Water-in-oil emulsion cosmetic

Abstract

To provide a water-in-oil emulsion cosmetic that is less prone to a deterioration of viscosity over time, while maintaining a good feeling of use.SOLUTION: A water-in-oil emulsion cosmetic contains the following (A)-(F), with the content of (A) being 0.2 mass% or more and 0.8 mass% or less relative to the whole. (A) Organic modified clay mineral, (B) particulate metal oxide, (C) polyether-modified silicone, (D) polyglycerol-modified silicone, (E) C12-22 hydroxy fatty acid and (F) cyclic silicone.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to water-in-oil emulsified cosmetics, particularly sunscreen cosmetics.

Background Art

[0002] Since the external phase of water-in-oil emulsified cosmetics is an oil phase, there may be a feeling of stickiness peculiar to oil. In order to provide a refreshing and non-sticky feeling in use for water-in-oil emulsified cosmetics and also to improve the makeup retention, silicone oil is blended in the oil phase. However, since silicone oil has poor compatibility with other general cosmetic oil agents such as hydrocarbons and ester oils, it is difficult to emulsify uniformly. In order to supplement the stability of water-in-oil emulsified cosmetics, organically modified clay minerals are used as thickeners for the oil phase. However, when a large amount of silicone oil is blended in the oil phase, the thickening effect of the organically modified clay mineral cannot be efficiently exerted, and problems may occur in the temporal stability such as a decrease in viscosity and phase separation.

[0003] Patent Document 1 proposes a water-in-oil emulsified cosmetic containing an organically modified clay mineral and a dextrin fatty acid ester, in which the temporal viscosity decrease is suppressed by blending di (caprylic acid / capric acid) propanediol, caprylyl methicone, and silicone resin-coated silicone rubber spherical powder.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a water-in-oil emulsified cosmetic that suppresses a decrease in viscosity over time while maintaining the feeling in use.

Means for Solving the Problem

[0006] The means for solving the problems of the present invention are as follows. 1. An oil-in-water type emulsified cosmetic containing the following (A) to (F) and containing (A) in an amount of 0.2% by mass or more and 0.8% by mass or less based on the whole. (A) Organically modified clay mineral (B) Fine particle metal oxide (C) Polyether-modified silicone (D) Polyglycerin-modified silicone (E) Hydroxy fatty acid having 12 to 22 carbon atoms (F) Cyclic silicone 2. The oil-in-water type emulsified cosmetic according to 1., wherein the (B) fine particle metal oxide contains titanium oxide or zinc oxide. 3. The oil-in-water type emulsified cosmetic according to 1. or 2., wherein the (C) polyether-modified silicone contains PEG-10 dimethicone or PEG-9 polydimethylsiloxyethyldimethylsilicone. 4. The oil-in-water type emulsified cosmetic according to any one of 1. to 3., wherein the (D) polyglycerin-modified silicone contains polyglyceryl-3 polydimethylsiloxyethyldimethylsilicone or lauryl polyglyceryl-3 polydimethylsiloxyethyldimethylsilicone. 5. The oil-in-water type emulsified cosmetic according to any one of 1. to 4., wherein the ratio of the aqueous phase based on the whole is 40% by mass or more. 6. A sunscreen cosmetic comprising the oil-in-water type emulsified cosmetic according to any one of 1. to 5.

Advantages of the Invention

[0007] The oil-in-water type emulsified cosmetic of the present invention has a small viscosity decrease over time, is excellent in stability, and hardly causes phase separation, precipitation, etc. The oil-in-water type emulsified cosmetic of the present invention provides a unique feeling of use having a refreshing feeling derived from silicone oil and a feeling of collapse derived from an organically modified clay mineral.

Modes for Carrying Out the Invention

[0008] The present invention relates to a water-in-oil emulsion cosmetic containing the following (A) to (F) and containing (A) in an amount of 0.2% by mass or more and 0.8% by mass or less based on the whole. (A) Organically modified clay mineral (B) Fine particle metal oxide (C) Polyether-modified silicone (D) Polyglycerin-modified silicone (E) Hydroxy fatty acid having 12 to 22 carbon atoms (F) Cyclic silicone

[0009] (A) Organically modified clay mineral Smectite, which is a swelling layered silicate, is a cationic clay mineral. What is obtained by substituting the cation of smectite with an organic cation such as a quaternary ammonium salt is an organically modified clay mineral. Examples of the mineral contained in smectite include hectorite, montmorillonite, bentonite, saponite, beidellite, nontronite, stibnite, vermiculite, volkonskoite, soconite, magadite, kenyaite, and the like. Examples of the organic cation include dimethyldistearylammonium chloride, dimethyldipalmitylammonium chloride, stearylbenzyldimethylammonium chloride, stearyltrimethylammonium chloride, lauryldimethylaminoacetic acid betaine, and the like. Examples of the organically modified clay mineral include disteardimonium hectorite, stearalconium hectorite, stearalconium bentonite, and the like.

[0010] The water-in-oil emulsion cosmetic of the present invention contains (A) an organically modified clay mineral in an amount of 0.2% by mass or more and 0.8% by mass or less based on the whole. If the blending amount of the organically modified clay mineral is less than 0.2% by mass, it may be difficult to maintain stability. If it exceeds 0.8% by mass, the resulting emulsion cosmetic may become sticky. The blending amount of the organically modified clay mineral is more preferably 0.25% by mass or more, even more preferably 0.3% by mass or more, and still more preferably 0.33% by mass or more with respect to the water-in-oil emulsion cosmetic. Also, this blending amount is more preferably 0.75% by mass or less, even more preferably 0.7% by mass or less, and still more preferably 0.68% by mass or less.

[0011] (B) Fine particle metal oxide The fine particle metal oxide is fine particles of a metal oxide such as titanium oxide, zinc oxide, cerium oxide, and iron oxide. In order to reduce the surface activity of the fine particle metal oxide, those having a surface coated with silica, aluminum hydroxide, etc. can also be used. In order to improve the dispersibility in the oily component, those having a part or all of the surface treated with a hydrophobizing agent can also be used. Also, those previously dispersed in an oil agent such as cyclopentasiloxane can be used. By blending the fine particle metal oxide, an ultraviolet shielding effect, a coloring effect, etc. can be imparted to the water-in-oil emulsion cosmetic of the present invention. Since the water-in-oil emulsion cosmetic of the present invention has an ultraviolet shielding effect by this (B) fine particle metal oxide, it can be suitably used as a sunscreen cosmetic.

[0012] As the fine particle metal oxide, various particle sizes and shapes that are available can be selected according to the purpose. For example, in the case of titanium oxide, those having shapes such as granular, needle-like, spindle-like, plate-like, and flaky can be used. In the case of zinc oxide, those having a spherical or plate-like hexagonal crystal system can be used. In the case of cerium oxide, spherical ones can be appropriately used. Also, those having different particle sizes and shapes of the same substance can be used in combination, or two or more substances can be arbitrarily combined and used. The fine particle metal oxide having an average particle diameter (median diameter) of the primary particles of 1 nm to 100 nm, more preferably 5 to 50 nm, is preferably used. When the average particle diameter of the primary particles of the fine particle metal oxide exceeds 100 nm, the scattering of the particles with respect to visible light increases, so that the transmittance of visible light, that is, the transparency decreases.

[0013] The blending amount of the (B) fine particle metal oxide in the water-in-oil emulsion cosmetic of the present invention may be appropriately set based on the type of the fine particle metal oxide, the desired ultraviolet shielding property, etc., and is not particularly limited. For example, it can be 1% by mass or more and 30% by mass or less with respect to the whole water-in-oil emulsion cosmetic, preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less.

[0014] (C) Polyether-modified silicone The polyether-modified silicone has a polyether chain as a side chain in the silicone chain of the main chain. It may contain an alkyl chain or a silicone chain in addition to the polyether chain as a side chain. Examples of the polyether-modified silicone include PEG-9 dimethicone, PEG-10 dimethicone, PEG-12 dimethicone, PEG-10 methyl ether dimethicone, PEG-11 methyl ether dimethicone, cetyl PEG / PPG-10 / 1 dimethicone, PEG / PPG-20 / 22 butyl ether dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, etc. One or more of these can be used in combination. Among these, it is preferable to use either or both of PEG-10 dimethicone and PEG-9 polydimethylsiloxyethyl dimethicone.

[0015] The blending amount of the (C) polyether-modified silicone in the water-in-oil emulsion cosmetic of the present invention is not particularly limited, but for example, it can be 0.1% by mass or more and 5% by mass or less based on the whole water-in-oil emulsion cosmetic. This blending amount is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 4.5% by mass or less, more preferably 4% by mass or less.

[0016] (D) Polyglycerin-modified silicone The polyglycerin-modified silicone has a structure in which a polyglycerin chain is introduced into a silicone chain. The silicone chain may be linear or branched, and may also be a partially crosslinked type in which the silicone chain is crosslinked with a polyglycerin chain. Examples of the polyglycerin-modified silicone include polyglyceryl-3 disiloxane dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, cetyl diglyceryl tris(trimethylsiloxy)silylethyl dimethicone, (lauryl dimethicone / polyglycerin-3) copolymer, (polyglyceryl-3 / lauryl polydimethylsiloxyethyl dimethicone) copolymer, etc., and one or more of these can be used in combination. Among these, it is preferable to use either or both of polyglyceryl-3 polydimethylsiloxyethyl dimethicone and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone.

[0017] The blending amount of the (D) polyglycerin-modified silicone in the water-in-oil emulsion cosmetic of the present invention is not particularly limited, but for example, it can be 0.01% by mass or more and 2% by mass or less based on the whole water-in-oil emulsion cosmetic, preferably 0.1% by mass or more, and preferably 1.5% by mass or less.

[0018] (E) Hydroxy fatty acid having 12 to 22 carbon atoms C12-22 hydroxy fatty acids refer to fatty acids with 12-22 carbon atoms and at least one hydroxyl group in the molecule, and their polymers (polyhydroxy fatty acids). The fatty acids may have 12-22 carbon atoms, be linear or branched, and be saturated or unsaturated. Examples of C12-22 hydroxy fatty acids include hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxybehenic acid, polyhydroxystearic acid, etc., and one or more of these can be used in combination. Fatty acids preferably have 14-22 carbon atoms, more preferably 16-20 carbon atoms, and even more preferably 18 carbon atoms. Among these, it is particularly preferable to use polyhydroxystearic acid.

[0019] The blending amount of (E) C12-22 hydroxy fatty acids in the water-in-oil emulsion cosmetic of the present invention is not particularly limited, but for example, it can be 0.01% by mass or more and 2% by mass or less based on the total amount of the water-in-oil emulsion cosmetic, preferably 0.1% by mass or more, and preferably 1.5% by mass or less.

[0020] (F) Cyclic silicone Examples of cyclic silicones include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc., and one or more of these can be used in combination.

[0021] The blending amount of (F) cyclic silicone in the water-in-oil emulsion cosmetic of the present invention is not particularly limited, but for example, it can be 10% by mass or more and 30% by mass or less based on the total amount of the water-in-oil emulsion cosmetic, preferably 15% by mass or more, and preferably 28% by mass or less.

[0022] · Aqueous phase The water-in-oil type emulsified cosmetic of the present invention has an aqueous phase component. The aqueous phase component includes water or an aqueous solvent compatible with water and water-soluble components dissolved therein. Specifically, in addition to water, examples of the aqueous solution include those containing ethanol, butylene glycol, pentylene glycol, glycerin, sorbitol, phenoxyethanol, sodium chloride, and the like. The aqueous phase component is preferably 40% by mass or more, more preferably 42% by mass or more, and even more preferably 45% by mass or more, based on the total amount of the water-in-oil type emulsified cosmetic. Also, the aqueous phase component is preferably 60% by mass or less, more preferably 58% by mass or less, and even more preferably 55% by mass or less, based on the total amount of the water-in-oil type emulsified cosmetic.

[0023] In the water-in-oil type emulsified cosmetic of the present invention, the total blending amount of (C), (D), and (E) is preferably 1% by mass or more and 6% by mass or less, more preferably 2% by mass or more, and even more preferably 5% by mass or less, based on the whole of the water-in-oil type emulsified cosmetic. Also, in the water-in-oil type emulsified cosmetic of the present invention, the ratio of (A) the organically modified clay mineral to the total of (C) to (E) is preferably 5% by mass or more and 20% by mass or less, more preferably 8% by mass or more, and even more preferably 15% by mass or less.

[0024] In addition to the above, the water-in-oil type emulsified cosmetic of the present invention can contain fats and oils such as ester oils and vegetable oils, hydrocarbons, higher fatty acids, higher alcohols, silicone oils, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, polyhydric alcohols, saccharides, sugar alcohols, water-soluble polymers, oil-soluble thickeners, preservatives, sequestering agents, ultraviolet absorbers, humectants such as hyaluronic acid, fragrances, pH adjusters, and the like. Also, other medicinal components and physiologically active components such as vitamins, skin activators, blood circulation promoters, active oxygen scavengers, anti-inflammatory agents, whitening agents, bactericides, and the like can be contained.

[0025] Examples of ester oils include octyldodecyl stearoyloxystearate, cetyl 2-ethylhexanoate, 1,3-butylene glycol diisononanoate, 1,3-butylene glycol di(2-ethylhexanoate), dipropylene glycol diisononanoate, dipropylene glycol di(2-ethylhexanoate), isononyl isononanoate, glyceryl tri(2-ethylhexanoate), glyceryl tricaprylate, glyceryl triisostearate, neopentyl glycol dicaprylate, and the like. Examples of fats and oils include liquid fats and oils such as camellia oil, evening primrose oil, macadamia nut oil, olive oil, rapeseed oil, corn oil, sesame oil, jojoba oil, germ oil, and wheat germ oil; solid fats and oils such as cocoa butter, coconut oil, hydrogenated coconut oil, palm oil, palm kernel oil, candelilla wax, candelilla wax kernel oil, hydrogenated oil, and hydrogenated castor oil; and waxes such as beeswax, candelilla wax, cotton wax, rice bran wax, lanolin, lanolin acetate, liquid lanolin, and sugarcane wax.

[0026] Examples of hydrocarbons include liquid paraffin, squalene, squalane, microcrystalline wax, and the like. Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), and the like. Examples of higher alcohols include straight-chain alcohols such as lauryl alcohol, stearyl alcohol, cetyl alcohol, and cetostearyl alcohol; and branched-chain alcohols such as monostearyl glycerin ether, lanolin alcohol, cholesterol, phytosterol, and octyldodecanol. Examples of silicone oils include chain polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane.

[0027] Examples of anionic surfactants include fatty acid salts such as sodium laurate, higher alkyl sulfate ester salts such as sodium lauryl sulfate, alkyl ether sulfate ester salts such as triethanolamine POE lauryl sulfate, N-acyl sarcosinic acid, sulfosuccinate salts, N-acyl amino acid salts, and the like. Examples of cationic surfactants include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, benzalkonium chloride, benzetonium chloride, and the like. Examples of amphoteric surfactants include betaine-based surfactants such as alkyl betaine and amide betaine. Examples of nonionic surfactants include polyglycerol fatty acid esters such as polyglyceryl-2 triisostearate, sorbitan fatty acid esters such as sorbitan monooleate, and hydrogenated castor oil derivatives.

[0028] Examples of polyhydric alcohols include glycerin, 1,3-butylene glycol, 1,2-pentanediol, propylene glycol, dipropylene glycol, isoprene glycol, polyethylene glycol, and the like. Examples of saccharides and sugar alcohols include glucose, fructose, sorbitol, maltitol, erythritol, trehalose, sucrose, xylitol, maltose, lactose, and the like. Examples of water-soluble polymers include gum arabic, tragacanth gum, galactan, guar gum, carrageenan, pectin, agar, quince seed, dextran, pullulan, carboxymethyl starch, collagen, casein, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium carboxymethyl cellulose, sodium alginate, carboxyvinyl polymer, and the like. Examples of oil-soluble thickeners include glyceryl eicosanedioate behenate, fatty acid dextrin ester, silicone cross-linked products, and the like.

[0029] Examples of the preservative include methyl paraben, ethyl paraben, phenoxyethanol, etc. Examples of the sequestering agent include edetate salts such as disodium ethylenediaminetetraacetate, edetic acid, and sodium edetate. Examples of the ultraviolet absorber include para - aminobenzoic acid, phenyl salicylate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, 2,4 - dihydroxybenzophenone, etc. However, in order to enhance safety, it is preferable not to incorporate an ultraviolet absorber. Examples of the humectant include polyethylene glycol, propylene glycol, dipropylene glycol, 1,3 - butylene glycol, 1,2 - pentanediol, glycerin, diglycerin, polyglycerin, xylitol, maltitol, maltose, sorbitol, glucose, fructose, sodium chondroitin sulfate, sodium hyaluronate, sodium lactate, pyrrolidone carboxylic acid, cyclodextrin, etc.

[0030] Examples of the active ingredient include vitamins such as vitamin A oil, vitamin A derivatives such as retinol, vitamin B2 derivatives such as riboflavin, B6 derivatives such as pyridoxine hydrochloride, vitamin C derivatives such as L - ascorbic acid, L - ascorbic acid phosphate ester, L - ascorbic acid monopalmitate, L - ascorbic acid dipalmitate, L - ascorbic acid - 2 - glucoside, pantothenic acid derivatives such as calcium pantothenate, vitamin D derivatives such as vitamin D2, cholecalciferol, vitamin E derivatives such as α - tocopherol, tocopherol acetate, DL - α - tocopherol nicotinate, etc.

[0031] Whitening agents such as glutathione and Japanese saxifrage extract, skin activators such as royal jelly and beech extract, blood circulation promoters such as capsaicin, gingerol, cantharidin tincture, ichthyol, caffeine, tannic acid, and γ-oryzanol, anti-inflammatory agents such as glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, and azulene, amino acids such as arginine, serine, leucine, and tryptophan, maltose sucrose condensate as a resident bacteria control agent, lysozyme chloride, etc. can be mentioned. Furthermore, various extracts such as chamomile extract, parsley extract, wine yeast extract, grapefruit extract, morning glory extract, rice extract, grape extract, hop extract, rice bran extract, loquat extract, magnolia bark extract, yokukinin extract, assembly extract, meadowsweet extract, birch extract, licorice extract, peony extract, soapwort extract, loofah extract, pepper extract, lemon extract, gentiana extract, perilla extract, aloe extract, rosemary extract, sage extract, thyme extract, tea extract, seaweed extract, cucumber extract, clove extract, carrot extract, chestnut extract, witch hazel extract, mulberry extract, etc. can be mentioned.

[0032] The water-in-oil emulsion cosmetic of the present invention can be prepared according to a conventional method, and for example, it can be prepared by the following method. (A) to (F) and other oils are added at room temperature or while heating as necessary, and stirred and mixed. Then, while stirring, the mixed aqueous phase is gradually added at room temperature or while heating as necessary.

Examples

[0033] Hereinafter, examples and comparative examples will be shown to explain the present invention in detail, but the present invention is not limited thereto.

[0034] (Evaluation method) 1. Measurement of viscosity The viscosity was measured under the conditions of a B-type viscometer, rotor No. 4, 12 rpm, and 30 seconds.

[0035] 2. Evaluation of viscosity on the day following preparation Regarding the viscosity the day after preparation (viscosity 24 hours after preparation), ○ was used when it was 10,000 mPas or more, and × was used when it was less than 10,000 mPas.

[0036] 3. Temporal stability of viscosity 1 Among those with a viscosity the day after preparation of 10,000 mPas or more, when the viscosity retention rate after storage at room temperature for 1 week (after 168 hours) was 90% or more and less than 150%, ○ was used; when it was 80% or more and less than 90% or 150% or more and less than 200%, △ was used; and when it was less than 80% or 200% or more, × was used. 4. Temporal stability of viscosity 2 Among those with a viscosity retention rate after storage at room temperature for 1 week of ○ or △, when the viscosity retention rate after storage at room temperature for 1 month was 70% or more and less than 170%, ○ was used; when it was 50% or more and less than 70% or 170% or more and less than 250%, △ was used; and when it was less than 50% or 250% or more, × was used.

[0037] With the formulations (mass %) shown in Tables 1 and 2, (A) to (F) and other oil agents were added at room temperature and stirred and mixed. Next, while gradually adding the aqueous phase mixed at room temperature, stirring was carried out to obtain an oil-in-water type emulsified cosmetic. The evaluation results of each cosmetic are shown in Table 3.

[0038]

Table 1

[0039]

Table 2

[0040]

Table 3

[0041] The oil-in-water type emulsified cosmetics of Examples 1 to 13 of the present invention, despite being formulated with silicone oil and organically modified clay minerals, had a small decrease in viscosity over time even after 1 week and further after 1 month, and were excellent in stability. Also, these oil-in-water type emulsified cosmetics had a unique feeling of use, such as a refreshing feeling and a non-collapsing feeling. On the other hand, the water-in-oil type emulsified cosmetics of Comparative Examples 1 to 3 and 5 had a viscosity reduction to 70% or less after one week and were inferior in stability. Further, the water-in-oil type emulsified cosmetic of Comparative Example 4 had insufficient viscosity.

Claims

1. An oil-in-water emulsion cosmetic comprising the following (A) to (F), and containing (A) in an amount of 0.2% by mass or more and 0.8% by mass or less based on the whole (however, excluding those containing 3.0 to 30.0% by mass of a volatile hydrocarbon oil having a boiling point of 220°C or lower at 1 atm). (A) Organically modified clay mineral (B) Fine particle metal oxide (C) Polyether-modified silicone (D) Polyglycerin-modified silicone (E) C12-22 hydroxy fatty acid (F) Cyclic silicone

2. The oil-in-water emulsion cosmetic according to Claim 1, wherein the fine particle metal oxide (B) contains titanium oxide or zinc oxide.

3. The oil-in-water emulsion cosmetic according to Claim 1 or 2, wherein the polyether-modified silicone (C) contains PEG-10 dimethicone or PEG-9 polydimethylsiloxyethyl dimethicone.

4. The oil-in-water emulsion cosmetic according to any one of Claims 1 to 3, wherein the polyglycerin-modified silicone (D) contains polyglyceryl-3 polydimethylsiloxyethyl dimethicone or lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone.

5. The oil-in-water emulsion cosmetic according to any one of Claims 1 to 4, wherein the proportion of the aqueous phase based on the whole is 40% by mass or more.

6. A sunscreen cosmetic comprising the oil-in-water emulsion cosmetic according to any one of Claims 1 to 5.

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