JP2008013487A - Colored external preparation for skin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means for stabilizing color of a colored aromatic quinone derivative by formulation without relying on an additive ingredient such as EDTA (ethylenediaminetetraacetic acid) or BHT (butylated hydroxytoluene). <P>SOLUTION: An external preparation for skin is obtained by including (1) the colored aromatic quinone derivative and (2) hydroquinone or a derivative thereof. The colored aromatic quinone derivative is preferably represented by structural formula (1) and shikonin is especially preferred. The hydroquinone derivative is preferably a glucoside of the hydroquinone and/or a salt thereof. The external preparation for skin is preferably an emulsified cosmetic. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a skin external preparation, and more particularly, to a skin external preparation suitable for cosmetics colored with a colored aromatic quinone derivative and having high coloring stability.

  The plant body contains various colored aromatic quinone derivatives, some of which are isolated and contained in a skin external preparation such as cosmetics as a medicinal component or a natural coloring component. Typical examples of such a colored aromatic quinone derivative include alkanine extracted from Alkanet, shikonin which is an optical isomer of alkyne extracted from purple root, and the like. Alkanine or shikonin is known to have anti-inflammatory action as well as coloring ability, and in this sense, it can be said to be a useful raw material for external preparation for skin (for example, see Patent Document 1 and Patent Document 2). In particular, in recent years, due to safety considerations, there has been an active movement to replace azo organic synthetic dyes with natural dyes. In this sense, these colored aromatic quinone derivatives can be said to be useful raw materials for skin external preparations. A particular problem in formulating these color aromatic quinone derivative skin external preparations is that the initial color is vivid and a preferable color can be obtained, but it is easily faded during storage. In order to prevent such discoloration, chelating agents such as EDTA and antioxidants such as BHT have been included, but considering safety concerns such as EDTA or BHT, such treatment is appropriate. Including things that cannot be said. That is, it can be said that development of a means for stabilizing the color of the colored aromatic quinone derivative by formulation is desired regardless of the additive components such as EDTA and BHT.

  On the other hand, hydroquinone and hydroquinone derivatives such as arbutin are usually colorless and have preferable actions as cosmetic functions such as melanin production inhibitory action, melanocyte growth inhibitory action, active oxygen scavenging action, rebound inhibitory action, In order to express such an action, techniques for blending in cosmetics are known (see, for example, Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6), but the stability of colored aromatic quinone derivatives is known. There is no known crystallization effect. In addition, there is a document disclosing the possibility of combining a colored aromatic quinone derivative and hydroquinone or a derivative thereof in combination with an external preparation for skin (for example, see Patent Document 7). No substantial disclosure has been made, and it is not known at all that the color storage stability of the colored aromatic quinone derivative in the preparation is significantly improved by such a combination.

JP 2004-149482 A JP 2005-325063 A JP 2004-238394 A JP 2004-196669 A JP 2001-322930 A JP 2001-206820 A JP 2005-289880 A

  The present invention has been made under such circumstances, and an object of the present invention is to provide means for stabilizing the color of a colored aromatic quinone derivative by formulation, irrespective of additive components such as EDTA and BHT.

In view of such a situation, the present inventors have sought for a means for stabilizing the color of the colored aromatic quinone derivative by formulation, irrespective of the additive components such as EDTA and BHT, and have made extensive research efforts. It has been found that the stability of the colored aromatic quinone derivative is remarkably improved by the coexistence of hydroquinone or a derivative thereof, and the present invention has been completed. That is, the present invention is as follows.
(1) An external preparation for skin comprising 1) a colored aromatic quinone derivative and 2) hydroquinone or a derivative thereof.
(2) The external preparation for skin according to (1), wherein the colored aromatic quinone derivative is represented by the structural formula (1).

構造式（１）
（但し、式中Ｒは炭素数２〜５のアルキル基又はアルケニル基を表す。）

Structural formula (1)
(In the formula, R represents an alkyl or alkenyl group having 2 to 5 carbon atoms.)

(3) The external preparation for skin according to (2), wherein the colored aromatic quinone derivative represented by the structural formula (1) is shikonin.

シコニン

Shikonin

(4) The skin external preparation according to any one of (1) to (3), wherein the hydroquinone derivative is a hydroquinone glucoside and / or a salt thereof.
(5) The external preparation for skin according to any one of (1) to (4), which is an emulsified cosmetic.

  ADVANTAGE OF THE INVENTION According to this invention, the means which stabilizes the color of a colored aromatic quinone derivative by formulation can be provided irrespective of additive components, such as EDTA and BHT.

<1> Colored aromatic quinone derivative which is an essential component of the external preparation for skin of the present invention The colored aromatic quinone derivative of the present invention is a compound having a quinone structure, has a color other than achromatic color, and has anti-inflammatory activity. Is a component that is also used for coloring purposes, and its source is derived from a natural product, specifically, an alkanine-based alkanine, purple root Preferable examples include shikonin based on citrus, cassamine based on safflower, and carminic acid based on scabies. Particularly preferred is a naphthoquinone derivative represented by the general formula (1), among which shikonin can be particularly preferably exemplified. Since all of these components have strong chromophore groups, they are often used as natural colorants. These are all excellent in initial colorability, but are known to fade due to light, temperature, etc., and include antioxidants such as BHA, BHT or tocopherol, and chelating agents such as edetic acid and ethylphosphonic acid. Although used to prevent fading, the external preparation for skin of the present invention can improve the color stability of such a colored aromatic quinone derivative without using such an antioxidant or chelating agent. These can also be contained in the form of a salt, and the salt can be used without particular limitation as long as it is used in an external preparation for skin, for example, alkali metal salts such as sodium salt and potassium salt, calcium salt Preferred examples include alkaline earth metal salts such as magnesium salts, organic amine salts such as ammonium salts, triethylamine salts, triethanolamine salts, and monoethanolamine salts, and basic amino acid salts such as lysine salts and alginates. In the external preparation for skin of the present invention, such a colored aromatic quinone derivative can contain only one species, or can contain two or more species in combination. The preferable content of the colored aromatic quinone derivative in the external preparation for skin of the present invention is preferably an amount necessary and sufficient for coloring the external preparation for skin, and specifically, the total amount is based on the total amount of the external preparation for skin. 0.0001 to 0.1% by mass, and more preferably 0.0005 to 0.05% by mass.

<2> Hydroquinone or its derivative which is an essential component of the skin external preparation of the present invention The skin external preparation of the present invention contains hydroquinone or a derivative thereof as an essential component. Preferred examples of the hydroquinone derivative include glycosides such as glucoside, arabinoside, galactoside, furanoside, riboside and maltoside, and alkyl ethers such as methoxide, ethoxide and propoxide, with glycosides being more preferred. Particularly preferred is glucoside. As the glucoside, there are an α-form and a β-form, and any of them can be used, and these two are particularly preferable because the β-form is a natural type. In the external preparation for skin of the present invention, such a component has an action of improving the storage stability in the preparation of the colored aromatic quinone derivative and preventing fading during storage. In order to express such an action, the hydroquinone or its derivative can use only one kind, or can contain two or more kinds. These can be contained in free form or in the form of a salt. These salts can be used without any particular limitation as long as they are used in skin external preparations, for example, alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts. Preferred examples include organic amine salts such as ammonium salt, triethylamine salt, triethanolamine salt, and monoethanolamine salt, and basic amino acid salts such as lysine salt and alginate. As content required in order to show such an effect, it is 0.01-10 mass% with respect to the skin external preparation whole quantity by the total amount, More preferably, it is 0.1-5 mass%.

<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 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. Suitable cosmetics include basic cosmetics such as lotions, emulsions, essences, creams and packs, UV protective cosmetics such as sun care lotions and sun care milk, make-up cosmetics such as under-makeup, control colors and foundations. Can be illustrated. In particular, since the effect as a colorant of a colored aromatic quinone derivative can be exhibited remarkably, it is preferably used for an emulsified preparation.

  The external preparation for skin of the present invention can contain, in addition to such components, optional components that are usually used in external preparations for skin. Such optional ingredients include, for example, macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, hydrogenated coconut oil Oil, wax, oils such as beeswax, owl, hardened castor oil, beeswax, candelilla wax, carnauba wax, botarou, lanolin, reduced lanolin, hard lanolin, jojoba wax , Hydrocarbons such as microcrystalline wax; higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid; cetyl alcohol, stearyl alcohol, isostearyl Higher alcohols such as alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, cetostearyl alcohol; cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, malic acid Diisostearyl, di-2-ethylhexanoic acid ethylene glycol, dicaprate neopentyl glycol, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, tri Synthetic ester oils such as trimethylolpropane isostearate and pentane erythritol tetra-2-ethylhexanoate; dimethylpolysiloxane, methylphenylpoly Linear polysiloxanes such as oxane and diphenylpolysiloxane; cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexanesiloxane; amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, Oil agents such as silicone oils such as modified polysiloxanes such as fluorine-modified polysiloxanes; Anionic surfactants such as fatty acid soap (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, triethanolamine ether of alkyl sulfates; Cationic surfactants such as stearyltrimethylammonium, benzalkonium chloride, laurylamine oxide; imidazoline-based amphoteric surfactants (2-cocoyl-2-imida Zolinium hydroxide-1-carboxyethyloxy disodium salt, etc.), betaine surfactants (alkyl betaine, amide betaine, sulfobetaine, etc.), and amphoteric surfactants such as acylmethyltaurine; sorbitan fatty acid esters (sorbitan) Monostearate, sorbitan sesquioleate, etc.), glycerin fatty acids (eg, glyceryl monostearate), propylene glycol fatty acid esters (eg, propylene glycol monostearate), hardened castor oil derivatives, glycerin alkyl ethers, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerin fatty acid ester Tells (POE-glycerol monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE alkylphenyl ethers (POE nonylphenyl) Ethers, etc.), Pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Tetronics, POE castor oil / hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), Nonionic surfactants such as sucrose fatty acid ester and alkyl glucoside; polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene Polyhydric alcohols such as recall, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octanediol; sodium pyrrolidonecarboxylate Moisturizing ingredients such as lactic acid and sodium lactate; powders such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, barium sulfate, etc. whose surface may be treated Body, the surface may be treated, inorganic pigments such as bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide; surface may be treated, mica Pearl agents such as titanium, fish phosphorus foil, bismuth oxychloride; red 202 which may be raked, red Color 228, Red 226, Yellow 4, Blue 404, Yellow 5, Red 505, Red 230, Red 223, Orange 201, Red 213, Yellow 204, Yellow 203, Blue 1 No., green 201, purple 201, red 204, etc .; organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer; para-aminobenzoic acid UV absorbers; anthranils Acid UV absorbers; salicylic acid UV absorbers; cinnamic acid UV absorbers; benzophenone UV absorbers; sugar UV absorbers; 2- (2′-hydroxy-5′-t-octylphenyl) benzo Ultraviolet absorbers such as triazole and 4-methoxy-4′-t-butyldibenzoylmethane; lower grades such as ethanol and isopropanol Alcohols; vitamin A or derivatives thereof, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or derivatives thereof, vitamin B such as vitamin B12, vitamin B15 or derivatives thereof; α-tocopherol, β- Preferred examples include vitamins E such as tocopherol, γ-tocopherol, vitamin E acetate, vitamins D, vitamin H, pantothenic acid, pantethine and the like; and antibacterial agents such as phenoxyethanol.

  Particularly preferred forms of the present invention are the antioxidants such as BHA and BHT, edetic acid, etidronic acid, etc., which can fully exhibit the effect of the present invention “can stabilize a colored aromatic quinone derivative without an antioxidant or chelating agent”. It is a form which does not contain the chelating agent.

  Particularly preferred among such optional components are carboxyvinyl polymers which may stabilize the emulsion system and may be alkyl-modified and / or salts thereof. Carboxyvinyl polymer and its salt are thickeners that have been used for a long time as a cosmetic raw material. Alkyl-modified thickeners such as “Pemlen TR-1” and “Pemlen” sold by Goodrich. “TR-2” or “Carbopol 1382” can be preferably exemplified. In addition, these salts can be used without particular limitation as long as they are used in a skin external preparation, for example, alkali metal salts such as sodium salt and potassium salt, alkaline earth such as calcium salt and magnesium salt Preferred examples include organic amine salts such as metal salts, ammonium salts, triethylamine salts, triethanolamine salts and monoethanolamine salts, and basic amino acid salts such as lysine salts and alginates. These can be used alone or in combination of two or more. The total content of such components is 0.05 to 5% by mass, and more preferably 0.1 to 1% by mass, based on the total amount of the external preparation for skin.

  The external preparation for skin of the present invention can be produced by treating these components according to a conventional method. In addition, among the essential components of the external preparation for skin of the present invention, the colored aromatic quinone derivative has a pharmacological action such as an anti-inflammatory action, and is intended for such pharmacological action but not for coloring. As long as the constitution of “1) containing a colored aromatic quinone derivative and 2) hydroquinone or its derivative” is satisfied, it belongs to the technical scope of the present invention. Similarly, hydroquinone and hydroquinone derivatives also have pharmacological actions such as antibacterial action and melanin production-inhibiting action, and even if the purpose is not to stabilize colored aromatic quinone derivatives for such action, “1) As long as the construction of “colored aromatic quinone derivative and 2) hydroquinone or its derivative” is satisfied, it belongs to the technical scope of the present invention.

  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, each of the components i, b, and c was heated to 80 ° C., and gradually added to b while stirring, and then neutralized by adding c, followed by stirring and cooling to obtain an emulsion 1. Comparative Example 1 in which the hydroquinone glucoside (β form) of this product was substituted with water and Comparative Example 2 in which magnesium ascorbate was substituted were also prepared in the same manner.

<Test Example 1>
Emulsion 1, Comparative Example 1 and Comparative Example 2 were subjected to a storage test for 1 month at 5 ° C. and 40 ° C., each sample was returned to 20 ° C. after storage, and measured with a Konica Minolta color difference meter CR300. The color difference (ΔE) of the 40 ° C. stored product relative to the color of the 5 ° C. stored product was determined. The results are shown in Table 2. This shows that the skin external preparation of the present invention is excellent in color stability.

  In the same manner as in Example 1, an emulsion 2 was prepared according to the following formulation. In the evaluation in Test Example 1, the color difference (ΔE) of the product stored at 40 ° C. with respect to the product stored at 5 ° C. was 0.57, and the same effect was recognized.

  In the same manner as in Example 1, an emulsion 3 was prepared according to the following formulation. Comparative Example 3 in which the hydroquinone glucoside (β-form) of this product was substituted with water and Comparative Example 4 in which magnesium ascorbate was substituted were also prepared and evaluated according to Test Example 1. The results are shown in Table 5. It can be seen that the same effect is also achieved in Casamin.

  In the same manner as in Example 1, an emulsion 4 was prepared according to the following formulation. Comparative Example 5 in which the hydroquinone glucoside (β form) of this product was substituted with water and Comparative Example 6 in which magnesium ascorbate was substituted were prepared in the same manner and evaluated according to Test Example 1. The results are shown in Table 7. It can be seen that carminic acid has the same effect.

  The present invention can be applied to skin external preparations such as cosmetics.

Claims (5)

An external preparation for skin, comprising 1) a colored aromatic quinone derivative and 2) hydroquinone or a derivative thereof. The skin external preparation according to claim 1, wherein the colored aromatic quinone derivative is represented by the structural formula (1).

Structural formula (1)
(In the formula, R represents an alkyl or alkenyl group having 2 to 5 carbon atoms.) The external preparation for skin according to claim 2, wherein the colored aromatic quinone derivative represented by the structural formula (1) is shikonin.

Shikonin The skin external preparation according to any one of claims 1 to 3, wherein the hydroquinone derivative is a hydroquinone glucoside and / or a salt thereof. It is an emulsified cosmetic, The skin external preparation in any one of Claims 1-4 characterized by the above-mentioned.