JP3878094B2 - Cosmetics for tanning - Google Patents
Cosmetics for tanning Download PDFInfo
- Publication number
- JP3878094B2 JP3878094B2 JP2002258322A JP2002258322A JP3878094B2 JP 3878094 B2 JP3878094 B2 JP 3878094B2 JP 2002258322 A JP2002258322 A JP 2002258322A JP 2002258322 A JP2002258322 A JP 2002258322A JP 3878094 B2 JP3878094 B2 JP 3878094B2
- Authority
- JP
- Japan
- Prior art keywords
- ascorbic acid
- skin
- external preparation
- acid
- monoglucosyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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- 125000002252 acyl group Chemical group 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 14
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
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Description
【０００１】
【発明の属する技術分野】
本発明は、皮膚外用剤に関し、更に詳細には、日焼けした肌に適用するのに好適な、皮膚外用剤に関する。
【０００２】
【従来の技術】
皮膚外用剤に於いて、界面活性剤は可溶化、乳化或いは分散を目的として広く使用されている。中でも、非イオン界面活性剤、特に親水性の非イオン界面活性剤は、肌への刺激が少ないため、化粧水、乳液、クリームなどの化粧料に汎用されている。この様な親水性の非イオン界面活性剤としては、脂肪酸、高級アルコール、水素添加されていても良いひまし油或いは脂肪酸モノグリセライドにエチレンオキサイドを付加重合させた、ポリオキシエチレン基を有するものが最もポピュラーなものとして知られている。確かに、この様な非イオン界面活性剤は一般的には皮膚に対しては刺激が少なく、マイルドなものであるが、例えば、日焼けした肌など皮膚バリア機能の変調や低下が起こった部分への適用では、一過性の刺激発現を起こしやすく、この様な刺激発現を防ぐ技術の開発が望まれていた。又、かかる日焼けした肌においては、活性酸素の通常以上の量の存在が確認されており、かかる活性酸素を消去することが、日焼けの後のメラニン色素の沈着や炎症の発生と持続を防ぐことにつながるので、この様な日焼け後の活性酸素の除去技術の開発が望まれていた。
【０００３】
一方、グルコシル−Ｌ−アスコルビン酸のアシル化誘導体は、生体に効率よく吸収され、生体内に於いてアスコルビン酸を遊離させ、かかるアスコルビン酸によって著しい美白効果を示すことは既に知られている。（特開平１１−２８６４９７）又、前記グルコシル−Ｌ−アスコルビン酸のアシル化誘導体の内、直鎖の構造のアシル基のものと種々の生薬の抽出物を組み合わせて、著しい美白作用を獲得する手段も既に知られている。（特開２００１−１６３７５５）しかしながら、１）グルコシル−Ｌ−アスコルビン酸のアシル化誘導体と２）ショ糖脂肪酸エステル及び／又はポリグリセリン脂肪酸エステルを含有する皮膚外用剤であって、３）前記グルコシル−Ｌ−アスコルビン酸のアシル化誘導体に於けるアシル基が炭素数８〜２０の分岐の脂肪族アシル基であることを組み合わせて、皮膚外用剤に含有させる技術、及び、かかる技術により得られた皮膚外用剤については全く知られていなかった。従って、この様な皮膚外用剤が日焼け肌の活性酸素を消去する作用に優れ、且つ、一過性の刺激発現も少ないことは全く知られていなかった。
【０００４】
【発明が解決しようとする課題】
本発明は、この様な状況下為されたものであり、日焼け後の活性酸素を効率的に除去する作用に優れ、且つ、該除去に際し、塗布する皮膚外用剤により、一過性の刺激を誘起しない、皮膚外用剤を提供することを課題とする。
【０００５】
【課題を解決するための手段】
この様な状況に鑑みて、日焼け後の活性酸素を効率的に除去する作用に優れ、且つ、該除去に際し、塗布する皮膚外用剤により、一過性の刺激を誘起しない、皮膚外用剤を求めて、鋭意研究努力を重ねた結果、１）グルコシル−Ｌ−アスコルビン酸のアシル化誘導体と２）ショ糖脂肪酸エステル及び／又はポリグリセリン脂肪酸エステルとを含有する皮膚外用剤であって、３）前記グルコシル−Ｌ−アスコルビン酸のアシル化誘導体に於けるアシル基が炭素数８〜２０の分岐の脂肪族アシル基である皮膚外用剤が、日焼けによって生じる活性酸素を消去する作用に優れながら、一過性の刺激発現も殆ど無いことを見出し、発明を完成させるに至った。即ち、本発明は、以下に示す技術に関するものである。
（１）１）グルコシル−Ｌ−アスコルビン酸のアシル化誘導体と２）ショ糖脂肪酸エステル及び／又はポリグリセリン脂肪酸エステルとを含有する皮膚外用剤であって、３）前記グルコシル−Ｌ−アスコルビン酸のアシル化誘導体に於けるアシル基が炭素数８〜２０の分岐の脂肪族アシル基であることを特徴とする、皮膚外用剤。
（２）グルコシル−Ｌ−アスコルビン酸のアシル化誘導体における、アシル基の構造が、次に示す一般式（Ｉ）に表されるものであることを特徴とする、（１）に記載の皮膚外用剤。
【化２】
（但し、式中ｍは２〜８の整数を表す。）
（３）グルコシル−Ｌ−アスコルビン酸のアシル化誘導体が、２−Ｏ−α−Ｄ−モノグルコシル−６−Ｏ−（２−プロピルペンタノイル）−Ｌ−アスコルビン酸（化合物１）、６−Ｏ−（２−ブチルヘキサノイル）−２−Ｏ−α−Ｄ−モノグルコシル−Ｌ−アスコルビン酸（化合物２）又は２−Ｏ−α−Ｄ−モノグルコシル−６−Ｏ−（２−ペンチルヘプタノイル）−Ｌ−アスコルビン酸（化合物３）であることを特徴とする、（１）又は（２）に記載の皮膚外用剤。
（４）ショ糖脂肪酸エステル及び／又はポリグリセリン脂肪酸エステルが、ショ糖モノステアリン酸エステル、ショ糖モノラウリン酸エステル、デカグリセリンモノステアリン酸エステル、デカグリセリンモノオレイン酸エステル及びデカグリセリンモノイソステアリン酸エステルから選択される１種乃至は２種以上である、（１）〜（３）何れか１項に記載の皮膚外用剤。
（５）日焼けした皮膚上に適用されるものであることを特徴とする、（１）〜（４）何れか１項に記載の皮膚外用剤。
（６）化粧料であることを特徴とする、（１）〜（５）何れか１項に記載の皮膚外用剤。
以下、本発明について更に詳細に説明を加える。
【０００６】
（１）本発明の皮膚外用剤の必須成分であるグルコシル−Ｌ−アスコルビン酸のアシル化誘導体
本発明の皮膚外用剤の必須成分である、グルコシル−Ｌ−アスコルビン酸のアシル化誘導体は、前記アシル基が炭素数８〜２０の分岐の脂肪族アシル基であることを特徴とする。かかるアシル基としては、例えば、イソオクタノイル基、イソパルミトイル基、イソステアロイル基、２−プロピルペンタノイル基、２−ブチルヘキサノイル基、２−ペンチルへプタノイル基などが好適に例示でき、これらの中では、上記一般式（Ｉ）の構造を有するアシル基が特に好ましく、具体的には、２−プロピルペンタノイル基、２−ブチルヘキサノイル基、２−ペンチルへプタノイル基が特に好ましく例示できる。かかるグルコシル−Ｌ−アスコルビン酸のアシル化誘導体は、諸種の方法により調製することができる。例えば、グリコシル−Ｌ−アスコルビン酸に適宜のアシル化剤を反応させれば、所望のアシル化誘導体が得られる。このとき、必要とあれば、反応系内に触媒を共存させてもよく、その触媒はリパーゼなどの酵素であってもよい。原料となるグリコシル−Ｌ−アスコルビン酸は、例えば、特開平３−１３９２８８号公報、特開平３−１３５９９２号公報及び特開平３−１８３４９２号公報に記載されているように、シクロマルトデキストリン・グルカノトランスフェラーゼなどの糖転移酵素の存在下でＬ−アスコルビン酸にシクロマルトデキストリンや澱粉加水分解物などのα−グルコシル化合物を反応させるか、あるいは、特開平６−２２８１８３号公報及び特開平６−２６３７９０号公報に記載されているように、β−ガラクトシダーゼの存在下で５，６−イソプロピリデン−Ｌ−アスコルビン酸にラクトースなどのβ−ガラクトシル化合物を反応させることによって得ることができる。ちなみに、２−グルコピラノシル−Ｌ−アスコルビン酸の市販品としては、例えば、『ＡＡ−２Ｇ』（固形分重量当りの２−Ｏ−α−Ｄ−モノグルコピラノシル−Ｌ−アスコルビン酸含量９８％以上、株式会社林原商事販売）が挙げられる。用途にもよるけれども、この発明においては、グリコシル−Ｌ−アスコルビン酸は必ずしも高度に精製されておらずともよく、調製方法に特有な類縁体や他の成分との未分離組成物であっても、実質的なアシル化を妨げない他の成分との混合物であってもよい。
【０００７】
化学反応による場合には、ヒドロキシル基を有する化合物をアシル化するための通常一般の方法を適用すればよく、個々の方法としては、例えば、酸又は酸ハライド、酸無水物若しくは酸エステルなどのアシル化剤を用いる方法が挙げられる。アシル化剤としては、２−エチルヘキサン酸、イソパルミチン酸、イソステアリン酸、２−プロピルペンタン酸、２−ブチルヘキサン酸、２−ペンチルへプタン酸などのカルボン酸、酸ハライド、酸無水物或いはカルボン酸エステルが好ましく例示できる。
【０００８】
反応は、通常、反応系への水の侵入を遮断した非水系で行なわれ、例えば、ピリジン、ジメチルスルホキシド、ジメチルホルムアミドなどの有機溶剤中、必要に応じて、ｐ−トルエンスルホン酸などの触媒を共存させて、グリコシル−Ｌ−アスコルビン酸にカルボン酸無水物を反応させるか、あるいは、濃硫酸などの触媒の存在下、グリコシル−Ｌ−アスコルビン酸にカルボン酸そのものを反応させる。反応条件としては、Ｌ−アスコルビン酸のアシル化に通常用いられる反応がそのまま適用できるが、グリコシル−Ｌ−アスコルビン酸１モルに対して、アシル化剤を３モル以下、望ましくは、２モル以下反応させるときには、反応がほぼ特異的に進行し、グリコシル−Ｌ−アスコルビン酸におけるＬ−アスコルビン酸残基の特定の部位にアシル基を導入することができる。例えば、２−Ｏ−α−Ｄ−モノグルコピラノシル−Ｌ−アスコルビン酸の場合、２モル以下のアシル化剤を反応させると、実質的に、Ｌ−アスコルビン酸残基における６位の位置のヒドロキシル基だけをアシル化することができる。また、公知の方法によってＬ−アスコルビン酸における６位のヒドロキシル基だけをアシル化した後、適宜有機溶剤又は有機溶剤と水との適宜混液中、例えば、シクロマルトデキストリン・グルカノトランスフェラーゼなどの糖転移酵素の存在下でそのアシル化されたＬ−アスコルビン酸にシクロマルトデキストリンや澱粉部分加水分解物などのα−グルコシル化合物を反応させるときには、Ｌ−アスコルビン酸残基における６位のヒドロキシル基だけがアシル化された２−グルコピラノシル−Ｌ−アスコルビン酸のモノアシル化誘導体を得ることができる。好ましいグルコシル−Ｌ−アスコルビン酸のアシル化誘導体としては、例えば、２−Ｏ−α−Ｄ−モノグルコシル−６−Ｏ−（２−プロピルペンタノイル）−Ｌ−アスコルビン酸 （化合物１）、６−Ｏ−（２−ブチルヘキサノイル）−２−Ｏ−α−Ｄ−モノグルコシル−Ｌ−アスコルビン酸（化合物２）又は２−Ｏ−α−Ｄ−モノグルコシル−６−Ｏ−（２−ペンチルヘプタノイル）−Ｌ−アスコルビン酸（化合物３）が例示できる。
【０００９】
酵素反応による場合には、グリコシル−Ｌ−アスコルビン酸及びアシル化剤を基質とし、通常、これらの基質と酵素に応じた適宜有機溶剤が用いられ、場合によっては、適宜分配率の水及び有機溶剤からなる二成分系が用いられる。酵素としてはリパーゼが一般的であり、酵素剤は固定化されていてもよい。有機溶剤として、例えば、ｓｅｃ−ブチルアルコール、ｔ−ブチルアルコール、ｔ−アミルアルコール、ジオキサン、テトラヒドロフラン、ジエチルエーテル、ジクロロメタン、ピリジンなどの親水性有機溶剤が用いられる。反応条件は、酵素法によるＬ−アスコルビン酸のアシル化の場合と同様に設定すればよく、酵素の種類にも特に制限がない。なお、グリコシル−Ｌ−アスコルビン酸、とりわけ、２−グルコピラノシル−Ｌ−アスコルビン酸は水溶液における安定性が著しく高いので、Ｌ−アスコルビン酸のアシル化の場合とは違って、複雑な条件設定の必要がない。
【００１０】
斯くして得られるアシル化誘導体は、Ｌ−アスコルビン酸の脂肪酸エステルを精製するための通常の方法を適用することにより精製することができる。個々の精製方法としては、例えば、塩析、透析、濾過、濃縮、分別沈澱、分液抽出、ゲルクロマトグラフィー、イオン交換クロマトグラフィー、高速液体クロマトグラフィー、ガスクロマトグラフィー、親和クロマトグラフィー、ゲル電気泳動、等電点電気泳動、結晶化などが挙げられ、これらは、反応条件並びに所望するアシル化誘導体の種類及び純度に応じて適宜組合せて適用される。この様な製造例を以下に示す。
【００１１】
＜製造例１＞
〈２−エチルヘキサン酸誘導体（６−Ｏ−（２−エチルヘキサノイル）−２−Ｏ−α−Ｄ−モノグルコシル−Ｌ−アスコルビン酸；化合物４）の調製〉
室温下、反応容器に２−グルコピラノシル−Ｌ−アスコルビン酸（商品名『ＡＡ−２Ｇ』、固形分重量当りの２−Ｏ−α−Ｄ−モノグルコピラノシル−Ｌ−アスコルビン酸含量９８％以上、株式会社林原商事販売）を２．７１ｇ（８．０ｍｍｏｌ）とり、アルゴン気流下、ピリジンを３５０ｍｌ加え、溶解するまで撹拌した。次に、ピリジン５０ｍｌに溶解した２−エチルヘキサン酸無水物（９．６ｍｍｏｌ）をアルゴン気流下、２分間かけて反応容器内に滴々加えた後、室温下で１３５分間反応させた。その後、反応容器内にメタノールを加え、濃縮し、乾固して反応を停止させた。
【００１２】
得られた反応混合物の固状物をカラムクロマトグラフィー用シリカゲル（商品名『ワコーゲル』、和光純薬工業株式会社製造）１３９．５ｇのカラムに負荷し、酢酸エチル５００ｍｌ、酢酸エチル／メタノール混液（容量比９：１）５００ｍｌ、酢酸エチル／メタノール混液（容量比８：２）５００ｍｌ及び酢酸エチル／メタノール混液（容量比７：３）５００ｍｌをこの順序でそれぞれ通液する一方、溶出液を１００ｍｌずつ採取した。各溶出画分の一部をそれぞれとり、これを薄層クロマトグラフィー用シリカゲルプレート（商品名『シリカゲル６０ Ｆ２５４』、メルク製造）に少量滴下し、乾燥させた後、酢酸エチル／メタノール混液（容量比６：４）を用いて展開し、メイン・スポットを掻き取り、酢酸エチルとエタノールの等量混合液１００ｍｌで２回抽出し、濾過、乾固し表記誘導体を分取した。構造は１Ｈ−ＮＭＲと１３Ｃ−ＮＭＲにより確認した。
【００１３】
＜製造例２＞
〈イソパルミチン酸誘導体（６−Ｏ−イソパルミトイル−２−Ｏ−α−Ｄ−モノグルコシル−Ｌ−アスコルビン酸；化合物５）の調製〉
製造例１と同様の手技で、酸無水物をイソパルミチン酸無水物に変えて表記化合物を得た。
【００１４】
＜製造例３＞
〈イソステアリン酸誘導体（６−Ｏ−イソステアロイル−２−Ｏ−α−Ｄ−モノグルコシル−Ｌ−アスコルビン酸；化合物６）の調製〉
製造例１と同様の手技で、酸無水物をイソステアリン酸無水物に変えて表記化合物を得た。
【００１５】
＜製造例４＞
〈２−プロピルペンタン酸誘導体（２−Ｏ−α−Ｄ−モノグルコシル−６−Ｏ−（２−プロピルペンタノイル）−Ｌ−アスコルビン酸；化合物１）の調製〉
製造例１と同様の手技で、酸無水物を２−プロピルペンタン酸無水物に変えて表記化合物を得た。
【００１６】
＜製造例５＞
〈２−ブチルヘキサン酸誘導体（６−Ｏ−（２−ブチルヘキサノイル）−２−Ｏ−α−Ｄ−モノグルコシル−Ｌ−アスコルビン酸；化合物２）の調製〉
製造例１と同様の手技で、酸無水物を２−ブチヘキサン酸無水物に変えて表記化合物を得た。
【００１７】
＜製造例６＞
〈２−ペンチルヘプタン酸誘導体（２−Ｏ−α−Ｄ−モノグルコシル−６−Ｏ−（２−ペンチルヘプタノイル）−Ｌ−アスコルビン酸；化合物３）の調製〉
製造例１と同様の手技で、酸無水物を２−ペンチルヘプタン酸無水物に変えて表記化合物を得た。
【００１８】
（２）本発明の皮膚外用剤の必須成分であるショ糖脂肪酸エステル及び／又はポリグリセリン脂肪酸エステル。
本発明の皮膚外用剤は、ショ糖脂肪酸エステル及び／又はポリグリセリン脂肪酸エステルを必須成分として含有する。ショ糖脂肪酸エステルとしては、ショ糖のモノ脂肪酸エステルが好ましく、脂肪酸部分としては、ラウリン酸、パルミチン酸、ステアリン酸、オレイン酸が好ましく例示できる。脂肪酸残基にすると、ラウリル基、パルミチル基、ステアリル基、オレイル基が好ましい。化合物としては、ショ糖モノステアレート及びショ糖モノラウレートが特に好ましい。ポリグリセリン脂肪酸エステルのポリグリセリンの部分としては、グリセリンの５〜２０量体が好ましく例示でき、脂肪酸部分としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸或いはベヘン酸等が好ましく例示できる。即ち、脂肪酸残基にすると、ラウリル基、ミリスチル基、パルミチル基、ステアリル基、オレイル基、リノリル基が好ましい。エステル化度は１分子あたり平均１〜３が好ましい。この様なものの多くが市販されており、この様な市販されているものの内、特に好ましいものとしては、デカグリセリンモノステアリン酸エステル、デカグリセリンモノオレイン酸エステル及びデカグリセリンモノイソステアリン酸エステル等が例示できる。これらショ糖脂肪酸エステル、ポリグリセリン脂肪酸エステルは唯一種を含有させることもできるし、二種以上を組み合わせて含有させることもできる。
【００１９】
（３）本発明の皮膚外用剤
本発明の皮膚外用剤は、上記必須成分である１）アシル基が炭素数８〜２０の分岐の脂肪族アシル基であるグルコシル−Ｌ−アスコルビン酸のアシル化誘導体と２）ショ糖脂肪酸エステル及び／又はポリグリセリン脂肪酸エステルを含有することを特徴とする。前記アシル基が炭素数８〜２０の分岐の脂肪族アシル基であるグルコシル−Ｌ−アスコルビン酸のアシル化誘導体は、唯一種を含有させることもできるし、二種以上を組み合わせて含有させることもできる。かかるアシル基が炭素数８〜２０の分岐の脂肪族アシル基であるグルコシル−Ｌ−アスコルビン酸のアシル化誘導体の本発明の皮膚外用剤に於ける、好ましい含有量は、総量で皮膚外用剤全量に対して、０．０１〜１０重量％であり、更に好ましくは、０．０５〜５重量％である。又、ショ糖脂肪酸エステル及び／又はポリグリセリン脂肪酸エステルの好ましい含有量は、総量で化粧料全量に対して、０．１〜１０重量％であり、更に好ましくは０．５〜５重量％である。
【００２０】
本発明の皮膚外用の組成物に於いては、上記の必須成分以外に、通常この様な組成物で使用される任意成分を含有することができる。かかる任意成分としては、例えば、スクワラン、ワセリン、マイクロクリスタリンワックス等の炭化水素類、ホホバ油、カルナウバワックス，オレイン酸オクチルドデシル等のエステル類、オリーブ油、牛脂、椰子油等のトリグリセライド類、ステアリン酸、オレイン酸、リチノレイン酸等の脂肪酸、オレイルアルコール、ステアリルアルコール、オクチルドデカノール等の高級アルコール、ポリエチレングリコール、グリセリン、１，３−ブタンジオール等の多価アルコール類、増粘・ゲル化剤、酸化防止剤、紫外線吸収剤、色剤、防腐剤、粉体等を例示することができる。これらの内、特に好ましい任意成分としては、保湿剤としてグリセリン、増粘剤としてカルボキシビニルポリマー及び／又はその塩が例示できる。グリセリンの好ましい含有量は１〜１０重量％であり、更に好ましくは２〜５重量％である。これは、この量範囲に於いてトラブル発生抑制作用が著しく得られるからである。又、カルボキシビニルポリマーの塩としてはアルカリ金属塩と有機アミン塩が好ましく例示でき、中でもカリウム塩とナトリウム塩が安定性への寄与の面で特に好ましい。カルボキシビニルポリマー及びその塩は総量で０．１〜１重量％含有するのが安定化と安全性のバランスから好ましい。これらの任意成分と必須成分とを常法に従って処理することにより、本発明の組成物は製造することができる。
【００２１】
【実施例】
以下に、実施例を挙げて、本発明について更に詳細に説明を加えるが、本発明が、かかる実施例にのみ限定されないことは言うまでもない。
【００２２】
＜実施例１＞
下記に示す処方に従って、本発明の皮膚外用剤であるローション化粧料を作成した。即ち、イ、ロの成分を７５℃に加熱し、攪拌、可溶化し、イに徐々にロを加え、中和した後、攪拌冷却し、ローション化粧料１を得た。
イ
１，３−ブタンジオール ５ 重量部
グリセリン ３ 重量部
１，２−ペンタンジオール ３ 重量部
ショ糖モノラウレート ０．５重量部
デカグリセリンモノオレート ０．１重量部
化合物３ ０．１重量部
カルボキシビニルポリマー ０．２重量部
フェノキシエタノール ０．３重量部
水 ５０ 重量部
ロ
１０％水酸化カリウム水溶液 １ 重量部
水 ３６．８重量部
【００２３】
＜実施例２＞
実施例１のローション化粧料１のｉｎ ｖｉｖｏでの活性酸素消去効果を調べた。即ち、ハートレー系白色種モルモット（雄性、３００〜３５０ｇ）１群３匹の背部を剃毛し、右半側を用いて予め紫外線（光源；ＳＥランプ）に対する最少紅斑量（ＭＥＤ）を測定した。この時左半側は覆いをして紫外線が当たらないようにした。その３日後左半側にＭＥＤの２／３量の紫外線を照射し、その後ローション化粧料１を０．１ｍｌ塗布して処置し、塗布後１０分に動物を屠殺し、照射部位の皮膚を切り出し直ちに凍結切片を作成した。凍結切片を蛍光顕微鏡下観察した。無処置群としては剃毛の処置のもの、光対照群としては、剃毛して紫外線照射し皮膚外用剤の処理を行わないものを用いた。比較例１としてはローション化粧料１の化合物３をアスコルビン酸に置換したものを、比較例２としては２−Ｏ−α−Ｄ−モノグルコシル−Ｌ−アスコルビン酸に置換したものを用いた。評価は顕微鏡像を画像として取り込み、３例の画像をモーフィングにより平均化し、平均画像を作成し、この群の平均画像同士を次の基準で検知可能な蛍光点の出現程度を比較し、スコアを判定した。活性酸素による損傷が大きいほど、蛍光顕微鏡像には蛍光点の出現が増える。基準は、無処置群の平均画像と同程度の蛍光点の出現をスコア１、光対照群と同程度の蛍光点の出現をスコア５とした。この間を等尺に配分し、スコア１〜５を設定した。結果を表１に示す。これより本発明の皮膚外用剤は、ｉｎ ｖｉｖｏにおける活性酸素を消去する作用に優れることがわかる。これは、本発明の必須成分である、化合物３の生体内への吸収が良いためであると考えられる。
【００２４】
【表１】
＜実施例３＞
本発明の皮膚外用剤であるローション化粧料１について、一過性の刺激を動物モデルで評価した。動物モデルは、ＩＣＲマウス・テール・スティンギングモデルを用いた。即ち、ＩＣＲマウス（雄性、４週齢）の尻尾を紙ヤスリで擦過し、損傷モデルを作成し、これに検体０．０１ｍｌを滴下し、その刺激により、飛翔する距離を求めた。例数は５匹とし、飛翔距離の平均値を群の代表値とした。検体は実施例２のローション化粧料１、比較例１、２、ローション化粧料１のショ糖モノラウレートとデカグリセリンモノオレートとをＰＯＥ（６０）硬化ヒマシ油に置換した比較例３、ＰＯＥ（２０）オレイルエーテルに置換した比較例４及びＰＯＥ（２０）ステアレートに置換した比較例５を用いた。結果を表２に示す。これより、本発明の皮膚外用剤は、一過性の刺激が極めて低いことがわかる。
【００２６】
【表２】
＜実施例４＞
実施例１の化合物３を他の分岐アシルエステルに代えて、ローション化粧料を作成し、実施例２、３の方法に従って評価した。結果を表３に示す。これより、化合物１、２、４、５及び６は化合物３同様、一過性の刺激発現が低く、且つ、活性酸素消去能に優れることがわかる。又、化合物１、２及び３が特に好ましいこともわかる。
イ
１，３−ブタンジオール ５ 重量部
グリセリン ３ 重量部
１，２−ペンタンジオール ３ 重量部
ショ糖モノラウレート ０．５重量部
デカグリセリンモノオレート ０．１重量部
化合物＊ ０．１重量部
カルボキシビニルポリマー ０．２重量部
フェノキシエタノール ０．３重量部
水 ５０ 重量部
ロ
１０％水酸化カリウム水溶液 １ 重量部
水 ３６．８重量部
＊詳細は表３に示す。
【００２８】
【表３】
＜実施例５＞
ローション化粧料１の界面活性剤である、ショ糖モノラウレートとデカグリセリンモノオレートとを代えて、実施例２、３の手技に従って評価した。結果を表４に示す。これより、本発明の皮膚外用剤は何れも化合物３同様、一過性の刺激発現が低く、且つ、活性酸素消去能に優れることがわかる。
イ
１，３−ブタンジオール ５ 重量部
グリセリン ３ 重量部
１，２−ペンタンジオール ３ 重量部
界面活性剤＊＊ ０．６重量部
化合物３ ０．１重量部
カルボキシビニルポリマー ０．２重量部
フェノキシエタノール ０．３重量部
水 ５０ 重量部
ロ
１０％水酸化カリウム水溶液 １ 重量部
水 ３６．８重量部
＊＊詳細は表４に記す。
【００３０】
【表４】
【発明の効果】
日焼け後の活性酸素を効率的に除去する作用に優れ、且つ、該除去に際し、塗布する皮膚外用剤により、一過性の刺激を誘起しない、皮膚外用剤を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an external preparation for skin, and more particularly to an external preparation for skin suitable for application to tanned skin.
[0002]
[Prior art]
In external preparations for skin, surfactants are widely used for the purpose of solubilization, emulsification or dispersion. Among these, nonionic surfactants, particularly hydrophilic nonionic surfactants, are widely used in cosmetics such as skin lotions, emulsions, and creams because they are less irritating to the skin. As such hydrophilic nonionic surfactants, those having a polyoxyethylene group obtained by addition polymerization of ethylene oxide to fatty acid, higher alcohol, hydrogenated castor oil or fatty acid monoglyceride are most popular. Known as a thing. Certainly, such nonionic surfactants are generally mild and mild to the skin, but for example, to areas where skin barrier function is modulated or reduced, such as tanned skin. In this application, it has been desired to develop a technique that easily causes transient stimulation and prevents such stimulation. Also, in such tanned skin, the presence of more than normal amounts of active oxygen has been confirmed, and eliminating such active oxygen prevents the occurrence and persistence of melanin pigmentation and inflammation after sunburn. Therefore, it has been desired to develop a technique for removing such active oxygen after sunburn.
[0003]
On the other hand, it is already known that acylated derivatives of glucosyl-L-ascorbic acid are efficiently absorbed by the living body, release ascorbic acid in the living body, and exhibit a marked whitening effect by such ascorbic acid. (Japanese Patent Laid-Open No. 11-286497) Further, among the acylated derivatives of glucosyl-L-ascorbic acid, a means for obtaining a remarkable whitening effect by combining an acyl group having a straight chain structure and extracts of various herbal medicines Is already known. (JP-A-2001-163755) However, 1) an external preparation for skin containing an acylated derivative of glucosyl-L-ascorbic acid and 2) a sucrose fatty acid ester and / or a polyglycerol fatty acid ester, and 3) the glucosyl- A technique for incorporating an acyl group in an acylated derivative of L-ascorbic acid into a branched aliphatic acyl group having 8 to 20 carbon atoms and containing it in an external preparation for skin, and skin obtained by such a technique The topical preparation was not known at all. Therefore, it has not been known at all that such an external preparation for skin is excellent in the action of eliminating the active oxygen of tanned skin and has little transient irritation.
[0004]
[Problems to be solved by the invention]
The present invention has been made under such circumstances, and is excellent in the action of efficiently removing active oxygen after sunburn, and at the time of the removal, a temporary irritation is applied by an external preparation for skin application. It is an object to provide an external preparation for skin that does not induce.
[0005]
In order to solve the problems]
In view of such circumstances, a skin external preparation that is excellent in the action of efficiently removing active oxygen after sunburn and that does not induce transient irritation by the applied external preparation for skin is required. As a result of intensive research efforts, 1) an external preparation for skin containing an acylated derivative of glucosyl-L-ascorbic acid and 2) a sucrose fatty acid ester and / or a polyglycerin fatty acid ester, 3) The skin external preparation in which the acyl group in the acylated derivative of glucosyl-L-ascorbic acid is a branched aliphatic acyl group having 8 to 20 carbon atoms has an excellent effect of eliminating active oxygen generated by sunburn, It was found that there was almost no sexual stimulation, and the present invention was completed. That is, this invention relates to the technique shown below.
(1) A skin external preparation containing 1) an acylated derivative of glucosyl-L-ascorbic acid and 2) a sucrose fatty acid ester and / or a polyglycerin fatty acid ester, and 3) of the glucosyl-L-ascorbic acid An external preparation for skin, wherein the acyl group in the acylated derivative is a branched aliphatic acyl group having 8 to 20 carbon atoms.
(2) The skin external application according to (1), wherein the acyl group structure in the acylated derivative of glucosyl-L-ascorbic acid is represented by the following general formula (I): Agent.
[Chemical formula 2]
(In the formula, m represents an integer of 2 to 8.)
(3) The acylated derivative of glucosyl-L-ascorbic acid is 2-O-α-D-monoglucosyl-6-O- (2-propylpentanoyl) -L-ascorbic acid (compound 1), 6-O. -(2-butylhexanoyl) -2-O-α-D-monoglucosyl-L-ascorbic acid (compound 2) or 2-O-α-D-monoglucosyl-6-O- (2-pentylheptanoyl ) -L-ascorbic acid (compound 3), The skin external preparation as described in (1) or (2) characterized by the above-mentioned.
(4) Sucrose fatty acid ester and / or polyglycerin fatty acid ester is from sucrose monostearate ester, sucrose monolaurate ester, decaglycerin monostearate ester, decaglycerin monooleate ester and decaglycerin monoisostearate ester The external preparation for skin according to any one of (1) to (3), which is one or more selected.
(5) The external preparation for skin according to any one of (1) to (4), which is applied on tanned skin.
(6) The skin external preparation according to any one of (1) to (5), which is a cosmetic.
Hereinafter, the present invention will be described in more detail.
[0006]
(1) Acylated derivative of glucosyl-L-ascorbic acid which is an essential component of the external preparation for skin of the present invention The acylated derivative of glucosyl-L-ascorbic acid which is an essential component of the external preparation for skin of the present invention is the acyl The group is a branched aliphatic acyl group having 8 to 20 carbon atoms. Examples of the acyl group include an isooctanoyl group, an isopalmitoyl group, an isostearoyl group, a 2-propylpentanoyl group, a 2-butylhexanoyl group, and a 2-pentylheptanoyl group. Among these, An acyl group having the structure of the general formula (I) is particularly preferable, and specific examples thereof include 2-propylpentanoyl group, 2-butylhexanoyl group, and 2-pentylheptanoyl group. Such acylated derivatives of glucosyl-L-ascorbic acid can be prepared by various methods. For example, the desired acylated derivative can be obtained by reacting glycosyl-L-ascorbic acid with an appropriate acylating agent. At this time, if necessary, a catalyst may coexist in the reaction system, and the catalyst may be an enzyme such as lipase. The glycosyl-L-ascorbic acid used as a raw material is, for example, cyclomaltodextrin / glucano as described in JP-A-3-139288, JP-A-3-135992 and JP-A-3-183492. In the presence of a glycosyltransferase such as transferase, L-ascorbic acid is reacted with an α-glucosyl compound such as cyclomaltodextrin or starch hydrolyzate, or JP-A-6-228183 and JP-A-6-263790. As described in the publication, it can be obtained by reacting 5,6-isopropylidene-L-ascorbic acid with a β-galactosyl compound such as lactose in the presence of β-galactosidase. Incidentally, as a commercially available product of 2-glucopyranosyl-L-ascorbic acid, for example, “AA-2G” (2-O-α-D-monoglucopyranosyl-L-ascorbic acid content per solid content weight 98% The above is Hayashibara Shoji Sales Co., Ltd.). Domo Re only depending on the application, in the present invention, glycosyl -L- ascorbate may even not necessarily highly purified, there in unseparated composition of specific analogues and other ingredients in the preparation method Alternatively, it may be a mixture with other components that do not prevent substantial acylation.
[0007]
In the case of a chemical reaction, a usual general method for acylating a compound having a hydroxyl group may be applied. Examples of individual methods include acyls such as acids or acid halides, acid anhydrides or acid esters. A method using an agent is mentioned. Examples of the acylating agent include 2-ethylhexanoic acid, isopalmitic acid, isostearic acid, 2-propylpentanoic acid, 2-butylhexanoic acid, 2-pentylheptanoic acid and other carboxylic acids, acid halides, acid anhydrides, or carboxylic acids. An acid ester can be preferably exemplified.
[0008]
The reaction is usually carried out in a non-aqueous system that blocks water from entering the reaction system. For example, in an organic solvent such as pyridine, dimethyl sulfoxide, or dimethylformamide, a catalyst such as p-toluenesulfonic acid is used as necessary. In the coexistence, carboxylic acid anhydride is reacted with glycosyl-L-ascorbic acid, or carboxylic acid itself is reacted with glycosyl-L-ascorbic acid in the presence of a catalyst such as concentrated sulfuric acid. As the reaction conditions, the reaction usually used for acylation of L-ascorbic acid can be applied as it is, but the reaction of acylating agent is 3 mol or less, preferably 2 mol or less, per mol of glycosyl-L-ascorbic acid. The reaction proceeds almost specifically and an acyl group can be introduced at a specific site of the L-ascorbic acid residue in glycosyl-L-ascorbic acid. For example, in the case of 2-O-α-D-monoglucopyranosyl-L-ascorbic acid, when 2 mol or less of acylating agent is reacted, the position of position 6 in the L-ascorbic acid residue is substantially increased. Only the hydroxyl group of can be acylated. Further, after acylating only the hydroxyl group at the 6-position in L-ascorbic acid by a known method, in an appropriate organic solvent or an appropriate mixture of an organic solvent and water, for example, sugar transfer such as cyclomaltodextrin / glucanotransferase When an α-glucosyl compound such as cyclomaltodextrin or partial starch hydrolyzate is reacted with the acylated L-ascorbic acid in the presence of an enzyme, only the hydroxyl group at the 6-position in the L-ascorbic acid residue is acylated. A monoacylated derivative of 2-glucopyranosyl-L-ascorbic acid can be obtained. Preferred acylated derivatives of glucosyl-L-ascorbic acid include, for example, 2-O-α-D-monoglucosyl-6-O- (2-propylpentanoyl) -L-ascorbic acid (Compound 1), 6- O- (2-butylhexanoyl) -2-O-α-D-monoglucosyl-L-ascorbic acid (compound 2) or 2-O-α-D-monoglucosyl-6-O- (2-pentylhepta Noyl) -L-ascorbic acid (compound 3).
[0009]
In the case of an enzymatic reaction, glycosyl-L-ascorbic acid and an acylating agent are used as substrates, and usually an appropriate organic solvent is used depending on the substrate and the enzyme. A two-component system consisting of Lipase is common as the enzyme, and the enzyme agent may be immobilized. Examples of the organic solvent include hydrophilic organic solvents such as sec-butyl alcohol, t-butyl alcohol, t-amyl alcohol, dioxane, tetrahydrofuran, diethyl ether, dichloromethane, and pyridine. The reaction conditions may be set in the same manner as in the case of acylation of L-ascorbic acid by an enzymatic method, and the type of enzyme is not particularly limited. Glycosyl-L-ascorbic acid, especially 2-glucopyranosyl-L-ascorbic acid, has extremely high stability in aqueous solution. Therefore, unlike in the case of acylation of L-ascorbic acid, it is necessary to set complicated conditions. Absent.
[0010]
The acylated derivative thus obtained can be purified by applying a usual method for purifying a fatty acid ester of L-ascorbic acid. Examples of individual purification methods include salting out, dialysis, filtration, concentration, fractional precipitation, liquid separation extraction, gel chromatography, ion exchange chromatography, high performance liquid chromatography, gas chromatography, affinity chromatography, gel electrophoresis. , Isoelectric focusing, crystallization, and the like, and these are applied in appropriate combination depending on the reaction conditions and the type and purity of the desired acylated derivative. An example of such production is shown below.
[0011]
<Production Example 1>
<Preparation of 2-ethylhexanoic acid derivative (6-O- (2-ethylhexanoyl) -2-O-α-D-monoglucosyl-L-ascorbic acid; compound 4)>
At room temperature, in a reaction vessel, 2-glucopyranosyl-L-ascorbic acid (trade name “AA-2G”, 2-O-α-D-monoglucopyranosyl-L-ascorbic acid content per solid content weight of 98% or more 2.71 g (8.0 mmol) of Hayashibara Shoji Co., Ltd.) was added, and 350 ml of pyridine was added under an argon stream and stirred until dissolved. Next, 2-ethylhexanoic anhydride (9.6 mmol) dissolved in 50 ml of pyridine was dropped into the reaction vessel over 2 minutes under an argon stream, and then reacted at room temperature for 135 minutes. Thereafter, methanol was added to the reaction vessel, concentrated and dried to stop the reaction.
[0012]
The resulting solid reaction mixture was loaded onto a 139.5 g column for silica gel for column chromatography (trade name “Wakogel”, manufactured by Wako Pure Chemical Industries, Ltd.), 500 ml of ethyl acetate, and ethyl acetate / methanol mixture (volume) Ratio 9: 1) 500 ml, ethyl acetate / methanol mixture (volume ratio 8: 2) 500 ml and ethyl acetate / methanol mixture (volume ratio 7: 3) 500 ml were passed in this order, while 100 ml of eluate was collected. did. A portion of each elution fraction was taken and dropped on a silica gel plate for thin layer chromatography (trade name “silica gel 60 F254”, manufactured by Merck), dried, and then mixed with ethyl acetate / methanol mixture (volume ratio). 6: 4), the main spot was scraped off, extracted twice with 100 ml of an equal volume mixture of ethyl acetate and ethanol, filtered and dried to separate the title derivative. The structure was confirmed by 1 H-NMR and 13 C-NMR.
[0013]
<Production Example 2>
<Preparation of Isopalmitic Acid Derivative (6-O-Isopalmitoyl-2-O-α-D-monoglucosyl-L-ascorbic acid; Compound 5)>
In the same manner as in Production Example 1, the acid anhydride was changed to isopalmitic acid anhydride to obtain the title compound.
[0014]
<Production Example 3>
<Preparation of isostearic acid derivative (6-O-isostearoyl-2-O-α-D-monoglucosyl-L-ascorbic acid; compound 6)>
In the same manner as in Production Example 1, the acid anhydride was changed to isostearic anhydride to obtain the title compound.
[0015]
<Production Example 4>
<Preparation of 2-propylpentanoic acid derivative (2-O-α-D-monoglucosyl-6-O- (2-propylpentanoyl) -L-ascorbic acid; compound 1)>
In the same manner as in Production Example 1, the acid anhydride was changed to 2-propylpentanoic acid anhydride to give the title compound.
[0016]
<Production Example 5>
<Preparation of 2-butylhexanoic acid derivative (6-O- (2-butylhexanoyl) -2-O-α-D-monoglucosyl-L-ascorbic acid; compound 2)>
In the same manner as in Production Example 1, the acid anhydride was changed to 2-butyhexanoic acid anhydride to obtain the title compound.
[0017]
<Production Example 6>
<Preparation of 2-pentylheptanoic acid derivative (2-O-α-D-monoglucosyl-6-O- (2-pentylheptanoyl) -L-ascorbic acid; compound 3)>
In the same manner as in Production Example 1, the acid anhydride was changed to 2-pentylheptanoic acid anhydride to obtain the title compound.
[0018]
(2) Sucrose fatty acid ester and / or polyglycerol fatty acid ester, which are essential components of the external preparation for skin of the present invention.
The skin external preparation of the present invention contains a sucrose fatty acid ester and / or a polyglycerin fatty acid ester as an essential component. As the sucrose fatty acid ester, a mono fatty acid ester of sucrose is preferable, and as the fatty acid portion, lauric acid, palmitic acid, stearic acid, and oleic acid can be preferably exemplified. As a fatty acid residue, a lauryl group, a palmityl group, a stearyl group, and an oleyl group are preferable. As the compound, sucrose monostearate and sucrose monolaurate are particularly preferable. As the polyglycerin part of the polyglycerin fatty acid ester, glycerin 5-20 mer can be preferably exemplified, and as the fatty acid part, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, etc. Can be preferably exemplified. That is, when it is a fatty acid residue, a lauryl group, a myristyl group, a palmityl group, a stearyl group, an oleyl group, and a linolyl group are preferable. The average degree of esterification is preferably 1 to 3 per molecule. Many of such products are commercially available, and among these commercially available products, particularly preferred are decaglycerin monostearate, decaglycerin monooleate and decaglycerin monoisostearate. it can. These sucrose fatty acid esters and polyglycerin fatty acid esters may contain only one species, or may contain two or more species in combination.
[0019]
(3) External preparation for skin of the present invention The external preparation for skin of the present invention is the essential component 1) acylation of glucosyl-L-ascorbic acid in which the acyl group is a branched aliphatic acyl group having 8 to 20 carbon atoms. It contains a derivative and 2) sucrose fatty acid ester and / or polyglycerin fatty acid ester. The acylated derivative of glucosyl-L-ascorbic acid in which the acyl group is a branched aliphatic acyl group having 8 to 20 carbon atoms may contain only one species or may contain two or more species in combination. it can. The preferred content of the acylated derivative of glucosyl-L-ascorbic acid in which the acyl group is a branched aliphatic acyl group having 8 to 20 carbon atoms in the external preparation for skin of the present invention is the total amount of the external preparation for skin. The content is 0.01 to 10% by weight, and more preferably 0.05 to 5% by weight. The preferable content of the sucrose fatty acid ester and / or polyglycerin fatty acid ester is 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total amount of the cosmetic. .
[0020]
In the composition for external use of the skin of the present invention, in addition to the above essential components, optional components usually used in such compositions can be contained. Such optional components include, for example, hydrocarbons such as squalane, petrolatum, microcrystalline wax, esters such as jojoba oil, carnauba wax, octyldodecyl oleate, triglycerides such as olive oil, beef tallow, coconut oil, stearic acid, etc. , Fatty acids such as oleic acid and ricinoleic acid, higher alcohols such as oleyl alcohol, stearyl alcohol, octyldodecanol, polyhydric alcohols such as polyethylene glycol, glycerin, 1,3-butanediol, thickening / gelling agents, oxidation Examples thereof include an inhibitor, an ultraviolet absorber, a colorant, an antiseptic, and a powder. Among these, particularly preferred optional components include glycerin as a humectant and carboxyvinyl polymer and / or a salt thereof as a thickener. The preferable content of glycerin is 1 to 10% by weight, more preferably 2 to 5% by weight. This is because the trouble occurrence suppressing effect is remarkably obtained in this amount range. Moreover, as a salt of a carboxyvinyl polymer, an alkali metal salt and an organic amine salt can be preferably exemplified, and among them, a potassium salt and a sodium salt are particularly preferable in terms of contribution to stability. The carboxyvinyl polymer and its salt are preferably contained in a total amount of 0.1 to 1% by weight from the balance of stability and safety. The composition of the present invention can be produced by treating these optional components and essential components according to a conventional method.
[0021]
【Example】
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.
[0022]
<Example 1>
A lotion cosmetic that is an external preparation for skin according to the present invention was prepared according to the formulation shown below. That is, ingredients (a) and (b) were heated to 75 ° C., stirred and solubilized, gradually added to (i), neutralized, then stirred and cooled to obtain a lotion cosmetic 1.
1,3-butanediol 5 parts by weight Glycerin 3 parts by weight 1,2-Pentanediol 3 parts by weight Sucrose monolaurate 0.5 parts by weight Decaglycerin monooleate 0.1 part by weight Compound 3 0.1 part by weight carboxy Vinyl polymer 0.2 parts by weight Phenoxyethanol 0.3 part by weight Water 50 parts by weight 10% aqueous potassium hydroxide solution 1 part by weight Water 36.8 parts by weight
<Example 2>
The in vivo active oxygen scavenging effect of the lotion cosmetic 1 of Example 1 was examined. That is, the back of three Hartley white guinea pigs (male, 300 to 350 g) per group was shaved, and the minimum erythema amount (MED) against ultraviolet rays (light source; SE lamp) was measured in advance using the right half side. At this time, the left half side was covered so as not to be exposed to ultraviolet rays. Three days later, the left half side was irradiated with 2/3 of ultraviolet rays of MED, and then 0.1 ml of lotion cosmetic 1 was applied for treatment, and the animal was sacrificed 10 minutes after application, and the skin at the irradiated site was cut out. Immediately frozen sections were prepared. The frozen section was observed under a fluorescence microscope. As the untreated group, those treated with shaving were used, and as the light control group, those which were shaved and irradiated with ultraviolet rays and were not treated with the external preparation for skin were used. As Comparative Example 1, a compound obtained by substituting compound 3 of lotion cosmetic 1 with ascorbic acid was used. As Comparative Example 2, a compound substituted with 2-O-α-D-monoglucosyl-L-ascorbic acid was used. Evaluation takes a microscopic image as an image, averages three images by morphing , creates an average image, compares the appearance of fluorescent spots that can be detected by the following criteria between the average images of this group, and scores Judged. The greater the damage caused by active oxygen, the more fluorescent spots appear in the fluorescence microscope image. The criteria were score 1 for the appearance of fluorescent spots comparable to the average image in the untreated group and score 5 for the appearance of fluorescent spots comparable to the light control group. This interval was distributed equally and scores 1 to 5 were set. The results are shown in Table 1. From this, it can be seen that the external preparation for skin of the present invention is excellent in the action of eliminating active oxygen in vivo. This is considered to be because the absorption of the compound 3, which is an essential component of the present invention, into the living body is good.
[0024]
[Table 1]
<Example 3>
For the lotion cosmetic 1 which is an external preparation for skin of the present invention, transient irritation was evaluated using an animal model. Animal model, using the ICR mouse tail stay down swinging model. That is, the tail of an ICR mouse (male, 4 weeks old) was scraped with a paper file to create a damage model, and 0.01 ml of a specimen was dropped on the model, and the flight distance was determined by the stimulation. The number of examples was 5, and the average value of the flight distance was the representative value of the group. The sample was Lotion Cosmetic 1 of Example 2, Comparative Examples 1 and 2, Comparative Example 3 in which sucrose monolaurate and decaglycerin monooleate of Lotion Cosmetic 1 were replaced with POE (60) hydrogenated castor oil, POE ( 20) Comparative Example 4 substituted with oleyl ether and Comparative Example 5 substituted with POE (20) stearate were used. The results are shown in Table 2. This shows that the external preparation for skin of the present invention has extremely low transient irritation.
[0026]
[Table 2]
<Example 4>
A lotion cosmetic was prepared by replacing Compound 3 of Example 1 with other branched acyl esters, and evaluated according to the methods of Examples 2 and 3. The results are shown in Table 3. From this, it can be seen that, like Compound 3, Compounds 1, 2, 4, 5 and 6 have low transient stimulus expression and are excellent in active oxygen scavenging ability. It can also be seen that compounds 1, 2 and 3 are particularly preferred.
1,3-Butanediol 5 parts by weight Glycerin 3 parts by weight 1,2-Pentanediol 3 parts by weight Sucrose monolaurate 0.5 part by weight Decaglycerin monooleate 0.1 part by weight Compound * 0.1 part by weight Carboxy Vinyl polymer 0.2 parts by weight Phenoxyethanol 0.3 part by weight Water 50 parts by weight 10% aqueous potassium hydroxide solution 1 part by weight Water 36.8 parts by weight * Details are shown in Table 3.
[0028]
[Table 3]
<Example 5>
Evaluation was performed according to the procedures of Examples 2 and 3 by replacing sucrose monolaurate and decaglycerin monooleate, which are surfactants of lotion cosmetic 1. The results are shown in Table 4. From this, it can be seen that the external preparation for skin of the present invention, like Compound 3, has a low expression of transient irritation and is excellent in active oxygen scavenging ability.
A 1,3-butanediol 5 parts by weight Glycerin 3 parts by weight 1,2-pentanediol 3 parts by weight Surfactant ** 0.6 part by weight Compound 3 0.1 part by weight Carboxyvinyl polymer 0.2 part by weight Phenoxyethanol 0 3 parts by weight of water 50 parts by weight of 10% aqueous potassium hydroxide solution 1 part by weight of water 36.8 parts by weight ** Details are given in Table 4.
[0030]
[Table 4]
【The invention's effect】
It is possible to provide an external preparation for skin that is excellent in the action of efficiently removing active oxygen after sunburn and that does not induce transient irritation by the applied external preparation for skin.
Claims (8)
２）ショ糖モノステアリン酸エステル、ショ糖モノラウリン酸エステル、デカグリセリンモノステアリン酸エステル、デカグリセリンモノオレイン酸エステル及びデカグリセリンモノイソステアリン酸エステルから選択される１種乃至は２種以上とを含有する皮膚外用剤。
（但し、式中ｍは２〜８の整数を表す。） 1) an acylated derivative of glucosyl-L-ascorbic acid having a branched acyl group having 8 to 20 carbon atoms branched at the 2-position represented by the following general formula (I) ;
2) Contains one or more selected from sucrose monostearate, sucrose monolaurate, decaglycerol monostearate, decaglycerol monooleate and decaglycerol monoisostearate Skin external preparation .
(In the formula, m represents an integer of 2 to 8.)
（但し、式中ｍは２〜８の整数を表す。）(In the formula, m represents an integer of 2 to 8.)
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| JP2002258322A JP3878094B2 (en) | 2002-09-04 | 2002-09-04 | Cosmetics for tanning |
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| JP2002258322A JP3878094B2 (en) | 2002-09-04 | 2002-09-04 | Cosmetics for tanning |
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