JP2012036113A - External preparation for skin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an external preparation for the skin, containing a base having good stability, and providing excellent use feeling, especially wet feeling and lack of squeaky feeling after being coated.SOLUTION: The external preparation for the skin includes 0.01-5 mass% of a polyoxyethylene-polyoxypropylene-added phytosterol and/or a polyoxyethylene-polyoxypropylene-added phytostanol represented by general formula (I) (wherein, R is a phytosterol residue or a phytostanol residue; m is a number of 5-100; and n is a number of 5-100) and 0.01-10 mass% of a block-type alkylene oxide derivative represented by general formula (II), RO-[(BO)(EO)(BO)]-R(II) (wherein, BO is an oxybutylene group; EO is an oxyethylene group; p, r and q are each an average number of added moles; 1≤q≤70; 1≤p+r≤70; the proportion of the oxyethylene group based on the total of the oxybutylene group and the oxyethylene group is 20-80 mass%; and Rand Rare each a 1C-4C hydrocarbon group).

Description

  The present invention relates to an external preparation for skin having good base stability and excellent use feeling, particularly moist feeling after application, and no squeaky feeling.

  There are various types of skin external preparations such as lotion, milky lotion, cream, etc. Among them, lotion is one of the essential items for basic cosmetics. In addition to water and water-soluble substances such as moisturizing ingredients, lotion has a base stabilization technology (solubilization technology) that uses a surfactant to stably incorporate water-insoluble substances such as fragrances, oils, and oil-soluble drugs. Various proposals have been made (see, for example, Patent Documents 1 and 2).

  However, with conventional surfactants, the stability of the base is improved by selecting the type or by adding a considerable amount, but it may be one of the causes of rough skin, and it does not fully satisfy the improvement in the feeling of use. . In recent years, a higher level of safety is expected for external preparations for skin, and the presence of a surfactant may be a problem from this viewpoint. In this way, surfactants are indispensable ingredients for many topical skin preparations from the viewpoint of improving the stability of the base. In some rare cases, they may cause rough skin, and they are formulated due to poor use feeling. There was a problem to be solved that the product value of the product may be greatly impaired.

  As a technique for solving the poor feeling of use, a method of blending trimethylglycine, which is a quaternary ammonium salt, into cosmetics has been proposed (for example, see Patent Document 3). However, although cosmetics containing trimethylglycine have improved use feeling such as “stickiness”, there is a problem to be solved, such as a tendency to be accompanied by “powder-like use feeling” due to the presence of trimethylglycine. In addition, a method of preventing “stickiness” by using a combination of mucopolysaccharide, gum quality such as xanthan gum and trimethylglycine has been proposed (see, for example, Patent Document 4). However, there was a problem that the feeling of use deteriorated.

  As a technique for solving these problems, a method of blending an alkylene oxide derivative that has low skin irritation, has an effect of improving skin roughness and has a good feeling in use (see, for example, Patent Document 5) is known. However, in these methods, it cannot be said that the feeling of moistness after application and the feeling of squeakiness are not sufficient, and further improvement has been desired.

JP 2001-302443 A JP 2005-47871 A JP-A-6-293625 JP-A-9-95432 Japanese Patent No. 3660656

  The present invention has been made in view of the above-described problems of the prior art, and in a skin external preparation such as skin lotion, the base stability is good, and the feeling of use, in particular, the moist feeling after application and the feeling of squeakiness are excellent. It is to provide a skin external preparation.

  As a result of the diligent research conducted by the present inventors in view of the above problems, a polyoxyethylene-polyoxypropylene-added phytosterol and / or polyoxyethylene-polyoxypropylene-added phytostanol and a block-type alkylene oxide derivative having a specific structure are blended. As a result, it was found that an external preparation for skin having excellent base stability and excellent use feeling, particularly moist feeling after application, and no squeaky feeling was obtained, and the present invention was completed.

That is, the external preparation for skin according to the present invention comprises (a) a polyoxyethylene-polyoxypropylene-added phytosterol and / or polyoxyethylene-polyoxypropylene-added phytostanol represented by the following general formula (I) in an amount of 0.01 to 5% by mass and (b) 0.01 to 10% by mass of a block type alkylene oxide derivative represented by the following general formula (II).
(In the formula, R represents a phytosterol residue or a phytostanol residue, m represents a number of 5 to 100, and n represents a number of 5 to 100.)
(Chemical formula 2)
R ¹ O — [(BO) _p (EO) _q (BO) _r ] —R ² (II)
(In the formula, BO is an oxybutylene group having 4 carbon atoms, EO is an oxyethylene group, p, r, and q are the average added moles of the oxybutylene group and oxyethylene group, respectively, 1 ≦ q ≦ 70, 1 ≦ p + r ≦ 70 The ratio of the oxyethylene group to the total of the oxybutylene group and the oxyethylene group is 20 to 80% by mass, and R ¹ and R ² may be the same or different and may be the same or different. It is a hydrogen group.)

  By blending a specific amount of polyoxyethylene-polyoxypropylene-added phytosterol and / or polyoxyethylene-polyoxypropylene-added phytostanol according to the present invention and a block type alkylene oxide derivative having a specific structure, lotion and the like It is possible to provide a skin external preparation having good base stability and excellent feeling in use, particularly moist feeling after application and squeaky feeling.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The (a) polyoxyethylene-polyoxypropylene-added phytosterol and / or polyoxyethylene-polyoxypropylene-added phytostanol used in the present invention is characterized by being represented by the following general formula (I).

In general formula (I), phytosterol, which is a parent compound of a phytosterol residue that R can take, is a plant-derived sterol (FDGunstone and BGHerslof, A Lipid Glossary, The Oily Press, Air, 1992), There is no limitation. That is, phytosterol residues that R can take include sitosterol residues, campesterol residues, stigmasterol residues, brassicasterol residues, avenasterol residues, ergosterol residues, and the like. Can be mentioned. It is also possible to be a mixture of two or more compounds in which R is a different phytosterol residue.
Similarly, phytostanol, which is a parent compound of the phytostanol residue that R can take, is a phytosterol hydrogenation or saturation counterpart, and is not particularly limited. That is, examples of the phytostanol residue that R can take include sitostanol, campestanol, stigmasteranol, brassicastanol, avenastanol, ergostanol, and the like. It is also possible to be a mixture of two or more compounds in which R is a different phytostanol residue.

Furthermore, the polyoxyethylene-polyoxypropylene addition compound represented by the general formula (I) is a compound in which R has one or more phytosterol residues, and also one or more phytostanol residues. It is also possible to mix | blend with the skin external preparation of this invention as a mixture of the compound which has this. M indicating the number of polyoxypropylene chains is 5 to 100, preferably 5 to 50. Similarly, n indicating the number of polyoxyethylene chains is 5 to 100, preferably 10 to 50.
The ratio of m to n is, in particular, from the viewpoint of suppressing the stickiness of the external preparation for skin of the present invention to improve usability and ensuring better stability over time. A range of 50: 1 is preferable, and a range of m: n = 1: 5 to 5: 1 is particularly preferable.

  The compound represented by the general formula (I) can be produced by a conventional method based on its chemical structure. For example, propylene oxide is added to phytosterol in the presence of a catalyst, and the first stage addition reaction is performed. After removing unreacted substances, ethylene oxide is added and the second stage addition reaction is performed. After removal of the reaction product, neutralization, dehydration, deodorization, and filtration can be performed for easy production.

  In the external preparation for skin according to the present invention, the polyoxyethylene-polyoxypropylene addition compound represented by the general formula (I) is blended in an amount of 0.01 to 5% by mass relative to the total amount of the composition. If it is less than 0.01% by mass, the effect of the blending may not be sufficiently exhibited, and if it exceeds 5% by mass, a refreshing feeling may be lost after use.

Specific examples of the polyoxyethylene-polyoxypropylene-added phytosterol and / or polyoxyethylene-polyoxypropylene-added phytostanol according to the present invention include, for example, POE (25) POP (20) phytosterol, POE (15). POP (30) phytosterol, POE (40) POP (20) phytosterol, POE (20) POP (5) phytosterol, POE (40) POP (30) phytosterol, POE (30) POP (30) phytosterol, POE (20) POP (10) phytosterol etc. are mentioned.
The POE and POP are abbreviations of polyoxyethylene and polyoxypropylene, respectively, and may be abbreviated as follows. The added moles of POE and POP are respectively the total added moles in the molecule.

The (b) block type alkylene oxide derivative used in the present invention is characterized by being represented by the following general formula (II).
(Chemical formula 4)
R ¹ O — [(BO) _p (EO) _q (BO) _r ] —R ² (II)

  In the general formula (II), BO is a oxybutylene group having 4 carbon atoms, and EO is an oxyethylene group. q is the average number of moles of oxyethylene group added, and 1 ≦ q ≦ 70, preferably 5 ≦ q ≦ 55. p and r are the average number of moles added of the oxybutylene group, and 1 ≦ p + r ≦ 70, preferably 5 ≦ p + r ≦ 60. When the oxybutylene group or oxyethylene group is 0, the smoothness is lowered, and when it exceeds 70, a sticky feeling tends to appear.

R ¹ and R ² are hydrocarbon groups having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, an N-propyl group, an isopropyl group, an N-butyl group, a sec-butyl group, and a tert-butyl group. . A methyl group and an ethyl group are preferred. When the hydrocarbon group has 5 or more carbon atoms, the moist feeling tends to decrease.
R ¹ and R ² may be the same type, or different types of hydrocarbon groups having 1 to 4 carbon atoms may be mixed. More preferably, a hydrocarbon group of R ¹ and R ² are the same or different carbon atoms and optionally 1 to 4.

Specific examples of the block-type alkylene oxide derivative represented by the general formula (II) blended in the external preparation for skin according to the present invention include POB (28) POE (11) dimethyl ether and POB (28) POE (20) dimethyl ether. , POB (32) POE (35) dimethyl ether, POB (21) POE (23) dimethyl ether, POB (17) POE (18) dimethyl ether, POB (14) POE (15) dimethyl ether, POB (32) POE (52) dimethyl ether , POB (28) POE (45) dimethyl ether, POB (17) POE (28) dimethyl ether, POB (10) POE (17) dimethyl ether, POB (6) POE (14) dimethyl ether, POB (14) POE (34) dimethyl ether , PO (22) POE (55) dimethyl ether, POB (19) POE (55) dimethyl ether, POB (12) POE (44) dimethyl ether, POB (3) POE (18) dimethyl ether, POB (7) POE (45) dimethyl ether, etc. Can be mentioned.
The POE and POB are abbreviations for polyoxyethylene and polyoxybutylene, respectively, and may be abbreviated as follows.

  The block-type alkylene oxide derivative blended in the present invention can be produced by a known method. For example, it can be obtained by subjecting a compound having a hydroxyl group to addition polymerization of ethylene oxide and an alkylene oxide having 3 to 4 carbon atoms, and then subjecting an alkyl halide to an ether reaction in the presence of an alkali catalyst.

  In the external preparation for skin according to the present invention, the amount of the alkylene oxide derivative represented by the general formula (II) is 0.01 to 10% by mass relative to the total amount of the composition. If it is less than 0.01% by mass, the effect of the blending may not be sufficiently exhibited, and if it exceeds 10% by mass, a squeaky feeling may occur.

  In the external preparation for skin of the present invention, in addition to the above (a) polyoxyethylene-polyoxypropylene-added phytosterol and / or polyoxyethylene-polyoxypropylene-added phytostanol, and (b) the block-type alkylene oxide derivative, usually Ingredients used in cosmetics and quasi-drugs can be blended and manufactured according to conventional methods. Specific components that can be blended are listed below, and the external preparation for skin of the present invention can be prepared by blending the components (a) and (b) and one or more of the following 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, bile salt, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Izayoi rose extract, yarrow extract, merirot extract and the like.

  Examples of the powder component include inorganic powders (for example, talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid. Aluminum, barium silicate, 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 (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc .; organic powder (eg, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene Powder of styrene and acrylic acid copolymer resin, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc .; inorganic white pigment (eg, zinc oxide); inorganic red pigment (eg, iron titanate) Inorganic purple pigments (eg, mango violet, cobalt violet, etc.); inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.); inorganic blue pigments (eg, ultramarine blue, bitumen, etc.) Pearl pigments (eg, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil); metal powder pigments (eg, aluminum powder, copper powder, etc.) ); Such as zirconium, barium or aluminum lakes Organic pigments (for example, red 201, red 202, red 204, red 205, red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205, yellow Organic pigments such as No. 401 and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5 No., Yellow No. 202, Yellow No. 203, Green No. 3 and Blue No. 1); natural pigments (for example, chlorophyll, β-carotene and the like) and the like.

  Examples of liquid oils 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 castor oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.

  Examples of the solid fat include cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cattle Leg fats, moles, hydrogenated 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, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugarcane wax, lanolin fatty acid isopropyl, hexyl laurate, and 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, and the like.

Examples of the hydrocarbon oil include liquid paraffin, ozokerite, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, and the like.
Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid ( DHA) and the like.

  Examples of higher alcohols include linear alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol); branched chain alcohols (eg, monostearyl glycerin ether (batyl alcohol) ), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol and the like.

  Synthetic 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 Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, apple Acid diisostearyl, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, Trimethylolpropane phosphate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, glycerin trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L -Glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyl myristate Sill, palmitic acid 2-hexyl decyl, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.

  Examples of the silicone oil include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexyl). Silicone resins, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic silicone And the like.

Moreover, you may mix | blend various surfactant with the skin external preparation concerning this invention.
Anionic surfactants include, for example, fatty acid soaps (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates (eg, POE-lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.); N-acyl sarcosine acid (eg, sodium lauroyl sarcosine, etc.); higher fatty acid amide sulfonates (eg, sodium N-myristoyl-N-methyl taurate, palm Oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc .; phosphate ester salt (POE-oleyl ether sodium phosphate, POE-stearyl ether phosphate, etc.); sulfosuccinate (example) For example, sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc .; alkyl benzene sulfonates (eg, sodium linear dodecyl benzene sulfonate, linear dodecyl benzene sulfone) Acid triethanolamine, linear dodecyl benzene sulfonic acid, etc.); higher fatty acid ester sulfates (for example, hydrogenated coconut oil fatty acid sodium glycerin sulfate, etc.); Disodium glutamate, monosodium N-myristoyl-L-glutamate, etc.); sulfated oil (eg funnel oil); POE POE-alkylallyl ether carboxylates; α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfates; higher fatty acid alkylolamide sulfates; lauroyl monoethanolamide succinic acid Sodium; N-palmitoyl aspartate ditriethanolamine; sodium caseinate and the like.

  Examples of the cationic surfactant include alkyltrimethylammonium salts (eg, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (eg, cetylpyridinium chloride, etc.); distearyldimethylammonium dialkyldimethylammonium chloride; Poly (N, N′-dimethyl-3,5-methylenepiperidinium chloride); alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkyl morpholinium salt; POE-alkylamine; Examples include alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

  Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (for example, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide). Side-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine) , Sulfobetaine, etc.).

  Examples of the lipophilic nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, Sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexyl); glycerin polyglycerin fatty acids (for example, mono-cotton oil fatty acid glycerin, mono-erucic acid glycerin, sesquioleate glycerin, monostearin) Glycerin acid, α, α′-oleic acid pyroglutamate glycerin, monostearate glycerin malate, etc.); propylene glycol fatty acid esters (eg, Propylene glycol stearate); hydrogenated castor oil derivatives; glycerol alkyl ethers, and the like.

  Examples of the hydrophilic nonionic surfactant include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate). POE sorbite fatty acid esters (eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.); POE-glycerin fatty acid esters (eg, POE- Glycerol monostearate, POE-glycerol monoisostearate, POE-monooleate such as POE-glycerol triisostearate, etc.); POE-fatty acid esters (eg POE-distearate, P E-monodiolate, ethylene glycol distearate, etc.); POE-alkyl ethers (for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-core) Stanol ether, etc.); Pluronic type (for example, Pluronic, etc.); POE • POP-alkyl ethers (for example, POE • POP-cetyl ether, POE • POP-2-decyltetradecyl ether, POE • POP-monobutyl ether, POE / POP-hydrogenated lanolin, POE / POP-glycerin ether, etc.); Tetra POE / tetra-POP-ethylenediamine condensates (for example, Tetronic, etc.); POE-castor oil hardened castor oil derivative For example, 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-hardened castor Oil maleic acid, etc.); POE-beeswax lanolin derivatives (eg POE-sorbite beeswax etc.); alkanolamides (eg coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide etc.); POE-propylene glycol fatty acid Examples include esters; POE-alkylamines; POE-fatty acid amides; sucrose fatty acid esters; alkyl ethoxydimethylamine oxides;

  Examples of natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, locust bean gum, guar gum, tamarind gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), Arge colloid (gypsum extract), starch (rice, corn, potato, wheat), glycyrrhizic acid); microbial polymer (eg, xanthan gum, dextran, succinoglucan, bull run); animal polymer (eg, collagen, casein) , Albumin, gelatin, etc.).

  Semi-synthetic water-soluble polymers include, for example, starch polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate) Hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder and the like); alginic acid polymers (for example, sodium alginate, propylene glycol alginate, etc.) and the like.

  Synthetic water-soluble polymers include, for example, vinyl polymers (eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer); polyoxyethylene polymers (eg, polyethylene glycol 20,000, 40). Acrylic polymer (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymer, and the like.

  Examples of thickeners other than the water-soluble polymer include, for example, dextrin, sodium pectate, sodium alginate, cellulose dialkyldimethylammonium sulfate, magnesium aluminum silicate, bentonite, hectorite, silicate A1Mg (beegum), laponite, Silicic anhydride etc. are mentioned.

  Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers (for example, 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, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA ethyl ester, etc.); anthranilic acid ultraviolet absorbers (for example, homomenthyl-N-acetylanthranylate, etc.); Salicylic acid ultraviolet absorbers (eg, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate); cinnamic acid ultraviolet absorber For example, octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate Mate, 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-diparamethoxycinnamate, etc.); benzofe UV absorbers (for example, 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-carboxybenzophenone, etc.); 3- (4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole; (2′-hydroxy-5′-methylphenylbenzotriazole; dibenzalazine; dianisoylmethane; 4-methoxy-4′-tert-butyldibenzoylmethane; 5- (3,3-dimethyl-2-norbornylidene) -3- Pentan-2-one and the like.

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

  Examples of the polyhydric alcohol include divalent alcohols (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, Pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trivalent alcohol (eg, glycerin, trimethylolpropane, etc.); tetravalent alcohol (eg, 1, 2, 6) Pentaerythritol such as hexanetriol, etc .; pentavalent alcohol (eg, xylitol, etc.); hexavalent alcohol (eg, sorbitol, mannitol, etc.); polyhydric alcohol polymer (eg, diethylene glycol, dipropylene glycol, Tylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); divalent alcohol alkyl ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol) Monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, 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 Dihydric alcohol alkyl ethers (for example, 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, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol Dibutyl alcohol ether ester (for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazebate, ethylene glycol disuccine) , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.); glycerin monoalkyl ether (example) Sugar alcohol (eg, sorbitol, maltitol, maltotriose, mannitol, erythritol, etc.); glycolide; tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol POP-butyl ether; POP / POE-butyl ether; tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphate; POP / POE-pentane erythritol ether, polyglycerin and the like.

  Examples of monosaccharides include tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.); tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-threose, etc.); pentose sugars (eg, L -Arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc .; hexose (eg D-glucose, D-talose, D-bucose , D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); pentose sugar (eg, aldoheptose, heproose, etc.); octose sugar (eg, octulose, etc.); deoxy sugar (eg, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.) Amino sugars (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.); uronic acids (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L) -Iduronic acid and the like).

Examples of the oligosaccharides include sucrose, gnocyanose, umbelliferose, lactose, planteose, isoliquinoses, α, α-trehalose, raffinose, lycnose, umbilicin, stachyose verbusose and the like.
Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of the amino acid derivative include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione, and pyrrolidone carboxylic acid.

  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 alkylene oxide derivative include POE (9) POP (2) dimethyl ether, POE (14) POP (7) dimethyl ether, POE (10) POP (10) dimethyl ether, POE (6) POP (14) dimethyl ether, POE ( 15) POP (5) dimethyl ether, POE (25) POP (25) dimethyl ether, POE (7) POP (12) dimethyl ether, POE (22) POP (40) dimethyl ether, POE (35) POP (40) dimethyl ether, POE ( 50) POP (40) dimethyl ether, POE (55) POP (30) dimethyl ether, POE (30) POP (34) dimethyl ether, POE (25) POP (30) dimethyl ether, POE (27) POP (14) dimethyl ether Ether, POE (55) POP (28) dimethyl ether, POE (36) POP (41) dimethyl ether, POE (7) POP (12) dimethyl ether, POE (17) POP (4) dimethyl ether.

  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 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, for example, preservatives (ethyl paraben, butyl paraben, etc.); whitening agents (eg, placenta extract, yukinoshita extract, arbutin, etc.); blood circulation promoters (nicotinic acid, benzyl nicotinate, nicotine) Acid tocopherol, nicotinic acid β-butoxy ester, minoxidil or its analog, vitamin Es, γ-oryzanol, alkoxycarbonylpyridine N-oxide, carpronium chloride, acetylcholine or a derivative thereof, and the like (for example, ginger, (Ubakaku, Auren, Shikon, Birch, Loquat, Carrot, Aloe, Zeniaoi, Iris, Grape, Loofah, Lily, Saffron, Senkyu, Pepper, Hypericum, Onionis, Garlic, Pepper, Chimpi, Toki, Button, Seaweed, etc.), Activation Agent (eg Panthenyl ethyl ether, nicotinamide, biotin, pantothenic acid, royal jelly, cholesterol derivatives and the like); antiseborrheic agents (for example, pyridoxines, thianthol and the like).

  The dosage form of the external preparation for skin of the present invention is arbitrary, solution system, solubilization system, emulsification system, powder dispersion system, water-oil two-layer system, water-oil-powder three-layer system, lotion, gel, mist, Any dosage form such as spray, mousse, roll-on, and stick may be used.

The present invention will be described more specifically with reference to the following examples. In addition, this invention is not limited by this. Unless otherwise specified, the blending amount indicates mass%.
First, the evaluation method used in the present invention will be described.

Evaluation (1): Base stability The skin external preparation (skin lotion) of each test example was filled in a transparent glass bottle immediately after production and allowed to stand at 50 ° C. for 4 weeks, and then the base was stabilized by visual observation based on the following criteria. Sexuality was evaluated.
<Evaluation criteria>
○: colorless and transparent △: slightly turbid ×: cloudy or separated

Evaluation (2): Moist feeling after application An actual use test of each test example was conducted by 10 professional panels on the moist feeling after application. The evaluation criteria are as follows.
A: Eight or more panelists recognized that there was a moist feeling after application.
○ 6 or more and less than 8 panelists recognized that there was a moist feeling after application.
Δ: 3 or more and less than 6 panelists recognized that there was a moist feeling after application.
X: Less than 3 panelists recognized that there was a moist feeling after application.

Evaluation (3): Absence of squeak after application An actual use test of each test example was conducted by 10 specialist panels for the absence of squeak after application. The evaluation criteria are as follows.
A: Eight or more panelists recognized that there was no squeak after application.
○: 6 or more and less than 8 panelists recognized that there was no squeak after application.
Δ: 3 or more and less than 6 panelists recognized that there was no squeak after application.
X: Less than 3 panelists recognized that there was no squeak after application.

In the compounding compositions shown in Table 1 and Table 2 below, a skin external preparation (skin lotion) was produced by a conventional method, and evaluation tests were performed on the above evaluations (1) to (3).
In addition, the block type alkylene oxide derivative in the following table shall have the following structures.
(Chemical formula 5)
^{_{R 1 O - [(BO)}} p (EO) q (BO) r] -R 2
For example, when an oxybutylene group and an oxyethylene group are used and p + r = 17 and q = 28, they are expressed as (BO) ₁₇ (EO) ₂₈ .

As Table 1 shows, Examples 1-4 which mix | blended the polyoxyethylene-polyoxypropylene addition phytosterol and the alkylene oxide derivative of a specific structure were excellent in any evaluation.
On the other hand, as shown in Table 2, polyoxyethylene-polyoxypropylene-added phytosterol and comparative example 1 using a compound in which the alkylene oxide derivative is only an oxyethylene group are not particularly squeaky, In Comparative Example 2 using a compound having only an oxybutylene group, the moist feeling is not particularly sufficient. Comparative Example 3 using a compound having hydrogen at both ends is not satisfactory in terms of moist and squeaky feeling. In Comparative Example 4 using a compound in which the bond form of alkylene oxide / ethylene oxide is a random type, the base stability is not sufficient. In Comparative Example 5 in which only the polyoxyethylene-polyoxypropylene-added phytosterol was blended, the base stability was good, but the feeling of use was not sufficient.

  Next, in the external preparation for skin containing the block type alkylene oxide derivative having a specific structure of the present invention, each of the examples and comparative examples comprising the composition shown in Table 3 below, in which the type of surfactant to be blended was changed. An external preparation for skin (skin lotion) was produced by a conventional method, and the above evaluations (1) to (3) were evaluated.

As shown in Table 3, Example 4 in which a block-type alkylene oxide derivative having a specific structure and a polyoxyethylene-polyoxypropylene-added phytosterol were blended was excellent in any evaluation. In Example 4, Example 5 in which polyoxyethylene-polyoxypropylene-added phytostanol was blended instead of polyoxyethylene-polyoxypropylene-added phytosterol was also excellent in all evaluations.
In Comparative Examples 6 to 10 in which a block type alkylene oxide derivative having a specific structure and other surfactants were blended, neither the base stability nor the feeling in use was sufficient.

  Next, in the external preparation for skin containing the polyoxyethylene-polyoxypropylene-added phytosterol as the component (a) and the block type alkylene oxide derivative as the component (b) in the present invention, the components (a) and (b) The skin external preparations (skin lotions) of the respective examples having the blending compositions shown in Table 4 below with different blending mass ratios were produced by a conventional method, and the above evaluations (1) to (3) were evaluated. .

As shown in Table 4, according to Examples 6 to 11, although there is a tendency that a slightly excellent use feeling is not exhibited when the blending mass ratio of the component (a) or the component (b) is small, in any evaluation It was excellent.
Therefore, considering the feeling of use, the blending mass ratio of the component (a) and the component (b) is preferably 1: 9 to 9: 1.

  Although the example of formulation of the skin external preparation of this invention is given to the following, the technical scope of this invention is not limited by these. The obtained external preparation for skin had good base stability and excellent use feeling, particularly moist feeling after application and squeaky feeling.

Formulation Example 1 Latex Squalane 2.5% by mass
Oleil Olate 3.0
Vaseline 1.5
POE (40) POP (20) Phytosterol 5.0
POB (7) POE (45) dimethyl ether 0.01
Fragrance 0.2
Preservative 0.3
Glycerin 5.0
Dipropylene glycol 3.0
Ethanol 5.0
Carboxyvinyl polymer 0.3
Potassium hydroxide 0.1
L-arginine L-aspartate 0.01
Edetate 0.05
Purified water residue

Formulation Example 2 Foundation Setanol 2.0% by mass
Deodorized lanolin 1.5
Jojoba oil 1.0
Vaseline 1.5
Squalane 4.0
Glycerol monostearate 4.0
POE (15) POP (30) phytosterol 0.1
POB (19) POE (55) dimethyl ether 3.0
Pyridoxine tripalmitate 0.1
Fragrance 0.3
Preservative appropriate amount Dipropylene glycol 10.0
1,3-butylene glycol 5.0
Nylon spherical powder 2.0
Silicone-treated titanium dioxide 3.0
Silicone-treated iron oxide 3.0
Silicone-treated mica 2.5
Metal soap treatment talc 1.0
Edetate trisodium 0.5
Purified water residue

Claims (1)

(A) 0.01 to 5% by mass of polyoxyethylene-polyoxypropylene-added phytosterol and / or polyoxyethylene-polyoxypropylene-added phytostanol represented by the following general formula (I), (b) the following general formula A skin external preparation containing 0.01 to 10% by mass of the block-type alkylene oxide derivative represented by (II).
(In the formula, R represents a phytosterol residue or a phytostanol residue, m represents a number of 5 to 100, and n represents a number of 5 to 100.)
(Chemical formula 2)
R ¹ O — [(BO) _p (EO) _q (BO) _r ] —R ² (II)
(In the formula, BO is an oxybutylene group having 4 carbon atoms, EO is an oxyethylene group, p, r, and q are the average added moles of the oxybutylene group and oxyethylene group, respectively, 1 ≦ q ≦ 70, 1 ≦ p + r ≦ 70 The ratio of the oxyethylene group to the total of the oxybutylene group and the oxyethylene group is 20 to 80% by mass, and R ¹ and R ² may be the same or different and may be the same or different. It is a hydrogen group.)