be obtained. May not be.
＜（Ｂ）ポリオキシアルキレン変性シリコーン＞
　本発明に係る化粧料に配合される（Ｂ）ポリオキシアルキレン変性シリコーン（以下、単に「（Ｂ）成分」と称する場合がある）は、疎水性基としてポリシロキサン構造、親水基としてポリオキシアルキレン構造を有する界面活性剤であり、ジメチコンのメチル基の一部をポリエチレングリコールで置換した水溶性のシリコーン系界面活性剤であることが好ましい。具体的には下記式（２）で表される。 <(B) Polyoxyalkylene-modified silicone>
The (B) polyoxyalkylene-modified silicone (hereinafter, may be simply referred to as “component (B)”) blended in the cosmetic according to the present invention has a polysiloxane structure as a hydrophobic group and a polyoxyalkylene as a hydrophilic group. It is a surfactant having a structure, and is preferably a water-soluble silicone-based surfactant in which a part of the methyl group of dimethicone is replaced with polyethylene glycol. Specifically, it is expressed by the following equation (2).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　前記式（２）中、Ｒ１は、水素または炭素数１～６のアルキル基であり、それぞれ同一でも、独立に異なっていてもよい。Ａは、少なくともその１つが式（３）：
－（ＣＨ２）ａ－（Ｃ２Ｈ４Ｏ）ｂ－（Ｃ３Ｈ６Ｏ）ｃ－Ｒ２　　　　　（３）
で示されるポリオキシアルキレン基であり、その他のＡは水素または炭素数１～６のアルキル基であり、それぞれ同一でも、独立に異なっていてもよい。式（３）中のＲ２は水素または炭素数１～６のアルキル基であり、ａは１～６、ｂは０～５０、ｃは０～５０の整数であり、ｂ＋ｃは少なくとも５以上である。前記式（２）のｍは１～２００の整数であり、ｎは０～５０の整数である。
　本発明の（Ｂ）ポリオキシアルキレン変性シリコーンとしては、グリフィンの式によるＨＬＢ計算においてＨＬＢが１０未満であることが好ましい。 In the above formula (2), R 1 is hydrogen or an alkyl group having 1 to 6 carbon atoms, and may be the same or independently different from each other. At least one of A is the formula (3):
-(CH 2 ) a- (C 2 H 4 O) b- (C 3 H 6 O) c-R 2 (3)
The other A is a hydrogen or an alkyl group having 1 to 6 carbon atoms, which may be the same or independently different from each other. R 2 in the formula (3) is hydrogen or an alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 6, b is an integer of 0 to 50, c is an integer of 0 to 50, and b + c is at least 5 or more. be. In the above equation (2), m is an integer of 1 to 200, and n is an integer of 0 to 50.
The (B) polyoxyalkylene-modified silicone of the present invention preferably has an HLB of less than 10 in the HLB calculation according to the Griffin formula.
　本発明に係る化粧料においては、（Ｂ）ポリオキシアルキレン変性シリコーンの中でも特に前記式（３）においてｃが０、ｂが１２であるＰＥＧ－１２ジメチコンが好ましい。また、ＰＥＧ－１２ジメチコンはＨＬＢが１０未満であることがさらに好ましい。 In the cosmetic according to the present invention, among the (B) polyoxyalkylene-modified silicones, PEG-12 dimethicone in which c is 0 and b is 12 in the above formula (3) is particularly preferable. Further, it is more preferable that PEG-12 dimethicone has an HLB of less than 10.
　ＰＥＧ－１２ジメチコンの市販品としては、ＤＯＷＳＩＬTM　ＥＳ－５３７３、ＳＨ３７７２Ｍ，ＳＨ３７７３Ｍ，ＳＨ３７７５Ｍ（いずれもダウ・東レ社製）、ＩＭ-２２（ワッカーケミカル社製）等が挙げられる。 Examples of commercially available products of PEG-12 dimethicone include DOWNSIL TM ES-5373, SH3772M, SH3773M, SH3775M (all manufactured by Dow Toray), IM-22 (manufactured by Wacker Chemical Co., Ltd.) and the like.
　（Ｂ）成分の配合量は、ナノディスクの前駆体であるベシクルを形成し得る限り特に限定されないが、例えば、化粧料全量に対して０．１～５．０質量％であり、好ましくは０．３～３．０質量％、さらに好ましくは０．８～２．０質量％である。配合量が０．１質量％未満であると十分にベシクルが形成されない場合があり、５．０質量％を超えるとベシクルの安定性が劣る場合がある。 The blending amount of the component (B) is not particularly limited as long as it can form a vesicle that is a precursor of nanodisks, but is, for example, 0.1 to 5.0% by mass, preferably 0, based on the total amount of cosmetics. .3 to 3.0% by mass, more preferably 0.8 to 2.0% by mass. If the blending amount is less than 0.1% by mass, vesicles may not be sufficiently formed, and if it exceeds 5.0% by mass, the stability of the vesicles may be inferior.
　本発明に係る化粧料は、（Ｂ）成分の界面活性剤からなるナノディスクを含有する。ナノディスクの前駆体であるベシクルは常法によって形成させることが可能である。具体的には、（Ａ）水性成分と（Ｂ）ポリオキシアルキレン変性シリコーンとを混合攪拌することによって、（Ｂ）成分からなるベシクルが形成される。ベシクル形成に際しては、（Ａ）水性成分の他に、水や通常化粧品に用いられる水性成分がベシクルの安定性を損なわない範囲の量で配合されていてもよい。なお、ベシクルの平均粒子径は、特に限定されるものではないが、通常３０ｎｍ～１５０ｎｍ程度である。 The cosmetic according to the present invention contains nanodiscs made of the surfactant of the component (B). Vesicles, which are precursors of nanodisks, can be formed by a conventional method. Specifically, a vesicle composed of the component (B) is formed by mixing and stirring (A) the aqueous component and (B) the polyoxyalkylene-modified silicone. In forming the vesicle, in addition to the (A) aqueous component, water or an aqueous component usually used in cosmetics may be blended in an amount within a range that does not impair the stability of the vesicle. The average particle size of the vesicle is not particularly limited, but is usually about 30 nm to 150 nm.
＜（Ｃ）油分＞
　本発明に係る化粧料に配合される（Ｃ）油分（以下、単に「（Ｃ）成分」と称する場合がある）は、少なくとも極性油を必須に含む油分を指す。ただし、本発明の（Ｃ）油分に低分子油分が配合される場合には、紫外線吸収剤を除く油分の合計量に対して低分子油分が占める割合を質量比にして５０％以下とすることを必要とする。 <(C) Oil content>
The (C) oil component (hereinafter, may be simply referred to as “(C) component”) blended in the cosmetics according to the present invention refers to an oil content that contains at least polar oil indispensable. However, when the oil content (C) of the present invention contains a low molecular weight oil content, the ratio of the low molecular weight oil content to the total amount of the oil content excluding the ultraviolet absorber shall be 50% or less in terms of mass ratio. Needs.
　本発明に係る化粧料に配合される極性油としては、エステル油、特にＩＯＢ値が０．１～０．６程度のエステル油、および、油溶性で極性の紫外線吸収剤が挙げられる。 Examples of the polar oil blended in the cosmetics according to the present invention include ester oils, particularly ester oils having an IOB value of about 0.1 to 0.6, and oil-soluble and polar ultraviolet absorbers.
　ＩＯＢ値が０．１～０．６程度のエステル油の具体例としては、限定されないが、セバシン酸ジイソプロピル、テトラエチルヘキサン酸ペンタエリスリチル、エチルヘキサン酸セチル、ホホバ油、ラウロイルグルタミン酸ジ（フィトステリル／オクチルドデシル）、トリイソステアリン、ジイソステアリン酸グリセリル、トリエチルヘキサノイン、ダイマージリノール酸（フィトステリル／ベヘニル）、ダイマージリノール酸（フィトステリル／イソステアリル／セチル／ステアリル／イソステアリル／セチル／ステアリル／ベヘニル）、パルミチン酸イソプロピル、マカダミアナッツ脂肪酸フィトステリル、テトラ（ベヘン酸／安息香酸／エチルヘキサン酸）ペンタエリスリチル、パルミチン酸エチルヘキシル、ミリスチン酸ミリスチル、ミリスチン酸イソプロピル、ジピバリン酸トリプロピレングリコール、ネオペンタン酸イソデシル等が挙げられる。 Specific examples of the ester oil having an IOB value of about 0.1 to 0.6 are not limited, but are limited to diisopropyl sebacate, pentaerythrityl tetraethylhexanoate, cetyl ethylhexanate, jojoba oil, and di (phytosteryl / octyl) lauroyl glutamate. Dodecyl), triisostea, glyceryl diisostearate, triethylhexanoin, dimer dilinoleic acid (phytosteryl / behenyl), dimerglinol acid (phytosteryl / isostearyl / cetyl / stearyl / isostearyl / cetyl / stearyl / behenyl), palmitic acid Examples thereof include isopropyl, macadamia nut fatty acid phytosteryl, tetra (bechenic acid / benzoic acid / ethylcaproic acid) pentaerythrityl, ethylhexyl palmitate, myristyl myristate, isopropyl myristate, tripropylene glycol dipivalate, isodecyl neopentate and the like.
　油溶性で極性の紫外線吸収剤の具体例としては、日焼け止め化粧料に通常配合されるものを使用することができ、特に限定されないが、具体例としては、メトキシケイヒ酸エチルヘキシル、オクトクリレン、ジメチコジエチルベンザルマロネート、ポリシリコーン－１５、ｔ－ブチルメトキシジベンゾイルメタン、エチルヘキシルトリアゾン、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、ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジン、オキシベンゾン－３、メチレンビスベンゾトリアゾリルテトラメチルブチルフェノール、フェニルベンズイミダゾールスルホン酸、ホモサレート、サリチル酸エチルへキシル、テレフタリリデンジカンフルスルホン酸、ドロメトリゾールトリシロキサン等の有機紫外線吸収剤を挙げることができる。
　本発明に用いる極性油としては、１種または２種以上を組み合わせて用いてもよい。 Specific examples of the oil-soluble and polar UV absorber may be those normally blended in sunscreen cosmetics, and are not particularly limited, but specific examples include ethylhexyl methoxycinnamate, octocrylene, and dimethico. Diethylbenzalmaronate, Polysilicone-15, t-butylmethoxydibenzoylmethane, ethylhexyltriazone, diethylaminohydroxybenzoylhexyl benzoate, bisethylhexyloxyphenol methoxyphenyltriazine, oxybenzon-3, methylenebisbenzotriazolyltetramethyl Examples thereof include organic UV absorbers such as butylphenol, phenylbenzimidazole sulfonic acid, homosalate, ethylhexyl salicylate, terephthalylidenedicanfursulfonic acid, and drometrizoletrisiloxane.
As the polar oil used in the present invention, one kind or a combination of two or more kinds may be used.
　本発明の（Ｃ）油分には、上記極性油に加えて、炭化水素油およびシリコーン油から選択される１種または２種以上がさらに配合されてよい。 In addition to the polar oil, the oil (C) of the present invention may further contain one or more selected from hydrocarbon oils and silicone oils.
　炭化水素油の具体例としては、イソドデカン、イソヘキサデカン、水添ポリデセン、イソパラフィン、流動パラフィン、オゾケライト、スクワラン、プリスタン、パラフィン、セレシン、スクワレン、ワセリン、マイクロクリスタリンワックス等が挙げられる。 Specific examples of the hydrocarbon oil include isododecane, isohexadecane, hydrogenated polydecene, isoparaffin, liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalane, petrolatum, microcrystalline wax and the like.
　シリコーン油の具体例としては、鎖状ポリシロキサン（例えば、ジメチルポリシロキサン、メチルフェニルポリシロキサン、ジフェニルポリシロキサン等）、環状ポリシロキサン（例えば、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン等）、３次元網目構造を形成しているシリコーン樹脂、シリコーンゴム、各種変性ポリシロキサン（アミノ変性ポリシロキサン、ポリエーテル変性ポリシロキサン、アルキル変性ポリシロキサン、フッ素変性ポリシロキサン等）、アクリルシリコーン類等が挙げられる。 Specific examples of the silicone oil include chain polysiloxane (eg, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.) and cyclic polysiloxane (eg, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethyl, etc.). Cyclohexanesiloxane, etc.), Silicone resin forming a three-dimensional network structure, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic Examples include silicones.
　本発明に係る化粧料においては、油分に低分子油分を配合する場合には、紫外線吸収剤を除く油分の合計配合量に対して低分子油分が占める割合を、質量比にして５０％以下としなければならない。紫外線吸収剤を除く油分の合計配合量に対する低分子油分の割合が５０％を超えると、十分な振動安定性が得られないからである。なお、本発明に係る化粧料においては、油分として低分子油分を配合しなくともよいので、紫外線吸収剤を除く油分の合計配合量に対して低分子油分が占める割合の下限は０％である。 In the cosmetics according to the present invention, when the low molecular weight oil is mixed with the oil, the ratio of the low molecular weight oil to the total amount of the oil excluding the ultraviolet absorber is set to 50% or less in terms of mass ratio. There must be. This is because if the ratio of the small molecule oil to the total amount of the oil excluding the ultraviolet absorber exceeds 50%, sufficient vibration stability cannot be obtained. Since it is not necessary to add a small molecule oil as an oil in the cosmetic according to the present invention, the lower limit of the ratio of the small molecule oil to the total amount of the oil excluding the ultraviolet absorber is 0%. ..
　本発明において、低分子油分とは、２５℃における揮発速度が毎時重量変化率３０％以上である油分を指す。ここで、揮発速度は、ガラスシャーレにろ紙をのせ、試料約０．２ｇを滴下し、重量法により２５℃の条件下で測定した毎時重量変化率の値を指す。低分子油分の具体例としては、イソドデカン、平均重合度６５０未満の低粘度揮発性シリコーン（低粘度ジメチコン）等が挙げられる。低分子油分の市販品としては、Ｃｒｅａｓｉｌ　ＩＤ　ＣＧ（島貿易社製）、ＫＦ－９６Ｌ－１．５ＣＳ（信越化学社製）等が挙げられる。Ｃｒｅａｓｉｌ　ＩＤ　ＣＧの揮発速度は９０％以上であり、ＫＦ－９６Ｌ－１．５ＣＳの揮発速度は約５０％である。 In the present invention, the small molecule oil content refers to an oil content having a volatilization rate at 25 ° C. and a weight change rate of 30% or more per hour. Here, the volatilization rate refers to the value of the rate of change in weight per hour measured under the condition of 25 ° C. by placing a filter paper on a glass petri dish, dropping about 0.2 g of a sample, and using a gravimetric method. Specific examples of the small molecule oil include isododecane, low-viscosity volatile silicone (low-viscosity dimethicone) having an average degree of polymerization of less than 650, and the like. Examples of commercially available small molecule oil products include Creasil ID CG (manufactured by Shima Trading Co., Ltd.) and KF-96L-1.5CS (manufactured by Shin-Etsu Chemical Co., Ltd.). The volatilization rate of Creasil ID CG is 90% or more, and the volatilization rate of KF-96L-1.5CS is about 50%.
　本発明の（Ｃ）油分としては少なくとも極性油を含めばよい。よって、本発明の化粧料は、油分として極性油のみを含む態様を包含する。
　本発明に係る化粧料に配合される（Ｃ）油分の配合量は、油相に紫外線散乱剤を配合する上で通常用いられる量であれば特に限定されないが、例えば、化粧料全量に対して１～４０質量％であることが挙げられる。（Ｃ）油分の配合量が４０質量％を超えると安定性や使用性が低下する傾向がある。紫外線吸収剤を配合する場合には、紫外線吸収剤により十分な紫外線防御効果を得る観点から、化粧料全量に対して、１質量％以上であることが好ましく、３～３０質量％あるいは５～２５質量％とすることがさらに好ましい。 At least polar oil may be included as the oil component (C) of the present invention. Therefore, the cosmetic of the present invention includes an embodiment containing only polar oil as an oil component.
The amount of the oil (C) blended in the cosmetic according to the present invention is not particularly limited as long as it is an amount normally used for blending an ultraviolet scattering agent in the oil phase, but for example, with respect to the total amount of the cosmetic. It is mentioned that it is 1 to 40% by mass. (C) If the blending amount of the oil exceeds 40% by mass, the stability and usability tend to decrease. When a UV absorber is blended, it is preferably 1% by mass or more, or 3 to 30% by mass or 5 to 25, based on the total amount of the cosmetic, from the viewpoint of obtaining a sufficient UV protection effect by the UV absorber. It is more preferable to use% by mass.
＜（Ｄ）紫外線散乱剤＞
　本発明に係る化粧料に配合される（Ｄ）紫外線散乱剤（以下、単に「（Ｄ）成分」と称する場合がある）は、特に制限されないが、化粧料に通常用いられるものから適宜選択することができる。具体例としては、金属酸化物、例えば、酸化チタン、酸化亜鉛、酸化鉄、酸化セリウム、酸化タングステン等を挙げることができる。本発明においては、酸化チタン、酸化亜鉛が好ましい。 <(D) UV scatterer>
The (D) ultraviolet scattering agent (hereinafter, may be simply referred to as “(D) component”) blended in the cosmetic according to the present invention is not particularly limited, but is appropriately selected from those usually used in cosmetics. be able to. Specific examples include metal oxides such as titanium oxide, zinc oxide, iron oxide, cerium oxide, and tungsten oxide. In the present invention, titanium oxide and zinc oxide are preferable.
　本発明に用いられる（Ｄ）紫外線散乱剤は、粒子表面が疎水性である限りにおいて、表面無処理のもの、疎水化処理を施したもののいずれであってもよい。表面を疎水化するために種種の疎水化表面処理を用いることができる。疎水化表面処理の方法としては、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、メチルフェニルポリシロキサン等のシリコーンオイルや、メチルトリメトキシシラン、エチルトリメトキシシラン、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等のアルキルシランや、トリフルオロメチルエチ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のフルオロアルキルシラン等を用いたシリコーン処理；パーフルオロアルキルリン酸エステル、パーフルオロアルコール等を用いたフッ素化合物処理；Ｎ－アシルグルタミン酸、Ｎ－アシルアスパラギン酸、Ｎ－アシルリジン等を用いたアミノ酸処理；レシチン処理；金属石鹸処理；脂肪酸処理；アルキルリン酸エステル処理等が挙げられる。 The (D) ultraviolet scattering agent used in the present invention may be either untreated or hydrophobized as long as the surface of the particles is hydrophobic. Various types of hydrophobizing surface treatments can be used to hydrophobize the surface. Examples of the method for hydrophobizing surface treatment include silicone oils such as methylhydrogenpolysiloxane, dimethylpolysiloxane, and methylphenylpolysiloxane, and methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, and the like. Silicone treatment with alkylsilane, fluoroalkylsilane such as trifluoromethylethyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane; fluorine compound treatment with perfluoroalkyl phosphate, perfluoroalcohol, etc .; N -Amino acid treatment using acylglutamic acid, N-acylaspartic acid, N-acyllysine and the like; lecithin treatment; metal soap treatment; fatty acid treatment; alkyl phosphate ester treatment and the like.
　（Ｄ）成分の配合量は特に限定されないが、通常は化粧料全量に対して１質量％以上、例えば１～３０質量％、好ましくは１～２０質量％である。配合量が１質量％未満では十分な紫外線防御効果が得られにくく、３０質量％を超えると安定性が悪くなる傾向がある。
　本発明に係る化粧料は、乳化安定性に優れるので、１０質量％を超える紫外線散乱剤の配合が可能である。 The blending amount of the component (D) is not particularly limited, but is usually 1% by mass or more, for example, 1 to 30% by mass, preferably 1 to 20% by mass with respect to the total amount of the cosmetic. If the blending amount is less than 1% by mass, it is difficult to obtain a sufficient UV protection effect, and if it exceeds 30% by mass, the stability tends to deteriorate.
Since the cosmetic according to the present invention has excellent emulsification stability, it is possible to add an ultraviolet scattering agent exceeding 10% by mass.
　本発明に係る化粧料は、（Ｄ）紫外線散乱剤が内相である油滴中に分散している水中油中粉体型組成物である。 The cosmetic according to the present invention is a powder-type composition in oil in water in which (D) an ultraviolet scattering agent is dispersed in oil droplets as an internal phase.
　本発明に係る化粧料においては、油相は化粧料全量に対して１～５０質量％であることが好ましい。 In the cosmetics according to the present invention, the oil phase is preferably 1 to 50% by mass with respect to the total amount of the cosmetics.
＜（Ｅ）アニオン性界面活性剤＞
　本発明に係る化粧料に配合される（Ｅ）アニオン性界面活性剤（以下、単に「（Ｅ）成分」と称する場合がある）は、通常化粧料に用いられるものであればよく、前記（Ｂ）ポリオキシアルキレン変性シリコーン等のシリコーン系界面活性剤以外のものであって、カルボン酸、スルホン酸、リン酸構造を有するもの等の陰イオン性の親水基を持つ界面活性剤をいう。アニオン性界面活性剤の配合によりナノディスクが安定化する。 <(E) Anionic surfactant>
The (E) anionic surfactant (hereinafter, may be simply referred to as "(E) component") blended in the cosmetics according to the present invention may be any one usually used for cosmetics, and the above-mentioned ( B) A surfactant other than a silicone-based surfactant such as polyoxyalkylene-modified silicone, which has an anionic hydrophilic group such as a carboxylic acid, a sulfonic acid, and a surfactant having a phosphoric acid structure. The formulation of anionic surfactant stabilizes the nanodisc.
　なかでも、クラフト点が室温より高いアニオン性界面活性剤を用いるのが好ましい。アニオン性界面活性剤のクラフト点が室温より低い場合には、シリコーン系界面活性剤とアニオン性界面活性剤が混ざりやすく、相互作用しやすくなるため、ベシクルからナノディスクへの転移が妨げられる傾向がある。 Above all, it is preferable to use an anionic surfactant having a Krafft temperature higher than room temperature. When the Krafft temperature of the anionic surfactant is lower than room temperature, the silicone-based surfactant and the anionic surfactant are likely to mix and interact with each other, which tends to prevent the transfer from the vesicle to the nanodisc. be.
　本発明に係る化粧料に配合される（Ｅ）アニオン性界面活性剤としては、スルホン酸塩型アニオン性界面活性剤が好ましい。スルホン酸塩型アニオン性界面活性剤としては、スルホコハク酸ジエステル塩、アルキルアリルスルホン酸塩、アルキルエーテルスルホン酸塩、スルホコハク酸エステル塩、アシルメチルタウリン塩、アシルタウリン塩、セチルリン酸カリウム、ココイルグルタミン酸カリウム等が挙げられる。なかでも、アシルメチルタウリン塩、セチルリン酸カリウムおよびココイルグルタミン酸カリウムから選択して用いるのが好ましい。 As the (E) anionic surfactant to be blended in the cosmetics according to the present invention, a sulfonate-type anionic surfactant is preferable. Examples of the sulfonate-type anionic surfactant include sulfosuccinic acid diester salt, alkylallyl sulfonate, alkyl ether sulfonate, sulfosuccinic acid ester salt, acylmethyl taurine salt, acyl taurine salt, potassium cetyl phosphate, and potassium cocoyl glutamate. And so on. Among them, it is preferable to select and use from acylmethyltaurine salt, potassium cetylphosphate and potassium cocoylglutamate.
　本発明においては、特にＮ－アシルメチルタウリン塩を（Ｅ）アニオン性界面活性剤として配合することが好ましい。さらに下記式（４）で表されるＮ－アシルメチルタウリン塩の中でもＮ－ステアロイル－Ｎ－メチルタウリン塩であることが好ましい。 In the present invention, it is particularly preferable to add the N-acylmethyl taurine salt as the (E) anionic surfactant. Further, among the N-acylmethyl taurine salts represented by the following formula (4), the N-stearoyl-N-methyl taurine salt is preferable.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　（Ｅ）成分の配合量は、化粧料全量に対して０．０１～１質量％であることが好ましく、０．０１～０．１質量％であることがさらに好ましく、０．０１～０．０６質量％であることがより好ましい。配合量が０．０１質量％未満であるとナノディスクが十分に安定しない場合があり、１質量％を超えるとナノディスクの前駆体であるベシクルが可溶化されたり、ナノディスクの形成が妨げられる場合がある。
　また、（Ｂ）ポリオキシアルキレン変性シリコーンと（Ｅ）アニオン性界面活性剤との配合量比が質量比にして１：０ ．０１～１：０．０６であることが好ましい。 The blending amount of the component (E) is preferably 0.01 to 1% by mass, more preferably 0.01 to 0.1% by mass, and 0.01 to 0. It is more preferably 06% by mass. If the blending amount is less than 0.01% by mass, the nanodisk may not be sufficiently stable, and if it exceeds 1% by mass, the vesicle that is the precursor of the nanodisk is solubilized or the formation of the nanodisk is hindered. In some cases.
Further, the mixing amount ratio of (B) polyoxyalkylene-modified silicone and (E) anionic surfactant is 1: 0 in terms of mass ratio. It is preferably 01 to 1: 0.06.
　一般的に日焼け止め化粧料に美白剤を配合することも行われるが、通常、塩型である美白剤を外相である水相に配合すると安定性が悪くなる傾向が知られている。本発明に係る化粧料は特定のシリコーン系界面活性剤により形成されるナノディスクにより乳化するとともに配合する油分を限定することによって乳化力が強化されるので、水相に塩型の美白剤を配合しても振動安定性に優れるという効果を奏する。 Generally, a whitening agent is added to sunscreen cosmetics, but it is generally known that when a salt-type whitening agent is added to the aqueous phase, which is the outer phase, the stability tends to deteriorate. Since the cosmetic according to the present invention is emulsified by nanodiscs formed of a specific silicone-based surfactant and the emulsifying power is enhanced by limiting the oil content to be blended, a salt-type whitening agent is blended in the aqueous phase. Even so, it has the effect of being excellent in vibration stability.
　本発明に係る化粧料に配合される（Ｆ）美白剤（以下、単に「（Ｆ）成分」と称する場合がある）は化粧料に通常配合されるものであれば特に限定されない。具体例としては、Ｌ－アスコルビン酸およびその誘導体、トラネキサム酸およびその誘導体、アルコキシサリチル酸およびその誘導体、グリチルリチン酸およびその誘導体、ニコチン酸およびその誘導体等が挙げられる。本発明に係る化粧料においては、前記薬剤の１種または２種以上を組み合わせて配合してもよい。 The (F) whitening agent (hereinafter, may be simply referred to as "(F) component") blended in the cosmetic according to the present invention is not particularly limited as long as it is normally blended in the cosmetic. Specific examples include L-ascorbic acid and its derivatives, tranexamic acid and its derivatives, alkoxysalicylic acid and its derivatives, glycyrrhizic acid and its derivatives, nicotinic acid and its derivatives, and the like. In the cosmetics according to the present invention, one kind or a combination of two or more kinds of the above-mentioned agents may be blended.
　Ｌ－アスコルビン酸の誘導体としては、Ｌ－アスコルビン酸モノステアレート、Ｌ－アスコルビン酸モノパルミテート、Ｌ－アスコルビン酸モノオレートなどのＬ－アスコルビン酸モノアルキルエステル類；Ｌ－アスコルビン酸モノリン酸エステル、Ｌ－アスコルビン酸－２－硫酸エステルなどのＬ－アスコルビン酸モノエステル類；Ｌ－アスコルビン酸ジステアレート、Ｌ－アスコルビン酸ジパルミテート、Ｌ－アスコルビン酸ジオレートなどのＬ－アスコルビン酸ジアルキルエステル類；Ｌ－アスコルビン酸トリステアレート、Ｌ－アスコルビン酸トリパルミテート、Ｌ－アスコルビン酸トリオレートなどのＬ－アスコルビン酸トリアルキルエステル類；Ｌ－アスコルビン酸トリリン酸エステルなどのＬ－アスコルビン酸トリエステル類；Ｌ－アスコルビン酸２－グルコシドなどのＬ－アスコルビン酸グルコシド類などが挙げられる。本発明では、Ｌ－アスコルビン酸、Ｌ－アスコルビン酸リン酸エステル、Ｌ－アスコルビン酸－２－硫酸エステル、Ｌ－アスコルビン酸２－グルコシドおよびこれらの塩が好ましく用いられる。 Derivatives of L-ascorbic acid include L-ascorbic acid monoalkyl esters such as L-ascorbic acid monostearate, L-ascorbic acid monopalmitate, and L-ascorbic acid monoolate; L-ascorbic acid monophosphate ester, L. -L-ascorbic acid monoesters such as ascorbic acid-2-sulfate ester; L-ascorbic acid dialkyl esters such as L-ascorbic acid distearate, L-ascorbic acid dipalmitate, L-ascorbic acid dioleate; L-ascorbic acid tri L-ascorbic acid trialkyl esters such as stearate, L-ascorbic acid tripalmitate, L-ascorbic acid triolate; L-ascorbic acid triesters such as L-ascorbic acid triphosphate; L-ascorbic acid 2 -L-ascorbic acid glucosides such as glucoside can be mentioned. In the present invention, L-ascorbic acid, L-ascorbic acid phosphate ester, L-ascorbic acid-2-sulfate ester, L-ascorbic acid 2-glucoside and salts thereof are preferably used.
　トラネキサム酸の誘導体としては、トラネキサム酸の二量体、（例えば、塩酸トランス－４－（トランス－アミノメチルシクロヘキサンカルボニル）アミノメチルシクロヘキサンカルボン酸、等）、トラネキサム酸とハイドロキノンのエステル体（例えば、４－（トランス－アミノメチルシクロヘキサンカルボン酸４’－ヒドロキシフェニルエステル、等）、トラネキサム酸とゲンチシン酸のエステル体（例えば、２－（トランス－４－アミノメチルシクロヘキシルカルボニルオキシ）－５－ヒドロキシ安息香酸、等）、トラネキサム酸のアミド体（例えば、トランス－４－アミノメチルシクロヘキサンカルボン酸メチルアミド、トランス－４－（ｐ－メトキシベンゾイル）アミノメチルシクロヘキサンカルボン酸、トランス－４－グアニジノメチルシクロヘキサンカルボン酸、等）などが挙げられる。本発明ではトラネキサム酸およびその塩が好ましく用いられる。 Derivatives of tranexamic acid include dimers of tranexamic acid (eg, trans-4- (trans-aminomethylcyclohexanecarbonyl) aminomethylcyclohexanecarboxylic acid, etc.), esters of tranexamic acid and hydroquinone (eg, 4). -(Trans-aminomethylcyclohexanecarboxylic acid 4'-hydroxyphenyl ester, etc.), ester of tranexamic acid and gentisic acid (eg 2- (trans-4-aminomethylcyclohexylcarbonyloxy) -5-hydroxybenzoic acid, Etc.), Amidos of tranexamic acid (eg, trans-4-aminomethylcyclohexanecarboxylic acid methylamide, trans-4- (p-methoxybenzoyl) aminomethylcyclohexanecarboxylic acid, trans-4-guanidinomethylcyclohexanecarboxylic acid, etc.) In the present invention, tranexamic acid and a salt thereof are preferably used.
　アルコキシサリチル酸の誘導体は、サリチル酸の３位、４位または５位のいずれかの水素原子がアルコキシ基にて置換されたものであり、置換基であるアルコキシ基は、好ましくはメトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基のいずれかであり、さらに好ましくはメトキシ基またはエトキシ基である。具体的に化合物名を例示すれば、３－メトキシサリチル酸、３－エトキシサリチル酸、４－メトキシサリチル酸、４－エトキシサリチル酸、４－プロポキシサリチル酸、４－イソプロポキシサリチル酸、４－ブトキシサリチル酸、５－メトキシサリチル酸、５－エトキシサリチル酸、５－プロポキシサリチル酸などが挙げられる。本発明ではメトキシサリチル酸およびその塩（メトキシサリチル酸カリウム塩）が好ましく用いられる。 The derivative of alkoxysalicylic acid is one in which the hydrogen atom at any of the 3-position, 4-position or 5-position of salicylic acid is substituted with an alkoxy group, and the alkoxy group as the substituent is preferably a methoxy group, an ethoxy group, or the like. It is any one of a propoxy group, an isopropoxy group, a butoxy group and an isobutoxy group, and more preferably a methoxy group or an ethoxy group. Specific examples of compound names include 3-methoxysalicylic acid, 3-ethoxysalicylic acid, 4-methoxysalicylic acid, 4-ethoxysalicylic acid, 4-propoxysalicylic acid, 4-isopropoxysalicylic acid, 4-butoxysalicylic acid, and 5-methoxysalicylic acid. , 5-ethoxysalicylic acid, 5-propoxysalicylic acid and the like. In the present invention, methoxysalicylic acid and a salt thereof (potassium methoxysalicylic acid salt) are preferably used.
　グリチルリチン酸の誘導体としては、グリチルリチン酸の塩、グリチルリチン酸と高級アルコールとのエステルなどが挙げられる。本発明ではグリチルリチン酸およびその塩（グリチルリチン酸ジカリウム塩、グリチルリチン酸モノアンモニウム塩等）が好ましく用いられる。 Examples of the derivative of glycyrrhizic acid include salts of glycyrrhizic acid and esters of glycyrrhizic acid and higher alcohols. In the present invention, glycyrrhizic acid and salts thereof (dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, etc.) are preferably used.
　上記薬剤の塩としては、特に限定されないが、例えば、ナトリウム塩、カリウム塩、カルシウム塩のようなアルカリ金属塩またはアルカリ土類金属塩のほか、アンモニウム塩、アミノ酸塩等が挙げられる。 The salt of the above-mentioned drug is not particularly limited, and examples thereof include alkali metal salts such as sodium salt, potassium salt and calcium salt, alkaline earth metal salts, ammonium salts, amino acid salts and the like.
　ニコチン酸およびその誘導体としては、ニコチン酸、ニコチン酸ベンジル、ニコチン酸アミド、ニコチン酸ｄｌ－α－トコフェロールなどが挙げられる。本発明ではニコチン酸アミドが好ましく用いられる。 Examples of nicotinic acid and its derivatives include nicotinic acid, benzyl nicotinate, nicotinic acid amide, and dl-α-tocopherol nicotinate. Nicotinamide is preferably used in the present invention.
　（Ｆ）美白剤の配合量は、化粧料全量に対して、０．０５～１０質量％であり、好ましくは０．１～７質量％、さらに好ましくは０．５～５質量％である。配合量が０．０５質量％未満では十分な薬効が得られにくく、１０質量％を超えると安定性や使用性が悪くなる傾向がある。
　本発明の（Ｆ）美白剤は、他の水性成分とともに水相中に溶解または分散していてよい。 The blending amount of the (F) whitening agent is 0.05 to 10% by mass, preferably 0.1 to 7% by mass, and more preferably 0.5 to 5% by mass with respect to the total amount of the cosmetic. If the blending amount is less than 0.05% by mass, it is difficult to obtain a sufficient medicinal effect, and if it exceeds 10% by mass, the stability and usability tend to deteriorate.
The (F) whitening agent of the present invention may be dissolved or dispersed in the aqueous phase together with other aqueous components.
（Ｇ）分散剤
　本発明に係る化粧料には、（Ｇ）分散剤を１種または２種以上配合することができる。分散剤の具体例としては、セスキイソステアリン酸ソルビタン、イソステアリン酸、パルミチン酸、ポリヒドロキシステアリン酸等が挙げられる。これらのなかでも、セスキイソステアリン酸ソルビタンとイソステアリン酸は、特に好適なものとして例示され、これらの一方または両方が配合されてよい。 (G) Dispersant The cosmetic according to the present invention may contain one or more (G) dispersants. Specific examples of the dispersant include sorbitan sesquiisostearate, isostearic acid, palmitic acid, polyhydroxystearic acid and the like. Among these, sorbitan sesquiisostearate and isostearic acid are exemplified as particularly suitable ones, and one or both of them may be blended.
　（Ｇ）分散剤は、本発明の化粧料における選択的配合成分であるから、必ず配合しなければならないものではないが、配合する場合には、当該配合の効果が認められる程度に、かつ、配合量が過度になって使用感を損なう等の弊害が認められない限度で配合することが好ましい。本発明に係る化粧料における（Ｇ）分散剤の好適な配合量としては、化粧料全量に対して０．０１～１質量％程度が好ましい。 (G) The dispersant is a selective compounding ingredient in the cosmetics of the present invention, and therefore must be blended, but when blended, the effect of the blending is recognized and the dispersant is blended. It is preferable to add the mixture to the extent that no adverse effects such as an excessive amount of the compounding and impairing the usability are observed. The suitable blending amount of the (G) dispersant in the cosmetic according to the present invention is preferably about 0.01 to 1% by mass with respect to the total amount of the cosmetic.
　本発明に係る化粧料に配合される水は、イオン交換水、精製水、水道水、天然水等、必要に応じて選択される。配合量は、本発明に係る必須成分と、その他の任意的配合成分の和に対する残量（化粧料全量に対する質量％）である。一般的には、化粧料全量に対して３０～７０質量％程度が好適である。 The water to be blended in the cosmetic according to the present invention is selected as necessary, such as ion-exchanged water, purified water, tap water, and natural water. The blending amount is the remaining amount (mass% with respect to the total amount of cosmetics) with respect to the sum of the essential ingredient according to the present invention and other optional blending ingredients. Generally, about 30 to 70% by mass is preferable with respect to the total amount of cosmetics.
　本発明に係る水中油型乳化化粧料には、上記成分の他に、本発明の目的・効果を損なわない範囲で、通常化粧品や医薬品等の皮膚外用剤に用いられる他の任意の添加成分、例えば、油脂、ロウ類、高級脂肪酸、高級アルコール、油相増粘剤、界面活性剤、水溶性紫外線吸収剤、顔料、キレート剤、低級アルコール、多価アルコール、ｐＨ調整剤、酸化防止剤、粉末成分、香料等を必要に応じて適宜配合することができる。ただし、これら例示に限定されるものではない。 In addition to the above-mentioned ingredients, the oil-in-water emulsified cosmetic according to the present invention includes any other additive ingredients usually used for external skin preparations such as cosmetics and pharmaceuticals, as long as the purpose and effect of the present invention are not impaired. For example, fats and oils, waxes, higher fatty acids, higher alcohols, oil phase thickeners, surfactants, water-soluble ultraviolet absorbers, pigments, chelating agents, lower alcohols, polyhydric alcohols, pH adjusters, antioxidants, powders. Ingredients, fragrances and the like can be appropriately blended as needed. However, the present invention is not limited to these examples.
　本発明に係るナノディスクの前駆体であるベシクルは、（Ｂ）ポリオキシアルキレン変性シリコーンを（Ａ）水性成分と十分に混合し、次いでその混合液を（Ａ）成分以外の水性成分を含む水相に攪拌しながら滴下することによって、ベシクル水分散液として製造することができる。前記（Ｂ）ポリオキシアルキレン変性シリコーンと（Ａ）水性成分の混合状態は、当該混合液が透明で一相状態であることが確認できればよく、例えば、室温～９０℃で１～３０分間混合を行うことで達成することができる。この方法により、動的光散乱法によって測定される平均粒子径が３０～１５０ｎｍであるベシクル粒子が得られる。 In the vesicle which is the precursor of the nanodisk according to the present invention, (B) polyoxyalkylene-modified silicone is sufficiently mixed with (A) an aqueous component, and then the mixed solution is water containing an aqueous component other than (A) component. It can be produced as a vesicle aqueous dispersion by dropping the mixture into the phase while stirring. The mixed state of the (B) polyoxyalkylene-modified silicone and the (A) aqueous component may be as long as it can be confirmed that the mixed solution is transparent and in a one-phase state. For example, mixing is performed at room temperature to 90 ° C. for 1 to 30 minutes. It can be achieved by doing. By this method, vesicle particles having an average particle size of 30 to 150 nm measured by a dynamic light scattering method can be obtained.
　本発明に係るベシクルは、常法により、ベシクルの二分子膜内部に油性成分を保持した形態として製造することもできる。具体的には、本発明に係るベシクルは、（Ｂ）ポリオキシアルキレン変性シリコーンと（Ａ）水性成分を混合する工程において、香料等の油溶性成分を添加して混合することにより、該油溶性成分をベシクルの二分子膜内に保持したベシクルとして製造されてもよい。 The vesicle according to the present invention can also be produced in a form in which an oily component is retained inside the bilayer membrane of the vesicle by a conventional method. Specifically, the vesicle according to the present invention is oil-soluble by adding and mixing an oil-soluble component such as a fragrance in the step of mixing (B) polyoxyalkylene-modified silicone and (A) an aqueous component. It may be produced as a vesicle in which the component is retained in the bilayer membrane of the vesicle.
　本発明に係る水中油型乳化化粧料は、ベシクルを含む水相中に、アニオン性界面活性剤と油分を添加し、強い攪拌力を加えながら分散することによって、ベシクルから転移したナノディスクによって乳化されたものである。本発明の化粧料は、ナノディスク（相）が油相（油滴）に付着した、水相－ナノディスク相－油相の三相構造により安定化される。
　よって、本発明に係る水中油型乳化化粧料は、ポリオキシアルキレン変性シリコーンからなるナノディスクが油水界面、つまり油相からなる油滴の周りに付着（局在）していることを特徴とする。前記ナノディスクは、その長径が２０ｎｍ～１０００ｎｍである。 The oil-in-water emulsified cosmetic according to the present invention is emulsified by nanodiscs transferred from vesicles by adding an anionic surfactant and oil to the aqueous phase containing vesicles and dispersing while applying strong stirring force. It was done. The cosmetic of the present invention is stabilized by a three-phase structure of aqueous phase-nanodisc phase-oil phase in which nanodiscs (phases) are attached to oil phases (oil droplets).
Therefore, the oil-in-water emulsified cosmetic according to the present invention is characterized in that nanodiscs made of polyoxyalkylene-modified silicone are attached (localized) around the oil-water interface, that is, around the oil droplets made of the oil phase. .. The major axis of the nanodisk is 20 nm to 1000 nm.
　本発明に係る水中油型乳化化粧料における水相－ナノディスク相－油相の三相構造は常法により形成させることができる。すなわち、撹拌下で、ポリオキシアルキレン変性シリコーンを水性成分へ滴下してベシクル粒子を形成させてベシクル水分散液を得て、このベシクル水分散液にアニオン性界面活性剤と別途混合溶解した油性成分を加え、強い攪拌力にて分散すると、ベシクルがナノディスクに転移し、水相－ナノディスク相－油相の三相構造となる。水相中に油性成分からなる油滴が乳化分散し、さらに油滴粒子表面にナノディスクが局在しているため、乳化安定性に優れるとともに、使用感（みずみずしさ、べたつきのなさ）にも優れている。なお、撹拌に用いられる撹拌装置は特に限定されるものではなく、例えばホモミキサー、ディスパー等を使用することができる。 The three-phase structure of the aqueous phase-nanodisc phase-oil phase in the oil-in-water emulsified cosmetic according to the present invention can be formed by a conventional method. That is, under stirring, polyoxyalkylene-modified silicone was dropped onto an aqueous component to form vesicle particles to obtain a vesicle aqueous dispersion, and an oily component separately mixed and dissolved with an anionic surfactant in this vesicle aqueous dispersion. Is added and dispersed with a strong stirring force, the vesicles are transferred to the nanodisks, forming a three-phase structure of aqueous phase-nanodisk phase-oil phase. Oil droplets composed of oily components are emulsified and dispersed in the aqueous phase, and nanodisks are localized on the surface of the oil droplet particles, so that the emulsification stability is excellent and the feeling of use (freshness, non-stickiness) is also improved. Are better. The stirring device used for stirring is not particularly limited, and for example, a homomixer, a disper, or the like can be used.
　なお、本発明においては、水相中に形成されるベシクル粒子は、前記したホモミキサー等で強シェアをかけることによって、十分に微小な粒子径に成型させ、水相中に均一分散させることができる。強シェアの程度は特に限定されないが、通常、ホモミキサーによる７０００～１２０００回転／分の条件で５分間程度とする。 In the present invention, the vesicle particles formed in the aqueous phase can be molded into a sufficiently fine particle size by applying a strong share with the above-mentioned homomixer or the like, and uniformly dispersed in the aqueous phase. can. The degree of strong share is not particularly limited, but is usually about 5 minutes under the condition of 7,000 to 12,000 rpm by a homomixer.
　本発明の化粧料は、水相中にベシクル粒子を形成させ、そのベシクル分散液にアニオン性界面活性剤を添加した後に、油性成分を加えて乳化することによって得られる。
　したがって、本発明に係る水中油型乳化化粧料の製造方法は、（Ａ）水性成分と（Ｂ）ポリオキシアルキレン変性シリコーンとを混合してベシクルを形成するベシクル形成工程と、ベシクル形成工程で得られたベシクル分散液に、アニオン性界面活性剤を添加して混合液を得る工程と、前記工程によって得られた混合液に別途混合溶解した油性成分を攪拌およびせん断力を加えながら乳化させる乳化工程と、を備える。 The cosmetic of the present invention is obtained by forming vesicle particles in an aqueous phase, adding an anionic surfactant to the vesicle dispersion, and then adding an oily component to emulsify.
Therefore, the method for producing an oil-in-water emulsified cosmetic according to the present invention is obtained by a vesicle forming step of mixing (A) an aqueous component and (B) a polyoxyalkylene-modified silicone to form a vesicle, and a vesicle forming step. A step of adding an anionic surfactant to the obtained vesicle dispersion to obtain a mixed solution, and an emulsification step of emulsifying an oily component separately mixed and dissolved in the mixed solution obtained by the above step while applying stirring and shearing force. And prepare.
　前記ベシクル形成工程においては、（Ａ）水性成分と（Ｂ）ポリオキシアルキレン変性シリコーンを予め溶解し、その溶解物を残りの水相成分と混合することで水相中にベシクルが分散したベシクル分散液を得てもよいし、（Ａ）水性成分と（Ａ）成分以外の水性成分とを含む水相に（Ｂ）ポリオキシアルキレン変性シリコーンを混合攪拌することで水相中にベシクルが分散したベシクル分散液を得てもよい。 In the vesicle forming step, (A) an aqueous component and (B) a polyoxyalkylene-modified silicone are previously dissolved, and the solution is mixed with the remaining aqueous phase components to disperse the vesicles in the aqueous phase. A liquid may be obtained, or the vesicles are dispersed in the aqueous phase by mixing and stirring (B) the polyoxyalkylene-modified silicone in the aqueous phase containing (A) an aqueous component and an aqueous component other than (A). A vesicle dispersion may be obtained.
　本発明に係る化粧料は、水中油型乳化物に特有のみずみずしい使用感触があり、優れた紫外線防御効果を発揮する。また、本発明に係るナノディスク含有乳化物は、通常の可溶化物では配合できない程度の多くの量の油分を配合できるにもかかわらずさっぱりした使用感が得られる。 The cosmetic according to the present invention has a fresh feeling of use peculiar to an oil-in-water emulsion and exhibits an excellent UV protection effect. In addition, the nanodisc-containing emulsion according to the present invention can be blended with a large amount of oil that cannot be blended with a normal solubilized product, yet a refreshing feeling of use can be obtained.
　本発明に係る化粧料は、クリーム状、乳液状、液状等の様々な剤型で好適に用いられる。製品形態としては、日焼け止め効果を有するスキンケア化粧料として、あるいは日焼け止め効果を有する下地、ファンデーション等のメーキャップ化粧料とすることができる。 The cosmetic according to the present invention is suitably used in various dosage forms such as creamy, milky liquid, and liquid. As a product form, it can be a skin care cosmetic having a sunscreen effect, or a make-up cosmetic such as a foundation or a foundation having a sunscreen effect.
　以下に実施例を挙げて本発明をさらに詳述するが、本発明はこれらにより何ら限定されるものではない。配合量は特記しない限り、その成分が配合される系に対する質量％で示す。各実施例について具体的に説明する前に、採用した評価方法について説明する。 The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Unless otherwise specified, the blending amount is shown in mass% with respect to the system in which the component is blended. Before concretely explaining each embodiment, the adopted evaluation method will be described.
１．振動安定性
　調製した試料３０ｍｌを樹脂チューブに入れ、３０分間、１０Ｈｚ以上の条件で振動を与え、静置後の試料の乳化分離および粉末の凝集状態を目視により観察した。評価は以下の基準に基づいて行った。
Ａ：乳化破壊や粉末の凝集が見られない。
Ｂ：乳化破壊や粉末の凝集があまり見られない。
Ｃ：乳化破壊や粉末の凝集が見られる。
Ｄ：乳化破壊や粉末の凝集が激しく見られる。 1. 1. Vibration stability 30 ml of the prepared sample was placed in a resin tube, vibrated for 30 minutes under the condition of 10 Hz or higher, and the emulsified separation and powder aggregation state of the sample after standing were visually observed. The evaluation was based on the following criteria.
A: No emulsification destruction or powder agglomeration is observed.
B: Emulsification destruction and powder agglomeration are rarely seen.
C: Emulsification destruction and powder agglomeration are observed.
D: Emulsification destruction and powder agglomeration are severely observed.
２．耐水性
　耐水性は、化粧料中に配合される紫外線防御剤（紫外線吸収剤および紫外線散乱剤）が有する紫外線防御能を水浴の前後で測定し、水浴後に残存する紫外線防御能の割合（吸光度の残存率）を算出することによって、耐水性の強度を測定した。具体的には、測定プレート（Ｓプレート）（５×５ｃｍのＶ溝ＰＭＭＡ板、ＳＰＦＭＡＳＴＥＲ－ＰＡ０１）に各例の化粧料（サンプル）を２ｍｇ／ｃｍ２の量で滴下し、６０秒間指で塗布し、１５分間乾燥した後に形成された塗膜の吸光度を株式会社日立製作所製Ｕ－３５００型自記録分光光度計にて測定した。紫外線吸収のないグリセリンをコントロールとし、吸光度（Ａｂｓ）を以下の式で算出した。
　Ａｂｓ＝－ｌｏｇ（Ｔ／Ｔｏ）
　Ｔ：サンプルの透過率、Ｔｏ：グリセリンの透過率
　測定したプレートを硬度５０～５００の水に十分に浸し、３０分間そのまま水中で撹拌した（３－１モーターで３００ｒｐｍ）。その後、表面の水滴がなくなるまで１５～３０分程度乾燥させ、再び吸光度を測定し、水浴前後のＡｂｓ積算値からＡｂｓ残存率（以下の式）を算出した。
　Ａｂｓ残存率（％）＝（水浴後のＡｂｓ積算値）／（水浴前のＡｂｓ積算値）×１００
　算出したＡｂｓ残存率に基づいて、以下の基準で判定した。
Ａ：８０％以上残存している。
Ｂ：６０％以上かつ８０％未満残存している。
Ｃ：６０％未満残存している。 2. 2. Water resistance Water resistance measures the UV protection ability of UV protection agents (UV absorbers and UV scattering agents) contained in cosmetics before and after bathing, and the ratio of UV protection ability remaining after bathing (absorbance). By calculating the residual rate), the strength of water resistance was measured. Specifically, the cosmetics (samples) of each example were dropped onto a measurement plate (S plate) (5 x 5 cm V-groove PMMA plate, SPFMASTER-PA01) in an amount of 2 mg / cm 2 and applied with a finger for 60 seconds. Then, the absorbance of the coating film formed after drying for 15 minutes was measured with a U-3500 type self-recording spectrophotometer manufactured by Hitachi, Ltd. The absorbance (Abs) was calculated by the following formula using glycerin having no ultraviolet absorption as a control.
Abs = -log (T / To)
T: Sample transmittance, To: Glycerin permeability The measured plate was sufficiently immersed in water having a hardness of 50 to 500 and stirred as it was in water for 30 minutes (300 rpm with a 3-1 motor). Then, it was dried for about 15 to 30 minutes until the water droplets on the surface disappeared, the absorbance was measured again, and the Abs residual ratio (the following formula) was calculated from the Abs integrated value before and after the water bath.
Abs residual rate (%) = (Abs integrated value after water bath) / (Abs integrated value before water bath) × 100
Based on the calculated Abs residual rate, the determination was made according to the following criteria.
A: 80% or more remains.
B: 60% or more and less than 80% remains.
C: Less than 60% remains.
（実施例１～１６、比較例１～７）
　表１および表２に掲げた組成を有する日焼け止め化粧料を調製した。具体的には、エタノールとベシクルを形成する両親媒性物質（ポリオキシアルキレン変性シリコーン、ポリオキシエチレン硬化ヒマシ油）とを混合攪拌した後、前記混合液にアニオン性界面活性剤と他の水性成分を混合して水相溶液を得て、油性成分および粉末成分を別途混合して得た油相溶液を、前記水相溶液に攪拌しながら混合することによって、水中油型乳化化粧料を得た。調製した試料について、前記した評価方法に従って振動安定性および耐水性を評価した。結果は表中に示す。 (Examples 1 to 16, Comparative Examples 1 to 7)
Sunscreen cosmetics having the compositions listed in Tables 1 and 2 were prepared. Specifically, after mixing and stirring ethanol and an amphoteric substance (polyoxyalkylene-modified silicone, polyoxyethylene hydrogenated castor oil) forming a vesicle, an anionic surfactant and other aqueous components are added to the mixed solution. Was mixed to obtain an aqueous phase solution, and the oil phase solution obtained by separately mixing the oily component and the powder component was mixed with the aqueous phase solution while stirring to obtain an oil-in-water emulsified cosmetic. .. The prepared sample was evaluated for vibration stability and water resistance according to the above-mentioned evaluation method. The results are shown in the table.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
＊１：ＫＦ－９６Ｌ－１．５ＣＳ（信越化学社製）揮発速度約５０％
＊２：ＫＦ－９６Ｌ－６Ｔ（信越化学社製）揮発速度１０％以下
＊３：ＫＦ－９６Ａ－２０ＣＳ（信越化学社製）揮発速度１０％以下 * 1: KF-96L-1.5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) Volatilization rate approx. 50%
* 2: KF-96L-6T (manufactured by Shin-Etsu Chemical Co., Ltd.) Volatilization rate of 10% or less * 3: KF-96A-20CS (manufactured by Shin-Etsu Chemical Co., Ltd.) Volatilization rate of 10% or less
　表１では、ベシクルを形成する両親媒性物質、（Ｅ）アニオン性界面活性剤、（Ｃ）油分を変えて調製した化粧料を示す。
　ベシクルを形成する両親媒性物質としてポリオキシエチレン硬化ヒマシ油を用い、（Ｅ）アニオン性界面活性剤を含まない比較例１および比較例２の化粧料は、耐水性が劣り、振動安定性が十分に得られない場合があった。また、本発明の（Ｂ）ポリオキシアルキレン変性シリコーンを用いた場合であっても、（Ｅ）アニオン性界面活性剤を含まない比較例３の化粧料は、振動安定性および耐水性がともに劣っていた。 Table 1 shows cosmetics prepared by changing the amphipathic substance forming the vesicle, (E) anionic surfactant, and (C) oil.
The cosmetics of Comparative Example 1 and Comparative Example 2 in which polyoxyethylene hydrogenated castor oil was used as an amphipathic substance forming a vesicle and did not contain (E) anionic surfactant had poor water resistance and vibration stability. Sometimes it wasn't enough. Further, even when the (B) polyoxyalkylene-modified silicone of the present invention is used, the cosmetic of Comparative Example 3 containing no (E) anionic surfactant is inferior in both vibration stability and water resistance. Was there.
　本発明の水中油型乳化化粧料である実施例１および実施例２の化粧料はいずれも振動安定性および耐水性に優れていた。本発明の（Ｂ）ポリオキシアルキレン変性シリコーンの代わりに両親媒性物質としてポリオキシエチレン硬化ヒマシ油を用いた比較例４の化粧料では、振動安定性は優れていたが、耐水性は劣っていた。 The cosmetics of Example 1 and Example 2, which are the oil-in-water emulsified cosmetics of the present invention, were both excellent in vibration stability and water resistance. In the cosmetic of Comparative Example 4 in which polyoxyethylene cured castor oil was used as an amphipathic substance instead of the (B) polyoxyalkylene-modified silicone of the present invention, the vibration stability was excellent, but the water resistance was inferior. rice field.
　本発明の（Ｅ）アニオン性界面活性剤としてセチルリン酸カリウム、ココイルグルタミン酸カリウムを用いた実施例３および実施例４の化粧料においても、十分な振動安定性および耐水性が得られた。 Sufficient vibration stability and water resistance were also obtained in the cosmetics of Examples 3 and 4 using potassium cetyl phosphate and potassium cocoyl glutamate as the (E) anionic surfactant of the present invention.
　また、油分として極性油（セバシン酸ジイソプロピル、エチルヘキサン酸セチル、紫外線吸収剤）を配合する実施例１～７および１１の化粧料、油分として極性油に加えシリコーン油または炭化水素油を配合する実施例８～１０の化粧料はいずれも、優れた振動安定性および耐水性を有していた。実施例７に示すように、紫外線吸収剤を含まなくとも極性油を配合すれば優れた振動安定性および耐水性が得られることが確認できた。 Further, the cosmetics of Examples 1 to 7 and 11 in which polar oil (diisopropyl sebacate, cetyl ethylhexanate, ultraviolet absorber) is blended as an oil component, and silicone oil or hydrocarbon oil is blended in addition to polar oil as an oil component. All of the cosmetics of Examples 8 to 10 had excellent vibration stability and water resistance. As shown in Example 7, it was confirmed that excellent vibration stability and water resistance can be obtained by blending polar oil without containing an ultraviolet absorber.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
＊１：ＫＦ－９６Ｌ－１．５ＣＳ（信越化学社製）揮発速度約５０％
＊２：ＫＦ－９６Ｌ－６Ｔ（信越化学社製）揮発速度１０％以下
＊３：ＫＦ－９６Ａ－２０ＣＳ（信越化学社製）揮発速度１０％以下 * 1: KF-96L-1.5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) Volatilization rate approx. 50%
* 2: KF-96L-6T (manufactured by Shin-Etsu Chemical Co., Ltd.) Volatilization rate of 10% or less * 3: KF-96A-20CS (manufactured by Shin-Etsu Chemical Co., Ltd.) Volatilization rate of 10% or less
　表２では、紫外線吸収剤を除く油分の合計量に対して低分子油分が占める割合を変えて調製した化粧料を示す。
　低分子油分である揮発速度９０％以上のイソドデカンまたは揮発速度約５０％のジメチコンを配合する化粧料のうち、紫外線吸収剤を除く油分の合計量に対するこれら低分子油分の割合が５０％を超える比較例５、比較例６および比較例７の化粧料では、振動安定性が著しく低下した。
　一方、紫外線吸収剤を除く油分の合計量に対する低分子油分の割合が５０％である化粧料（実施例１２、実施例１４、実施例１５）、２５％である化粧料（実施例１３、実施例１６）はいずれも、十分な振動安定性を有していた。 Table 2 shows cosmetics prepared by changing the ratio of small molecule oil to the total amount of oil excluding ultraviolet absorbers.
Comparison of cosmetics containing isododecane with a volatilization rate of 90% or more, which is a low molecular weight oil, or dimethicone with a volatility rate of about 50%, in which the ratio of these low molecular weight oils to the total amount of oils excluding UV absorbers exceeds 50%. In the cosmetics of Example 5, Comparative Example 6 and Comparative Example 7, the vibration stability was significantly reduced.
On the other hand, cosmetics in which the ratio of the small molecule oil content to the total amount of oil excluding the ultraviolet absorber is 50% (Example 12, Example 14, Example 15) and cosmetics in which the ratio is 25% (Example 13, Implementation). All of Examples 16) had sufficient vibration stability.
（処方例）
　以下に、本発明の水中油型乳化化粧料の処方例を挙げる。本発明はこれらの処方例によって何ら限定されるものではなく、特許請求の範囲によって特定されるものであることはいうまでもない。なお、配合量はすべて製品全量に対する質量％で表す。 (Prescription example)
The following is a prescription example of the oil-in-water emulsified cosmetic of the present invention. It goes without saying that the present invention is not limited to these prescription examples, and is specified by the scope of claims. In addition, all the compounding amounts are expressed by mass% with respect to the total amount of products.
処方例１．日焼け止め美容液
成分名称　　　　　　　　　　　　　　　　　　　　　　配合量（質量％）
水　　　　　　　　　　　　　　　　　　　　　　　　　　残余
トラネキサム酸　　　　　　　　　　　　　　　　　　　　２
メトキシサリチル酸Ｋ　　　　　　　　　　　　　　　　　１
ＥＤＴＡ－３Ｎａ　　　　　　　　　　　　　　　　　　　０．０５
グリセリン　　　　　　　　　　　　　　　　　　　　　　２
１，３－ブチレングリコール　　　　　　　　　　　　　　８
フェノキシエタノール　　　　　　　　　　　　　　　　　０．５
（ジメチルアクリルアミド／アクリロイルジメチルタウリンＮａ）クロスポ
リマー　　　　　　　　　　　　　　　　　　　　　　　　１
ステアロキシヒドロキシプロピルメチルセルロース　　　　０．１
キサンタンガム　　　　　　　　　　　　　　　　　　　　０．１
ステアロイルメチルタウリンＮａ　　　　　　　　　　　　０．０１
エタノール　　　　　　　　　　　　　　　　　　　　　　８
ＰＥＧ－１２ジメチコン　　　　　　　　　　　　　　　　１．５
ジメチコン　　　　　　　　　　　　　　　　　　　　　　２
セバシン酸ジイソプロピル　　　　　　　　　　　　　　　８
シリコーン処理酸化チタン　　　　　　　　　　　　　　　２
シリコーン処理黄色酸化鉄　　　　　　　　　　　　　　　０．０１
シリコーン処理赤色酸化鉄　　　　　　　　　　　　　　　０．０１
メトキシケイヒ酸エチルヘキシル　　　　　　　　　　　　５
ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジン
　　　　　　　　　　　　　　　　　　　　　　　　　　　２
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　　２
セスキイソステアリン酸ソルビタン　　　　　　　　　　　０．５
イソステアリン酸　　　　　　　　　　　　　　　　　　　０．５
シリカ・シリコーン処理酸化亜鉛　　　　　　　　　　　１２ Prescription example 1. Sunscreen serum Ingredient name Blending amount (mass%)
Water Residual Tranexamic Acid 2
Methoxysalicylic acid K 1
EDTA-3Na 0.05
Glycerin 2
1,3-butylene glycol 8
Phenoxyethanol 0.5
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Cross Polymer 1
Stearoxyhydroxypropylmethylcellulose 0.1
Xanthan gum 0.1
Stearoyl Methyl Taurine Na 0.01
Ethanol 8
PEG-12 Dimethicone 1.5
Dimethicone 2
Diisopropyl sebacate 8
Silicone treated titanium oxide 2
Silicone treated yellow iron oxide 0.01
Silicone treated red iron oxide 0.01
Ethylhexyl methoxycinnamate 5
Bisethylhexyloxyphenol methoxyphenyl triazine 2
Diethylaminohydroxybenzoyl hexyl benzoate 2
Sorbitan sesquiisostearate 0.5
Isostearic acid 0.5
Zinc oxide treated with silica / silicone 12
処方例２．日焼け止め美容液
成分名称　　　　　　　　　　　　　　　　　　　　　　配合量（質量％）
水　　　　　　　　　　　　　　　　　　　　　　　　　　残余
ナイアシンアミド　　　　　　　　　　　　　　　　　　　５
ＥＤＴＡ－３Ｎａ　　　　　　　　　　　　　　　　　　　０．０５
グリセリン　　　　　　　　　　　　　　　　　　　　　　２
１，３－ブチレングリコール　　　　　　　　　　　　　　８
フェノキシエタノール　　　　　　　　　　　　　　　　　０．５
（ジメチルアクリルアミド／アクリロイルジメチルタウリンＮａ）クロスポ
リマー　　　　　　　　　　　　　　　　　　　　　　　　０．５
ステアロキシヒドロキシプロピルメチルセルロース　　　　０．１
キサンタンガム　　　　　　　　　　　　　　　　　　　　０．１
ステアロイルメチルタウリンＮａ　　　　　　　　　　　　０．０１
エタノール　　　　　　　　　　　　　　　　　　　　　　８
ＰＥＧ－１２ジメチコン　　　　　　　　　　　　　　　　１．５
セバシン酸ジイソプロピル　　　　　　　　　　　　　　　８
シリコーン処理酸化チタン　　　　　　　　　　　　　　　２
シリコーン処理黄色酸化鉄　　　　　　　　　　　　　　　０．０１
シリコーン処理赤色酸化鉄　　　　　　　　　　　　　　　０．０１
メトキシケイヒ酸エチルヘキシル　　　　　　　　　　　　５
ｔ－ブチルメトキシジベンゾイルメタン　　　　　　　　　２
エチルヘキシルトリアゾン　　　　　　　　　　　　　　　１
セスキイソステアリン酸ソルビタン　　　　　　　　　　　０．５
イソステアリン酸　　　　　　　　　　　　　　　　　　　０．５
シリカ・シリコーン処理酸化亜鉛　　　　　　　　　　　１２ Prescription example 2. Sunscreen serum Ingredient name Blending amount (mass%)
Water Residual Niacinamide 5
EDTA-3Na 0.05
Glycerin 2
1,3-butylene glycol 8
Phenoxyethanol 0.5
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Cross Polymer 0.5
Stearoxyhydroxypropylmethylcellulose 0.1
Xanthan gum 0.1
Stearoyl Methyl Taurine Na 0.01
Ethanol 8
PEG-12 Dimethicone 1.5
Diisopropyl sebacate 8
Silicone treated titanium oxide 2
Silicone treated yellow iron oxide 0.01
Silicone treated red iron oxide 0.01
Ethylhexyl methoxycinnamate 5
t-Butylmethoxydibenzoylmethane 2
Ethylhexyl triazone 1
Sorbitan sesquiisostearate 0.5
Isostearic acid 0.5
Zinc oxide treated with silica / silicone 12
処方例３．ファンデーション
成分名称　　　　　　　　　　　　　　　　　　　　　　配合量（質量％）
水　　　　　　　　　　　　　　　　　　　　　　　　　　残余
ＥＤＴＡ－３Ｎａ　　　　　　　　　　　　　　　　　　　０．０５
グリセリン　　　　　　　　　　　　　　　　　　　　　　２
１，３－ブチレングリコール　　　　　　　　　　　　　　８
フェノキシエタノール　　　　　　　　　　　　　　　　　０．５
（ジメチルアクリルアミド／アクリロイルジメチルタウリンＮａ）クロスポ
リマー　　　　　　　　　　　　　　　　　　　　　　　　０．５
ステアロキシヒドロキシプロピルメチルセルロース　　　　０．１
キサンタンガム　　　　　　　　　　　　　　　　　　　　０．１
ステアロイルメチルタウリンＮａ　　　　　　　　　　　　０．０１
エタノール　　　　　　　　　　　　　　　　　　　　　　８
ＰＥＧ－１２ジメチコン　　　　　　　　　　　　　　　　１．５
セバシン酸ジイソプロピル　　　　　　　　　　　　　　　８
シリコーン処理酸化チタン　　　　　　　　　　　　　　　５
シリコーン処理黄色酸化鉄　　　　　　　　　　　　　　　４
シリコーン処理赤色酸化鉄　　　　　　　　　　　　　　　２
シリコーン処理黒色酸化鉄　　　　　　　　　　　　　　　０．１
メトキシケイヒ酸エチルヘキシル　　　　　　　　　　　　５
ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジン
　　　　　　　　　　　　　　　　　　　　　　　　　　　２
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　　２
セスキイソステアリン酸ソルビタン　　　　　　　　　　　０．５
イソステアリン酸　　　　　　　　　　　　　　　　　　　０．５
シリカ・シリコーン処理酸化亜鉛　　　　　　　　　　　１２ Prescription example 3. Foundation ingredient name Blending amount (mass%)
Water residue EDTA-3Na 0.05
Glycerin 2
1,3-butylene glycol 8
Phenoxyethanol 0.5
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Cross Polymer 0.5
Stearoxyhydroxypropylmethylcellulose 0.1
Xanthan gum 0.1
Stearoyl Methyl Taurine Na 0.01
Ethanol 8
PEG-12 Dimethicone 1.5
Diisopropyl sebacate 8
Silicone treated titanium oxide 5
Silicone treated yellow iron oxide 4
Silicone treated red iron oxide 2
Silicone treated black iron oxide 0.1
Ethylhexyl methoxycinnamate 5
Bisethylhexyloxyphenol methoxyphenyl triazine 2
Diethylaminohydroxybenzoyl hexyl benzoate 2
Sorbitan sesquiisostearate 0.5
Isostearic acid 0.5
Zinc oxide treated with silica / silicone 12
処方例４．ファンデーション
成分名称　　　　　　　　　　　　　　　　　　　　　　配合量（質量％）
水　　　　　　　　　　　　　　　　　　　　　　　　　　残余
ＥＤＴＡ－３Ｎａ　　　　　　　　　　　　　　　　　　　０．０５
グリセリン　　　　　　　　　　　　　　　　　　　　　　２
１，３－ブチレングリコール　　　　　　　　　　　　　　８
フェノキシエタノール　　　　　　　　　　　　　　　　　０．５
（ジメチルアクリルアミド／アクリロイルジメチルタウリンＮａ）クロスポ
リマー　　　　　　　　　　　　　　　　　　　　　　　　０．５
ステアロキシヒドロキシプロピルメチルセルロース　　　　０．１
キサンタンガム　　　　　　　　　　　　　　　　　　　　０．１
ステアロイルメチルタウリンＮａ　　　　　　　　　　　　０．０１
エタノール　　　　　　　　　　　　　　　　　　　　　　５
ＰＥＧ－１２ジメチコン　　　　　　　　　　　　　　　　１．５
セバシン酸ジイソプロピル　　　　　　　　　　　　　　　８
アミノ酸・エステル（セバシン酸イソステアリル、ステアロイルグルタミン
酸２Ｎａ、水酸化Ａｌ）処理酸化チタン　　　　　　　　　５
アミノ酸・エステル（セバシン酸イソステアリル、ステアロイルグルタミン
酸２Ｎａ、水酸化Ａｌ）処理黄色酸化鉄　　　　　　　　　１
アミノ酸・エステル（セバシン酸イソステアリル、ステアロイルグルタミン
酸２Ｎａ、水酸化Ａｌ）処理赤色酸化鉄　　　　　　　　　４
アミノ酸・エステル（セバシン酸イソステアリル、ステアロイルグルタミン
酸２Ｎａ、水酸化Ａｌ）処理黒色酸化鉄　　　　　　　　　０．１
サリチル酸エチルヘキシル　　　　　　　　　　　　　　　５
オクトクリレン　　　　　　　　　　　　　　　　　　　　５
ホモサレート　　　　　　　　　　　　　　　　　　　　　５
セスキイソステアリン酸ソルビタン　　　　　　　　　　　０．５
イソステアリン酸　　　　　　　　　　　　　　　　　　　０．５
シリカ・シリコーン処理酸化亜鉛　　　　　　　　　　　１２ Prescription example 4. Foundation ingredient name Blending amount (mass%)
Water residue EDTA-3Na 0.05
Glycerin 2
1,3-butylene glycol 8
Phenoxyethanol 0.5
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Cross Polymer 0.5
Stearoxyhydroxypropylmethylcellulose 0.1
Xanthan gum 0.1
Stearoyl Methyl Taurine Na 0.01
Ethanol 5
PEG-12 Dimethicone 1.5
Diisopropyl sebacate 8
Amino acid ester (isostearyl sebacate, stearoyl glutamic acid 2Na, aluminum hydroxide) treated titanium oxide 5
Amino acid ester (isostearyl sebacate, stearoyl glutamic acid 2Na, aluminum hydroxide) treated yellow iron oxide 1
Amino acid / ester (isostearyl sebacate, stearoyl glutamic acid 2Na, aluminum hydroxide) treated red iron oxide 4
Amino acid ester (isostearyl sebacate, stearoyl glutamic acid 2Na, aluminum hydroxide) treated black iron oxide 0.1
Ethylhexyl salicylate 5
Octocrylene 5
Homo salate 5
Sorbitan sesquiisostearate 0.5
Isostearic acid 0.5
Zinc oxide treated with silica / silicone 12
処方例５．ファンデーション
成分名称　　　　　　　　　　　　　　　　　　　　　　配合量（質量％）
水　　　　　　　　　　　　　　　　　　　　　　　　　　残余
ＥＤＴＡ－３Ｎａ　　　　　　　　　　　　　　　　　　　０．０５
グリセリン　　　　　　　　　　　　　　　　　　　　　　２
１，３－ブチレングリコール　　　　　　　　　　　　　　８
フェノキシエタノール　　　　　　　　　　　　　　　　　０．５
（ジメチルアクリルアミド／アクリロイルジメチルタウリンＮａ）クロスポ
リマー　　　　　　　　　　　　　　　　　　　　　　　　０．５
ステアロキシヒドロキシプロピルメチルセルロース　　　　０．１
キサンタンガム　　　　　　　　　　　　　　　　　　　　０．１
ステアロイルメチルタウリンＮａ　　　　　　　　　　　　０．０１
エタノール　　　　　　　　　　　　　　　　　　　　　　５
ＰＥＧ－１２ジメチコン　　　　　　　　　　　　　　　　１．５
セバシン酸ジイソプロピル　　　　　　　　　　　　　　　８
アミノ酸・エステル（セバシン酸イソステアリル、ステアロイルグルタミン
酸２Ｎａ、水酸化Ａｌ）処理酸化チタン　　　　　　　　　５
アミノ酸・エステル（セバシン酸イソステアリル、ステアロイルグルタミン
酸２Ｎａ、水酸化Ａｌ）処理黄色酸化鉄　　　　　　　　　１
アミノ酸・エステル（セバシン酸イソステアリル、ステアロイルグルタミン
酸２Ｎａ、水酸化Ａｌ）処理赤色酸化鉄　　　　　　　　　４
アミノ酸・エステル（セバシン酸イソステアリル、ステアロイルグルタミン
酸２Ｎａ、水酸化Ａｌ）処理黒色酸化鉄　　　　　　　　　０．１
メトキシケイヒ酸エチルヘキシル　　　　　　　　　　　　５
ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジン
　　　　　　　　　　　　　　　　　　　　　　　　　　　２
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　　２
セスキイソステアリン酸ソルビタン　　　　　　　　　　　０．５
イソステアリン酸　　　　　　　　　　　　　　　　　　　０．５
シリカ・シリコーン処理酸化亜鉛　　　　　　　　　　　１２ Prescription example 5. Foundation ingredient name Blending amount (mass%)
Water residue EDTA-3Na 0.05
Glycerin 2
1,3-butylene glycol 8
Phenoxyethanol 0.5
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Cross Polymer 0.5
Stearoxyhydroxypropylmethylcellulose 0.1
Xanthan gum 0.1
Stearoyl Methyl Taurine Na 0.01
Ethanol 5
PEG-12 Dimethicone 1.5
Diisopropyl sebacate 8
Amino acid ester (isostearyl sebacate, stearoyl glutamic acid 2Na, aluminum hydroxide) treated titanium oxide 5
Amino acid ester (isostearyl sebacate, stearoyl glutamic acid 2Na, aluminum hydroxide) treated yellow iron oxide 1
Amino acid / ester (isostearyl sebacate, stearoyl glutamic acid 2Na, aluminum hydroxide) treated red iron oxide 4
Amino acid ester (isostearyl sebacate, stearoyl glutamic acid 2Na, aluminum hydroxide) treated black iron oxide 0.1
Ethylhexyl methoxycinnamate 5
Bisethylhexyloxyphenol methoxyphenyl triazine 2
Diethylaminohydroxybenzoyl hexyl benzoate 2
Sorbitan sesquiisostearate 0.5
Isostearic acid 0.5
Zinc oxide treated with silica / silicone 12
処方例６．日焼け止め
成分名称　　　　　　　　　　　　　　　　　　　　　　配合量（質量％）
水　　　　　　　　　　　　　　　　　　　　　　　　　　残余
パルミチン酸デキストリン　　　　　　　　　　　　　　　１
ＰＥＧ／ＰＰＧ－９／２ジメチルエーテル　　　　　　　　２
ＥＤＴＡ－３Ｎａ　　　　　　　　　　　　　　　　　　　０．０５
グリセリン　　　　　　　　　　　　　　　　　　　　　　２
１，３－ブチレングリコール　　　　　　　　　　　　　　８
フェノキシエタノール　　　　　　　　　　　　　　　　　０．５
（ジメチルアクリルアミド／アクリロイルジメチルタウリンＮａ）クロスポ
リマー　　　　　　　　　　　　　　　　　　　　　　　　０．５
ステアロキシヒドロキシプロピルメチルセルロース　　　　０．１
キサンタンガム　　　　　　　　　　　　　　　　　　　　０．１
ステアロイルメチルタウリンＮａ　　　　　　　　　　　　０．０１
エタノール　　　　　　　　　　　　　　　　　　　　　　８
ＰＥＧ－１２ジメチコン　　　　　　　　　　　　　　　　１．５
セバシン酸ジイソプロピル　　　　　　　　　　　　　　　８
メトキシケイヒ酸エチルヘキシル　　　　　　　　　　　　５
ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジン
　　　　　　　　　　　　　　　　　　　　　　　　　　　２
エチルヘキシルトリアゾン　　　　　　　　　　　　　　　１
セスキイソステアリン酸ソルビタン　　　　　　　　　　　０．５
イソステアリン酸　　　　　　　　　　　　　　　　　　　０．５
シリカ・シリコーン処理酸化亜鉛　　　　　　　　　　　１２ Prescription example 6. Sunscreen ingredient name Blending amount (mass%)
Water Residual Dextrin Palmitate 1
PEG / PPG-9 / 2 dimethyl ether 2
EDTA-3Na 0.05
Glycerin 2
1,3-butylene glycol 8
Phenoxyethanol 0.5
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Cross Polymer 0.5
Stearoxyhydroxypropylmethylcellulose 0.1
Xanthan gum 0.1
Stearoyl Methyl Taurine Na 0.01
Ethanol 8
PEG-12 Dimethicone 1.5
Diisopropyl sebacate 8
Ethylhexyl methoxycinnamate 5
Bisethylhexyloxyphenol methoxyphenyl triazine 2
Ethylhexyl triazone 1
Sorbitan sesquiisostearate 0.5
Isostearic acid 0.5
Zinc oxide treated with silica / silicone 12
処方例７．日焼け止め
成分名称　　　　　　　　　　　　　　　　　　　　　　配合量（質量％）
水　　　　　　　　　　　　　　　　　　　　　　　　　　残余
ＥＤＴＡ－３Ｎａ　　　　　　　　　　　　　　　　　　　０．０５
グリセリン　　　　　　　　　　　　　　　　　　　　　　２
１，３－ブチレングリコール　　　　　　　　　　　　　　８
フェノキシエタノール　　　　　　　　　　　　　　　　　０．５
（ジメチルアクリルアミド／アクリロイルジメチルタウリンＮａ）クロスポ
リマー　　　　　　　　　　　　　　　　　　　　　　　　０．５
ステアロキシヒドロキシプロピルメチルセルロース　　　　０．１
キサンタンガム　　　　　　　　　　　　　　　　　　　　０．１
ステアロイルメチルタウリンＮａ　　　　　　　　　　　　０．０１
エタノール　　　　　　　　　　　　　　　　　　　　　　８
ＰＥＧ－１２ジメチコン　　　　　　　　　　　　　　　　１．５
セバシン酸ジイソプロピル　　　　　　　　　　　　　　　８
トリエチルヘキサノイン　　　　　　　　　　　　　　　１０
セスキイソステアリン酸ソルビタン　　　　　　　　　　　０．５
イソステアリン酸　　　　　　　　　　　　　　　　　　　０．５
シリカ・シリコーン処理酸化亜鉛　　　　　　　　　　　１２
シリコーン処理酸化チタン　　　　　　　　　　　　　　　５ Prescription example 7. Sunscreen ingredient name Blending amount (mass%)
Water residue EDTA-3Na 0.05
Glycerin 2
1,3-butylene glycol 8
Phenoxyethanol 0.5
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Cross Polymer 0.5
Stearoxyhydroxypropylmethylcellulose 0.1
Xanthan gum 0.1
Stearoyl Methyl Taurine Na 0.01
Ethanol 8
PEG-12 Dimethicone 1.5
Diisopropyl sebacate 8
Triethylhexanoin 10
Sorbitan sesquiisostearate 0.5
Isostearic acid 0.5
Zinc oxide treated with silica / silicone 12
Silicone treated titanium oxide 5

Claims (10)

  1. （Ａ）１価アルコールおよび２価アルコールから選択される水性成分、
    （Ｂ）ポリオキシアルキレン変性シリコーン、
    （Ｃ）極性油を含む油分、
    （Ｄ）疎水化表面を有する紫外線散乱剤、および、
    （Ｅ）アニオン性界面活性剤
    を含み、
    前記（Ａ）水性成分が、１価アルコール単独の場合には化粧料全量に対して１～１５質量％であり、２価アルコール単独の場合には化粧料全量に対して１～２０質量％であり、１価アルコールと２価アルコールとの組み合わせである場合にはその合計量が化粧料全量に対して１～４５質量％であり、
    前記（Ｃ）油分として低分子油分を配合する場合には、紫外線吸収剤を除く油分の合計量に対して低分子油分が占める割合が質量比にして５０％以下である、水中油型日焼け止め化粧料。     (A) Aqueous component selected from monohydric alcohols and divalent alcohols,
    (B) Polyoxyalkylene modified silicone,
    (C) Oil containing polar oil,
    (D) An ultraviolet scattering agent having a hydrophobic surface, and
    (E) Containing anionic surfactant,
    When the aqueous component (A) is monohydric alcohol alone, it is 1 to 15% by mass with respect to the total amount of cosmetics, and when dihydric alcohol is alone, it is 1 to 20% by mass with respect to the total amount of cosmetics. Yes, in the case of a combination of monohydric alcohol and dihydric alcohol, the total amount is 1 to 45% by mass with respect to the total amount of cosmetics.
    When a low molecular weight oil is blended as the oil (C), the ratio of the low molecular weight oil to the total amount of the oil excluding the ultraviolet absorber is 50% or less in terms of mass ratio, which is an oil-in-water sunscreen. Cosmetics.
  2. 前記低分子油分が、２５℃における揮発速度が毎時重量変化率３０％以上の油分である、請求項１に記載の水中油型日焼け止め化粧料。 The oil-in-water sunscreen cosmetic according to claim 1, wherein the small molecule oil is an oil having a volatilization rate at 25 ° C. and a weight change rate of 30% or more per hour.
  3. 前記低分子油分が、イソドデカンおよび平均重合度６５０未満のジメチコンからなる群から選択される１種以上である、請求項１または２に記載の水中油型日焼け止め化粧料。 The oil-in-water sunscreen cosmetic according to claim 1 or 2, wherein the low molecular weight oil is at least one selected from the group consisting of isododecane and dimethicone having an average degree of polymerization of less than 650.
  4. 前記極性油として紫外線吸収剤を配合する場合には、紫外線吸収剤の配合量が、化粧料全量に対して５～２５質量％である、請求項１から３のいずれか一項に記載の水中油型日焼け止め化粧料。 The water according to any one of claims 1 to 3, wherein when the ultraviolet absorber is blended as the polar oil, the blending amount of the UV absorber is 5 to 25% by mass with respect to the total amount of the cosmetic. Oil-type sunscreen cosmetics.
  5. 前記（Ｂ）ポリオキシアルキレン変性シリコーンからなるナノディスクが油水界面に付着している、請求項１から４のいずれか一項に記載の水中油型日焼け止め化粧料。 The oil-in-water sunscreen cosmetic according to any one of claims 1 to 4, wherein the nanodisc made of (B) polyoxyalkylene-modified silicone is attached to the oil-water interface.
  6. 前記（Ｃ）油分が、炭化水素油およびシリコーン油から選択される１種以上をさらに含む、請求項１から５のいずれか一項に記載の水中油型日焼け止め化粧料。 The oil-in-water sunscreen cosmetic according to any one of claims 1 to 5, wherein the oil (C) further contains one or more selected from hydrocarbon oils and silicone oils.
  7. 前記（Ｂ）成分が、ＰＥＧ－１２ジメチコンである、請求項１から６のいずれか一項に記載の水中油型日焼け止め化粧料。 The oil-in-water sunscreen cosmetic according to any one of claims 1 to 6, wherein the component (B) is PEG-12 dimethicone.
  8. 前記（Ｅ）アニオン性界面活性剤がＮ－アシルメチルタウリン塩である、請求項１から７のいずれか一項に記載の水中油型日焼け止め化粧料。 The oil-in-water sunscreen cosmetic according to any one of claims 1 to 7, wherein the (E) anionic surfactant is an N-acylmethyl taurine salt.
  9. さらに、（Ｆ）美白剤を含む、請求項１から８のいずれか一項に記載の水中油型日焼け止め化粧料。 The underwater oil-type sunscreen cosmetic according to any one of claims 1 to 8, further comprising (F) a whitening agent.
  10. さらに、（Ｇ）分散剤を含む、請求項１から９のいずれか一項に記載の水中油型日焼け止め化粧料。 The oil-in-water sunscreen cosmetic according to any one of claims 1 to 9, further comprising (G) a dispersant.
PCT/JP2021/029915 2020-12-25 2021-08-16 Oil-in-water type sunscreen cosmetic WO2022137636A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009102236A (en) * 2007-10-22 2009-05-14 Shiseido Co Ltd Oil-in-water type emulsified composition and its manufacturing method
JP2014070032A (en) * 2012-09-28 2014-04-21 Shiseido Co Ltd Oil-in-water type emulsion composition
JP2014214134A (en) * 2013-04-26 2014-11-17 株式会社 資生堂 Aqueous composition
JP2018076308A (en) * 2016-10-28 2018-05-17 ロート製薬株式会社 External composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009102236A (en) * 2007-10-22 2009-05-14 Shiseido Co Ltd Oil-in-water type emulsified composition and its manufacturing method
JP2014070032A (en) * 2012-09-28 2014-04-21 Shiseido Co Ltd Oil-in-water type emulsion composition
JP2014214134A (en) * 2013-04-26 2014-11-17 株式会社 資生堂 Aqueous composition
JP2018076308A (en) * 2016-10-28 2018-05-17 ロート製薬株式会社 External composition

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