JP2009019049A - Water-in-oil emulsified external preparation for skin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-in-oil emulsified external preparation for skin, having good moisture confining property, use feeling and stability. <P>SOLUTION: The water-in-oil emulsified external preparation for skin comprises an oil phase containing a mixture of an ester compound obtained by esterifying ingredients (A), (B) and (C), an ester oil, a surfactant and an oil component other than the ester oil at specific amounts of the ester compound and the ester oil, and a water phase containing an aqueous solution of a water-soluble inorganic salt at a specific amount of the inorganic salt wherein the mass ratio of the oil phase to the water phase is a specific value, and contains neither ethyl cellulose nor ethyl hydroxyethyl cellulose, where (A) is a polyhydric alcohol, (B) is an 8-30C fatty acid and/or hydroxy fatty acid and (C) is a 12-30C dibasic carboxylic acid. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an external preparation for skin, and more specifically, water-in-oil emulsification that can be used as cosmetics, quasi-drugs, pharmaceuticals, etc., with significantly improved moisture occlusion, usability (= feel for use) and stability. It relates to an external preparation for skin.

  The purpose of skin care cosmetics such as creams is to make skin weakened by supplementing the skin with moisture and oil, and its most important function is the transpiration of moisture to give the skin moisture and flexibility. It is an inhibitory function (hereinafter referred to as moisture occlusion). Moisture occlusiveness refers to the effect that a thin film formed on the skin by oil or the like keeps the moisture that evaporates from the skin without releasing it into the outside air, and keeps it on the skin. Great effect. Cosmetics based on oil and water are generally composed of a water-in-oil emulsion in which water phase droplets are dispersed in an oil continuous phase, and an oil-in-water emulsion in which oil phase droplets are dispersed in a water continuous phase. It is known that water-in-oil emulsions are superior to oil-in-water emulsions in many respects such as protecting the skin and maintaining flexibility.

  It has been already reported that the non-polar oils such as petroleum jelly and liquid paraffin are large in the oil occlusion property of the oil agent, and that the force decreases as the polarity such as ester oil increases. In fact, skin troubles such as rough skin are often caused by dry skin, and as a countermeasure, vaseline is applied to effectively suppress moisture transpiration from the skin, thereby improving those skin problems. It is known to be done. For this reason, as a cosmetic or external preparation having a large moisture occlusive property, those containing petrolatum are commercially available.

  However, non-polar oils such as petroleum jelly and liquid paraffin are generally less compatible with sebum, so they slip on the skin even after application, and the hand with non-polar oil as the main component is applied with a slippery pen. There were many cases where problems such as not being able to hold well and oil being transferred to clothes and papers that were touched. In addition, in the case of cosmetics such as a foundation in which powder is blended with them, there is also a problem that when the applied skin touches the clothes, the powder easily moves into the clothes.

  On the other hand, it is relatively difficult to maintain the emulsified state for a long period of time using a product using a water-in-oil emulsion. In order to improve the emulsification stability, a conventional method is to increase the viscosity of the emulsion by adding a large amount of wax to the continuous oil phase. Phenomena such as softening and melting of waxes blended in response to various temperature changes occurred, and the emulsion stability was not sufficient. Further, in terms of the feeling of use, there are problems such as stickiness, oiliness, and heavy spread caused by waxes.

  Ester oils as polar oils such as isooctyl palmitate, neopentyl glycol dicaprate, glyceryl tri-2-ethylhexanoate, etc. are generally used as hydrocarbon oils such as petroleum jelly, liquid paraffin, and some waxes. In comparison, it has excellent miscibility with sebum, does not slip on the skin, has a good fit, is difficult to shine, and has excellent breathability and less oiliness. It is commonly used as a fee. In addition, because it is well-familiar with the skin, there are almost no problems such as transfer of oil to clothes, etc., as in cosmetics with petrolatum.

  However, ester oil is rich in breathability, so it does not reach far from petrolatum in water occlusion, and water-in-oil emulsified cosmetics based on ester oil do not satisfy the main purpose of oil content, and are rough. The improvement effect was small. Furthermore, when ester oil is blended with a conventional water-in-oil emulsion, phase separation or the like occurs, and there is a difficulty in emulsion stability. Therefore, although the feeling of use is excellent, there are many restrictions on the blending of ester oil, and the amount that actually improves the sensory function is rarely used.

  By the way, in recent years, there is an increasing concern about the effect of ultraviolet irradiation on the skin, and the demand for cosmetics for sunscreens is increasing. Commercially available sunscreen cosmetics are generally and typically water-in-oil emulsified cosmetics, and UV absorbent oils are necessary to increase SPF (Sun Protection Factor) values. For example, UV absorbers are widely used as ester oils such as paramethoxycinnamate and N, N-dimethylparaaminobenzoate. However, ester oils having a functional group capable of absorbing ultraviolet rays are particularly high in polarity, so it is difficult to emulsify them and maintain their stability. In order to prepare it, it is only possible to cope with a method of blending a large amount of waxes or a combination of waxes, and it is often necessary to limit the blending amount of such ester oil.

Under such circumstances, there has been a demand for a water-in-oil type emulsified skin external preparation that achieves a water-occlusion property similar to petrolatum and has excellent emulsification stability while having skin conformability of ester oil.
Some oily substances obtained by esterifying polyhydric alcohols, medium-chain or long-chain fatty acids, and medium-chain dibasic acids have good tackiness and are used as oil-in-water emulsified oils. Since it contributes to the emulsion stability, it is known to be incorporated into lipsticks or oil-in-water creams.

  In view of such circumstances, the present invention provides a water-in-oil emulsified skin external preparation that improves the above-mentioned problems, is excellent in moisture occlusion, has a good feeling in use, and has excellent emulsification stability. The issue is to provide.

  In view of the above circumstances, the present inventors have intensively studied to obtain a water-in-oil type emulsified skin external preparation having good moisture occlusiveness, stability, and usability. As a result, specific ester compounds are combined with ester oil in the oil phase. It was found that the above-mentioned problems can be achieved by blending a water-soluble inorganic salt in the water phase, and the present invention has been completed.

That is, the present invention includes an ester compound obtained by esterifying the following components (A), (B) and (C), an ester oil, a surfactant and a mixture of oils other than the ester oil, and an aqueous phase. Contains an aqueous solution of a water-soluble inorganic salt, a water-in-oil emulsified skin external preparation characterized by:
(A) Polyhydric alcohol (B) C8-C30 fatty acid and / or hydroxy fatty acid (C) C12-C30 dibasic carboxylic acid.

  According to the present invention, when a specific ester compound is contained in the oil phase and a water-soluble inorganic salt is contained in the water phase, moisture can be obtained even when polar oil such as ester oil is used as the main component of the oil phase. An excellent water-in-oil type skin external preparation having excellent occlusive properties, good feeling in use, good skin fit, almost no oil transfer to clothes, etc., excellent emulsification stability, and versatility.

The present invention is described in detail below.
The oil phase of the water-in-oil type emulsified skin external preparation of the present invention basically comprises the above ester compound, ester oil, surfactant for emulsification, and oils other than ester oil (solid oil and fat, waxes, etc.). Composed.
The ester compound used in the present invention is an ester obtained by esterifying a polyhydric alcohol (A), a fatty acid having 8 to 30 carbon atoms or a hydroxy fatty acid (B), and a dibasic carboxylic acid (C) having 12 to 30 carbon atoms. A compound. Although there is no restriction | limiting in particular about the mixing ratio between these components in esterification, Component (A): Component (B): Component (C) = 1.0 mol: 1.0-2.5 mol: 0.00. It is preferable that it is 25-1.0 mol. There is no restriction | limiting in particular about the esterification method, A well-known esterification method can be used. The resulting ester compound is obtained as a mixture of ester compounds having different contents of the component (A) residue, the component (B) residue and the component (C) residue, and can usually be used as a mixture.

  The ester compound in the oil phase of the water-in-oil type emulsified skin external preparation of the present invention has a function of gelling the oil content in the oil phase, that is, the oil content other than the ester oil and the ester oil. It is considered that the usability of the emulsified skin external preparation is improved and the dispersion stability of the aqueous phase is improved. In other words, the ester compound forms a uniform gel of oil, stabilizes the dispersion of the aqueous phase by confining it in the gel without separating the aqueous phase, and thereby water-in-oil emulsification It is thought to improve the usability of external preparations for skin.

  As the polyhydric alcohol which is a component of the ester compound used in the present invention, those having 3 or more, particularly 3 to 6 hydroxyl groups are preferable. For example, glycerin, glycerin condensate, trimethylolpropane, pentaerythrit, Examples include methylolethane, sorbit, xylitol, sucrose, glucose, fructose, mannitol and the like.

  The fatty acid or hydroxy fatty acid having 8 to 30 carbon atoms, which is a component of the ester compound used in the present invention, may have a hydrocarbon group or hydroxy hydrocarbon group which may be linear or branched, and saturated. Or may be unsaturated. For example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, ricinoleic acid, palmitooleic acid, isooctylic acid (2 -Ethylhexanoic acid, etc.), isononanoic acid (3,5,5-trimethylhexanoic acid, etc.), isopalmitic acid, isostearic acid (2-heptylundecanoic acid, multimethyl branched type manufactured by Emery), serotic acid, Examples include montanic acid and melicic acid. In order to further improve the long-term stability of a water-in-oil emulsified skin external preparation, straight-chain long-chain saturated fatty acids having 16 to 28 carbon atoms such as palmitic acid, stearic acid, behenic acid, serotic acid, montanic acid, etc. It is desirable to use one or more of these. Fatty acids having 7 or less carbon atoms are unsuitable for skin irritation and hydrolytic stability. On the other hand, when the number of carbon atoms is 31 or more, the esterification reaction does not easily proceed, and it becomes difficult to obtain the desired ester compound according to the present invention, which is inappropriate.

  The dibasic carboxylic acid having 12 to 30 carbon atoms, which is a component of the ester compound used in the present invention, may be linear or branched, and may be saturated or unsaturated. Are preferably saturated, for example, eicosanedioic acid, dodecanedioic acid, 1,10-decamethylenedioic acid, 1,12-dodecamethylenedioic acid, 1,15-pentadecamethylenedioic acid, 1,28-octa. Examples include cosamethylene diacid, 1,7-ethyl octadecanedioic acid, and the like.

  When a dibasic carboxylic acid having 11 or less carbon atoms is used, even if a water phase is added to an oil phase containing the resulting ester compound as a component and emulsified to obtain a water-in-oil emulsion, a sufficient thickening effect can be obtained. It cannot be obtained and the aqueous phase is immediately separated, and a stable emulsified composition cannot be obtained. This is presumed to be because the tendency of the ester compound not to exhibit the property of gelling the oil in the oil phase increases. On the other hand, when a dibasic carboxylic acid having 31 or more carbon atoms is used, the esterification reaction is difficult to proceed, and the physical properties of the resulting product are not stable. From the above viewpoint, the dibasic carboxylic acid preferably has 14 to 28 carbon atoms, more preferably 16 to 28 carbon atoms.

  In the present invention, use of glyceryl behenate eicosane diacid, which is an ester compound obtained by esterifying glycerin, behenic acid and eicosane diacid as the ester compound, makes it possible to use the water-in-oil type emulsified skin external preparation. It is particularly preferable in terms of stability.

  The ester compound must be contained in the oil phase in an amount of 0.1 to 30% by mass, preferably 0.5 to 0.5%, based on the total mass of the oil other than the ester compound, ester oil, surfactant and ester oil. It is -25 mass%, More preferably, it is 1-20 mass%. When the blending amount is less than 0.1% by mass, sufficient effects cannot be obtained in stability and usability. On the other hand, if it exceeds 30% by mass, the spread becomes worse and the usability is impaired.

  Further, it is considered that the ester compound forms an oil film having an appropriate water permeability after being applied to the skin, thereby controlling the water retention. Conventionally, for the purpose of stabilizing emulsification, an amorphous microcrystalline wax is a wax often blended in a water-in-oil emulsified cosmetic, but the ester compound used in the present invention is more water occlusive. Since it is excellent and almost comparable to that of petrolatum, it can be expected that when this is blended in an oil phase to prepare a water-in-oil type emulsified skin external preparation, it has excellent water retention. In general, cosmetics containing ester oil as the main component of the oil phase may feel dissatisfied with the water-occlusion property after application, but this problem is solved by adding this ester compound. The On the other hand, because it has a structure with many ester bonds, it has excellent affinity with sebum and has less stickiness due to oil. Can be prevented. For this reason, the water-in-oil type emulsified skin external preparation of the present invention does not feel sticky as when stabilized with a wax composition, and still has a good moistness as if there is always enough moisture on the skin. It is thought that it became a feeling.

  The results of actual investigation on the water retention of ester compounds, microcrystalline wax and petrolatum are shown below for reference. The water permeability of the oil agent and the ester compound was evaluated by the moisture permeation amount of the oily film prepared to the thickness of the filter paper according to the method of JIS Z0208 “Testing moisture permeability of moisture-proof packaging material (cup method)”. A moisture permeable cup having a moisture permeable surface of φ60 mm was used, 20 g of glycerin was used as a moisture absorbent, and beeswax: paraffin wax (= 60: 40) was used as a sealing agent. As the sample, a 5C filter paper impregnated with a constant amount (7 to 9 mg / cm 2) to form a film with a constant thickness is used. The filter paper is placed on a moisture permeable cup containing 20 g of glycerin, sealed with a sealing agent, and the total mass is measured. A high-humidity atmosphere (25 ° C., 80%) is made with a saturated aqueous ammonium chloride solution and left there for 3 hours, and then the mass is measured. As a blank test, the moisture permeation amount is measured in the same manner on a filter paper not impregnated with the sample, and the amount is set to a moisture permeability of 100%. The moisture permeability of each sample was expressed as a percentage by dividing the mass difference (moisture permeability) before and after being left at high humidity by the moisture permeability of the blank test. The results are shown in Table 1.

  As the ester oil blended in the oil phase of the water-in-oil type emulsified skin external preparation of the present invention, ester oils that can be usually used for cosmetics and the like can be used. Examples of such ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, Myristyl lactate, octyldodecyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, dicaprin Neopentyl glycol acid, diisostearyl malate, glycerin di-2-heptylundecanoate, trime tri-2-ethylhexanoate Roll propane, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, tri (capryl / caprin / myristine / stearic acid) glyceride, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic acid oleyl, acetoglyceride, 2-heptylundecyl palmitate, adipic acid Diisobutyl, (adipic acid, 2-ethylhexanoic acid, stearic acid) glycerin oligoester, (2-hexyldecanoic acid, sebacic acid) diglyceryl oligoester, N- Lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, adipic acid 2-hexyldecyl, diisopropyl sebacate, 2-ethylhexyl succinate, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, sunflower oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat Germ oil, sasanqua oil, castor oil, flaxseed oil, safflower oil, grape seed oil, cottonseed oil, enoy oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil , Germ oil, evening primrose oil, glyceryl trioctanoate, triisopalmi Examples thereof include glyceryl tinate, ethyl acetate, butyl acetate, and triethyl citrate.

  Among ester oils, those containing branched fatty acids and / or branched alcohols as constituent components are called branched ester oils. Among ester oils, branched ester oils have better skin fit, but are less water occlusive. In the present invention, the ester compound improves the low water blocking property, which is a disadvantage of ester oils. Therefore, even if a branched ester oil is added, sufficient water blocking property can be maintained and the skin is well-familiar. Can be strengthened.

  About the compounding quantity of the ester oil in the oil phase of the water-in-oil emulsified skin external preparation of the present invention, an amount that can give a good feeling of use such as elongation and goodness when applied to the skin. As long as it is, there is no particular limitation and it is difficult to define it uniformly, but it is usually 1 to 99% by mass based on the total mass of oil components other than the ester compound, ester oil, surfactant and ester oil. Preferably, it is 10-90 mass%, More preferably, it is 20-75 mass%.

  The ratio of the ester compound to the ester oil in the oil phase of the water-in-oil emulsified skin external preparation of the present invention is preferably 1:99 to 95: 5, and more preferably 5:95 to 95: 5. The ratio is more preferably 10:90 to 90:10. When the amount of the ester compound is less than 1:99, the water occlusion generally tends to be insufficient, and further, phase separation occurs and the emulsion stability tends to be impaired. On the other hand, when the amount of the ester compound is more than 95: 5, the elongation tends to be poor when applied on the skin, and the feeling tends to be heavy.

  Conventionally, various surfactants are added to obtain a water-in-oil type emulsified skin external preparation. Also in the present invention, synthetic surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, lipophilic nonionic surfactants, hydrophilic nonionic surfactants, or natural surfactants One type or a combination of two or more types can be used. In the present invention, the stability of the water-in-oil emulsion is improved by the ester compound and the water-soluble inorganic salt contained in each of the oil phase and the water phase, and the type of surfactant used as an emulsifier is not limited. However, specific examples are as follows.

  Examples of the anionic surfactant include soap bases, fatty acid soaps such as sodium laurate and sodium palmitate, higher alkyl sulfates such as sodium lauryl sulfate and potassium lauryl sulfate, POE-lauryl sulfate triethanolamine, POE- Alkyl ether sulfates such as sodium lauryl sulfate, N-acyl sarcosine acid such as sodium lauroyl sarcosine, N-myristoyl-N-methyl taurine sodium, coconut oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium and other higher fatty acid amides Sulfonates, phosphate ester salts such as sodium POE-oleyl ether phosphate, POE-stearyl ether phosphate, sodium di-2-ethylhexylsulfosuccinate, monolaur Sulfosuccinates such as sodium monoethanolamide polyoxyethylene sulfosulphate, sodium lauryl polypropylene glycol sulfosuccinate, sodium linear dodecyl benzene sulfonate, triethanolamine linear dodecyl benzene sulfonate, alkyl benzene sulfonates such as linear dodecyl benzene sulfonate N-acyl glutamate, such as monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, monosodium N-myristoyl-L-glutamate, higher fatty acid ester sulfates such as hydrogenated coconut oil fatty acid sodium glycerol sulfate, funnel oil Sulfated oil such as POE-alkyl ether carboxylic acid, POE-alkyl allyl ether carboxylate, α-olefin Examples include sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfate, higher fatty acid alkylolamide sulfate, sodium lauroyl monoethanolamide succinate, ditriethanolamine N-palmitoyl aspartate, and sodium caseinate. .

  Examples of cationic surfactants include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride and lauryltrimethylammonium chloride, distearyldimethylammonium dialkyldimethylammonium chloride, and poly (N, N′-dimethyl-3,5-methylene chloride). Piperidinium), alkyl pyridinium salts such as cetyl pyridinium chloride, alkyl quaternary ammonium salts, alkyl dimethyl benzyl ammonium salts, alkyl isoquinolinium salts, dialkyl morpholinium salts, POE-alkyl amines, alkyl amine salts, polyamine fatty acids Examples thereof include organically modified clay minerals such as derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, benzethonium chloride, and organically modified montmorillonite.

  Examples of amphoteric surfactants include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy 2 Imidazoline-based amphoteric surfactants such as sodium salts, betaine-based surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaines, amide betaines, sulfobetaines Etc.

  Examples of the lipophilic nonionic surfactant include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2 -Sorbitan fatty acid esters such as diglycerol sorbitan tetrahexyl hexylate, diglycerol sorbitan tetrahexyl-2-ethylhexylate, mono-cotton oil fatty acid glycerin, glyceryl monoerucate, glyceryl sesquioleate, glyceryl monostearate, α, α'-oleic acid pyro Glycerin fatty acid esters such as glyceryl glutamate, glyceryl monostearate, glyceryl monooleate, diglyceryl monoisostearate, diisostearate di Polyglycerin fatty acid esters such as glyceryl, condensed ricinoleate diglyceryl, tetraglyceryl condensed ricinoleate, propylene glycol fatty acid esters such as propylene glycol monostearate, hardened castor oil derivatives, glycerin alkyl ethers and the like.

Examples of the hydrophilic nonionic surfactant include POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan fatty acid esters such as POE-sorbitan tetraoleate, and POE-sorbitol. POE-sorbite fatty acid esters such as monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, POE-glycerol monostearate, POE-glycerol monoisostearate, POE- POE such as POE-glycerin fatty acid esters such as glycerol triisostearate, POE-monooleate, POE-distearate, POE-monodiolate, ethylene glycol distearate Fatty acid esters, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-alkyl ethers such as POE-cholestanol ether, Pluronic type such as Pluronic , POE / POP-cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP-monobutyl ether, POE / POP-hydrogenated lanolin, POE / POP-alkyl ethers such as POE / POP-glycerin ether Tetra POE / Tetra POP-ethylenediamine condensates such as Tetronic, POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE-castor oil-hardened castor oil derivatives such as POE-hardened castor oil maleic acid, POE-beeswallow lanolin derivatives such as POE-sorbite beeswax, palm oil fatty acid Alkanolamides such as diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, POE-propylene glycol fatty acid ester, POE-alkylamine, POE-fatty acid amide, sucrose fatty acid ester, POE-nonylphenylformaldehyde condensate, alkylethoxydimethyl Amine oxide, trioleyl phosphate, polyglyceryl monolaurate, polyglyceryl monostearate, polyglyceryl monooleate, polyglyceryl distearate And polyglycerin fatty acid esters such as polyglyceryl dioleate, and modified silicones such as methylpolysiloxane / cetylmethylpolysiloxane / poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer.

  Examples of natural surfactants include lecithins such as soybean phospholipid, hydrogenated soybean phospholipid, egg yolk phospholipid, and hydrogenated egg yolk phospholipid, soybean saponin, and the like.

  The blending amount of the surfactant in the oil phase is not particularly limited as long as a stable water-in-oil emulsified skin external preparation can be obtained, but the oil content other than the ester compound, ester oil, surfactant and ester oil is not limited. Usually, 0.01 to 40% by mass is preferable, 0.05 to 30% by mass is more preferable, and 0.1 to 20% by mass is even more preferable based on the total mass.

  Oils other than the ester oil constituting the oil phase of the water-in-oil emulsified skin external preparation of the present invention are not particularly limited, and oils other than the ester oil are used in various oils usually used in cosmetics or external preparations. Examples thereof include solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, and silicone oils. Specific examples of oil other than ester oil are listed below.

  Examples of the solid fat include cacao butter, palm oil, beef tallow, sheep fat, horse tallow, palm kernel oil, pork tallow, beef bone fat, molasses kernel oil, beef leg fat, molasses, hydrogenated palm oil, hydrogenated palm oil, Examples include hardened beef tallow, hardened oil, hardened castor oil, and the like.

Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, kapok wax, sugar cane wax, lanolin, lanolin acetate, liquid lanolin, lanolin fatty acid isopropyl, reduced lanolin, hard lanolin, Hexyl laurate, jojoba wax, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol,
Examples include POE hydrogenated lanolin alcohol ether.

  Examples of the hydrocarbon oil include liquid paraffin, isoparaffin, paraffin, ozokerite, squalane, pristane, ceresin, squalene, petrolatum, microcrystalline wax, paraffin wax, α-olefin oligomer, and the like.

  Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tolic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), Examples include docosahexaenoic acid (DHA).

  Examples of higher alcohols include linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerol ether (batyl alcohol), 2-decyltetradecinol, and lanolin. Examples thereof include branched chain alcohols such as alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, and octyldodecanol.

  Examples of the silicone oil include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetrahydrotetramethylcyclohexane. Examples thereof include cyclic polysiloxanes such as tetrasiloxane, polyoxyethylene polyalkylsiloxanes, and the like.

  Although there is no restriction | limiting in particular about content of oil components other than ester oil in the oil phase of the water-in-oil type emulsion skin external preparation of this invention, The total mass of oil components other than ester compound, ester oil, surfactant, and ester oil is used. As a standard, 0.01 to 98% by mass is usually preferable.

  The water phase of the water-in-oil emulsified skin external preparation of the present invention is basically composed of a water-soluble inorganic salt and water. The water-soluble inorganic salt contained in the aqueous phase is preferably an alkali metal salt or alkaline earth metal salt of a strong inorganic acid, and more preferably an alkali metal salt of a strong inorganic acid. Examples of strong inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and hydrochloric acid, sulfuric acid, and phosphoric acid are particularly preferable. Examples of the alkali metal include sodium and potassium. Particularly, sodium and potassium are preferable. Examples of the alkaline earth metal include magnesium and calcium. Magnesium and calcium are particularly preferable. Specifically, sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate and the like are preferable. Particularly preferred are sodium chloride, potassium chloride and sodium sulfate. These can be used alone or as a mixture in an arbitrary ratio. The blending amount of the water-soluble inorganic salt in the aqueous phase needs to be 0.01% by mass to 10% by mass based on the total mass of the water-soluble inorganic salt and water, and is 0.1 to 5% by mass. It is preferable that it is 0.5-5 mass%.

  By containing a water-soluble inorganic salt in the aqueous phase, it is considered that the inorganic salt controls moisture transpiration and moisture absorption on the skin. This makes it possible to obtain a water-in-oil emulsified skin preparation for external use that has a moist feeling after application in addition to the moisture occlusion enhanced by the ester compound.

  Furthermore, when such a water-soluble inorganic salt is not added to the aqueous phase, a stable water-in-oil emulsion composition is not formed, and the aqueous phase is 2 to 3 days after the preparation of the emulsion composition. Separation occurs. Further, when the amount of the water-soluble inorganic salt added to the aqueous phase is less than 0.01% by mass based on the total mass of the water-soluble inorganic salt and water, the same tendency is shown, and the time elapsed compared to the case of no addition. The emulsification stability is slightly good, but eventually the aqueous phase is separated. Addition of 0.01 to 10% by mass, particularly 0.1 to 5% by mass, eliminates such a problem. On the other hand, when it mixes exceeding 10 mass% with respect to an aqueous phase, it will become the thing of the sticky touch when it apply | coated to skin.

  The mass ratio of the oil phase to the water phase of the water-in-oil emulsified skin external preparation of the present invention is 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30. is there. When the oil / water ratio is more than 10:90, the storage stability tends to deteriorate, which is not preferable. On the other hand, when there is less water phase than 90:10, the stickiness feeling by oil becomes strong and is not preferable in terms of usability.

  In addition to the above components, the water-in-oil emulsified skin external preparation of the present invention impairs the effects of the present invention as necessary for the purpose of improving sensory properties, imparting moisture retention, imparting skin nutrition, preventing quality deterioration, etc. Various components that are generally used in cosmetics, pharmaceuticals and the like (hereinafter referred to as physical property improving agents) can be blended within a range that does not exist. Examples of such physical property improvers include powder components, humectants, natural water-soluble polymers, semi-synthetic water-soluble polymers, synthetic water-soluble polymers, inorganic water-soluble polymers, ultraviolet absorbers, metals Examples include sequestering agents, lower alcohols, polyhydric alcohols, monosaccharides, oligosaccharides, polysaccharides, amino acids, organic amines, synthetic resin emulsions, pH adjusters, vitamins, antioxidants, antioxidant assistants, and fragrances. These can be used alone or in combination of two or more.

  As powder components, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, lithia mica, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, silicic acid Barium, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate, (baked gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder, metal soap (Zinc myristate, calcium palmitate, aluminum stearate), inorganic powders such as boron nitride, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene and acrylic Copolymer resin powder of phosphoric acid, benzoguanamine resin powder, polytetrafluoroethylene powder, organic powder such as cellulose powder, inorganic white pigment such as titanium dioxide and zinc oxide, inorganic such as iron oxide (Bengara) and iron titanate Red pigments, inorganic brown pigments such as iron oxide, inorganic yellow pigments such as yellow iron oxide and loess, inorganic black pigments such as black iron oxide, carbon black and low-order titanium oxide, mango violet, cobalt violet Inorganic purple pigments such as inorganic oxide pigments such as chromium oxide, chromium hydroxide and cobalt titanate, inorganic blue pigments such as ultramarine and bitumen, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc , Colored titanium oxide coated mica, bismuth oxychloride, pearl pigments such as fish scale foil, aluminum powder, -Metal powder pigments such as powder, red 201, red 202, red 204, red 205, red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205 , Organic pigments such as yellow 401 and blue 404, red 3, red 104, red 106, red 227, red 230, red 401, red 505, orange 205, yellow 4, Examples thereof include organic pigments such as zirconium, barium or aluminum lake such as yellow No. 5, yellow 202, yellow No. 203, green No. 3 and blue No. 1, and natural pigments such as chlorophyll and β-carotene. However, the powder may be any powder applicable to general cosmetics, and is not limited to the above components.

  Examples of the humectant include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate. Sodium lactate, urea, bile salt, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Isaiyobara extract, yarrow extract, merirot extract and the like.

  Examples of natural water-soluble polymers include arabia gum, tragacanth gum, galactan, guar gum, carob gum, caraya gum, carrageenan, locust bean gum, tamarind gum, pectin, agar, quince seed (malmello), alge colloid (cuckoo extract), starch ( Plant polymers such as rice, corn, potato, and wheat), microbial polymers such as xanthan gum, dextran, succinoglucan, and bullulan, and animal polymers such as collagen, casein, albumin, and gelatin.

  Examples of semi-synthetic water-soluble polymers include starch polymers such as carboxymethyl starch and methylhydroxypropyl starch, methylcellulose, nitrocellulose, methylhydroxypropylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, carboxymethylcellulose, and carboxymethylcellulose. Examples thereof include cellulose polymers such as sodium, crystalline cellulose and cellulose powder, and alginic acid polymers such as sodium alginate and propylene glycol alginate.

  Examples of the synthetic water-soluble polymer include vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, and carboxyvinyl polymer (Carbopol), polyethylene glycol 20,000, 40,000, 60,000 and the like. Examples include polyoxyethylene polymers, polyoxyethylene polyoxypropylene copolymer copolymers, acrylic polymers such as sodium polyacrylate, polyethyl acrylate, and polyacrylamide, polyethyleneimine, and cationic polymers.

  Examples of the inorganic water-soluble polymer include bentonite, AlMg silicate (beegum), laponite, hectorite, and anhydrous silicic acid.

  Examples of the ultraviolet absorber include paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester. Benzoic acid ultraviolet absorbers such as N, N-dimethyl PABA butyl ester and N, N-dimethyl PABA ethyl ester, anthranilic acid ultraviolet absorbers such as homomenthyl-N-acetylanthranilate, amyl salicylate, menthyl salicylate, Salicylic acid-based UV absorbers such as homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, octylcinnamate, ethyl-4-isopropyl Nannamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl- p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano- Cinnamic acid-based UV absorbers such as β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, 2,4-dihydroxybenzophenone, 2,2'- Hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4 Benzophenone ultraviolet absorbers such as n-octoxybenzophenone and 4-hydroxy-3-carboxybenzophenone, 3- (4′-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanin Acid, urocanic acid Ester, 2-phenyl-5-methylbenzoxazole, 2,2′-hydroxy-5-methylphenylbenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2 '-Hydroxy-5'-methylphenyl) benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentane 2-one, 2,4,6-trianilino-p- (carbo-2′-ethylhexyl-1′-oxy) 1,3,5-triazine and the like. Many of these (eg, benzoic acid, anthranilic acid, salicylic acid, cinnamic acid, etc.) are ester oils.

  Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate. Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate and the like.

  Examples of the lower alcohol include methanol, ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, Divalent alcohols such as 2-butene-1,4-diol, hexylene glycol and octylene glycol, trivalent alcohols such as glycerin, trimethylolpropane and 1,2,6-hexanetriol, and 4 such as pentaerythritol Polyhydric alcohols, pentahydric alcohols such as xylitol, hexahydric alcohols such as sorbitol, mannitol, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin , Polyethylene glycol, triglycerin, tetraglycerin, polyglycerin and other polyhydric alcohol polymers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene Divalent alcohol alkyl ethers such as glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, Diethylene glycol Noethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono Dihydric alcohol alkyl ethers such as butyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, ethylene glycol monomethyl ether acetate, ethylene group Recall monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazinate, ethylene glycol disuccinate, diethylene glycol monoethyl ether estate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene Divalent alcohol ether esters such as glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, glycerin monoalkyl ethers such as xyl alcohol, ceralkyl alcohol, and batyl alcohol, sorbitol, maltitol, maltoto Orth, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitose, sugar alcohols such as amylolytic sugar reducing alcohol, glyceryl solid, tetrahydrofurfuryl alcohol,
POE-tetrahydrofurfuryl alcohol, POP-butyl ether, POP / POE-butyl ether, tripolyoxypropylene glycerol ether, POP-glycerol ether, POP-glycerol ether phosphate, POP / POE-pentane erythritol ether, and the like.

  Examples of monosaccharides include tricarbon sugars such as D-glyceryl aldehyde and dihydroxyacetone, tetracarbon sugars such as D-erythrose, D-erythrulose, D-threose and erythritol, L-arabinose, D-xylose and L-lyxose. Pentoses such as D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, D-glucose, D-talose, D-bucose, D-galactose, D-fructose, L-galactose, Hexasaccharides such as L-mannose and D-tagatose, heptosaccharides such as aldheptose and heprose, octoses such as octulose, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L -Deoxy sugars such as mannose, D-glucosamine, D-galactosamine, sialic acid, a Nouron acid, an amino sugar such as muramic acid, D- glucuronic acid, D- mannuronic acid, L- guluronic acid, D- galacturonic acid, uronic acids such as L- iduronic acid.

  Examples of the oligosaccharides include sucrose, gnocyanose, umbelliferose, lactose, planteose, isoliquinoses, α, α-trehalose, raffinose, lycnose, umbilicin, stachyose verbus course and the like.

  Examples of the polysaccharide include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, kerato sulfate. , Locust bingham, succinoglucan, caronic acid and the like.

  Examples of amino acids include neutral amino acids such as threonine and cysteine, and basic amino acids such as hydroxylysine. Examples of the amino acid derivative include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione, pyrrolidone carboxylic acid and the like.

  Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and the like. Is mentioned.

  Examples of the synthetic resin emulsion include an acrylic resin emulsion, a polyethyl acrylate emulsion, an acrylic resin liquid, a polyacryl alkyl ester emulsion, and a polyvinyl acetate resin emulsion.

  Examples of the pH adjusting agent include buffers such as lactic acid-sodium lactate and citric acid-sodium citrate.

  Examples of vitamins include vitamins A, B1, B2, B6, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.

  Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.

  Examples of the antioxidant assistant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

  Other ingredients that can be added include antiseptics such as ethyl paraben and ptyl paraben, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, anti-inflammatory agents such as hinokitiol, zinc oxide, and allantoin, whitening of placenta extract, yukinoshita extract, etc. Agent, Oat, Auren, Shikon, Peonies, Assembly, Birch, Sage, Loquat, Carrot, Aloe, Zeniaoi, Iris, Grape, Yokuinin, Loofah, Lily, Saffron, Senkyu, Ginger, Hypericum, Onionis, Garlic, Pepper, Chimpi , Extract of Toki, seaweed, royal jelly, photosensitizer, cholesterol derivative, juvenile blood extract, activator, nonyl acid valenylamide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, di Geron, cantalis tincture, ictamol, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin, γ-oryzanol and other blood circulation promoters, sulfur, thianthol And antiseborrheic agents such as tranexamic acid, thiotaurine, and hypotaurine.

  The preparation method for obtaining the water-in-oil emulsified skin external preparation of the present invention does not require any special means or apparatus, and a conventional method for obtaining a water-in-oil emulsified composition is used. For example, oil components other than ester compounds, ester oils, surfactants and ester oils are dissolved by heating as oil phases, and oil-soluble or lipophilic properties such as preservatives and antioxidants are required. Add accordingly and warm to 60-80 ° C. The water-soluble inorganic salt of the present invention and, if necessary, a water-soluble or hydrophilic property improving agent such as a humectant are added to purified water as an aqueous phase, and the mixture is heated to 60 to 80 ° C. The aqueous phase is gradually added to the oil phase to perform preliminary emulsification, and the emulsified particles are made uniform with a homomixer, followed by deaeration, filtration and cooling.

  The form of the water-in-oil emulsified skin external preparation of the present invention is not particularly limited, but for example, cream, emulsion, foundation, makeup base, blusher, eye shadow, eyeliner, eyebrow, mascara, massage material, hand cream Includes all water-in-oil products such as ointments, emulsified water-containing lips, and hair creams.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited only to the following examples. In the following examples, the blending amount is mass%.

  A total amount of 400 g of a water-in-oil emulsified cream was prepared using a conventional method with the blending compositions shown in Tables 2 to 4, and evaluated for water occlusion, usability and stability.

[Moisture occlusion test method]
In order to evaluate the water blocking property of the oil film formed by the product of the present invention, the water permeation amount test described above was performed. Since the method of forming the oil film on the filter paper is slightly different from the above, the following method is used. About 2 g of water-in-oil emulsified cream (about 5 g only for Comparative Example 10) is uniformly spread on a 5C filter paper and placed in a constant temperature and humidity chamber having a temperature of 40 ° C. and a humidity of 30% for 20 hours to evaporate water. The excess oil on the filter paper is wiped off with a waste cloth, and the impregnation amount is adjusted to 7 to 9 mg / cm2. Measurement was performed in the same manner as in the test method for the amount of water permeation, and the water permeability was determined. Water occlusiveness was evaluated according to the following criteria, and the results are shown in Tables 5-7.

`` Criteria for moisture obstruction ''
A: Water permeability is less than 7.5%, B: Water permeability is 7.5% or more and less than 10.0%, Δ: Water permeability is 10.0% or more, less than 15.0%, X: Moisture permeability is 15.0% or more

"Usability test method"
Ten prepared panelists actually used the prepared water-in-oil emulsified cream, and the usability was evaluated by a sensory test. Usability was evaluated according to the following criteria, and the results are shown in Tables 5-7.

"Usability criteria"
A: Eight or more out of 10 people judged that there was no stickiness and usability was good. ○: 6 or more out of 10 people judged that there was no stickiness and usability was good. (Triangle | delta): Four or more people out of 10 judged that there was no stickiness and usability was good. X: Less than 4 out of 10 people judged that there was no stickiness and usability was good.

"Stability test method"
The prepared water-in-oil emulsified cream was filled in a glass bottle, and the stability was evaluated immediately after emulsification and after standing at 5 ° C., room temperature, and 40 ° C. for 1 month. The stability was evaluated according to the following criteria, and the results are shown in Tables 5-7.

"Stability criteria"
○: No abnormality such as separation was observed, and the stability was good. Δ: Slight separation or the like is observed in the oil phase or water phase. X: The oil phase or the water phase is considerably separated and the stability is poor.

  As is clear from Tables 5 to 7, it was confirmed that the water-in-oil type emulsified creams of Examples 1 to 7 were remarkably improved in water occlusiveness, usability and stability over the comparative examples. Furthermore, when the creamed hand touched clothes or paper, the oil content hardly transferred, resulting in a very good feeling of use. Comparative Examples 1 to 3 are those in which either or both of the ester compound and the water-soluble inorganic salt, which are essential components of the present invention, are not added. Also became a problem. Moreover, although Comparative Examples 4-7 deviate from the ratio of the essential components of the present invention, those having a low blending amount are poor in both water occlusion and stability (Comparative Examples 4 and 6). In the case where the value was high, the feeling in use was poor (Comparative Examples 5 and 7). On the other hand, the stability of emulsification was attempted with the microcrystalline wax that was used in the past, but in order to increase the stability, a large amount of microcrystalline wax had to be blended and not only was sticky. The skin slipped on the skin and the oil content was transferred to clothes, etc., and the evaluation of the feeling of use was low (Comparative Examples 8 and 9). Further, in Comparative Examples 10 and 11, those having an aqueous phase of more than 90% by mass and less than 10% by mass were prepared. However, when the amount was more than 90% by mass, the stability was poor, and when the amount was less than 10% by mass, stickiness was observed. Strong and uncomfortable to use.

  As is clear from Tables 5 to 7, the water-in-oil type emulsified creams of Examples 1 to 7 are excellent in moisture occlusiveness and can be expected to have an effect of improving rough skin. 10 housewives who actually do a lot of water work, applied the cream of Example 1 to their hands before going to bed for a week, and spent the rest of their lives as usual. Replied that she was no longer worried about rough skin.

Other examples of the water-in-oil emulsified skin external preparation of the present invention are shown below.
Example 8 Emollient cream eicosane diacid behenate glyceryl 5 (trade name Nomcoat HK-G, manufactured by Nisshin Oil Co., Ltd.)
Diglyceryl diisostearate 5
Liquid paraffin 20
Isooctyl palmitate 15
Methylphenylpolysiloxane 5
Glycerin 5
3 Butylene glycol 5
1% citrate buffer (citric acid 1, sodium citrate 9) 30
Sodium chloride 0.2
Disodium hydrogen phosphate 0.1
Hyaluronic acid 0.1
Carboxymethylcellulose 0.5
Preservative Appropriate amount of perfume Appropriate amount of ion-exchanged water Remaining amount

  In the emollient cream obtained in Example 8, the moisture occlusion, usability, and stability (5 ° C .: ○, room temperature) were evaluated in the evaluation of moisture occlusion, usability and stability performed in Examples 1-7. : ○, 40 ° C: ○). In addition, when this emollient cream was continuously used in areas where rough skin was a concern, rough skin was effectively improved.

Example 9 Water-in-oil emulsification ointment Glyceryl behenate eicosane diacid (trade name Nomucoat HK-G, manufactured by Nisshin Oil Co., Ltd.) 5
Polyoxyethylene polyalkylsiloxane 0.5
Glyceryl trioctanoate 20
Corn oil 20
Paraffin wax 1
Sorbitol 5
1.3-Butylene glycol 5
Dipotassium glycyrrhizinate 0.2
Urea 10
Sodium chloride 0.1
Sodium sulfate 0.1
Preservative Appropriate amount of purified water Remaining amount

  The water-in-oil emulsified ointment obtained in Example 9 was evaluated in terms of water occlusiveness, usability and stability in Examples 1 to 7, with water occlusiveness ◎, usability ◎, stability (5 ° C : ○, room temperature: ○, 40 ° C .: ○). Moreover, when this water-in-oil type emulsifying ointment was continuously used for the part which is worried about rough skin, the rough skin was effectively improved.

Example 10 Emulsion behenic acid eicosane diacid glycerin (trade name Nomcoat HK-G, manufactured by Nisshin Oil Co., Ltd.) 1
Polyoxyethylene polyalkylsiloxane 0.2
Glyceryl tri-2-ethylhexanoate 10
Liquid paraffin 15
Squalane 10
Decamethylcyclopentasiloxane 10
Methylphenylpolysiloxane 10
Stearyl glycyrrhetinate 0.1
Sorbitan sesquioleate 4
POE (20) sorbitan monooleate 1
Propylene glycol 8
Glycerin 5
Potassium chloride 0.5
Dipotassium hydrogen phosphate 0.5
Preservative Appropriate amount of perfume Appropriate amount of ion-exchanged water Remaining amount

  The emulsion obtained in Example 10 was subjected to the evaluation of moisture occlusion, usability and stability performed in Examples 1 to 7, and moisture occlusion ◎, usability ◎, stability (5 ° C: ◯, room temperature: ○, 40 ° C .: ○). Moreover, when this water-in-oil type emulsifying ointment was continuously used for the part which is worried about rough skin, the rough skin was effectively improved.

Example 11 Sunscreen Cream Eicosane Diacid Behenate Glyceryl (trade name Nomucoat HK-G, manufactured by Nisshin Oil Co., Ltd.) 4
2-Ethylhexyl-p-methoxycinnamate 10
4-Methoxy-4′-t-butyldibenzoylmethane 2
Glyceryl tri-2-ethylhexanoate 10
Squalane 10
Octamethylcyclotetrasiloxane 5
Tocopherol acetate 0.1
Glycerol monooleate 3.5
POE (20) sorbitan monooleate 1
Hydrophobic treated fine particle titanium dioxide 3
Hydrophobic treated fine particle zinc oxide 3
3-Butylene glycol 10
EDTA · 2Na 0.1
Sodium chloride 1.0
Preservative Appropriate amount of perfume Appropriate amount of ion-exchanged water Remaining amount

  The sunscreen cream obtained in Example 11 was subjected to moisture occlusion ◎, usability ◎, stability (5 ° C: ○ in the evaluation of water occlusiveness, usability and stability performed in Examples 1-7. And room temperature: ◯, 40 ° C .: ◯). In addition, this sunscreen cream was well-familiar with the skin, and even when the skin with sunscreen applied touched the clothes, the powder did not move, and the feeling of use was very satisfactory. . Furthermore, in Example 11, it was possible to easily mix ester oil as an ultraviolet absorber, which was difficult to realize a skin-friendly sensory and emulsion stability.

Example 12 W / O Emulsion Foundation Eicosane Diacid Behenate Glyceryl (Brand Name Nomucoat HK-G, Nisshin Oil Co., Ltd.) 0.2
Liquid paraffin 5
Methylphenylpolysiloxane 5
Glyceryl tri-2-ethylhexanoate 5
Polyoxyethylene-modified dimethylpolysiloxane 4
Sericite 5
Kaolin 3
Titanium dioxide 12
Bengala 0.5
Yellow iron oxide 1
Black iron oxide 0.1
3 Butylene glycol 5
Sodium sulfate 0.2
Dispersant Appropriate amount Preservative Appropriate amount Fragrance Appropriate amount Ion-exchanged water Remaining amount

The W / O emulsified foundation obtained in Example 12 was evaluated in terms of water occlusiveness, usability and stability in Examples 1 to 7, with water occlusive property ◎, usability ◎, stability (5 ° C: ○, room temperature: ○, 40 ° C .: ○). Further, this W / O emulsified foundation was well-familiar with the skin, and even when the skin to which the foundation was applied touched the clothes, the powder did not move, and the feeling of use was very satisfactory.

Claims (13)

The oil phase contains an ester compound obtained by esterifying the following components (A), (B) and (C), an ester oil, a surfactant, and a mixture of oils other than the ester oil, and the water phase is a water-soluble inorganic salt. Water-in-oil emulsified skin external preparation containing an aqueous solution of the above, wherein the compounding amount of the ester compound and ester oil in the oil phase is based on the total mass of the oil other than the ester compound, ester oil, surfactant and ester oil As for ester compound 1-20 mass%, ester oil 10-90 mass%, and the compounding quantity of the water-soluble inorganic salt in an aqueous phase is 0.01-10 based on the total mass of water-soluble inorganic salt and water. The water-in-oil type emulsified skin external preparation with a mass ratio of 10:90 to 90:10, substantially containing neither ethylcellulose nor ethylhydroxyethylcellulose:
(A) Polyhydric alcohol (B) C8-C30 fatty acid and / or hydroxy fatty acid (C) C12-C30 dibasic carboxylic acid.   The water-in-oil emulsified skin external preparation according to claim 1, which contains neither ethylcellulose nor ethylhydroxyethylcellulose, or a total amount of both of them less than 0.01% by mass based on the total amount of the water-in-oil emulsified skin external preparation. .   The water-in-oil type emulsified skin external preparation according to claim 2, which contains neither ethylcellulose nor ethylhydroxyethylcellulose.   The mixing ratio in the esterification is component (A): component (B): component (C) = 1.0 mol: 1.0-2.5 mol: 0.25-1.0 mol 4. The water-in-oil type emulsified skin external preparation according to any one of 3 above.   The water-in-oil type emulsified skin external preparation according to any one of claims 1 to 4, wherein the polyhydric alcohol has 3 to 6 hydroxyl groups.   The water-in-oil according to claim 5, wherein the polyhydric alcohol is at least one selected from glycerin, glycerin condensate, trimethylolpropane, pentaerythritol, trimethylolethane, sorbitol, xylitol, sucrose, glucose, fructose and mannitol. Type emulsified skin external preparation.   The water-in-oil type emulsified skin external preparation according to claim 6, wherein the component (A) is glycerin, (B) is behenic acid and (C) is eicosane diacid.   Ester oil is isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, octyl lactate Dodecyl, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, monoisostearate N-alkyl glycol, neopentyl glycol dicaprate, Diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, tri Trimethylolpropane sostearate, pentaerythritol tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, tri (capryl / caprin / myristine / stearic acid) glyceride, trimethylolpropane triisostearate, cetyl 2-ethyl Hexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, ( Adipic acid, 2-ethylhexanoic acid, stearic acid) glycerin oligoester, (2-hexyldecanoic acid, sebacic acid) diglyceryl oligoester, N-lauroyl-L-gluta 2-octyldodecyl minate, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyl adipate Decyl, diisopropyl sebacate, 2-ethylhexyl succinate, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, sunflower oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, Sasanka oil, castor oil, flaxseed oil, safflower oil, grape seed oil, cottonseed oil, eno oil, soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnabari oil, Japanese kiri oil, jojoba oil, germ oil , Evening primrose oil, glycerin trioctanoate, glycerin triisopalmitate, acetic acid The water-in-oil emulsified skin external preparation according to any one of claims 1 to 7, which is at least one selected from ethyl, butyl acetate and triethyl citrate.   The water-in-oil type emulsified skin external preparation according to any one of claims 1 to 7, wherein the ester oil is a branched ester oil.   The oil-in-water emulsification according to any one of claims 1 to 9, wherein the oil other than the ester oil is at least one selected from solid fats, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, and silicone oils. Skin external preparation.   The water-in-oil emulsified skin external preparation according to any one of claims 1 to 10, wherein the water-soluble inorganic salt is at least one selected from alkali metal salts and alkaline earth metal salts of strong inorganic acids.   The blending amount of the surfactant in the oil phase is 0.01 to 40% by mass based on the total mass of the oil other than the ester compound, ester oil, surfactant and ester oil. The water-in-oil type emulsified skin external preparation of 1 item | term. As physical property improvers generally used in external preparations for skin, powder components, humectants, natural water-soluble polymers, semi-synthetic water-soluble polymers, synthetic water-soluble polymers, inorganic water-soluble polymers, UV absorbers Sequestering agents, lower alcohols, polyhydric alcohols, monosaccharides, oligosaccharides, polysaccharides, amino acids, organic amines, synthetic resin emulsions, pH adjusters, vitamins, antioxidants, antioxidant aids and perfumes. The water-in-oil emulsified skin external preparation according to any one of claims 1 to 12, wherein at least one kind is blended.