JP2022177621A - Water-in-oil emulsion cosmetic - Google Patents

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 The present invention relates to a water-in-oil emulsified cosmetic, particularly a sunscreen cosmetic.

A water-in-oil type emulsified cosmetic has an oil-based external phase, and therefore may have a sticky feel peculiar to oil. Silicone oil is blended into the oil phase of water-in-oil emulsified cosmetics in order to provide a refreshing and non-sticky feel during use and to improve makeup longevity. However, silicone oil has poor compatibility with general cosmetic oils such as other hydrocarbons and ester oils, making it difficult to emulsify uniformly.
An organically modified clay mineral is used as a thickener for the oil phase in order to supplement the stability of the water-in-oil emulsified cosmetic. 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 exhibited, and problems such as viscosity reduction and phase separation may occur with aging stability.

Patent Document 1 describes a water-in-oil emulsified cosmetic composition containing an organically modified clay mineral and a dextrin fatty acid ester, comprising di(caprylic/capric) propanediol, caprylyl methicone, and silicone resin-coated silicone rubber spherical powder. A water-in-oil emulsified cosmetic has been proposed that suppresses a decrease in viscosity over time by blending.

JP 2015-189671 A

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 a feeling of use.

Means for solving the problems of the present invention are as follows.
1. A water-in-oil emulsified cosmetic comprising the following (A) to (F) and containing 0.2% by mass or more and 0.8% by mass or less of (A) based on the total.
(A) Organically modified clay mineral (B) Fine metal oxide (C) Polyether-modified silicone (D) Polyglycerin-modified silicone (E) C12-C22 hydroxy fatty acid (F) Cyclic silicone2. (B) The particulate metal oxide contains titanium oxide or zinc oxide. The water-in-oil emulsified cosmetic according to 1.
3. (C) Polyether-modified silicone contains PEG-10 dimethicone or PEG-9 polydimethylsiloxyethyl dimethicone 1. or 2. The water-in-oil emulsified cosmetic according to 1.
4. (D) The polyglycerin-modified silicone contains polyglyceryl-3 polydimethylsiloxyethyl dimethicone or lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone.1. ~3. The water-in-oil emulsified cosmetic according to any one of .
5. 1. The ratio of the aqueous phase to the whole is 40% by mass or more. ~ 4. The water-in-oil emulsified cosmetic according to any one of .
6.1. ~ 5. A sunscreen cosmetic comprising the water-in-oil emulsified cosmetic according to any one of .

The water-in-oil type emulsified cosmetic composition of the present invention exhibits little decrease in viscosity over time, is excellent in stability, and hardly causes phase separation, precipitation, and the like. The water-in-oil type emulsified cosmetic composition of the present invention provides a unique feeling of use with a refreshing feeling of use derived from the silicone oil and a crumbling feeling derived from the organically modified clay mineral.

The present invention includes the following (A) to (F), and relates to a water-in-oil emulsified cosmetic containing 0.2% by mass or more and 0.8% by mass or less of (A) based on the whole.
(A) Organically modified clay mineral (B) Fine metal oxide particles (C) Polyether-modified silicone (D) Polyglycerin-modified silicone (E) C12-22 hydroxy fatty acid (F) Cyclic silicone

(A) Organically Modified Clay Mineral Smectite, which is a swelling layered silicate, is a cationic clay mineral. Organically modified clay minerals are smectite cations replaced with organic cations such as quaternary ammonium salts. Minerals contained in smectite include hectorite, montmorillonite, bentonite, saponite, beidellite, nontronite, stevensite, vermiculite, volkonskoite, soconite, magadite, and kenyalite. Examples of organic cations include dimethyldistearylammonium chloride, dimethyldipalmitylammonium chloride, stearylbenzyldimethylammonium chloride, stearyltrimethylammonium chloride, betaine lauryldimethylaminoacetate, and the like. Examples of organically modified clay minerals include disteardimonium hectorite, stearalkonium hectorite, stearalkonium bentonite, and the like.

The water-in-oil emulsified cosmetic composition of the present invention contains 0.2% by mass or more and 0.8% by mass or less of (A) an organically modified clay mineral. If the amount of the organically modified clay mineral blended is less than 0.2% by mass, it may be difficult to maintain stability, and if it exceeds 0.8% by mass, the resulting emulsified cosmetic may become sticky. The blending amount of the organically modified clay mineral is more preferably 0.25% by mass or more, further preferably 0.3% by mass or more, more preferably 0.33% by mass, relative to the water-in-oil emulsified cosmetic. % or more is even more preferable. Further, the blending amount is more preferably 0.75% by mass or less, even more preferably 0.7% by mass or less, and even more preferably 0.68% by mass or less.

(B) Fine Metal Oxide Fine metal oxides are fine particles of metal oxides such as titanium oxide, zinc oxide, cerium oxide and iron oxide. In order to reduce the surface activity of the fine metal oxide, the surface of the fine metal oxide may be coated with silica, aluminum hydroxide, or the like. It is also possible to use one that has been entirely treated with a hydrophobizing agent. Further, it is also possible to use one that has been previously dispersed in an oil agent such as cyclopentasiloxane. By blending the fine metal oxide particles, the water-in-oil emulsified cosmetic composition of the present invention can be imparted with an ultraviolet shielding effect, a coloring effect, and the like. The water-in-oil emulsified cosmetic of the present invention can be suitably used as a sunscreen cosmetic because it has an ultraviolet shielding effect due to the fine particle metal oxide (B).

As fine particles of metal oxide, those having various available particle sizes and shapes may be selected according to the purpose. For example, titanium oxide is granular, needle-shaped, spindle-shaped, plate-shaped, and flake-shaped, zinc oxide is spherical or plate-shaped hexagonal, and cerium oxide is A spherical one can be used as appropriate. In addition, the same substance with different particle sizes and shapes may be used in combination, or two or more substances may be used in arbitrary combination.
Fine metal oxide particles having an average particle diameter (median diameter) of primary particles of 1 nm to 100 nm, more preferably 5 to 50 nm, are suitably used. If the average particle size of the primary particles of the fine-particle metal oxide is larger than 100 nm, the scattering of visible light by the particles increases, and the transmittance of visible light, that is, the transparency decreases.

The amount of the (B) fine-particle metal oxide compounded in the water-in-oil emulsified cosmetic composition of the present invention may be appropriately set based on the type of the fine-particle metal oxide, the desired ultraviolet shielding property, etc., but is not particularly limited. , with respect to the entire water-in-oil emulsified cosmetic, it can be 1% by mass or more and 30% by mass or less, preferably 5% by mass or more, more preferably 10% by mass or more, and It is preferably 25% by mass or less, more preferably 20% by mass or less.

(C) Polyether-modified silicone A polyether-modified silicone has a polyether chain as a side chain on the main silicone chain. Side chains may include alkyl chains and silicone chains in addition to polyether chains. Polyether-modified silicones include, for example, 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., may be used alone or in combination of two or more thereof. Among these, it is preferable to use either or both of PEG-10 dimethicone and PEG-9 polydimethylsiloxyethyl dimethicone.

The amount of the polyether-modified silicone (C) to be added to the water-in-oil emulsified cosmetic composition of the present invention is not particularly limited, but is, for example, 0.1% by mass or more relative to the entire water-in-oil emulsified cosmetic composition. It can be 5% by mass or less. This amount is preferably 0.5% by mass or more, more preferably 1% by mass or more, and is preferably 4.5% by mass or less, and is preferably 4% by mass or less. more preferred.

(D) Polyglycerin-modified silicone 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, or may be of a partially crosslinked type in which the silicone chain is crosslinked with a polyglycerin chain. Polyglycerin-modified silicones include polyglyceryl-3 disiloxane dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, cetyl diglyceryl tris(trimethylsiloxy)silylethyl dimethicone, (lauryl dimethicone/poly Glycerin-3) crosspolymer, (polyglyceryl-3/laurylpolydimethylsiloxyethyldimethicone) crosspolymer, etc., may be used alone or in combination of two or more thereof. Among these, it is preferable to use either or both of polyglyceryl-3 polydimethylsiloxyethyl dimethicone and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone.

The amount of the (D) polyglycerin-modified silicone blended into the water-in-oil emulsified cosmetic of the present invention is not particularly limited, but for example, 0.01% by mass or more relative to the entire water-in-oil emulsified cosmetic. It can be 2% by mass or less, preferably 0.1% by mass or more, and preferably 1.5% by mass or less.

(E) C12-C22 Hydroxy Fatty Acid A C12-C22 hydroxy fatty acid is a C12-C22 fatty acid having at least one hydroxyl group in the molecule, or a polymer thereof (polyhydroxy fatty acid). The fatty acid may have 12 to 22 carbon atoms, may be linear or branched, and may be saturated or unsaturated. Examples of hydroxy fatty acids having 12 to 22 carbon atoms include hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxybehenic acid, polyhydroxystearic acid, etc., and one or more of these may be used. Can be used together. The fatty acid preferably has 14 to 22 carbon atoms, more preferably 16 to 20 carbon atoms, and even more preferably 18 carbon atoms. Among these, it is particularly preferable to use polyhydroxystearic acid.

The amount of (E) a hydroxy fatty acid with 12 to 22 carbon atoms to be blended in the water-in-oil emulsified cosmetic of the present invention is not particularly limited, but for example, 0.01 relative to the entire water-in-oil emulsified cosmetic. It can be from 0.1% by mass to 2% by mass, preferably 0.1% by mass or more, and preferably 1.5% by mass or less.

(F) Cyclic Silicone Cyclic silicones include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc., and these may be used alone or in combination of two or more. can.

The amount of the (F) cyclic silicone compounded in the water-in-oil emulsified cosmetic composition of the present invention is not particularly limited, but is, for example, 10% by mass or more and 30% by mass or less with respect to the entire water-in-oil emulsified cosmetic composition. It is preferably 15% by mass or more, and preferably 28% by mass or less.

- Aqueous phase The water-in-oil 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 a water-soluble component dissolved therein. Specifically, in addition to water, aqueous solutions containing ethanol, butylene glycol, pentylene glycol, glycerin, sorbitol, phenoxyethanol, sodium chloride and the like can be mentioned. The water-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, relative to the total amount of the water-in-oil emulsified cosmetic. In addition, the water 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 with respect to the total amount of the water-in-oil emulsified cosmetic. .

In the water-in-oil emulsified cosmetic of the present invention, the total amount of (C), (D), and (E) is 1% by mass or more and 6% by mass with respect to the entire water-in-oil emulsified cosmetic. It is preferably less than or equal to, more preferably 2% by mass or more, and more preferably 5% by mass or less.
In addition, in the water-in-oil 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, It is more preferably 8% by mass or more, and more preferably 15% by mass or less.

In addition to the above, the water-in-oil type emulsified cosmetic of the present invention may include oils and fats such as ester oils and vegetable oils, hydrocarbons, higher fatty acids, higher alcohols, silicone oils, anionic surfactants, and cationic surfactants. , amphoteric surfactants, nonionic surfactants, polyhydric alcohols, sugars, sugar alcohols, water-soluble polymers, oil-soluble thickeners, preservatives, sequestering agents, UV absorbers, hyaluronic acid Moisturizers, perfumes, pH adjusters, etc. can be contained. In addition, other medicinal and physiologically active ingredients such as vitamins, skin activators, blood circulation promoters, active oxygen scavengers, anti-inflammatory agents, whitening agents and bactericides can also be incorporated.

Examples of ester oils include octyldodecyl stearoyloxystearate, cetyl 2-ethylhexanoate, 1,3-butylene glycol diisononanoate, 1,3-butylene glycol di2-ethylhexanoate, dipropylene glycol diisononanoate, di2 dipropylene glycol-ethylhexanoate, isononyl isononanoate, glyceryl tri-2-ethylhexanoate, glyceryl tricaprate, glyceryl triisostearate, neopentyl glycol dicaprate and the like.
Examples of oils and fats include liquid oils such as camellia oil, evening primrose oil, macadamia nut oil, olive oil, rapeseed oil, corn oil, sesame oil, jojoba oil, germ oil, wheat germ oil, cacao butter, coconut oil, hardened coconut oil, palm solid fats and oils such as oil, palm kernel oil, Japanese wax, Japanese wax kernel oil, hydrogenated oil, hydrogenated castor oil; waxes such as beeswax, candelilla wax, cotton wax, bran wax, lanolin, lanolin acetate, liquid lanolin, sugarcane wax; be done.

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), and eicosapentaenoic acid (EPA).
Examples of higher alcohols include straight chain alcohols such as lauryl alcohol, stearyl alcohol, cetyl alcohol and cetostearyl alcohol, 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.

Examples of anionic surfactants include fatty acid salts such as sodium laurate, higher alkyl sulfate salts such as sodium lauryl sulfate, alkyl ether sulfate salts such as POE triethanolamine lauryl sulfate, N-acylsarcosinate, and sulfosuccinate. , N-acylamino acid salts and the like.
Examples of cationic surfactants include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, benzalkonium chloride, and benzethonium chloride.
Examples of amphoteric surfactants include betaine-based surfactants such as alkylbetaines and amidobetaines.
Examples of nonionic surfactants include polyglycerin fatty acid esters such as polyglyceryl-2 triisostearate, sorbitan fatty acid esters such as sorbitan monooleate, and hydrogenated castor oil derivatives.

Examples of polyhydric alcohols include glycerin, 1,3-butylene glycol, 1,2-pentanediol, propylene glycol, dipropylene glycol, isoprene glycol and polyethylene glycol.
Examples of sugars and sugar alcohols include glucose, fructose, sorbitol, maltitol, erythritol, trehalose, sucrose, xylitol, maltose and lactose.
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, methylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, Carboxymethylcellulose sodium, sodium alginate, carboxyvinyl polymer and the like can be mentioned.
Examples of oil-soluble thickeners include glyceryl behenate eicosanedioate, fatty acid dextrin esters, and crosslinked silicones.

Examples of antiseptics include methylparaben, ethylparaben, phenoxyethanol and the like.
Examples of sequestering agents include disodium ethylenediaminetetraacetate, edetic acid, and edetate salts such as sodium edetate.
Examples of UV absorbers that can be blended include para-aminobenzoic acid, phenyl salicylate, isopropyl para-methoxycinnamate, octyl para-methoxycinnamate, and 2,4-dihydroxybenzophenone. However, in order to improve safety, it is preferable not to mix an ultraviolet absorber.
Moisturizers such as 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 and the like.

As medicinal ingredients, for example, vitamin A oil, vitamin A such as retinol, vitamin B2 such as riboflavin, B6 such as pyridoxine hydrochloride, L-ascorbic acid, L-ascorbic acid phosphate, L-ascorbic acid mono Palmitate, L-ascorbic acid dipalmitate, L-ascorbic acid-2-glucoside and other vitamin Cs, calcium pantothenate and other pantothenic acids, vitamin D2, cholecalciferol and other vitamin Ds, α-tocopherol , tocopherol acetate, and DL-α-tocopherol nicotinate.

Whitening agents such as glutathione and saxifrage extract, skin activators such as royal jelly and beech tree extract, blood circulation enhancers such as capsaicin, gingerone, cantharis tincture, ictamol, caffeine, tannic acid, γ-oryzanol, and glycyrrhizic acid derivatives , glycyrrhetinic acid derivatives, antiphlogistic agents such as azulene, amino acids such as arginine, serine, leucine and tryptophan, maltose sucrose condensates as indigenous bacteria control agents, lysozyme chloride and the like.
In addition, chamomile extract, parsley extract, wine yeast extract, grapefruit extract, honeysuckle extract, rice extract, grape extract, hop extract, rice bran extract, loquat extract, Phellodendron bark extract, coix seed extract, assembly extract, melilot extract, birch extract, licorice extract, peony extract , soapwort extract, luffa extract, capsicum extract, lemon extract, gentian extract, perilla extract, aloe extract, rosemary extract, sage extract, thyme extract, tea extract, seaweed extract, cucumber extract, clove extract, carrot extract, horse chestnut extract, Various extracts such as hamamelis extract and mulberry extract can be used.

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

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these.

(Evaluation method)
1. Measurement of Viscosity Viscosity was measured using a Brookfield viscometer, rotor No. Measured under conditions of 4, 12 rpm, 30 seconds.

2. Evaluation of Viscosity on the Day After Preparation The viscosity on the day after preparation (viscosity after 24 hours of preparation) was evaluated as ◯ when it was 10,000 mPas or more, and as x when it was less than 10,000 mPas.

3. Viscosity stability over time 1
Among those with a next-day viscosity of 10,000 mPas or more, the viscosity retention rate after one week of room temperature storage (after 168 hours) is 90% or more and less than 150%. , less than 80% or 200% or more were evaluated as x.
4. Viscosity stability over time 2
Among those with a viscosity retention rate of 0 or △ after 1 week of room temperature storage, ○ indicates that the viscosity retention rate is 70% or more and less than 170% after 1 month of room temperature storage, 50% or more and less than 70%, or 170% or more and 250%. Less than Δ was evaluated, and less than 50% or 250% or more was evaluated as ×.

(A) to (F) and other oil agents were added at room temperature according to the formulations (% by mass) shown in Tables 1 and 2, and stirred and mixed. Subsequently, the aqueous phase mixed at room temperature was gradually added and stirred to obtain a water-in-oil emulsified cosmetic.
Table 3 shows the evaluation results of each cosmetic.

The water-in-oil emulsified cosmetics of Examples 1 to 13 of the present invention, despite the fact that the silicone oil and the organically modified clay mineral were blended, remained viscous over time after one week and even after one month. The drop was small and the stability was excellent. In addition, these water-in-oil type emulsified cosmetics had a unique feeling of freshness and collapse.
On the other hand, the water-in-oil type emulsified cosmetics of Comparative Examples 1 to 3 and 5 had a viscosity of 70% or less after one week, and were inferior in stability. In addition, the water-in-oil emulsified cosmetic of Comparative Example 4 lacked viscosity.

Claims (6)

A water-in-oil emulsified cosmetic comprising the following (A) to (F) and containing 0.2% by mass or more and 0.8% by mass or less of (A) based on the total.
(A) Organically modified clay mineral (B) Fine metal oxide particles (C) Polyether-modified silicone (D) Polyglycerin-modified silicone (E) C12-22 hydroxy fatty acid (F) Cyclic silicone 2. The water-in-oil emulsified cosmetic composition according to claim 1, wherein (B) the fine particle metal oxide contains titanium oxide or zinc oxide. 3. The water-in-oil emulsified cosmetic composition according to claim 1, wherein (C) the polyether-modified silicone contains PEG-10 dimethicone or PEG-9 polydimethylsiloxyethyl dimethicone. (D) The water-in-oil emulsion according to any one of claims 1 to 3, wherein the polyglycerin-modified silicone contains polyglyceryl-3 polydimethylsiloxyethyl dimethicone or lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone. cosmetics. 5. The water-in-oil emulsified cosmetic composition according to any one of claims 1 to 4, wherein the proportion of the aqueous phase to the whole is 40% by mass or more. A sunscreen cosmetic comprising the water-in-oil emulsified cosmetic according to any one of claims 1 to 5.