JP2003286149A - Skin care preparation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a skin care preparation sustaining refrigerant effects for a long time, hardly irritating the skin and providing excellent feeling in use. <P>SOLUTION: This skin care preparation contains a refrigerant and an alkylene oxide derivative of the formula (I): R<SP>1</SP>O-[(AO)<SB>m</SB>(EO)<SB>n</SB>]-R<SP>2</SP>(I) (wherein, AO is a 3-4C oxyalkylene group; EO is an oxyethylene group; (m) and (n) are the average numbers of added moles of the oxyalkylene group and the oxyethylene group satisfying the relations of 1≤m≤70 and 1≤n≤70, respectively; the percentage of the oxyethylene group based on the total of the 3-4C oxyalkylene group and the oxyethylene group is 20-80 wt.%; R<SP>1</SP>and R<SP>2</SP>are the same or different and each a 1-4C hydrocarbon group or hydrogen atom, with the proviso that the proportion of the number of the hydrogen based on the number of the hydrocarbon groups of R<SP>1</SP>and R<SP>2</SP>is ≤0.15). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an external preparation for skin, and more particularly, to improvement of its lasting refreshing effect, skin irritation, and touch feeling.

[0002]

2. Description of the Related Art In external preparations for skin, refreshing agents represented by menthol and camphor are generally used to give a refreshing refreshing feeling to the skin, and also improve swelling, poor circulation, mucosal swelling, local anti-inflammatory, It is also used for the purpose of antipruritus and pain relief.

[0003]

Menthol and camphor are volatilized from the external preparation base and exert their effect. However, if the concentration of these is low, the effect does not last, and the concentration of the cooling agent is increased to improve the sustainability. However, there is a problem in that the skin irritation is too strong to cause a tingling sensation or redness when the value is increased. In addition, in recent years, improvement and prevention of swelling and sagging of the eyes, sleepiness,
Many products are applied to the eyes and mouth for the purpose of improving stuffy nose. Thus, when applied to a relatively delicate site close to the mucous membrane, the blending amount of the cooling agent is limited, so that it is more difficult to obtain a formulation having a long-lasting cooling effect. Of course, in the external preparation for skin, its feeling of use is also a very important factor, and it is required to have smoothness, moisturization, non-greasiness and the like.

The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is an external preparation for skin which has a refreshing effect lasting for a long time and has no skin irritation such as a tingling sensation and an excellent feeling in use. To provide.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in view of the above-mentioned problems, when a specific alkylene oxide derivative is added to a skin external preparation together with a cooling agent, the sustainability of the cooling effect is improved. The inventors have found that an external preparation for the skin having no skin irritation and an excellent feeling in use can be obtained, and completed the present invention.

That is, the external preparation for skin according to the present invention is
It is characterized by containing a cooling agent and an alkylene oxide derivative represented by the following general formula (I).

Embedded image R ¹ O — [(AO) _m (EO) _n ] -R ² (I) (In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms;
O is an oxyethylene group, m and n each have 3 to 4 carbon atoms
The average number of moles of oxyalkylene group and oxyethylene group added is 1 ≦ m ≦ 70, 1 ≦ n ≦ 70, and the ratio of the oxyethylene group to the total of the oxyalkylene group and the oxyethylene group is 20 to 80 mass. %. The oxyalkylene group and oxyethylene group may be added in blocks or randomly. R ¹ and R ²
Are the same or different hydrocarbon groups having 1 to 4 carbon atoms or hydrogen atoms, and the ratio of the number of hydrogen atoms to the number of hydrocarbon groups of R ¹ and R ² is 0.15 or less. )

In the external preparation for skin of the present invention, the alkylene oxide derivative (I) is preferably such that oxyalkylene groups and oxyethylene groups are randomly added. In addition, the alkylene oxide derivative (I) is
It is preferable to add 1 to 80% by mass. It is also preferred that the cooling agent is menthol or camphor.
Further, it is preferable to add 0.001 to 20% by mass of a cooling agent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As a cooling agent used in the present invention, when it is applied to the skin, it is volatilized from the base material to give a refreshing refreshing feeling to the skin, an effect of improving swelling and sagging, an anti-inflammatory effect, It is capable of exerting an analgesic effect, an antipruritic effect, etc. (in the present invention, these are collectively referred to as a cooling effect),
It means a drug (mainly a terpene-based compound or a component similar thereto) that can be incorporated into an external preparation. It should be noted that lower alcohols such as ethanol and volatile solvents such as volatile oils also give a refreshing feeling, but these are usually not included in the refreshing agent (of course, there is no problem in combination with the cooling agent).

The preferred cooling agents are menthol and camphor. Menthol and camphor can be used as natural products and synthetic products. Menthol includes l-menthol, dl-menthol, peppermint oil and the like, and camphor includes d-camphor and dl-camphor. In the present invention, two or more cooling agents can be used in combination. The amount of the cooling agent to be added to the external preparation for skin of the present invention varies depending on the purpose of use of the external preparation, etc., but is generally 0.001 to 20% by mass, preferably 0.01 to
It is 10% by mass. The cooling agent may be added to the external preparation for skin by a conventional method. For example, any method such as solubilization, dispersion, and emulsification can be used.

In the alkylene oxide derivative represented by the general formula (I), AO is an oxyalkylene group having 3 to 4 carbon atoms, and examples thereof include an oxypropylene group, an oxybutylene group, an oxyisobutylene group, a trimethylene group and a tetramethylene group. Groups and the like. Preferred are oxypropylene group and oxybutylene group. m is the average number of moles of addition of an oxyalkylene group having 3 to 4 carbon atoms, and 1 ≦ m ≦ 70, preferably 2 ≦ m ≦ 20. n
Is the average number of moles of oxyethylene groups added, and 1 ≦ n ≦
70, preferably 2 ≦ n ≦ 20. When the oxyalkylene group or oxyethylene group having 3 to 4 carbon atoms is 0, the effect of the present invention is not sufficiently exerted, and when it exceeds 70, a sticky feeling appears and a smooth feeling is not sufficiently obtained.

The ratio of oxyethylene groups to the total of oxyalkylene groups having 3 to 4 carbon atoms and oxyethylene groups is preferably 20 to 80% by mass. If the proportion of oxyethylene groups is less than 20% by weight, the effect of the present invention is not sufficiently exhibited, and if it exceeds 80% by mass, the smoothness tends to be poor. Ethylene oxide and carbon number 3
The order of adding the alkylene oxides of 4 is not particularly specified. The oxyethylene group and the oxyalkylene group having 3 to 4 carbon atoms may be added in a block form or in a random form. Preferably, those added randomly are mentioned.

R ¹ and R ² are a hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom, and the hydrocarbon group is a methyl group,
Examples thereof include an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. Preferred are a methyl group and an ethyl group. Hydrocarbon groups having 5 or more carbon atoms tend to reduce the effects of the present invention. R ¹ and R ² may be the same or different.

R¹And R^TwoEach uses only one kind
Also, a mixture of hydrocarbon groups having 1 to 4 carbon atoms and hydrogen atoms
Also, hydrocarbon groups having 1 to 4 carbon atoms may be mixed. However
And R ¹And R^TwoOf the hydrocarbon groups of, hydrocarbon groups and water
The existence ratio of elementary atoms depends on the number of hydrocarbon groups (X)
Ratio Y / X of the number (Y) of elementary atoms is 0.15 or less, preferably
Or less than 0.06. Y / X ratio exceeds 0.15
If so, the effect of the present invention tends to decrease.

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

The amount of the alkylene oxide derivative compounded in the external preparation for skin of the present invention is not particularly limited, but is preferably 0.1 to 80.0% by mass, more preferably 5.0 to 40.% of the total amount of the external preparation for skin. It is 0 mass%. If the amount is too small, the effect of the present invention is not sufficiently exerted, and if too large, after use,
You may feel sticky.

The alkylene oxide derivative (I) of the present invention has the effects of enhancing the sustainability of the effect of a cooling agent and reducing skin irritation such as tingling sensation. The mechanism of action is not clear, but it is considered that the presence of the alkylene oxide derivative (I) causes the refreshing agent to evaporate little by little from the skin external preparation base, and the mild refreshing feeling lasts for a long time. FIG. 1 shows a model diagram of an O / W type emulsion composition containing menthol. Alkylene oxide derivative In the system (a) containing no alkylene oxide derivative, menthol is vigorously released. On the other hand, in the system (b) in which the alkylene oxide derivative is blended, the alkylene oxide derivative is easily compatible with water and menthol, so that menthol is retained in the base, and as a result, menthol is released little by little, resulting in a mild cooling. Feeling lasts and irritation such as tingling is reduced.

The external preparation for skin of the present invention is prepared by incorporating the above-mentioned essential components into an existing external preparation base for skin.
In the external preparation for skin of the present invention, in addition to the essential components described above, other components usually used in external preparations for skin such as cosmetics and pharmaceuticals, for example, powder components, liquid oils and fats, solid oils and fats, waxes, hydrocarbons and higher fatty acids. , Higher alcohols, esters, silicones, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, moisturizers, water-soluble polymers, thickeners, film agents, UV absorbers, metal ions Blocking agents, lower alcohols, polyhydric alcohols, sugars, amino acids,
Organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, water, etc. are appropriately blended as necessary, and according to the intended dosage form, a conventional method is used. It can be manufactured. Specific examples of the ingredients that can be mixed are listed below, but the external preparation for skin of the present invention can be prepared by mixing the above essential ingredients and any one or more of the following ingredients.

The moisturizer used in the present invention is, for example,
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 carboxylic acid salt, short-chain soluble collagen, diglycerin (EO) PO adduct, Iris yezoensis extract, Achillea millefolium extract, Merrilot extract and the like.

Examples of powder components include inorganic powders (eg, talc, kaolin, mica, sericite,
Muscovite, phlogopite, synthetic mica, phlogopite, biotite, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, tungstate metal salt, magnesium, Silica, zeolite, barium sulfate, calcined calcium sulfate (calculated gypsum), calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, metal soap (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc .; organic Powder (for example, polyamide resin powder (nylon powder), polyethylene powder, polymethylmethacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder) Powder, cellulose powder, etc .; inorganic white pigment (eg titanium dioxide, zinc oxide etc.); inorganic red pigment (eg iron oxide (red iron oxide), iron titanate etc.); inorganic brown pigment (eg γ-oxidation) Inorganic yellow pigments (eg yellow iron oxide, ocher etc.); Inorganic black pigments (eg black iron oxide, low order titanium oxide etc.); Inorganic purple pigments (eg mango violet, cobalt violet etc.) ); Inorganic green pigments (for example, chromium oxide,
Chromium hydroxide, cobalt titanate, etc .; Inorganic blue pigments (eg, ultramarine blue, navy blue, 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, etc.); metal powder pigments (eg, aluminum powder,
Copper powder, etc.); Organic pigments such as zirconium, barium or aluminum lakes (for example, Red No. 201,
Red No. 202, Red No. 204, Red No. 205, Red No. 22
No. 0, Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401
And organic pigments such as Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230
No., Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3
And Blue No. 1); natural pigments (eg, chlorophyll, β-carotene, etc.) and the like.

Examples of the liquid oil and fat include avocado oil,
Camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern oil, castor oil, linseed oil, safflower oil, cottonseed oil, eno oil, Soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnamon oil, Japanese tung oil, jojoba oil, germ oil, triglycerin and the like can be mentioned.

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

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

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

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

Examples of higher alcohols include straight chain alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.); branched chain alcohols (eg, monostearyl glycerin ether). (Batyl alcohol), 2-
Decyltetradecinol, lanolin alcohol, cholesterol, phytosterols, hexyldecanol,
(Isostearyl alcohol, octyldodecanol, etc.)
Etc.

The synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate,
Decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, 1
Cholesteryl 2-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, di-2-heptylundecanoic acid Glycerin, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, glyceryl trioctanoate, glyceryl triisopalmitate, tri Trimethylolpropane isostearate, cetyl 2-
Ethyl hexanoate, 2-ethylhexyl palmitate, glycerin 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-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate and the like can be mentioned.

Examples of the silicone oil include linear polysiloxanes (eg, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (eg, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, etc.) Dodecamethylcyclohexasiloxane, etc.) Silicone resin forming a three-dimensional network structure, silicone rubber, various modified polysiloxanes (amino modified polysiloxane, polyether modified polysiloxane, alkyl modified polysiloxane, fluorine modified polysiloxane, etc.) Etc.

Examples of the anionic surfactant include fatty acid soap (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfate ester salt (eg, sodium lauryl sulfate, potassium lauryl sulfate); alkyl ether sulfate ester salt. (For example,
POE-triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.); N-acyl sarcosinic acid (eg,
Lauroyl sarcosine sodium, etc .; Higher fatty acid amide sulfonate (eg, N-myristoyl-N-methyl taurine sodium, coconut oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc.); Phosphate ester salt (POE-oleyl ether) Sodium phosphate, POE-stearyl ether phosphoric acid, etc.); sulfosuccinate (eg, sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.);
Alkylbenzene sulfonates (eg, sodium linear dodecylbenzene sulfonate, triethanolamine linear dodecylbenzene sulfonate, linear dodecyl benzene sulfonic acid, etc.); higher fatty acid ester sulfate ester salts (eg, hardened coconut oil fatty acid glycerin sodium sulfate, etc.); N-acyl glutamate (eg, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N-myristoyl-L-monosodium glutamate, etc.); sulfated oil (eg, funnel oil, etc.); POE-alkyl ether carvone Acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate; secondary alcohol sulfate ester salt; higher fatty acid alkylolamide sulfate salt; lauroyl mono Ethanolamide sodium succinate; N-palmitoyl aspartic acid ditriethanolamine; sodium caseinate and the like.

Examples of the cationic surfactant include alkyl trimethyl ammonium salts (eg stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, etc.); alkyl pyridinium salts (eg,
Cetylpyridinium chloride, etc.); Distearyldimethylammonium dialkyldimethylammonium chloride; Poly (N, N'-dimethyl-3,5-methylenepiperidinium) chloride;
Alkyl quaternary ammonium salts; Alkyl dimethyl benzyl ammonium salts; Alkyl isoquinolinium salts; Dialkyl morphonium salts; POE-alkyl amines; Alkyl amine salts; Polyamine fatty acid derivatives; Amyl alcohol fatty acid derivatives; Benzalkonium chloride; Benzethonium chloride Etc.

Examples of the amphoteric surfactant include, for example, imidazoline-based amphoteric surfactants (eg, 2-undecyl-N, N, N).
-(Hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc .; betaine surfactant (eg, 2-heptadecyl-N- Carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amidobetaine, sulfobetaine, etc.) and the like.

Examples of lipophilic nonionic surfactants include sorbitan fatty acid esters (eg, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquis). Oleate, sorbitan trioleate, penta-2-ethylhexyl diglycerol sorbitan, tetra-2-ethylhexyl diglycerol sorbitan, etc.); glycerin polyglycerin fatty acids (eg monocotton oil fatty acid glycerin, monoerucic acid glycerin, sesquioleate glycerin) , Glyceryl monostearate, α, α '
-Glycerin oleate pyroglutamate, glyceryl monostearate malic acid, etc.); propylene glycol fatty acid esters (eg, propylene glycol monostearate etc.); hydrogenated castor oil derivative; glycerin alkyl ether and the like.

Examples of hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (eg, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate). POE-sorbit fatty acid esters (eg POE-sorbit monolaurate, POE-sorbit monooleate, POE-sorbit pentaoleate, POE-sorbit monostearate, etc.); POE-glycerin fatty acid esters (eg , POE-glycerin monostearate, POE-glycerin monoisostearate, PO
E-glycerin triisostearate and other POE-monooleates, etc .; POE-fatty acid esters (eg, POE-distearate, POE-monodioleate, ethylene glycol distearate, etc.); POE-alkyl ethers (eg, POE-lauryl ether) , POE-oleyl ether, PO
E-stearyl ether, POE-behenyl ether, POE-2-
Octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic types (eg, Pluronics); POE / POP-alkyl ethers (eg, POE / PO)
P-cetyl ether, POE / POP-2-decyl tetradecyl 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 derivative (eg POE-castor oil, POE- hydrogenated castor oil, POE- hydrogenated castor oil monoisostearate, POE- hydrogenated castor oil triisostearate, POE- hydrogenated Castor oil monopyroglutamic acid monoisostearate diester, POE-hardened castor oil maleic acid etc.); POE-beeswax lanolin derivative (eg POE-sorbit beeswax etc.); alkanolamide (eg coconut oil fatty acid diethanolamide, lauric acid monoester) Ethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid ester;
POE-alkylamines; POE-fatty acid amides; sucrose fatty acid esters; alkylethoxydimethylamine oxides;
Trioleyl phosphoric acid etc. are mentioned.

Examples of natural water-soluble polymers include plant-based polymers (eg, gum arabic, tragacanth, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), algecoloid (cassius extract). ), Starch (rice, corn, potato, wheat), glycyrrhizic acid); microbial macromolecules (eg, xanthan gum, dextran, succinoglucan, vullan, etc.); animal macromolecules (eg, collagen, casein,
Albumin, gelatin, etc.) and the like.

As the semi-synthetic water-soluble polymer, for example,
Starch-based polymers (for example, carboxymethyl starch, methyl hydroxypropyl starch, etc.); Cellulose-based polymers (methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, carboxymethyl cellulose sodium, Crystalline cellulose,
Cellulose powder, etc.); alginic acid-based polymers (eg, sodium alginate, propylene glycol alginate, etc.) and the like.

As the synthetic water-soluble polymer, for example, vinyl-based polymer (eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer, etc.); polyoxyethylene-based polymer (eg, polyethylene glycol 20,000, 40,000, 6
Examples include polyoxyethylene-polyoxypropylene copolymers of 0,000); acrylic polymers (eg, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymers and the like.

Examples of the thickener include gum arabic,
Carrageenan, karaya gum, tragacanth gum, carob gum, quince seed (quince), casein, dextrin, gelatin, sodium pectate, sodium alginate, methyl cellulose, ethyl cellulose,
CMC, hydroxyethyl cellulose, hydroxypropyl cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, dialkyldimethylammonium sulfate cellulose, xanthan gum, magnesium aluminum silicate, bentonite,
Hectorite, silicic acid A1Mg (vegan), laponite,
Examples thereof include anhydrous silicic acid.

Examples of the ultraviolet absorber include benzoic acid type ultraviolet absorbers (for example, para-aminobenzoic acid (hereinafter, P
Abbreviated as ABA), 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-based UV absorbers (eg, homomenthyl-N-acetylanthranilate, etc.); Salicylic acid-based UV absorbers (eg, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate) , Benzyl salicylate, p-isopropanol phenyl salicylate, etc.); cinnamic acid-based UV absorbers (eg, octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-)
2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate Mate, 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-5'-methylphenylbenzotriazole;dibenzalazine;dianisoylmethane; 4-methoxy
-4'-t-butyldibenzoylmethane; 5- (3,3-dimethyl-2-
Norbornylidene) -3-pentan-2-one and the like.

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

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

Examples of the polyhydric alcohol include dihydric alcohols (eg, 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.);
Tetrahydric alcohol (eg, pentaerythritol such as 1,2,6-hexanetriol); pentahydric alcohol (eg, xylitol); hexahydric alcohol (eg, sorbitol, mannitol); polyhydric alcohol polymer (eg, , Diethylene glycol, dipropylene glycol, triethylene 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 Cole mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc .; 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, pro Pyrene 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 butyl ether, etc.); dihydric alcohol ether ester (eg, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl) Ether acetate, ethylene glycol diabate, ethylene glycol disuccinate, 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); glycerol monoalkyl ethers (e.g., hexyl alcohol, selachyl alcohol, batyl alcohol); sugar alcohols (e.g.,
Sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch-decomposing sugar, maltose, xylitose, starch-decomposing sugar reducing alcohol, etc.); Glysolid; Tetrahydrofurfuryl alcohol; POE-Tetrahydrofur Furyl alcohol; POP-butyl ether;
POP / POE-butyl ether; tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphoric acid; POP / POE-pentane erythritol ether, polyglycerin and the like.

As the monosaccharide, for example, tricarbon sugar (for example,
D-glyceryl aldehyde, dihydroxyacetone, etc.);
Four-carbon sugar (for example, D-erythrose, D-erythrulose,
D-threose, erythritol, etc.); pentoses (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.); heptacarbon sugar (eg, aldoheptose, heprose, etc.); octose sugar (eg, octulose); , 2-deoxy-D-ribose, 6-deoxy-L-
Galactose, 6-deoxy-L-mannose, etc.); Amino sugar (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.); Uronic acid (eg, D-glucuronic acid, D-mannuronic acid) , L-guluronic acid, D-galacturonic acid, L-iduronic acid, etc.) and the like.

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

Examples of polysaccharides include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran. , Keratosulfate, locust bean gum, succinoglucan, caronic acid and the like.

Examples of the 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 sodium acyl sarcosine (sodium lauroyl sarcosine), acyl glutamate, sodium acyl β-alanine, 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 can be mentioned. Examples of the polymer emulsion include acrylic resin emulsion, polyethyl acrylate emulsion, acrylic resin solution, polyacrylic alkyl ester emulsion, polyvinyl acetate resin emulsion, natural rubber latex and the like.

Examples of the pH adjusting agent include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate. Examples of vitamins include vitamins A, B ₁ , B ₂ and B.
₆ , C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.

Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like. Examples of the antioxidant aid include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, ethylenediaminetetraacetic acid and the like.

Other components that can be blended are, for example,
Antiseptic (ethyl paraben, butyl paraben, etc.); anti-inflammatory agent (eg, glycyrrhizic acid derivative, glycyrrhetinic acid derivative, salicylic acid derivative, hinokitiol, zinc oxide, allantoin, etc.); whitening agent (eg placenta extract,
Yukinoshita extract, arbutin, etc.); Various extracts (for example, pearl oyster, citrus, peony, cembly, birch, sage, loquat, carrot, aloe, mallow, iris, grape, yokuinin, loofah, lily,
Saffron, Senkyu, Showkyu, Hypericum,
Ononis, garlic, capsicum, chimpi, touki, seaweed, etc.), activator (eg, royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoter (eg, nonyl acid warenylamide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester (Ester, capsaicin, zingerone, cantharisin tincture, ictamol, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthin, γ-oryzanol); Leaks (eg, sulfur, thiantol, etc.); Anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.)
Etc.

The dosage form of the external preparation for skin of the present invention is arbitrary,
Any formulation such as solution system, solubilization system, emulsification system, powder dispersion system, water-oil two-layer system, water-oil-powder three-layer system, gel, mist, spray, mousse, roll-on may be used. A preparation in which a sheet such as a non-woven fabric is impregnated or applied is also possible. Further, the product form of the external preparation for skin of the present invention is also optional, such as facial cosmetics such as lotions, emulsions, creams, packs and lip balms; makeup cosmetics such as foundations, lipsticks and eye shadows; body cosmetics;
Aromatic cosmetics; skin cleansing agents such as make-up removers and body shampoos; hair cosmetics such as hair liquids, hair tonics, hair conditioners, shampoos, rinses, hair restorers; ointments and the like. Since the cooling agent is preferably present in a dissolved state in the external preparation from the viewpoint of usability, the external preparation base used in the present invention is a solvent suitable for dissolving the cooling agent, for example, a lower solvent such as ethanol. It preferably contains alcohol or oil.

[0050]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The present invention is not limited to this. First, the evaluation method adopted in the present invention will be described.

"Evaluation (1): Compatibility with skin" The familiarity with the skin during use was evaluated by 10 expert panelists. The evaluation criteria are as follows. ⊚: 8 or more professional panelists recognized that they were familiar with the skin during use. ◯ ... 6 or more and less than 8 specialized panelists recognized that they were well adapted to the skin during use. Δ: 3 or more and less than 6 specialized panelists recognized that they were well adapted to the skin during use. ×: Less than 3 professional panelists recognized that they were well fit to the skin during use.

"Evaluation (2): Smoothness of skin" Smoothness of the skin during use and after use was evaluated by 10 professional panelists. The evaluation criteria are as follows. ⊚: 8 or more professional panelists recognized that the skin was smooth during and after use. ○: 6 or more and less than 8 specialized panelists recognized that the skin was smooth during and after use. Δ: 3 or more and less than 6 specialized panelists recognized that the skin was smooth during and after use. X: Less than 3 specialized panelists recognized that the skin was smooth during and after use.

"Evaluation (3): No stickiness on skin" The stickiness on the skin during use and after use was evaluated by 10 professional panelists. The evaluation criteria are as follows. ⊚: 8 or more professional panelists recognized that the skin was not sticky during and after use. ○: 6 or more and less than 8 specialized panelists recognized that the skin was not sticky during and after use. Δ: 3 or more and less than 6 professional panelists recognized that the skin was not sticky during and after use. X: Less than 3 specialized panelists recognized that the skin was not sticky during and after use.

"Evaluation (4): Skin irritation test" The sensation of tingling when a sample was applied to the inner part of the upper arm of a panel of 10 people was scored according to the following criteria, and the average value was calculated. 0: No tingling sensation is observed. 1 ... Slight tingling or redness is observed. 2 ... A tingling sensation or redness is recognized. 3 ... A tingling sensation and redness are recognized. The evaluation criteria of the "skin irritation test" are as follows. ◎… Average value of 10 panelists: 0 or more and less than 0.1 ○… Average value of 10 panelists: 0.1 or more and less than 0.15 △… Average value of 10 panelists: 0.15 or more and less than 0.2 ×… Average value of 10 panelists: 0.2 or more

[Evaluation (5): Persistence of cooling effect] The presence or absence of a cooling feeling 120 minutes after use was evaluated by 10 professional panelists. The evaluation criteria are as follows. ⊚: 8 or more professional panelists recognized that the refreshing feeling was lasting. ○: 6 or more and less than 8 specialized panelists recognized that the refreshing feeling is sustained. B: 3 or more and less than 6 specialized panelists recognized that the refreshing feeling was sustained. X: Less than 3 specialized panelists recognized that the refreshing feeling was sustained.

Next, the alkylene oxide derivative according to the present invention is
A method of synthesizing the conductor will be described. In addition, in the following examples
Where EO is an oxyethylene group and PO is an oxypropylene group.
Group, [(EO) / (PO)] represents a random bond.
You The alkylene oxide derivative used in the present invention is
It was produced according to the following synthesis example.Synthesis Example 1 Synthesis of block polymer Polyoxyethylene (10 mol) Polyoxypropylene
(10 mol) dimethyl ether (compound 13)

[0057]

[Chemical 3] CH_ThreeO (EO)₅(PO)₁₀(EO)₅CH_Three 76 g of propylene glycol and potassium hydroxide as a catalyst
The autoclave was charged with 3.1 g of aluminum.
Replace the air in the tank with dry nitrogen and
The catalyst was completely dissolved at 0 ° C. Next, using a dropping device,
522 g of pyrene oxide was added dropwise and stirred for 2 hours.
Continuously add 440 g of ethylene oxide with a dropping device.
The mixture was added dropwise and stirred for 2 hours. Next, potassium hydroxide 22
After charging 4 g and replacing the system with dry nitrogen, methyl chloride was added.
188 g of resin at a temperature of 80 to 130 ° C and press it for 5 hours to react.
Let Then take out the reaction composition from the autoclave
Then, neutralize with hydrochloric acid to adjust the pH to 6-7 and remove the water content.
Decompression to remove-0.095 MPa (50 mmHg),
It was treated at 100 ° C. for 1 hour. The salt generated after further treatment is removed.
Filtration to remove the compound 13 alkyleneoxy
A derivative was obtained. Samples before reacting with methyl chloride
And purified, the hydroxyl value is 110,
Compound 13 has a hydroxyl value of 0.3, relative to the number of terminal methyl groups
The ratio of the number of hydrogen atoms is 0.003, which is almost completely hydrogen.
Atom has been converted to a methyl group.

[0058]Synthesis example 2 Synthesis example of random polymer Polyoxyethylene (10 mol) Polyoxypropylene
(10 mol) dimethyl ether (compound 2)

[0059]

[Chemical 4] CH_ThreeO [(EO)₁₀/ (PO)₁₀] CH_Three 76 g of propylene glycol and potassium hydroxide as a catalyst
The autoclave was charged with 3.1 g of aluminum.
Replace the air in the tank with dry nitrogen and
The catalyst was completely dissolved at 0 ° C. Next, using a dropping device,
440 g of lenoxide and 522 g of propylene oxide
The mixture was added dropwise and stirred for 2 hours. Next, potassium hydroxide
After charging 224 g of Um and replacing the system with dry nitrogen,
188 g of methyl chloride is pressed in at a temperature of 80 to 130 ° C, and at 5
Reacted for a while. Then the reaction composition from the autoclave
Water taken out and neutralized with hydrochloric acid to pH 6-7
Reduced pressure-0.095 MPa (50 mmH
g), treated at 100 ° C. for 1 hour. Generated after further processing
Filtration was performed to remove salts, and the alkylene oxide of compound 2 was removed.
A xide derivative was obtained. Before reacting the methyl chloride
The product obtained by pulling and purifying had a hydroxyl value of 107,
Compound 2 has a hydroxyl value of 0.4, which corresponds to the number of terminal methyl groups
The ratio of the number of hydrogen atoms is 0.004, which is almost completely water.
Elemental atoms have been converted to methyl groups.

[Effect of Alkylene Oxide Derivative] The effect of the alkylene oxide derivative according to the present invention on the cooling effect and irritation was examined. That is, a skin external preparation was prepared with the following basic composition for testing and evaluated. Basic composition for test (1) Ethanol 5.0 mass% (2) Glycerin 3.0 (3) 1,3-Butylene glycol 5.0 (4) L-menthol 0.1 (5) Test compound 5.0 ( 6) Purified water residual

[0061]

[Table 1] ―――――――――――――――――――――――――――――――――― Test Compound Stimulation Coolness Persistence Evaluation (4) (5 ) ―――――――――――――――――――――――――――――――――― CH ₃ O [(EO) ₆ / (PO) ₁₄ ] CH ₃ ◎ ◎ CH ₃ O [(EO) ₁₆ / (PO) ₅ ] CH ₃ ◎ ◎ CH ₃ O [(EO) ₂₅ / (PO) ₂₅ ] CH ₃ ◎ ◎ Glycerin △ × Deionized water × × ――――――――――――――――――――――――――――――――――

As can be seen from Table 1, when a general humectant such as glycerin is blended, the skin irritation (feeling of tingling) due to the refreshing agent is slightly improved, but the sustainability of the refreshing feeling is not improved. In addition, stickiness may occur due to an increase in the amount of the moisturizer. On the other hand, when an EO / PO derivative having a hydrocarbon group bonded to both ends was blended, a mild cooling sensation lasted for a long time, and no skin irritation (feeling of stickiness) or stickiness was observed.

Therefore, the present inventors investigated the change in the release property of menthol with and without the alkylene oxide derivative. The results are shown in Figure 2. In FIG. 2, an ethanol solution was used as a control, a 10% alkylene oxide derivative-containing ethanol solution was used as a sample, and the initial concentration of menthol in each solution was 1%. Examples of the alkylene oxide derivative include (CH ₃ O [(EO) ₁₅ / (PO) ₅ ] C
H ₃₎ was used. Leave both solutions in an open system at room temperature,
The concentration of menthol was measured by sampling with time, and the residual rate was calculated.

As can be seen from FIG. 2, when the alkylene oxide derivative is not added, most of the menthol is released all at once in the first hour. For this reason, the effect of menthol is not sustained, and a tingling sensation tends to occur. On the other hand, when the alkylene oxide derivative is blended, the effect is sustained for a long time because menthol is gradually released, and it is considered that there is no tingling sensation and a mild refreshing sensation is maintained. Furthermore, the inventors of the present invention proceeded with the study on alkylene oxide derivatives. In addition, the composition prepared by the said basic composition was used for each test.

[Determination of R ¹ and R ² ] First, the present inventors examined the correlation between R ¹ and R ² of the alkylene oxide derivative and suitability as an external preparation for skin. The results are shown in Table 2. The EO and PO parts of both compounds were [(EO)
₁₀ / (PO) ₁₀ ].

[0066]

[Table 2] ―――――――――――――――――――――――――――――――――― Test Compound Familiar Smoothness, Stickiness, Stimulation, Coolness Sustainability No. R ¹ R ² (1) (2) (3) (4) (5) ――――――――――――――――――――――――――――――― ――― 1 H H × × △ △ × 2 CH ₃ CH ₃ ◎ ◎ ◎ ◎ ◎ ◎ 3 C ₂ H ₅ CH ₃ ◎ ◎ ◎ ◎ ◎ 4 C ₄ H ₉ C ₄ H ₉ ○ ○ ○ ○ ○ 5 C ₆ H ₉ CH ₃ △ △ △ ○ ○ 6 C ₁₂ H ₂₅ CH ₃ △ △ △ △ △ ――――――――――――――――――――――――――――――――――

As is clear from Table 2, when the carbon numbers of both R ¹ and R ² are 1 to 4 (compounds 2, 3 and 4),
In all cases, a refreshing feeling lasting effect and a good feeling in use were observed, and there was almost no skin irritation such as a tingling sensation. On the other hand, when R ¹ and R ² were hydrogen (compound 1) and R ¹ was C12 (compound 6), neither evaluation was preferable. On the other hand, R
^{Even when the} total number of carbon atoms of ¹ and R ² was 7, which was smaller than that of compound 4, when R ¹ was C 6 (compound 5), the feeling of use tended to be impaired. From the above, in the alkylene oxide derivative according to the present invention, both R ¹ and R ² need to be hydrocarbon groups having 1 to 4 carbon atoms.

In the actual manufacturing, R ¹ , R ²
Since not all of the above are substituted with hydrocarbon groups, the permissible abundance ratio of the unsubstituted (H) compound was examined. The unsubstituted ratio is represented by the ratio Y / X of the number (Y) of hydrogen atoms to the number (X) of hydrocarbon groups. In Table 3 below, 1: 2 = 95: 5 means Compound 1
And Compound 2 were mixed at a ratio of 95: 5 and adjusted to a predetermined Y / X.

[0069]

[Table 3] ―――――――――――――――――――――――――――――――――― Compounds Familiar, smooth, sticky, stimulus, persistence No. R ¹ R ² Y / X (1) (2) (3) (4) (5) ―――――――――――――――――――――――――――――― ―――― 1 H H − × × △ △ × 2 CH ₃ CH ₃ 0.003 ◎ ◎ ◎ ◎ ◎ 1: 2 = 95: 5 0.054 ◎ ◎ ◎ ◎ ◎ ◎ 1: 2 = 80: 20 0.203 ○ △ △ △ ○ ――――――――――――――――――――――――――――――――――

As is clear from Table 3, R ¹ , R ²
If there is an unreacted substance, there is no great effect if the amount is small (Y / X = 0.054), but Y / X
When it becomes 0.203, each evaluation obviously drops. Further, as a result of detailed study by the present inventors, it became clear that Y / X needs to be 0.15 or less.

[Oxyalkylene Group, Oxyethylene Group] Next, the present inventors examined the presence of the oxyalkylene group and oxyethylene group in the alkylene oxide derivative and their suitability as an external skin preparation. The results are shown in Table 4 below. In addition, in the alkylene oxide derivatives of the compound 2 and the compounds 7 to 11, R ¹ = R ² = CH ₃
Is.

[0072]

[Table 4]   ――――――――――――――――――――――――――――――――――   Compound Familiar, smoothness, stickiness, stimulation, refreshing sensation     No. EO PO (1) (2) (3) (4) (5)   ――――――――――――――――――――――――――――――――――     7 200 ○ ○ ○ △ △     8 15 5 ◎ ◎ ◎ ◎ ◎ ◎     2 10 10 ◎ ◎ ◎ ◎ ◎ ◎     9 6 14 ◎ ◎ ◎ ◎ ◎     10 20 Difficult to adjust (low water solubility)     11 25 25 ◎ ◎ ○ ◎ ◎ ◎     12 Chemicals 5 △ ○ △ △ ×   ――――――――――――――――――――――――――――――――――

[0073]

[Chemical 5]

As is clear from Table 4, the presence of both the oxyalkylene group and the oxyethylene group is indispensable for the effect of the present invention. Further, since the compound 12 shown in Chemical formula 5 has a low effect, it is considered that the effect of the present invention is not merely the effect of adjusting hydrophilicity and hydrophobicity. As a result of further detailed study by the present inventors, the preferable ratio of the oxyethylene group to the total of the oxyalkylene group and the oxyethylene group is 2
It became clear that it was 0 to 80 mass%.

Further, the present inventors compared the block polymer and the random polymer having the same number of alkylene groups and oxyethylene groups.

[0076]

[Table 5] ―――――――――――――――――――――――――――――――――― Compound Stickiness (Evaluation 3) ―――――― ―――――――――――――――――――――――――――― 13 CH ₃ O (EO) ₅ (PO) ₁₀ (EO) ₅ CH ₃ ○ 2 CH ₃ O [(EO) ₁₀ / (PO) ₁₀ ] CH ₃ ◎ ――――――――――――――――――――――――――――――――――

As is clear from Table 5, the effect of the present invention can be obtained with either a block polymer or a random polymer, but an excellent feeling of use can be obtained particularly in the case of a random polymer. .

[Amount to be added to external skin preparation] Next, the present inventors further studied the amount to be added to the external skin preparation of the alkylene oxide derivative. In the basic composition,
The compound 8 was used to prepare a skin external preparation by changing the compounding amount. The increase and decrease was adjusted with purified water. The results of each evaluation are shown in Table 6.

[0079]

[Table 6]   ――――――――――――――――――――――――――――――――――   Compound 8 Familiar, smooth, sticky, stimulating, refreshing sensation   Compounding amount (%) (1) (2) (3) (4) (5)   ――――――――――――――――――――――――――――――――――       0 × × × × ×       0.1 ○○○○○       5.0 ◎ ◎ ◎ ◎ ◎     40.0 ◎ ◎ ◎ ◎ ◎     80.0 ◎ ◎ ○ ◎ ◎   ――――――――――――――――――――――――――――――――――

From the results shown in Table 6, the addition effect of the alkylene oxide derivative according to the present invention is recognized from about 0.1% by mass, but particularly remarkable is 5.0% by mass or more. However, when it is 80% by mass or more, it tends to start to be slightly sticky, so that it is preferable to mix it up to about 40% by mass.

Hereinafter, preferred examples of compounding the external preparation for skin according to the present invention will be described. Formulation Example 1 Lotion A. Alcohol phase ethanol 5.0 mass% POE oleyl alcohol ether 2.0 compound 6 3.0 2-ethylhexyl-p-dimethyl aminobenzoate 0.18 l-menthol 0.01 perfume 0.05 B.I. Aqueous phase 1,3 Butylene glycol 9.5 Sodium pyrrolidonecarboxylate 0.5 Nicotinic acid amide 0.3 Glycerin 5.0 Purified water to 100 (Production method and evaluation) The alcohol phase of A is added to the aqueous phase of B, and it is acceptable. It was solubilized to obtain a lotion. The obtained lotion had a good refreshing feeling, no irritation, and a good feeling in use.

Formulation Example 2 Emulsion (O / W) A. Oil phase Stearic acid 3.0% by mass Cetanol 1.0 Lanolin derivative 3.0 Liquid paraffin 5.0 2-Ethylhexyl stearate 3.0 l-Menthol 0.3 d-camphor 0.1 POE cetyl ether 2.0 Glyceryl Monostearate 2.0 Preservative Suitable amount Perfume Suitable amount B. Aqueous phase 1,3-butylene glycol 6.0 Triethanolamine 1.0 Compound 2 20.0 Purified water to 100 (Production method and evaluation) Aqueous phase B is mixed and dissolved and kept at 70 ° C.
After the oil component of the oil phase A is heated and dissolved at 70 to 80 ° C, the other components are sequentially added to 70 ° C. The oil phase was added to the aqueous phase with stirring to emulsify to obtain an emulsion. The obtained emulsion had a good refreshing feeling, no irritation, and a good feeling in use.

Formulation Example 3 Carmine Lotion A. Ethanol phase Ethanol 15% by mass Glycerin 21, 3-butylene glycol 2 Compound 13 10 Fragrance Suitable amount B. Powder phase Red iron oxide 0.15 Zinc oxide 0.5 Kaolin 2.0 C.I. Aqueous phase Camphor 0.2 Phenol 0.02 Purified water to 100 (Production method and evaluation) Ethanol phase A is mixed and dissolved.
The aqueous phase was mixed and dissolved, and the powder phase and the ethanol phase were added thereto and stirred, and the powder was dispersed to obtain a carmine lotion. The obtained lotion had an excellent refreshing feeling, no irritation, and a good feeling in use.

Formulation Example 4 Cream (O / W) A. Oil phase Stearyl alcohol 6.0% by mass Stearic acid 2.0 Hydrogenated lanolin 4.0 Squalane 9.0 Octyldodecanol 10.0 l-Menthol 0.3 d-camphor 0.1 POE cetyl ether 3.0 Glyceryl mono Stearate 2.0 Preservative Suitable amount Perfume Suitable amount B. Aqueous phase 1,3-butylene glycol 6.0 PEG1500 4.0 Compound 2 20.0 Purified water to 100 (Production method and evaluation) Aqueous phase B is mixed and dissolved and kept at 70 ° C.
After the oil component of the oil phase A is heated and dissolved at 70 to 80 ° C, the other components are sequentially added to 70 ° C. Add the oil phase to the water phase while stirring and homogenize the emulsified particles with a homomixer,
Deaeration, filtration and cooling gave a cream. The obtained cream had a good refreshing feeling, no irritation, and a good feeling in use.

Formulation Example 5 Gel (Aqueous Moisture Gel) A. Moisturizing agent phase Dipropylene glycol 7.0 mass% POE oleyl alcohol ether 2.0 l-menthol 0.01 Perfume 0.05 Preservative A suitable amount B. Aqueous phase Carboxy vinyl polymer 0.4 Methyl cellulose 0.2 PEG1500 8.0 Compound 2 3.0 Potassium hydroxide 0.1 Browning agent Proper amount Chelating agent Proper amount Coloring agent Proper amount Purified water to 100 (Production method and evaluation) Purification After the water-soluble polymer is uniformly dissolved in water, PEG 1500, compound 2, a browning inhibitor, a coloring agent and a chelating agent are added to prepare an aqueous phase B. Next, a surfactant is added to dipropylene glycol and dissolved by heating at 50 to 55 ° C., and a humectant phase A containing a preservative, a fragrance and menthol is gradually added to the aqueous phase B prepared above while stirring. Added. Finally, an alkaline aqueous solution is added, and the mixture is sufficiently stirred for neutralization. The obtained gel had a good refreshing feeling, no irritation, and a good feeling in use.

Formulation Example 6 Deodorant Stick (Wax Stick) Aluminum Chlorohydrate 23.0% by Mass Talc 15.0 Solid Paraffin Wax 2.0 Stearyl Alcohol 8.0 Liquid Paraffin 14.5 Cyclic Dimethyl Polysiloxane 26.5 Sorbitan Fatty acid ester 1.0 Compound 6 10.0 l-Menthol 0.01 Perfume Suitable amount (production method and evaluation) Liquid paraffin is heated and melted and mixed with solid paraffin, stearyl alcohol and sorbitan fatty acid ester. Further, powder, compound 6, 1-menthol, cyclic dimethylpolysiloxane, and fragrance are added, uniformly dispersed and mixed by using a homomixer, poured into a mold, and cooled and solidified. The obtained wax-based stick had a good refreshing feeling, no irritation, and a good feeling in use.

Formulation 7 Hair Growth Agent Ethyl Alcohol 60.0% by Mass Compound 13 5.0 Hinokitiol Appropriate Senburi Extract Appropriate Vitamin B6 Appropriate Vitamin E Derivative Appropriate Propylene Glycol 2.0 Fragrance Appropriate 1-Menthol 0.01 Perfume solubilizing agent Appropriate amount Purified water to 100 (Production method and evaluation) Other components except purified water are sequentially added to ethyl alcohol to dissolve, and purified water is added to solubilize and homogenize, and then filtered. The obtained hair growth stimulant had a long-lasting refreshing feeling, was not irritating, and had a good feeling in use.

[0088]

EFFECTS OF THE INVENTION According to the present invention, by blending a cooling agent and a specific alkylene oxide derivative, the cooling effect lasts for a long period of time, and there is no irritation such as tingling, and the skin feels good to use. An external preparation can be provided.

[Brief description of drawings]

FIG. 1 is a model diagram of menthol release in an alkylene oxide derivative-free system (a) and a system (b) according to the present invention.

FIG. 2 is a graph showing changes in menthol release properties with and without the alkylene oxide derivative according to the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takashi Omori             2-2-1 Hayabuchi, Tsuzuki-ku, Yokohama-shi, Kanagawa               Shiseido Research Center Co., Ltd.             Beach) (72) Inventor Hiroyuki Kagoki             2-2-1 Hayabuchi, Tsuzuki-ku, Yokohama-shi, Kanagawa               Shiseido Research Center Co., Ltd.             Beach) F-term (reference) 4C083 AA122 AB032 AB212 AB222                       AB232 AB432 AC022 AC061                       AC062 AC072 AC102 AC122                       AC181 AC182 AC211 AC212                       AC242 AC342 AC392 AC442                       AC472 AC542 AC552 AC612                       AC852 AD042 AD092 AD172                       AD262 AD512 AD632 AD662                       BB60 CC02 CC04 CC17 CC37                       DD11 DD33 DD41 EE06 EE10                       EE18 EE22

Claims (5)

[Claims] 1. A skin external preparation containing a cooling agent and an alkylene oxide derivative represented by the following general formula (I). Embedded image R ¹ O — [(AO) _m (EO) _n ] -R ² (I) (wherein AO is an oxyalkylene group having 3 to 4 carbon atoms, E
O is an oxyethylene group, m and n each have 3 to 4 carbon atoms
The average number of moles of oxyalkylene group and oxyethylene group added is 1 ≦ m ≦ 70, 1 ≦ n ≦ 70, and the ratio of the oxyethylene group to the total of the oxyalkylene group and the oxyethylene group is 20 to 80 mass. %. The oxyalkylene group and oxyethylene group may be added in blocks or randomly. R ¹ and R ²
Are the same or different hydrocarbon groups having 1 to 4 carbon atoms or hydrogen atoms, and the ratio of the number of hydrogen atoms to the number of hydrocarbon groups of R ¹ and R ² is 0.15 or less. ) 2. The external skin preparation according to claim 1, wherein the alkylene oxide derivative (I) has oxyalkylene groups and oxyethylene groups randomly added. 3. The external skin preparation according to claim 1, wherein the alkylene oxide derivative (I) is 0.1 to 80.
A skin external preparation characterized by being blended in a mass%. 4. The external skin preparation according to claim 1, wherein the cooling agent is menthol or camphor. 5. The external preparation for skin according to claim 1, which contains 0.001 to 20% by mass of a cooling agent.