WO2017141919A1 - 油中水型乳化化粧料 - Google Patents
油中水型乳化化粧料 Download PDFInfo
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- WO2017141919A1 WO2017141919A1 PCT/JP2017/005373 JP2017005373W WO2017141919A1 WO 2017141919 A1 WO2017141919 A1 WO 2017141919A1 JP 2017005373 W JP2017005373 W JP 2017005373W WO 2017141919 A1 WO2017141919 A1 WO 2017141919A1
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- oil
- dextrin
- water
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/31—Hydrocarbons
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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
- A61K8/18—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
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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
- A61K8/18—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
- A61K8/345—Alcohols containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
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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
- A61K8/18—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
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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
- A61K8/18—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
- A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- A61K8/8117—Homopolymers or copolymers of aromatic olefines, e.g. polystyrene; Compositions of derivatives of such polymers
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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
- A61K8/18—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
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
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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
- A61K8/18—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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/08—Preparations containing skin colorants, e.g. pigments for cheeks, e.g. rouge
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- 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 a water-in-oil emulsified cosmetic, and more particularly relates to a water-in-oil emulsified cosmetic having an excellent secondary adhesion prevention effect and excellent usability.
- water-in-oil emulsified cosmetics have been used for skin external preparations because they can efficiently spread oil-soluble active ingredients such as emollient oils, UV absorbers, oil-soluble drugs, etc. on the skin. It is a dosage form and is frequently used especially in makeup cosmetics because of its high water resistance.
- cosmetics that can maintain a beautiful cosmetic film without being damaged by a large amount of sweat or sebum.
- hot flashes there is a demand for cosmetics called “hot flashes” that do not collapse even when sudden sweating occurs.
- water-in-oil emulsified cosmetics have important functions such as water resistance and prevention of color transfer (secondary adhesion prevention effect) by mixing with sebum, and there are various methods for enhancing these functions. Consideration has been made. For example, by using a specific volatile organopolysiloxane, oil-soluble resin, water-repellent powder, and water in combination, the technology can improve the lightness of application, non-stickiness, secondary adhesion prevention effect, and long-lasting makeup.
- Patent Document 1 (meth) acrylic acid / (meth) alkyl acrylate copolymer emulsion, partially crosslinked organopolysiloxane polymer, volatile silicone, and substantially no surfactant Technology that improves transparency, water resistance, sebum resistance, smooth feel, storage stability (see Patent Document 2), or volatile oil, resin that does not dissolve in volatile oil, melting point 75 ° C or higher
- Patent Document 2 or volatile oil, resin that does not dissolve in volatile oil, melting point 75 ° C or higher
- the combined use of solid oil and dextrin fatty acid ester improves lightness, smoothness, secondary adhesion prevention effect, water resistance, oil resistance, makeup durability, and uniformity of makeup film during application.
- Technology see Patent Document 3 are known to.
- the cosmetic obtained in Patent Document 3 has a problem that it gives a feeling of tension as the film formed by the high melting point wax is hard, and feels dry as the solvent evaporates. For this reason, the water-in-oil emulsification that is lightly spread at the time of application, has a water-resistant and secondary adhesion prevention effect, but does not have a sticking burden, and also has a long-lasting moisturizing feeling. Providing cosmetics was a challenge.
- the present inventors have conducted extensive research and have found that alkyl styrene / styrene copolymer dispersions, oil-soluble resins, polyhydric alcohols, partially crosslinked organopolysiloxanes using volatile hydrocarbon oil as a dispersion medium.
- siloxane By containing siloxane, the spread at the time of application is light, the decorative film after application is excellent in water resistance and secondary adhesion prevention effect, but there is no sticky feeling, and it also has excellent moisturizing feeling It has been found that a water-in-oil emulsified cosmetic can be obtained.
- Alkyl acrylate / styrene copolymer dispersions form coatings themselves, but partially crosslinked organopolysiloxanes can be made flexible by combining oil-soluble resins with coatings that have stronger bonding points.
- the makeup film with significantly improved water resistance and secondary adhesion prevention effect, excellent followability to the skin, and extremely low burden, the polyhydric alcohol is blocked and the moisture transpiration of the skin is suppressed.
- the inventors have found that the sustainability of the moisturizing feeling is dramatically increased, and have completed the present invention.
- the present invention provides the following components (A) to (D); (A) Alkyl acrylate / styrene copolymer dispersion using volatile hydrocarbon oil as dispersion medium (B) Oil-soluble resin (C) Polyhydric alcohol (D) Partially cross-linked organopolysiloxane Type emulsified cosmetic.
- the present invention is a water-in-oil that has a light stretch spread at the time of application, and that the decorative film after application is excellent in water resistance and secondary adhesion prevention effect, but does not have a squeezing burden and is also excellent in maintaining a moisturizing feeling.
- the present invention relates to a type emulsified cosmetic.
- the component (A) used in the present invention is a dispersion in which an alkyl acrylate / styrene copolymer is dispersed in a volatile hydrocarbon oil.
- distributing alkyl acrylate styrene copolymer is INCI (International Nomenclature Cosmetic labeling names), and is listed as STYRENE / ACRYLATES COPOLYMER, and one or more of alkyl acrylate and alkyl methacrylate, It can be obtained by polymerizing styrene.
- non-aqueous dispersions Non Aqua Dispersion, and non-aqueous emulsion is also synonymous.
- the alkyl acrylate / styrene copolymer is not particularly limited, but preferably contains alkyl acrylate and alkyl methacrylate and styrene in a mass ratio of 70/30 to 90/10, and the number average molecular weight is 50,000 to 300,000 ( Those having a polystyrene equivalent value by gel permeation chromatography) are preferably used. Within this range, it is not dissolved in the volatile hydrocarbon oil, and a good dispersion state can be maintained. Further, it is preferable that the resin particles have an average particle diameter of 0.1 to 2.0 ⁇ m by the centrifugal sedimentation method so that there is little change in the viscosity of the dispersion and the precipitation of the particles hardly occurs.
- the volatile hydrocarbon oil used as the dispersion medium for the component (A) is not particularly limited as long as it is generally used in cosmetics.
- hydrocarbons having a boiling point of 260 ° C. or less at normal pressure isooctane (2 , 2,4-trimethylpentane, 2,3-dimethylhexane, etc.), isododecane (2,2,4,6,6-pentamethylheptane, etc.), isohexadecane, isoeicosaene and other hydrocarbons having side chains, isoparaffin, Or, a mixture, isobutene, n-butene or the like may be polymerized or copolymerized (the degree of polymerization is preferably 4 to 6) and then hydrogenated, and the like.
- saturated hydrocarbon oils having a side chain having 4 to 18 carbon atoms are more preferred because they have good dispersibility of the alkyl acrylate / styrene copolymer, accelerate drying and form a strong coating film by volatilization.
- Commercially available products of these volatile hydrocarbon oils include IP solvent 1620 MU, IP solvent 2028 MU (all manufactured by Idemitsu Petrochemical Co., Ltd.), Isopar (manufactured by Esso Chemical Co., Ltd.), Marcazole R (manufactured by Maruzen Petrochemical Co., Ltd.), etc. Is mentioned.
- Component (A) is a dispersion in which an alkyl acrylate / styrene copolymer is dispersed in volatile hydrocarbon oil.
- volatile hydrocarbon oil alkyl acrylate or alkyl methacrylate and
- the copolymer can be obtained by dispersing in a volatile hydrocarbon oil.
- the alkyl acrylate / styrene copolymer is preferably contained in the component (A) in an amount of 30 to 60% by mass (hereinafter simply referred to as “%”), more preferably 35 to 50%, still more preferably 40 to Includes 50%. Within this range, the component (A) is easily mixed uniformly in the cosmetic.
- % 30 to 60% by mass
- the component (A) is easily mixed uniformly in the cosmetic.
- a commercially available dispersion can be used, and examples thereof include Nisset U-3700A (manufactured by Nippon Carbide).
- the content of component (A) in the present invention is not particularly limited depending on the copolymer concentration, but is preferably 0.1 to 10% in the cosmetic in terms of solid content, more preferably 0.8. It is 5 to 7.5%, particularly preferably 1 to 6%. This range is preferable because it is more excellent in water resistance and no burden.
- the oil-soluble resin of component (B) used in the present invention is soluble in an oil agent such as volatile oil and forms a film. If it is normally used for cosmetics, it can use without being restrict
- Component (B) is excellent in sebum resistance and forms a hard and strong coating film. Therefore, it is contained in combination with component (A), and the bonding point of the coating film formed by fusion of the dispersion is determined. By making it stronger, the secondary adhesion preventing effect can be remarkably improved.
- Specific examples include terpene resins, silicone resins, hydrocarbon resins, rosin acid resins, vinyl acetate resins, acrylic resins, and the like, and use one or a combination of two or more as required. Can do.
- silicone resins such as trimethylsiloxysilicic acid, polymethylsilsesquioxane, (acrylates / dimethicone) copolymer, and the like are more preferable because they are more effective in preventing secondary adhesion.
- silicon KF-7312J solid content 50%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.
- silicon KF-9021 solid content 50%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.
- BY11-018 solid content 30%, solvent: cyclopentasiloxane, manufactured by Toray Dow Corning
- silicon KP-541 solid content 60%, solvent: isopropanol, manufactured by Shin-Etsu Chemical Co., Ltd.
- SR-1000 mimentive
- the component (B) the component (A): an acrylate and / or methacrylate containing a cycloalkyl group
- the component (B) an acrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms
- the acrylic copolymer has a component (A) content of 50 to 90% by mass and components (B) and / or (C) content of 10 to 50% by mass in the total amount of constituent monomers. And at least 30% by weight is more preferably dissolved in light isoparaffin at 25 ° C.
- light isoparaffin refers to a mixture of hydrocarbons mainly composed of isoparaffin, and specifically, is a saturated hydrocarbon having 9 to 12 carbon atoms having a side chain, which is 95% by volume in the distillation test of JIS-K2254. A temperature of 200 ° C. or lower.
- the acrylic copolymer is preferably composed of component (A) and component (B), composed of component (A) and component (C), and component (A), component (B) and component. (C), more preferably, only component (A) and component (B), or only component (A), component (B) and component (C).
- the above acrylic copolymer requires component (A), component (B), component (C), and optional components as necessary, or component (A) and component (B).
- component (A), component (C), and optional components can be obtained by polymerizing component (A), component (C), and optionally component, if necessary, in the presence of an organic solvent in the absence of water. .
- the acrylic copolymer is composed of the component (A) and the component (B), and the component (A) is 50 to 90 parts by mass, and the component (B) is 10 to 50 parts by mass.
- An acrylic copolymer in which 10 to 50 parts by mass are polymerized can be preferably exemplified.
- Component (A) a cycloalkyl group-containing acrylate and / or methacrylate, is a lipophilic polymerizable monomer and forms a skeleton having water resistance and a transparent and hard film-forming ability.
- Specific examples include cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, tricyclodecyl acrylate, tricyclodecyl methacrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, and the like. These can be used individually by 1 type or in mixture of 2 or more types. Among these, cyclohexyl methacrylate is particularly preferable because it has a good radical polymerizability, a high yield, and a suitable glass transition point for forming a hard film.
- the acrylate and / or methacrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms as component (B) is an oleophilic polymerizable monomer that imparts flexibility and adhesion to the film, resulting in a light isoparaffin. Increase the solubility of.
- Specific examples include octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isononyl acrylate, isononyl methacrylate, lauryl acrylate, lauryl methacrylate, and the like. A mixture of the above can be used. Of these, 2-ethylhexyl methacrylate and lauryl methacrylate are preferable, and 2-ethylhexyl methacrylate is particularly preferable.
- organopolysiloxane macromonomer containing a radically polymerizable group at one end of the component (C) examples include ester compounds in which an organopolysiloxane is linked to acrylic acid or methacrylic acid via a divalent hydrocarbon group.
- an organopolysiloxane macromonomer represented by the following formula (2) can be exemplified.
- m is 1 to 10, preferably 1 to 4
- n is an integer of 0 to 200
- R 1 represents hydrogen or a methyl group
- R 2 to R 8 represents an alkyl group having 1 to 5 carbon atoms. Show. These can be used individually by 1 type or in mixture of 2 or more types.
- the organopolysiloxane macromonomer containing a radically polymerizable group at one end of the component (C) imparts water resistance to the film and enhances the solubility in light isoparaffin. More specifically, the dimethylpolysiloxane macromonomer shown by General formula (1) can be mentioned.
- the degree of polymerization n indicating the repeating unit of the dimethylpolysiloxane group is preferably 0 to 200, more preferably 5 to 150. When the degree of polymerization n is less than 5, sufficient water resistance may not be obtained, and when it exceeds 150, it may be difficult to obtain a transparent and uniform film.
- the acrylic copolymer those containing only the component (A) and the component (B) are preferable from the viewpoint of enhancing the effect of the present invention.
- the component (A) is cyclohexyl methacrylate and the component (B) is 2-ethylhexyl methacrylate.
- Particularly preferred are methacrylohexyl / ethyl hexyl methacrylate copolymers using
- the content ratio of cyclohexyl methacrylate to 2-ethylhexyl methacrylate in the methacrylohexyl / ethylhexyl methacrylate copolymer is preferably 0.5: 1 to 5: 1, and 2: 1 to 5: 1. More preferably, it is more preferably 2: 1 to 4: 1, and particularly preferably 2.5: 1 to 4: 1.
- Commercially available products include Plastic Size L-250 manufactured by Kyoyo Chemical Industry Co., Ltd.
- the acrylic copolymer of the component (B) can contain a polymerizable monomer other than the components (A) to (C) as a constituent monomer as long as the effects of the present invention are not impaired.
- the polymerizable monomer other than the components (A) to (C) is not particularly limited, but styrene, substituted styrene, vinyl acetate, acrylic acid, methacrylic acid, other acrylic esters and methacrylic esters, maleic anhydride, Maleic acid ester, fumaric acid ester, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, acrylonitrile, fluorinated olefin, acrylamide, methacrylamide, methylacrylamide, methylmethacrylamide, dimethylmethacrylamide, N-isopropylacrylamide, N-vinyl Pyrrolidone, N-vinylacetamide, t-butyl acrylate, t-butyl meth
- the blending amount of the component (A) is 50 to 90% by weight, preferably 50 to 80% by weight, based on the total amount of the constituent monomers. If the amount is less than 50% by mass, a film having sufficient hardness cannot be obtained. If the amount exceeds 90% by mass, the solubility in light isoparaffin is deteriorated.
- the amount of the component (B) is 10 to 50% by mass, preferably 15 to 45% by mass, based on the total amount of the constituent monomers.
- the amount of the component (C) is 10 to 50% by mass, preferably 15 to 45% by mass, based on the total amount of the constituent monomers. If it is less than 10% by mass, the solubility in light isoparaffin will deteriorate, and if it exceeds 50% by mass, a film with sufficient hardness cannot be obtained, and there are drawbacks such as stickiness, tackiness, and film non-uniformity. Arise.
- the total amount is 10 to 50% by mass, preferably 15 to 45% by mass.
- the total amount of component (B) and component (C) exceeds 50% by mass, a film with sufficient hardness cannot be obtained, and defects such as stickiness, tackiness, and film non-uniformity are observed.
- the total blending amount is less than 10% by mass, the solubility in light isoparaffin is deteriorated.
- the blending amount of the optional component may be within a range of 30% by mass or less of the total amount of the constituent monomers, and is preferably 20% by mass or less, for example, 0.01 to 10% by mass.
- the weight average molecular weight of the acrylic copolymer is not particularly limited, but is preferably in the range of 1.0 ⁇ 10 4 to 2.0 ⁇ 10 5 .
- the weight average molecular weight is measured by liquid gel permeation chromatography (GPC) using tetrahydrofuran as an eluent and using a calibration curve prepared with a linear polystyrene standard and a refractive index detector.
- GPC liquid gel permeation chromatography
- the acrylic copolymer is a known polymerization method using the above components (A) to (C) and, if necessary, other optional components as constituent monomers in the presence of an organic solvent (in the absence of water). Can be obtained by random polymerization.
- organic peroxides such as benzoyl peroxide and lauroyl peroxide, ⁇ , ⁇ ′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2, Polymerization may be performed in the presence of a radical polymerization initiator such as an azo compound such as 2′-azobis (2-methylbutyronitrile), a persulfuric polymerization initiator such as potassium persulfate or ammonium persulfate, and a solution.
- a radical polymerization initiator such as an azo compound such as 2′-azobis (2-methylbutyronitrile
- a persulfuric polymerization initiator such as potassium persulfate or ammoni
- a polymerization method, a suspension polymerization method, a bulk polymerization method, a precipitation polymerization method and the like can be used.
- the solution polymerization method is particularly preferable because it is easy to adjust the molecular weight of the obtained acrylic copolymer to the optimum range.
- organic solvent used in the polymerization of the acrylic copolymer examples include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, isopropanol, Examples thereof include alcohols such as ethanol and methanol, and these can be used alone or in combination. Moreover, it can also superpose
- paraffinic solvents such as light isoparaffin, isododecane, and isohexadecane.
- the polymerization reaction temperature of the acrylic copolymer is not particularly limited as long as it is within a temperature range in which a normal radical polymerization initiator can be used, but is usually in the range of 40 to 120 ° C. While the reaction temperature varies depending on the radical polymerization initiator to be used, the type of monomer, and the reaction temperature, it is usually carried out for 2 to 24 hours. If the polymerization time is too short, the amount of residual monomer is large and the yield is lowered, which is not preferable.
- the acrylic copolymer is dissolved in a paraffin solvent when reacted, or diluted with other hydrocarbons, esters, triglycerides and other oils as necessary, or to other oils Solvent replacement can also be performed.
- An acrylic copolymer composition containing such an oil-soluble cycloalkyl group is also included in the present invention.
- the solvent of the solution can be removed and the acrylic copolymer can be taken out as a solid, and the acrylic copolymer polymer obtained can be used as an acrylic copolymer solution by dissolving in light isoparaffin. You can also. Two or more of the above acrylic copolymers and their solutions can be used in combination.
- a fatty acid ester of dextrin having an average degree of polymerization of glucose of 3 to 150, a branched saturated fatty acid having 4 to 26 carbon atoms, more than 50 mol% and not more than 100 mol% with respect to all fatty acids, and 1 or 2 types selected from the group consisting of linear saturated fatty acids having 2 to 22 carbon atoms, linear or branched unsaturated fatty acids having 6 to 30 carbon atoms and cyclic saturated or unsaturated fatty acids having 6 to 30 carbon atoms
- a dextrin fatty acid ester containing 0 mol% or more and less than 50 mol% of the total fatty acid and having a fatty acid substitution degree per glucose unit of 1.0 to 3.0 is also preferably used.
- a suitable dextrin fatty acid ester is an esterified product of dextrin and fatty acid, and the degree of substitution of fatty acid for dextrin is 1.0 to 3.0, preferably 1.2 to 2.8, per glucose unit. .
- the degree of substitution is less than 1.0, the dissolution temperature in liquid oil or the like is as high as 100 ° C. or higher, and coloring or a specific odor is not preferable.
- Suitable dextrin fatty acid esters have the following properties: 1) A suitable dextrin fatty acid ester does not gel when mixed with liquid oil. “Liquid oil does not gel” means that when liquid paraffin having a kinematic viscosity of 8 mm 2 / s at 40 ° C. according to ASTM D445 measurement method is used as a liquid oil, the flow contains 5% by mass of a suitable dextrin fatty acid ester.
- a film formed by a suitable dextrin fatty acid ester has a specific range of tackiness. The “tackiness” is determined by applying the dextrin fatty acid ester to a support and bringing the other support into surface contact from a state where they are separated from each other, then retracting them and separating them.
- a light liquid isoparaffin solution containing 40% by mass of the dextrin fatty acid ester is formed on a glass plate with a 400 ⁇ m-thick applicator and dried.
- Texture analyzers eg texture analyzer TA.
- XTplus manufactured by Stable Micro Systems
- a probe made of a 12.5 mm diameter cylindrical polyacetal resin manufactured by Delrin (registered trademark) DuPont
- Delrin registered trademark
- the dextrin used in a suitable dextrin fatty acid ester is preferably a dextrin having an average glucose polymerization degree of 3 to 150, particularly 10 to 100.
- the average degree of polymerization of glucose is 2 or less, the obtained dextrin ester becomes wax-like and the solubility in an oil agent decreases.
- the average degree of polymerization of glucose exceeds 150, there may be a problem that the dissolution temperature of the dextrin ester in the oil agent becomes high or the solubility becomes poor.
- the sugar chain of dextrin may be linear, branched or cyclic.
- the fatty acid used in a suitable dextrin fatty acid ester is essentially one or more of branched saturated fatty acids having 4 to 26 carbon atoms, and further is a straight-chain saturated fatty acid having 2 to 22 carbon atoms, having 6 to 30 carbon atoms.
- the fatty acids When the fatty acids are collectively represented, they may be referred to as “other fatty acids”.
- the composition ratio of the fatty acid is such that one or more of the branched saturated fatty acids having 4 to 26 carbon atoms is more than 50 mol% and not more than 100 mol%, preferably not less than 55 mol% and not more than 100 mol%, based on the total fatty acids.
- the other fatty acid is 0 mol% or more and less than 50 mol%, preferably 0 mol% or more and 45 mol% or less.
- Examples of the branched saturated fatty acid having 4 to 26 carbon atoms used in the preferred form include isobutyric acid, isovaleric acid, 2-ethylbutyric acid, ethylmethylacetic acid, isoheptanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, Examples include isotridecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachidic acid, isohexacosanoic acid, and the like, and one or more of these can be appropriately selected or used in combination. Of these, those having 12 to 22 carbon atoms are preferred, isostearic acid is particularly preferred, and there is no particular limitation on the difference in structure.
- isostearic acid means one or a mixture of two or more branched stearic acids.
- 5,7,7-trimethyl-2- (1,3,3-trimethylbutyl) -octanoic acid is converted to a branched aldehyde having 9 carbons by oxo reaction of isobutylene dimer, and then carbon is obtained by aldol condensation of this aldehyde.
- the branched unsaturated aldehyde of formula 18 can be produced by hydrogenation and oxidation (hereinafter abbreviated as “aldol condensation type”), which is commercially available from, for example, Nissan Chemical Industries, Ltd.
- 2-Heptylundecanoic acid can be produced by subjecting nonyl alcohol to a gerbet reaction followed by oxidation, which is commercially available from, for example, Mitsubishi Kasei Co., Ltd.
- a methyl branched type in which the starting alcohol is not linearly saturated is also commercially available from Nissan Chemical Industries, Ltd. (hereinafter abbreviated as “gerbet reaction type”).
- methyl-branched isostearic acid is obtained as a by-product at the time of dimer production of oleic acid, for example [for example, J. Amer. Oil Chem. Soc.
- dimer acid which is a starting material of emery type isostearic acid may include not only oleic acid but also linoleic acid, linolenic acid and the like. In the present invention, this emery type is particularly preferable.
- linear saturated fatty acid having 2 to 22 carbon atoms examples include acetic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and the like. These 1 type (s) or 2 or more types can be suitably selected or combined and used. Of these, those having 8 to 22 carbon atoms are preferred, and those having 12 to 22 carbon atoms are particularly preferred.
- Examples of the straight-chain or branched unsaturated fatty acid having 6 to 30 carbon atoms used in the preferred form include, for example, cis-4-decene (obtusil) acid, 9-decene (caprolein) acid, cis -4-dodecene (lindel) acid, cis-4-tetradecene (tuzu) acid, cis-5-tetradecene (fisetelin) acid, cis-9-tetradecene (myristolein) acid, cis-6-hexadecenoic acid, cis- 9-hexadecene (palmitolein) acid, cis-9-octadecene (oleic) acid, trans-9-octadecenoic acid (elaidic acid), cis-11-octadecene (asclepine) acid, cis-11-eicosene (gondrain) acid
- Examples of the unsaturated fatty acid include sorbic acid, linoleic acid, hiragoic acid, punicic acid, linolenic acid, ⁇ -linolenic acid, moloctic acid, stearidonic acid, arachidonic acid, EPA, succinic acid, DHA, nisic acid, stearolic acid, Examples include crepenic acid and xymenic acid.
- the cyclic saturated or unsaturated fatty acid having 6 to 30 carbon atoms used in a preferred form means a saturated or unsaturated fatty acid having 6 to 30 carbon atoms having a cyclic structure in at least a part of the basic skeleton.
- alleprilic acid allepuric acid, goluric acid, ⁇ -cyclopentylic acid, ⁇ -cyclohexyl acid, ⁇ -cyclopentylethyl acid, ⁇ -cyclohexylmethyl acid, ⁇ -cyclohexyl acid; 5 (6) -carboxyl Examples include -4-hexyl-2-cyclohexene-1-octanoic acid, malvalic acid, sterlic acid, hydonocarpic acid, and scholmooglic acid.
- examples of the dextrin fatty acid ester in the case where the branched saturated fatty acid alone is used as the fatty acid include the following.
- examples of the dextrin fatty acid ester in the case where a mixed fatty acid of a branched saturated fatty acid and another fatty acid is used as the fatty acid include the following.
- dextrin having an average degree of polymerization of glucose of 3 to 150 and one or more of branched saturated fatty acid derivatives having 4 to 26 carbon atoms, more than 50 mol% and not more than 100 mol% with respect to all fatty acid derivatives, and 1 type selected from the group consisting of linear saturated fatty acid derivatives having 2 to 22 carbon atoms, linear or branched unsaturated fatty acid derivatives having 6 to 30 carbon atoms and cyclic saturated or unsaturated fatty acid derivatives having 6 to 30 carbon atoms Alternatively, two or more kinds (hereinafter referred to as “other fatty acid derivatives” when these fatty acid derivatives are collectively expressed) are reacted with a fatty acid derivative containing 0 mol% or more and less than 50 mol% with respect to the total fatty acid derivatives.
- one or more of the branched saturated fatty acid derivatives having 4 to 26 carbon atoms with respect to the total fatty acid derivatives are more than 50 mol% and not more than 100 mol%, and other fatty acid derivatives are 0 mol% with respect to the total fatty acid derivatives. More than 50 mol% is used.
- a halide or acid anhydride of the fatty acid is used as the fatty acid derivative used in the esterification reaction with the dextrin.
- a halide or acid anhydride of the fatty acid is used as the fatty acid derivative used in the esterification reaction with the dextrin.
- dextrin is dispersed in a reaction solvent, and a catalyst is added as necessary.
- the above-mentioned fatty acid halide, acid anhydride or the like is added and reacted.
- these acids are mixed and added and reacted at the same time.
- a branched saturated fatty acid derivative having low reactivity is reacted, and then another fatty acid derivative. Is reacted.
- reaction solvent a solvent such as formamide such as dimethylformamide and formamide; acetamide; ketone; aromatic compounds such as benzene, toluene and xylene; and a solvent such as dioxane can be used as appropriate.
- reaction catalyst tertiary amino compounds such as pyridine and picoline can be used.
- the reaction temperature is appropriately selected depending on the starting fatty acid and the like, but a temperature of 0 ° C. to 100 ° C. is preferred.
- the semi-solid content is washed several times with methanol and dried to obtain 107 g of a pale yellow resinous substance.
- resinous materials obtained by the above example derived dextrin from IR spectrum 1000 ⁇ 1200 cm -1, derived from ester 1742 cm -1, can see a peak derived from alkyl 2800 ⁇ 3000 cm -1, also after alkali decomposition From the amount of fatty acid and gas chromatography, it can be confirmed that the degree of substitution is 2.2, isostearic acid is 60 mol%, and other fatty acids are 40 mol% (internal palmitic acid is 10 mol%).
- Unifilmma HVY manufactured by Chiba Miller
- component (B) in the present invention is not particularly limited, but is preferably 0.1 to 10% in the cosmetic, more preferably 0.3 to 8%, and particularly preferably 0.5 to 5%. %. This range is preferable in that it is more excellent in preventing secondary adhesion.
- the polyhydric alcohol of component (C) used in the present invention can be used without particular limitation as long as it is usually used in cosmetics, and specifically, propylene glycol, dipropylene glycol, butylene glycol, triglyceride. Propylene glycol, caprylyl glycol, glycerin, diglycerin, ethylene glycol, polyethylene glycol, hexanediol and the like can be mentioned, and one or more can be used in combination as necessary.
- component (C) When component (C) is combined with component (A), it plays the role of a lubricant and lightly spreads and spreads during application, and is blocked in the coating film to suppress moisture transpiration and moisturizing feeling. The sustainability of can be dramatically improved.
- tripropylene glycol (INCI name, TRIPROPYLENE GLYCOL or PPG-3) realizes the lightness of spreading without sticking to the end, and also has excellent skin familiarity, so it stands out for the sustainability of moisturizing feeling. It is more preferable because of its superiority.
- Examples of commercially available products include New Pole PP-200 (manufactured by Sanyo Chemical Industries).
- the content of component (C) in the present invention is not particularly limited, but is preferably 1 to 30%, more preferably 3 to 25%, and particularly preferably 5 to 20%. Within this range, it is preferable in that it is excellent in lightness of spreading and sustaining a moisturizing feeling.
- a methacrylohexyl / ethyl hexyl methacrylate copolymer which is a resin with a fast film formation, as a component (B), and a combination of tripropylene glycol as a component (C).
- the partially cross-linked organopolysiloxane of component (D) used in the present invention is an organopolysiloxane polymer having a three-dimensional cross-linked structure and can be used without particular limitation as long as it is usually used in cosmetics. it can.
- partially crosslinked methylpolysiloxanes such as (dimethicone / vinyldimethicone) crosspolymer, partially crosslinked methylphenylpolysiloxanes such as (dimethicone / phenyldimethicone) crosspolymer, (vinyldimethicone / lauryldimethicone) crosspolymer, Partially cross-linked alkyl-modified silicones such as (dimethicone / phenylvinyl dimethicone) cross-polymer, partially cross-linked silicone-alkyl co-modified silicones such as (lauryl polydimethylsiloxyethyl dimethicone) / bis-polymer, dimethicone / (PEG-10) / 15)) Partially cross-linked polyether-modified silicone such as cross-polymer, partially cross-linked alkyl-polyether co-modified silicone such as PEG-15 lauryl dimethi
- Component (D) can be combined with components (A) and (B) to impart flexibility to the oil-soluble resin and realize a cosmetic film with very little burden.
- Component (D) is uniformly dispersed when swollen with an oil agent, and the effect of improving the hardness of the decorative film becomes more prominent, and is often marketed as a mixture with the oil agent.
- KSG-16 solid content 20-30%), KSG-18 (solid content 10-20%), KSG-41A (solid content 20-30%), KSG-042Z (solid 15-25%), KSG-210 (solid content 20-30%), KSG-310 (solid content 25-35%), KSG-320Z (solid content 20-30%), KSG-710 (solid content 20 ⁇ 30%), KSG-810 (solid content 25-35%), KSG-820Z (solid content 20-30%), KSG-850Z (solid content 20-30%), KSG-1510 (solid content 5-10) %), KSG-1610 (solid 15-20%), KSG-18A (solid content 10-20%), KSG-016F (solid content 20-30%), KSG-045Z (solid content 15-25%), KSG-048Z (solid content 15 -25%), KSG-240 (solid content 15-25%), KSG-320Z (solid content 20-30%), KSG-350Z (solid content 20-30%), KSG-360Z (solid content 30-40) %), KSG-380Z
- a partially crosslinked polyglycerin-modified silicone and a partially crosslinked silicone-alkyl-polyglycerin co-modified silicone are particularly preferable. Specifically, KSG-710, KSG-820Z KSG-850Z is preferred.
- component (D) in particular, a partially crosslinked polyglycerin-modified silicone and / or a partially crosslinked silicone / alkyl / polyglycerol co-modified silicone, a partially crosslinked methylpolysiloxane, and / or Alternatively, a combination of a partially crosslinked methylphenyl polysiloxane and / or a partially crosslinked silicone / alkyl co-modified silicone is preferable.
- KSG-710, KSG-820Z, KSG-850Z, and KSG-15 KSG-1510, KSG-16, KSG-1610, KSG-18A, KSG-19, KSG-016F, KSG-042Z, KSG-045Z, and KSG-048Z are preferred.
- component (D) in particular, a partially crosslinked polyglycerin-modified silicone and / or a partially crosslinked silicone-alkyl-polyglycerin co-modified silicone, a partially crosslinked polyether-modified silicone, and And / or a combination with a partially cross-linked silicone / alkyl / polyether co-modified silicone, specifically, KSG-710, KSG-820Z, KSG-850Z, KSG-210, KSG-240, KSG-320Z , KSG-350Z, KSG-360Z, and KSG-380Z are preferred.
- the content of the component (D) in the present invention is not particularly limited, but is preferably 0.1 to 5%, more preferably 0.2 to 4%, and particularly preferably 0.5 to 3%. Within this range, it is preferable in that a decorative film with less burden is obtained.
- the water-in-oil emulsified cosmetic composition of the present invention contains the component (E) spherical silica, which can remarkably increase the lightness of elongation at the time of application.
- Any component (E) can be used as long as it is used in ordinary cosmetics, but those having an average particle size of 1 to 30 ⁇ m, preferably 3 to 15 ⁇ m, have good elongation. It is more preferable in that it is more excellent.
- the average particle size is determined by a Coulter counter. Examples of commercially available products include Sunsphere NP-100 (manufactured by AGC S-Tech).
- the content of component (E) in the present invention is not particularly limited, but is preferably 0.1 to 10%, more preferably 0.5 to 7%, and particularly preferably 1 to 5%. If it is this range, a more satisfactory thing will be obtained at the point which is excellent in the lightness of extension spread.
- the water-in-oil emulsified cosmetic of the present invention has an oil phase as a continuous phase and water as a dispersed phase.
- the water content is not particularly limited, but is preferably 5 to 60% in the cosmetic, more preferably 10 to 50%, and particularly preferably 15 to 40%.
- the water-in-oil emulsified cosmetic of the present invention includes the above components, oils such as solid oils, semi-solid oils, and liquid oils commonly used in cosmetics, surfactants, gelling agents, polymers, and colorants. , Powders, ultraviolet absorbers, antiseptics, antibacterial agents, antioxidants, fragrances, cosmetic ingredients, and the like can be appropriately contained within a range that does not hinder the effects of the present invention.
- Oils include liquid oils such as liquid paraffin and squalane, solid oils such as paraffin wax, ceresin wax, microcrystalline wax, polyethylene wax and Fischer-Tropsch wax, olive oil, castor oil, jojoba oil, mink oil, macadamian nut oil, etc.
- Surfactants include stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid, oleic acid, 12-hydroxystearic acid, poly-12-hydroxystearic acid, fatty acid soaps, acyl glutamates, alkyl phosphates, Anionic surfactants such as polyoxyalkylene-added alkyl phosphates, cationic surfactants such as alkylamine salts and alkyl quaternary ammonium salts, glycerin fatty acid esters and alkylene glycol adducts thereof, propylene glycol fatty acid esters And non-ionic products such as alkylene glycol adducts thereof, sorbitan fatty acid esters and alkylene glycol adducts thereof, sucrose fatty acid esters, polyoxyalkylene-modified organopolysiloxanes, glycerin-modified organopolysiloxanes, etc.
- Gelling agents include dextrin palmitate, (palmitic acid / ethylhexanoic acid) dextrin, inulin stearate, organically modified bentonite, fumed silicic anhydride, aluminum isostearate, zinc stearate, magnesium stearate, etc.
- UV absorbers include cinnamic acid derivatives, aminobenzoic acid derivatives, salicylic acid derivatives, Examples include benzophenone derivatives, phenylbenzimidazole derivatives, phenylbenzotriazole derivatives, and paraoxybenzoic acid derivatives. Phenoxyethanol, preservatives such as alkane diols, rosemary extract, chamomile extract, collagen, hyaluronic acid, cosmetic ingredients ceramide and the like.
- the colorant and powder are not particularly limited by the shape of a plate, spindle, needle, etc., the particle size of fumes, fine particles, pigment grade, etc., the particle structure of porous, nonporous, etc. Examples thereof include powders, glitter powders, organic powders, pigment powders, and composite powders.
- the water-in-oil emulsified cosmetic of the present invention can be applied to a base, a foundation, a cosmetic liquid, a sunscreen cosmetic, etc., and preferably a base, a foundation, a BB cream, etc. Makeup cosmetics, more preferably foundations.
- the usage method includes a method of using with a hand or a finger, a method of using it by impregnating a puff, a sponge or the like.
- the property can be implemented as cosmetics having various properties such as gel and liquid.
- Examples 1 to 20 and Comparative Examples 1 to 5 Water-in-oil emulsion type foundation (liquid) A water-in-oil emulsion foundation having the formulation shown in Table 1 below was prepared, and water resistance, secondary adhesion prevention effect, lightness of spread, lack of burden, and persistence of moisturizing feeling were evaluated by the following methods. The results are also shown in Table 1.
- evaluation methods The following evaluation methods were evaluated for the following evaluation items (i) to (e).
- evaluation item I.
- Each panel member evaluated in 5 grades by the following absolute evaluation, the average value was calculated for each sample, and the determination was made according to the following criteria.
- the water-in-oil emulsified foundations of Examples 1 to 20 of the present invention have water resistance, secondary adhesion preventing effect, compared with the water-in-oil emulsified foundations of Comparative Examples 1 to 5. It was excellent in all of the lightness of spreading, lack of burden, and sustaining moisturizing feeling. On the other hand, in Comparative Example 1 in which the component (A) is not contained, the strength of the decorative film is weak, so that it easily collapses, and further, moisture transpiration of the skin over time cannot be suppressed. A satisfactory product was not obtained in terms of the effect of preventing the subsequent adhesion and sustaining the moisturizing feeling.
- Comparative Example 2 using an alkyl acrylate / styrene copolymer dispersion using water as a dispersion medium in place of the component (A), the decorative film is easy to be familiar with water, so the water resistance is poor and the flexibility of the coating film is reduced. Since it lacks, it cannot follow the movement of the skin, and further, it cannot suppress the moisture transpiration of the skin over time, so it was not possible to obtain a satisfactory one in terms of water resistance, lack of burden, and persistence of moisture retention .
- Comparative Example 3 containing no component (B) the bonding point of the coating film formed by fusing the component (A) is weak, so it is easy to become familiar with sebum and is inferior in the secondary adhesion preventing effect. It was.
- Comparative Example 4 In Comparative Example 4 in which the component (C) is not contained, it is easy to feel the weight of the extension spread due to the components (A) and (B), and furthermore, moisture transpiration of the skin over time cannot be suppressed. However, it was not enough in terms of the lightness and sustaining moisturizing feeling. In Comparative Example 5 in which the component (D) was not contained, it was easy to feel the hardness of the decorative film made of the oil-soluble resin, and a satisfactory one was not obtained in terms of no burden.
- Example 14 using trimethylsiloxysilicic acid, which is a hard resin, as the component (B), all of water resistance, secondary adhesion preventing effect, lightness of spreading, no feeling of burden, and persistence of moisture retention In addition to being excellent in, it was excellent in the effect of imparting firmness to the skin.
- Example 15 using a flexible (Acrylates / Dimethicone) copolymer as the component (B), all of water resistance, secondary adhesion preventing effect, lightness of spreading, no feeling of burden, and persistence of moisture retention. In addition, it was excellent in the effect of preventing the swaying of the cosmetic film at a site with a large movement associated with facial expressions such as around the eyes and around the mouth.
- the gloss of the decorative film was excellent.
- Examples 17 and 18 using methacrylohexyl / ethyl hexyl methacrylate copolymer as a component (B), which is a fast film forming resin, water resistance, secondary adhesion preventing effect, lightness of spreading, and burden feeling In addition, it was excellent not only in the persistence of the moisturizing feeling, but also in that a uniform decorative film without uneven coating was produced.
- Example 19 using hydrogenated pentaerythrityl rosinate as a component (B) is also effective in all of water resistance, secondary adhesion prevention effect, lightness of spreading, lack of burden, and persistence of moisture retention. I found out that
- Example 21 Water-in-oil emulsion type base (cream) (Ingredient) (%) (1) Titanium oxide treated with 3% dimethylpolysiloxane 1.5 (2) Dimethylpolysiloxane 2% treated yellow iron oxide 0.1 (3) Treated with 2% dimethylpolysiloxane 0.1% (4) Dimethylpolysiloxane 3% zinc oxide 10.0 (5) Dimethylpolysiloxane 3% treated talc 1.0 (6) Dimethylpolysiloxane 2% treated mica titanium 2.0 (7) PEG-9 Dimethicone * 10 2.0 (8) Decamethylcyclopentasiloxane 15.0 (9) 2-Ethylhexyl paramethoxycinnamate 8.0 (10) 2- (4-Diethylamino-2-hydroxybenzoyl) Benzoic acid hexyl ester 1.0 (11) Alkyl acrylate / styrene copolymer dispersion * 4 0.5 (12) (Acrylates / Dimethicon
- the water-in-oil emulsified type base of the present invention (cream-like) is lightly spread at the time of application, and the decorative film after application is excellent in water resistance and secondary adhesion prevention effect, but there is no sense of tension that is stuck, Furthermore, it was excellent in sustaining the moisturizing feeling.
- Example 22 Water-in-oil emulsion sunscreen cosmetic (liquid) (Ingredient) (%) (1) Decamethylcyclopentasiloxane 10.0 (2) PEG-3 dimethicone * 15 4.0 (3) Zinc oxide * 2 15.0 (4) 2-Ethylhexyl paramethoxycinnamate 3.0 (5) 4-tert-butyl-4′-methoxy-dibenzoylmethane 1.0 (6) Polysilicone-15 3.0 (7) Hydrogenated polyisobutene * 16 5.0 (8) Trimethylsiloxysilicic acid * 17 8.0 (9) Neopentyl glycol diethylhexanoate 1.0 (10) Cetyl 2-ethylhexanoate 1.0 (11) Propylene glycol dicaprate 1.0 (12) 2-decyltetradecanol 8.0 (13) Alkyl acrylate / styrene copolymer dispersion * 4 16.0 (14) (Dimethicone / Phenylviny
- the water-in-oil emulsified sunscreen cosmetic (liquid) of the present invention has a light stretch spread at the time of application, and the coated film after application is excellent in water resistance and secondary adhesion prevention effect, but has a feeling of tension. Furthermore, it was excellent in sustaining the moisturizing feeling.
- Example 23 Water-in-oil emulsified blusher (gel) (Ingredient) (%) (1) Triethoxycaprylylsilane 3% treated titanium oxide 3.0 (2) Triethoxycaprylylsilane 3% treated red 226 0.5 (3) Triethoxycaprylylsilane 3% treated yellow 4 0.2 (4) 3% black iron oxide treated with triethoxycaprylylsilane 0.1 (5) Methyltrimethicone 5.0 (6) Isododecane 10.0 (7) Trimethylsiloxysilicic acid * 20 7.5 (8) Dextrin isostearate * 21 0.5 (9) Alkyl acrylate / styrene copolymer dispersion * 22 8.0 (10) Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 1.5 (11) PEG / PPG-10 / 3 oleyl ether dimethicone * 23 1.0 (12) (Dimethicone / polyglycerin-3)
- the water-in-oil emulsified blusher (gel-like) of the present invention has a light stretch spread at the time of application, and the cosmetic film after application is excellent in water resistance and secondary adhesion preventing effect, but there is no sense of tension that is stuck, Furthermore, it was excellent in sustaining the moisturizing feeling.
- Example 24 Water-in-oil emulsification type sunscreen cosmetic (liquid) (Ingredient) (%) (1) Zinc oxide * 2 10.0 (2) Dimethylsilylated silica 5.0 (3) Polyhydroxystearic acid 1.0 (4) 2-ethylhexyl paramethoxycinnamate 10.0 (5) Diethylaminohydroxybenzoyl hexyl benzoate 2.0 (6) Bisethylhexyloxyphenol methoxyphenyltriazine 1.0 (7) Polysilicone-15 3.0 (8) PEG-9 polydimethylsiloxyethyl dimethicone 0.5 (9) Decamethylcyclopentasiloxane 5.0 (10) Dimethicone 3.0 (11) Propylene glycol dicaprate 20.0 (12) (Dimethicone / (PEG-10 / 15)) Crosspolymer * 27 1.0 (13) (Vinyl Dimethicone / Lauryl Dimethicone) Cross Polymer * 28 2.0 (14) Alkyl
- the water-in-oil emulsified sunscreen cosmetic (liquid) of the present invention has a light stretch spread at the time of application, and the coated film after application is excellent in water resistance and secondary adhesion prevention effect, but has a feeling of tension. Furthermore, it was excellent in sustaining the moisturizing feeling.
- Example 26 Water-in-oil emulsified sunscreen cosmetic (solid form) (Ingredient) (%) (1) Decamethylcyclopentasiloxane 20.0 (2) Zinc oxide * 2 15.0 (3) Dimethylsilylated silica 3.0 (4) PEG-9 polydimethylsiloxyethyl dimethicone 1.0 (5) Triethylhexanoin 10.0 (6) Cetyl 2-ethylhexanoate 5.0 (7) 2-Methylhexyl paramethoxycinnamate 5.0 (8) 4-tert-butyl-4′-methoxy-dibenzoylmethane 1.0 (9) Polysilicone-15 3.0 (10) Diethylhexanoic acid neopentyl glycol 3.0 (11) Propylene glycol dicaprate 3.0 (12) Alkyl acrylate / styrene copolymer dispersion * 4 1.5 (13) Dipropylene glycol 1.0 (14) Polymethylsilsesquiox
- the water-in-oil emulsified sunscreen cosmetic (solid form) of the present invention has a light stretch spread at the time of application, and the cosmetic film after application is excellent in water resistance and secondary adhesion prevention effect, but also a sense of strain In addition, it was excellent in sustaining the moisturizing feeling.
- Example 26 Water-in-oil emulsified sunscreen cosmetic (spray form) (Ingredient) (%) (Stock solution) (1) 2-Ethylhexyl paramethoxycinnamate 8.0 (2) Diethylaminohydroxybenzoyl hexyl benzoate 0.5 (3) Bisethylhexyloxyphenol methoxyphenyl triazine 2.0 (4) Propylene glycol dicaprate 30.0 (5) Alkyl benzoate 1.0 (6) Isododecane 5.0 (7) Alkyl acrylate / styrene copolymer dispersion * 22 5.0 (8) (Vinyl dimethicone / methicone silsesquioxane) crosspolymer * 29 3.0 (9) (Dimethicone / Phenyl vinyl dimethicone) cross polymer * 18 1.0 (10) Polymethylsilsesquioxane * 3 2.0 (11) Spherical silica * 32 0.5 (12) Pur
- the water-in-oil emulsified sunscreen cosmetics (spray form) of the present invention have a light stretch spread at the time of application, and the coated film after application is excellent in water resistance and secondary adhesion prevention effect, but also a sense of strain In addition, it was excellent in sustaining the moisturizing feeling.
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Abstract
Description
従来より、油中水型乳化化粧料は、耐水性、および皮脂と混じりあうことによる色移りの防止(二次付着防止効果)といった機能が重要であり、これらの機能を高めるような手法について種々検討が行われてきた。例えば、特定の揮発性オルガノポリシロキサン、油溶性樹脂、撥水性粉体、水を併用することで、塗布時の伸びの軽さ、べたつきのなさ、二次付着防止効果、化粧持ちを向上させる技術(特許文献1参照)や、(メタ)アクリル酸・(メタ)アクリル酸アルキル共重合体エマルジョン、部分架橋型オルガノポリシロキサン重合物、揮発性シリコーンを含有し、界面活性剤を実質的に含有しないことで、透明性、耐水性、耐皮脂性、滑らかな感触、保存安定性を向上させる技術(特許文献2参照)、あるいは、揮発性油剤、揮発性油剤に溶解しない樹脂、融点が75℃以上である固形油、デキストリン脂肪酸エステルを併用することで、塗布時の伸びの軽さ、なめらかさ、二次付着防止効果、耐水性、耐油性、化粧持ち、化粧膜の均一性を向上させる技術(特許文献3参照)が知られている。
そのため、塗布時の伸び広がりが軽く、塗布後の化粧膜が耐水性と二次付着防止効果に優れながらも、つっぱるような負担感がなく、さらに保湿感の持続にも優れる油中水型乳化化粧料を提供することが課題であった。
(A)揮発性炭化水素油を分散媒とするアクリル酸アルキル・スチレン共重合体ディスパージョン
(B)油溶性樹脂
(C)多価アルコール
(D)部分架橋型オルガノポリシロキサン
を含有する油中水型乳化化粧料である。
本発明に用いられる成分(A)は、アクリル酸アルキル・スチレン共重合体を揮発性炭化水素油に分散したディスパージョンである。分散するアクリル酸アルキル・スチレン共重合体は、INCI名(International Nomenclature Cosmetic Ingredient labeling names)で、STYRENE/ACRYLATES COPOLYMERとして収載されているものであり、アクリル酸アルキル及びメタクリル酸アルキルの1種以上と、スチレンを重合して得ることができる。これらは揮発性炭化水素油に溶解せずに、ディスパージョンの形態を有し、一般的に非水ディスパージョン(NAD=Non Aqua Dispersion、非水エマルションも同義)と称されるものである。アクリル酸アルキル・スチレン共重合体は、特に限定されないが、アクリル酸アルキル及びメタクリル酸アルキルとスチレンとを70/30~90/10の質量比で含むものが好ましく、数平均分子量は50000~300000(ゲルパーミュレーションクロマトグラフィによるポリスチレン換算値)のものが好ましく用いられる。この範囲であると、揮発性炭化水素油に溶解せず、良好なディスパージョン状態を保つことができる。また、樹脂粒子は、遠心沈降法による平均粒子径が0.1~2.0μmであると、ディスパージョンの粘度変化が少なく、粒子の沈殿も生じにくく好ましい。
具体的には、上記アクリル系共重合体は、構成モノマー総量中、成分(A)の配合量が50~90質量%、成分(B)及び/又は(C)の配合量が10~50質量%であり、且つ、軽質イソパラフィンに25℃で少なくとも30質量%溶解することがより好ましい。
式中、mは1~10、好ましくは1~4、nは0~200の整数、R1は、水素又はメチル基を示し、R2~R8は、炭素数1~5のアルキル基を示す。
これらは1種単独で又は2種以上混合して用いることができる。
ジメチルポリシロキサン基の繰返し単位を示す重合度nは0~200が好ましく、さらに好ましくは5~150である。重合度nが5未満である場合には、充分な耐水性を得ることができないおそれがあり、150を超えると透明で均一な皮膜を得ることが困難になる場合がある。
ここで、メタクリロヘキシル/メタクリル酸エチルヘキシルコポリマーにおける、シクロヘキシルメタクリレートと2-エチルヘキシルメタクリレートとの含有比は、0.5:1~5:1であることが好ましく、2:1~5:1であることがより好ましく、2:1~4:1であることがさらにに好ましく、2.5:1~4:1であることが特に好ましい。
市販品としては、互応化学工業社製プラサイズL-250が挙げられる。
1)好適なデキストリン脂肪酸エステルは、液状油に混合したときに液状油がゲル化しない。
「液状油がゲル化しない」とは、ASTM D445測定方法による40℃における動粘度が8mm2/sである流動パラフィンを液状油とする場合、好適なデキストリン脂肪酸エステルを5質量%含有する該流動パラフィンを100℃で溶解し、24時間後25℃で粘度を測定したとき、粘度が、Yamco DIGITAL VISCOMATE粘度計VM-100A(振動式)(山一電機社製)の検出限界以下であることを意味する。なお、ゲル化する場合には、粘度が検出されることで確認できる。
2)好適なデキストリン脂肪酸エステルが形成する皮膜が特定範囲のタック性を有する。
「タック性」を、支持体に該デキストリン脂肪酸エステルを塗布し、もうひとつの支持体を相互に離れた状態から面接触させた後に、後退させて別離させ、後退を開始してから完全に別離するまでの接触点にかかる荷重変化(最大応力値)で表す場合、該デキストリン脂肪酸エステルを40質量%含有する軽質流動イソパラフィン溶液をガラス板に400μm厚のアプリケーターで成膜し、乾燥させた皮膜に、テクスチャーアナライザー、たとえば、テクスチャーアナライザーTA.XTplus(Stable Micro Systems社製)を用いて、プローブとして直径12.5mm円柱状のポリアセタール樹脂(Delrin(登録商標)デュポン社製)製プローブを使用し、100gの荷重をかけ10秒保持後に0.5mm/秒で離したときの荷重変化、すなわちタック性が30~1,000gである。
デキストリンイソ酪酸エステル
デキストリンエチルメチル酢酸エステル
デキストリンイソヘプタン酸エステルデキストリン2-エチルヘキサン酸エステル
デキストリンイソノナン酸エステル
デキストリンイソデカン酸エステル
デキストリンイソパルミチン酸エステル
デキストリンイソステアリン酸エステル
デキストリンイソアラキン酸エステル
デキストリンイソヘキサコサン酸エステル
デキストリン(イソ吉草酸/イソステアリン酸)エステル
デキストリン(イソ酪酸/カプリル酸)エステル
デキストリン(2-エチルヘキサン酸/カプリル酸)エステル
デキストリン(イソアラキン酸/カプリル酸)エステル
デキストリン(イソパルミチン酸/カプリル酸)エステル
デキストリン(エチルメチル酢酸/ラウリン酸)エステル
デキストリン(2-エチルヘキサン酸/ラウリン酸)エステル
デキストリン(イソヘプタン酸/ラウリン酸/ベヘン酸)エステル
デキストリン(イソステアリン酸/ミリスチン酸)エステル
デキストリン(イソヘキサコサン酸/ミリスチン酸)エステル
デキストリン(2-エチルヘキサン酸/パルミチン酸)エステル
デキストリン(イソステアリン酸/パルミチン酸)エステル
デキストリン(イソステアリン酸/イソ吉草酸/パルミチン酸)エステル
デキストリン(イソノナン酸/パルミチン酸/カプロン酸)エステル
デキストリン(2-エチルヘキサン酸/パルミチン酸/ステアリン酸)エステル
デキストリン(イソデカン酸/パルミチン酸)エステル
デキストリン(イソパルミチン酸/ステアリン酸)エステル
デキストリン(イソステアリン酸/アラキン酸)エステル
デキストリン(2-エチルヘキサン酸/アラキン酸)エステル
デキストリン(2-エチル酪酸/ベヘン酸)エステル
デキストリン(イソノナン酸/リノール酸)エステル
デキストリン(イソパルミチン酸/アラキドン酸)エステル
デキストリン(イソパルミチン酸/カプリル酸/リノール酸)エステル
デキストリン(イソステアリン酸/ステアリン酸/オレイン酸)エステル
デキストリン(イソアラキン酸/パルミチン酸/ショールムーグリン酸)エステル
製造方法としては、特に限定されず、公知の製法を採用することができるが、たとえば以下のようにして製造することができる。
その場合、全脂肪酸誘導体に対して炭素数4~26の分岐飽和脂肪酸誘導体の1種又は2種以上を50mol%より多く100mol%以下、及び、その他の脂肪酸誘導体を全脂肪酸誘導体に対して0mol%以上50mol%未満使用する。
1)及び2)のいずれも場合も、まず、デキストリンを反応溶媒に分散し、必要に応じて触媒を添加する。これに、上記脂肪酸のハロゲン化物、酸無水物等を添加して反応させる。1)の製造法の場合は、これらの酸を混合して同時に添加反応させ、2)の製造法の場合は、まず反応性の低い分岐飽和脂肪酸誘導体を反応させた後、次いでその他の脂肪酸誘導体を添加反応させる。
平均グルコース重合度30のデキストリン21.41g(0.132mol)をジメチルホルムアミド71g、3-メチルピリジン62g(0.666mol)とからなる混合溶媒に70℃で分散させ、イソステアリン酸クロライド(エメリー型)120g(0.396mol)を30分間かけて滴下する。滴下終了後、反応温度を80℃として5時間反応させる。反応終了後、反応液をメタノールに分散させ、上層を除去する。半固形分をメタノールで数回洗浄後、乾燥して淡黄色の樹脂状物質107gを得る。
上記例にて得られる樹脂状物質について、IRスペクトルから1000~1200cm-1にデキストリン由来、1742cm-1にエステル由来、2800~3000cm-1にアルキル由来のピークを確認でき、また、アルカリ分解後の脂肪酸量とガスクロマトグラフィーから、置換度2.2、イソステアリン酸60mol%、その他の脂肪酸40mol%(内パルミチン酸10mol%)であることが確認できる。
なお、部分架橋型のポリマーとは、クロスリンクしたポリマーを意味する。
本発明の実施形態では、成分(D)として、特に、部分架橋型ポリグリセリン変性シリコーン、及び/又は、部分架橋型シリコーン・アルキル・ポリグリセリン共変性シリコーンと、部分架橋型メチルポリシロキサン、及び/又は、部分架橋型メチルフェニルポリシロキサン、及び/又は、部分架橋型シリコーン・アルキル共変性シリコーンとの組み合わせが好ましく、具体的には、KSG-710、KSG-820Z、KSG-850Zと、KSG-15、KSG-1510、KSG-16、KSG-1610、KSG-18A、KSG-19、KSG-016F、KSG-042Z、KSG-045Z、KSG-048Zとの組み合わせが好ましい。
本発明の実施形態では、成分(D)として、特に、部分架橋型ポリグリセリン変性シリコーン、及び/又は、部分架橋型シリコーン・アルキル・ポリグリセリン共変性シリコーンと、部分架橋型ポリエーテル変性シリコーン、及び/又は、部分架橋型シリコーン・アルキル・ポリエーテル共変性シリコーンとの組み合わせが好ましく、具体的には、KSG-710、KSG-820Z、KSG-850Zと、KSG-210、KSG-240、KSG-320Z、KSG-350Z、KSG-360Z、KSG-380Zとの組み合わせが好ましい。
実施例1~20および比較例1~5:油中水乳化型ファンデーション(液状)
下記表1に示す処方の油中水乳化型ファンデーションを調製し、耐水性、二次付着防止効果、伸び広がりの軽さ、負担感のなさ、保湿感の持続を下記の方法により評価した。その結果も併せて表1に示す。
*2:トリイソステアリン酸イソプロピルチタン3%、ハイドロゲンジメチコン5%処理
*3:SILFROM FLEXIBLE RESIN(モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製)
*4:ニッセツ U-3700A(日本カーバイド工業社製)
*5:シリコン KSG-710(固形分25%、溶媒:ジメチコン、信越化学工業社製)
*6:シリコン KSG-16(固形分25%、溶媒:ジメチコン、信越化学工業社製)
*7:サンスフェア NP-100(AGCエスアイテック社製)
*8:ヨドゾール GH41F(アクゾノーベル社製)
*9:ニューポール PP-200(三洋化成工業社製)
*30:下記のとおり調製した。
還流冷却器、温度計、窒素導入管及び攪拌装置を取り付けた四つ口のセパラブルフラスコにシクロヘキシルメタクリレート22.5g、2-エチルヘキシルメタクリレート7.5g及びトルエン70gを添加し、窒素ガスを導入して充分に窒素雰囲気にした後、100℃まで加温し、AIBN0.15gを添加して3時間還流し重合させた。得られた反応物にメタノールを注入してアクリル系共重合体を沈殿析出させ、沈殿物を濾別後、真空乾燥してシクロアルキル基含有アクリル系共重合体固形分27.4gを得た。ポリスチレン換算による重量平均分子量は5.0×104であった。
*31:エステルガムHP(荒川化学工業社製)
A.成分(1)~(9)を均一に分散する。
B.成分(10)~(16)、(32)~(36)を加温して均一に溶解した後、Aに加えて均一に混合する。
C.Bに成分(17)~(24)を加え均一に混合する。
D.成分(25)~(31)を均一に混合する。
E.CにDを徐々に添加し、分散乳化する。
F:Eを脱泡し、容器に充填する。
下記イ~ホの評価項目について、各々下記方法により評価を行った。
(評価項目)
イ.耐水性
ロ.二次付着防止効果
専門パネル20名に試料を塗布してもらい、3時間経過した後に、評価項目イについては水で濡らしたコットンを肌に10秒間押し当て、剥がした後のコットンへの色の移り具合を評価し、評価項目ロについてはティッシュで軽く押さえた後のティッシュへの色の移り具合を評価した。パネル各人が下記絶対評価にて5段階に評価し、各試料ごとに平均値を算出し、下記判定基準により判定した。
<絶対評価基準>
(評点):(評価)
4 :非常に良い
3 :良い
2 :普通
1 :悪い
0 :非常に悪い
<判定基準>
(判定):(評点の平均点)
◎ :3.5点を超える :非常に良好
○ :2.5点を超える3.5点以下:良好
△ :1点を超える2.5点以下 :やや不良
× :1点以下 :不良
ハ.伸び広がりの軽さ
ニ.負担感のなさ
ホ.保湿感の持続
専門パネル20名に試料を塗布してもらい、ハについては使用時、ニについては塗布直後に肌がつっぱるような負担感を感じるかどうか、ホについては塗布後に通常の生活をしてもらい6時間後の保湿感について、下記絶対評価基準にて7段階に評価し評点を付け、各試料のパネル全員の評点合計から、その平均値を算出し、下記判定基準により判定した。
<絶対評価基準>
(評点):(評価)
6 :非常に良い
5 :良い
4 :やや良い
3 :普通
2 :やや悪い
1 :悪い
0 :非常に悪い
<判定基準>
(判定):(評点の平均点)
◎ :5点を超える :非常に良好
○ :3.5点を超える5点以下:良好
△ :1点を超える3.5点以下:やや不良
× :1点以下 :不良
これに対して、成分(A)が含有されていない比較例1では、化粧膜の強度が弱いために崩れやすく、さらに経時での肌の水分蒸散を抑制することができないため、耐水性、二次付着防止効果、保湿感の持続の点で満足のいくものが得られなかった。
成分(A)の代わりに水を分散媒とするアクリル酸アルキル・スチレン共重合体ディスパージョンを用いた比較例2では、化粧膜が水と馴染みやすいため耐水性に劣り、塗膜の柔軟性に欠けるため肌の動きに追従できず、さらに経時での肌の水分蒸散を抑制することができないため、耐水性、負担感のなさ、保湿感の持続の点で満足のいくものが得られなかった。
成分(B)が含有されていない比較例3では、成分(A)が融着して形成される塗膜の結合点が弱いために皮脂と馴染みやすく、二次付着防止効果に劣るものであった。
成分(C)が含有されていない比較例4では、成分(A)および(B)による伸び広がりの重さを感じやすく、さらに経時での肌の水分蒸散を抑制することができないため、伸び広がりの軽さ、保湿感の持続の点で十分でなかった。
成分(D)が含有されていない比較例5では、油溶性樹脂による化粧膜の硬さを感じやすく、負担感のなさの点で満足のいくものが得られなかった。
成分(B)として、硬質な樹脂であるトリメチルシロキシケイ酸を用いた実施例14では、、耐水性、二次付着防止効果、伸び広がりの軽さ、負担感のなさ、保湿感の持続の全てにおいて優れるだけでなく、肌にハリ感を付与する効果に優れたものであった。
成分(B)として、柔軟性に富む(アクリレーツ/ジメチコン)コポリマーを用いた実施例15では、耐水性、二次付着防止効果、伸び広がりの軽さ、負担感のなさ、保湿感の持続の全てにおいて優れるだけでなく、目周りや口周りといった表情に伴う動作が大きい部位における化粧膜のよれを防止する効果に優れたものであった。
成分(B)として、ツヤに富むイソステアリン酸デキストリンを用いた実施例16では、耐水性、二次付着防止効果、伸び広がりの軽さ、負担感のなさ、保湿感の持続の全てにおいて優れるだけでなく、化粧膜のツヤに優れたものであった。
成分(B)として、成膜が速い樹脂であるメタクリロヘキシル/メタクリル酸エチルヘキシルコポリマーンを用いた実施例17、18では、耐水性、二次付着防止効果、伸び広がりの軽さ、負担感のなさ、保湿感の持続の全てにおいて優れるだけでなく、塗りむらがなく均一な化粧膜が生成する点において優れた
ものであった。
成分(B)として、水添ロジン酸ペンタエリスリチルを用いた実施例19でも耐水性、二次付着防止効果、伸び広がりの軽さ、負担感のなさ、保湿感の持続の全てにおいて効果が得られることがわかった。
(成分) (%)
(1)ジメチルポリシロキサン3%処理酸化チタン 1.5
(2)ジメチルポリシロキサン2%処理黄酸化鉄 0.1
(3)ジメチルポリシロキサン2%処理グンジョウ 0.1
(4)ジメチルポリシロキサン3%酸化亜鉛 10.0
(5)ジメチルポリシロキサン3%処理タルク 1.0
(6)ジメチルポリシロキサン2%処理雲母チタン 2.0
(7)PEG-9ジメチコン *10 2.0
(8)デカメチルシクロペンタシロキサン 15.0
(9)パラメトキシケイ皮酸2-エチルへキシル 8.0
(10)2-(4-ジエチルアミノ-2-ヒドロキシベンゾイル)
安息香酸へキシルエステル 1.0
(11)アクリル酸アルキル・スチレン共重合体ディスパージョン *4 0.5
(12)(アクリレーツ/ジメチコン)コポリマー *11 1.0
(13)(ジメチコン/(PEG-10/15))クロスポリマー *12 4.0
(14)セスキイソステアリン酸ソルビタン 0.3
(15)イソノナン酸イソトリデシル 2.0
(16)トリ(カプリル・カプリン酸)グリセリル 3.0
(17)ジメチコン 3.0
(18)ラベンダー油 0.1
(19)球状シリカ(中空、平均粒子径18μm) *13 0.3
(20)窒化ホウ素 3.0
(21)メタクリル酸メチルクロスポリマー・ポリイソプレン複合粉体 *14 1.0
(22)精製水 残量
(23)トリプロピレングリコール 15.0
(24)プロピレングリコール 10.0
(25)グリセリン 5.0
(26)エチルアルコール 5.0
(27)水溶性コラーゲン 0.5
*10:KF-6019(信越化学工業社製)
*11:シリコン KP-545(固形分30%、信越化学工業社製)
*12:シリコン KSG-210(固形分25%、信越化学工業社製)
*13:SILICA MICRO BEAD BA-1(日揮触媒化成社製)
*14:ガンツパ-ルGMI-0804(ガンツ化成社製)
A.成分(1)~(8)を均一に分散する。
B.成分(9)~(10)を加温して均一に溶解した後、Aに加えて均一に混合する。
C.Bに成分(11)~(21)を加え均一に混合する。
D.成分(22)~(27)を均一に混合する。
E.CにDを徐々に添加し、分散乳化する。
F:Eを脱泡し、容器に充填する。
(成分) (%)
(1)デカメチルシクロペンタシロキサン 10.0
(2)PEG-3ジメチコン *15 4.0
(3)酸化亜鉛 *2 15.0
(4)パラメトキシケイ皮酸2-エチルへキシル 3.0
(5)4-tert-ブチル-4’-メトキシ-ジベンゾイルメタン 1.0
(6)ポリシリコーン-15 3.0
(7)水添ポリイソブテン *16 5.0
(8)トリメチルシロキシケイ酸 *17 8.0
(9)ジエチルヘキサン酸ネオペンチルグリコール 1.0
(10)2-エチルヘキサン酸セチル 1.0
(11)ジカプリン酸プロピレングリコール 1.0
(12)2-デシルテトラデカノール 8.0
(13)アクリル酸アルキル・スチレン共重合体ディスパージョン *4 16.0
(14)(ジメチコン/フェニルビニルジメチコン)クロスポリマー *18 0.3
(15)球状シリカ(平均粒子径3~5μm)*19 5.0
(16)メタクリル酸メチルクロスポリマー(平均粒子径15μm) 1.0
(17)精製水 残量
(18)塩化ナトリウム 0.2
(19)トリプロピレングリコール 1.0
(20)1,3-ブチレングリコール 0.5
(21)グルコシルトレハロース 2.0
(22)ポリビニルピロリドン 0.5
(23)エタノール 5.0
(24)メチルパラベン 0.1
*15:シリコン KF-6015(信越化学工業社製)
*16:IPソルベント 2028 MU(出光石油化学社製)
*17:シリコン KF-7312J(固形分50%、溶媒:シクロペンタシロキサン、信越化学工業社製)
*18:KSG-18(固形分15%、溶媒:ジフェニルシロキシフェニルトリメチコン、信越化学工業社製)
*19:サンスフェア NP-30(AGCエスアイテック社製)
A.成分(1)~(3)を均一に分散する。
B.成分(4)~(8)を加温して均一に溶解した後、Aに加えて均一に混合する。
C.Bに成分(9)~(16)を加え均一に混合する。
D.成分(17)~(24)を均一に混合する。
E.CにDを徐々に添加し、分散乳化する。
F:Eを脱泡し、容器に充填する。
(成分) (%)
(1)トリエトキシカプリリルシラン3%処理酸化チタン 3.0
(2)トリエトキシカプリリルシラン3%処理赤226 0.5
(3)トリエトキシカプリリルシラン3%処理黄4 0.2
(4)トリエトキシカプリリルシラン3%処理黒酸化鉄 0.1
(5)メチルトリメチコン 5.0
(6)イソドデカン 10.0
(7)トリメチルシロキシケイ酸 *20 7.5
(8)イソステアリン酸デキストリン *21 0.5
(9)アクリル酸アルキル・スチレン共重合体ディスパージョン *22 8.0
(10)ラウリルPEG-9ポリジメチルシロキシエチルジメチコン 1.5
(11)PEG/PPG-10/3オレイルエーテルジメチコン *23 1.0
(12)(ジメチコン/ポリグリセリン-3)クロスポリマー *5 3.0
(13)トリ2-エチルヘキサン酸グリセリル 2.0
(14)リンゴ酸ジイソステアリル 0.5
(15)パルミチン酸デキストリン *24 5.0
(16)スクワラン 1.0
(17)雲母チタン 10.0
(18)酸化チタン被覆ガラス末 *25 3.0
(19)有機変性ベントナイト *26 3.0
(20)マイカ 2.0
(21)球状シリカ *7 10.0
(22)精製水 残量
(23)トリプロプレングリコール 5.0
(24)エタノール 3.0
(25)パラオキシ安息香酸メチル 0.1
(26)香料 0.2
*20:SR-1000(モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製)
*21:ユニフィルマHVY(千葉製粉社製)
*22:*4と同じアクリル酸アルキル・スチレン共重合体の固形分50%、分散媒:イソドデカンとしたディスパージョン。下記のとおり調製した。
(メタ)アクリレートモノマーとスチレンと重合開始剤とを、分散媒のイソドデカンに添加し撹拌して重合を行った。重合溶液を濾過し、濾物について減圧下でモノマーを除去して、分散媒がイソドデカンのディスパージョンを得た。
*23:シリコンKF-6026((信越化学工業社製))
*24:レオパール TL-2(千葉製粉社製)
*25:メタシャイン1080RC-R(日本板硝子社製)、パーフルオロオクチルトリエトキシシラン3%処理
*26:BENTONE 27V(ELEMENTIS社製)
A.成分(1)~(5)を均一に分散する。
B.成分(6)~(8)を均一に溶解した後、Aに加えて均一に混合する。
C.Bに成分(9)~(21)を加え均一に混合する。
D.成分(22)~(26)を均一に混合する。
E.CにDを徐々に添加し、分散乳化する。
F:Eを脱泡し、容器に充填する。
(成分) (%)
(1)酸化亜鉛 *2 10.0
(2)ジメチルシリル化シリカ 5.0
(3)ポリヒドロキシステアリン酸 1.0
(4)パラメトキシケイ皮酸2-エチルへキシル 10.0
(5)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 2.0
(6)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 1.0
(7)ポリシリコーン-15 3.0
(8)PEG-9ポリジメチルシロキシエチルジメチコン 0.5
(9)デカメチルシクロペンタシロキサン 5.0
(10)ジメチコン 3.0
(11)ジカプリン酸プロピレングリコール 20.0
(12)(ジメチコン/(PEG-10/15))クロスポリマー *27 1.0
(13)(ビニルジメチコン/ラウリルジメチコン)クロスポリマー *28 2.0
(14)アクリル酸アルキル・スチレン共重合体ディスパージョン *4 10.0
(15)(アクリレーツ/ジメチコン)コポリマー *11 8.0
(16)精製水 残量
(17)エデト酸二ナトリウム 0.05
(18)1,2-ヘキサンジオール 0.5
(19)カプリリルグリコール 2.0
(20)エタノール 13.0
(21)メチルパラベン 0.1
*27:KSG-210(固形分25%、溶媒:ジメチコン、信越化学工業社製)
*28:KSG-43(固形分30%、溶媒:トリ2-エチルヘキサン酸グリセリル、信越化学工業社製)
A.成分(1)~(3)を均一に分散する。
B.成分(4)~(11)を加温して均一に溶解した後、Aに加えて均一に混合する。
C.Bに成分(12)~(15)を加え均一に混合する。
D.成分(16)~(21)を均一に混合する。
E.CにDを徐々に添加し、分散乳化する。
F:Eを脱泡し、容器に充填する。
(成分) (%)
(1)デカメチルシクロペンタシロキサン 20.0
(2)酸化亜鉛 *2 15.0
(3)ジメチルシリル化シリカ 3.0
(4)PEG-9ポリジメチルシロキシエチルジメチコン 1.0
(5)トリエチルヘキサノイン 10.0
(6)2-エチルヘキサン酸セチル 5.0
(7)パラメトキシケイ皮酸2-エチルへキシル 5.0
(8)4-tert-ブチル-4’-メトキシ-ジベンゾイルメタン 1.0
(9)ポリシリコーン-15 3.0
(10)ジエチルヘキサン酸ネオペンチルグリコール 3.0
(11)ジカプリン酸プロピレングリコール 3.0
(12)アクリル酸アルキル・スチレン共重合体ディスパージョン *4 1.5
(13)ジプロピレングリコール 1.0
(14)ポリメチルシルセスキオキサン*3 5.0
(15)球状シリカ(平均粒子径3~5μm)*19 5.0
(16)精製水 残量
(17)塩化ナトリウム 0.2
(18)ポリエチレン 10.0
(19)マイクロクリスタリンワックス 2.0
A.成分(1)~(6)を均一に分散する。
B.成分(7)~(13)を均一に溶解した後、Aに加えて均一に混合する。
C.Bに成分(14)、(15)を加え均一に混合する。
D.成分(16)、(17)を均一に混合する。
E.CにDを徐々に添加し、分散乳化する。
F:Eに(18)、(19)を加え、100℃まで加熱し混合溶解したのち、容器に充填する。
(成分) (%)
(原液)
(1)パラメトキシケイ皮酸2-エチルへキシル 8.0
(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 0.5
(3)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 2.0
(4)ジカプリン酸プロピレングリコール 30.0
(5)安息香酸アルキル 1.0
(6)イソドデカン 5.0
(7)アクリル酸アルキル・スチレン共重合体ディスパージョン *22 5.0
(8)(ビニルジメチコン/メチコンシルセスキオキサン)クロスポリマー *29 3.0
(9)(ジメチコン/フェニルビニルジメチコン)クロスポリマー *18 1.0
(10)ポリメチルシルセスキオキサン *3 2.0
(11)球状シリカ *32 0.5
(12)精製水 5.0
(13)1,2-ヘキサンジオール 0.5
(14)カプリリルグリコール 0.5
(15)エタノール 残量
(噴射剤)
(16)LPG 100.0
*29:KSP-100(信越化学工業社製)
*32:ゴッドボール E-90C(鈴木油脂工業社製)
A.成分(1)~(5)を均一に分散する。
B.成分(6)~(11)を均一に溶解した後、Aに加えて均一に混合する。
C.成分(12)~(15)を均一に混合する。
D.BにCを徐々に添加し、分散乳化する。
E:(原液):(噴射剤)=30:70となるよう容器に充填する。
Claims (4)
- 次の成分(A)~(D);
(A)揮発性炭化水素油を分散媒とするアクリル酸アルキル・スチレン共重合体ディスパージョン
(B)油溶性樹脂
(C)多価アルコール
(D)部分架橋型オルガノポリシロキサン
を含有する油中水型乳化化粧料。 - 前記成分(C)がトリプロピレングリコールを含有する請求項1に記載の油中水型乳化化粧料。
- さらに、成分(E)球状シリカを含有する請求項1又は2に記載の油中水型乳化化粧料。
- 前記成分(B)がトリメチルシロキシケイ酸、ポリメチルシルセスキオキサン、(アクリレーツ/ジメチコン)コポリマー、イソステアリン酸デキストリン、及びアクリル系共重合体から選ばれる1種又は2種以上である請求項1~3のいずれか一項に記載の油中水型乳化化粧料。
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CN201780010393.6A CN108601722B (zh) | 2016-02-15 | 2017-02-14 | 油包水型乳化化妆品 |
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KR (1) | KR102596805B1 (ja) |
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WO2019111831A1 (ja) * | 2017-12-04 | 2019-06-13 | 花王株式会社 | 油中水型乳化化粧料 |
JP2020090449A (ja) * | 2018-12-04 | 2020-06-11 | 株式会社コーセー | エアゾール型化粧料 |
EP3597691A4 (en) * | 2018-04-27 | 2021-01-06 | Kokyu Alcohol Kogyo Co., Ltd. | NEW COMPOSITION AND EMULSIFIED COMPOSITION |
JP2021050149A (ja) * | 2019-09-24 | 2021-04-01 | 株式会社マンダム | エアゾール組成物 |
JP2021066677A (ja) * | 2019-10-18 | 2021-04-30 | 日油株式会社 | 油中水型乳化化粧料 |
WO2024091603A1 (en) * | 2022-10-28 | 2024-05-02 | L'oréal | Cosmetic water in oil composition comprising polyvinylpyrrolidone as thickener |
US12005137B2 (en) | 2022-10-28 | 2024-06-11 | L'oreal | Cosmetic composition |
Families Citing this family (1)
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JP2023525939A (ja) * | 2020-06-29 | 2023-06-19 | ロレアル | トリイソステアリン酸イソプロピルチタンで被覆された顔料を含む組成物 |
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- 2017-02-14 WO PCT/JP2017/005373 patent/WO2017141919A1/ja active Application Filing
- 2017-02-14 CN CN201780010393.6A patent/CN108601722B/zh active Active
- 2017-02-14 JP JP2018500129A patent/JP6869942B2/ja active Active
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JP7272783B2 (ja) | 2017-12-04 | 2023-05-12 | 花王株式会社 | 油中水型乳化化粧料 |
JP2019099576A (ja) * | 2017-12-04 | 2019-06-24 | 花王株式会社 | 油中水型乳化化粧料 |
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WO2019111831A1 (ja) * | 2017-12-04 | 2019-06-13 | 花王株式会社 | 油中水型乳化化粧料 |
EP3597691A4 (en) * | 2018-04-27 | 2021-01-06 | Kokyu Alcohol Kogyo Co., Ltd. | NEW COMPOSITION AND EMULSIFIED COMPOSITION |
JP2020090449A (ja) * | 2018-12-04 | 2020-06-11 | 株式会社コーセー | エアゾール型化粧料 |
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JP2021066677A (ja) * | 2019-10-18 | 2021-04-30 | 日油株式会社 | 油中水型乳化化粧料 |
JP7251443B2 (ja) | 2019-10-18 | 2023-04-04 | 日油株式会社 | 油中水型乳化化粧料 |
WO2024091603A1 (en) * | 2022-10-28 | 2024-05-02 | L'oréal | Cosmetic water in oil composition comprising polyvinylpyrrolidone as thickener |
US12005137B2 (en) | 2022-10-28 | 2024-06-11 | L'oreal | Cosmetic composition |
Also Published As
Publication number | Publication date |
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CN108601722B (zh) | 2021-06-11 |
JPWO2017141919A1 (ja) | 2018-12-06 |
KR102596805B1 (ko) | 2023-11-01 |
HK1255381A1 (zh) | 2019-08-16 |
TW201739441A (zh) | 2017-11-16 |
JP6869942B2 (ja) | 2021-05-12 |
CN108601722A (zh) | 2018-09-28 |
KR20180108640A (ko) | 2018-10-04 |
TWI698257B (zh) | 2020-07-11 |
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