JP2007254346A - Skin care preparation of water-in-oil type emulsion emulsion dosage form - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a skin care preparation having excellent low-temperature stability and useful for a cosmetic of water-in-oil type emulsion dosage form. <P>SOLUTION: The skin care preparation comprises (1) an organic-modified clay mineral and (2) a sphingoglycolipid and/or phytosterol glycoside. The emulsion dosage form of the skin care preparation is a water-in-oil type emulsion dosage form. The sphingoglycolipid and/or phytosterol glycoside is preferably contained in a microemulsion form. The microemulsion is preferably a microemulsion formed by a phospholipid. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a skin external preparation, and more particularly, to a skin external preparation suitable for a cosmetic in the form of a water-in-oil formulation that is excellent in stability at low temperatures.

  The water-in-oil emulsion has oily components in the continuous phase, and therefore has higher moisture retention due to the blocking effect than the oil-in-water emulsion, and has excellent properties for transdermal absorbability of the oily active ingredient. Yes. On the other hand, as a feeling of use, it has an oily and heavy defect. As a method of overcoming these disadvantages and taking advantage of the advantages of water-in-oil emulsions, various attempts have been made to produce high-in-water water-in-oil emulsions, and organic modifications such as dimethyl distearyl ammonium chloride-modified hectorite. Techniques for producing high-in-water water-in-oil emulsions using clay minerals have been developed (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3). However, even when such a technique is used, when a nonpolar oil such as silicone is contained in an amount of 15 to 30% by mass, it is included when a physical stress is applied in a low temperature range below 0 ° C. There was a problem that the water phase could be liberated. The silicone relieves the oily feel of the water-in-oil emulsion and, in the case of volatile substances such as cyclomethicone such as decamethylpentacyclosiloxane, has the effect of suppressing the finished fat deposits. It was also a semi-essential component in the water-in-oil emulsion composition. That is, it can be said that development of a means for improving the stability of the system in a low temperature region is desired in a high internal phase water-in-oil emulsion using an organically modified clay mineral. In particular, as a severe condition, when a slope is formed and stored under a storage condition below 0 ° C., it has been desired to develop a means for preventing the water phase that is a discontinuous phase from being liberated on the slope. In particular, in cosmetics that prevent scuffing and beating of limbs, the conditions of use are naturally cold conditions, so it is necessary to consider improving the stability of the system in such a low temperature range. More than a topical skin preparation.

  On the other hand, plant glycosphingolipids and sterol glycosides have useful effects on the skin, such as improving the skin barrier function and synchronizing the cell cycle of the skin. It is known that these ingredients, which are difficult to dissolve in water and oil, are processed into microemulsions using phospholipids and polyhydric alcohols, and then added to an emulsification system to increase the effectiveness. It is already known that this can be done (see, for example, Patent Document 4). However, it is quite known that the inclusion of such a component in the water phase of water-in-oil emulsifier has the effect of maintaining the emulsion system even when physical stress is applied to the emulsion under low temperature storage conditions. It wasn't.

JP 2005-255623 A JP 2004-292373 A JP 2001-58937 A JP-A-9-301820

  The present invention has been made under such circumstances, and in a skin external preparation in the form of a water-in-oil emulsifier, as a severe condition, when the slope is formed and stored under storage conditions below 0 ° C., It is an object of the present invention to provide means for preventing the aqueous phase that is a discontinuous phase from being liberated. In the present invention, the water-in-oil emulsifier form means a generic name of an emulsion having an oil phase as a continuous phase, and includes a form in which an emulsion is contained in an aqueous phase as a discontinuous phase.

In view of such a situation, in the external preparation for skin external use in the form of a water-in-oil emulsifier, the present inventors, as a severe condition, formed a slope and stored it under storage conditions below 0 ° C., discontinuous on the slope. As a result of intensive research efforts to find a means to prevent the release of the aqueous phase, which is a phase, such a water separation can be achieved by strengthening the internal phase structure with glycosphingolipids and / or phytosterol glycosides. We have found that the phenomenon can be prevented and have completed the invention.
(1) A skin external preparation characterized by containing 1) an organically modified clay mineral and 2) a glycosphingolipid and / or a phytosterol glycoside.
(2) The skin external preparation is in a water-in-oil emulsifier form, and the sphingoglycolipid and / or phytosterol glycoside is contained in the form of a microemulsion. The skin external preparation as described.
(3) The external preparation for skin according to (2), wherein the microemulsion is a microemulsion formed of phospholipid.
(4) The skin external preparation according to any one of (1) to (3), further comprising 15 to 30% by mass of dimethicone or cyclomethicone.
(5) The external preparation for skin according to any one of (1) to (4), further comprising 1 to 10% by mass of a polyether-modified methylpolysiloxane.
(6) The external preparation for skin according to any one of (1) to (5), which is a cosmetic for rough skin.
(7) The external preparation for skin according to any one of (1) to (6), wherein the rough skin is cracks and / or scratches on limbs.

  ADVANTAGE OF THE INVENTION According to this invention, when a slope is formed as severe conditions and it preserve | saves on the preservation | save conditions less than 0 degreeC, the means which prevents releasing the water phase which is a discontinuous phase on a slope can be provided.

(1) Organically modified clay mineral which is an essential component of the external preparation for skin of the present invention The external preparation for skin of the present invention is characterized by containing an organically modified clay mineral as an essential component. Here, organic modification means that a part or all of the properties of an organic compound is made into a clay mineral by causing a part of the organic compound to form a strong or loose bond via a covalent bond or an ionic bond. This means that it is imparted to minerals. Examples of such modifications include a method of binding a quaternary amine group and an anion portion of a clay mineral, and a method of binding a carboxyl group and a cation portion of a clay mineral. A method of combining the group and the anion portion of the clay mineral is particularly preferable.

  Although it does not necessarily limit as a compound which has a quaternary amino group which modifies a clay mineral, The compound called quaternium is illustrated. Quotanium is a low molecular weight substituted quaternary ammonium salt, and is preferably a cosmetic raw material registered in International Standard Cosmetic Ingredients (INCI). Furthermore, the compound having a quaternary amino group that modifies the clay mineral is preferably a quaternium compound contained in a conventional external skin preparation among quaternium compounds. Preferred examples of the quaternium compound used in conventional external preparations for skin include stearyl trimethyl ammonium chloride and dimethyl distearyl ammonium chloride. Stearyl trimethyl ammonium chloride, dimethyl distearyl ammonium chloride and the like are preferable because they can form a stable water-in-oil emulsion structure together with clay minerals.

  On the other hand, as a clay mineral (unmodified clay mineral) modified with a compound having a quaternary amino group, any clay mineral contained in a conventional skin external preparation can be used without any particular limitation. Preferred clay minerals contained in conventional skin external preparations include smectite-type hectorite, bentonite and montmorillonite; kaolinite; illite; marine clay mineral (sea mud); desert rose clay mineral; Among these, bentonite, hectorite, montmorillonite or kaolinite which can stabilize the water-in-oil emulsion structure is preferably exemplified.

An example of a method for producing a clay mineral modified with a compound having a quaternary amino group contained in the external preparation for skin of the present invention will be described below.
The unmodified clay mineral is dispersed in a dispersion medium. The dispersant is preferably an aqueous solvent, and may be water. A compound having a quaternary amino group is further added to the dispersion containing the dispersed unmodified clay mineral and stirred well. The compound having a quaternary amino group may be added after being dissolved in water. The amount of the compound having a quaternary amino group to be added is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15% by mass with respect to the amount of the dispersed unmodified clay mineral. This is because by taking such a configuration, a preferable feeling of use is exhibited in the emulsification system. After stirring, the dispersoid is filtered, dehydrated and dried to obtain the modified clay mineral in the present invention. Or the modified clay mineral in this invention can also be obtained by removing a dispersing agent by concentrating under reduced pressure without filtering a dispersoid, and making it dry. The obtained modified clay mineral is preferably pulverized to a desired size (preferably having a particle size of 1 to 1000 μm) and contained in the skin external preparation of the present invention.

  The modified clay mineral in the present invention can be prepared and used as described above, but a commercially available one can also be used. Some modified clay minerals on the market are used as external preparations for skin such as cosmetics. Preferable examples of commercially available modified clay minerals include dimethyl distearyl ammonium modified hectorite sold under the name “Benton 38V” by Elementis.

  In the skin external preparation of this invention, this component is contained preferably 0.5-10 mass%, More preferably, 1-5 mass% is contained. Such an ingredient acts as an emulsifier in the above-mentioned content range to form a high internal phase water-in-oil emulsifier form.

(2) Glycosphingolipid and / or phytosterol glycoside which is an essential component of the external preparation for skin of the present invention The skin external preparation of the present invention contains sphingoglycolipid and / or phytosterol glycoside as an essential component And The glycosphingolipid has a structure represented by the following general formulas (1) to (2), and the sugar residue in the formula is preferably a glucose residue, such as plants such as rice bran, bran (wheat germ), It is present in cocoons, straw, soybeans, cocoons, corn, etc., and these plant materials are extracted with an organic solvent such as hexane, petroleum ether, chloroform after removing fats and sugars by pretreatment according to known methods. Further, it can be obtained by purification by a purification means such as column chromatography. Phytosterol is a general term for plant sterols, and plant sterols include stigmasterol, campesterol, sitosterol, and the like, and these are collectively called phytosterols. As phytosterol, a sterol fraction containing a plurality of phytosterols can be taken out from a plant such as wheat germ and used. Such glucosides of phytosterols, specifically phytosterol glucosides, are also present in plants and are often present in fractions similar to glycosphingolipids. It is similar. In many cases, the glycosphingolipid is mixed during fractionation and purification, and such a mixture extract of glycosphingolipid and phytosterol glycoside can be used in the external preparation for skin of the present invention. In the external preparation for skin of the present invention, such a glycosphingolipid and / or phytosterol glycoside has low solubility in both an oily component and an aqueous component. It is preferable to form and contain an emulsion. Phospholipids such as phosphatidylinositol, phosphatidylglycerol, phosphatidylethanolamine, lecithin, or their lyso form are 0.3 to 3 times the weight of plant-derived glycosphingolipid and phytosterol glycoside, and monohydric alcohol such as ethanol is 5 -20 times weight, 1,3-butanediol, dipropylene glycol, isoprene glycol, 1,2-pentanediol, 1,2-hexanediol and other dihydric alcohols are used 5-30 times weight, sphingoglycolipid and phytosterol It is preferable to dissolve the glycoside in an aqueous system to form a microemulsion and to contain it. For such microemulsions, there are cosmetic raw materials processed in such a form, and such cosmetic raw materials can be purchased and used. As such a commercially available raw material for cosmetics, “FR-1” sold by Okayasu Shoten Co., Ltd. exists. This comprises 1% by weight of a mixture of glycosphingolipid and phytosterol glycoside in a weight ratio of 80:20 to 90:10, 0.5% by weight soybean lecithin, 10% by weight 1,3-butanediol, , 8% by mass ethanol dispersed in the remaining water as a microemulsion. Okayasu Shoten Co., Ltd. also sells “Phytosteside” which is a mixture of phytosterol glycoside and glycosphingolipid at a mass ratio of 80:20 to 90:10. These components may be used to form a microemulsion with phospholipid, 1,3-butanediol, ethanol and water. In the external preparation for skin of the present invention, such a component has an action of reinforcing the structure of the emulsified particles that are the discontinuous phase of the water-in-oil emulsification system and preventing the aqueous phase from protruding from the water-in-oil emulsified structure. In order to exert such an effect, the total amount of the glycosphingolipid and / or phytosterol glycoside is preferably 0.0005 to 0.1% by mass, and 0.0001 to 0.01% by mass is contained. It is more preferable. This is because if the amount is too small, the above-mentioned effect may not be achieved, and if it is too large, the crystal may be precipitated without being included in the system.

一般式（１）
（但し式中Ｒ１は糖残基を表し、Ｒ２破綻素数１２〜２４のアルキル基を表す。）

General formula (1)
(In the formula, R1 represents a sugar residue, and R2 represents an alkyl group having 12 to 24 disruptive elements.)

一般式（２）
（但し式中Ｒ１は糖残基を表し、Ｒ２破綻素数１２〜２４のアルキル基を表す。）

General formula (2)
(In the formula, R1 represents a sugar residue, and R2 represents an alkyl group having 12 to 24 disruptive elements.)

(3) The skin external preparation of this invention The skin external preparation of this invention contains the said essential component, It is characterized by the above-mentioned. In the external preparation for skin of the present invention, a water-in-oil emulsifier form is preferred. This is because the organically modified clay mineral, which is an essential component, is very suitable for producing a water-in-oil emulsifier type composition. In particular, a high internal phase water-in-oil emulsifier form is preferred. Here, the high internal phase water-in-oil emulsifier form means that the sum of the mass of water, the mass of ethanol, and the mass of polyhydric alcohol exceeds 50 mass%. Further, as described above, when taking the water-in-oil emulsifier form, it is preferable to contain silicone in order to compensate for the drawbacks of the feeling of use and finish of the water-in-oil emulsifier form. Is preferably contained in an amount of 10 to 35% by mass, more preferably 20 to 30% by mass. Among these, dimethicone or cyclomethicone is preferably 10 to 30% by mass, and more preferably 15 to 25% by mass. In particular, the mass of cyclomethicone is preferably 50% or more with respect to the sum of the masses of dimethicone and cyclomethicone. Examples of silicones other than dimethicone and cyclomethicone include polyether-modified methyl polysiloxanes such as POE-modified methyl polysiloxane, POP-modified methyl polysiloxane, and POP / POE-modified methyl polysiloxane, which may contain such components. This is preferable because the water-in-oil emulsion system can be stabilized. The preferable content of such polyether-modified methylpolysiloxane is more preferably 0.5 to 5% by mass and 1 to 3% by mass.

  In addition to the components described above, the external preparation for skin of the present invention can contain optional components that are usually used in external preparations for skin. The external preparation for skin of the present invention can contain, in addition to such components, optional components that are usually used in external preparations for skin. Such optional ingredients include, for example, macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, hydrogenated coconut oil Oil, wax, oil such as beeswax, canola wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum , Hydrocarbons such as microcrystalline wax; higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid; cetyl alcohol, stearyl alcohol, isostearyl Higher alcohols such as alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, cetostearyl alcohol; cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, malic acid Diisostearyl, di-2-ethylhexanoic acid ethylene glycol, dicaprate neopentyl glycol, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, tri Oil agents such as synthetic ester oils such as trimethylolpropane isostearate and pentane erythritol tetra-2-ethylhexanoate; fatty acid soap (sodium laurate) Anionic surfactants such as potassium lauryl sulfate, alkyl sulfate triethanolamine ether; cationic surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride, laurylamine oxide; imidazoline-based amphoteric Amphoterics such as surfactants (2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.), betaine surfactants (alkyl betaine, amide betaine, sulfobetaine, etc.), acylmethyl taurine, etc. Surfactants: sorbitan fatty acid esters (such as sorbitan monostearate and sorbitan sesquioleate), glycerin fatty acids (such as glyceryl monostearate), propylene glycol fatty acid esters (monostearic acid) Propylene glycol, etc.), hydrogenated castor oil derivative, glycerin alkyl ether, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbite monolaurate, etc.) POE glycerol fatty acid esters (POE-glycerol monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE alkylphenyl ethers (POE nonylphenyl ether, etc.), Pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Tetro Non-ionic surfactants such as sucrose, POE castor oil / hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), sucrose fatty acid ester, alkyl glucoside; polyethylene glycol, glycerin, 1,3-butylene Glycol, erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octane Polyhydric alcohols such as diol; moisturizing ingredients such as sodium pyrrolidonecarboxylate, lactic acid, sodium lactate; surface-treated mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic anhydride (silica) Powders such as aluminum oxide and barium sulfate; inorganic pigments such as bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, and zinc oxide that may be treated on the surface; Pearl agents such as titanium mica, fish phosphorus foil, bismuth oxychloride which may be treated; red 202, red 228, red 226, yellow 4, blue 404, which may be raked, Organics such as yellow 5, red 505, red 230, red 223, orange 201, red 213, yellow 204, yellow 203, blue 1, green 201, purple 201, red 204 Pigments; Organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomers; Paraaminobenzoic acid UV absorbers; Anthranilic acid UV A linear absorber; a salicylic acid ultraviolet absorber; a cinnamic acid ultraviolet absorber; a benzophenone ultraviolet absorber; a sugar ultraviolet absorber; 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole; UV absorbers such as 4-methoxy-4′-t-butyldibenzoylmethane; lower alcohols such as ethanol and isopropanol; vitamin A or derivatives thereof, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, Vitamin B2 such as vitamin B2 or derivatives thereof, vitamin B12, vitamin B15 or derivatives thereof; vitamin E such as α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, vitamin D, vitamin H, pantothenic acid , Pantethine, pyrroloquinoline quinones and other vitamins ; And antibacterial agents such as phenoxyethanol can be preferably exemplified.

  Among such optional components, particularly preferred are polyhydric alcohols that can stabilize the emulsified state. Particularly preferred are glycerin, diglycerin, 1,3-butanediol, 1,2-pentanediol, 1,2-hexanediol, and isoprene glycol. Such a component may contain only one species or may contain two or more species in combination. The preferred content is 10 to 30% by mass, more preferably 15 to 25% by mass, based on the total amount of the external preparation for skin, as a total amount.

  The external preparation for skin of the present invention can be produced by treating these components according to a conventional method. The external preparation for skin of the present invention is not particularly limited as long as it is externally applied to the skin. For example, basic cosmetics such as lotions, essences, emulsions, creams, packs, foundations, under-makeups, Makeup cosmetics such as control colors, highlights, UV protective cosmetics such as sun care milk and sun care cream, cleaning products such as rinses, shampoos, body shampoos, cosmetics for hair such as hair creams and hair packs, antifungals Suitable examples include skin external medicines, anti-inflammatory skin external medicines, steroid skin external medicines, skin external disinfectants, and skin external goods, among which cosmetics are preferred, and application to hand creams is particularly preferred. This is because the glycosphingolipids and phytosterol glycosides, which are components that reinforce the structure of the emulsion particles, have an effect of improving skin roughness, and this effect is a transdermal water dispersion-suppressing effect of a high internal phase water-in-oil emulsifier type. This is because it acts synergistically and effectively acts on severe rough skin such as cracks and scratches.

  Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited to such examples.

  According to the formulation shown below, a cosmetic preparation in the form of a water-in-oil emulsifier, which is an external preparation for skin of the present invention, was produced. That is, the components of a and b are heated to 80 ° C., and k is kneaded to form a gel. C is added and dissolved therein, and the mixture is gradually added with emulsification and stirring. Upon cooling, a cosmetic 1 in the form of a water-in-oil emulsifier was obtained. In the same manner, Comparative Example 1 in which “Benton 38V” was replaced with “Silicone KF6017”, Comparative Example 2 in which “FR-1” was replaced with water, and “Benton 38V” in “Silicone KF6017”, and FR Comparative Example 3 in which “-1” was replaced with water was also prepared.

<Test Example 1>
A cream bottle for 50 g is filled with 25 g of cosmetic 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 diagonally so that a slope of 45 ° C. is formed, and a constant temperature room of 40 ° C. is maintained while maintaining the slope. For one month, water droplets generated on the slope at 40 ° C. were collected with a spoid, and the water droplets were weighed. The results are shown in Table 2. From this, it can be seen that the cosmetic 1 of the present invention firmly holds the emulsion particles and suppresses the formation of water droplets on the slope. In addition, in the filling that forms a horizontal surface that does not form an inclined surface that is not easily subjected to physical stress on the outside, none of the samples produced water droplets under storage conditions of 40 ° C. for one month. In Comparative Example 1, a minute insoluble matter was generated.

  In the same manner as cosmetic 1 in Example 1, cosmetic 2 as an external preparation for skin of the present invention was prepared according to the following formulation. In the evaluation of Test Example 1, the release of water droplets was not observed.

  In the same manner as cosmetic 1 in Example 1, cosmetic 3 as an external preparation for skin of the present invention was prepared according to the following formulation. In the evaluation of Test Example 1, the release of water droplets was not observed.

  Using a paneler, the skin roughness improvement effect in the skin roughness model created by tape stripping was evaluated for cosmetics 1 to 3 and comparative examples 1 to 3. That is, four 3 cm × 5 cm sites were created on the left and right forearms, tape stripping was performed 15 times for each site, and transcutaneous dissipated moisture (TEWL) was measured with “Tevameter” manufactured by Integral. Thereafter, 50 μl of the sample was applied once a day, this operation was continued for 6 days, and TEWL was measured again on the 7th day. The TEWL improvement rate (%) was calculated by subtracting the TEWL value on the seventh day from the TEWL value on the first day, dividing by the TEWL value on the first day, and multiplying by 100. The n number was 15. The results are shown in Table 5. This shows that the skin external preparation of this invention is excellent in the rough skin improvement effect. It is also speculated that there is an optimum range for the content of glycosphingolipids and phytosterol glycosides to improve rough skin.

  The present invention can be applied to skin external preparations such as cosmetics.

Claims (7)

A skin external preparation characterized by containing 1) an organically modified clay mineral and 2) a glycosphingolipid and / or a phytosterol glycoside. The skin according to claim 1, wherein the external preparation for skin is a water-in-oil emulsifier, and the glycosphingolipid and / or phytosterol glycoside is contained in the form of a microemulsion. Topical agent. The skin external preparation according to claim 2, wherein the microemulsion is a microemulsion formed of phospholipid. The skin external preparation according to any one of claims 1 to 3, further comprising 15 to 30% by mass of dimethicone or cyclomethicone. Furthermore, 1-10 mass% of polyether modified methyl polysiloxane is contained, The skin external preparation in any one of Claims 1-4 characterized by the above-mentioned. The skin external preparation according to any one of claims 1 to 5, which is a cosmetic for rough skin. The skin external preparation according to any one of claims 1 to 6, wherein the rough skin is cracks and / or scratches of limbs.