WO2021125219A1 - Composition d'émulsion huile dans eau - Google Patents

Composition d'émulsion huile dans eau Download PDF

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Publication number
WO2021125219A1
WO2021125219A1 PCT/JP2020/046930 JP2020046930W WO2021125219A1 WO 2021125219 A1 WO2021125219 A1 WO 2021125219A1 JP 2020046930 W JP2020046930 W JP 2020046930W WO 2021125219 A1 WO2021125219 A1 WO 2021125219A1
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Prior art keywords
oil
water
acid
monomer
carbon atoms
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PCT/JP2020/046930
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English (en)
Japanese (ja)
Inventor
隆志 福原
由紀 杉山
匠 渡辺
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株式会社 資生堂
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Priority to JP2021565616A priority Critical patent/JPWO2021125219A1/ja
Publication of WO2021125219A1 publication Critical patent/WO2021125219A1/fr

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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
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/63—Steroids; 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
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin

Definitions

  • the present invention relates to an oil-in-water emulsified composition, and more particularly to an oil-in-water emulsified composition obtained by emulsifying a water-holding oil with core-corona type microparticles.
  • Synthetic polymer fine particles are one of the microparticles that are particularly widely used, and are classified into several types according to their composition and morphology.
  • core-corona type particles Particles in which different polymer chains are connected (corona part) to the peripheral part so as to cover the spherical central part as a "core part” are called core-corona type particles, and the present inventors are hydrophobic.
  • core-corona type particles Particles in which different polymer chains are connected (corona part) to the peripheral part so as to cover the spherical central part as a "core part”
  • the present inventors are hydrophobic.
  • amphipathic core corona-type microparticles having a structure in which a corona portion composed of hydrophilic groups is arranged around a core portion Patent Document 1.
  • These core-corona type microparticles are used as an emulsifier to produce an oil-in-water emulsified composition because the core part is excellent in organic solvent swelling property and the hydrophilic part can be stably dispersed in water due to the hydrophilicity of the corona part.
  • Pickering emulsion is known as an oil-in-water emulsified particle using powder as an emulsifier. While the emulsified particles are easily united by stirring or impact, an oil-in-water emulsified particle using core-corona type microparticles is used. The emulsified particles are very stable to physical impact. Further, in general, an emulsification system obtained by emulsification with a surfactant is strongly affected by temperature, but an emulsification system obtained by core-corona type microparticles is not easily affected by temperature changes.
  • the core-corona type microparticles are also used as a whitening agent (Patent Document 3) for whitening cosmetics in an aqueous system and a capsule (Patent Documents 4, 5 and 6) utilizing the swelling ability of an organic solvent. It is known that it can be done.
  • Patent Document 2 As described above, for the core-corona type microparticles, an emulsifier (for example, Patent Document 2) that produces an oil-in-water emulsification system, an aqueous whitening agent (Patent Document 3), and a poorly water-soluble component are blended in the water system.
  • Patent Document 4 has been widely known for its use as an emulsifier.
  • an emulsified composition emulsified with a surfactant has a problem that if the blending amount of the surfactant is increased in order to improve the emulsification stability, a sticky feeling is generated and the usability is deteriorated.
  • a large amount of water-holding oil which is excellent in improving the moisturizing feeling of the skin and making the skin feel soft and fluffy after application, is blended, there is a problem that the conventional surfactant cannot maintain the emulsification stability. there were.
  • the present invention has been made on the problems of the oil-in-water emulsification composition, and has excellent emulsification stability and non-stickiness, while providing a moisturizing feeling and a fluffy feeling of the skin after application.
  • An object of the present invention is to provide an excellent oil-in-water emulsified composition.
  • the present application includes the following inventions.
  • the core-corona type microparticles (a) are represented by the polyethylene oxide macromonomer represented by the following formula (1), the acrylic acid / methacrylic acid derivative monomer represented by the following formula (2), and the following formula (3).
  • the monomer selected from the acrylamide / methacrylicamide derivative monomer (hereinafter, “derivative monomer”) is selected from the following (A) to (E) in the presence or absence of the crosslinkable monomer represented by the following formula (4).
  • Oil-in-water emulsion composition which is a core-corona type microparticle obtained by radical polymerization under conditions;
  • A The molar ratio represented by the charged molar amount of the polyethylene oxide macromonomer / the charged molar amount of the derivative monomer is 1:10 to 1:250.
  • the amount of the crosslinkable monomer charged is 0 to 1.5% by mass with respect to the amount of the derivative monomer charged.
  • the macromonomer represented by the following formula (1) has a monomer composition obtained by mixing one or more of an acrylic acid derivative or a methacrylic acid derivative having a polyethylene glycol group having a repeating unit of 8 to 200.
  • the acrylate derivative monomer represented by the following formula (2) is an acrylic acid derivative or a methacrylic acid derivative having a substituent containing an alkyl group having 1 to 12 carbon atoms.
  • the acrylamide derivative monomer represented by the following formula (3) has a monomer composition in which one or more of an acrylamide derivative or a methacrylamide derivative having a substituent containing an alkyl group having 1 to 18 carbon atoms is mixed.
  • the polymerization solvent is a water-alcohol mixed solvent, and the alcohol is one or more selected from ethanol, dipropylene glycol, 1,3-butylene glycol, and isoprene glycol.
  • R 1 represents an alkyl group having 1 to 3 carbon atoms
  • n is a number of 8 to 200.
  • X represents H or CH 3 .
  • R 2 represents an alkyl group having 1 to 3 carbon atoms
  • R 3 represents an alkyl group having 1 to 12 carbon atoms.
  • R 4 represents H or an alkyl group having 1 to 3 carbon atoms
  • R 5 and R 6 represent a substituent containing H or an alkyl group having 1 to 18 carbon atoms.
  • R 7 and R 8 each independently represent an alkyl group having 1 to 3 carbon atoms, and m is a number of 0 to 2 carbon atoms.
  • the present invention provides an oil-in-water emulsified composition which is extremely excellent in emulsion stability, is not sticky, and is also excellent in moisturizing feeling and fluffy feeling of skin after application.
  • the oil-in-water emulsified composition according to the present invention does not lose its emulsified state due to stirring or vibration unlike a conventional pickering emulsion, and has a temperature similar to that of an emulsion obtained by a conventional surfactant. Since there is little change in the physical properties of the surfactant due to the above, the temperature stability is also good.
  • the oil-in-water emulsified composition according to the present invention is produced by using (b) a water-holding oil and (c) an aqueous phase component and (a) core-corona type microparticles as emulsifiers.
  • the core-corona particles that can be suitably used in the present invention have a core portion made of a polymer having a relatively high hydrophobicity, and the corona portion is a nonionic polymer. Particles stabilized with a polyethylene oxide chain. Due to the polyethylene oxide chain in the corona part, it has excellent dispersion stability in water and acid resistance and salt resistance.
  • the particle size is preferably substantially constant, and the average particle size is preferably in the range of 50 to 400 nm, preferably 100 to 300 nm.
  • the dispersity is less than 0.2, preferably less than 0.05.
  • Patent Documents 2, 5, 6 and 7. Methods for producing core-corona type particles are reported in Patent Documents 2, 5, 6 and 7. It is disclosed that both are obtained by radical polymerization of a specific polyethylene oxide macromonomer and a specific derivative monomer in the presence or absence of a specific crosslinkable monomer in a water-ethanol mixed solvent. There is. It is also possible to replace the dispersion with water by dialyzing the obtained polymerization solution with water.
  • the core-corona type particles that can be used in the present invention can be obtained, for example, by radically polymerizing the monomers represented by the following formulas (1) to (4) under specific conditions.
  • Polyethylene oxide macromonomer for example, a commercially available product marketed by Aldrich or a commercially available product such as Blemmer (registered trademark) sold by NOF Corporation can be used.
  • R 1 is an alkyl group having 1 to 3 carbon atoms, and n is a number of 8 to 200.
  • X is H or CH 3 .
  • acrylic acid / methacrylic acid derivative monomer represented by the formula (2)
  • a commercially available product commercially available from Aldrich or Tokyo Kasei can be used.
  • R 2 is an alkyl group having 1 to 3 carbon atoms.
  • R 3 is an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.
  • acrylate / methacrylic acid derivative monomer examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, decyl acrylate, and acrylic.
  • Examples thereof include dodecyl acetate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate and the like.
  • These acrylic acid / methacrylic acid derivative monomers are general-purpose raw materials and can be easily obtained as general industrial raw materials.
  • ⁇ Acrylamide / methacrylamide derivative monomer examples include t-butylacrylamide, N, N-dimethylacrylamide, N- [3- (dimethylamino) propyl] acrylamide, t-butylmethacrylamide, and octyl.
  • Acrylamide, octylmethacrylamide, octadecylacrylamide and the like can be preferably used.
  • t-butyl acrylamide, N, N-dimethylacrylamide, and N- [3- (dimethylamino) propyl] acrylamide are particularly preferable.
  • R 4 represents H or an alkyl group having 1 to 3 carbon atoms
  • R 5 and R 6 represent a substituent containing H or an alkyl group having 1 to 18 carbon atoms.
  • the crosslinkable monomer represented by the formula (4) can be obtained as a commercial product or an industrial raw material.
  • the crosslinkable monomer is preferably hydrophobic.
  • the value of m is preferably 0 to 2.
  • EGDMA ethylene glycol dimethacrylate
  • Blemmer registered trademark
  • R 7 and R 8 each independently represent an alkyl group having 1 to 3 carbon atoms, and m is a number of 0 to 2 carbon atoms.
  • the core-corona type particle dispersion liquid which is a raw material for cosmetics according to the present invention may be a product obtained by radically polymerizing the above-mentioned monomers under the following conditions (A) to (E).
  • A) The molar ratio represented by the charged molar amount of the polyethylene oxide macromonomer / the charged molar amount of the “derivative monomer” is 1:10 to 1:250.
  • B) The amount of the crosslinkable monomer charged is 0 to 1.5% by mass with respect to the amount of the "derivative monomer” charged.
  • the monomer represented by the formula (2) (C) has a monomer composition in which one or more of an acrylic acid derivative or a methacrylic acid derivative having an alkyl group having 1 to 12 carbon atoms is mixed.
  • the acrylamide derivative monomer represented by the formula (3) has a monomer composition obtained by mixing one or more of an acrylamide derivative or a methacrylamide derivative having a substituent containing an alkyl group having 1 to 18 carbon atoms, and the above-mentioned "derivative".
  • the "monomer” has a monomer composition of one or a mixture of two or more selected from the monomers represented by the following formula (2) and the following formula (3).
  • the polymerization solvent is a water-alcohol mixed solvent, and the alcohol is one or more selected from ethanol, dipropylene glycol, 1,3-butylene glycol, and isoprene glycol.
  • the amount of the crosslinkable monomer charged relative to the amount of the” derivative monomer “charged” is defined as the crosslink density (% by mass). Define.
  • the crosslink density of the core-corona type particles used in the present invention is such that the amount of the crosslinkable monomer charged is 0 to 1 with respect to the amount of the “derivative monomer” charged, depending on the condition (B). Must be 5% by weight.
  • the amount of the charged mole is preferably 1:10 to 1: 200, more preferably 1:25 to 1: 100.
  • the molar amount of the "derivative monomer” is 10 times or less the molar amount of the polyethylene oxide macromonomer, the polymer to be polymerized becomes water-soluble and core-corona type polymer particles are not formed.
  • the molar amount of the "derivative monomer” is 250 times or more the molar amount of the polyethylene oxide macromonomer, the dispersion stabilization by the polyethylene oxide macromonomer becomes incomplete and the particles aggregate and precipitate.
  • the particles in which the "derivative polymer" of the core portion is crosslinked can be polymerized. If the amount of the crosslinkable monomer charged exceeds 1.5% by mass, the particles agglomerate with each other, and suitable particles having a narrow particle size distribution cannot be polymerized.
  • the amount charged thereof is preferably 0.2 to 1.0, more preferably 0.2 to 0.8, and most preferably 0.2 to 0.5% by mass.
  • the monomer represented by the formula (2) needs to have a monomer composition obtained by mixing one or more methacrylic acid derivatives having an alkyl group having 1 to 12 carbon atoms.
  • the monomer may become too hydrophilic and emulsion polymerization may not be successful.
  • the number of carbon atoms is 13 or more, the particles may aggregate because the hydrophobicity of the particles is too high.
  • the acrylamide derivative monomer represented by the formula (3) is an acrylamide derivative or a methacrylamide derivative having a substituent containing an alkyl group having 1 to 18 carbon atoms.
  • the “derivative monomer” according to the present invention is one selected from an acrylic acid derivative monomer or a methacrylic acid derivative monomer represented by the formula (2), and an acrylamide derivative monomer or a methacrylamide derivative monomer represented by the formula (3). It is necessary to have a monomer composition mixed with two or more kinds.
  • the polymerization solvent needs to be a water-alcohol mixed solvent.
  • the alcohol those capable of dissolving the "derivative monomer” represented by the formulas (2) and (3) and the crosslinkable monomer represented by the formula (4) are preferable.
  • the alcohol used in the present invention needs to be one or more selected from ethanol, dipropylene glycol, 1,3-butylene glycol, and isoprene glycol. Considering that it can be industrially produced, that is, the polymer solution can be used as a raw material as it is without a purification process such as dialysis, the solvent to be mixed with water is ethanol, propanol, butanol, etc. when applied to the skin. It is necessary that the alcohol is not an organic solvent that may be irritating, but an alcohol that can be widely blended in cosmetics.
  • the polymerization solvent it is necessary to add alcohol in order to uniformly dissolve the hydrophobic monomer.
  • the mixing ratio of alcohol is 10 to 90 volume ratio.
  • the mixing ratio of the alcohol When the mixing ratio of the alcohol is lower than the 10 volume ratio, the dissolving ability of the monomer becomes extremely low, the polymerization proceeds in the state of monomer droplets to form a huge mass, and core-corona type particles are not generated. If the mixing ratio of alcohol exceeds 90% by volume, an emulsion of hydrophobic monomers is not formed due to hydrophobic interaction, and emulsion polymerization does not proceed, so that core-corona type particles cannot be obtained.
  • the polymerization solvent preferably has high monomer solubility, and is preferably not too high in viscosity and boiling point in consideration of production and purification steps (distillation, etc.).
  • ethanol, dipropylene glycol, 1,3-butylene glycol, isoprene glycol and the like can be preferably used as the alcohol used as the polymerization solvent. Of these, ethanol is particularly preferable.
  • polymerization initiator used in the polymerization system a commercially available polymerization initiator used for ordinary water-soluble thermal radical polymerization can be used. In this polymerization system, even if the polymerization is carried out without strictly controlling the stirring conditions, it is possible to obtain a very narrow particle size distribution of the particles to be polymerized.
  • crosslinkable monomer represented by the formula (4) When the crosslinkable monomer represented by the formula (4) is not used, for example, polymerization may be carried out under the conditions described in JP-A-2017-175011.
  • the blending amount of (a) core-corona type particles for producing an oil-in-water emulsified composition is preferably 0.1 to 10% by mass with respect to the total amount of the composition as a net content conversion value of the particles. , More preferably 0.3 to 5% by mass, and most preferably 0.5 to 2% by mass. If the blending amount is less than 0.1%, it may be difficult to obtain a stable cosmetic. If the blending amount exceeds 10%, powderiness or stickiness may occur.
  • the oil-in-water emulsified composition of the present invention can be produced according to a conventional method. Even if (a) core-corona type particles are mixed and dispersed in water or an aqueous phase component, and (b) an aqueous oil component is added, stirred and sheared to emulsify the particles. Good.
  • the water-holding oil content needs to be 3% by mass or more and 20% by mass or less. It is preferably 5 to 15% by mass. More preferably, it is 5 to 10% by mass.
  • the water-holding oil content used in the present invention is an oil content having a water-holding ratio of 100% or more calculated by the formula (1) by performing the following water-holding test method.
  • -Water holding test method A sample (oil-based component) for measuring the water holding rate is weighed (initial amount), heated to 70 ° C, and then stirred while gradually adding water heated to 70 ° C to each sample. .. The amount of water added up to the end point was measured with the time point when water emerged on the sample surface as the end point.
  • Water holding rate [(amount of added water (g) + initial amount of sample (g)) / initial amount of sample (g)] ⁇ 100
  • water-holding oil component of the present invention examples include N-lauroyl-L-glutamic acid ester, N-myristoyl-N-methyl- ⁇ -alanine ester, alkyl carboxylic acid, glycerin fatty acid ester, isostearic acid ester, pentaerythritol ester, and cholesterol. And its derivatives, phytosterols and their derivatives, lanolin and its derivatives and the like.
  • N-lauroyl-L-glutamic acid ester examples include N-lauroyl-L-glutamic acid di (phytosteryl 2-octyldodecyl) [commercially available "Eldu PS-203", etc.], N-lauroyl-L-glutamic acid di.
  • N-myristoylation-N-methyl- ⁇ -alanine ester examples include N-myristoylation-methylalanine (phytosteryl decyltetradecyl) [commercially available "Eldu APS-307" (manufactured by Ajinomoto Healthy Supply Co., Ltd.)] and the like. Can be mentioned.
  • alkyl carboxylate examples include: diisostearyl malate, diethylhexyl succinate, and the like.
  • glycerin fatty acid ester examples include glyceryl diisostearate [commercially available products such as “San Espor G-218" (manufactured by Taiyo Kagaku Co., Ltd.)], diglyceryl triisostearate, tetraglyceryl pentastearate, and the like.
  • pentaerythritol ester examples include tetra (bechenic acid, benzoic acid, ethylhexanoic acid) pentaerythrityl [commercially available "Saracos P-B822" (manufactured by Nisshin Oillio Group), etc.], tetra (ethylhexanoic acid / Pentaerystil (benzoic acid) [Commercial products such as “Saracos P-B8 (75)" and “Saracos BO-63” (both manufactured by Nisshin Oillio Group)], Dipentaerythrityl tripolyhydroxystearate [Commercial products "Saracos” WO-6 "(manufactured by Nisshin Oillio Group), etc.], Hexa (hydroxystearic acid, stearic acid, logic acid) Dipentaerythrityl [Commercial products” Cosmol 168ARV “,” Cosmol 168AR "
  • cholesterol and its derivatives include cholesterol, cholestanol, dehydrocholesterol, lanolin fatty acid cholesteryl, cholesteryl isostearate, cholesteryl hydroxystearate, cholesteryl ricinoleate, macadamia nut oil fatty acid cholesteryl and the like.
  • phytosterols and their derivatives include phytosterols, phytosterols, dehydrophytosterols, lanolin fatty acid phytosterols, phytosterol isostearate, phytosteryl hydroxystearate, phytosterol ricinoleate, macadamia nut oil fatty acid phytosterols. Kasha)] and the like.
  • N-lauroyl-L-glutamic acid diester alkylcarboxylic acid, pentaerythritol ester, glycerin fatty acid ester, and phytosterol derivative can be preferably used.
  • the oil-in-water emulsified composition according to the present invention may contain an oil phase component other than the above-mentioned water-holding oil component.
  • Oil layer components other than water-holding oils include hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, liquid fats and oils, solid fats and oils, waxes, fragrances, etc., which are usually used in cosmetics and non-medicinal products. Can be mentioned.
  • hydrocarbon oil examples include isododecane, isohexadecane, isoparaffin, liquid paraffin, ozokerite, squalane, pristan, paraffin, selecin, squalene, petrolatum, microcrystalline wax and the like.
  • higher fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undesylene acid, tollic acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid ( DHA) and the like.
  • higher alcohols examples include linear alcohols (eg, lauryl alcohols, cetyl alcohols, stearyl alcohols, behenyl alcohols, myristyl alcohols, oleyl alcohols, cetostearyl alcohols, etc.) and branched alcohols (eg, monostearyl glycerin ethers (bacyl alcohols)).
  • linear alcohols eg, lauryl alcohols, cetyl alcohols, stearyl alcohols, behenyl alcohols, myristyl alcohols, oleyl alcohols, cetostearyl alcohols, etc.
  • branched alcohols eg, monostearyl glycerin ethers (bacyl alcohols)
  • Examples of synthetic ester oils include octyl octanate, nonyl nonanoate, cetyl octanate, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, and dimethyl.
  • silicone oil examples include chain polysiloxane (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.) and cyclic polysiloxane (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexane).
  • chain polysiloxane for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.
  • cyclic polysiloxane for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexane.
  • Silicone resin Silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) forming a three-dimensional network structure, acrylic silicone Kind and the like.
  • Liquid fats and oils include, for example, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern ka oil, castor oil, flaxseed oil. , Saflower oil, cotton seed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnamon oil, Japanese millet oil, jojoba oil, germ oil, triglycerin and the like.
  • solid fats and oils include coconut oil, coconut oil, horse fat, hardened coconut oil, palm oil, beef tallow, sheep tallow, hardened beef tallow, palm kernel oil, lard, beef tallow, mokurou kernel oil, hardened oil, and cow.
  • Examples include leg tallow, coconut oil, and hydrogenated palm oil.
  • waxes examples include honey wax, candelilla wax, cotton wax, carnauba wax, baby wax, ibotarou, whale wax, montan wax, lanolin, lanolin, capoc wax, lanolin acetate, liquid lanolin, sugar cane, lanolin fatty acid isopropyl, hexyl laurate, and the like.
  • waxes include honey wax, candelilla wax, cotton wax, carnauba wax, baby wax, ibotarou, whale wax, montan wax, lanolin, lanolin, capoc wax, lanolin acetate, liquid lanolin, sugar cane, lanolin fatty acid isopropyl, hexyl laurate, and the like.
  • Examples thereof include reduced lanolin, jojobaro, hard lanolin, cellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin
  • fragrance examples include natural fragrances obtained from animals or plants, synthetic fragrances produced by chemical synthesis means, and blended fragrances which are mixtures thereof, and are not particularly limited. By blending a fragrance, it is possible to obtain a cosmetic having an excellent long-lasting fragrance.
  • fragrance examples include acetibenol, anisaldehyde, anetol, amyl acetate, amyl salicylate, allyl amyl glycolate, allyl caproate, aldehyde C6-20, ambretteride, ambrettolide, ambroxane, and ionone.
  • the physical properties of the surfactant and the physical properties of the oil have a great influence on the emulsifying property, and when the oil phase component is changed, the type of the surfactant is also changed. It was necessary to take action.
  • the oil-in-water emulsified composition of the present invention is emulsified using (a) core-corona type microparticles, the emulsifying property and stability are less affected by the type of oil, and a wider variety than before. It is possible to mix the oil content of.
  • Aqueous phase component As the aqueous phase component, water, a water-soluble alcohol, a thickener, etc., which are usually used for cosmetics, non-medicinal products, etc., can be blended, and if desired, a moisturizer. , Chelating agent, preservative, pigment and the like can be appropriately blended.
  • the water contained in the oil-in-water emulsified composition of the present invention is not particularly limited, and examples thereof include purified water, ion-exchanged water, and tap water.
  • Water-soluble alcohols include, for example, lower alcohols, polyhydric alcohols, polyhydric alcohol polymers, dihydric alcohol alkyl ethers, dihydric alcohol ether esters, glycerin monoalkyl ethers, sugar alcohols, monosaccharides, oligosaccharides, polysaccharides and Examples thereof include derivatives thereof.
  • Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.
  • polyhydric alcohol examples include divalent alcohols (eg, dipropylene glycol, 1,3-butylene glycol, ethylene glycol, trimethylene glycol, 1,2-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, and the like.
  • divalent alcohols eg, dipropylene glycol, 1,3-butylene glycol, ethylene glycol, trimethylene glycol, 1,2-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, and the like.
  • monosaccharides examples include trisaccharides (eg, D-glycerylaldehyde, dihydroxyacetone, etc.), tetrasaccharides (eg, D-erythroth, D-erythrose, D-treose, erythritol, etc.), and the like.
  • Five-carbon sugars eg, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-librose, D-xylrose, L- Xylrose, etc.
  • Deoxy sugar eg, D-glucose, D-talose, D-busicouse, D-galactos, D-fructouse, L-galactos, L- Mannos, D-tagatos, etc.
  • seven-carbon sugars eg, aldoheptos, heproth, etc.
  • eight-carbon sugars eg, octulouse, etc.
  • deoxy sugars eg, 2-deoxy-D, etc.) -Ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.
  • amino sugars eg, D-glucosamine, D-galactosamine, sialic acid, amino
  • oligosaccharides include sucrose, gunthianose, umbelliferose, lactose, planteos, isolikunoses, ⁇ , ⁇ -trehalose, raffinose, lycnoses, umbilicin, stachyose velvas and the like.
  • polysaccharides examples include cellulose, quince seed, starch, galactan, dermatan sulfate, glycogen, arabic gum, heparan sulfate-tragant gum, keratan sulfate, chondroitin, xanthan gum, guagam, dextran, keratosulfate, locust bean gum, succinoglucan and the like. Can be mentioned.
  • Examples of other polyols include polyoxyethylene methylglucoside (Glucam E-10) and polyoxypropylene methylglucoside (Glucam P-10).
  • thickeners examples include arabic gum, carrageenan, color yag gum, tragacanto gum, carob gum, quince seed (malmero), casein, dextrin, gelatin, sodium pectinate, sodium aragite, methyl cellulose, ethyl cellulose, CMC, hydroxyethyl cellulose, hydroxypropyl.
  • Natural water-soluble polymers include, for example, plant-based polymers (eg, arabic gum, tragacanto gum, galactan, guagam, carob gum, carrageenan, pectin, canten, quince seed (malmero), algae colloid (cassaw extract), starch. (Rice, corn, potato, wheat), glycyrrhizinic acid), microbial macromolecules (eg, xanthan gum, dextran, succinoglucan, purulan, etc.), animal macromolecules (eg, collagen, casein, albumin, gelatin, etc.), etc. Can be mentioned.
  • plant-based polymers eg, arabic gum, tragacanto gum, galactan, guagam, carob gum, carrageenan, pectin, canten, quince seed (malmero), algae colloid (cassaw extract), starch. (Rice, corn, potato, wheat), glycyrrhizinic acid), microbial macromolecules (
  • semi-synthetic water-soluble polymer examples include starch-based polymers (for example, carboxymethyl starch, methyl hydroxypropyl starch, etc.) and cellulosic polymers (methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, etc.). , Hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.), alginic acid-based polymers (for example, sodium alginate, propylene glycol alginate, etc.) and the like.
  • starch-based polymers for example, carboxymethyl starch, methyl hydroxypropyl starch, etc.
  • cellulosic polymers methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, etc.
  • Examples of the synthetic water-soluble polymer include vinyl-based polymers (for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer, etc.) and polyoxyethylene-based polymers (for example, polyethylene glycol 20,000 and 40). , 000, 60,000, etc.), acrylic polymers (eg, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.), polyethyleneimine, cationic polymers, and the like.
  • vinyl-based polymers for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer, etc.
  • polyoxyethylene-based polymers for example, polyethylene glycol 20,000 and 40.
  • acrylic polymers eg, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.
  • polyethyleneimine cationic polymers
  • Moisturizers include, for example, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocolagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salts, DL-pyrrolidone carboxylate, short chain soluble collagen, etc.
  • Examples thereof include diglycerin (EO) PO adduct, Izayoi rose extract, Hyaluronic acid extract, Merilot extract and the like.
  • metal ion sequestering agent examples include 1-hydroxyethane-1,1-diphosphonic acid, 1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate, sodium citrate, and polyphosphate.
  • metal ion sequestering agent examples include sodium, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, and trisodium ethylenediaminehydroxyethyl triacetate.
  • amino acids examples include neutral amino acids (for example, threonine, cysteine, etc.), basic amino acids (for example, hydroxylysine, etc.) and the like.
  • amino acid derivative examples include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl ⁇ -alanine sodium, glutathione and the like.
  • pH adjuster examples include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
  • the amount of the aqueous phase component blended in the oil-in-water emulsified composition of the present invention is not particularly limited.
  • an oil-in-water emulsified composition can be obtained even in an embodiment in which a large amount of water-holding oil is blended.
  • the oil-in-water emulsified composition according to the present invention contains other components usually used for cosmetics, non-medicinal products, etc., such as ultraviolet absorbers, powders, and organic amines, as long as the effects of the present invention are not impaired. , Polymer emulsions, vitamins, antioxidants and the like can be appropriately blended.
  • water-soluble ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4, 4'-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-Ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone and other benzophenone-based ultraviolet absorbers, phenylbenzimidazole-5- Sulfonic acid and its salts, benzoimidazole-based ultraviolet absorbers such as phenylene-bis-benzoimidazole-tetrasulfonic acid and its
  • oil-soluble ultraviolet absorber examples include paraaminobenzoic acid (PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxyPABA ethyl ester, N, N-dimethyl PABA ethyl ester, and N.
  • PABA paraaminobenzoic acid
  • PABA monoglycerin ester N, N-dipropoxy PABA ethyl ester
  • N N-diethoxyPABA ethyl ester
  • N N-dimethyl PABA ethyl ester
  • N-dimethyl PABA butyl ester and other benzoic acid-based UV absorbers N-dimethyl PABA butyl ester and other benzoic acid-based UV absorbers; homomentyl-N-acetylanthranilate and other anthranylic acid-based UV absorbers; Salicylic acid-based ultraviolet absorbers such as salicylate and p-isopropanolphenyl salicylate; octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2.
  • the powder component examples include inorganic powders (for example, talc, kaolin, mica, silk mica (serisite), white mica, gold mica, synthetic mica, red mica, black mica, permiculite, magnesium carbonate, calcium carbonate, silicic acid.
  • inorganic powders for example, talc, kaolin, mica, silk mica (serisite), white mica, gold mica, synthetic mica, red mica, black mica, permiculite, magnesium carbonate, calcium carbonate, silicic acid.
  • Inorganic purple pigments eg, mango violet, cobalt violet, etc.
  • inorganic green pigments eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.
  • inorganic blue pigments eg, ultramarine, etc.
  • pearl pigments eg, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, etc.
  • metal powder pigments eg, aluminum powder
  • organic pigments such as zirconium, barium or aluminum lake (eg, red 201, red 202, red 204, red 205, red 220, red 226, red 228, red Organic pigments such as 405, orange 203, orange 204, yellow 205, yellow 401, and blue 404, red 3, red 104, red 106, red 227, red 230, red 401.
  • natural pigments for example, chlorophyll, ⁇ -carotene, etc.
  • organic amines examples include monoethanolamine, diethanolamine, triethanolamine, morpholine, tetrakis (2-hydroxypropyl) ethylenediamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, and 2-amino. -2-methyl-1-propanol and the like can be mentioned.
  • polymer emulsion examples include an acrylic resin emulsion, an ethyl polyacrylate emulsion, an acrylic resin solution, a polyacrylic alkyl ester emulsion, a polyvinyl acetate resin emulsion, and a natural rubber latex.
  • vitamins examples include vitamins A, B1, B2, B6, C, E and their derivatives, pantothenic acid and its derivatives, biotin and the like.
  • antioxidants examples include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.
  • antioxidant aid include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, ethylenediaminetetraacetic acid and the like.
  • compoundable ingredients include, for example, preservatives (methylparaben, ethylparaben, butylparaben, phenoxyethanol, etc.), anti-inflammatory agents (eg, glycyrrhizinic acid derivative, glycyrrhetinic acid derivative, salicylic acid derivative, hinokithiol, zinc oxide, allantin, etc.), Whitening agents (eg, placenta extract, yukinoshita extract, albutin, etc.), various extracts (eg, sardine, sardine, shikon, shakuyaku, assembly, birch, sage, biwa, carrot, aloe, zegna oi, iris, grape, yoquinin , Hechima, lily, saffron, senkyu, shokyu, otogirisou, ononis, garlic, pepper, chimpanzee, seaweed, etc., activator (eg,
  • the oil-in-water emulsified composition of the present invention it is preferable not to contain a surfactant in order to realize non-stickiness.
  • a surfactant when a surfactant is contained, it shall be 1.5% by mass or less.
  • the purpose is not the purpose of the emulsifier, but the control of the feeling of use, the control of drug permeability, or the improvement of the detergency when blended in a skin or hair cleansing agent.
  • oil-in-water emulsified composition of the present invention is not limited, but it is suitable as, for example, skin cosmetics, hair cosmetics, skin external preparations, and the like.
  • the blending amount represents mass%.
  • the blending amount of the core-corona type microparticles in Table 3-5 is a pure content conversion value of the microparticles.
  • Emulsified particle size of the sample was measured using an optical microscope.
  • Test Example 1 Manufacture of core-corona type microparticles ⁇ Manufacturing method> A polyethylene oxide macromonomer, a "derivative monomer”, and a crosslinkable monomer (Production Example 1 only) were added to a water-alcohol mixed solvent in a three-necked flask provided with a reflux tube and a nitrogen introduction tube. After sufficiently dissolving or dispersing, 1 mol% of the polymerization initiator 2,2'-azobis (2-methylpropionamidine dihydrochloride) with respect to the total amount of the monomers is dissolved and added in a small amount of water, and further dissolved or dispersed. I let you.
  • the uniformly dissolved or dispersed polymerization solution was subjected to nitrogen substitution for 20 minutes to remove dissolved oxygen, and then the polymerization was carried out in an oil bath at 65 to 70 ° C. for 8 hours while stirring with a magnetic stirrer. After completion of the polymerization, the polymerization liquid was returned to room temperature to obtain a core-corona type microparticle dispersion liquid (Production Examples 1 and 2).
  • Blemmer PME-4000 manufactured by NOF CORPORATION, n ⁇ 90 in the macromonomer represented by the formula (1) was used as the polyethylene oxide macromonomer.
  • the "derivative monomer” includes methyl methacrylate (MMA), butyl methacrylate (n-BMA), t-butyl acrylamide (t-BAA), and N- [3- (dimethylamino) propyl].
  • Acrylamide (DMAPA) was used.
  • microparticles The particle size of the core-corona type microparticles (hereinafter, sometimes simply referred to as “microparticles”) was measured using a Zetasizer manufactured by Malvern. A measurement sample with a microgel concentration of about 0.1% of the microparticle dispersion was prepared by water dilution, and after removing dust with a 0.45 micrometer filter, the scattering intensity at 25 ° C was measured at a scattering angle of 173 ° (backward scattering). The average particle size and the degree of dispersion were calculated using the analysis software installed in the measuring device.
  • the particle size is analyzed by the cumulant analysis method, and the dispersion is a value obtained by standardizing the value of the secondary cumulant obtained by the cumulant analysis.
  • This dispersity is a commonly used parameter and can be automatically analyzed by using a commercially available dynamic light scattering measuring device.
  • the viscosity of the solvent required for the particle size analysis the viscosity of pure water at 25 ° C., that is, a value of 0.89 mPa ⁇ s was used.
  • the particle size and dispersity of the obtained core-corona type microparticles were 206.1 nm and 0.052 in Production Example 1 and 210.3 nm and 0.018 in Production Example 2.
  • Test Example 2 Production of oil-in-water emulsified cosmetics Using the core-corona type microparticles produced in Test Example 1, an oil-in-water emulsified cosmetic containing water-holding oil was prepared, and emulsification stability was determined according to the following method. Analyzed. The prescription and results are shown in the table. ⁇ Manufacturing method> (C) The core-corona type microparticle dispersion liquid produced in Test Example 1 was added to the aqueous phase component and mixed by stirring to uniformly disperse the core-corona type microparticles in the aqueous phase component. .. To the mixed solution, (b) a water-holding oil component and other oil phase components were heated and mixed, and shear-mixed with a homomixer until uniform to obtain an emulsified composition.
  • the inventor examined whether the water-holding oil could be emulsified using core-corona type particles.
  • the present inventors also examined whether the skin feels plump, moisturizing, sticky, and refreshing after applying a lumber in which water-holding oil is emulsified with core-corona type particles together with other oils.

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Abstract

L'invention concerne une composition d'émulsion huile dans eau qui présente une stabilité d'émulsion extrêmement exceptionnelle et a également une non adhésivité exceptionnelle. L'invention concerne une composition d'émulsion huile dans eau caractérisée en ce qu'elle contient (a) 0,1 % en masse ou plus d'un microgel de type noyau-couronne, (b) une fraction d'huile hydratante, et (c) un composant de phase aqueuse, la composition d'émulsion d'huile dans 'eau étant en outre caractérisée en ce que la (b) fraction d'huile hydratante est dans une quantité supérieure ou égale à 3 % en masse.
PCT/JP2020/046930 2019-12-19 2020-12-16 Composition d'émulsion huile dans eau WO2021125219A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007008860A (ja) * 2005-06-30 2007-01-18 Milbon Co Ltd 毛髪処理剤
JP2009292734A (ja) * 2008-06-02 2009-12-17 Shiseido Co Ltd 水中油型乳化皮膚化粧料
JP2012041318A (ja) * 2010-08-23 2012-03-01 Mikimoto Pharmaceut Co Ltd シワ形成抑制用基剤
JP2013147486A (ja) * 2011-12-22 2013-08-01 Shiseido Co Ltd コロナ−コア型ミクロゲル乳化剤及び水中油型乳化組成物
JP2018052925A (ja) * 2016-09-27 2018-04-05 株式会社 資生堂 コア−コロナ型ミクロ粒子を用いた化粧料原料及び水中油型乳化化粧料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007008860A (ja) * 2005-06-30 2007-01-18 Milbon Co Ltd 毛髪処理剤
JP2009292734A (ja) * 2008-06-02 2009-12-17 Shiseido Co Ltd 水中油型乳化皮膚化粧料
JP2012041318A (ja) * 2010-08-23 2012-03-01 Mikimoto Pharmaceut Co Ltd シワ形成抑制用基剤
JP2013147486A (ja) * 2011-12-22 2013-08-01 Shiseido Co Ltd コロナ−コア型ミクロゲル乳化剤及び水中油型乳化組成物
JP2018052925A (ja) * 2016-09-27 2018-04-05 株式会社 資生堂 コア−コロナ型ミクロ粒子を用いた化粧料原料及び水中油型乳化化粧料

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