WO2017187977A1 - 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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- WO2017187977A1 WO2017187977A1 PCT/JP2017/014935 JP2017014935W WO2017187977A1 WO 2017187977 A1 WO2017187977 A1 WO 2017187977A1 JP 2017014935 W JP2017014935 W JP 2017014935W WO 2017187977 A1 WO2017187977 A1 WO 2017187977A1
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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
- A61K8/19—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
- A61K8/02—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
- A61K8/0241—Containing particulates characterized by their shape and/or structure
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- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- 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
- A61K8/25—Silicon; Compounds thereof
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- A61K8/26—Aluminium; Compounds thereof
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- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
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- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
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- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
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- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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- 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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- 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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- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
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- A—HUMAN NECESSITIES
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Definitions
- the present invention relates to a water-in-oil emulsified cosmetic. More specifically, the present invention relates to a water-in-oil emulsified cosmetic that has unprecedented properties in that the coloring effect and color uniformity are improved by contact with moisture such as sweat, pool water, seawater, rain, etc. immediately after application. .
- Emulsified cosmetics containing coloring materials are applied to various makeup cosmetics and hair care cosmetics such as emulsified foundations, BB creams, body lotions, and white hair concealers.
- water-in-oil emulsified cosmetics have a continuous phase as an oil phase component, and leave an oil film that hardly permeates moisture on the skin surface.
- the outflow of coloring materials due to moisture such as sweat is still a problem, and research and development to prevent the occurrence of color fading, color unevenness, and dirt in severe usage conditions continues. Has been made.
- UV damage is one of the most important issues in skin care, body care, and hair care. Recently, it has been severe in outdoor activities such as swimming in the swimming pool, the sea, and winter skiing. It is considered that it is important to protect from ultraviolet rays not only in ultraviolet conditions but also in daily life. For this reason, what has the ultraviolet-ray protective effect is desired also in normal makeup cosmetics, hair care cosmetics, etc.
- UV absorbers and UV scatterers are also considered to have a problem of spillage due to contact with moisture.
- Various attempts have been made to improve the strength (Patent Document 1, Patent Document 2).
- Patent Document 1 Even if a resin or a film agent for imparting water resistance is highly blended, it is difficult to completely prevent the ultraviolet absorber, the ultraviolet scattering agent, and the like from flowing out.
- the present invention is an oil having an unprecedented innovative property that the coloring effect and color uniformity are not lowered by contact with moisture such as sweat, pool water, seawater, and rain, and the effect is improved.
- An object is to provide a water-in-water emulsified cosmetic.
- the present inventors have determined that the organically modified clay mineral and other oil phase thickeners have a predetermined mass ratio with respect to the nonvolatile liquid oil component excluding silicone oil.
- the uniformity of the film is higher than when applied to water or sweat, and the emulsified cosmetic having the above-mentioned novel characteristics is obtained. As a result, the present invention was completed.
- the present invention (A) Organically modified clay mineral, (B) (A) oil phase thickener other than the organically modified clay mineral, (C) Non-volatile liquid oil other than silicone oil, (D) a silicone-based surfactant having an HLB of less than 8, (E) A water-in-oil emulsified cosmetic containing a coloring material and having a weight ratio of [(A) + (B)] / (C) of 0.04 or more and less than 0.68 is provided. .
- the coloring effect and color uniformity after contact with moisture such as sweat, pool water, seawater, rain, etc. are more prominent than immediately after the cosmetic is applied to the skin or hair.
- the water-in-oil emulsified cosmetic according to the present invention has the conventional common sense that the color development effect and color uniformity are rather improved by contact with moisture, which has been the cause of effect deterioration in conventional cosmetics. Is an innovative cosmetic with the opposite characteristics.
- the cosmetic of the present invention exhibits an excellent coloring effect and UV protection effect without adding a high amount of resin or coating agent for imparting water resistance, it has no coating feeling and is in use (when applied) ), And can be easily removed with general-purpose cleaning agents and soap.
- the water-in-oil emulsified cosmetic of the present invention is (A) Organically modified clay mineral, (B) Oil phase thickener other than (A) organically modified clay mineral, (C) Nonvolatile liquid oil other than silicone oil, (D) Silicone interface with HLB less than 8. It contains an activator and (E) coloring material, and the weight ratio of [(A) + (B)] / (C) is 0.04 or more and less than 0.68.
- each component which comprises the emulsified cosmetics of this invention is explained in full detail.
- Organically modified clay mineral (hereinafter simply referred to as “component (A)”) is a kind of colloidal hydrous aluminum silicate having a three-layer structure, and is a clay mineral represented by the following general formula (1). Those modified with a quaternary ammonium salt type cationic surfactant can be used.
- component (A) is a kind of colloidal hydrous aluminum silicate having a three-layer structure, and is a clay mineral represented by the following general formula (1).
- Those modified with a quaternary ammonium salt type cationic surfactant can be used.
- natural or synthetic montmorillonite group such as montmorillonite, saponite, hectorite (in this case, (OH) group in the formula is replaced with fluorine)
- montmorillonite group such as montmorillonite, saponite, hectorite (in this case, (OH) group in the formula is replaced with fluorine)
- commercially available products include bee gum, kunipia, laponite, etc.
- clay minerals such as sodium silicic mica and synthetic mica known as sodium or lithium teniolite (commercially available is Dimonite: Topy Industries Co., Ltd.) with quaternary ammonium salt type cationic surfactant Is obtained.
- the quaternary ammonium salt type cationic surfactant used here is represented by the following general formula (2).
- R 1 is an alkyl group having 10 to 22 carbon atoms or benzyl group
- R 2 is a methyl group or alkyl group having 10 to 22 carbon atoms
- R 3 and R 4 are alkyl groups having 1 to 3 carbon atoms or hydroxy group
- X represents a halogen atom or a methyl sulfate residue.
- Examples of the quaternary ammonium salt type cationic surfactant include dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium.
- Chloride cetyldimethylethylammonium chloride, stearyldimethylethylammonium chloride, aralkyldimethylethylammonium chloride, behenyldimethylethylammonium chloride, myristyldiethylmethylammonium chloride, cetyldiethylmethylammonium chloride, stearyldiethylmethylammonium chloride, ara Rudiethylmethylammonium chloride, behenyldiethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride, benzylmethylethylcetylammonium chloride, benzylmethylethylstearylammonium chloride, benzyldi
- component (A) include dimethyl disteammonium hectorite (disteardimonium hectorite), dimethylalkylammonium hectorite, benzyldimethylstearylammonium hectorite, distearyldimethylammonium chloride-treated aluminum magnesium silicate. Etc. Of these, dimethyl disteammonium hectorite is particularly preferable. Benton 27 (benzyldimethylstearylammonium chloride-treated hectorite: manufactured by Elementis Japan) and Benton 38 (distearyldimethylammonium chloride-treated hectorite: manufactured by Elementis Japan) are preferable as commercial products. In this invention, the component applicable to (A) can be used 1 type or in combination of 2 or more types.
- Component (A) is blended in an amount of 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, more preferably 0.4 to 1% by weight, based on the total amount of the water-in-oil emulsified cosmetic. It is. When the blending amount of the component (A) is less than 0.1% by mass, sufficient stability is difficult to obtain, and when it exceeds 3% by mass, the viscosity becomes high and the elongation on the skin becomes heavy. It is not preferable.
- the oil phase thickener (hereinafter simply referred to as “component (B)”) is capable of adjusting the viscosity of the oil phase in addition to the component (A).
- Sucrose fatty acid esters, fatty acids solid at room temperature or salts thereof, vegetable hardened oils and the like are preferable, and it is particularly preferable to blend two or more selected from these.
- the dextrin fatty acid ester is an ester of dextrin or reduced dextrin and a higher fatty acid, and can be used without particular limitation as long as it is generally used in cosmetics. It is preferable to use dextrin or reduced dextrin having an average sugar polymerization degree of 3 to 100.
- the constituent fatty acid of the dextrin fatty acid ester it is preferable to use a saturated fatty acid having 8 to 22 carbon atoms.
- Specific examples include dextrin palmitate, dextrin oleate, dextrin stearate, dextrin myristate, dextrin (palmitic acid / 2-ethylhexanoic acid), and the like.
- sucrose fatty acid ester a linear or branched fatty acid saturated or unsaturated fatty acid having 12 to 22 carbon atoms can be preferably used. Specifically, sucrose caprylate, sucrose caprate, sucrose laurate, sucrose myristic ester, sucrose palmitate, sucrose stearate, sucrose oleate, sucrose elca An acid ester etc. can be mentioned.
- the fatty acid can be used at room temperature, and examples thereof include myristic acid, palmitic acid, stearic acid, and behenic acid.
- Examples of fatty acid salts include calcium salts, magnesium salts, aluminum salts, and the like.
- Plant hardened oils include palm kernel hardened oil, hardened castor oil, hydrogenated peanut oil, hydrogenated rapeseed seed oil, hydrogenated palm oil, hydrogenated camellia oil, hydrogenated soybean oil, hydrogenated olive oil, hydrogenated macadamia nut oil, Examples thereof include hydrogenated sunflower oil, hydrogenated wheat germ oil, hydrogenated rice germ oil, hydrogenated rice nutka oil, hydrogenated cottonseed oil, and hydrogenated avocado oil.
- Component (B) is blended in an amount of 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, more preferably 0.4 to 8% by weight, based on the total amount of the water-in-oil emulsified cosmetic. It is. When the blending amount of the component (B) is less than 0.1% by mass, sufficient stability is difficult to obtain, and when it exceeds 15% by mass, the viscosity becomes high and the elongation on the skin becomes heavy. It is not preferable.
- the cosmetic of the present invention is a water-in-oil emulsified cosmetic and always contains an oil component constituting the outer phase (continuous phase).
- the oil component in the present invention includes a non-volatile liquid oil component and may further include a volatile oil component.
- the “nonvolatile liquid oil” in the present specification does not show volatility at normal temperature (25 ° C.) and normal pressure (1 atm (9.8 ⁇ 10 4 Pa)) (for example, the boiling point at normal pressure is about 200 ° C. or more) means a liquid oil that is fluid at normal temperature and pressure and is not solid, and includes silicone oil and non-volatile oils (hydrocarbon oil, ester oil, etc.) other than silicone oil.
- a non-volatile liquid oil component other than silicone oil (hereinafter simply referred to as “component (C)”) is essential.
- the component (C) includes an oily ultraviolet absorber as described later. Accordingly, (C) the non-volatile liquid oil other than silicone oil may be entirely composed of an ultraviolet absorber. By blending an ultraviolet absorber, not only the coloring effect and color uniformity when in contact with moisture, but also an improvement in the ultraviolet protection effect can be expected.
- the non-volatile liquid oil other than the ultraviolet absorber contained in the component (C) includes, for example, hydrocarbon oil, vegetable oil, ester oil, high molecular weight polyoxyalkylene glycol, and the like.
- specific examples include linseed oil, camellia oil, macadamia nut oil, corn oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, kyounin oil, cinnamon oil, jojoba oil, grape oil, almond oil, rapeseed oil, Sesame oil, sunflower oil, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, tea seed oil, evening primrose oil, egg yolk oil, liver oil, triglycerin, glyceryl trioctanoate, glyceryl triisopalmitate, etc.
- Fatty acids liquid at normal temperature such as isostearic acid; Octanoic acid esters such as cetyl octanoate; Isooctanoic acid esters such as glyceryl tri-2-ethylhexanoate and pentaerythritol tetra-2-ethylhexanoate; Lauric acid Lauric acid esters such as hexyl, isopropyl myristate, myristic Myristic acid ester such as octyldodecyl acid, palmitic acid ester such as octyl palmitate, stearic acid ester such as isocetyl stearate, isostearic acid ester such as isopropyl isostearate, isopalmitic acid ester such as octyl isopalmitate, isodecyl oleate Oleic acid ester such as diisopropyl adipate, ester oil
- the liquid and oily ultraviolet absorber contained in the component (C) is not particularly limited, but specific examples thereof include ethylhexyl methoxycinnamate, octocrylene, polysilicon-15, homosalate, ethylhexyl salicylate and the like.
- An organic ultraviolet absorber can be mentioned.
- Solid ultraviolet absorbers such as hexyl diethylaminohydroxybenzoylbenzoate, bisethylhexyloxyphenol methoxyphenyltriazine, t-butylmethoxydibenzoylmethane, ethylhexyltriazone, oxybenzone-3, methylenebisbenzotriazolyltetramethylbutylphenol (C) Not included in the component.
- the blending amount of the component (C) is 3% by mass or more, more preferably 5 to 50% by mass, and more preferably 7 to 30% by mass with respect to the total amount of the water-in-oil emulsified cosmetic.
- the blending amount of the component (C) is out of the above range, the effect of the present invention cannot be achieved, and the emulsion stability and usability may be impaired.
- the cosmetic of the present invention preferably contains a volatile oil component as the oil component in addition to the component (C).
- volatile oil volatile hydrocarbon oil and volatile silicone oil can be blended, and it is particularly preferable to blend volatile silicone oil.
- the volatile hydrocarbon oil content is not particularly limited as long as it is a hydrocarbon oil having volatility at room temperature (25 ° C.) conventionally used in cosmetics and the like. Specific examples include isododecane, isohexadecane, hydrogenated polyisobutene, and the like.
- Volatile silicone oils include silicone oils that are volatile at room temperature and are conventionally used in cosmetics, such as volatile linear silicone oils (volatile dimethicone) and volatile cyclic silicone oils (volatile). Sex cyclomethicone).
- volatile dimethicone low-viscosity dimethylpolysiloxane such as decamethyltetrasiloxane can be used, and commercially available products are KF-96L-1.5cs and KF-96L-2cs (both manufactured by Shin-Etsu Chemical Co., Ltd.).
- Etc examples of volatile cyclomethicone include decamethylcyclopentasiloxane (D5).
- the blending amount of the volatile oil is not particularly limited, but is usually about 1 to 40% by mass with respect to the total amount of the water-in-oil emulsified cosmetic.
- the total amount of the components (A) and (B) involved in adjusting the viscosity of the oil phase has a predetermined weight ratio with respect to the total amount of the component (C).
- a silicone-based surfactant (hereinafter simply referred to as “component (D)”) is particularly limited as long as it has a silicone skeleton (polysiloxane structure) and has an HLB of less than 8.
- component (D) silicone-based surfactant
- polyoxyalkylene-modified silicone, polyoxyalkylene-alkyl co-modified silicone, polyglycerin-modified silicone, and / or polyglycerin-alkyl co-modified silicone are preferably used.
- Oxyalkylene alkyl-modified silicone is more preferable.
- the polyoxyalkylene-modified silicone used in the present invention has a linear or branched organopolysiloxane as a main skeleton and a polyoxyalkylene group in a side chain, and is represented by the following general formula (3), for example. Things.
- R is an alkyl group having 1 to 3 carbon atoms or a phenyl group (preferably methyl group)
- R ′ is hydrogen or an alkyl group having 1 to 12 carbon atoms (preferably hydrogen or methyl group)
- q Is 1 to 50 preferably 3
- m is 1 to 100
- n and x are 1 to 50
- y is 0 to 50, respectively.
- KF-6017 PEG-10 dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd.
- the organopolysiloxane main skeleton may have another organopolysiloxane chain in the side chain.
- a polyoxyalkylene-modified silicone is KF-6028 (PEG-9 polydimethylsiloxyethyl dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd.).
- the polyoxyalkylene / alkyl-modified silicone used in the present invention has a linear or branched organopolysiloxane as a main skeleton, a polyoxyalkylene group and an alkyl group having 4 or more carbon atoms in the side chain, For example, what is shown by following General formula (4) is mentioned.
- R is an alkyl group having 1 to 3 carbon atoms or a phenyl group (preferably methyl group)
- R ′ is hydrogen or an alkyl group having 1 to 12 carbon atoms (preferably hydrogen)
- p is 6 to 6 30 (preferably 10 to 18, particularly preferably 12 to 16)
- q is 1 to 50 (preferably 3)
- m is 1 to 100
- n, w and x are 1 to 50
- y is 0 to 50, respectively. is there.
- One suitable example of the polyoxyalkylene / alkyl co-modified silicone is ABIL EM90 (cetyl PEG / PPG-10 / 1 dimethicone, manufactured by Evonik Goldschmidt).
- the organopolysiloxane main skeleton may have another organopolysiloxane chain in the side chain.
- a polyoxyalkylene / alkyl-modified silicone is KF-6038 (lauryl PEG-9 polydimethylsiloxyethyl dimethicone, manufactured by Shin-Etsu Silicone).
- R 1 represents a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group
- R 2 represents an alkylene group having 2 to 11 carbon atoms
- p is 10 to 120.
- q is 1 to 11.
- Specific examples include bisbutyl dimethicone polyglyceryl-3 and the like.
- the polyglycerin / alkyl co-modified silicone has a linear or branched organopolysiloxane as a main skeleton, and has a polyglycerin group and an alkyl group having 4 or more carbon atoms in the side chain.
- Component (D) is blended in an amount of 0.1 to 8% by weight, more preferably 0.2 to 7% by weight, and more preferably 0.4 to 5% by weight, based on the total amount of the water-in-oil emulsified cosmetic. It is. When the blending amount of the component (D) is less than 0.1% by mass, sufficient stability is difficult to obtain, and when it exceeds 8% by mass, the viscosity becomes high and the elongation on the skin becomes heavy. It is not preferable.
- the (E) coloring material (hereinafter simply referred to as “(E) component”) blended in the water-in-oil emulsified cosmetic according to the present invention is usually blended in makeup cosmetics such as pigments and pearl pigments. Things can be used.
- inorganic white pigments titanium dioxide, zinc oxide
- inorganic red pigments iron oxide (bengara), iron titanate
- inorganic brown pigments ⁇ -iron oxide
- inorganic yellow pigments Yellow iron oxide, ocher
- inorganic black pigment black iron oxide, carbon, low-order titanium oxide
- inorganic purple pigment mango violet, cobalt violet
- inorganic green pigment chromium oxide, chromium hydroxide, titanic acid) Cobalt
- inorganic blue pigments ultraviolet, bitumen
- pearl pigments titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil
- metal powder pigments Alluminum powder, copper powder
- organic pigments red 202, red 205, red 220, red 228, red 405, orange 203
- zirconium bar
- 202 Green No. 3, Blue No. 1
- natural pigments chlororophyll, carcinoids ( ⁇ -carotene), calsamine, cochineal, chalcone, curcumin, betanin, flavonol, flavone, anthocyanidin, anthraquinone, naphthoquinone
- function 1 type or 2 or more types can be selected from the active pigments (boron nitride, photochromic pigment, synthetic fluorine phlogopite, iron-containing synthetic fluorine phlogopite, and fine particle composite powder (hybrid fine powder)).
- the invention is not limited to this.
- the weight average particle diameter is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less.
- a particulate colorant having a weight average particle diameter of 300 ⁇ m or less there is a tendency that the color development effect and the improvement in color uniformity when coming into contact with moisture become remarkable.
- the surface of the powdered colorant may be untreated or treated with an organosilane compound, silicone compound, fluorine compound, silane coupling agent, fluororesin, fatty acid, fatty acid soap, lauroyllysine, etc. You may use what gave.
- the color materials it is preferable to add a pearl pigment since the amount of diffuse reflection after the water bath is remarkably increased. There is a tendency that the glossiness of the skin increases as the amount of diffuse reflection light increases.
- the blending amount of the component (E) is 0.3% by mass or more, more preferably 0.5 to 20% by mass with respect to the total amount of the water-in-oil emulsified cosmetic. If the blending amount of the component (E) is less than 0.3% by mass, it is difficult to obtain a sufficient coloring effect, and even if blended in excess of 20% by mass, the stability is unfavorable.
- water-in-oil emulsified cosmetic of the present invention in addition to the above essential components, components usually used in cosmetics such as a whitening agent, a moisturizer, an antioxidant, an oily active agent, a surfactant, and a water phase increasing agent.
- a sticky agent, alcohol, spherical powder component, aqueous active agent and the like may be appropriately blended as necessary, and can be produced by a conventional method.
- spherical resin powder in an amount of about 1 to 30% by mass, since the usability can be further improved and a smooth and good feel can be obtained.
- the spherical resin powder can be arbitrarily used without particular limitation as long as it is blended with general cosmetics.
- the particle size of the spherical resin powder to be blended is not particularly limited, but for example, a particle size of about 1 to 50 ⁇ m is preferably used. Moreover, these resin powders may be hydrophobized.
- Examples of the commercially available spherical organic resin powder include Ganzpearl (manufactured by Aika Kogyo Co., Ltd.), and examples of the commercially available spherical silicone resin powder include Trefill E-505C, Trefil E-506C, Trefil E-506S, and Trefil.
- Examples include HP40T (above, Toray Dow Corning Silicone Co., Ltd.), Tospearl 145A (manufactured by Toshiba Silicone Co., Ltd.), silicone powder KSP-100, KSP-300 (Shin-Etsu Chemical Co., Ltd.), and the like.
- the water-in-oil emulsified cosmetic of the present invention can be used as a foundation, a makeup base, a makeup cosmetic, a hair cosmetic, etc., optionally having a sunscreen effect.
- the present invention will be described in more detail with specific examples, but the present invention is not limited to the following examples.
- the compounding quantity in a following example etc. shows the mass% unless there is particular notice.
- an ultraviolet protective agent was blended in place of the coloring material of the present invention (component (E)) in order to examine the change in the effect of the blended component due to contact with moisture through the ultraviolet protective effect.
- the change in color development was directly examined from the amount of diffuse reflection before and after the water bath or the color difference.
- Diffuse reflected light increase rate (%) (diffuse reflected light amount after bathing) / (diffuse reflected light amount before bathing) ⁇ 100
- Color difference ⁇ E [( before L water bath ⁇ after L water bath ) 2 + ( before a water bath ⁇ after a water bath ) 2 + ( before b water bath ⁇ after b water bath ) 2 ] 1/2
- the color difference ⁇ E before and after the water bath was determined by the same method as the in vitro condition except that the sample was directly applied to the skin under the in vivo condition.
- Formulation Example 1 BB cream (ingredient name) Purified water Residual decamethyltetrasiloxane 20 Trimethylsiloxysilicic acid 10 PEG-9 Polydimethylsiloxyethyl dimethicone 1 Bisbutyl dimethicone polyglyceryl-3 1 Isostearic acid 1 Ethyl hexyl methoxycinnamate 5 Isopropyl myristate 3 Dextrin palmitate 2 Titanium oxide 24 n-octylsilylated black iron oxide 0.5 n-Octylsilylated yellow iron oxide 1 n-Octylsilylated Bengala 1 Mica titanium 3 Black iron oxide coated mica titanium 1 Polymethyl methacrylate 5 Methylsiloxane network polymer 2 Disteadimonium hectorite 1 Edetate trisodium 0.3 Sorbitol 1 Alcohol 10
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Abstract
Description
(A)有機変性粘土鉱物、
(B)上記(A)有機変性粘土鉱物以外の油相増粘剤、
(C)シリコーン油以外の不揮発性液状油分、
(D)HLBが8未満のシリコーン系界面活性剤、
(E)色材
を含有し、[(A)+(B)]/(C)の重量比が0.04以上0.68未満である、油中水型乳化化粧料を提供するものである。
(A)有機変性粘土鉱物、(B)前記(A)有機変性粘土鉱物以外の油相増粘剤、(C)シリコーン油以外の不揮発性液状油分、(D)HLBが8未満のシリコーン系界面活性剤、(E)色材を含有し、[(A)+(B)]/(C)の重量比が0.04以上0.68未満であることを特徴としている。以下、本発明の乳化化粧料を構成する各成分について詳述する。
(A)有機変性粘土鉱物(以下、単に「(A)成分」と称する)は、三層構造を有するコロイド性含水ケイ酸アルミニウムの一種で、下記一般式(1)で表される粘土鉱物を第四級アンモニウム塩型カチオン界面活性剤で変性したものを使用することができる。
(X,Y)2―3(Si,Al)4O10(OH)2Z1/3・nH2O (1)
(但し、X=Al,Fe(III),Mn(III),Cr(III)、Y=Mg,Fe(II),Ni,Zn,Li、Z=K,Na,Ca)
本発明では、(A)に該当する成分を1種又は2種以上を組み合わせて用いることができる。
(B)油相増粘剤(以下、単に「(B)成分」と称する)は、前記(A)成分以外に油相の粘度を調整することができるものであり、例えば、デキストリン脂肪酸エステル、ショ糖脂肪酸エステル、あるいは常温で固形の脂肪酸又はその塩、植物性硬化油等が好ましく、これらから選択される二種以上を配合するのが特に好ましい。
デキストリン脂肪酸エステルは、デキストリンまたは還元デキストリンと高級脂肪酸とのエステルであり、化粧料に一般的に使用されているものであれば特に制限されず使用することができる。デキストリンまたは還元デキストリンは平均糖重合度が3~100のものを用いるのが好ましい。また、デキストリン脂肪酸エステルの構成脂肪酸としては、炭素数8~22の飽和脂肪酸を用いるのが好ましい。具体的には、パルミチン酸デキストリン、オレイン酸デキストリン、ステアリン酸デキストリン、ミリスチン酸デキストリン、(パルミチン酸/2-エチルヘキサン酸)デキストリン等を挙げることができる。
本発明の化粧料は油中水型乳化化粧料であり、外相(連続相)を構成する油分を必ず含有している。本発明における油分は不揮発性液状油分を含み、さらに揮発性油分を含んでいてもよい。
本明細書における「不揮発性液状油分」とは、常温(25℃)・常圧(1気圧(9.8×104Pa))で揮発性を示さず(例えば、常圧での沸点が約200℃以上)、常温・常圧で流動性を有し、固形でない液状の油分を意味し、シリコーン油及びシリコーン油以外の不揮発性油(炭化水素油、エステル油等)を包含する。
本発明においては、シリコーン油以外の不揮発性液状油分(以下、単に「(C)成分」と称する)を必須に含有する。この(C)成分には、後述するように油性の紫外線吸収剤も含まれる。従って、(C)シリコーン油以外の不揮発性液状油分が全て紫外線吸収剤からなる場合もある。紫外線吸収剤を配合することにより、水分と接触した際に発色効果や色の均一性だけでなく、紫外線防御効果の向上も期待できる。
具体例としては、アマニ油、ツバキ油、マカデミアナッツ油、トウモロコシ油、オリーブ油、アボカド油、サザンカ油、ヒマシ油、サフラワー油、キョウニン油、シナモン油、ホホバ油、ブドウ油、アルモンド油、ナタネ油、ゴマ油、ヒマワリ油、小麦胚芽油、米胚芽油、米ヌカ油、綿実油、大豆油、落花生油、茶実油、月見草油、卵黄油、肝油、トリグリセリン、トリオクタン酸グリセリル、トリイソパルミチン酸グリセリル等の液状油脂;イソステアリン酸等の常温で液状の脂肪酸;オクタン酸セチル等のオクタン酸エステル、トリ-2-エチルヘキサン酸グリセリル、テトラ-2-エチルヘキサン酸ペンタエリスリット等のイソオクタン酸エステル、ラウリン酸ヘキシル等のラウリン酸エステル、ミリスチン酸イソプロピル、ミリスチン酸オクチルドデシル等のミリスチン酸エステル、パルミチン酸オクチル等のパルミチン酸エステル、ステアリン酸イソセチル等のステアリン酸エステル、イソステアリン酸イソプロピル等のイソステアリン酸エステル、イソパルミチン酸オクチル等のイソパルミチン酸エステル、オレイン酸イソデシル等のオレイン酸エステル、アジピン酸ジイソプロピル等のアジピン酸ジエステル、セバシン酸ジエチル、セバシン酸ジイソプロピル等のセバシン酸ジエステル、リンゴ酸ジイソステアリル等のエステル油;流動パラフィン、スクワラン等の炭化水素油;ポリオキシブチレンポリオキシプロピレングリコール等が挙げられる。
なお、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル、ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジン、t-ブチルメトキシジベンゾイルメタン、エチルヘキシルトリアゾン、オキシベンゾン-3、メチレンビスベンゾトリアゾリルテトラメチルブチルフェノール等の固形の紫外線吸収剤は(C)成分に含まれない。
揮発性炭化水素油分は、従来から化粧料等に使用されている常温(25℃)で揮発性を有する炭化水素油であれば特に限定されない。具体例としては、イソドデカン、イソヘキサデカン、水添ポリイソブテン等を挙げることができる。
本発明に係る油中水型乳化化粧料では、油相の粘度調節に関わる前記(A)及び(B)成分の合計量が、(C)成分の合計量に対して、所定の重量比を有することを必要とする。
即ち、[(A)+(B)]/(C)の重量比が、0.04以上0.68未満であることを必須とし、さらにこの比率が0.045以上0.5未満であることがより好ましい。当該比率が0.04未満又は0.68以上では、水分との接触による発色効果及び色の均一性の向上が見られなくなる。
(D)シリコーン系界面活性剤(以下、単に「(D)成分」と称する)は、シリコーン骨格(ポリシロキサン構造)を有し、HLBが8未満の界面活性剤であれば特に限定されるものではなく、例えば、ポリオキシアルキレン変性シリコーン、ポリオキシアルキレン・アルキル共変性シリコーン、ポリグリセリン変性シリコーン、及び/又はポリグリセリン・アルキル共変性シリコーンの使用が好ましく、なかでも、ポリオキシアルキレン変性シリコーン、ポリオキシアルキレン・アルキル変性シリコーンがより好ましい。
本発明において用いられるポリオキシアルキレン変性シリコーンは、直鎖又は分岐鎖のオルガノポリシロキサンを主骨格として、側鎖にポリオキシアルキレン基を有するものであり、例えば、下記一般式(3)で示されるものが挙げられる。
ポリグリセリン・アルキル共変性シリコーンは、直鎖又は分岐鎖のオルガノポリシロキサンを主骨格として、側鎖にポリグリセリン基と炭素数4以上のアルキル基とを有するものであり、KF-6105(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、信越化学工業(株)社製)が挙げられる。
本発明に係る油中水型乳化化粧料に配合される(E)色材(以下、単に「(E)成分」と称する)は、顔料、パール顔料等の、メーキャップ化粧料に通常配合されるものを使用することができる。
粉末状の色材は表面未処理のものを用いてもよく、また、オルガノシラン系化合物、シリコーン化合物、フッ素化合物、シランカップリング剤、フッ素樹脂、脂肪酸、脂肪酸セッケン、ラウロイルリジン等により表面処理を施したものを用いてもよい。
製造例1~38では、水分との接触による配合成分の効果の変化を紫外線防御効果を介して調べるために、本発明の色材((E)成分)の代わりに紫外線防御剤を配合した。一方、(E)成分を含む製造例39~59では、水浴前後の拡散反射光量又は色差から発色の変化を直接調べた。
下記の表1に掲げた組成を有する油中水型乳化化粧料を、油性成分を加温して溶解し粉末を分散させたものに、別途溶かした水相を添加し、攪拌処理にて乳化することにより調製した。
測定プレート(Sプレート)(5×5cmのV溝PMMA板、SPFMASTER-PA01)に各例の化粧料(サンプル)を2mg/cm2の量で滴下し、60秒間指で塗布し、15分間乾燥した後、その吸光度を株式会社日立製作所社製U-3500型自記録分光光度計にて測定した。無塗布のSプレートをコントロールとし、吸光度(Abs)を以下の式で算出した。
Abs=-log(T/To)
T:サンプルの透過率、To:無塗布のSプレートの透過率
測定したプレートを硬度50~500の水に十分に浸し、30分間そのまま水中で撹拌した(3-1モーターで300rpm)。その後、表面の水滴がなくなるまで15~30分程度乾燥させ、再び吸光度を測定し、水浴前後のAbs積算値からAbs変化率(以下の式)を紫外線防御能向上効果として算出した。
紫外線防御能向上効果:
Abs変化率(%)=(水浴後のAbs積算値)/(水浴前のAbs積算値)×100
下記の表2に掲げた組成を有する油中水型乳化化粧料を調製し、上記と同様に水浴前後の吸光度変化率を求めた。
表1及び表2の結果から、[(A)+(B)]/(C)の重量比を本発明に規定する範囲に制御することにより、配合成分(紫外線防御剤)の効果が水浴によって高まったことがわかる。この吸光度の増加は塗布膜が汗や水で失われず、塗布膜の均一性が向上したことを示している。
下記の表5及び表6に掲げた組成を有する油中水型乳化化粧料を調製し、上記と同様に水浴前後の吸光度変化率を求めた。
下記の表7に掲げた組成を有する油中水型乳化化粧料を調製し、上記と同様に水浴前後の吸光度変化率を求めた。
下記の表8及び表9に掲げた組成を有するメーキャップ化粧料を、油性成分を加温して溶解し粉末成分を分散させたものに、別途溶かした水相を添加し、攪拌処理にて乳化することにより調製した。
バイオスキン♯420(顔料0.5g)に塗布量2mg/cm2で試料を塗布し、SAMBA Hair System(ボサノヴァテクノロジー社)を用いて水浴前の拡散反射光量(積算値)を測定した。次いで、水道水に20分間浸した後に、表面の水滴がなくなるまで15~30分程度乾燥させ、水浴後の拡散反射光量(積算値)を測定した。水浴前後の拡散反射光量から以下の式により水浴による拡散反射光増加率を求めた。
拡散反射光増加率(%)=(水浴後の拡散反射光量)/(水浴前の拡散反射光量)×100
これに対し、[(A)+(B)]/(C)の重量比が0.04以上0.68未満を満たす化粧料(製造例40~50)では、水浴後でも拡散反射光量に変化がないか、むしろ増加が確認された。特に、色材((E)成分)としてパール顔料を配合した場合には、いずれも水浴により拡散反射光量が増加した(製造例41~50)。
下記の表10に掲げた組成を有するメーキャップ化粧料を調製し、in vitro条件又はin vivo条件で水浴前後の色差ΔEを測定した。
in vitro条件ではバイオスキン♯420(顔料0.5g)に塗布量2mg/cm2で試料を塗布し、非接触画像色彩計を用いて、水浴前のL値a値b値及び水浴後のL値a値b値を測定した。水浴前後の測定値から以下の式により水浴前後の色差ΔEを求めた。
色差ΔE=[(L水浴前-L水浴後)2+(a水浴前-a水浴後) 2+(b水浴前-b水浴後)2]1/2
一方、in vivo条件では肌に直接試料を塗布したこと以外は、in vitro条件と同じ方法で水浴前後の色差ΔEを求めた。
これに対し、[(A)+(B)]/(C)の重量比が0.04以上0.68未満を満たす化粧料(製造例52~54及び56)では、水浴前後の色差ΔEが小さかった。
下記の表11に掲げた組成を有するワンデータイプの白髪染め化粧料を調製した。白髪ストランドを試料で染色し、非接触画像色彩計を用いて水浴前後のa値及びb値を調べた。さらに、見た目の発色効果及び色の均一性を水浴前と比較した。
評価基準
A:水浴前より向上が感じられた。
B:水浴前と比べて僅かに劣化していることが感じられた。
C:水浴前よりも明らかに劣化していることが感じられた。
(成分名) 配合量(質量%)
精製水 残余
デカメチルテトラシロキサン 20
トリメチルシロキシケイ酸 10
PEG-9 ポリジメチルシロキシエチルジメチコン 1
ビスブチルジメチコンポリグリセリル-3 1
イソステアリン酸 1
メトキシケイヒ酸エチルヘキシル 5
ミリスチン酸イソプロピル 3
パルミチン酸デキストリン 2
酸化チタン 24
n-オクチルシリル化黒酸化鉄 0.5
n-オクチルシリル化黄酸化鉄 1
n-オクチルシリル化ベンガラ 1
雲母チタン 3
黒酸化鉄被覆雲母チタン 1
ポリメタクリル酸メチル 5
メチルシロキサン網状重合体 2
ジステアルジモニウムヘクトライト 1
エデト酸3ナトリウム 0.3
ソルビトール 1
アルコール 10
(成分名) 配合量(質量%)
精製水 残余
デカメチルテトラシロキサン 10
トリメチルシロキシケイ酸 3
ラウリルPEG-9ポリジメチルシロキシエチルジメチコン 5
イソステアリン酸 1
メトキシケイヒ酸エチルヘキシル 8
ホモサレート 5
サリチル酸オクチル 3
4-tert-ブチル-4’-メトキシジベンゾイルメタン 2
ミリスチン酸イソプロピル 3
パルミチン酸デキストリン 2
パーム硬化油 2
雲母チタン 2
黒酸化鉄被覆雲母チタン 1
ポリメタクリル酸メチル 3
メチルシロキサン網状重合体 2
ジステアルジモニウムヘクトライト 0.3
エデト酸3ナトリウム 0.3
グリセリン 1
アルコール 10
Claims (8)
- (A)有機変性粘土鉱物、
(B)上記(A)有機変性粘土鉱物以外の油相増粘剤、
(C)シリコーン油以外の不揮発性液状油分、
(D)HLBが8未満のシリコーン系界面活性剤、
(E)色材
を含有し、[(A)+(B)]/(C)の重量比が0.04以上0.68未満である、油中水型乳化化粧料。 - (B)油相増粘剤が、パルミチン酸デキストリン、ショ糖脂肪酸エステル、(パルミチン酸/2-エチルヘキサン酸)デキストリン、常温で固形の脂肪酸及び植物性硬化油から選択される1種以上である、請求項1に記載の油中水型乳化化粧料。
- (A)有機変性粘土鉱物がジメチルジステアルアンモニウムヘクトライトである、請求項1又は2記載の油中水型乳化化粧料。
- (C)シリコーン油以外の不揮発性液状油分の配合量が3質量%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。
- (A)有機変性粘土鉱物に該当する成分及び(B)油相増粘剤に該当する成分を、合わせて3種以上含有する、請求項1~4のいずれか一項に記載の油中水型乳化化粧料。
- (E)色材の配合量が0.3質量%以上である、請求項1~5のいずれか一項に記載の油中水型乳化化粧料。
- (E)色材が粒子状である場合の色材の重量平均粒子径が300μm以下である、請求項1~6のいずれか一項に記載の油中水型乳化化粧料。
- (C)シリコーン油以外の不揮発性液状油分が紫外線吸収剤を含む、請求項1~7のいずれか一項に記載の油中水型乳化化粧料。
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EP3449902A1 (en) | 2019-03-06 |
US20190117531A1 (en) | 2019-04-25 |
HK1258071A1 (zh) | 2019-11-01 |
CN109069394B (zh) | 2021-08-24 |
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JP7021077B2 (ja) | 2022-02-16 |
TWI757283B (zh) | 2022-03-11 |
CN109069394A (zh) | 2018-12-21 |
JPWO2017187977A1 (ja) | 2019-02-28 |
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