JP6086706B2 - Skin external composition having high UV absorption effect - Google Patents

Description

The present invention relates to an external composition for skin, and more particularly, to an external composition for skin having a high ultraviolet absorption effect and a high transdermal absorption effect of a drug.

Skin symptoms such as wrinkles, spots and sagging are skin aging symptoms that manifest with aging due to genetic factors, temperature changes, UV and chemical exposure, and accumulation of physical stimuli. Such skin symptoms greatly affect the visual impression of others, so keeping the beauty of the skin beautiful is an important concern especially for women. Among these skin symptoms, it has been clarified that skin symptoms such as blotches, freckles, and pigmentation after sunburn are caused by increased production of melanin due to activation of pigment cells (melanocytes) present in the skin. Yes. In addition, excessive or chronic enhancement of melanin production in melanocytes can be cured by inducing cell transport of keratinocytes by causing phenomena such as excessive transport of melanin to keratinocytes (keratinocytes), accumulation and delayed discharge. Causes pigmentation accompanied by exacerbation of skin symptoms such as hard spots, dullness, and delamination. In order to prevent or improve pigmentation including deterioration of skin symptoms caused by such increased melanin production, various active ingredients have been researched and developed. In particular, the development of ingredients having a whitening effect has been actively conducted. For example, whitening agents such as ascorbic acid, hydrogen peroxide, colloidal sulfur, glutathione, hydroquinone, and catechols are known, and skins containing such ingredients are blended. External preparations are also widely used. In addition to research on whitening agents, detailed studies on pigmentation mechanisms have also been made, and whitening agents having various mechanisms based on the results, such as melanin production inhibitors (Patent Document 1), tyrosinase enzyme inhibition. Agents (Patent Document 2), tyrosinase enzyme gene expression inhibitors, α-MSH inhibitors (Patent Document 3), antioxidants (Patent Document 4) and the like have been reported.

In particular, the whitening effect was not sufficient for pigmentation involving a decrease in cell function of keratinocytes. However, in recent years, it has been found that cysteic acid derivatives are effective against pigmentation accompanied by symptoms such as excessive transport, accumulation and delayed discharge of melanin to keratinocytes due to increased melanin production, and incurable skin, dullness, and rough skin. (Patent Document 5).

On the other hand, as an attempt to achieve a higher whitening effect, research for improving transdermal absorbability or storage property (Patent Document 6) by devising prescription ingredients has been performed. In addition, it has been reported that percutaneous absorbability is controlled by a method using hydroxylated phospholipid or the like (Patent Document 7). However, even in these methods, in the case of a compound that has a three-dimensionally bulky branched structure and is water-soluble (for example, cysteic acid derivatives), transdermal absorption is limited or has low rapid efficacy, and high whitening. The situation was difficult to obtain. Therefore, a formulation and a dosage form that can realize high transdermal absorbability of these compounds have been demanded.

On the other hand, studies have been conducted on blending ultraviolet absorbers and ultraviolet scattering agents. In particular, in the case of ultraviolet absorbers, decomposition at high temperatures is likely to occur. Therefore, a method for stabilizing the ultraviolet absorbers to maintain a high ultraviolet-cutting effect has been reported (Patent Document 8). However, these methods are not sufficient, and discoloration and odor change of the composition for external use on skin due to decomposition of the ultraviolet absorber at high temperature has been a problem.

However, it is quite known that cysteic acid derivatives stabilize UV absorbers and that UV absorbers enhance the transdermal absorbability of cysteic acid derivatives, which are water-soluble compounds having a sterically bulky branched structure. It was not done.

JP 2008-208073 A JP 2009-196895 A JP 2001-220347 A JP 2010-037299 A International Publication No. 2011/088706 JP 2007-332115 A JP 2008-115109 A JP 2009-035551 A

Skin that has a highly sterically bulky branched structure and a water-soluble compound that can achieve high transdermal absorbability and suppresses decomposition of the UV absorber at high temperatures, and has a high UV-cutting effect. An object of the present invention was to provide a composition for external use.

In view of such circumstances, the present inventors have studied raw materials that can be used in the cosmetics field, and as a result of intensive research aimed at new skin external compositions, the following new skin external compositions as shown below. However, the present inventors have found that the problem can be solved and completed the present invention. That is, the present invention is as follows.

<1> 1) 0.01 to 5% by mass of the compound represented by the following general formula (Formula 1) and / or pharmacologically acceptable salt thereof with respect to the total amount of the composition, and 2) UV absorption A composition for external use on skin, comprising an agent.
[In the formula, R ₁ represents a hydrogen atom, R ₂ represents a hydrogen atom, R ₃ represents a phenyl group, methylphenyl group, methoxyphenyl group, or a biphenyl group, n is 1 or An integer of 2 and m represents 0 . ]
<2> Said 2) UV absorber is homomenthyl salicylate, 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester, diparamethoxycinnamate mono-2-ethylhexanoate glyceryl , Paraaminobenzoic acid and its ester, 4-tert-butyl-4′-methoxydibenzoylmethane, 4- (2-β-glucopyranosiloxane) propoxy-2-hydroxybenzophenone, octyl salicylate, 2,5-diisopropylsilica cinnamate, 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester, cinoxate, dihydroxy dimethoxy benzophenone, sodium dihydroxy dimethoxy benzophenone disulfonic acid, dihydroxybenzophenone, dimethicone co diethyl benzalmalonate 1- (3,4-dimethoxyphenyl) -4,4-dimethyl-1,3-pentanedione, dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl, tetrahydroxybenzophenone, terephthalylidene dicanfursulfonic acid 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, drometrizole trisiloxane, para Amyl dimethylaminobenzoate, 2-ethylhexyl paradimethylaminobenzoate, isopropyl paramethoxycinnamate / diisopropylcinnamate ester, 2-ethylhexyl paramethoxycinnamate, 2,4-bis-[{4- (2 -Ethylhexyl Oxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid and its trihydrate, hydroxymethoxybenzophenone sodium sulfonate, phenyl benzimidazole sulfonic acid, and ferulic acid, 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol 1) or 2 or more types selected from the above, the composition for external application to the skin according to <1>.
<3> Furthermore, 3) The composition for external use of skin as described in <1> or <2> characterized by containing metal oxide powder.
<4> Further 4) The external composition for skin according to any one of <1> to <3>, comprising 4-n-butylresorcinol.

According to the present invention, high transdermal absorbability can be achieved even for a compound that has a three-dimensionally bulky branched structure and is water-soluble, and that suppresses decomposition of the UV absorber at a high temperature and has high UV light. An external composition for skin having a cutting effect can be provided.

<Compounds represented by the general formula (Formula 1) and / or pharmacologically acceptable salts thereof used in the present invention>
Among the compounds represented by the general formula (Formula 1), N- (o-toluyl) cysteic acid, N- (m-toluyl) cysteic acid, N- (p-toluyl) cysteic acid, N- (p- Preferable examples include methoxybenzoyl) cysteic acid, (N-biphenylcarbonyl) cysteic acid, N- (p-toluyl) homocysteic acid and / or pharmacologically acceptable salts thereof, and N- (p-toluyl) ) Cysteinic acid, N- (p-methoxybenzoyl) cysteic acid and / or pharmacologically acceptable salts thereof can be more preferably exemplified. As a production method, it has already been disclosed in Patent Document WO2010-058730 and is generally known. In the composition for external use of skin of this invention, you may contain individually 1 type among this compound, and may contain it in combination of 2 or more types. The total amount of the skin external composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 2% by mass.

N- (p-Toluyl) cysteic acid

N- (p-methoxybenzoyl) cysteic acid

<Ultraviolet absorber used in the present invention>
As the ultraviolet absorber, any cinnamate-based ultraviolet absorber, benzophenone-based ultraviolet absorber, benzoic acid can be applied as long as it is used in the field of skin external preparations such as cosmetics. Illustrative are UV-based UV absorbers, salicylic acid-based UV absorbers, dibenzoylmethane-based UV absorbers, anthranilic acid-based UV absorbers, and urocanic acid-based UV absorbers. Specifically, homomenthyl salicylate, 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester, diparamethoxycinnamic acid mono-2-ethylhexanoate glyceryl, paraaminobenzoic acid and its Ester, 4-tert-butyl-4′-methoxydibenzoylmethane, 4- (2-β-glucopyranosiloxane) propoxy-2-hydroxybenzophenone, octyl salicylate, methyl 2,5-diisopropylcinnamate, 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester, cinoxate, dihydroxy dimethoxy benzophenone, sodium dihydroxy dimethoxy benzophenone disulfonic acid, dihydroxybenzophenone, dimethicone co diethyl benzalmalonate, 1- (3, -Dimethoxyphenyl) -4,4-dimethyl-1,3-pentanedione, dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl, tetrahydroxybenzophenone, terephthalylidene dicanfursulfonic acid, 2,4,6-tris [ 4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, methyl bis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, drometrizol trisiloxane, paradimethylaminobenzoic acid amyl, paradimethylamino 2-ethylhexyl benzoate, isopropyl paramethoxycinnamate / diisopropylcinnamate ester mixture, 2-ethylhexyl paramethoxycinnamate, 2,4-bis-[{4- (2-ethylhexyloxy) -2-hi Roxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid and its trihydrate, hydroxymethoxybenzophenonesulfonic acid sodium, phenyl Preferred examples include benzimidazolesulfonic acid, ferulic acid, 2,2′-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) and the like. I can do it. The total amount of the skin external composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass.

<Metal oxide powder used in the present invention>
The metal oxide powder can be applied without particular limitation as long as it is used in the field of skin external preparations such as cosmetics. For example, zinc, iron, aluminum, magnesium, titanium, Examples include barium, manganese, cerium, cobalt, calcium, cadmium, strontium, copper, chromium, zirconium, gold, silver, etc. Among these, those belonging to amphoteric metals are preferable, and titanium, zinc, iron, cerium are preferable. Can be illustrated. Moreover, it may be surface-treated, and a commercially available metal oxide that has been surface-treated with an organic material such as silicone or fatty acid, or an inorganic material such as silica or alumina can also be used. Examples of such commercially available powders include “titanium oxide MT-100TV (average primary particle size: 15 nm, surface treatment: aluminum hydroxide, fatty acid; manufactured by Teika Co., Ltd.)”, “titanium oxide TTO-V-4” (Primary particle diameter: 5 to 15 nm Surface treatment: aluminum hydroxide, stearic acid; manufactured by Ishihara Sangyo Co., Ltd.) "," Zinc oxide MZ-505S (Average primary particle diameter: 25 nm Surface treatment: Hydrogen Dimethicone; manufactured by Teika Corporation) ”,“ Titanium oxide type Taipei CR-50 (average primary particle size: 250 nm; manufactured by Ishihara Sangyo Co., Ltd.) ”,“ TAROX synthetic iron oxide LL-100P, TAROX synthetic iron oxide R-516P, TAROX synthetic iron oxide BL- ” 100P (both average primary particle diameter: 100 nm; manufactured by Titanium Industry Co., Ltd.) ”. The preferred particle size of the metal oxide powder is a particle size measured with a Coulter counter and is preferably 0.001 μm to 1 μm. The total amount of the skin external composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass.

<4-n-butylresorcinol used in the present invention>
The 4-n-butylresorcinol used in the present invention can be applied without particular limitation as long as it is used in the field of skin external preparations such as cosmetics. The total amount of the skin external composition is preferably 0.01 to 3% by mass, more preferably 0.1 to 0.5% by mass.

The external composition for skin referred to in the present invention is not particularly limited as long as it is externally administered to the skin. For example, cosmetics including quasi-drugs, skin external goods and the like can be suitably exemplified. Of these, cosmetics are particularly preferred. In addition, the external composition for skin of the present invention can take any of the conventionally known emulsion dosage forms, essence dosage forms, cream dosage forms, and powder-containing dosage forms. As the cosmetic, any of basic cosmetics, hair cosmetics, and makeup cosmetics can be applied.

In the composition for external use of the skin of the present invention, in addition to the above-mentioned components, optional components usually used in cosmetics and external preparations for skin can be contained. Examples of such optional ingredients include 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, and hardened coconut oil. Oils such as hardened oil, mole, castor oil, beeswax, candelilla wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax, waxes, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum , Hydrocarbons such as microcrystalline wax, higher fatty acids such as oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, cetyl alcohol, stearyl alcohol, isostearyl alcohol, Higher alcohols such as alcohol, octyldodecanol, myristyl alcohol, cetostearyl alcohol, cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, diacid malate Isostearyl, ethylene glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, glycerin di-2-heptylundecanoate, glycerin tri-2-ethylhexanoate, tri-2-ethylhexanoate trimethylolpropane, triisostearin Synthetic ester oils such as acid trimethylolpropane, tetra-2-ethylhexanoic acid pentane erythritol, dimethylpolysiloxane, methylphenylpolysiloxane, diphenyl Linear polysiloxanes such as polypolysiloxane, cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified Oil agents such as silicone oils such as modified polysiloxanes such as polysiloxane, fatty acid soap (sodium laurate, sodium palmitate, etc.), anionic surfactants such as potassium lauryl sulfate, alkyl sulfate triethanolamine ether, stearyl trimethyl chloride Cationic surfactants such as ammonium, benzalkonium chloride, laurylamine oxide, betaine surfactants (alkyl betaines, amide betaines, sulfobetaines, etc.) ), Imidazoline-based amphoteric surfactants (2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.), amphoteric surfactants such as acylmethyltaurine, sorbitan fatty acid esters (sorbitan monoester) Stearate, sorbitan sesquioleate, etc.)
Glycerin fatty 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, monostearic acid) Polyoxyethylene 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 alkylphenyl ethers (POE nonylphenyl ether, etc.), Pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Te Tronics, POE castor oil / hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), nonionic surfactants such as sucrose fatty acid ester, alkyl glucoside, polyethylene glycol, glycerin, 1,3-butylene glycol Erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexylene glycol, 1,2-he Polyhydric alcohols such as sundiol, 1,2-octanediol, moisturizing ingredients such as sodium pyrrolidonecarboxylate, lactic acid, sodium lactate, guar gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum , Curdlan, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylhydroxypropylcellulose, chondroitin sulfate, dermatan sulfate, glycogen, heparan sulfate, hyaluronic acid, sodium hyaluronate, tragacanth gum, keratan sulfate, chondroitin, mucoitin sulfate, hydroxyethyl guar gum, carboxy Methyl guar gum, dextran, keratosulfate, locust bean gum, succinoglucan, caronic acid, chitin, Thickeners such as tosan, carboxymethyl chitin, agar, polyvinyl alcohol, polyvinyl pyrrolidone, carboxy vinyl polymer, alkyl-modified carboxy vinyl polymer, sodium polyacrylate, polyethylene glycol, bentonite, surface may be treated, mica, Powders such as talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic anhydride (silica), aluminum oxide, barium sulfate, surface may be treated, bengara, yellow iron oxide, black iron oxide, Cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide inorganic pigments, surface may be treated, pearlescent agents such as titanium mica, fish phosphorus foil, bismuth oxychloride, red may be raked 202, Red 228, Red 226, Yellow 4, Blue 40 No. 4, Yellow No. 5, Red No. 505, Red No. 230, Red No. 223, Orange No. 201, Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, Red No. 204 Organic dyes such as polyethylene powder, polymethyl methacrylate, nylon powder, organic powders such as organopolysiloxane elastomers, lower alcohols such as ethanol and isopropanol, vitamin A or derivatives thereof, vitamin B ₆ hydrochloride, vitamins B ₆ tripalmitate, vitamin B ₆ dioctanoate, vitamin B ₂ or its derivative, vitamin B ₁₂ such as vitamin B ₁₂ , vitamin B ₁₅ or its derivative, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, etc. Vitamin E, Vitamin D, Vitamin H, Pantothene Preferred examples include vitamins such as acid, pantethine and pyrroloquinoline quinone.

<Production Example of Composition for External Use of Skin of the Present Invention>
The composition for external use of the skin of the present invention was prepared according to the formulation shown below. That is, (A) of Example 1 in Table 1 was heated to 60 ° C. and stirred and mixed at 5000 rpm in an emulsifier, and each was uniformly dissolved and dispersed in (A) (B), (C), (D) and (E) were added, and then the stirring speed was reduced to 1000 rpm, and the mixture was cooled to 30 ° C. to obtain the external composition for skin of Example 1.

<External skin composition of the present invention>
Example 2 was prepared by replacing N- (p-toluyl) cysteic acid with N- (p-methoxybenzoyl) cysteic acid. Further, in contrast to Example 1, the concentration of N- (p-toluyl) cysteic acid was reduced, compared to Example 3, Comparative Example 1, increased Comparative Example 3 and Example 2, N- (p-methoxybenzoyl) cysteine was used. Examples 5 and 6 with increased concentration of paramethoxycinnamic acid-2-ethylhexyl compared to Examples 4 and 2 with reduced acid concentration, Comparative Example 2, with increased Comparative Example 4 and Examples 1 and 2, titanium oxide Is replaced with zinc oxide in Examples 7, 8; titanium oxide is removed in Examples 9, 10 and Examples 1 and 2; 4-n-butylresorcinol is removed in Examples 11, 12; Examples 13 and 14 in which iron oxide was substituted, Comparative Examples 5 and 6 in which paramethoxycinnamic acid-2-ethylhexyl was deleted, or a part or all of paramethoxycinnamic acid-2-ethylhexyl in Example 1 was replaced with another Replaced with UV absorber (with pure water (Adjusted by 100% by mass) In Examples 17, 16, 21, and 20 obtained by substituting 2-ethylhexyl paramethoxycinnamate of Example 2 with other ultraviolet absorbers. The same applies to Comparative Example 7 in which N- (p-toluyl) cysteic acid was replaced with another antioxidant, and Comparative Example 8 in which N- (p-methoxybenzoyl) cysteic acid in Example 2 was replaced with another antioxidant. Prepared. It shows in Tables 1-4.

<Test Example 1 SPF value of composition for external use on skin>
The sample was applied to Vitro skin at 2 mg / cm ² , dried at room temperature for 20 minutes, and then SPF value was measured using SPF Analyzer System UV-1000S (manufactured by labsphere). As a result, it shows in Tables 1-4.

<Test Example 2 Evaluation of transdermal absorbability of external composition for skin>
Six panels of 1 cm × 1 cm were provided on the inner part of the forearm of 10 panelists, and 7 μL of the test sample, which was the above-prepared skin external composition, was applied to each panel and allowed to stand at 20 ° C. for 1 hour, followed by tetrahydrofuran (THF) The skin was wiped off with a cotton wool impregnated with 100% of the cotton, and this cotton wool was extracted three times with 100 ml of THF, and the recovered amount of N- (p-toluyl) cysteic acid or N- (p-methoxybenzoyl) cysteic acid in the extract was determined. Quantified by high performance liquid chromatography. The recovery rate was defined as transdermal absorbability (the lower the value, the higher the transdermal absorbability). Each test sample was evaluated twice, and the averages are shown in Tables 1 to 4.

<Test Example 3 Evaluation of color and odor of composition for external use on skin>
After preparing the test sample, it was stored at 50 ° C. for one month, and the color and odor were evaluated. However, on the day before the evaluation, the test sample stored at 50 ° C. was stored at 5 ° C. for 24 hours, and this was compared with a sample stored separately at 5 ° C. immediately after the test sample preparation. The criteria for each evaluation are shown below. The results are shown in Tables 1-4.

[Color and odor evaluation criteria]
0: Same as stored at 5 ° C.
1: A slight difference is seen compared with a 5 degreeC storage goods. It is a level that cannot be understood unless it is compared with products stored at 5 ° C.
2: A difference is seen compared with a 5 degreeC storage goods. Even if it is not compared with a product stored at 5 ° C., it can be easily understood.
3: A big difference is seen compared with a 5 degreeC storage goods. It is not suitable as a composition for external use on the skin.

From the results of Tables 1 to 4, according to the present invention, even in a compound that has a three-dimensionally bulky branched structure and is water-soluble, high transdermal absorbability can be realized, and an ultraviolet absorber can be used. It is possible to provide an external composition for skin that suppresses decomposition at a high temperature and has a high UV-cutting effect.

The present invention relates to an external composition for skin, and more specifically, can be applied to an external composition for skin having a high ultraviolet absorption effect and a high transdermal absorption effect of a drug.

Claims (4)

1) 0.01 to 5% by mass of the compound represented by the following general formula (Chemical Formula 1) and / or a pharmacologically acceptable salt thereof with respect to the total amount of the composition, and 2) containing an ultraviolet absorber An external composition for skin.
[In the formula, _{R 1} represents a hydrogen atom, _{R 2} represents a hydrogen atom, _{R 3} is a phenyl group, methylcarbamoyl
Represents a ruphenyl group, a methoxyphenyl group, or a biphenyl group , n represents an integer of 1 or 2, and m represents 0 . ] 2) UV absorber is homomenthyl salicylate, 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester, diparamethoxycinnamate mono-2-ethylhexanoate glyceryl, paraaminobenzoate Acid and its ester, 4-tert-butyl-4′-methoxydibenzoylmethane, 4- (2-β-glucopyranosiloxane) propoxy-2-hydroxybenzophenone, octyl salicylate, methyl 2,5-diisopropylcinnamate 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester, cinoxate, dihydroxy dimethoxy benzophenone, sodium dihydroxy dimethoxy benzophenone disulfonic acid, dihydroxybenzophenone, dimethicone co diethyl benzalmalonate 1- (3,4-dimethoxyphenyl) -4,4-dimethyl-1,3-pentanedione, dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl, tetrahydroxybenzophenone, terephthalylidene dicanfursulfonic acid, 2, 4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, drometrizol trisiloxane, paradimethylaminobenzoic acid Amyl acid, 2-ethylhexyl paradimethylaminobenzoate, isopropyl paramethoxycinnamate / diisopropyl cinnamate ester, 2-ethylhexyl paramethoxycinnamate, 2,4-bis-[{4- (2-ethylhexyloxy) ) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid and its trihydrate, hydroxymethoxybenzophenonesulfone Acid sodium, phenylbenzimidazolesulfonic acid, ferulic acid, and 2,2′-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) The composition for external use of the skin according to claim 1, comprising one or more selected from the group consisting of: Furthermore, 3) metal oxide powder is contained, The external composition for skin of Claim 1 or 2 characterized by the above-mentioned. Furthermore, 4) 4-n-butyl resorcinol is contained, The composition for external use of the skin of any one of Claims 1-3 characterized by the above-mentioned.