JP3519301B2 - External preparation for skin - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an external preparation for skin. More specifically, it relates to a skin external preparation comprising a water-in-oil type emulsion composition with markedly improved usability and stability.

[0002]

2. Description of the Related Art Conventionally, in the development of external preparations for skin, many studies have been conducted on emulsion compositions, which have an important position.

Particularly in recent years, as reported in JP-A-9-301824 and JP-A-8-268833, a water-in-oil type emulsion base using a polymer is safe and has distinctive usability. It is being actively researched from the viewpoint of etc.

[0004]

However, when an emulsifying base using a polymer is applied to a skin external preparation, a characteristic usability such as a water-repellent feeling peculiar to polymer emulsification and a film-like feeling is exhibited. On the other hand, there is a problem in that the polymer itself gives a sticky feeling.

If the amount of the polymer is reduced in order to reduce the stickiness resulting from such polymer emulsification, the stickiness is slightly reduced, but the emulsion stability is extremely lowered, which is a fatal point in the emulsion formulation. Therefore, there has been a strong demand for the development of an external preparation for skin which has good stability and usability.

[0006] The present inventors have been made in view of the above circumstances, stability, in order to obtain a good skin external preparation usability both a result of extensive studies on an oil using a polymer water-emulsifying bases, ethyl
The present invention has been completed by finding that the above problems can be solved by adding a specific ester compound to the oil phase of an emulsion base containing cellulose .

An object of the present invention is to provide a skin external preparation comprising a water-in-oil type emulsion composition, which has markedly improved usability and stability.

[0008]

That SUMMARY OF THE INVENTION The present invention is, e
Glycerin and behenic acid were added to the oil phase containing chill cellulose.
And an external preparation for skin comprising an ester compound obtained by esterifying eicosane diacid .

[0009]

Further, the present invention provides the above-mentioned external preparation for skin, wherein the external preparation for skin is a water-in-oil type emulsion composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described in detail below.

The ethyl cellulose used in the present invention dissolves in the oil phase of the skin external preparation as an oil-soluble polymer and functions as a polymer emulsifier.

The amount of ethyl cellulose blended is preferably 0.001 to 10% by weight, more preferably 0.05 to 5% by weight, based on the total amount of the skin external preparation. When the amount is less than 0.001% by weight, sufficient emulsion stability cannot be obtained. On the contrary, when the amount is more than 10% by weight, the viscoelasticity is high and the emulsification becomes difficult.

[0014]

The ester compound used in the present invention has a function of gelling oil, and it is considered that this function improves usability of the external preparation for skin.

[0016]

[0017]

[0018]

In the present invention, glycerin behenic acid eicosandicarboxylic acid, which is an ester compound obtained by esterifying glycerin with behenic acid and eicosane diacid, is particularly preferably used in terms of usability and stability over time.

Glycerin behenic acid eicosane dicarboxylic acid is prepared by mixing glycerin, behenic acid and eicosane diacid at an arbitrary mixing ratio to form an ester, thereby reducing the contents of glycerin unit, behenic acid unit and eicosane diacid unit. It is obtained in the form of a mixture of different ester compounds.

The compounding amount of the ester compound in the present invention is 0.01 to 10.0% by weight, preferably 0.1 to 5.0% by weight based on the total amount of the skin external preparation. If the blending amount is less than 0.01% by weight, sufficient effects cannot be obtained in stability and usability. Further, if it exceeds 10.0% by weight, spreadability is deteriorated and usability is impaired.

The oil component constituting the oil phase in which ethyl cellulose is dissolved is not particularly limited, and various oil components usually used in external preparations for skin can be used. The specific examples of oil are listed below.

Examples of liquid oils and fats include avocado oil,
Camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern oil, castor oil, linseed oil, safflower oil, cottonseed oil, eno oil, Soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnamon oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin,
Examples thereof include glycerin trioctanoate and glycerin triisopalmitate.

Examples of the solid fats and oils include cacao butter, coconut oil, horse fat, hardened coconut oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, lard, beef bone oil, sorghum kernel oil, and hardened oil. Examples thereof include oil, beef tallow, owl, hydrogenated castor oil, and the like.

Examples of the waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ivorot wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin,
Sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, etc. To be

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

Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid (beheninic acid), oleic acid, undecylenic acid, tallic acid, isostearic acid, linoleic acid, linoleic acid,
Examples thereof include eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA).

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

The synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate,
Decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, 1
Cholesteryl 2-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, di-2-heptylundecanoic acid Glycerin, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, trimethylolpropane triisostearate, cetyl 2-ethyl Hexanoate, 2-ethylhexyl palmitate, glycerin trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, Luminic acid 2-heptylundecyl, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, myristic acid 2-
Hexyldecyl, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate,
2-ethylhexyl succinate, ethyl acetate, butyl acetate,
Triethyl citrate and the like can be mentioned.

Examples of the silicone oil include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane and methylhydrogenpolysiloxane, decamethylpolysiloxane, dodecamethylpolysiloxane and tetramethyltetrahydrogenpolysiloxane. Examples thereof include cyclic polysiloxane.

When ethyl cellulose is used in the present invention, a dissolution aid such as ethanol is used to dissolve it in the oil phase. The amount of ethanol, which is a solubilizing agent, to be incorporated in the external preparation for skin is not limited. Further, it is also possible to remove ethanol by a known method such as heating and evaporation after dissolving ethyl cellulose and uniformly adding oil, and in the present invention, an auxiliary solvent such as ethanol is not necessarily present in the skin external preparation. It need not be compounded.

The external preparation for skin of the present invention contains, in addition to the above-mentioned essential components, various components generally used in cosmetics, pharmaceuticals and the like, if necessary, within a range that does not impair the effects of the present invention, to obtain a desired product. Can be produced by a conventional method. For example, powder components, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, moisturizers, water-soluble polymer compounds, thickeners, film agents, ultraviolet absorbers, sequestering agents. , Lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, synthetic resin emulsions, pH adjusting agents, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, water, etc. It can be appropriately compounded and can be produced by a conventional method depending on the intended dosage form. Specific ingredients that can be mixed are listed below, but the external preparation for skin of the present invention can be prepared by mixing the above essential ingredients and one or more of the following ingredients.

As powder components, talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, phlogopite, biotite, lithia mica, permiculite,
Magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, tungstate metal salt, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate, (calculated gypsum), calcium phosphate , Fluorapatite, Hydroxyapatite, Ceramic powder, Metal soap (Zinc myristate, Calcium palmitate, Aluminum stearate), Inorganic powder such as boron nitride, Polyamide resin powder (Nylon powder), Polyethylene powder, Polymethylmethacrylate powder, Polystyrene powder, styrene-acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder, organic powder such as cellulose powder, titanium dioxide, inorganic white such as zinc oxide Pigments, iron oxide (red iron oxide),
Inorganic red pigments such as iron titanate, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and ocher, iron black oxide, inorganic black pigments such as low-order titanium oxide. Inorganic purple pigments such as mango violet and cobalt violet, inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate, inorganic blue pigments such as ultramarine blue and navy blue, titanium oxide coated mica, titanium oxide coated oxychloride Bismuth, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, pearl pigment such as fish scale foil, aluminum powder,
Metal powder pigments such as copper powder, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red 220
No., Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401
And organic pigments such as Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230
No., Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3
And organic pigments such as barium or aluminum lakes such as No. 1 and Blue No. 1 and natural pigments such as chlorophyll and β-carotene. However, the powder is not limited to the above components as long as it is a powder applicable to general cosmetics.

Examples of the anionic surfactant include a base for soap, fatty acid soap such as sodium laurate and sodium palmitate, higher alkyl sulfate ester salt such as sodium lauryl sulfate and potassium lauryl sulfate, POE-triethanolamine lauryl sulfate. , POE-alkyl ether sulfate salts such as sodium lauryl sulfate, N-acyl sarcosinic acid such as sodium lauroyl sarcosine, N-myristoyl-N-methyl taurine sodium, coconut oil fatty acid methyl tauride sodium, sodium lauryl methyl tauride etc. Higher fatty acid amide sulfonate, POE-sodium oleyl ether phosphate, POE-phosphate ester salts such as stearyl ether phosphate, sodium di-2-ethylhexyl sulfosuccinate,
Monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, sulfosuccinates such as sodium lauryl polypropylene glycol sulfosuccinate, sodium linear dodecylbenzene sulfonate,
Alkylbenzene sulfonates such as linear dodecylbenzene sulfonic acid triethanolamine, linear dodecyl benzene sulfonic acid, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate,
N-myristoyl-L-monosodium glutamate and other N-
Acyl glutamate, higher fatty acid ester sulfate ester salt such as hydrogenated coconut oil fatty acid glycerin sodium sulfate,
Sulfated oil such as funnel oil, POE-alkyl ether carboxylic acid, POE-alkyl allyl ether carboxylate, α-olefin sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfate ester salt, higher fatty acid alkylolamide Examples thereof include sulfate ester salts, sodium lauroyl monoethanolamide succinate, ditriethanolamine N-palmitoyl aspartate, and sodium caseinate.

Examples of the cationic surfactant include alkyl trimethyl ammonium salts such as stearyl trimethyl ammonium chloride and lauryl trimethyl ammonium chloride, distearyl dimethyl ammonium dialkyl dimethyl ammonium salt, and poly (N, N'-dimethyl chloride).
-3,5-methylenepiperidinium), an alkylpyridinium salt such as cetylpyridinium chloride, an alkyl quaternary ammonium salt, an alkyldimethylbenzylammonium salt, an alkylisoquinolinium salt, a dialkylmorphonium salt, a POE-alkylamine, Examples thereof include alkylamine salts, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride and benzethonium chloride.

Examples of the amphoteric surfactant include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-
Imidazoline amphoteric surfactants such as sodium imidazoline, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, 2-heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine And betaine-based surfactants such as lauryl dimethylamino acetic acid betaine, alkyl betaine, amidobetaine and sulfobetaine.

Examples of lipophilic nonionic surfactants include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, Penta-2-ethylhexyl diglycerol sorbitan,
Tetra-2-ethylhexylate diglycerol sorbitan and other sorbitan fatty acid esters, monocotton oil fatty acid glycerin, glyceryl monoerucate, glyceryl sesquioleate, glyceryl monostearate, α, α'-glyceryl pyroglutamate oleate, glyceryl monostearate Examples thereof include glycerin polyglycerin fatty acid such as malic acid, propylene glycol fatty acid ester such as propylene glycol monostearate, hydrogenated castor oil derivative, and glycerin alkyl ether.

Examples of hydrophilic nonionic surfactants include POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, and other POE-sorbitan fatty acid esters, POE-sorbit monolaurate, POE-sorbit monooleate, POE-sorbit pentaoleate, POE-sorbit monostearate and other POE sorbit fatty acid esters, POE-glycerin monostearate, POE-glycerin monoisostearate, POE-glycerin triisostearate and other POE-glycerin fatty acid esters, POE-monooleate, POE-distearate,
POE-monodioleate, POE-fatty acid esters such as ethylene glycol distearate, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether,
POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether and other POE-alkyl ethers, pluronic and other pluronic types, POE / POP
-POE ・ POP- such as cetyl ether, POE ・ POP-2-decyltetradecyl ether, POE ・ POP-monobutyl ether, POE ・ POP-hydrogenated lanolin, POE ・ POP-glycerin ether
Alkyl ethers, Tetronic such as tetra-POE / tetra-POP-ethylenediamine condensates, POE-castor oil, PO
E-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearate diester, POE-hardened castor oil maleic acid and other POE- Castor oil Hardened castor oil derivative, POE-Sorbit beeswax, etc.
E- beeswax lanolin derivative, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, alkanolamides such as fatty acid isopropanolamide, POE-propylene glycol fatty acid ester, POE-alkylamine, POE-fatty acid amide, sucrose fatty acid ester, POE -Nonyl phenyl formaldehyde condensate, alkyl ethoxy dimethyl amine oxide, trioleyl phosphoric acid etc. are mentioned.

Examples of moisturizers include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-. Examples thereof include hydroxy stearate, sodium lactate, bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Isaioba rose extract, Yarrow millet extract and Merrilot extract.

Examples of the natural water-soluble polymer include, for example, araavia gum, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), algae colloid (cassius extract), starch (rice, corn, Potato, wheat), plant-based polymers such as glycyrrhizinate, microbial-based polymers such as xanthan gum, dextran, succinoglucan, and vullan, collagen,
Animal-based polymers such as casein, albumin and gelatin can be mentioned.

As the semi-synthetic water-soluble polymer, for example,
Starch-based polymers such as carboxymethyl starch and methyl hydroxypropyl starch, methyl cellulose, nitrocellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder And the like, and alginic acid-based polymers such as sodium alginate and propylene glycol alginate.

The synthetic water-soluble polymer includes, for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, vinyl polymers such as carboxyvinyl polymer (Carbopol), polyethylene glycol.
Polyoxyethylene-based polymers such as 20,000, 40,000 and 60,000, polyoxyethylene-polyoxypropylene copolymer copolymer-based polymers, sodium-acrylate, polyethyl acrylate, acrylic polymers such as polyacrylamide, polyethyleneimine, Examples include cationic polymers.

Examples of the inorganic water-soluble polymer include bentonite, silicic acid A1Mg (veegum), laponite, hectorite, and silicic acid anhydride.

Examples of the thickener include gum arabic,
Carrageenan, karaya gum, tragacanth gum, carob gum, quince seed (quince), casein, dextrin, gelatin, sodium pectate, sodium alginate, methyl cellulose, ethyl cellulose,
CMC, hydroxyethyl cellulose, hydroxypropyl cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, dialkyldimethylammonium sulfate cellulose, xanthan gum, magnesium aluminum silicate, bentonite,
Hectorite and the like can be mentioned.

Examples of the ultraviolet absorber include para-aminobenzoic 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, N, N-dimethyl PABA butyl ester, N, N-
Benzoic acid-based UV absorbers such as dimethyl PABA ethyl ester, anthranilate-based UV absorbers such as homomenthyl-N-acetylanthranilate, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p -Salicylic acid type UV absorbers such as isopropanol phenyl salicylate, octyl cinnamate, ethyl-4-isopropyl cinnamate, 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-β-phenylcinnamate, 2- Ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-
Cinnamic acid-based ultraviolet absorbers such as diparamethoxycinnamate, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-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-n-octoxybenzophenone, 4-hydroxy-3-carboxy Benzophenone-based UV absorbers such as benzophenone, 3- (4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methyl Benzoxazole, 2,2'-hydroxy-5
-Methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2-
(2'-hydroxy-5'-methylphenylbenzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy
-4'-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-
Norbornylidene) -3-pentan-2-one, 2,4,6-trianilino-p- (carbo-2'-ethylhexyl-1'-oxy) 1,
Examples include 3,5-triazine and the like.

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

As the lower alcohol, for example, methanol, ethanol, propanol, isopropanol,
Examples thereof include isobutyl alcohol and t-butyl alcohol.

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 and pentamethylene. Glycol, 2-butene-1,4-diol, dihydric alcohol such as hexylene glycol and octylene glycol, trihydric alcohol such as glycerin, trimethylolpropane and 1,2,6-hexanetriol, pentaerythritol. Etc., tetravalent alcohols such as xylitol, hexavalent alcohols such as sorbitol, mannitol, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol. Polyol, 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,
Dihydric alcohol alkyl ethers such as ethylene 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 monoethyl 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, Dihydric alcohol alkyl ethers such as ropylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether and dipropylene glycol butyl ether, ethylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadibate, ethylene glycol disuccinate, diethylene glycol monoethyl ether state, diethylene glycol monobutyl ether acetate , Dihydric alcohol ether esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc., glycerin monoalkyl such as xyl alcohol, ceracyl alcohol, batyl alcohol, etc. Ether, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol,
Glucose, fructose, starch-decomposing sugar, maltose, xylitol, sugar-decomposing sugar such as reducing alcohol, glycolid, tetrahydrofurfuryl alcohol, POE-tetrahydrofurfuryl alcohol, POP-butyl ether, POP / POE-butyl ether,
Tripolyoxypropylene glycerin ether, POP-glycerin ether, POP-glycerin ether phosphoric acid, PO
P • POE-pentane erythritol ether and the like can be mentioned.

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 and D-xylose. L-lyxose, D-arabinose, D-ribose, D-ribulose,
Pentose sugars such as D-xylulose and L-xylulose, D-glucose, D-talose, D-busicose, D-galactose, D-
Fructose, L-galactose, L-mannose, D-tagatose and other hexoses, aldoheptose, heptulose and other heptasaccharides, octulose and other octoses, 2-deoxy-D-ribose, 6-deoxy-L-galactose , Deoxy sugars such as 6-deoxy-L-mannose, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, amino sugars such as muramic acid, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D -Examples include uronic acids such as galacturonic acid and L-iduronic acid.

Examples of oligosaccharides include sucrose, guanthianose, umbelliferose, lactose, planteose, isoliknoses, α, α-trehalose,
Raffinose, lychnose, umbilicin, stachyose bell bass course, etc. may be mentioned.

Examples of the polysaccharides 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 and dextran. , Keratosulfate, 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 sodium acyl sarcosine (sodium lauroyl sarcosine), acyl glutamate, sodium acyl β-alanine, glutathione, and pyrrolidone carboxylic acid.

Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1. -Propanol and the like can be mentioned.

Examples of synthetic resin emulsions include:
Examples thereof include acrylic resin emulsion, polyethyl acrylate emulsion, acrylic resin solution, polyacrylic alkyl ester emulsion, and 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.

As the antioxidant aid, for example, phosphoric acid,
Examples thereof include citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid and ethylenediaminetetraacetic acid.

Other compoundable ingredients include preservatives such as ethylparaben and butylparaben, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, and the like.
Anti-inflammatory agents such as hinokitiol, zinc oxide, allantoin,
Whitening agents such as placenta extract, Yukinoshita extract, psyllium,
Coptis, Sikon, Peony, Assemblage, Birch, Sage, Loquat, Carrot, Aloe, Mallow, Iris, Grape, Yokuinin, Loofah, Lily, Saffron, Senkyu, Ginger, Hypericum, Ononis, Garlic, Capsicum, Chimp, Toki, Seaweed Extract such as royal jelly, photosensitizer, cholesterol derivative,
Activator such as infant blood extract, nonyl acid warenylamide,
Nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, zingerone, cantharisin tincture, ictamol, tannic acid, α-borneol, nicotinic acid tocopherol, inositol hexanicotinate, cyclanderate, cinnarizine, tolazoline, acetylcholine, verapamil , Cepharanthin,
Examples include blood circulation promoters such as γ-oryzanol, antiseborrheic agents such as sulfur and thiantol, tranexamic acid, thiotaurine, and hypotaurine.

Since the external preparation for skin of the water-in-oil type emulsion composition of the present invention is prepared by polymer emulsification as an essential component, the above-mentioned surfactant is not necessary, but the range does not impair the effects of the present invention. It may be supplementarily blended with.

[0061]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. In the following examples, the blending amount is% by weight.
Is.

A skin external preparation of a water-in-oil type emulsion composition was prepared by a conventional method with the composition shown in "Table 1". The prepared external preparation for skin was filled in a glass bottle, and the stability was evaluated immediately after emulsification and after standing at 0 ° C., room temperature, 50 ° C. for one month. The stability was evaluated according to the following criteria, and the results are shown in "Table 2".

[Stability Judgment Criteria] O: No abnormality such as separation was observed, and stability was good. Δ: A slight separation is observed in the oil phase or the water phase. X: Significant separation was observed in the oil phase or the water phase and the stability was poor.

A skin external preparation prepared by 10 specialist panels was actually used, and a sensory test was conducted to evaluate the usability. Usability was evaluated according to the following criteria, and the results are shown in "Table 2".

"Usability Judgment Criteria" ⊚: 8 or more out of 10 people did not have stickiness and were judged to have good usability. ◯: 6 or more out of 10 people judged that there was no stickiness and the usability was good. Δ: 4 or more out of 10 people judged that there was no stickiness and the usability was good. Poor: Less than 4 out of 10 people did not have stickiness and were judged to have good usability.

[0066]

[Table 1] -------------------------------------------------- --------------------- Raw Material Name Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 -------------------------------------------------- --------------------- Ethyl cellulose (* 1) 0.2 0.5 1.0 1.0 0.2 0.5 10 Ester Compound (* 2) 0 0 0 1.0 1.0 1.0 1.0 Ethanol              2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amber Diisooctyl acid 20 20 20 20 20 20 20 Methylphenylpolysiloxane Acid 10 10 10 10 10 10 Decamethylcyclopentasiloxane   10 10 10 10 10 10 Isostearin Acid 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Ion Exchanged water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount -------------------------------------------------- --------------------- (* 1) N-22 HERCULES product (* 2) Eicosane behenate glyceryl diate (Brand name Nomcoat HK-G, Nissin Essential Oil (Made by)

[0067]

[Table 2] -------------------------------------------------- ---------------------                   Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 -------------------------------------------------- --------------------- Stability test results  Immediately after emulsification △ ○ ○ ○ ○ ○  One month later     0 ° C × △ ○ ○ ○ ○   37 ° C × △ △ ○ ○ ○   50 ° C × × × ○ ○ ○ -------------------------------------------------- --------------------- Sensory test results △ × × ◎ ◎ ◎ -------------------------------------------------- ---------------------

As is clear from "Table 2", it was confirmed that the external preparations for skin of Examples had markedly improved usability and stability as compared with Comparative Examples.

Other examples of the external preparation for skin of the present invention will be shown below. All of the external preparations for skin obtained in the following examples were good in the stability and usability evaluations performed in Examples 1 to 3.

Example 4 Sunblock Cream Ethylcellulose 0.5 (N-22 HERCULES) Ethanol 2 Isooctyl methoxycinnamate 10 Butylmethoxydibenzoylmethane 2 Octyltriazone 2 (trade name Ubinar T150, BASF AG) Glyceryl trioctanoate 10 Diisooctyl succinate 10 Octamethyltetrasiloxane 5 Isostearic acid 3 Hydrophobized fine particles titanium dioxide 3 Hydrophobized fine particles zinc oxide 3 Becosic acid eicosane diacid glyceryl 1 (trade name: Nomcoat HK-G, Nisshin Essential Oil) Co., Ltd.) 1,3-butylene glycol 10 EDTA / 3Na2H ₂ O 0.1 glutathione 0.3 tocopherol acetate 0.1 preservative appropriate amount fragrance appropriate amount ion-exchanged water residual amount

“Example 5 Emulsion” Ethylcellulose 0.1 (N-22 HERCULES) Polyoxyethylene polyalkylsiloxane 0.2 Glycerin trioctanoate 15 Diisooctyl succinate 15 Decamethylcyclopentasiloxane 20 Methylphenylpolysiloxane 15 Behen Acid eicosane diacid glycerin 0.1 (trade name: Nomcoat HK-G, manufactured by Nisshin Seiyaku Co., Ltd.) Propylene glycol 8 glycerin 5 EDTA / 3Na2H ₂ O 0.1 glycyrrhetinic acid 0.1 Preservative proper amount perfume appropriate amount ion Exchanged water balance

“Example 6 Emollient Cream” Ethylcellulose 1 (manufactured by N-22 HERCULES) Isostearyl alcohol 2 Isostearate 2 Cetyl octanoate 5 Diisooctyl succinate 10 Methylphenylpolysiloxane 10 Glyceryl behenate dicosylate 1 (trade name) Nomcoat HK-G, manufactured by Nisshin Seiyaku Co., Ltd.) Propylene glycol 81,3 butylene glycol 5 hyaluronic acid 0.1 carboxymethyl cellulose 0.5 EDTA / 3Na2H ₂ O 0.1 birch extract 0.1 preservative proper amount Fragrance Suitable amount Ion-exchanged water Remaining amount

[0073] "Example 7 W / O emulsion foundation" Ethyl cellulose 0.5 (N-22 HERCULES product) Liquid paraffin 5 Methylphenyl polysiloxane 10 Isostearyl alcohol 2 Eicosane behenate glyceryl diate 0.2 (Product name: Nom Coat HK-G, manufactured by Nisshin Seiyu Co., Ltd.) Sericite 5 Kaolin 3 Titanium dioxide 12 Bengal 0.5 Yellow iron oxide 1 Black iron oxide 0.1 1,3 butylene glycol 5 Dispersant Appropriate amount Preservative Appropriate amount Fragrance suitable amount Deionized water balance

[0074]

INDUSTRIAL APPLICABILITY According to the present invention, by adding a specific ester compound to the oil phase containing ethyl cellulose and / or ethyl hydroxyethyl cellulose, it is possible to provide a skin external preparation having good stability and usability. .

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Fumiaki Matsuzaki Inventor Fumiaki Matsuzaki, 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Shiseido Co., Ltd. Research Center (56) Reference JP-A-8-268833 (JP, A) JP JP-A-9-301824 (JP, A) JP-A-8-268834 (JP, A) JP-A-59-62515 (JP, A) JP-A-10-273433 (JP, A) JP-A-10-25224 (JP , A) JP-A-9-104613 (JP, A) JP-A-10-175818 (JP, A) JP-A-10-175819 (JP, A) International Publication 96/029975 (WO, A1) (58) Survey Areas (Int.Cl. ⁷ , DB name) A61K ^7/ 00-7/50 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] In the oil phase containing 1. A ethylcellulose, glyceryl
Esterification of serine with behenic acid and eicosane diacid
A skin external preparation containing the resulting ester compound. 2. A skin external preparation according to claim 1, wherein the skin external preparation is a water-in-oil emulsion composition.