JP2004075635A - Moisturizing agent and external preparation for skin - Google Patents
Moisturizing agent and external preparation for skin Download PDFInfo
- Publication number
- JP2004075635A JP2004075635A JP2002240497A JP2002240497A JP2004075635A JP 2004075635 A JP2004075635 A JP 2004075635A JP 2002240497 A JP2002240497 A JP 2002240497A JP 2002240497 A JP2002240497 A JP 2002240497A JP 2004075635 A JP2004075635 A JP 2004075635A
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- JP
- Japan
- Prior art keywords
- skin
- molecular weight
- alginic acid
- salts
- external preparation
- 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.)
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000003020 moisturizing effect Effects 0.000 title abstract description 21
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- 230000000694 effects Effects 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 2
- 210000003491 skin Anatomy 0.000 description 39
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、比較的低分子量のアルギン酸及び／又はその塩類を有効成分として含む溶解性がよく、使いやすい保湿剤、該保湿剤を配合してなる、優れた保湿効果及び肌あれ改善効果を有する皮膚外用剤に関する。
【０００２】
【従来の技術】
従来、保湿剤としては、皮膚の恒常性維持や冬場の乾燥から肌を守る等の目的で、グリセリン、プロピレングリコール及びソルビトールに代表される水溶性多価アルコール；ヒアルロン酸及びキサンタンガムに代表される水溶性高分子；ピロリドンカルボン酸塩及びアミノ酸に代表される天然保湿因子；セラミドに代表される細胞間脂質、等が使用されている。
【０００３】
これらの保湿剤はそれなりの効果を有するものの、水溶性多価アルコール及び水溶性高分子を配合した皮膚化粧料は、塗布時及び塗布直後にべたつき感を有するものが多く、官能特性上必ずしも好ましいものではなかった。また、天然保湿因子及び細胞間脂質を配合した皮膚化粧料及び浴用剤は、配合する際、配合濃度及び適合製剤に制限を受けるため、剤型が制限され、充分に効果を発現しないことが多かった。
【０００４】
そこで、近年、低湿度下での水分保持力の高い保湿成分として、キチン、キトサン及びそれらの誘導体、蛋白加水分解物、ヒアルロン酸等の酸性ムコ多糖類、植物抽出物、アルギン酸及び／又はその塩類、等の様々な保湿成分について研究されている（特開昭６１−３７７１０号公報、特開平１０−２７９４６６号公報等参照）が、これら保湿力の高い保湿成分は、不快なべたつきを有しており感触が重くなるという欠点があった。
【０００５】
これらの中でも、前記アルギン酸及び／又はその塩類は、一般に平均重合度が１，０００〜１０，０００程度（平均分子量は４００，０００〜４，０００，０００程度）である（マリンバイオ−海洋バイオ新素材・新物質−、株式会社シーエムシー（１９８９）ｐｐ．２３８）。このような高分子量のアルギン酸及び／又はその塩類は、溶媒に速やかに溶解させることが困難であり、高分子量のアルギン酸及び／又はその塩類が高濃度に溶解すると極めて粘稠な溶液となり、濁りや着色する等の欠点を有し、臭いが気になり、皮膚に直接塗布する皮膚外用剤としては、使用し難いという問題点がある。また、高分子量のアルギン酸及び／又はその塩類は、熱に弱く、機械的衝撃により分子鎖が切断され、溶液の粘度低下を生じる（安定剤とその利用技術（１９８１）ｐｐ．４０８）という問題点もある。
一方、利用面として、高分子量のアルギン酸及び／又はその塩類は、皮膚保護剤に増粘、安定化、使用感（感触）を付与することを目的として用いられている（安定剤とその利用技術（１９８１）ｐｐ．３９９）。
【０００６】
【発明が解決しようとする課題】
本発明は、かかる現状に鑑みてなされたものであり、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、比較的低分子量のアルギン酸及び／又はその塩類を含有する溶解性がよく、使いやすい保湿剤、該保湿剤を配合した、肌の水分を保持し得、肌あれを防止することができる皮膚外用剤を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明者は、前記課題を解決するため鋭意検討を重ねた結果、平均分子量１０，０００〜１００，０００の比較的低分子量のアルギン酸及び／又はその塩類が、溶解性がよく、粘度が低いため使いやすく、優れた保湿効果及び肌あれ改善効果を有しており、これを皮膚外用剤に配合することにより肌の水分を保持し、肌あれを効果的に防止し得ることを知見した。
【０００８】
即ち、前記課題を解決するための手段としては、下記の通りである。
＜１＞ 平均分子量が１０，０００〜１００，０００であるアルギン酸及びその塩類から選ばれる１種又は２種以上を有効成分として含むことを特徴とする保湿剤である。
＜２＞ アルギン酸及び／又はその塩類の平均分子量が４０，０００〜７０，０００である前記＜１＞に記載の保湿剤である。
＜３＞ アルギン酸の塩類が、カリウム塩、ナトリウム塩、アンモニウム塩、及びカルシウム塩から選ばれる前記＜１＞又は＜２＞に記載の保湿剤である。
＜４＞ 前記＜１＞から＜３＞のいずれかに記載の保湿剤を含有してなることを特徴とする皮膚外用剤である。
【０００９】
また、本発明においては、更に下記の態様も好ましい。
＜５＞ アルギン酸及び／又はその塩類が、コンブ、マコンブ、ワカメ、ヒジキ、アラメ、カジメ等の褐藻類を原料とする前記＜１＞から＜３＞のいずれかに記載の保湿剤である。
＜６＞ アルギン酸及び／又はその塩類の１質量％水溶液の粘度が１．５〜３０ｃｐ（２０℃）である前記＜１＞から＜３＞及び＜５＞のいずれかに記載の保湿剤である。
＜７＞ アルギン酸及び／又はその塩類の０．２〜１．０質量％水溶液を用いた生体角層水付加試験における吸水能が５００以上である前記＜１＞から＜３＞及び＜５＞から＜６＞のいずれかに記載の保湿剤である。
＜８＞ アルギン酸及び／又はその塩類の０．２〜１．０質量％水溶液を用いた生体角層水付加試験における水分保持能が絶対値表示で、０．０１５以下である前記＜１＞から＜３＞及び＜５＞から＜７＞のいずれかに記載の保湿剤である。
＜９＞ 保湿剤の配合量が、皮膚外用剤全量に対し乾燥固形分で０．０００５〜１０質量％の範囲である前記＜４＞に記載の皮膚外用剤である。
【００１０】
【発明の実施の形態】
以下、本発明について更に詳しく説明する。
＜保湿剤＞
本発明の保湿剤は、平均分子量が１０，０００〜１００，０００であるアルギン酸及びその塩類から選ばれる１種又は２種以上を有効成分として含有する。
前記アルギン酸及びその塩類は、平均分子量が１０，０００〜１００，０００であれば、その種類、原料及び製法について特に制限されない。従って、本発明で使用するアルギン酸及び／又はその塩類は、天然物由来ものであってもよいし、合成によって得られたものであってもよい。
【００１１】
前記アルギン酸及びその塩類の平均分子量は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）法による測定で１０，０００〜１００，０００が好ましく、４０，０００〜７０，０００がより好ましい。
平均分子量が大きすぎると溶媒に速やかに溶解させることが困難であり、陽イオンとの反応性が高く粘稠な溶液となり、ベタつきの原因となる。一方、分子量が小さすぎると低粘度であるが、使用感、保湿性が乏しい原因となる。
また、前記アルギン酸及び／又はその塩類は、１質量％水溶液にした場合の粘度が１．５〜３０ｃｐ（２０℃）の範囲内にあるものが好ましく、１．５〜１０ｃｐの範囲内にあるものがより好ましい。
【００１２】
ここで、前記アルギン酸は、β−（１→４）−Ｄ−マンヌロン酸（以下、「Ｍ」と略記する）、α−（１→４）−Ｌ−グルクロン酸（以下、「Ｇ」と略記する）の２種類のウロン酸からなる直線状多糖であり、（１）Ｍ−Ｍ結合のみからなるＭブロック、（２）Ｇ−Ｇ結合のみからなるＧブロック、（３）ＭとＧとがランダムに配列したランダムブロック、の３種のブロックが共存するブロックヘテロポリマーであり、そのＭ／Ｇ比は藻の種属、季節、藻体の部分により異なっている。
【００１３】
前記Ｍ及びＧの各ユニットが持つカルボキシル基（−ＣＯＯ）は、イオン交換しやすく、様々な陽イオンと容易にイオン交換することができる。
即ち、前記アルギン酸は、水系において、カルボキシル基（−ＣＯＯ）と対をなす陽イオンの種類により物性が著しく変化する。前記陽イオンとしては、例えば、ナトリウムイオン、カリウムイオン、カルシウムイオン、アルミニウムイオン、アンモニウムイオンなどが挙げられ、これら陽イオンの影響により、高粘度、ゲル化を生じる。この特長を利用し、増粘剤、ゲル化剤、乳化安定剤、皮膜形成剤、保形剤、凝集剤などとして利用されている。また、アルギン酸の平均分子量が大きくなると、陽イオンとの反応性の高いカルボキシル基（−ＣＯＯ）数が多くなるため、陽イオンの影響をより受けやすくなるので、この点からも比較的低分子量のアルギン酸及び／又はその塩が好ましい。
前記アルギン酸塩類としては、カリウム塩、ナトリウム塩及びアンモニウム塩などが挙げられ、これらの中でも、ナトリウム塩が好ましい。
【００１４】
本発明で使用する平均分子量が１０，０００〜１００，０００であるアルギン酸及び／又はその塩類は、例えば、高分子量のアルギン酸を取得した後、これを低分子化することによって容易に調製することができる。
具体的には、高分子量のアルギン酸は、コンブ、マコンブ、ワカメ、ヒジキ、アラメ、カジメ等の褐藻類の細胞間に豊富に含まれている。従って、褐藻類を、例えば、希硫酸で洗浄した後、炭酸ナトリウム溶液で抽出して、硫酸で沈殿させる方法を用いることによって、高分子量のアルギン酸を取得することができる。こうして得られた高分子量のアルギン酸は、公知の方法のいずれかを用いることによって容易に低分子化することができる。例えば、高分子量のアルギン酸に酵素を作用させる方法、アルカリ抽出する方法、次亜塩素酸ナトリウムや過酸化水素などを反応させる方法、熱分解する方法、加圧分解する方法、又はこれらを組み合わせた方法、などを用いて平均分子量が１０，０００〜１００，０００のアルギン酸を調製することができる。
また、低分子量のアルギン酸塩類は、上記のようにして調製した低分子アルギン酸に塩基を作用させることによって得ることができる。
【００１５】
このようにして得られた平均分子量が１０，０００〜１００，０００のアルギン酸及び／又はその塩類は、溶解性が良く、粘度が低いため使いやすい。また、色、臭いがないため皮膚外用剤に配合した際に使用感が良い。なお、本発明のアルギン酸及び／又はその塩類は、汎用されるアルギン酸及び／又はその塩類と比べて平均分子量は低いが、保湿性は良好である。
【００１６】
前記アルギン酸及び／又はその塩類の０．２〜１．０質量％水溶液を用いた生体角層水付加試験における吸水能が５００以上が好ましく、５１０以上がより好ましい。
前記アルギン酸及び／又はその塩類の０．２〜１．０質量％水溶液を用いた生体角層水付加試験における水分保持能が絶対値表示で、０．０１５以下が好ましく、０．０１４６以下が好ましい。
このことは、後述する実施例の結果から明らかである。
【００１７】
なお、本発明のアルギン酸及び／又はその塩類は、単独でも保湿剤になり得るが、他の保湿剤、その他の酸化防止剤、助剤を併用してもよい。
また、製剤化に当たりアラビアガム、デキストリン、ブドウ糖、乳糖、界面活性剤、エタノール、プロピレングリコール、グリセリン等を配合することも、取り扱い性の向上に有効である。
【００１８】
＜皮膚外用剤＞
本発明の皮膚外用剤は、前記本発明の平均分子量が１０，０００〜１００，０００であるアルギン酸及びその塩類から選ばれる１種又は２種以上からなる保湿剤を含有し、優れた保湿効果を有するものである。
ここで、「皮膚外用剤」とは、皮膚に適用される各種薬剤を意味し、例えば、化粧料、医薬部外品、医薬品、等が含まれる。皮膚外用剤の具体例としては、肌に対するものとして、軟膏、パップ、クリーム、乳液、エッセンス、ローション、パック、ゼリー、ファンデーション、マスカラ、アイカラー、アイライナー、リップカラー、リップクリーム、ネイルカラー等を例示でき、頭皮に対するものとして、トニック、リンス、シャンプー、アストリンゼント、ヘアクリーム、ヘアブロー、ヘアフォーム、ヘアスプレー、ヘアジェル等を例示できる。
【００１９】
本発明の皮膚外用剤は通常の外用剤として知られる種々の形態の基剤に配合して調製することができる。
本発明の保湿剤である平均分子量が１０，０００〜１００，０００のアルギン酸及び／又はその塩類の皮膚外用剤への配合量は、皮膚外用剤全量に対し乾燥固形分として、好ましくは０．０００５〜１０質量％の範囲であり、より好ましくは０．０１〜２．０質量％の範囲である。この範囲であれば、優れた保湿効果と肌あれ改善効果が得られる。
なお、本発明の皮膚外用剤には、前記アルギン酸及び／又はその塩類以外にも公知の保湿剤を配合することができる。
【００２０】
本発明の皮膚外用剤には、その形態に応じて、本発明の効果を損なわない範囲で、例えば、収斂剤、殺菌・抗菌剤、美白剤、紫外線吸収剤、細胞賦活剤、消炎・抗アレルギー剤、抗酸化・活性酸素消去剤、精製水、低級アルコール、多価アルコール、油脂、粉体、界面活性剤、色素、防腐剤、香料、等を併用することができる。
【００２１】
以上に説明した本発明の保湿剤及び皮膚外用剤は、ヒトに対して好適に適用されるものであるが、本発明の作用効果が奏される限り、ヒト以外の動物に対して適用されてもよい。
【００２２】
【実施例】
以下、実施例により本発明を更に具体的に説明するが、本発明はこれら例に何ら制約されるものではない。
【００２３】
〔実施例１〕
下記試験試料（１）〜（４）を調製し、その保湿効果を下記試験方法により調べた。
＜試験試料（１）〜（４）＞
（１）陰性コントロール：水
（２）陽性コントロール：０．０５質量％ヒアルロン酸水溶液
（３）１．０質量％低分子量アルギン酸ナトリウム（Ａ）水溶液
平均分子量４０，０００、起源：コンブ科マコンブ（Ｌａｍｉｎａｒｉａｊａｐｏｎｉｃａ ＡＲＥＳＣＨ．）等の褐藻類
（４）１．０質量％低分子量アルギン酸ナトリウム（Ｂ）水溶液
平均分子量７０，０００、起源：コンブ科マコンブ（Ｌａｍｉｎａｒｉａｊａｐｏｎｉｃａ ＡＲＥＳＣＨ．）等の褐藻類
【００２４】
＜試験方法＞
前記各試験試料をパネラーの前腕内側に塗布した後、生体角層水負荷試験（ｉｎ ｖｉｖｏ ｗａｔｅｒ ｓｏｒｐｔｉｏｎ−ｄｅｓｏｒｐｔｉｏｎ ｔｅｓｔ）を行い、吸水能、水分保持能（λ）を求めた。結果を表１及び図１に示す。
【００２５】
ここで、吸水能は、水負荷直後の伝導度（Ｗｍａｘ）から負荷前の伝導度（Ｗ０）を引いたものである。水負荷直後から１２０秒までの伝導度の描く曲線はＷ＝Ｗｍａｘ・ｅ−λｔの指数関数に従っている。λの値は水分放出定数として水分保持能評価で用いられている。この値の絶対値が小さいほど水分保持能が高いことを示す。
測定には皮表角層水分量測定装置（アイ．ビイ．エス株式会社製；ＳＫＩＣＯＮ−２００）を用いた。皮膚コンダクタンス値が大きいほど一般に皮膚の電気抵抗が小さく、皮膚の角層水分含量が多いことが認められている（Ｔ．Ｙａｍａｍｕｒａ， Ｆｒａｇｒａｎｃｅ Ｊｏｕｒｎａｌ， ２１（１０）， ３５−４２（１９９３））。
なお、測定環境は２０℃、ＲＨ＝５０％の恒温恒湿室で行った。
【００２６】
【表１】
〔実施例２〕
下記試験試料（１）〜（４）を調製し、その保湿効果を上記実施例１と同じ試験方法により調べた。結果を表２及び図２に示す。
＜試験試料（１）〜（４）＞
（１）陰性コントロール：水
（２）陽性コントロール：０．０５質量％ヒアルロン酸水溶液
（３）０．５質量％低分子量アルギン酸ナトリウム（Ａ）水溶液
平均分子量４０，０００、起源：コンブ科マコンブ（Ｌａｍｉｎａｒｉａｊａｐｏｎｉｃａ ＡＲＥＳＣＨ．）等の褐藻類
（４）０．２質量％低分子量アルギン酸ナトリウム（Ａ）水溶液
平均分子量４０，０００、起源：コンブ科マコンブ（Ｌａｍｉｎａｒｉａｊａｐｏｎｉｃａ ＡＲＥＳＣＨ．）等の褐藻類
【００２８】
【表２】
表１，２及び図１，２の結果から、平均分子量が４０，０００〜７０，０００であるアルギン酸ナトリウム０．５質量％〜１．０質量％水溶液において優れた吸水能、水分保持能が得られることが認められた。
【００３０】
〔実施例３〕
下記表３に示した処方の対照品及び本発明品５〜７の化粧水を調製し、下記方法により肌への使用試験を行った。
【００３１】
【表３】
＜試験方法＞
２０〜４０代の女性１５名を３群、５名ずつに分け、朝夕１日２回、２週間、洗顔後、右顔面に実施例品を、左顔面に対照品を使用した。その際、使用時の感触、使用後のべたつき、使用２週間後の肌のしっとり感、肌の滑らかさ、肌荒れ改善効果の５項目について下記基準により評価を行った。結果を表４に示す。
【００３３】
−評価基準−
３点を平均点とし、５点が、非常に良好又は改善があった、４点が、良好又は改善があった、２点が、あまり良好でない又はあまり改善がない、１点が、良好でない又は改善なし、とした。
【００３４】
【表４】
【００３５】
〔配合実施例１〕
下記組成の乳液を常法により製造した。
ホホバ油 ４．０ｇ
プラセンタエキス ０．１ｇ
オリーブ油 ２．０ｇ
スクワラン ２．０ｇ
セタノール ２．０ｇ
モノステアリン酸グリセリル ２．０ｇ
ポリオキシエチレンセチルエーテル（２０Ｅ．Ｏ） ２．５ｇ
オレイン酸ポリオキシエチレンソルビタン（２０Ｅ．Ｏ） ２．０ｇ
１．３−ブチレングリコール ３．０ｇ
黄杞葉エキス ０．１ｇ
イチョウ葉エキス ０．１ｇ
グリチルリチン酸ジカリウム ０．１ｇ
コンキオリン ０．１ｇ
オウバクエキス ０．１ｇ
ヒノキチオール ０．１５ｇ
香料 ０．０５ｇ
平均分子量４万のアルギン酸ナトリウム２．５質量％水溶液 ２．０ｇ
精製水 残部（全量を１００ｇとする）
【００３６】
〔配合実施例２〕
下記組成のクリームを常法により製造した。
流動パラフィン ５．０ｇ
ミツロウ ４．０ｇ
セタノール ３．０ｇ
スクワラン １０．０ｇ
ラノリン ２．０ｇ
ステアリン酸 １．０ｇ
オレイン酸ポリオキシエチレンソルビタン（２０Ｅ．Ｏ） １．５ｇ
モノステアリン酸グリセリル ３．０ｇ
１．３−ブチレングリコール ６．０ｇ
パラオキシ安息香酸メチル １．５ｇ
油溶性カンゾウエキス ０．１ｇ
海藻エキス ０．１ｇ
キシロビオースミクスチャー ０．５ｇ
クジンエキス ０．１ｇ
香料 ０．１ｇ
平均分子量６万のアルギン酸ナトリウム５質量％水溶液 ５．０ｇ
精製水 残部（全量を１００ｇとする）
【００３７】
〔配合実施例３〕
下記組成のパックを常法により製造した。
ポリビニルアルコール １５ｇ
ポリエチレングリコール ３ｇ
プロピレングリコール ７ｇ
エタノール １０ｇ
パラオキシ安息香酸エチル ０．０５ｇ
酵母エキス ０．１ｇ
シソエキス ０．１ｇ
ワレモコウエキス ０．１ｇ
シナノキエキス ０．１ｇ
グリチルレチン酸ステアリル ０．１ｇ
香料 ０．０５ｇ
平均分子量７万のアルギン酸ナトリウム５質量％水溶液 １０．０ｇ
精製水 残部（全量を１００ｇとする）
【００３８】
【発明の効果】
本発明によれば、比較的低分子量のアルギン酸及び／又はその塩類を有効成分として含有する溶解性がよく、粘度が低いため使いやすい保湿剤を配合することにより、皮膚の水分保持機能（保湿効果、肌あれ改善効果）に優れた皮膚外用剤を提供できる
【図面の簡単な説明】
【図１】図１は、実施例１の生体角層水負荷試験における時間と伝導度との関係を示すグラフである。
【図２】図２は、実施例２の生体角層水負荷試験における時間と伝導度との関係を示すグラフである。[0001]
TECHNICAL FIELD OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention has a good solubility, containing a relatively low molecular weight alginic acid and / or a salt thereof as an active ingredient, is easy to use, and has an excellent moisturizing effect and a skin roughness improving effect obtained by blending the moisturizing agent. It relates to a skin external preparation.
[0002]
[Prior art]
Conventionally, as moisturizers, water-soluble polyhydric alcohols represented by glycerin, propylene glycol and sorbitol; water-soluble represented by hyaluronic acid and xanthan gum for the purpose of maintaining skin homeostasis and protecting the skin from drying in winter. A natural moisturizing factor typified by a pyrrolidone carboxylate and an amino acid; an intercellular lipid typified by a ceramide, and the like.
[0003]
Although these moisturizers have a certain effect, skin cosmetics containing a water-soluble polyhydric alcohol and a water-soluble polymer often have a sticky feeling at the time of application and immediately after the application, and are necessarily preferable in terms of sensory characteristics. Was not. In addition, skin cosmetics and bath preparations containing natural moisturizing factors and intercellular lipids are restricted by the compounding concentration and compatible preparations when they are added, so that the dosage forms are limited and often do not exhibit sufficient effects. Was.
[0004]
Therefore, in recent years, chitin, chitosan and derivatives thereof, protein hydrolysates, acidic mucopolysaccharides such as hyaluronic acid, plant extracts, alginic acid and / or salts thereof as moisturizing components having a high water retention ability under low humidity. Various moisturizing components have been studied (see, for example, JP-A-61-37710 and JP-A-10-279466), but these moisturizing components having a high moisturizing power have unpleasant stickiness. There was a drawback that the feel was heavy.
[0005]
Among them, the alginic acid and / or salts thereof generally have an average degree of polymerization of about 1,000 to 10,000 (average molecular weight of about 400,000 to 4,000,000) (Marine Bio-Marine Bio New Materials and New Substances, CMC Corporation (1989) pp. 238). Such high molecular weight alginic acid and / or its salts are difficult to dissolve quickly in a solvent, and when the high molecular weight alginic acid and / or its salts are dissolved in a high concentration, it becomes an extremely viscous solution and becomes turbid. It has drawbacks such as discoloration, and it has a problem that it is difficult to use as an external preparation for skin which is directly applied to the skin because of its odor. In addition, high molecular weight alginic acid and / or its salts are weak to heat, molecular chains are cut by mechanical impact, and the viscosity of the solution is reduced (stabilizer and its utilization technology (1981) pp. 408). There is also.
On the other hand, as an application surface, high-molecular-weight alginic acid and / or its salts are used for the purpose of thickening, stabilizing, and imparting a feeling of use (feel) to the skin protective agent (stabilizer and its utilization technology). (1981) pp. 399).
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of such circumstances, and has as its object to solve the above-described various problems in the related art and achieve the following objects. That is, the present invention has a good solubility, contains a relatively low molecular weight alginic acid and / or a salt thereof, and is easy to use. A moisturizer containing the moisturizer, can retain the moisture of the skin, and prevents rough skin. It is an object of the present invention to provide a skin external preparation which can be used.
[0007]
[Means for Solving the Problems]
The present inventor has conducted intensive studies to solve the above problems, and as a result, a relatively low molecular weight alginic acid and / or a salt thereof having an average molecular weight of 10,000 to 100,000 has good solubility and low viscosity. It has been found that it is easy to use and has an excellent moisturizing effect and an effect of improving rough skin. By adding this to an external preparation for skin, the moisture of the skin can be maintained and the rough skin can be effectively prevented.
[0008]
That is, means for solving the above problems are as follows.
<1> A humectant comprising, as an active ingredient, one or more selected from alginic acid having an average molecular weight of 10,000 to 100,000 and salts thereof.
<2> The humectant according to <1>, wherein the alginic acid and / or salts thereof have an average molecular weight of 40,000 to 70,000.
<3> The humectant according to <1> or <2>, wherein the salt of alginic acid is selected from a potassium salt, a sodium salt, an ammonium salt, and a calcium salt.
<4> An external preparation for skin, comprising the humectant according to any one of <1> to <3>.
[0009]
In the present invention, the following embodiments are further preferable.
<5> The humectant according to any one of <1> to <3>, wherein the alginic acid and / or salts thereof are brown algae such as kelp, makombu, wakame, hijiki, alame, squid and the like.
<6> The humectant according to any one of <1> to <3> and <5>, wherein a 1% by mass aqueous solution of alginic acid and / or a salt thereof has a viscosity of 1.5 to 30 cp (20 ° C). .
<7> From the above <1> to <3> and <5>, which have a water absorption capacity of 500 or more in a living body stratum corneum water addition test using a 0.2 to 1.0% by mass aqueous solution of alginic acid and / or salts thereof. The humectant according to any one of <6>.
<8> From the above <1>, in which the water retention ability in a living body stratum corneum water addition test using a 0.2 to 1.0% by mass aqueous solution of alginic acid and / or salts thereof is 0.015 or less in absolute value. The humectant according to any one of <3> and <5> to <7>.
<9> The skin external preparation according to <4>, wherein the amount of the humectant is in the range of 0.0005 to 10% by mass in terms of dry solid content based on the total amount of the skin external preparation.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in more detail.
<Moisturizer>
The humectant of the present invention contains, as an active ingredient, one or more selected from alginic acid having an average molecular weight of 10,000 to 100,000 and salts thereof.
The type, raw material and production method of the alginic acid and salts thereof are not particularly limited as long as the average molecular weight is 10,000 to 100,000. Therefore, alginic acid and / or its salts used in the present invention may be derived from natural products or may be obtained by synthesis.
[0011]
The average molecular weight of the alginic acid and salts thereof is preferably from 10,000 to 100,000, more preferably from 40,000 to 70,000, as measured by GPC (gel permeation chromatography).
If the average molecular weight is too large, it is difficult to rapidly dissolve the compound in a solvent, and a viscous solution having high reactivity with cations is formed, which causes stickiness. On the other hand, if the molecular weight is too small, the viscosity is low, but the feeling of use and the moisture retention are poor.
The alginic acid and / or salts thereof preferably have a viscosity of 1.5 to 30 cp (20 ° C.) in a 1% by mass aqueous solution, and preferably have a viscosity of 1.5 to 10 cp. Is more preferred.
[0012]
Here, the alginic acid is β- (1 → 4) -D-mannuronic acid (hereinafter abbreviated as “M”), α- (1 → 4) -L-glucuronic acid (hereinafter abbreviated as “G”). Is a linear polysaccharide consisting of two types of uronic acids, (1) an M block consisting only of MM bonds, (2) a G block consisting only of GG bonds, and (3) M and G It is a block heteropolymer in which three types of blocks, ie, randomly arranged random blocks, coexist, and its M / G ratio differs depending on the species of alga, the season, and the alga body.
[0013]
The carboxyl group (—COO) of each of the M and G units is easily ion-exchanged and easily ion-exchanged with various cations.
That is, the physical properties of the alginic acid significantly change in an aqueous system depending on the type of a cation paired with a carboxyl group (—COO). Examples of the cation include a sodium ion, a potassium ion, a calcium ion, an aluminum ion, an ammonium ion, and the like, and high viscosity and gelation are caused by the influence of these cations. Utilizing this feature, it is used as a thickener, a gelling agent, an emulsion stabilizer, a film-forming agent, a shape-retaining agent, a flocculant and the like. In addition, when the average molecular weight of alginic acid increases, the number of carboxyl groups (—COO) having high reactivity with cations increases, so that it becomes more susceptible to cations. Alginic acid and / or its salts are preferred.
Examples of the alginate salts include a potassium salt, a sodium salt, and an ammonium salt, and among them, a sodium salt is preferable.
[0014]
The alginic acid and / or salts thereof having an average molecular weight of 10,000 to 100,000 used in the present invention can be easily prepared by, for example, obtaining a high molecular weight alginic acid and reducing the molecular weight of the alginic acid. it can.
Specifically, high molecular weight alginic acid is abundantly contained between cells of brown algae such as kelp, makombu, wakame, hijiki, alame, squid and the like. Therefore, a high-molecular-weight alginic acid can be obtained by using a method in which brown algae are washed with, for example, diluted sulfuric acid, extracted with a sodium carbonate solution, and precipitated with sulfuric acid. The high molecular weight alginic acid thus obtained can be easily reduced in molecular weight by using any of the known methods. For example, a method of allowing an enzyme to act on high molecular weight alginic acid, a method of extracting with alkali, a method of reacting sodium hypochlorite or hydrogen peroxide, a method of thermal decomposition, a method of pressure decomposition, or a method combining these , Etc., can be used to prepare alginic acid having an average molecular weight of 10,000 to 100,000.
Further, low molecular weight alginates can be obtained by allowing a base to act on the low molecular weight alginic acid prepared as described above.
[0015]
The thus-obtained alginic acid having an average molecular weight of 10,000 to 100,000 and / or salts thereof has good solubility and low viscosity, and thus is easy to use. In addition, since it has no color or odor, it has a good feeling when used in an external preparation for skin. The alginic acid and / or salts thereof of the present invention have a low average molecular weight as compared with commonly used alginic acids and / or salts thereof, but have good moisture retention.
[0016]
The water absorption capacity in a living body stratum corneum water addition test using a 0.2 to 1.0% by mass aqueous solution of the alginic acid and / or salts thereof is preferably 500 or more, and more preferably 510 or more.
The absolute value of the water retention capacity in a living body stratum corneum water addition test using a 0.2 to 1.0% by mass aqueous solution of the alginic acid and / or salts thereof is preferably 0.015 or less, and more preferably 0.0146 or less. .
This is clear from the results of the examples described later.
[0017]
The alginic acid and / or salts thereof of the present invention can be used alone as a humectant, but may be used in combination with other humectants, other antioxidants and auxiliaries.
It is also effective to improve handleability to mix gum arabic, dextrin, glucose, lactose, a surfactant, ethanol, propylene glycol, glycerin and the like in the formulation.
[0018]
<Skin external preparation>
The external preparation for skin of the present invention contains a humectant consisting of one or more selected from alginic acid and salts thereof having an average molecular weight of 10,000 to 100,000 of the present invention, and has an excellent moisturizing effect. Have
Here, the “skin external preparation” means various drugs applied to the skin, and includes, for example, cosmetics, quasi-drugs, pharmaceuticals, and the like. Specific examples of skin external preparations include, for skin, ointments, cataplasms, creams, emulsions, essences, lotions, packs, jellies, foundations, mascaras, eye colors, eyeliners, lip colors, lip balms, nail colors, etc. Examples of the scalp include tonic, rinse, shampoo, astringent, hair cream, hair blow, hair foam, hair spray, and hair gel.
[0019]
The external preparation for skin of the present invention can be prepared by mixing with various types of bases known as ordinary external preparations.
The amount of alginic acid and / or a salt thereof having an average molecular weight of 10,000 to 100,000, which is the humectant of the present invention, in the skin external preparation is preferably 0.0005 as a dry solid content based on the total amount of the skin external preparation. The range is from 10 to 10% by mass, and more preferably from 0.01 to 2.0% by mass. Within this range, an excellent moisturizing effect and an effect of improving skin roughness can be obtained.
The external preparation for skin of the present invention may contain a known moisturizer in addition to the alginic acid and / or its salts.
[0020]
Depending on the form, the external preparation for skin of the present invention may be, for example, an astringent, a bactericidal / antibacterial agent, a whitening agent, an ultraviolet absorber, a cell activator, an anti-inflammatory / antiallergic agent within a range that does not impair the effects of the present invention. Agents, antioxidants and active oxygen scavengers, purified water, lower alcohols, polyhydric alcohols, fats and oils, powders, surfactants, pigments, preservatives, fragrances and the like can be used in combination.
[0021]
The moisturizing agent and the skin external preparation of the present invention described above are preferably applied to humans, but are applied to non-human animals as long as the effects of the present invention are exerted. Is also good.
[0022]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[0023]
[Example 1]
The following test samples (1) to (4) were prepared, and their moisturizing effects were examined by the following test methods.
<Test samples (1) to (4)>
(1) Negative control: water (2) Positive control: 0.05% by mass hyaluronic acid aqueous solution (3) 1.0% by mass low molecular weight sodium alginate (A) aqueous solution Average molecular weight 40,000, Origin: Laminaria japonica (4) 1.0 mass% low molecular weight sodium alginate (B) aqueous solution, average molecular weight 70,000, origin: brown algae such as Laminaria japonica ARESCH.
<Test method>
After applying each of the test samples to the inside of the forearm of the panel, a water stratification test (in vivo water sorption-desorption test) was performed to determine the water absorption capacity and water retention capacity (λ). The results are shown in Table 1 and FIG.
[0025]
Here, water absorption capacity is obtained by subtracting the immediately water loading conductivity (W max) from the load before the conductivity of the (W 0). The curve drawn by the conductivity from immediately after the water load to 120 seconds follows an exponential function of W = W max · e −λt . The value of λ is used as a water release constant in the evaluation of water retention capacity. The smaller the absolute value of this value, the higher the water retention ability.
A skin surface horny layer moisture content measuring device (SKICON-200, manufactured by I.B.S. Co., Ltd.) was used for the measurement. It has been recognized that the higher the skin conductance value, the lower the electrical resistance of the skin generally and the higher the water content of the stratum corneum (T. Yamamura, Fragrance Journal, 21 (10), 35-42 (1993)).
The measurement was performed in a constant temperature and humidity room at 20 ° C. and RH = 50%.
[0026]
[Table 1]
[Example 2]
The following test samples (1) to (4) were prepared, and their moisturizing effects were examined by the same test method as in Example 1 above. The results are shown in Table 2 and FIG.
<Test samples (1) to (4)>
(1) Negative control: water (2) Positive control: 0.05% by mass hyaluronic acid aqueous solution (3) 0.5% by mass low molecular weight sodium alginate (A) aqueous solution Average molecular weight 40,000, Origin: Laminaria japonica Brown alga (4) 0.2 mass% low molecular weight sodium alginate (A) aqueous solution average molecular weight 40,000, origin: brown algae such as Laminaria japonica ARESCH.
[Table 2]
From the results in Tables 1 and 2, and FIGS. 1 and 2, excellent water absorption and water retention were obtained in a 0.5% to 1.0% by weight aqueous solution of sodium alginate having an average molecular weight of 40,000 to 70,000. It was recognized that
[0030]
[Example 3]
Control lotions having the formulations shown in Table 3 below and the lotions of the products 5 to 7 of the present invention were prepared and subjected to a skin use test by the following method.
[0031]
[Table 3]
<Test method>
Fifteen women in their 20s and 40s were divided into three groups and five women. After washing the face twice a day for two weeks in the morning and evening, the example product was used on the right face and the control product was used on the left face. At that time, the following criteria were used to evaluate the following five criteria: feel during use, stickiness after use, moist feeling of skin after two weeks of use, smoothness of skin, and effect of improving skin roughness. Table 4 shows the results.
[0033]
-Evaluation criteria-
3 points were averaged, 5 points were very good or improved, 4 points were good or improved, 2 points were not very good or little improved, and 1 point was not good Or, there was no improvement.
[0034]
[Table 4]
[0035]
[Formulation Example 1]
An emulsion having the following composition was produced by a conventional method.
Jojoba oil 4.0 g
Placenta extract 0.1g
Olive oil 2.0g
Squalane 2.0g
2.0 g of Cetanol
Glyceryl monostearate 2.0 g
2.5 g of polyoxyethylene cetyl ether (20EO)
2.0 g of polyoxyethylene sorbitan oleate (20EO)
1.3-butylene glycol 3.0 g
Yellow ginger extract 0.1g
Ginkgo biloba extract 0.1g
Dipotassium glycyrrhizinate 0.1 g
Conchiolin 0.1g
Oubaku extract 0.1 g
Hinokitiol 0.15g
Spice 0.05g
2.5g% aqueous solution of sodium alginate with average molecular weight of 40,000g
Remaining purified water (total amount is 100 g)
[0036]
[Formulation Example 2]
A cream having the following composition was produced by a conventional method.
Liquid paraffin 5.0 g
Beeswax 4.0g
3.0 g of cetanol
Squalane 10.0g
Lanolin 2.0g
1.0 g of stearic acid
1.5 g of polyoxyethylene sorbitan oleate (20EO)
Glyceryl monostearate 3.0 g
1.3-butylene glycol 6.0 g
1.5 g of methyl paraoxybenzoate
Oil-soluble Licorice extract 0.1 g
Seaweed extract 0.1g
Xylobiose mixture 0.5g
Kujin extract 0.1g
Spice 0.1g
5.0 g of a 5% by mass aqueous solution of sodium alginate having an average molecular weight of 60,000
Remaining purified water (total amount is 100 g)
[0037]
[Compounding Example 3]
A pack having the following composition was produced by a conventional method.
15 g of polyvinyl alcohol
3 g of polyethylene glycol
7 g of propylene glycol
10 g of ethanol
Ethyl paraoxybenzoate 0.05g
Yeast extract 0.1g
Perilla extract 0.1 g
Waremokou Extract 0.1g
Linden extract 0.1g
Stearyl glycyrrhetinate 0.1 g
Spice 0.05g
Sodium alginate 5 mass% aqueous solution with average molecular weight of 70,000 10.0 g
Remaining purified water (total amount is 100 g)
[0038]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the water retention function of skin (moisturizing effect) is contained by mix | blending a good solubility which has relatively low molecular weight alginic acid and / or its salt as an active ingredient, and has a low viscosity and is easy to use. Skin external preparation with excellent skin roughness improvement effect) [Brief description of drawings]
FIG. 1 is a graph showing a relationship between time and conductivity in a living body stratum corneum water load test of Example 1.
FIG. 2 is a graph showing a relationship between time and conductivity in a living body stratum corneum water load test of Example 2.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002240497A JP2004075635A (en) | 2002-08-21 | 2002-08-21 | Moisturizing agent and external preparation for skin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002240497A JP2004075635A (en) | 2002-08-21 | 2002-08-21 | Moisturizing agent and external preparation for skin |
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| Publication Number | Publication Date |
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| JP2004075635A true JP2004075635A (en) | 2004-03-11 |
Family
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| JP2002240497A Pending JP2004075635A (en) | 2002-08-21 | 2002-08-21 | Moisturizing agent and external preparation for skin |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008115098A (en) * | 2006-11-02 | 2008-05-22 | Hoyu Co Ltd | Moisturizer for skin and external preparation for skin |
| JP2009057343A (en) * | 2007-09-03 | 2009-03-19 | Kikkoman Corp | Sodium absorption inhibition composition |
| JP2009149734A (en) * | 2007-12-19 | 2009-07-09 | Kao Corp | Method for producing low molecular weight alginic acid or a derivative thereof |
| WO2010084734A1 (en) * | 2009-01-20 | 2010-07-29 | 花王株式会社 | Purified alginic acid or salt thereof |
| CN101104649B (en) * | 2006-07-12 | 2011-05-18 | 谭攸恒 | Potassium alginate and composition thereof |
| JP2015529679A (en) * | 2012-09-14 | 2015-10-08 | イーエルシー マネージメント エルエルシー | Methods and compositions for improving selective degradation metabolism in keratin surface cells |
| JP2019023191A (en) * | 2012-08-13 | 2019-02-14 | ビーエーエスエフ ビューティ ケア ソリューションズ フランス エスエーエスＢＡＳＦ Ｂｅａｕｔｙ Ｃａｒｅ Ｓｏｌｕｔｉｏｎｓ Ｆｒａｎｃｅ Ｓ．Ａ．Ｓ． | Moisturizing ingredients for cosmetics or pharmaceuticals |
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