JP2007332115A - Skin care preparation containing 4-alkylresorcinol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means for improving the retention of 4-alkylresorcinol and/or its salt on the skin in a skin care preparation containing 4-alkylresorcinol and/or its salt. <P>SOLUTION: 4-Alkylresorcinol, etc., are formed in the form of a drug preparation together with a dimer acid diester such as hydrogenated dimer dilinolic acid di(phytosteryl/isostearyl/cetyl/stearyl/behenyl) ester. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a skin external preparation containing 4-alkylresorcinol, and more particularly to a skin external preparation suitable for cosmetics including quasi drugs.

  It is known that 4-alkylresorcinol and its salts such as 4-n-butylresorcinol, 4-n-hexylresorcinol and 4-cyclohexylresorcinol have excellent antibacterial activity and melanin production inhibitory activity ( Non-patent document 1, Patent document 1). Among these, 4-n-butylresorcinol and / or a salt thereof is known to contain skin external preparations such as cosmetics for the purpose of preventing acne and pigmentation (Patent Document 2, Patent Document 3, etc.) ). However, since these substances are highly water-soluble, there is a problem that even if they are used as an active ingredient of an external preparation for skin, they are easily removed by sweat or water, and the time for storing them on the skin is short. In particular, external preparations for the purpose of inhibiting melanin production are mainly used in summer when melanin production is enhanced, and thus are required to be hard to be removed by sweat or water. In such a background, it has been desired to develop means for improving the retention on the skin of a skin external preparation containing 4-alkylresorcinol and / or a salt thereof.

  On the other hand, dimer acid diesters have been known to be used in cosmetics as oils for enhancing the usability of the cosmetics and giving the skin and hair gloss (Patent Documents 4, 5, etc.). However, it has not been known that dimer acid diesters improve the retention of 4-alkylresorcinol and / or its salts on the skin.

JP 2005-527534 Gazette JP 2003-252748 A JP 2005-343864 A JP 2004-269396 A JP 2005-206573 A Supervised by Takeda et al. "Advances in cosmetics evaluation technology and future prospects", published by Yakuji Nippo Inc., March 31, 2001

  The present invention has been made under such circumstances, and it is an object of the present invention to provide a means for improving the retention of the skin in an external preparation for skin containing 4-alkylresorcinol and / or a salt thereof. To do.

  In the external preparation for skin containing 4-alkylresorcinol and / or a salt thereof (hereinafter also referred to as 4-alkylresorcinol and the like), the present inventors improve the storage properties of 4-alkylresorcinol and the like on the skin. As a result of diligent research efforts to find a means, formulation of 4-alkylresorcinol together with dimer acid diester improves the retention of 4-alkylresorcinol in skin preparations on the skin. And found the invention. That is, the present invention is as follows.

(1) A skin external preparation characterized by containing 1) 4-alkylresorcinol and / or a salt thereof, and 2) a diester of dimer acid.
(2) The external preparation for skin according to (1), wherein the 4-alkylresorcinol is 4-n-butylresorcinol.
(3) The skin external preparation according to (1) or (2), wherein the content of 4-alkylresorcinol and / or a salt thereof is 0.05 to 5% by mass.
(4) Dimer acid diesters are hydrogenated dimer dilinoleic acid di (phytosteryl / isostearyl / cetyl / stearyl / behenyl), hydrogenated dimer dilinoleic acid (isostearyl / phytosteryl) and hydrogenated dimer dilinoleic acid dimer. The external preparation for skin according to any one of (1) to (3), wherein the external preparation is one or more selected from linoleil.
(5) Content of diester of dimer acid is 0.05-5 mass%, The skin external preparation as described in any one of (1)-(4) characterized by the above-mentioned.

  The external preparation for skin of the present invention is excellent in the storage properties of 4-alkylresorcinol and / or its salt on the skin, such as 4-n-butylresorcinol, and thus is not easily affected by makeup collapse due to sweat or water. Can sufficiently exhibit the antibacterial action and the melanin production inhibitory action.

<1> 4-Alkylresorcinol and / or salt thereof, which is an essential component of the skin external preparation of the present invention. The skin external preparation of the present invention contains 4-alkylresorcinol and / or a salt thereof. The alkyl group in 4-alkylresorcinol is preferably an alkyl group having 3 to 10 carbon atoms, and among them, an alkyl group having 3 to 6 carbon atoms is preferable. Specific examples include n-propyl group, isopropyl group, n-butyl group, tert-butyl group, amyl group, n-hexyl group, cyclohexyl group, octyl group and isooctyl group. In the skin external preparation of the present invention, 4-n-butylresorcinol is particularly preferably used. 4-alkylresorcinol, such as 4-n-butylresorcinol, is a known substance and can be prepared according to conventional methods, for example, Lille, J .; Bitter, LA; Peiner, V. Trudy-Nauchono-Issledovatel ' It can be produced according to the method described in skii Institut Slantsev (1969), No. 18, 127-34. That is, as a method for producing 4-n-butylresorcinol, resorcin and butanoic acid are condensed in the presence of zinc chloride and reduced with zinc amalgam / hydrochloric acid, or resorcin and n-butyl alcohol at 200 to 400 ° C. A method of condensation can be exemplified. Here, it is possible to synthesize other 4-alkylresorcinols by substituting n-butyl alcohol with other alcohols such as n-hexyl alcohol and cyclohexyl alcohol. 4-n-hexylresorcinol is commercially available from Aldrich, and can be purchased and used.

  The salt of 4-alkylresorcinol may be any salt that is usually used in cosmetics and is physiologically acceptable. For example, alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, organic amine salts such as ammonium salt, triethylamine and triethanolamine, and basic amino acid salts such as lysine and arginine are preferably exemplified. The

The skin external preparation of the present invention may contain one of 4-alkylresorcinol and a salt thereof alone, or may contain two or more in combination.
The content of 4-alkylresorcinol and the like in the external preparation for skin of the present invention is preferably 0.05 to 5% by mass, and preferably 0.1 to 0.5% by mass with respect to the total amount of external preparation for skin. % Is more preferable. This is because if the amount is too small, the effects of the present invention may not be exhibited, and if the amount is too large, the effect may reach its peak.

<2> Dimer acid diester which is an essential component of the skin external preparation of the present invention The skin external preparation of the present invention is characterized by containing a dimer acid diester as an essential component. The diester of dimer acid can be obtained by esterifying dimer acid according to a conventional method. Here, the dimer acid is an aliphatic dibasic acid obtained by an intermolecular polymerization reaction of an unsaturated fatty acid. The dimer acid constituting the dimer acid diester of the present invention is preferably an aliphatic dibasic acid having 36 carbon atoms which is a dimer (dimer) of an unsaturated fatty acid having 18 carbon atoms. In addition, the dimer acid may be either one having a cyclic structure in the molecule or one in which carbon of each fatty acid is bonded at one point, or may be a mixture of two or more.
Since the industrial production method of dimer acid is almost standardized, it can be obtained according to such a method. The polymerization product contains monomer acid and trimer acid which are by-products, but may be used in a state in which these are included, or may be used by increasing the purification degree of dimer acid by thin film distillation or the like. Also good. The unsaturated fatty acid constituting the dimer acid is not particularly limited as long as it can be safely used for an external preparation for skin, but is preferably an unsaturated fatty acid having 18 carbon atoms, particularly olein obtained from plants such as soybeans. Acid and linoleic acid are preferred. Moreover, dimer acid is marketed, for example, as a commercial item of dimer dilinoleic acid, Tsunodim (made by Chikushi Foods Co., Ltd.) etc. is mentioned. Since such a commercial product contains about 70 to 100% by mass of dimer acid, such a commercial product is used as it is or as an ester by increasing the content of dimer acid by thin film distillation or the like. Can do.
In addition, when the dimer acid has an unsaturated bond, hydrogen is added to part or all of the dimer acid, and a dimer acid hydrogenated product, which is partially or completely saturated, is derived into a diester. You can also. In the present invention, such a hydrogenated product of dimer acid (hydrogenated dimer acid) is also included in the concept of dimer acid.

  The alcohol used for obtaining the diester of dimer acid is not particularly limited as long as it can be safely used in a skin external preparation, and higher alcohol, dimer alcohol obtained by reducing dimer acid, and the like can be preferably exemplified. . As the higher alcohol, for example, chain alcohols such as isostearyl alcohol, linoleyl alcohol, and behenyl alcohol, and aliphatic cyclic alcohols such as cholesterol and phytosterol can be used. Dimer linoleyl alcohol, dimer oleyl alcohol, etc. can be used as the dimer alcohol obtained by reducing dimer acid. The dimer of dimer acid of the present invention may be a diester using only one of the above alcohols or a mixed alcohol diester using two or more.

Examples of dimer acid diesters used in the external preparation for skin of the present invention include dimer dilinoleate diisostearyl, hydrogenated dimer dilinoleate diisostearyl, dimer dilinoleate diphytosteryl, hydrogenated dimer dilinoleate diphytosteryl, dimer Dimerlinoleyl merlinoleate, dibehenyl dimer linoleate, dimer linoleic acid dimer linoleyl, dimer linoleic acid dimer linoleyl, dimer linoleic acid dihydrogen (phytosteryl / isostearyl / cetyl) / Stearyl / behenyl) and the like are preferable. The diester of dimer acid can also be purchased and used. A commercial item has a diester of dimer acid as a main component, The content is 70 mass% or more normally, Preferably it is 90 mass% or more. Commercially available products include, for example, hydrogenated dimer dilinoleate di (phytosteryl / isostearyl / cetyl / stearyl / behenyl) “Plandour S”, “Plandour H” (Plandool-S, Plandool-H; Chemical product), hydrogenated dimer dilinoleic acid (isostearyl / phytosteryl) “Rusplan PI-DA” (LUSPLANPI-DA; manufactured by Nippon Seika Co., Ltd.), hydrogenated dimer dilinoleic acid dimer dilinoleyl. "Rusplan DD-DA5"(LUSPLANDD-DA5; manufactured by Nippon Seika Co., Ltd.) and "Rusplan D
“D-DA7” (LUSPLAN DD-DA7; manufactured by Nippon Seika Co., Ltd.) is preferred. In the external preparation for skin of the present invention, the diester of dimer acid exhibits the action of improving the storage properties of the 4-alkylresorcinol on the skin.

In the skin external preparation of this invention, the dimer acid diester may be contained individually by 1 type, and may be contained in combination of 2 or more types.
The content of the dimer acid diester in the external preparation for skin of the present invention is preferably 0.05 to 5% by mass, and preferably 0.1 to 2% by mass, based on the total amount of the external preparation for skin. It is more preferable. This is because if the amount is too small, the effects of the present invention may not be exhibited. If the amount is too large, the effect may reach a limit, while the feeling of use may be impaired.

<3> External preparation for skin of the present invention The external preparation for skin of the present invention is characterized by containing the essential components. The content ratio of 4-alkylresorcinol and / or a salt thereof and the diester of dimer acid is not particularly limited, but is usually preferably 1:10 to 10: 1. The external preparation for skin of the present invention can be applied without particular limitation as long as it is externally administered to the skin. For example, cosmetics (including quasi-drugs), external pharmaceutical compositions for skin, skin External miscellaneous goods etc. can be illustrated suitably, and cosmetics are particularly preferred among them. In addition, when using 4-n-butyl resorcinol etc., it is more desirable to apply to a quasi drug among cosmetics.
The dosage form of the external preparation for skin is not particularly limited, and can be, for example, a solubilized lotion dosage form, a thickening essence dosage form, an emulsifier form, and the like. When used as a cosmetic, it can be a lotion, emulsion, essence, cream, pack, or the like. The external preparation for skin of the present invention can be used for the purpose of treating, preventing or improving a specific skin disease or symptom according to various actions possessed by 4-alkylresorcinol and the like. For skin use, anti-melanin production, antibacterial, acne care, anti-oxidation, whitening skin preparations, and cosmetics (including quasi-drugs) for preventing or improving pigmentation. Specifically, cosmetics such as sun care lotion and sun care milk, basic cosmetics for UV protection, under makeup, control colors, and foundations are preferable.

  The external preparation for skin of the present invention can further contain optional components usually used in external preparations for skin. Such optional components can be used without particular limitation as long as they do not impair the effects of the present invention, and oils and waxes, hydrocarbons, higher fatty acids, higher alcohols, synthetic ester oils, Oils, surfactants, polyhydric alcohols, moisturizing ingredients, powders, inorganic pigments, organic dyes, organic powders, UV absorbers, lower alcohols, vitamins, antibacterial agents, increase Examples include a viscous agent and various medicinal ingredients. Moreover, these arbitrary components can be mix | blended with the compounding quantity of the range which does not inhibit the effect of this invention.

  Examples of oils and waxes include macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, palm oil, palm oil, liquid lanolin, hardened palm oil, Hardened oil, mole, hardened castor oil, beeswax, candelilla wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax and the like.

  Examples of hydrocarbons include liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, and microcrystalline wax.

  Examples of higher fatty acids include oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and undecylenic acid.

Examples of higher alcohols include cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, cetostearyl alcohol, and the like.

  Synthetic ester oils include, for example, stearyl stearate, glyceryl triisostearate, cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, diisosodium malate Stearyl, ethylene glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, glycerin di-2-heptylundecanoate, glycerin tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, triisostearic acid Examples include trimethylolpropane, tetra-2-ethylhexanoic acid pentane erythritol, and N-acyl glutamic acid dialkyl esters.

  Examples of oils include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane; cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexanesiloxane; amino-modified Examples thereof include silicone oils such as polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, and modified polysiloxane such as fluorine-modified polysiloxane.

  Examples of the surfactants include anionic surfactants such as fatty acid soap (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, alkylsulfuric triethanolamine ether; stearyltrimethylammonium chloride, benzalkonium chloride, Cationic surfactants such as laurylamine oxide; imidazoline-based amphoteric surfactants (such as 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt), betaine-based surfactants (alkylbetaines, Amidobetaine, sulfobetaine, etc.), amphoteric surfactants such as acylmethyltaurine; sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, sorbitan sesquistearate, etc.), glycerin fat Acids (such as glyceryl monostearate), propylene glycol fatty acid esters (such as propylene glycol monostearate), hydrogenated castor oil derivatives, glycerin alkyl ethers, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene monostearate) Sorbitan, etc.), POE sorbite fatty acid esters (POE-sorbite monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE alkyl phenyl ethers (POE nonylphenyl ether, etc.), Pluronic ( Registered trademark), POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Tetronic (registered trademark), POE castor oil / hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.) And nonionic surfactants such as sucrose fatty acid esters and alkyl glucosides.

  Examples of polyhydric alcohols include polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octanediol and the like can be mentioned.

  Examples of the moisturizing components include sodium pyrrolidonecarboxylate, lactic acid, sodium lactate and the like.

  Examples of the powders include mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, barium sulfate and the like whose surface may be treated.

  Examples of the inorganic pigments include bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide, titanium mica, and bismuth oxychloride whose surface may be treated. .

  Examples of organic pigments include pearl agents such as fish phosphorus foil whose surface may be treated; red 202, red 228, red 226, yellow 4 and blue which may be raked 404, Yellow 5, Red 505, Red 230, Red 223, Orange 201, Red 213, Yellow 204, Yellow 203, Blue 1, Green 201, Purple 201, Red 204 Etc.

  Examples of the organic powders include polyethylene powder, polymethyl methacrylate, nylon powder, and organopolysiloxane elastomer.

  Examples of UV absorbers include paraaminobenzoic UV absorbers; anthranilic acid UV absorbers; salicylic acid UV absorbers; cinnamic acid UV absorbers; benzophenone UV absorbers; sugar UV absorbers 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 4-methoxy-4′-t-butyldibenzoylmethane and the like.

Examples of lower alcohols include ethanol and isopropanol.
Examples of vitamins include vitamin B such as vitamin A or a derivative thereof, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or a derivative thereof, vitamin B12, vitamin B15 or a derivative thereof; α- Examples include tocopherol, β-tocopherol, γ-tocopherol, vitamin E such as vitamin E acetate, vitamin D, vitamin H, pantothenic acid, pantethine, pyrroloquinoline quinone and the like.
Examples of the antibacterial agent include phenoxyethanol.

  Examples of thickeners include guar gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum, curdlan, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl hydroxypropyl cellulose, chondroitin sulfate, dermatan sulfate, Glycogen, heparan sulfate, hyaluronic acid, sodium hyaluronate, tragacanth gum, keratan sulfate, chondroitin, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, carolinic acid, chitin, chitosan, Carboxymethyl chitin, agar, polyvinyl alcohol, polyvinyl pyrrolidone, carboxy vinyl polymer And / or a salt thereof, alkyl-modified carboxyvinyl polymer and / or its salts, sodium polyacrylate, polyethylene glycol (PEG), bentonite and the like.

  Examples of the various medicinal ingredients include a camellia extract, a rosemary extract, a birch extract, and a kujin extract.

  The external preparation for skin of the present invention can be produced by treating these components according to a conventional method.

  Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited to such examples.

  In accordance with the formulation shown below, a milky lotion (cosmetic) which is an external preparation for skin of the present invention was produced. That is, the components (A), (B), and (C) were heated to 80 ° C., and (B) was gradually added to (A) with stirring, and then (C) was added to neutralize and cooling with stirring. Thus, an emulsion of Example 1 was obtained. At the same time, Comparative Example 1 in which Plandour-H in (A) was replaced with glyceryl triisostearate was also produced in the same manner.

[Ingredient] [Content (mass%)]
(A)
Behenyl alcohol 1
Stearyl stearate 1
Glyceryl triisostearate 10
Dimethicone 5
Sorbitan sesquistearate 1
"Plandool-H" * 0.5
POE (25) stearic acid ester 2
Isostearic acid 3
"El Dew PS-203" ** 0.1
(B)
Carboxyvinyl polymer 0.3
Ribbon extract (made by INDENA, Italy) 0.1
1,3-butanediol 8
1,2-pentanediol 2
PEG400 2
4-n-butylresorcinol 0.3
Water 50
(C)
Water 13.5
Potassium hydroxide 0.2
Total 100
* Hydrogenated dimer dilinoleic acid di (phytosteryl / isostearyl / cetyl / stearyl / behenyl); manufactured by Nippon Seika Co., Ltd. ** N-lauroyl glutamate (phytosteryl / octyldodecyl); manufactured by Ajinomoto Co., Inc.

<Test Example 1>
The emulsions of Example 1 and Comparative Example 1 were compared in terms of their storage properties on the skin. That is, three 2 cm × 4 cm portions were prepared on the inner side of the forearm, one in Example 1, one in Comparative Example 1, and the other in 30 μl of sterile distilled water (control). It was uniformly applied using a stick. The subject was allowed to enter a constant temperature room at 30 ° C. for 2 hours. The subject was then transferred to a constant temperature room at 20 ° C., the site was wiped with sterile gauze impregnated with sterile distilled water, transferred to a petri dish filled with Sabouraud medium, stamped, and kept at 37 ° C. for 72 hours. The growth of the skin fungus was observed by counting the number of colonies. The results are shown in Table 1.

  When the emulsion containing the hydrogenated dimer dilinoleate of Example 1 (phytosteryl / isostearyl / cetyl / stearyl / behenyl) and 4-n-butylresorcinol was applied, after 2 hours of application to the skin, The presence of fungus was not observed. On the other hand, when an emulsion containing no hydrogenated dimer dilinoleate (phytosteryl / isostearyl / cetyl / stearyl / behenyl) of Comparative Example 1 was applied, the presence of fungi was observed. From this, by including the diester of dimer acid in the cosmetic containing 4-alkylresorcinol, the storage property to the application site of 4-alkylresorcinol is enhanced, and the antibacterial action of 4-alkylresorcinol is sufficiently exhibited. I found out.

  In Example 1, “Plandour-H” was replaced with the dimer acid diester of Table 2, and the emulsions (cosmetics) of Examples 2 to 4, which are the external preparations for skin of the present invention, were produced. When these were evaluated by the method of Test Example 1, the number of colonies was 0 in all cases. From this, it was found that, when any dimer acid diester shown in Table 2 below was used, the retention property of 4-alkylresorcinol on the application site was enhanced, and the antibacterial action of 4-alkylresorcinol was sufficiently exhibited.

  In Example 1, 4-n-butylresorcinol was replaced with 4-hexylresorcinol (Sigma-Aldrich), and the emulsion (cosmetics) of Example 5, which is a skin external preparation of the present invention, was produced in the same manner. When these were evaluated by the method of Test Example 1, the number of colonies was 0. From this, it was found that the diester of dimer acid has an action of enhancing the storage property to the application site with respect to 4-hexylresorcinol.

  The present invention is useful for external preparations for skin such as cosmetics.

Claims (5)

  A skin external preparation characterized by comprising 1) 4-alkylresorcinol and / or a salt thereof, and 2) a diester of dimer acid.   The external preparation for skin according to claim 1, wherein the 4-alkylresorcinol is 4-n-butylresorcinol.   Content of 4-alkyl resorcinol and / or its salt is 0.05-5 mass%, The skin external preparation of Claim 1 or 2 characterized by the above-mentioned.   Dimer acid diesters from hydrogenated dimer dilinoleic acid di (phytosteryl / isostearyl / cetyl / stearyl / behenyl), hydrogenated dimer dilinoleic acid (isostearyl / phytosteryl) and hydrogenated dimer dilinoleic acid dimer dilinoleyl The external preparation for skin according to any one of claims 1 to 3, wherein the external preparation is one or more selected.   The skin external preparation according to any one of claims 1 to 4, wherein the diester content of dimer acid is 0.05 to 5% by mass.