JP2008088084A - Skin care preparation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a skin care preparation which has a good skin roughness-improving effect, is specific in a sense of use, especially in smoothness and in emulsion stability, and is free from a sticky sense. <P>SOLUTION: This skin care preparation contains a block type alkylene oxide derivative represented by formula (I) [Y is the hydroxyl group-removed residue of a polyhydric alcohol having three to six hydroxyl groups; (k) is the number of the hydroxyl groups of the polyhydric alcohol; EO is oxyethylene group; AO is a 3 to 6C oxyalkylene which is added in a block-like state; a×k, b×k and c×k are each the average addition mole number of the oxyethylene groups, the 3 to 6C oxyalkylene groups and the oxyethylene groups; 0≤a×k≤100, 1≤b×k≤100, 0≤c×k≤100, wherein (a+c)×k>1; Y is especially preferably glycerol; AO is especially preferably an oxybuthylene group]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an external preparation for skin, and particularly to an improvement of an external preparation for skin containing a block-type alkylene oxide derivative as an active ingredient.

  As an important element in evaluating the external preparation for skin, there are a function of maintaining a beautiful skin state and a feeling of use. On the other hand, as a typical means for improving the stability of the base, there is a compounding of a surfactant.

  In order to maintain a beautiful skin state, it is important to prevent or ameliorate rough skin, to prepare the skin crevice and cuticle, and to smooth the turnover of epidermal cells. Rough skin is a skin trouble triggered by external factors such as dryness or ultraviolet rays, irritating substances such as surfactants, or internal factors such as disorder of hormone balance. Decreased stratum corneum barrier function, decreased stratum corneum water content, increased epidermal turnover, roughening of stratum corneum due to generation of scaling (scaling) has become a major cosmetic issue. .

  Conventionally, as an active ingredient having an effect of preventing and improving rough skin, a moisturizer such as a polyol compound such as sorbitol, propylene glycol and glycerin, a mucopolysaccharide such as hyaluronic acid (see, for example, Patent Document 1), NMF ( Drugs such as amino acids and tranexamic acid as natural moisturizing factors (see, for example, Patent Document 2) and various extract extracts (see, for example, Patent Document 3) have been blended in skin external preparations. In addition, a method of supplementing the stratum corneum barrier function with an occlusive agent such as petrolatum ointment (see, for example, Patent Document 4) and a method of activating skin cells with vitamins, hormones, etc. (see, for example, Patent Document 5) are used. I came.

  However, humectants such as glycerin have to increase the blending amount in order to increase the moisturizing effect and the rough skin improving effect, and as a result, the stability and usability of the base may be lowered. In addition, when such a base is applied to the skin, there are problems to be solved such as repelling by sebum and deterioration of the familiarity to the skin. Polysaccharides were precipitated in a prescription system with a lot of alcohol, and amino acids such as DL-threonine had drawbacks such as coloring and odor. Drugs such as tranexamic acid have problems with stability over time, and when an occlusive agent such as petrolatum is used, it has the disadvantage of giving it an oily and unpleasant feel such as stickiness. Furthermore, when an extract, a vitamin, a hormone, or the like is used, there are problems to be solved in terms of safety related to side effects and stability related to aging.

  When preparing an external preparation for skin, particularly an emulsion, it is usual to add a surfactant to improve the stability of the base. Although the blending effect of the surfactant improves the stability of the base by blending a considerable amount, it sometimes contributes to the deterioration of the feeling of use. If the blending amount of the surfactant is reduced, the stability of the base tends to deteriorate, and it is one of the problems at the time of preparing the emulsion to make the stability and the feeling of use compatible.

In order to reduce the above-mentioned feeling of use, i.e., stickiness, polyhydric alcohol or the like was blended, but the feeling was not sufficiently improved. In view of the above, it has been desired to develop a component that has an effect of improving rough skin, has a good feeling in use, and improves the stability of the base.
JP-A-6-32728 JP 2006-160758 A Japanese Patent No. 3667291 JP-A-9-10025 Japanese Unexamined Patent Publication No. 7-277743

  The present invention has been made in view of the above-mentioned circumstances, and the problem is to provide a skin external preparation having an effect of improving rough skin, excellent in use feeling, particularly smooth, without stickiness, and excellent in stability. There is to do.

  As a result of intensive investigations by the present inventors in order to solve the above-mentioned problems, by incorporating a block-type alkylene oxide derivative having a specific structure into an external preparation for skin, it has an effect of improving skin roughness, and feel and stability in use. The present inventors have found that a skin external preparation excellent in skin resistance can be obtained, and have completed the present invention.

（式中、Ｙは３〜６個の水酸基を有する多価アルコールの水酸基を除いた残基、ｋは前記多価アルコールの水酸基数、ＥＯはオキシエチレン基、ＡＯは炭素数３〜６のオキシアルキレン基でそれぞれブロック状に付加されている。ａ×ｋ、ｂ×ｋおよびｃ×ｋはそれぞれオキシエチレン基、炭素数３〜６のオキシアルキレン基、オキシエチレン基の平均付加モル数であり、０≦ａ×ｋ≦１００、１≦ｂ×ｋ≦１００、０≦ｃ×ｋ≦１００、ただし（ａ＋ｃ）×ｋ＞１である。式（Ｉ）中の全オキシエチレン基と炭素数３〜６のオキシアルキレン基の合計に対する、式（Ｉ）中の全オキシエチレン基の割合は、１０〜８０質量％である。Ｒは同一もしくは異なってもよい炭素数１〜４の炭化水素基である。） That is, the skin external preparation of the present invention is characterized by containing a block-type alkylene oxide derivative represented by the following formula (I).

(In the formula, Y is a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 6 hydroxyl groups, k is the number of hydroxyl groups of the polyhydric alcohol, EO is an oxyethylene group, and AO is an oxy of 3 to 6 carbon atoms. Each of which is added in the form of a block with an alkylene group, wherein a × k, b × k and c × k are the average number of moles of oxyethylene group, oxyalkylene group having 3 to 6 carbon atoms, and oxyethylene group, 0 ≦ a × k ≦ 100, 1 ≦ b × k ≦ 100, 0 ≦ c × k ≦ 100, where (a + c) × k> 1 In the formula (I), all oxyethylene groups and 3 to 3 carbon atoms The ratio of all oxyethylene groups in formula (I) to the total of 6 oxyalkylene groups is 10 to 80% by mass, R is the same or different hydrocarbon group having 1 to 4 carbon atoms. .)

In the external preparation for skin, it is preferable that AO of the block-type alkylene oxide derivative represented by the formula (I) is an oxybutylene group.
Moreover, in the said skin external preparation, a of the block type alkylene oxide derivative shown by the said formula (I) is 0, and the addition order of AO and EO is (AO)-(EO) with respect to Y in a formula. ) Is preferred.

In the external preparation for skin, it is preferable to blend 0.01 to 70% by mass of the block type alkylene oxide derivative represented by the formula (I).
Moreover, this invention provides the rough skin improving agent which uses the block-type alkylene oxide derivative shown by said Formula (I) as an active ingredient.
Moreover, this invention provides the usability improver which uses the block-type alkylene oxide derivative shown by said Formula (I) as an active ingredient.
In the present invention, the usability improver means an agent that can improve the feeling of use, particularly smoothness and stickiness, when the agent is applied to the skin.

  According to the present invention, by adding a block type alkylene oxide derivative having a specific structure to an external preparation for skin, it has an effect of improving skin roughness, has excellent use feeling, particularly smoothness, has no stickiness, and has excellent stability. An external preparation for skin can be obtained.

Hereinafter, preferred embodiments of the present invention will be described.
(A) Block-type alkylene oxide derivative The skin external preparation according to the present invention contains a block-type alkylene oxide derivative represented by the following formula (I).

In the alkylene oxide derivative represented by the formula (I), Y is a residue excluding the hydroxyl group of the polyhydric alcohol having 3 to 6 hydroxyl groups, k is the number of hydroxyl groups of the polyhydric alcohol, and 3 to 6 It is. Examples of the compound having 3 to 6 hydroxyl groups include glycerin with k = 3, trimethylolpropane, hexylene glycol, erythritol with k = 4, pentaerythritol, xylitol with k = 5, sorbitol with k = 6 And inositol. The block-type alkylene oxide derivative blended in the external preparation for skin according to the present invention has a basic skeleton in which the hydroxyl group is removed from one or a mixture of two or more polyhydric alcohols having 3 to 6 hydroxyl groups. And
In the present invention, Y is more preferably a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 4 hydroxyl groups, that is, it is preferable that 3 ≦ k ≦ 4 is satisfied. When k is 2 or less, smoothness tends to be inferior when blended with a skin external preparation, and when k is 7 or more, a sticky feeling tends to occur.

  EO is an oxyethylene group having 2 carbon atoms. AO is an oxyalkylene group having 3 to 6 carbon atoms, and specific examples include an oxypropylene group, an oxybutylene group, an oxyisobutylene group, an oxy t-butylene group, an oxypentylene group, and an oxyhexylene group. . Preferred are an oxypropylene group and an oxybutylene group, and more preferred is an oxybutylene group.

  b × k is the average added mole number of AO, and 1 ≦ b × k ≦ 100, preferably 3 ≦ b × k ≦ 70. a × k and c × k are average added moles of EO, 0 ≦ a × k ≦ 100, 0 ≦ c × k ≦ 100, preferably 3 ≦ a × k ≦ 70, 3 ≦ c × k ≦ 70. Moreover, the preferable range of the average addition mole number of all the oxyethylene groups in the said formula (I) is 1 <(a + c) * k <= 200, More preferably, it is 6 <= (a + c) * k <= 140. AO becomes a hydrophobic site in the block-type alkylene oxide derivative according to the present invention, and when b × k is 0, it tends to be inferior in stability when blended in a skin external preparation, and it is used with a moistness exceeding 100 There is a tendency to feel inferior. Further, when a × k or c × k is 0, stability tends to be inferior when blended with an external preparation for skin, and when it exceeds 100, stickiness tends to occur.

The ratio of the total EO in the said formula (I) with respect to the sum total of AO and EO in the said formula (I) is 10-80 mass%, More preferably, it is 20-70 mass%. When it is less than 10% by mass, it tends to be inferior to a moist feel, and when it is more than 80% by mass, a sticky feeling tends to occur.
The addition form of AO and EO is block-like, and the addition order is (AO)-(EO) order, (EO)-(AO) order, (EO)-( Any of the order of AO)-(EO) may be sufficient. In the present invention, the order of (AO)-(EO) with respect to Y in the formula is particularly preferable. In the order of (AO)-(EO) with respect to Y in the formula, it corresponds to a in the formula being 0.

  R is a hydrocarbon group having 1 to 4 carbon atoms. Examples of the hydrocarbon group 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. It is done. In the present invention, a methyl group and an ethyl group are preferable. When the carbon number is greater than 5, the moist feeling of use tends to be inferior. In the block-type alkylene oxide derivative blended in the external preparation for skin according to the present invention, R may be the same or different in one molecule, and the block-type alkylene having the same R in one molecule. It may be one oxide derivative or a mixture of two or more having different Rs.

Specific examples of the alkylene oxide derivative blended in the external preparation for skin according to the present invention include POB (30) POE (30) glyceryl trimethyl ether, POB (30) POE (35) glyceryl trimethyl ether, and POB (17) POE. (28) Glyceryl trimethyl ether, POB (27) POE (45) glyceryl trimethyl ether, POB (14) POE (34) glyceryl trimethyl ether, POB (22) POE (55) glyceryl trimethyl ether, POB (19) POE (55) ) Glyceryl trimethyl ether, POB (40) POE (80) glyceryl trimethyl ether, POB (80) POE (40) glyceryl trimethyl ether, POB (30) POE (30) glyceryl triethyl ether, POB 30) POE (35) glyceryl triethyl ether, POB (14) POE (34) glyceryl triethyl ether, POB (30) POE (30) glyceryl tripropyl ether, POE (30) POP (30) glyceryl triethyl ether, POE (35) ) POP (40) glyceryl trimethyl ether, POE (41) POP (48) glyceryl trimethyl ether, and the like.
The POE, POP, and POB are abbreviations for polyoxyethylene, polyoxypropylene, and polyoxybutylene, respectively, and may be abbreviated as follows.

  The alkylene oxide derivative blended in the external preparation for skin according to the present invention can be produced by a known method. For example, it is obtained by subjecting a polyhydric alcohol having a hydroxyl group to addition polymerization of ethylene oxide and an alkylene oxide having 3 to 6 carbon atoms, and then subjecting an alkyl halide to an ether reaction in the presence of an alkali catalyst.

  By blending an alkylene oxide derivative with a specific structure produced as described above into a skin external preparation, it has an effect of improving skin roughness, has excellent use feeling, particularly smoothness, has no stickiness, and has excellent stability. A skin external preparation can be obtained. In the external preparation for skin according to the present invention, the amount of the alkylene oxide derivative having the above specific structure is preferably 0.01 to 70% by mass, more preferably 0.1 to 20% by mass with respect to the entire composition. It is preferable. If it is less than 0.01% by mass, the effect of the blending may not be sufficiently exhibited, and if it exceeds 70% by mass, a sticky feeling may occur.

  In the external preparation for skin according to the present invention, components usually used for external preparations for skin of cosmetics and quasi-drugs can be appropriately blended within the range not impairing the effects of the present invention. Specific ingredients that can be blended are listed below. The skin external preparation of the present invention can be prepared by blending the alkylene oxide derivative having the above specific structure 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, sugar cane 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, squalane, 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.

  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, monoisostearic acid-N-alkyl glycol, neopentyl glycol dicaprate, apple Acid diisostearyl, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, triisostearate 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, myristic acid-2-hexyl Rudeshiru, palmitic acid-2-hexyl decyl adipate 2-hexyl decyl, diisopropyl sebacate, succinic acid-2-ethylhexyl, 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, N-myristoyl-N-methyl taurine sodium, coconut oil fatty acid) Methyl tauride sodium, lauryl methyl tauride sodium, etc.); Phosphate ester salts (POE oleyl ether sodium phosphate, POE stearyl ether phosphate, etc.); Sodium 2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc .; alkylbenzene sulfonates (for example, sodium lineardodecylbenzenesulfonate, triethanolamine lineardodecylbenzenesulfonate) Higher fatty acid ester sulfate (for example, hydrogenated coconut oil fatty acid sodium glyceryl sulfate, etc.); N-acyl glutamate (for example, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N-myristoyl-L-monoglutamate monosodium, etc.); sulfated oil (eg funnel oil, etc.); POE alkyl allyl ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate salt; secondary alcohol sulfate ester salt; higher fatty acid alkylolamide sulfate ester salt; sodium lauroyl monoethanolamide succinate; 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 amine 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 hydrophilic nonionic surfactants include POE sorbitan fatty acid esters (for example, POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monooleate, POE sorbitan tetraoleate, etc.); POE sorbite fatty acid ester (Eg POE sorbite monolaurate, POE sorbite monooleate, POE sorbite pentaoleate, POE sorbite monostearate, etc.); POE glycerin fatty acid esters (eg POE glycerin monostearate, POE glycerin monoisostearate) POE monooleate such as POE glycerin triisostearate); POE fatty acid esters (for example, POE distearate, POE monodiolate, distearies) POE alkyl ethers (for example, POE lauryl ether, POE oleyl ether, POE stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE cholestanol ether, etc.); Pluronic type (for example, 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 hydrogenated castor oil derivatives (for example, POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate, P) OE hydrogenated castor oil triisostearate, POE hydrogenated castor oil monopyroglutamic acid monoisostearic acid diester, POE hydrogenated castor oil maleic acid, etc .; POE beeswax lanolin derivatives (eg POE sorbite beeswax etc.); Oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE propylene glycol fatty acid ester; POE alkylamine; POE fatty acid amide; sucrose fatty acid ester; alkylethoxydimethylamine oxide; .

  Examples of natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (eg, xanthan gum, dextran, succinoglucan, bullulan, etc.); animal polymers (eg, collagen, casein, albumin, gelatin, etc.), etc. Is mentioned.

  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, 40,000, 60,000). Etc.); acrylic polymers (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide and the like); polyethyleneimine; cationic polymers and the like.

  Examples of the thickener include gum arabic, carrageenan, caraya gum, gum tragacanth, carob gum, quince seed (malmello), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, CMC, hydroxyethylcellulose, hydroxypropyl Cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, cellulose dialkyldimethylammonium sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, AlMg silicate (Beegum), Examples thereof include laponite and silicic anhydride.

  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-acetyl anthranilate etc.); Salicylic acid-based UV absorbers (eg, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate); 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.); benzophenone 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- (2'-hydroxy Dibenzalazine; dianisoylmethane; 2-methoxy-2'-t-butyldibenzoylmethane; 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one Etc.

  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) Xyl alcohol, ceralkyl alcohol, batyl alcohol, etc.); sugar alcohols (eg, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitol, amylolytic sugar) Reduced alcohol, etc.); Glysolid; 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 Examples include ether and polyglycerin.

  Examples of monosaccharides include tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.); tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-treose, erythritol, 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) -Bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); pentose sugar (eg, aldheptose, heproose, etc.); octose sugar (eg, octulose, etc.); For example, 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, etc.).

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 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. The blending amount is expressed in mass% unless otherwise specified.

First, a method for evaluating an external preparation for skin used in the following examples will be described. The application site of the external preparation for skin is the cheek.
The composition of the conventional skin external preparation used as a control is as follows.
(Water phase)
(1) Glycerin 10.0% by mass
(2) Carboxyvinyl polymer 0.1
(3) Potassium hydroxide 5.0
(4) Sorbitol 3.0
(5) Ethanol 4.0
(6) Purified water residue (oil phase)
(7) Liquid paraffin 5.0
(8) Glyceryl tri-2-ethylhexanoate 4.0
(9) Cetyl octanoate 2.0
(10) Preservative appropriate amount (11) Perfume appropriate amount

Evaluation (1): Smoothness of skin About the smoothness of the skin during and after use of the topical skin preparation,
The following skin external preparations in the test examples shown below and the conventional skin external preparation (composition containing glycerin as a humectant) are actually used as a control, and scored according to the following scoring criteria. Here, the score is determined with the control skin external preparation set to zero. In addition, the average value which divided the sum total of the score by each panel by the panel number of persons was calculated, and it was set as the evaluation result according to the following evaluation criteria.
Scoring criteria +3: Feels very smooth compared to the control skin external preparation.
+2: Feels smoother than the control skin external preparation.
+1: It feels slightly smoother than the control skin external preparation.
0: Neither can be said.
-1: It does not feel much smoother than the control skin external preparation.
-2: It does not feel smooth compared to the control skin external preparation.
-3: It does not feel smooth at all compared with the external preparation for control skin.
Evaluation criteria A: The average value of 10 panelists is +1.5 points or more.
B: The average value of 10 panelists is 0 or more and less than 1.5 points.
C: The average value of 10 panelists is −1.5 points or more and less than 0 points.
D: The average value of 10 panelists is less than -1.5 points

Evaluation (2): No stickiness sensation Regarding the lack of stickiness after applying the topical skin preparation to the skin, 10 specialist panelists gave skin preparations for the following test examples and conventional skin preparations for control ( The composition which mix | blended glycerin as a moisturizer is actually used, and the score determination by the following scoring standard is performed. Here, the score is determined with the control skin external preparation set to zero. In addition, the average value which divided the sum total of the score by each panel by the panel number of persons was calculated, and it was set as the evaluation result according to the following evaluation criteria.
Scoring criteria +3: I feel that there is no stickiness compared to the control skin external preparation.
+2: I feel that there is no stickiness compared to the control skin external preparation.
+1: Feels less sticky than the control skin external preparation.
0: Neither can be said.
-1: A slightly sticky feeling is felt compared with the control skin external preparation.
-2: Feels sticky compared to the control skin external preparation.
-3: Feels very sticky compared to the control skin external preparation.
Evaluation criteria A: The average value of 10 panelists is +1.5 points or more.
B: The average value of 10 panelists is 0 or more and less than 1.5 points.
C: The average value of 10 panelists is −1.5 points or more and less than 0 points.
D: The average value of 10 panelists is less than -1.5 points

Evaluation (3): Moist feeling (moisturizing effect)
The moisturizing effect (moisturizing effect) 2 hours after application of the skin external preparation on the skin was performed by 10 specialist panels, and the skin external preparation of the test example shown below and the conventional skin external preparation (glycerin moisturized as a control). (Composition blended as an agent) is actually used, and scored according to the following scoring standards. Here, the score is determined with the control skin external preparation set to zero. In addition, the average value which divided the sum total of the score by each panel by the panel number of persons was calculated, and it was set as the evaluation result according to the following evaluation criteria.
Scoring criteria +3: Compared to the external preparation for control skin, there is a very moist feeling.
+2: There is a moist feeling compared to the control skin external preparation.
+1: There is a slightly moist feeling compared to the control skin external preparation.
0: Neither can be said.
-1: There is not much moist feeling compared with the control skin external preparation.
-2: There is no moist feeling compared with the control skin external preparation.
-3: No moist feeling compared to the control skin external preparation.
Evaluation criteria A: The average value of 10 panelists is +1.5 points or more.
B: The average value of 10 panelists is 0 or more and less than 1.5 points.
C: The average value of 10 panelists is −1.5 points or more and less than 0 points.
D: The average value of 10 panelists is less than -1.5 points

Evaluation (4) Skin Roughness Improvement Effect Test A skin roughness improvement effect test was carried out by the method shown below by applying a skin external preparation by 10 subjects having rough skin on the face (part: cheek).
Test method: Different skin external preparations (skin external preparations and control skin external preparations for each test example) were applied to the left and right cheeks once a day for 1 week, and scored according to the following scoring standards the day after the end of the period. Went. Here, the score is determined with the control skin external preparation set to zero. In addition, the average value which divided the sum total of the score by each panel by the panel number of persons was calculated, and it was set as the evaluation result according to the following evaluation criteria.
Scoring criteria +3: It feels that the rough skin has been greatly improved as compared with the control external preparation for skin.
+2: It feels that rough skin has been improved compared to the external preparation for control skin.
+1: It feels that rough skin is slightly improved as compared with the external preparation for control skin.
0: Neither can be said.
-1: It does not feel that rough skin is improved much compared with the control skin external preparation.
-2: It does not feel that rough skin is improved as compared with the control skin external preparation.
-3: It does not feel that the rough skin is improved at all as compared with the control skin external preparation.
Evaluation criteria A: The average value of 10 panelists is +1.5 points or more.
B: The average value of 10 panelists is 0 or more and less than 1.5 points.
C: The average value of 10 panelists is −1.5 points or more and less than 0 points.
D: The average value of 10 panelists is less than -1.5 points

Evaluation (5): Skin irritation test A 24-hour occlusion patch test was performed on the inner side of the upper arm of 10 subjects, and then the average value was calculated according to the following scoring criteria. The evaluation criteria are as follows.
Scoring standard 0 point: No abnormality is recognized.
1 point: Slight redness was observed.
2 points: Redness was observed.
3 points: Redness and papules were observed.
Evaluation criteria A: The average value of 10 panelists is less than 0.15 points.
B: The average value of 10 panelists is 0.15 or more and less than 0.2.
C: The average value of 10 panelists is 0.2 or more and less than 0.3.
D: The average value of 10 panelists is 0.3 points or more.

Evaluation (6): Stability The skin external preparations of each test example were evaluated for stability based on the following criteria immediately after production and by visual observation after filling in a glass bottle and leaving at 50 ° C. for 6 weeks.
A: There was no change in appearance.
B: Slight oil phase or water phase separation was observed.
C: Separation of oil phase or water phase was considerably observed.

In the formulation shown in Tables 1 to 3 below, the present inventors manufactured a skin external preparation by a conventional method, and performed an evaluation test on the evaluation items (1) to (6).
First, a skin moisturizer and a topical skin preparation each containing a block-type alkylene oxide derivative were examined. The results are shown in Table 1 below.

In addition, the block type alkylene oxide derivative in the following table | surface shall have a structure of the following formula | equation (II). For example, when a + c + e = 30 and b + d + f = 30, they are expressed as (BO) ₃₀ (EO) ₃₀ .

From the results shown in Table 1, the external preparation for skin containing glycerin used as a control as a moisturizer is inferior in stability. When the blending amount of glycerin is suppressed (Test Example 2), the moisturizing effect represented by moist feeling and the rough skin improving effect are reduced.
On the other hand, the skin external preparation of Test Example 1 containing a block-type alkylene oxide derivative is excellent in all the above evaluations, and has a balanced use feeling and moisturizing effect, rough skin improving effect, and stability. Admitted. Further, in the composition containing no humectant such as glycerin or an alkylene oxide derivative (Test Example 4), the moisturizing effect and the rough skin improving effect cannot be expected as a matter of course, and the stability was also inferior.

Subsequently, the inventors proceeded with studies on various alkylene oxide derivatives. The results are shown in Table 2 below.

  When the structure of the alkylene oxide derivative to be blended is composed of only the oxyethylene part or only the oxybutylene part (Test Examples 11 and 12), these substances do not function as a surfactant, so the stability is extremely high. It is inferior to. Furthermore, Test Example 11 containing an alkylene oxide derivative containing only an oxyethylene part is particularly inferior in the feeling of use and rough skin, and the Test Example 12 containing an alkylene oxide derivative containing only an oxybutylene part has a moisturizing effect. It was inferior in the point of the rough skin improvement effect.

Furthermore, in Test Example 13 in which an alkylene oxide derivative having hydrogen at its terminal is blended, the feeling of use and the effect of improving skin roughness are not sufficient. There was also a problem in terms of skin irritation. Further, when a random type alkylene oxide derivative was blended (Test Example 14), the function as a surfactant was inferior, resulting in poor stability.
Further, even when POE (60) hydrogenated castor oil, which has been conventionally used as a surfactant, is added to a skin external preparation for stability (Test Example 15), a moisturizing effect feeling and a rough skin improving effect can be obtained. is not.
On the other hand, in the test example which mix | blended the various block type alkylene oxide derivatives mix | blended with Test Examples 5-10, it was excellent in any evaluation of (1)-(6).

As is clear from the above results, when a block-type alkylene oxide derivative having a specific structure is added to the external preparation for skin, it has an effect of improving rough skin, has excellent use feeling, particularly smoothness, does not feel sticky, and is moisturizing. Since it has excellent effect and also has a surfactant function, it can be a base having excellent stability.
Next, Table 3 below shows the results of studying suitable blending amounts of the block-type alkylene oxide derivative having a specific structure in the external preparation for skin.

  As is apparent from the results of Table 3 above, when the blending amount of the block-type alkylene oxide derivative having a specific structure is in the range of 0.01 to 70% by mass, the effect of improving skin roughness is obtained as compared with the conventional skin external preparation. It is clear that it has an excellent moisturizing effect. In consideration of the feeling of use such as smoothness to the skin and lack of stickiness, the blending amount of the alkylene oxide derivative is particularly preferably 0.1 to 20% by mass.

Hereinafter, some synthesis examples of various alkylene oxide derivatives blended in the above-described skin external preparation of the above test examples will be shown.
<Synthesis Example 1>
Synthesis of polyoxybutylene (30 mol) polyoxyethylene (30 mol) trimethylglyceryl ether (block type alkylene oxide derivative) 92 g of glycerin and 18 g of potassium hydroxide as a catalyst were charged into the autoclave, and the air in the autoclave was replaced with dry nitrogen. Then, the catalyst was completely dissolved at 140 ° C. with stirring. Next, 2160 g of butylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 1320 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 400 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 300 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid and adjusted to pH 6 to 7, and treated at a reduced pressure of -0.088 MPa (gauge pressure) at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and a block-type alkylene oxide derivative was obtained.
Samples that were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 49, the alkylene oxide derivative 1 had a hydroxyl value of 0.4, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.008. An atom is converted to a methyl group.

<Synthesis Example 2>
Synthesis of polyoxyethylene (57 mol) trimethylglyceryl ether (alkylene oxide derivative) 92 g of glycerin and 18 g of potassium hydroxide as a catalyst were charged into an autoclave, and the air in the autoclave was replaced with dry nitrogen, and then stirred at 140 ° C. The catalyst was completely dissolved. Next, 2508 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 400 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 300 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid and adjusted to pH 6 to 7, and treated at a reduced pressure of -0.088 MPa (gauge pressure) at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and an alkylene oxide derivative was obtained.
Samples which were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 66, and the alkylene oxide derivative 1 had a hydroxyl value of 0.60.009, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was almost completely hydrogen atoms. Has been converted to a methyl group.

<Synthesis Example 3>
Synthesis of polyoxybutylene (30 mol) polyoxyethylene (30 mol) glyceryl ether (block type alkylene oxide derivative) 92 g of glycerol and 18 g of potassium hydroxide as a catalyst were charged into the autoclave, and the air in the autoclave was replaced with dry nitrogen. Thereafter, the catalyst was completely dissolved at 140 ° C. with stirring. Next, 2160 g of butylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 1320 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid and adjusted to pH 6 to 7, and treated at a reduced pressure of -0.088 MPa (gauge pressure) at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and a block-type alkylene oxide derivative was obtained.

<Synthesis Example 4>
Synthesis of polyoxybutylene (30 mol) polyoxyethylene (30 mol) tributyl glyceryl ether (block-type alkylene oxide derivative) 92 g of glycerol and 18 g of potassium hydroxide as a catalyst were charged into the autoclave, and the air in the autoclave was replaced with dry nitrogen. Then, the catalyst was completely dissolved at 140 ° C. with stirring. Next, 2160 g of butylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 1320 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Next, after charging 800 g of potassium hydroxide and replacing the inside with dry nitrogen, 1200 g of butyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid and adjusted to pH 6 to 7, and treated at a reduced pressure of -0.088 MPa (gauge pressure) at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and a block-type alkylene oxide derivative was obtained.
Samples which were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 50, the alkylene oxide derivative 1 had a hydroxyl value of 1.5, and the ratio of the number of hydrogen atoms to the number of terminal butyl groups was 0.03, indicating that hydrogen was almost completely removed. Atoms are converted to butyl groups.

<Synthesis Example 5>
Synthesis of polyoxybutylene (30 mol) polyoxyethylene (30 mol) glyceryl ether (random alkylene oxide derivative) 92 g of glycerin and 18 g of potassium hydroxide as a catalyst were charged into the autoclave, and the air in the autoclave was replaced with dry nitrogen. Thereafter, the catalyst was completely dissolved at 140 ° C. with stirring. Next, a mixture of 2160 g of butylene oxide and 1320 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 400 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 300 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid to adjust to pH 6 to 7, and treated at a reduced pressure of -0.088 MPa (gauge pressure) at 100 ° C for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and a random alkylene oxide derivative was obtained.
Samples which were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 47, the resulting random alkylene oxide derivative 5 compound had a hydroxyl value of 0.5, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.011. The hydrogen atom is almost completely converted to a methyl group.

  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 an effect of improving rough skin, was excellent in use feeling, particularly smooth, had no stickiness, and was excellent in emulsification stability.

（式（III）中、ａ＋ｃ＋ｅ＝３０、ｂ＋ｄ＋ｆ＝３５であり、ＢＯはオキシブチレン基、ＥＯはオキシエチレン基を示す。）
（５）月見草油 ０．２
（６）香料 ０．１
（７）防腐剤 適量
Ｂ相
（８）１，３−ブチレングリコール １．５
（９）エタノール ２．０
（１０）カルボキシビニルポリマー ０．２
（１１）水酸化カリウム ０．１
（１２）Ｌ−アルギニンＬ−アスパラギン酸塩 ０．０１
（１３）エデト酸塩 ０．０５
（１４）精製水 残余
（製法）
Ａ相とＢ相を各々７０℃に加熱し溶解した後、Ａ相をＢ相に加えて乳化機を用いて乳化した。得られた乳化物を熱交換機を用いて冷却し、目的の乳液を得た。 Formulation Example 1: Emulsion (formulation component) (mass%)
Phase A (1) Squalane 4.0
(2) Oleyl oleate 2.5
(3) Vaseline 1.5
(4) POB (30) POE (35) Trimethyl glyceryl ether 2.0

(In formula (III), a + c + e = 30 and b + d + f = 35, BO represents an oxybutylene group, and EO represents an oxyethylene group.)
(5) Evening primrose oil 0.2
(6) Fragrance 0.1
(7) Preservative Appropriate amount Phase B (8) 1,3-butylene glycol 1.5
(9) Ethanol 2.0
(10) Carboxyvinyl polymer 0.2
(11) Potassium hydroxide 0.1
(12) L-arginine L-aspartate 0.01
(13) Edetate 0.05
(14) Purified water residue (production method)
The A phase and the B phase were each heated to 70 ° C. and dissolved, and then the A phase was added to the B phase and emulsified using an emulsifier. The obtained emulsion was cooled using a heat exchanger to obtain the desired emulsion.

Formulation Example 2: Cream (formulation component) (mass%)
Phase A (1) Stearic acid 10.0
(2) Stearyl alcohol 3.5
(3) Butyl stearate 6.0
(4) POB (30) POE (35) Trimethyl glyceryl ether 1.5
(In the formula (III), a + c + e = 30 and b + d + f = 35, BO represents an oxybutylene group, and EO represents an oxyethylene group.)
(5) Glycerol monostearate 2.5
(6) Vitamin E acetate 0.5
(7) Vitamin A palmitate 0.1
(8) Macadamia nut oil 0.5
(9) Fragrance 0.15
(10) Preservative Appropriate amount Phase B (11) Glycerin 6.0
(12) 1,2-pentanediol 2.0
(13) Sodium hyaluronate 1.5
(14) Potassium hydroxide 2.0
(15) Ascorbic acid magnesium phosphate 0.1
(16) L-arginine hydrochloride 0.01
(17) Trisodium edetate 0.05
(18) Purified water residue (production method)
The A phase and the B phase were each heated to 70 ° C. and dissolved, and then the A phase was added to the B phase and emulsified using an emulsifier. The obtained emulsion was cooled using a heat exchanger to obtain the desired cream.

Formulation Example 3: Lotion (Formulation component) (mass%)
Phase A (1) Ethanol 5.0
(2) POB (32) POE (52) Trimethyl glyceryl ether 0.2
(In the formula (III), a + c + e = 32 and b + d + f = 52, BO represents an oxybutylene group, and EO represents an oxyethylene group.)
(3) 2-Ethylhexyl-P-dimethylaminobenzoate 0.1
(4) Preservative appropriate amount (5) Fragrance 0.1
Phase B (6) Sodium pyrrolidonecarboxylate 0.3
(7) Nicotinamide 0.2
(8) Dimorpholinopyridazinone 0.1
(9) Aloe extract 0.2
(10) Purified water residue (production method)
After each of the A phase and the B phase was dissolved, the A phase was added to the B phase and solubilized to obtain the desired lotion.

Formulation Example 4: Foundation (blending component) (mass%)
Phase A (1) Cetanol 3.5
(2) Deodorized lanolin 4.0
(3) Jojoba oil 5.0
(4) Vaseline 2.0
(5) Squalane 6.0
(6) Glycerol monostearate 2.5
(7) POB (17) POE (28) Trimethyl glyceryl ether 1.5
(In the formula (III), a + c + e = 17 and b + d + f = 28, BO represents an oxybutylene group, and EO represents an oxyethylene group.)
(8) Pyridoxine tripalmitate 0.1
(9) Fragrance 0.3
(10) Preservative Appropriate amount Phase B (11) Propylene glycol 10.0
(12) Nylon spherical powder 2.0
(13) Silicone-treated titanium dioxide 5.0
(14) Silicone-treated iron oxide 2.0
(15) Silicone-treated mica 1.0
(16) Metal soap treated talc 2.0
(17) edetate trisodium 0.5
(18) Purified water residue (production method)
The A phase and the B phase were each heated to 70 ° C. and dissolved, and then the A phase was added to the B phase and emulsified using an emulsifier. The obtained emulsion was cooled using a heat exchanger to obtain the desired foundation.

Formulation Example 5: Lotion mask (formulation component) (mass%)
Phase A (1) Ethanol 8.0
(2) POE (41) POP (48) Trimethyl glyceryl ether 0.5
(In the formula (III), a + c + e = 41, b + d + f = 48, BO represents an oxybutylene group, and EO represents an oxyethylene group.)
(3) Lactic acid menthyl 0.002
(4) Fragrance 0.01
(5) Preservative Appropriate amount Phase B (6) Birch extract 0.2
(7) Caustic potash appropriate amount (8) Purified water Residual (Production method)
A phase was added to the B phase to prepare a lotion, and this was further impregnated into a nonwoven fabric to obtain the intended lotion mask.

Claims (6)

A skin external preparation comprising a block-type alkylene oxide derivative represented by the following formula (I):

(In the formula, Y is a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 6 hydroxyl groups, k is the number of hydroxyl groups of the polyhydric alcohol, EO is an oxyethylene group, and AO is an oxy of 3 to 6 carbon atoms. Each of which is added in the form of a block with an alkylene group, wherein a × k, b × k and c × k are the average number of moles of oxyethylene group, oxyalkylene group having 3 to 6 carbon atoms, and oxyethylene group, 0 ≦ a × k ≦ 100, 1 ≦ b × k ≦ 100, 0 ≦ c × k ≦ 100, where (a + c) × k> 1 In the formula (I), all oxyethylene groups and 3 to 3 carbon atoms The ratio of all oxyethylene groups in formula (I) to the total of 6 oxyalkylene groups is 10 to 80% by mass, R is the same or different hydrocarbon group having 1 to 4 carbon atoms. .)   The skin external preparation according to claim 1, wherein AO of the block-type alkylene oxide derivative represented by the formula (I) is an oxybutylene group.   The external preparation for skin according to claim 1 or 2, wherein a in the block-type alkylene oxide derivative represented by the formula (I) is 0, and the addition order of AO and EO is A topical skin preparation characterized by being AO)-(EO).   The skin external preparation in any one of Claims 1-3 WHEREIN: 0.01-70 mass% of block-type alkylene oxide derivatives shown by the said formula (I) are mix | blended, The skin external preparation characterized by the above-mentioned.   A rough skin improving agent comprising the block type alkylene oxide derivative represented by the formula (I) as an active ingredient. Usability improver comprising the block type alkylene oxide derivative represented by the formula (I) as an active ingredient.