WO2020100573A1 - 油中水型組成物 - Google Patents
油中水型組成物 Download PDFInfo
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- WO2020100573A1 WO2020100573A1 PCT/JP2019/042348 JP2019042348W WO2020100573A1 WO 2020100573 A1 WO2020100573 A1 WO 2020100573A1 JP 2019042348 W JP2019042348 W JP 2019042348W WO 2020100573 A1 WO2020100573 A1 WO 2020100573A1
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- water
- component
- oil
- mass
- oil composition
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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
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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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
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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
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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
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
Definitions
- the present invention relates to a water-in-oil type composition, and more particularly to a water-in-oil type composition having excellent coating film uniformity, water resistance, stability over time, and usability.
- Patent Document 1 is a high internal phase water-in-oil sunscreen cosmetic having a water phase ratio of 50% by mass or more, wherein (A) a cross-linked polyglycerin / alkyl co-modified silicone is 0.1 to 10% by mass, and (B) A sunscreen cosmetic containing an ultraviolet absorber is disclosed.
- Patent Document 2 discloses (a) hydrophobized zinc oxide and hydrophobized titanium oxide: 10 to 30% by mass, (b) lipophilic nonionic surfactant: 0.5 to 5% by mass, (c) N- Lauroyl L-glutamine di (phytosteryl, 2-octyldodecyl), macadamia nut fatty acid phytosteryl, macadamia nut fatty acid cholesteryl, 1 or 2 or more kinds of oil content: 1 to 5% by mass, (d) volatile silicone oil Disclosed is a water-in-oil type emulsion sunscreen cosmetic characterized by containing 10 to 40% by mass of a hydrocarbon oil and (e) water: 5 to 30% by mass.
- Patent Document 1 is a cross-linking agent for skin external preparations and cosmetics having an ultraviolet protection effect, since the water-in-oil type composition is difficult to adapt to water because the outer phase is oil, and thus has high water resistance. Since it is essential to contain a specific amount of the type polyglycerin / alkyl co-modified silicone, when the coating film comes into contact with water, emulsification occurs, so that the coating film has low water resistance. As a result, metal oxides and the like may be stripped off, and the ultraviolet protection effect may be inferior.
- Patent Document 2 requires a specific amount of a surfactant, and as a result, the stickiness is strong and the usability may be deteriorated. Further, when the coating film and water come into contact with each other, emulsification occurs, which may reduce the water resistance.
- the present inventor has employed a Pickering emulsion in which metal oxide powder such as zinc oxide or titanium oxide is stably contained to emulsify the powder (for example, Patent Documents 3 to 5 and Non-Patent Documents). 1)) to develop a water-in-oil type composition having improved water resistance.
- the technique of patent document 3 has 1) an oil phase 2) an aqueous phase and 3) a) an average particle size of less than 200 nm, which particles b) have both hydrophilic and lipophilic properties and thus an amphiphile.
- One or more finely divided inorganic pigments which have a characteristic of character and are aligned along the water / oil interface and which are selected from the group of c) metal oxides and d) optionally surface coatings.
- Patent Document 4 is (a) 1 to 40% by mass of a powder component which is not dispersed in water, (b) 0.001 to 1% by mass of a hydrophilic surfactant, (c) an oil phase component, and (d) Disclosed is a water-in-oil type emulsion composition characterized by containing an aqueous phase component.
- Patent Document 5 includes a) a continuous phase that is an oily phase, a) a water-in-oil emulsion in the form of a dispersed phase which is b) an aqueous phase, and c) particles having a number average particle size of 200 nm or more and 1 ⁇ m or less and which has been surface-treated with at least one N-acylated glutamate.
- a cosmetic composition Said N-acylated glutamate is ionically bound to said particles with a hydroxide of a metal selected from Mg, Al, Ca, Zn, Said particles are present at the interface between said continuous phase and said dispersed phase and comprise at most 1% by weight of at least one emulsifier, relative to the total weight of said composition, A cosmetic composition is disclosed.
- Patent Documents 3 to 5 Even if the techniques of Patent Documents 3 to 5 are used, there are still cases where not only the stickiness is strong and the usability is poor due to the oily feeling of use, but also the uniformity and water resistance of the coating film are poor. Further, depending on the type of oil agent contained, the stability over time may be inferior. That is, a water-in-oil type composition which has excellent uniformity of coating film, water resistance, stability over time, and good usability without stickiness has not been known so far.
- the present inventor paid attention to powder, and further diligently studied to obtain a water-in-oil type composition that solves the above-mentioned problems by using zinc oxide surface-treated with silica and a hydrophobizing agent.
- the following water-in-oil type compositions were found to have excellent coating film uniformity and water resistance, good stability over time, and excellent usability.
- the present invention provides a water-in-oil composition, wherein the water-in-oil composition is a Pickering emulsion.
- the present invention provides a water-in-oil composition in which the content of the component (B) is 5 to 30% by mass.
- the present invention provides a water-in-oil type composition in which the content mass ratio (B) / (C) of the component (B) and the component (C) is 0.1 to 8.
- the present invention provides a water-in-oil composition in which the average particle size of emulsion droplets of the water-in-oil composition is 10 to 500 ⁇ m.
- a water-in-oil composition containing a liquid polar oil at 25 ° C. and a solid polar oil at 25 ° C. as the component (B) is provided.
- the present invention provides a water-in-oil composition in which the content ratio (water phase) / (oil phase) of the water phase and the oil phase is 0.3 to 5.
- the present invention provides a water-in-oil type composition in which the content ratio (water phase) / (A) of the water phase and the component (A) is 0.75 to 10.
- 1. Weigh 1 g, and immediately after weighing, mix with a shaker YS-8D (manufactured by Yayoi Co., Ltd.) under the conditions of 250 times / minute for 30 seconds, and then, in a plastic cell having an optical path length of 10 mm and an optical path width of 10 mm.
- 5 g is a photograph of the appearance of the solution 3 minutes after mixing, and the samples are the components (1), (2), (3), (4), and (5) in order from the left. ) Solution.
- 1. Weigh 1 g, and immediately after weighing, mix
- MZY-500SHE manufactured by Teika
- Teika which is the component (1) in Tables 1 to 4
- FINEX-52W-LP2 manufactured by Sakai Chemical Industry
- MZ which is the component (4).
- -500 is an image obtained by observing each with a transmission electron microscope (H-7650, manufactured by Hitachi High Technologies) (measurement condition: accelerating voltage 80 KV).
- the transmittance of light having a wavelength of 700 nm (hereinafter, may be simply referred to as “transmittance”) when mixed in is 0.8 to 20.
- the zinc oxide in the component (A) of the present invention is a powder capable of blocking ultraviolet rays by absorbing, scattering, reflecting, extinguishing ultraviolet rays, etc., and the particle diameter and shape are not particularly limited.
- the average particle diameter of the zinc oxide of the component (A) of the present invention is not particularly limited, but one having an average particle diameter of 1 to 200 nm is preferable from the viewpoint of ease of handling when blended in a cosmetic product and stability over time. It is preferably 10 to 100 nm, and more preferably 10 to 100 nm.
- the method for measuring the average particle size of zinc oxide as the component (A) of the present invention is calculated from the result of measuring the particle size of 100 particles in an arbitrary visual field using a scanning electron microscope.
- the shape of the zinc oxide of the component (A) of the present invention is not particularly limited, but from the viewpoint of stability over time and usability, an amorphous shape is preferable and the aspect ratio (major axis diameter / minor axis diameter) is 1.2. More preferably, it is from 1.6 to 1.6.
- the silica in the component (A) of the present invention is not particularly limited, and those normally used for cosmetics and external preparations for skin can be used.
- a hydrophilizing agent such as polyethylene glycol or a hydrophilic surfactant
- the hydrophilicity thereof is insufficient, so that the oil-water of the component (A) is used. It may be inferior in selective orientation to the interface and may not be excellent in stability over time.
- hydrophobizing agent in the component (A) of the present invention those used in known surface treatment methods can be used.
- the surface treatment may be carried out by a method such as soap treatment or metal oxide powder treatment, and the surface treatment may be carried out with one kind or two or more kinds thereof.
- hydrophobizing agents selected from silicone treatment, silane coupling agent treatment, titanium coupling agent treatment, and fatty acid treatment from the viewpoint of the orientation and dispersibility of component (A) at the oil / water interface, and stability over time.
- silicone treatment silane coupling agent treatment, titanium coupling agent treatment, and fatty acid treatment from the viewpoint of the orientation and dispersibility of component (A) at the oil / water interface, and stability over time.
- silicone treatment silane coupling agent treatment
- titanium coupling agent treatment titanium coupling agent treatment
- fatty acid treatment from the viewpoint of the orientation and dispersibility of component (A) at the oil / water interface, and stability over time.
- silicone treatment silane coupling agent treatment
- titanium coupling agent treatment titanium coupling agent treatment
- fatty acid treatment from the viewpoint of the orientation and dispersibility of component (A) at the oil / water interface, and stability over time.
- silicone treatment silane coupling agent treatment
- titanium coupling agent treatment titanium coupling agent treatment
- fatty acid treatment from the viewpoint of the orientation and dis
- the transmittance of light having a wavelength of 700 nm when mixed at 0.25 mass% in a water / ethanol solvent can be measured as follows.
- 0.1 g of the component (A) was weighed so as to be 0.25% by mass with respect to 40 g, and immediately after the weighing, a shaker YS was used.
- -8D manufactured by Yayoi
- the powder surface to be dispersed in the solvent has a high hydrophilicity, the powder surface has high wettability, so that the powder does not move to the gas-liquid interface and the transmittance is low.
- the transmittance of light with a wavelength of 700 nm when mixed at 0.25 mass% in water / ethanol solvent is the hydrophilicity of the powder surface dispersed in the solvent. It is considered to be correlated with hydrophobicity.
- the transmittance is preferably 1 to 18, more preferably 1 to 16, and more preferably 3 to 12 from the viewpoint of stability over time. Even more preferable.
- a method for adjusting the transmittance of light having a wavelength of 700 nm when the component (A) of the present invention is mixed in water / ethanol solvent (mass ratio water: ethanol 3: 1) at 0.25 mass%.
- a known surface treatment method for example, by appropriately changing the surface treatment amount of silica or a hydrophobizing agent, or by appropriately changing the particle size of silica or the like.
- the transmittance tends to increase by increasing the surface treatment amount of silica, and the transmittance tends to decrease by increasing the surface treatment amount of the hydrophobizing agent.
- the amounts of the silica and the hydrophobizing agent in the component (A) of the present invention are not particularly limited. From the viewpoint of stability over time, the amount of silica treated is preferably 0.5 to 10% by mass, and more preferably 1 to 4% by mass, based on the mass of zinc oxide as the component (A). From the viewpoint of stability over time, the treatment amount of the hydrophobizing agent is preferably 0.5 to 20% by mass, and more preferably 1 to 10% by mass, based on the mass of the zinc oxide as the component (A).
- examples of commercially available products of component (A) include MZY-500SHE (manufactured by Teika).
- FIG. 2 shows MZY-500SHE (manufactured by Teika) which is the component (1) in Tables 1 to 3, FINEX-52W-LP2 (manufactured by Sakai Chemical Industry) which is the component (2), and MZ which is the component (4).
- -500 manufactured by Teika
- H-7650 transmission electron microscope
- accelerating voltage 80 KV accelerating voltage 80 KV
- the component (2) has a characteristic that the contour of the particle and the contrast of the entire particle are clear, and that it is composed only of zinc oxide.
- the contour of the particle is slightly unclear, but the contrast of the entire particle is clear, and silica having a relatively low electron density compared to zinc oxide covers the zinc oxide surface unevenly. It is considered that the difference in these surface states can be recognized.
- the content of the component (A) is 5 to 30 mass% with respect to the total amount of the water-in-oil composition. If the content of the component (A) is less than 5% by mass, water resistance and stability over time may be poor, and if it exceeds 30% by mass, usability may be poor.
- the content of the component (A) is not particularly limited as long as it is 5 to 30% by mass, but from the viewpoint of water resistance and stability over time, 8 to 30% by mass is preferable, and 10 to 25% by mass is particularly preferable.
- the component (B) polar oil in the present invention is a polar oil, and those normally used for cosmetics and external skin preparations can be used.
- the component (B) polar oil is not particularly limited, and examples thereof include glyceryl tri (caprylic / capric acid), glyceryl tri-2-ethylhexanoate, glyceryl triisostearate, diglyceryl triisostearate, glyceryl triisopalmitate, Glyceryl tricaprylate, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, pentaerythritol rosinate, neo dioctanoate Pentyl glycol, cholesterol fatty acid ester, N-lauroyl-L-glutamic acid di (cholesteryl behenyl octyldodecyl
- Is p-aminobenzoic acid ethyl p-aminobenzoate, glyceryl p-aminobenzoate, amyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, ethyl p-dihydroxypropylbenzoate, 2 Examples include hexyl benzoate and the like- ⁇ 4- (diethylamino) -2-hydroxybenzoyl ⁇ cinnamic acid-based compounds include 2-ethylhexyl p-methoxycinnamate and 2-ethoxyethyl 4-methoxycinnamate.
- salicylic acid-based compounds examples include 2-ethylhexyl salicylate, phenyl salicylate, and homomenthyl salicylate
- dibenzoylmethane-based compounds examples include 4-tert-4′-methoxydibenzoylmethane, and 2-2′-methylene.
- liquid polar oil at 25 ° C. as the component (B), and as the liquid polar oil at 25 ° C., tri (capryl-capric acid) is preferable.
- Triglycerides such as glyceryl, glyceryl tri-2-ethylhexanoate, glyceryl triisostearate, glyceryl triisopalmitate and glyceryl tricaprylate, 2-ethylhexyl p-methoxycinnamate, isopropyl myristate, alkyl benzoate (C12-) 15), preferably one or more selected from diisopropyl adipate, diisopropyl sebacate, and isononyl isononanoate.
- Triglycerides such as glyceryl, glyceryl tri-2-ethylhexanoate, glyceryl triisostearate, glyceryl triisopalmitate and glyceryl tricaprylate, 2-ethylhexyl p-methoxycinnamate, isopropyl myristate, alkyl benzoate (C12-
- the liquid in the present invention has fluidity at normal temperature (25 ° C.) and normal pressure.
- the solid polar oil at 25 ° C. may be hexyl 2- ⁇ 4- (diethylamino) -2-hydroxybenzoyl ⁇ benzoate.
- component (B) polar oil examples include, for example, M Fine Oil CCT-1 (manufactured by Miyoshi Oil & Fats Co., Ltd.), TI (manufactured by Nisshin OilliO Group), TISG (manufactured by High Alcohol Industry Co., Ltd.), and ISO.
- Esteride G-NP National Mimatsu
- Ubinar MC 80 Ubinar MC 80N (BASF Japan)
- IPM Nippon Seika
- FINSOLV TN Innospec Active Chemicals LLC
- Sarakos 99 manufactured by Nisshin Oillio Group, Inc.
- the content of the component (B) polar oil used in the present invention is not particularly limited, but is 5 to 30% by mass with respect to the total amount of the water-in-oil composition in terms of uniform coating film and excellent usability. It is preferable that the amount is 10 to 25% by mass.
- the fluidity of the oil phase at the time of coating film formation at the time of coating becomes suitable, and the water resistance is further improved. It is preferable because the coating film has good properties.
- the mass ratio of the liquid polar oil at 25 ° C. and the solid polar oil at 25 ° C. is preferably 1 to 250, more preferably 2.5 to 150, and particularly preferably 3 to 15.
- component (C) silicone oil of the present invention those normally used for cosmetics and external preparations for skin can be used.
- the component (C) silicone oil of the present invention is not particularly limited, but is preferably liquid at 25 ° C. from the viewpoint of excellent stability over time and usability.
- the silicone oil include dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, methyltrimethicone, polyether-modified methylpolysiloxane, oleyl-modified methylpolysiloxane, polyvinylpyrrolidone-modified methylpolysiloxane.
- Examples thereof include siloxane and the like, and one or more of these can be appropriately selected and used.
- 2 cs dimethylpolysiloxane at 25 ° C. 6 cs dimethylpolysiloxane at 25 ° C., 10 cs dimethylpolysiloxane at 25 ° C., trimethicone, and cyclomethicone.
- One or two or more are preferable, and one or more selected from cyclomethicone, 2 cs dimethylpolysiloxane at 25 ° C., and 6 cs dimethylpolysiloxane at 25 ° C. are more preferable from the viewpoint of stability over time. ..
- Examples of commercially available products of the component (C) silicone oil include KF-96A-1cs / 1, 5cs / 2cs / 5cs / 6cs / 10cs / 20cs / 30cs / 50cs / 100cs / 200cs / 300c / 350cs / 500cs / 1000cs / 3000cs.
- the content of the component (C) silicone oil used in the present invention is not particularly limited, but it is 3 to 40% by mass based on the total amount of the water-in-oil composition because of its uniform coating film and excellent stability over time. Is more preferable, 5 to 30% by mass is more preferable, 7.5 to 20% by mass is still more preferable, and 13 to 18% by mass is particularly preferable.
- the content mass ratio (B) / (C) of the component (B) and the component (C) is 0.1 in terms of uniformity of the coating film, stability over time, and usability. It is preferably ⁇ 8, more preferably 0.4 to 3.3, still more preferably 1 to 3.3, and particularly preferably 1 to 2.
- component (D) water in the present invention those normally used for cosmetics and external preparations for skin can be used and are not particularly limited.
- component (D) water tap water may be used, or purified water purified by distillation or the like, hot spring water, deep water, or the like may be used.
- plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, and rose water may be used.
- the amount of the water phase in the water-in-oil composition of the present invention is not particularly limited, but is preferably 10 to 60% by mass, more preferably 20 to 55% by mass, and 30 from the viewpoint of excellent stability over time and usability. Even more preferred is ⁇ 50% by weight.
- a component having an octanol / water partition coefficient of less than 1 can constitute an aqueous phase.
- an aqueous component such as component (D), a polyhydric alcohol, a water-soluble polymer, a water-soluble film-forming resin, and a moisturizer can form an aqueous phase.
- the amount of the oil phase in the water-in-oil composition of the present invention is not particularly limited, but is preferably 20 to 60% by mass, and more preferably 25 to 50% by mass from the viewpoint of excellent stability over time and usability. preferable.
- the amount of the oil phase in the water-in-oil type composition of the present invention is calculated by excluding the amount of the component (A).
- a component having an octanol / water partition coefficient of 1 or more can constitute an oil phase.
- the component (B), the component (C), and other oily components can form an oil phase.
- the content ratio (water phase) / (oil phase) of the water phase and the oil phase is preferably 0.3 to 5 from the viewpoint of excellent stability over time and usability. It is preferably 0.7 to 2, and more preferably 0.7 to 2.
- the content ratio (aqueous phase) / (A) of the aqueous phase to the component (A) is preferably 0., from the viewpoint of excellent uniformity of the coating film, stability over time, and usability. It is preferably from 75 to 10, and more preferably from 1 to 4.
- the water-in-oil type composition of the present invention contains, in addition to the above-mentioned components (A) to (D), components usually used in cosmetics and external preparations for the skin, such as component (B) and component (C).
- components usually used in cosmetics and external preparations for the skin such as component (B) and component (C).
- component (B) and component (C) components usually used in cosmetics and external preparations for the skin.
- component (B) and component (C) components usually used in cosmetics and external preparations for the skin, such as component (B) and component (C).
- Other than oily components, powders other than component (A), surfactants, fibers, polyhydric alcohols, water-soluble polymers, water-soluble film-forming resins, water-based components such as humectants, antioxidants, defoamers , Cosmetic ingredients, preservatives, fragrances and the like can be contained within a range that does not impair the effects of the present invention.
- the oily component other than the component (B) and the component (C) is not particularly limited as long as it is usually used for cosmetics and external preparations for skin, and the origin of animal oil, vegetable oil, synthetic oil, semi-solid oil, liquid oil, etc. Hydrocarbons, fats and oils, fluorine-based oils and the like can be used regardless of the properties of the volatile oil and the like. Specific examples thereof include liquid paraffin, squalane, petrolatum, hydrocarbons of polyisobutylene, and fluorinated oil agents such as perfluorodecane, perfluorooctane and perfluoropolyether.
- the powders other than the component (A) are generally used in cosmetics and external preparations for the skin, such as plate-like and needle-like shapes, smoke-like particles, fine particles, particle size such as pigment grade, porous It is not particularly limited by the particle structure such as porosity, and examples thereof include inorganic powders, glittering powders, organic powders, pigment powders, metal powders, composite powders and the like.
- colored inorganic pigments such as iron oxide, carbon black, chromium oxide, chromium hydroxide, dark blue, and ultramarine, talc, muscovite, phlogopite, phlogopite, biotite, synthetic mica, sericite (seri Site), synthetic sericite, barium sulfate, kaolin, silicon carbide, bentonite, smectite, diatomaceous earth, aluminum silicate, magnesium aluminum metasilicate, calcium silicate, barium silicate, magnesium silicate, magnesium carbonate, hydroxyapatite, White powder such as boron nitride, titanium oxide-coated mica, titanium oxide-coated bismuth oxychloride, iron oxide mica titanium, dark blue-treated mica titanium, carmine-treated mica titanium, bismuth oxychloride, fish scale foil, polyethylene terephthalate / aluminum / epoxy laminate Powder, polyethylene terephthalate / polyolefin laminated
- organic low molecular powder silk powder, cellulose powder, dextrin powder
- Natural organic powders such as Red No. 201, Red No. 202, Red No. 205, Red No. 226, Red No. 228, Orange No. 203, Orange No. 204, Blue No. 404, Yellow No. 401, etc., Red No. 3, Red No. No. 104, Red No. 106, Orange No. 205, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1, etc.
- organic pigment powder such as zirconium, barium or aluminum lake, or further aluminum powder, gold powder, silver powder, etc.
- Examples thereof include metal powders, fine particles of titanium oxide-coated mica titanium, barium sulfate-coated titanium mica, composite powders of titanium dioxide-containing silicon dioxide, nylon, polyester, rayon, cellulose, and the like.
- One kind or two or more kinds can be used, and a surface-treated or compounded one may be used.
- the surface treatment agent include fluorine compounds, silicone oil, powders, oil agents, gelling agents, surfactants and the like.
- the surfactant is not particularly limited as long as it is used in cosmetics and external preparations for skin, and may be contained in a range that does not impair the effects of the present invention. It is 1% by mass or less based on the total amount of the water-based composition. When the content of the surfactant exceeds 1% by mass, the uniformity, water resistance and usability of the coating film may be poor.
- the content of the surfactant is not particularly limited as long as it is 1 mass% or less, but from the viewpoint of water resistance and usability, it is preferably 0.6 mass% or less, more preferably 0.3 mass% or less, Even more preferably, it is not more than 1% by mass.
- the surfactant is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants.
- the surfactant is not particularly limited, but specifically, as the nonionic surfactant, sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, Sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester Polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxy Alkylene-modified organopolysiloxane, poly
- anionic surfactant examples include polyoxylene lauryl ether sulfate, ammonium polyoxylene lauryl ether sulfate, polyoxylene lauryl ether sulfate triethanolamine, and other polyoxylene lauryl ether sulfates; sodium lauryl sulfate, alkyl lauryl sulfate, triethanolamine, and the like.
- Cationic surfactants include alkylamine salts, amine salts such as polyamine and aminoalcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridinium salts, imidazolium salts, etc., stearyltrimethylammonium chloride, chloride Behenyl trimethyl ammonium, cetyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dibehenyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, dilauryl dimethyl ammonium chloride, dipolyoxyethylene (15EO) coconut oil alkyl Methylammonium, dipolyoxyethylene (4EO) lauryl ether dimethylammonium, dicocoylethylhydroxyethylmonium sulphate, distearoylethylhydroxyethylmonium m
- betaine acetate-type surfactants include octyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, coconut oil fatty acid alkyldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, cetyl.
- Examples include dimethylaminoacetic acid betaine, coconut oil fatty acid amide propyldimethylaminoacetic acid betaine, lauric acid amidopropyldimethylaminoacetic acid betaine, lauryldihydroxyethylaminoacetic acid betaine, cetyldihydroxyethylaminoacetic acid betaine, and the like, and an imidazoline-type surfactant.
- Examples thereof include N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine sodium, N-coconut oil fatty acid acyl-N-carboxymethoxyethyl-N-carboxymethylethylenediamine disodium and the like.
- the antioxidant is not particularly limited as long as it is usually used for cosmetics and external preparations for skin, and examples thereof include tocopherol and ascorbic acid.
- examples of the preservatives include paraoxybenzoic acid ester, phenoxyethanol and 1,2-penta. Examples include diol and the like.
- the cosmetic ingredient is not particularly limited as long as it is generally used for cosmetics and external preparations for skin, and examples thereof include astaxanthin, vitamins, anti-inflammatory agents, herbal medicines and the like.
- the method for producing the water-in-oil composition of the present invention is not particularly limited.
- other optional components and the like are added to the components (A), (B) and (C), and the mixture is heated to 90 ° C. and uniformly mixed.
- it can be obtained by adding an aqueous phase and emulsifying and mixing with a disper mixer or the like.
- it is preferable not to take the roller treatment step from the viewpoint of improving the yield of the water-in-oil type composition.
- a roller treatment step is often used to improve dispersibility in the water-in-oil composition, but the component ( Since A) itself exhibits high dispersibility in the water-in-oil composition, it can be incorporated without the roller treatment step.
- the properties of the water-in-oil composition of the present invention are not particularly limited, and may be liquid, gel, cream, semi-solid, solid, stick or the like.
- the water-in-oil composition of the present invention is not particularly limited, but is preferably Pickering emulsion.
- the Pickering emulsion is an emulsion prepared by adsorbing powder on the interface (for example, see Non-Patent Document 1).
- the average particle size of the emulsion droplets of the water-in-oil composition of the present invention is not particularly limited, but in view of stability over time and usability, the average particle size is preferably 10 to 500 ⁇ m, and 20 to 300 ⁇ m. It is more preferable that the thickness is 150 to 300 ⁇ m.
- the average particle size of the emulsion droplets of the water-in-oil composition of the present invention is measured using an optical microscope (manufactured by Olympus Co., Ltd.) at room temperature to measure the particle size of 100 emulsion droplets, and the average thereof. This can be done by calculating the value.
- the average particle size is preferably 10 to 500 ⁇ m, more preferably 20 to 300 ⁇ m, and even more preferably 150 to 300 ⁇ m.
- the emulsified particle size of the water-in-oil type composition of the present invention is a suitable value, it is considered that the size of the water droplets released from the emulsified droplets when applied is suitable.
- the coating film has good uniformity and excellent water resistance.
- the average particle size of the emulsified droplets of the water-in-oil type composition of the present invention is, in addition to the stirring speed and stirring time in the emulsification and mixing treatment, the mass ratio of the components (B) and (C) It can be adjusted by adjusting the value of (B) / (C).
- the content mass ratio (B) / (C) is increased, the average particle size of the emulsion droplets tends to be increased.
- the content mass ratio (B) / (C) is preferably 0.1 to 8, and the emulsification
- the content mass ratio (B) / (C) is preferably 0.4 to 3.3
- the average particle size of the emulsified droplets is 150 to 300 ⁇ m.
- the content mass ratio (B) / (C) is preferably 1 to 3.3
- the content mass ratio (B) / (C) is required to make the average particle diameter of the emulsified droplets 150 to 200 ⁇ m. Is preferably 1 to 2.
- the water-in-oil composition of the present invention is not particularly limited, but can be used as a cosmetic, an external preparation for skin, and the like.
- the cosmetics include solid preparations for external use, liquid preparations for external use, sprays, ointments, creams, gels, patches and the like, emulsions, lotions, pack cosmetics, facial cleansers, cosmetics for massage, and hair.
- Examples of the external preparation for skin include liniments, lotions, ointments and the like.
- a sunscreen, a cosmetic for eyes, a cosmetic for lip care and a makeup preparation are preferable, and a sunscreen and a makeup preparation are more preferable.
- the transmittance of the powder was evaluated by the following (evaluation method) for the components (1) to (5). Further, water-in-oil type sunscreens having the formulations shown in Tables 1 to 4 were prepared, and 2. Uniformity of coating film, 3. Water resistance, 4. Stability over time, 5. Usability was evaluated by the following (evaluation method). Five items were evaluated comprehensively, and those with passing scores in all evaluation items with ABC as a passing score were acceptable, and those other than that were not acceptable. Further, in Examples, the particle diameter of 100 emulsion droplets was measured at room temperature using an optical microscope (manufactured by Olympus Corporation), and the average value thereof was calculated to measure the average particle diameter of the emulsion droplets. The evaluation results are also shown in Tables 1 to 4.
- Judgment criteria 1> (Judgment): (variation coefficient value) A: 0 or more and 0.25 or less B: 0.25 or more and 0.50 or less C: 0.50 or more and 0.75 or less D: 0.75 or more and 1.00 or less E: 1.00 or more
- the water tank was rotated so that the water flow rate in front of the flat plate was 24 to 28 cm / s, and the rotation speed of the water tank was 45 rpm. Thereafter, the polymethylmethacrylate plate coated with each sample was fixed to a flat plate, the flat plate was fixed in a water tank container at a position of 1 cm from the bottom surface and immersed, and the water tank container was rotated to start a water bath. After 80 minutes, the flat plate on which the polymethylmethacrylate plate was fixed was taken out from the water tank container and dried at room temperature for 15 minutes, and similarly, the SPF value was measured 3 times, and the average value was taken as the residual value.
- ⁇ Criteria 2> (Judgment): (residual value) A: The residual rate exceeds 90% B: The residual rate exceeds 75% and 90% or less C: The residual rate exceeds 60% and 75% or less D: The residual rate exceeds 45% and 60% or less E: The residual rate 45% or less
- the separation layer exceeds 5 mm and 1.0 mm or less, and shakes each sample up and down 3 times.
- the separation layer disappears.
- A Components (6) to (13) are uniformly mixed and dissolved at 80 ° C.
- B Components (1) to (5) and components (14) to (22) are uniformly mixed and dispersed by a roll mill and mixed with A.
- C Components (23) to (29) are uniformly mixed.
- D Add C to B and emulsify with a disper mixer at 2000 rpm for 5 minutes at room temperature.
- E D was filled in a container to obtain a water-in-oil type sunscreen.
- the coating film was inferior in uniformity, water resistance, stability over time, and usability. It is considered that this is because the component (4) did not exhibit amphipathic properties and thus did not emulsify well.
- Comparative Example 4 in which the transmittance of 700 nm light was not 0.8 to 20, the coating film was inferior in uniformity, temporal stability, and usability. It is considered that this is because the component (5) was inferior in the selective orientation to the oil-water interface and the emulsification did not occur favorably.
- Comparative Example 5 in which the amount of the component (A) was less than 5% by mass, the uniformity of coating film, water resistance, stability over time, and usability were inferior to those in Examples. It is considered that this is because the amount of the component (A) adsorbed on the interface was insufficient and the emulsification did not occur favorably.
- Comparative Example 6 in which the component (A) exceeded 30% by mass, the uniformity and usability of the coating film were poor. This is because an excessive amount of the component (A) that could not be adsorbed at the interface was dispersed in the oil phase, and the feel of the component (A) itself became dominant at the time of application, so that a fresh feeling of use was not obtained and a strong stickiness was obtained. Therefore, it is considered to have lacked usability.
- Comparative Example 7 in which the content of the surfactant was more than 1% by mass, the uniformity, water resistance and temporal stability of the coating film were inferior to those in the Examples.
- the sunscreen of each Example was highly evaluated in each item, but especially Examples 1, 14, and 15 in which the emulsified droplets were in the range of 150 to 300 ⁇ m were evaluated as A in all items, It had a particularly fresh and good usability. It is also recognized that the average particle size of the emulsion droplets tends to increase as the content mass ratio (B) / (C) increases, and the content of the content mass ratio should be within the range of 150 to 300 ⁇ m. It was confirmed that (B) / (C) is preferably in the range of 1 to 3.3. On the other hand, in Comparative Example 8 containing no component (B), the uniformity and usability of the coating film were poor. In Comparative Example 9 containing no component (C), the uniformity, water resistance and temporal stability of the coating film were poor.
- Example 16 Water-in-oil type liquid foundation (component) (mass%) (1) Zinc oxide surface-treated with silica and a hydrophobic treatment agent * 98 (2) Titanium dioxide treated with isopropyl titanium triisostearate * 10 8 (3) Titanium dioxide treated with methyl hydrogen polysiloxane * 11 2 (4) 2-Ethylhexyl p-methoxycinnamate 5 (5) 2- ⁇ 4- (diethylamino) -2-hydroxybenzoyl ⁇ Hexyl benzoate 1.5 (6) 2,4-bis [ ⁇ 4- (2-ethylhexyloxy) -2-hydroxy ⁇ -Phenyl] -6- (4-methoxyphenyl)-(1,3,5)- Triazine 0.5 (7) Glyceryl tri (caprylic capric acid) 3 (8) Hexyl laurate 3 (9) Hydrogenated polyisobutene * 12 3 (10) Cyclomethicone 10 (11) Methyltrimethicone 5 (12)
- the transmittance measured by the method described in the powder transmittance is 1.5%, and the average particle diameter is 25 nm.
- A Components (4) to (8) are uniformly mixed and dissolved at 80 ° C.
- B Components (1) to (3) and components (9) to (15) are uniformly mixed and dispersed by a disper mixer at 2000 rpm at room temperature for 5 minutes, and mixed with A.
- C Components (16) to (28) are uniformly mixed.
- D Add C to B and emulsify with a disper mixer at 2000 rpm for 5 minutes at room temperature.
- E D was filled in a container to obtain a water-in-oil type liquid foundation.
- the water-in-oil type liquid foundation of Example 16 was excellent in coating film uniformity, water resistance, stability over time, and usability.
- Example 17 Water-in-oil type daytime beauty essence (ingredient) (mass%) (1) Zinc oxide surface-treated with silica and a hydrophobic treatment agent * 16 10 (2) Titanium dioxide treated with dimethylpolysiloxane * 17 1 (3) Titanium dioxide treated with triethoxycaprylylsilane * 18 1 (4) 2-Ethylhexyl p-methoxycinnamate 5 (5) 2,4,6 tris [ ⁇ 4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine 1.5 (6) Diisopropyl adipate 5 (7) Isononyl isononanoate 2 (8) Glyceryl triisostearate 0.1 (9) Squalane 3 (10) Astaxanthin 0.002 (11) Isododecane 3 (12) Cyclomethicone 10 (13) Dimethyl polysiloxane * 193 (14) Dimethylpolysiloxane * 20 3 (15) Sorbitan
- the transmittance measured by the method described in the powder transmittance is 18%, and the average particle diameter is 25 nm.
- A Components (4) to (8) are uniformly mixed and dissolved at 80 ° C.
- B Components (1) to (3) and components (9) to (17) are uniformly mixed and dispersed by a roll mill and mixed with A.
- C Components (18) to (32) are mixed uniformly.
- D Add C to B and emulsify with a disper mixer at 2000 rpm for 5 minutes at room temperature.
- E D was filled in a container to obtain a water-in-oil type daytime beauty essence.
- the water-in-oil type daytime beauty essence of Example 17 was excellent in coating film uniformity, water resistance, stability over time, and usability.
- Example 18 Water-in-oil type makeup base (component) (mass%) (1) Zinc oxide surface-treated with silica and a hydrophobic treatment agent * 23 12 (2) Titanium dioxide treated with sodium lauroyl aspartate * 24 2.5 (3) Titanium dioxide treated with sodium lauroyl glutamate * 25 2.5 (4) 2-Ethylhexyl p-methoxycinnamate 4 (5) 2,4,6 tris [ ⁇ 4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine 1 (6) 2- ⁇ 4- (diethylamino) -2-hydroxybenzoyl ⁇ Hexyl benzoate 1 (7) 2,4-bis [ ⁇ 4- (2-ethylhexyloxy) -2-hydroxy ⁇ -Phenyl] -6- (4-methoxyphenyl)-(1,3,5)- Triazine 1 (8) Diglyceryl triisostearate 0.3 (9) Alkyl benzoate (C12-15)
- the transmittance measured by the method described in the powder transmittance is 5%, and the average particle diameter is 25 nm.
- A Components (4) to (8) are uniformly mixed and dissolved at 80 ° C.
- B Components (1) to (3) and components (9) to (16) are uniformly mixed and dispersed by a roll mill and mixed with A.
- C Components (17) to (38) are mixed uniformly.
- D Add C to B and emulsify with a disper mixer at 2000 rpm for 5 minutes at room temperature.
- E D was filled in a container to obtain a water-in-oil type makeup base.
- the water-in-oil type makeup base of Example 18 was excellent in uniformity of coating film, water resistance, stability over time, and usability.
- Example 19 Water-in-oil type sunscreen stick (component) (mass%) (1) Zinc oxide surface-treated with silica and a hydrophobic treatment agent * 308 (2) Hydroxypropyl bispalmitate MEA treated titanium dioxide * 31 2 (3) Perfluorooctyltriethoxysilane treated titanium dioxide * 32 1 (4) Titanium dioxide treated with Mg stearate * 33 1 (5) 2-Ethylhexyl p-methoxycinnamate 6 (6) 2- ⁇ 4- (diethylamino) -2-hydroxybenzoyl ⁇ Hexyl benzoate 1 (7) 2,4-bis [ ⁇ 4- (2-ethylhexyloxy) -2-hydroxy ⁇ -Phenyl] -6- (4-methoxyphenyl)-(1,3,5)- Triazine 1 (8) 2,4,6 tris [ ⁇ 4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine 1 (9) Die
- the transmittance measured by the method described in the powder transmittance is 15% and the average particle diameter is 25 nm.
- the water-in-oil type sunscreen stick of Example 19 was excellent in coating film uniformity, water resistance, stability over time, and usability.
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Abstract
Description
紫外線防御効果を有する皮膚外用剤や化粧料として、油中水型組成物の技術が開示されている(例えば、特許文献1、2参照)。
b)水相である分散相、及び
c)数平均粒径が200nm以上1μm以下であり、少なくとも1種のN-アシル化グルタミン酸塩で表面処理されている粒子
を含む油中水エマルジョンの形態の化粧品組成物であって、
前記N-アシル化グルタミン酸塩がMg、Al、Ca、Znから選択される金属の水酸化物で前記粒子にイオン結合されており、
前記粒子が前記連続相と前記分散相との間の界面に存在し、かつ
前記組成物の総重量に対して1重量%以下の少なくとも1種の乳化剤を含む、
化粧品組成物を開示する。
すなわち、塗膜の均一性、耐水性、経時安定性に優れ、べたつき等のない良好な使用性を有する油中水型組成物はこれまでに知られていなかった。
以下の成分(A)~(D);
成分(A)シリカおよび疎水化処理剤により表面処理された酸化亜鉛 5~30質量%
成分(B)極性油
成分(C)シリコーン油
成分(D)水
を含有し、
成分(A)は、水/エタノール溶媒 (質量比 水:エタノール=3:1)中に0.25質量%で混合した際の、波長700nmの光の透過率が0.8~20であるものであって、
界面活性剤の含有量が1質量%以下である油中水型組成物を提供するものである。
水/エタノール混合溶媒 (質量比 水:エタノール=3:1) 40gに対し、0.25質量%となるよう、成分(A)を、0.1g秤量し、その秤量直後に、振とう器YS-8D(ヤヨイ社製)で250回/分、30秒間の条件で混合を行う。混合の後、光路長10mm×光路幅10mmのプラスチックセルに3.5g入れ、混合後3分経過時点の溶液を、分光光度計UV-2500PC(島津製作所社製)を用いて、波長:700nmにて測定することができる。また、リファレンスには水/エタノール混合溶媒 (質量比 水:エタノール=3:1)を使用することができる。
また、25℃にて液状極性油と25℃における固形極性油を合わせて含有する場合、耐水性の点から、25℃における液状極性油と25℃における固形極性油の含有質量割合(25℃における液状極性油)/(25℃における固形極性油)は1~250が好ましく、2.5~150がより好ましく、特に3~15が好ましい。
また、本発明の油中水型組成物の乳化滴の平均粒径の測定は、光学顕微鏡(オリンパス社製)を用いて、室温にて乳化滴100個の粒径を測定し、それらの平均値を算出することにより行うことができる。
本発明の油中水型組成物を塗布する際に、乳化滴の中から放出される水滴が目視で観察されるほどに大粒であると、べたつきが無く、さらには瑞々しいという良好な使用性を有するが、そのためには、上述のとおり、平均粒径が10~500μmであることが好ましく、20~300μmであることがより好ましく、150~300μmであることがさらにより好ましい。本発明の油中水型組成物の乳化粒径は好適な値である時に、塗布する際に乳化滴の中から放出される水滴の大きさが好適となると考えられる。
さらに、塗布する際に乳化滴の中から放出される水滴の大きさが好適である際には、塗膜形成時の水相と油相の局在化が好適となるため、結果的に、塗膜の均一性も良好となり、耐水性も優れる。
さらに、表1~4に示す処方の油中水型日焼け止めを調製し、2.塗膜の均一性、3.耐水性、4.経時安定性、5.使用性について下記(評価方法)により評価した。5項目を総合的に評価し、ABCを合格点として、全評価項目において合格点を得たものを可、それ以外は不可とした。また実施例について、光学顕微鏡(オリンパス社製)を用いて、室温にて乳化滴100個の粒径を測定し、それらの平均値を算出して乳化滴の平均粒径の測定を行った。それらの評価結果を併せて表1~4に示す。
1.粉体の透過率
2.塗膜の均一性
3.耐水性
4.経時安定性
5.使用性
1.粉体の透過率
水/エタノール混合溶媒 (質量比 水:エタノール=3:1) 40gに対し、0.25質量%となるよう、成分(1)~(5)を、0.1g秤量し、その秤量直後に、振とう器YS-8D(ヤヨイ社製)で250回/分、30秒間の条件で混合を行った。混合の後、光路長10mm×光路幅10mmのプラスチックセルに3.5g入れ、混合後3分経過時点の溶液を、分光光度計UV-2500PC(島津製作所社製)を用いて、波長:700nmにて測定し、測定値(%)を得た。また、リファレンスには水/エタノール混合溶媒 (質量比 水:エタノール=3:1)を使用した。
実施例1~21、比較例1~9の各試料をポリメチルメタクリレート板に、厚さ50μmで塗布し、15分間室温にて乾燥後、SPF アナライザー UV-2000S(Labsphere社製)にてSPF値を10か所測定し、得られた標準偏差を平均値で除した変動係数を下記<判定基準1>により判定した。
(判定):(変動係数の値)
A :0以上0.25以下
B :0.25を超え0.50以下
C :0.50を超え0.75以下
D :0.75を超え1.00以下
E :1.00を超える
実施例1~21、比較例1~9の各試料をポリメチルメタクリレート板に、厚さ50μmで塗布し、15分間室温にて乾燥後、SPF アナライザー UV-2000S(Labsphere社製)にてSPF値を3回測定して、その平均値を初期値とした。その後、直径が50cm、深さが15cmのタライ状の水槽容器に11cmの深さで25℃の水を入れ、ポリメチルメタクリレート板を固定した平板を水槽容器の回転軸から21cmの距離で、10cmの深さで浸漬するように設置し、その状態で水槽容器を回転させ、平板前の水流の流速が24~28cm/s、水槽容器の回転速度が45rpmになるように調整した。その後、各試料を塗布したポリメチルメタクリレート板を平板に固定し、該平板を水槽容器に底面から1cmの位置に固定して浸漬させ、水槽容器を回転させて水浴を開始した。80分間経過した後、ポリメチルメタクリレート板を固定した平板を水槽容器内から取り出し、15分間室温にて乾燥させ、同様にSPF値を3回測定して、その平均値を残存値とした。水浴処理の前後でのSPF値の残存率(=(残存値)/(初期値))を算出し、下記<判定基準2>により判定した。
<判定基準2>
(判定):(残存率の値)
A :残存率が90%を超える
B :残存率が75%を超え90%以下
C :残存率が60%を超え75%以下
D :残存率が45%を超え60%以下
E :残存率が45%以下
実施例1~21、比較例1~9の各試料30gをガラス瓶(6号規格、PS-NO.6)に測りとり、50℃の恒温槽に1月保管し、1月後の各試料の状態を目視にて確認し、下記<判定基準3>により、判定した。
<判定基準3>
(判定):(外観の状態)
A :水相の分離が確認されない
B :水相の分離層が0.5mm以下で確認され、各試料を3回上下に振ると、分離層が消失する
C :水相の分離層が0.5mmを超え1.0mm以下で確認され、各試料を3回上下に振ると、分離層が消失する
D :水相の分離層が1.0mmを超え1.5mm以下で確認され、各試料を3回上下に振ると、分離層が消失する
E :水相の分離層が1.5mmを超え1.0mm以下で確認され、各試料を3回上下に振っても、分離層が消失しない
20代~40代の女性で官能評価の訓練を受け、一定の基準で評価が可能な専門パネルを10名選定した。専門パネルが実施例1~21、比較例1~9の各試料5gについて、上腕部に塗布し、もう一方の手の中指及び薬指で優しく円を描くことにより施用し、その際に感じる使用性を下記<絶対評価基準>にて5段階に評価し、評点を付け、各試料ごとに、パネル全員の評点の合計から、その平均点を算出し、下記<判定基準4>により、判定した。
<絶対評価基準>
(評点):(使用性)
5点 :施用の際、円を5サイクル以内で、描く際に水滴が観察され、べたつきを感じないうえに、非常にみずみずしい
4点 :施用の際、円を5サイクルを超え、10サイクル以内で、描く際に水滴が観察され、べたつきを感じないうえに、みずみずしい
3点 :施用の際、円を10サイクルを超えて、描く際に水滴が観察されないが、ほとんどべたつきを感じない
2点 :施用の際、円を10サイクルを超えて、描く際に水滴が観察されないが、ややべたつきを感じる塗擦が15サイクルを超え、20サイクル以内で水滴が観察される
1点 :施用の際、円を10サイクルを超えて、描く際に水滴が観察されないが、強いべたつきを感じる
<判定基準4>
(判定):(評点の平均点)
A :4.2点以上 :非常に良好
B :4.2点未満3.4点以上 :良好
C :3.4点未満2.6点以上 :やや良好
D :2.6点未満1.8点以上 :やや不良
E :1.8点未満 :不良
※2:FINEX-52W-LP2(堺化学工業社製) 平均粒子径20nm、不定形
※3:MZY-505S(テイカ社製) 平均粒子径25nm、不定形
※4:MZ-500(テイカ社製) 平均粒子径25nm、不定形
※5:NAI-チタンMP-1133(三好化成社製) 平均粒子径250nm
※6:D-400(根上工業社製) 平均粒子径15μm
※7:トスパール2000B(モメンティブ・パフォーマンス・マテリアル・ジャパン社製) 平均粒子径6μm
※8:PEMULEN TR-1(LUBRIZOL ADVANCED MATERIALS社製)
A:成分(6)~(13)を80℃で均一に混合溶解する。
B:成分(1)~(5)及び成分(14)~(22)をロールミルにて均一に混合分散し、Aと混合する。
C:成分(23)~(29)を均一に混合する。
D:BにCを加え、ディスパーミキサーで2000rpm、室温で5分間乳化する。
E:Dを容器に充填し、油中水型日焼け止めを得た。
一方、成分(A)を含有せず、シリカおよび疎水化処理剤により表面処理された酸化亜鉛であって、かつ、水/エタノール溶媒 (質量比 水:エタノール=3:1)中に0.25質量%で混合した際の、波長700nmの光の透過率が0.8~20でないものを用いた比較例1では、塗膜の均一性、経時安定性、使用性に劣っていた。これは、成分(2)が、両親媒性を発揮しないため、乳化が良好に起こらなかったためと考えられる。
成分(A)を含有せず、疎水化処理剤により表面処理された酸化亜鉛であって、かつ、水/エタノール溶媒 (質量比 水:エタノール=3:1)中に0.25質量%で混合した際の、波長700nmの光の透過率が0.8~20でないものを用いた比較例2では、塗膜の均一性、経時安定性、使用性に劣っていた。これは、成分(3)が、両親媒性を発揮しないため、乳化が良好に起こらなかったためと考えられる。
成分(A)を含有せず、無処理酸化亜鉛であって、かつ、水/エタノール溶媒 (質量比 水:エタノール=3:1)中に0.25質量%で混合した際の、波長700nmの光の透過率が0.8~20でないものを用いた比較例3では、塗膜の均一性、耐水性、経時安定性、使用性に劣っていた。これは、成分(4)が、両親媒性を発揮しないため、乳化が良好に起こらなかったためと考えられる。
成分(A)を含有せず、ステアロイルグルタミン酸2Na処理酸化チタンであって、かつ、水/エタノール溶媒 (質量比 水:エタノール=3:1)中に0.25質量%で混合した際の、波長700nmの光の透過率が0.8~20でないものを用いた比較例4では、塗膜の均一性、経時安定性、使用性に劣っていた。これは、成分(5)が、油水界面への選択的配向に劣り、乳化が良好に起こらなかったためと考えられる。
成分(A)が、30質量%を超える比較例6では、塗膜の均一性、使用性に劣っていた。これは、成分(A)が、界面に吸着しきれなかった過剰量が油相中に分散し、塗布時に成分(A)自体の感触が支配的となり、みずみずしい使用感が得られず、強いべたつきを感じるため、使用性に欠けたと考えられる。
また界面活性剤の含有量が1質量%を超える比較例7では、実施例と比べ塗膜の均一性、耐水性、経時安定性に劣っていた。
一方、成分(B)を含有していない比較例8では、塗膜の均一性、使用性に劣っていた。
成分(C)を含有していない比較例9では、塗膜の均一性、耐水性、経時安定性に劣っていた。
(成分) (質量%)
(1)シリカおよび疎水処理剤により表面処理された酸化亜鉛
※9 8
(2)トリイソステアリン酸イソプロピルチタン処理二酸化チタン
※10 8
(3)メチルハイドロジェンポリシロキサン処理二酸化チタン
※11 2
(4)p-メトキシケイ皮酸-2-エチルヘキシル 5
(5)2-{4-(ジエチルアミノ)-2-ヒドロキシベンゾイル}
安息香酸ヘキシル 1.5
(6)2,4-ビス[{4-(2-エチルヘキシロキシ)-2-ヒドロキシ}
-フェニル]-6-(4-メトキシフェニル)-(1,3,5)-
トリアジン 0.5
(7)トリ(カプリル・カプリン酸)グリセリル 3
(8)ラウリン酸ヘキシル 3
(9)水添ポリイソブテン※12 3
(10)シクロメチコン 10
(11)メチルトリメチコン 5
(12)フェニルトリメチコン※13 2
(13)ラウリルPEG-9ポリジメチルシロキシエチルジメチコン
0.2
(14)無水ケイ酸※14 1.5
(15)トリエトキシカプリリルシラン処理セリサイト※15 2
(16)精製水 残量
(17)エタノール 5
(18)プロピレングリコール 5
(19)フェノキシエタノール 0.3
(20)加水分解ヒアルロン酸 0.5
(21)加水分解コラーゲン 0.5
(22)テアニン 0.5
(23)セリン 0.2
(24)塩化ナトリウム 0.2
(25)ソルビトール 2
(26)シロキクラゲ多糖体 0.01
(27)ボタンピ抽出物 0.03
(28)アスコルビン酸 0.001
※9:(評価方法)1.粉体の透過率 に記載の手法で測定した透過率が1.5%、平均粒子径25nm
※10:ITT-2 TiO2 CR-50(KOBO PRODUCTS社製) 平均粒子径250nm
※11:MT-05(テイカ社製) 平均粒子径10nm
※12:パールリーム4(日油社製)
※13:SH556 FLUID(東レ・ダウコーニング社製)
※14:CHIFFONSIL P-3R(日揮触媒化成社製) 平均粒子径5μm
※15:OTS-2 セリサイトFSE(大東化成工業社製) 平均粒子径10μm
A:成分(4)~(8)を80℃で均一に混合溶解する。
B:成分(1)~(3)及び成分(9)~(15)をディスパーミキサーで2000rpm、室温で5分間均一に混合分散し、Aと混合する。
C:成分(16)~(28)を均一に混合する。
D:BにCを加え、ディスパーミキサーで2000rpm、室温で5分間乳化する。
E:Dを容器に充填し、油中水型リキッドファンデーションを得た。
(成分) (質量%)
(1)シリカおよび疎水処理剤により表面処理された酸化亜鉛
※16 10
(2)ジメチルポリシロキサン処理二酸化チタン※17 1
(3)トリエトキシカプリリルシラン処理二酸化チタン※18 1
(4)p-メトキシケイ皮酸-2-エチルヘキシル 5
(5)2,4,6トリス[{4-(2-エチルヘキルオキシカルボニル)アニ
リノ]-1,3,5-トリアジン 1.5
(6)アジピン酸ジイソプロピル 5
(7)イソノナン酸イソノニル 2
(8)トリイソステアリン酸グリセリル 0.1
(9)スクワラン 3
(10)アスタキサンチン 0.002
(11)イソドデカン 3
(12)シクロメチコン 10
(13)ジメチルポリシロキサン※19 3
(14)ジメチルポリシロキサン※20 3
(15)セスキイソステアリン酸ソルビタン 0.2
(16)架橋型シリコーン・網状型シリコーンブロック共重合体
※21 2
(17)ポリメタクリル酸メチル※22 2
(18)精製水 残量
(19)エタノール 5
(20)トリプロピレングリコール 5
(21)グリセリン 2.5
(22)ジグリセリン 0.5
(23)1,3-ブチレングリコール 5
(24)フェノキシエタノール 0.2
(25)ポリオキシエチレンメチルグルコシド 0.5
(26)アセチル化ヒアルロン酸ナトリウム 0.1
(27)ヒアルロン酸プロピレングリコール 0.2
(28)塩化ナトリウム 0.2
(29)エリスリトール 3
(30)スイゼンジノリ多糖体 0.05
(31)マグワ根皮エキス 0.05
(32)アスコルビン酸グルコシド 0.2
※16:(評価方法)1.粉体の透過率 に記載の手法で測定した透過率が18%、平均粒子径25nm
※17:SA-チタンMP-1133(三好化成社製) 平均粒子径250nm
※18:OTS-2 TiO2 MP-1133(大東化成工業社製) 平均粒子径250nm
※19:KF-96A-1.5cs(信越化学工業社製)
※20:KF-96A-6cs(信越化学工業社製)
※21:KSP-101(信越化学工業社製) 平均粒子径12μm
※22:マツモトマイクロスフェアー M101(松本油脂製薬社製) 平均粒子径9μm
A:成分(4)~(8)を80℃で均一に混合溶解する。
B:成分(1)~(3)及び成分(9)~(17)をロールミルにて均一に混合分散し、Aと混合する。
C:成分(18)~(32)を均一に混合する。
D:BにCを加え、ディスパーミキサーで2000rpm、室温で5分間乳化する。
E:Dを容器に充填し、油中水型日中用美容液を得た。
(成分) (質量%)
(1)シリカおよび疎水処理剤により表面処理された酸化亜鉛
※23 12
(2)ラウロイルアスパラギン酸ナトリウム処理二酸化チタン
※24 2.5
(3)ラウロイルグルタミン酸ナトリウム処理二酸化チタン
※25 2.5
(4)p-メトキシケイ皮酸-2-エチルヘキシル 4
(5)2,4,6トリス[{4-(2-エチルヘキルオキシカルボニル)アニ
リノ]-1,3,5-トリアジン 1
(6)2-{4-(ジエチルアミノ)-2-ヒドロキシベンゾイル}
安息香酸ヘキシル 1
(7)2,4-ビス[{4-(2-エチルヘキシロキシ)-2-ヒドロキシ}
-フェニル]-6-(4-メトキシフェニル)-(1,3,5)-
トリアジン 1
(8)トリイソステアリン酸ジグリセリル 0.3
(9)安息香酸アルキル(C12-15) 5
(10)トリメリト酸トリ2-エチルヘキシル 2
(11)イソドデカン 2.5
(12)シクロメチコン 14
(13)ジメチルポリシロキサン※26 2
(14)ジメチルポリシロキサン※27 2
(15)トリメチルシロキシケイ酸 2
(16)ラウリルポリグリセリル-3ポリジメチルシロキシエチルジメチコ
ン 0.2
(17)ナイロン-12※28 3
(18)ラウロイルリシン 0.1
(19)精製水 残量
(20)エタノール 3
(21)1,2-ペンタンジオール 0.5
(22)フェノキシエタノール 0.2
(23)ジプロピレングリコール 3
(24)1,3-ブチレングリコール 5
(25)ポリエチレングリコール※29 2
(26)(エイコサン二酸・テトラデカン二酸)ポリグリセリル-10
0.1
(27)トリスビフェニルトリアジン 1
(28)メチレンビスベンゾトリアゾリルテトラメチルブチルフェノール
1
(29)ヒアルロン酸ヒドロキシプロピルトリモニウム 0.3
(30)サクシニルアテロコラーゲン 0.5
(31)N-アセチル-L-ヒドロキシプロリン 0.5
(32)クエン酸ナトリウム 0.05
(33)塩化カリウム 0.2
(34)エクトイン 1
(35)(PEG-240・デシルテトラデセス-20・HDI)
コポリマー 0.05
(36)2-メタクリロイルオキシエチルホスホリルコリン・メタクリル酸
ブチル共重合体液 0.5
(37)腐植土抽出物 0.05
(38)リン酸L-アスコルビルマグネシウム 0.2
※23:(評価方法)1.粉体の透過率 に記載の手法で測定した透過率が5%、平均粒子径25nm
※24:ASI TiO2 CR-50(大東化成工業社製) 平均粒子径250nm
※25:ASL-1 TiO2 MP-1133(大東化成工業社製) 平均粒子径250nm
※26:KF-96A-1cs(信越化学工業社製)
※27:KF-96A-20cs(信越化学工業社製)
※28:オルガソール 2002D(アルケマ社製) 平均粒子径20μm
※29:PEG-400(東邦化学工業社製)
A:成分(4)~(8)を80℃で均一に混合溶解する。
B:成分(1)~(3)及び成分(9)~(16)をロールミルにて均一に混合分散し、Aと混合する。
C:成分(17)~(38)を均一に混合する。
D:BにCを加え、ディスパーミキサーで2000rpm、室温で5分間乳化する。
E:Dを容器に充填し、油中水型化粧下地を得た。
(成分) (質量%)
(1)シリカおよび疎水処理剤により表面処理された酸化亜鉛
※30 8
(2)ヒドロキシプロピルビスパルミタドMEA処理二酸化チタン
※31 2
(3)パーフルオロオクチルトリエトキシシラン処理二酸化チタン
※32 1
(4)ステアリン酸Mg処理二酸化チタン※33 1
(5)p-メトキシケイ皮酸-2-エチルヘキシル 6
(6)2-{4-(ジエチルアミノ)-2-ヒドロキシベンゾイル}
安息香酸ヘキシル 1
(7)2,4-ビス[{4-(2-エチルヘキシロキシ)-2-ヒドロキシ}
-フェニル]-6-(4-メトキシフェニル)-(1,3,5)-
トリアジン 1
(8)2,4,6トリス[{4-(2-エチルヘキルオキシカルボニル)アニ
リノ]-1,3,5-トリアジン 1
(9)セバシン酸ジエチル 4
(10)コハク酸ジエチルヘキシル 4
(11)ジネオペンタン酸メチルペンタンジオール 4
(12)ダイマージリノール酸(フィトステリル・イソステアリル・セチル
・ステアリル・ベヘニル) 2
(13)トコフェロール 0.02
(14)ポリエチレン※34 5
(15)マイクロクリスタリンワックス※35 4
(16)パラフィン※36 2
(17)ジメチルポリシロキサン※37 10
(18)ワセリン 2
(19)(ジメチコン・ポリグリセリン-3)クロスポリマー 0.1
(20)(PEG-15・ラウリルジメチコン)クロスポリマー 0.1
(21)無水ケイ酸※38 3
(22)ジメチコノール・アミノプロピルトリエトキシシラン処理タルク
※39 2
(23)精製水 残量
(24)1,3-ブチレングリコール 2
(25)グリセリン 2
(26)ポリオキシエチレングリセリン(26.EO.) 2
(27)ポリオキシプロピレンジグリセリルエーテル 2
(28)シクロヘキサン-1,4-ジカルボン酸ビスエトキシジグリコール
0.5
(29)フェノキシエタノール 0.2
(30)スイカズラ花エキス 0.5
(31)エリスリトール 1
(32)トレハロース 1
(33)トリメチルグリシン 1
(34)メントール 0.2
※30:(評価方法)1.粉体の透過率 に記載の手法で測定した透過率が15%、平均粒子径25nm
※31:X-CERA TiO2 R250(大東化成工業社製) 平均粒子径250nm
※32:FHS-3 TiO2 MP-1133(大東化成工業社製) 平均粒子径250nm
※33:MST-1 TiO2 R250(大東化成工業社製) 平均粒子径250nm
※34:PERFORMALENE 500(New Phase Technologies社製)
※35:MULTIWAX W445(Sonneborn社製)
※36:PARACERA 256(Paramelt社製)
※37:KF-96A-5cs(信越化学工業社製)
※38:コスメシリカCQ4(富士シリシア化学社製) 平均粒子径4μm
※39:SE-TA-EX(三好化成社製) 平均粒子径15μm
A:成分(5)~(16)を90℃で均一に混合溶解する。
B:成分(1)~(4)及び成分(17)~(22)をロールミルにて均一に混合分散し、Aと混合する。
C:成分(23)~(34)を均一に混合する。
D:90℃でBにCを加え、ディスパーミキサーで2000rpm、90℃で5分間乳化する。
E:Dを容器に充填し、冷却固化し、油中水型日焼け止めスティックを得た。
Claims (8)
- 以下の成分(A)~(D);
成分(A)シリカおよび疎水化処理剤により表面処理された酸化亜鉛5~30質量%
成分(B)極性油
成分(C)シリコーン油
成分(D)水
を含有し、
成分(A)は、水/エタノール溶媒 (質量比 水:エタノール=3:1)中に0.25質量%で混合した際の、波長700nmの光の透過率が0.8~20であるものであって、
界面活性剤の含有量が1質量%以下である油中水型組成物。 - 前記油中水型組成物がピッカリングエマルションである請求項1に記載の油中水型組成物。
- 前記成分(B)の含有量が5~30質量%である請求項1又は2記載の油中水型組成物。
- 前記成分(B)および前記成分(C)の含有質量割合(B)/(C)が、0.1~8である請求項1~3のいずれか1項に記載の油中水型組成物。
- 前記油中水型組成物の乳化滴の平均粒径が10~500μmである請求項1~4のいずれか1項に記載の油中水型組成物。
- 前記成分(B)として、25℃における液状極性油と25℃における固形極性油を含有する請求項1~5のいずれか1項に記載の油中水型組成物。
- 水相と油相の含有質量割合(水相)/(油相)が、0.3~5である請求項1~6のいずれか1項に記載の油中水型組成物。
- 水相と前記成分(A)の含有質量割合(水相)/(A)が、0.75~10である請求項1~7のいずれか1項に記載の油中水型組成物。
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WO2022149546A1 (ja) * | 2021-01-08 | 2022-07-14 | ピアス株式会社 | 皮膚外用組成物 |
WO2023085106A1 (ja) * | 2021-11-10 | 2023-05-19 | 株式会社 資生堂 | 油中水型乳化化粧料 |
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JP2016141671A (ja) * | 2015-02-05 | 2016-08-08 | 株式会社ノエビア | 油中水乳化型紫外線防御用化粧料 |
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EP1167462B1 (en) * | 1999-01-11 | 2010-12-22 | Showa Denko K.K. | Cosmetic preparation, surface-hydrophobized silica-coated metal oxide particles, sol of surface-hydrophobized silica-coated metal oxide, and processes for producing these |
JP2002154915A (ja) * | 2000-09-11 | 2002-05-28 | Showa Denko Kk | 化粧料 |
JP5477883B2 (ja) | 2007-02-23 | 2014-04-23 | 株式会社 資生堂 | 油中水型乳化組成物 |
JP5361089B2 (ja) | 2011-08-26 | 2013-12-04 | 株式会社 資生堂 | 油中水型乳化日焼け止め化粧料 |
JP2016145157A (ja) | 2015-02-06 | 2016-08-12 | ポーラ化成工業株式会社 | 日焼け止め化粧料 |
JP7260981B2 (ja) * | 2018-09-14 | 2023-04-19 | 花王株式会社 | 油中水型乳化化粧料 |
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JP2001518112A (ja) * | 1997-03-25 | 2001-10-09 | バイヤースドルフ・アクチエンゲゼルシヤフト | 乳化剤を含まない油中水型の微細分散系 |
JP2014097935A (ja) * | 2012-11-13 | 2014-05-29 | Shiseido Co Ltd | 油中水型乳化日焼け止め化粧料 |
JP2016141671A (ja) * | 2015-02-05 | 2016-08-08 | 株式会社ノエビア | 油中水乳化型紫外線防御用化粧料 |
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WO2022149546A1 (ja) * | 2021-01-08 | 2022-07-14 | ピアス株式会社 | 皮膚外用組成物 |
WO2023085106A1 (ja) * | 2021-11-10 | 2023-05-19 | 株式会社 資生堂 | 油中水型乳化化粧料 |
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JP7354141B2 (ja) | 2023-10-02 |
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CN112969443A (zh) | 2021-06-15 |
JPWO2020100573A1 (ja) | 2021-10-21 |
KR20210092758A (ko) | 2021-07-26 |
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