JP4126819B2 - Skin cosmetics - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は化粧水、乳液、クリーム、パック等の皮膚用の化粧料に関し、さらに詳しくは使用時の感触が軽く使用後もべたつかず、保湿効果の持続性および水洗い後の保湿効果に優れ、肌荒れ改善効果、しわとり効果に優れるとともに肌にはりを与え、経時安定性にも優れる皮膚化粧料に関する。
【０００２】
【従来の技術】
通常、人の皮膚表面は皮脂膜に覆われていて水分の蒸散が適度に抑制されている。そして、皮膚の水分を適切な範囲に保つことは皮膚の健康の面から見て非常に大切なことであり、水分が不足すると肌荒れ等を生じやすくなる。洗顔や入浴を行うと一時的に皮脂膜が取り除かれてしまい肌の水分が失われやすくなることから化粧水、乳液、クリーム、美容液等の保湿化粧料を使用して水分を補う必要がある。
ここで、一般に化粧料には保湿剤としてグリセリン、１，３−ブチレングリコール、ソルビトール等の多価アルコールやピロリドンカルボン酸塩等が配合されているが、これらは高湿度下における水分保持力には優れているものの低湿度下における水分保持力に難があり、保湿効果の持続性が保てなかった。
【０００３】
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、キトサンおよびそれらの誘導体、蛋白加水分解物、ヒアルロン酸等の酸性ムコ多糖類、植物抽出物等様々な物質が研究されているが、これら保湿力の高い保湿成分は不快なベタツキを有しており、感触が重くなるという欠点があった。また、これら成分は一般に水溶性であることから使用後に水洗い等をすると簡単に流れ落ちてしまい、再度使用しないと保湿効果が得られなかった。それらの中で、木通（モクツウ）はアケビまたはその他同属植物の蔓性の茎を採取し、輪切りにして乾燥させたもの等を古来より漢方薬の成分として用いられてきた生薬であり、ストレス胃潰瘍発生予防効果｛薬第９５巻１１７９頁（１９７５年）｝、利尿作用｛Ｃｈｅｍ．Ｐｈａｒ．Ｂｕｌｌ．第２７巻１４６４頁（１９７９年）｝、抗炎症作用｛日本薬学会第９０年会発表講演要旨集（１９７０年）｝を有することが公知である。そして、特開昭６４−４２４１１号公報および特開平８−１３３９５６号公報においてその抽出エキスが高い美白効果を有することが示されており、その抽出エキスを使用した美白効果の高い化粧料や皮膚外用剤が提案されている。さらに、特開平１０−７５８１号公報において木通（モクツウ）の抽出エキスが皮膚保湿能力を高める作用を有することが示されており、その抽出エキスを含有した保湿効果の高い皮膚外用剤が提案されている。また、レンゲソウはマメ科の２年草であり、この抽出エキスにおいても高い保湿作用、美白作用、細胞賦活作用等を有することが判っている。そして、特開平１−１１７８１４号公報においてこのエキスを使用した化粧料が提案されている。しかし、これら木通抽出エキスやレンゲソウ抽出エキスを配合した化粧料や皮膚外用剤は、経時で着色や沈殿を生じたりして安定性が悪いだけでなく少なからずべたつきを有して感触が悪くなり易く、しかも肌荒れ改善効果や肌にはりを与える効果が弱かった。さらに、使用後に水洗い等をすると保湿効果が損なわれた。
【０００４】
一方、２−メタクリロイルオキシエチルホスホリルコリン（以下ＭＰＣとする）は生体膜の主成分であるリン脂質（ホスファチジルコリン）の極性基と同一の構造を有するモノマーであり、そのホモポリマーおよび他の疎水性モノマーや親水性モノマーとのコポリマーは高い保湿作用と被膜形成能を有することが報告されている。しかし、これらのＭＰＣ含有ポリマーは高い保湿作用と被膜形成能を有することから皮膚に塗布すると水分の蒸散とともに引っかかりを生じてのびが悪くなるという欠点があった。ＭＰＣ含有ポリマーを使用した化粧料としては特開平５−７０３２１号公報、特開平６−１５７２６９号公報、特開平６−１５７２７０号公報および特開平６−１５７２７１号公報等に記載の化粧料があるが、いずれも使用時ののびが悪いだけでなく、肌にはりを与える効果やしわとり効果が弱かった。
【０００５】
【発明が解決しようとする課題】
本発明は上記課題を解決し、使用時の感触が軽く使用後もべたつかず、保湿効果の持続性および水洗い後の保湿効果に優れ、肌荒れ改善効果およびしわとり効果に優れるとともに肌にはりを与え、経時安定性にも優れる皮膚化粧料を提供することを目的とする。
【０００６】
【課題を解決するための手段】
すなわち本発明は、ａ．木通（モクツウ）またはレンゲソウの抽出エキスを乾燥残留物として０．００００５〜２重量％、ｂ．式（Ｉ）で示される化合物と（メタ）アクリル酸アルキルエステルを重量比で１００／０〜１０／９０として６０〜１００重量％含有する単量体を重合してなるポリマー０．００１〜１０重量％含有することを特徴とする皮膚化粧料であり、また、さらにｃ．多価アルコールまたはその部分エステル化合物０．１〜３０重量％含有することを特徴とする皮膚化粧料である。
【０００７】
【化２】
（Ｒ1は水素原子またはメチル基、Ｒ2、Ｒ3およびＲ4は炭素数１〜８のアルキル基、ｎは２〜４である。）
【０００９】
【発明の実施の形態】
本発明に用いられる木通の抽出エキスは、アケビの蔓性の茎をそのままもしくは乾燥後に炭化水素、エステル、ケトン、エーテル、ハロゲン化炭化水素、アルコールおよび水から選ばれる１種または２種以上と共に加熱還流あるいは浸漬して得られるが、好ましくは水またはエタノール、プロピルアルコール、イソプロピルアルコール、ブタノールなどのアルコールの１種または２種以上で抽出したものであり、更に好ましくは水で抽出したものである。
【００１０】
また、本発明に用いられるレンゲソウの抽出エキスは、マメ科レンゲソウの全草または種子をそのままもしくは乾燥後に炭化水素、エステル、ケトン、エーテル、ハロゲン化炭化水素、アルコールおよび水から選ばれる１種または２種以上と共に加熱還流あるいは浸漬して得るが、好ましくは水またはエタノール、プロピルアルコール、イソプロピルアルコール、１，３−ブチレングリコールなどのアルコールの１種または２種以上で抽出したものであり、更に好ましくは水、エタノール、１，３−ブチレングリコールの１種または２種以上の混合液で抽出したものである。
本発明の木通またはレンゲソウの抽出エキスとは抽出溶液そのものもしくはその濃縮物を言う。
【００１１】
本発明に用いられる式（Ｉ）で示される化合物において、Ｒ1は水素原子またはメチル基であり、Ｒ2、Ｒ3およびＲ4は炭素数１〜８のアルキル基であり、ｎは２〜４である。その中でも好ましくは式（ＩＩ）で示される２−メタクリロイルオキシエチルホスホリルコリン（ＭＰＣ）である。
【００１２】
【化３】
ｂ．成分であるポリマーは式（Ｉ）で示される化合物と（メタ）アクリル酸アルキルエステルを重量比で１００／０〜１０／９０の構成比として含有し、好ましくは１００／０〜３０／７０、更に好ましくは９５／５〜５０／５０の構成比として含有するポリマー（以下ＰＣポリマーとする）である。そして、ＰＣポリマー中の式（Ｉ）で示される化合物と（メタ）アクリル酸アルキルエステルの量は合わせて６０〜１００重量％であり、好ましくは７０〜１００重量％、更に好ましくは８０〜１００重量％である。上記の範囲をはずれると、保湿効果の持続性、水洗い後の保湿効果および肌荒れ改善効果が悪くなる。
また、ＰＣポリマーの重量平均分子量は１０，０００〜１０，０００，０００が好ましく、更に好ましくは５０，０００〜１，０００，０００である。
【００１４】
式（Ｉ）で示される化合物および（メタ）アクリル酸アルキルエステルが１００重量％とならない場合は、式（Ｉ）で示される化合物および（メタ）アクリル酸アルキルエステルと他の単量体を共重合させることができる。
式（Ｉ）で示される化合物および（メタ）アクリル酸アルキルエステルと共重合性を有する他の単量体は付加重合可能な二重結合を有する化合物であり、本発明の効果を損なわないものであればよく、例えばエチレン、プロピレン、ブテン、イソブテン、スチレン等のオレフィン性炭化水素およびそれらの異性化オレフィン、多量化オレフィン、またはこれらに各種誘導体を導入したオレフィン性化合物；アクリル酸、メタクリル酸、ビニル酢酸、イタコン酸、クロトン酸、マレイン酸、フマル酸等のエチレン性不飽和カルボン酸およびそれらの多量体、無水物、炭素数１〜６の１価アルコール以外のアルコールとのエステル、またはこれらにカルボニル基、アミノ基、シアノ基、ニトリル基などを導入したエチレン性不飽和カルボン酸誘導体；ビニルアルコールおよびこれと各種カルボン酸とのエステル、各種アルコールとのエーテル、またはこれらにカルボニル基、アミノ基、シアノ基、ニトリル基などを導入したエチレン性不飽和カルボン酸誘導体、ビニルアルコールおよびこれらに各種カルボン酸とのエステル、各種アルコールとのエーテル、またはこれらにカルボニル基、アミノ基、シアノ基、ニトリル基などを導入したビニルアルコール誘導体などが挙げられる。
【００１５】
（メタ）アクリル酸アルキルエステルを構成するアルコールはメチルアルコール、エチルアルコール、プロピルアルコール、イソプロピルアルコール、ブチルアルコール、イソブチルアルコール、ｔｅｒｔ−ブチルアルコールなどの炭素数１〜１８のアルコールであり、好ましくは炭素数２〜１２のアルコール、更に好ましくは炭素数３〜４のアルコールである。
【００１６】
本発明に用いられるｃ．成分は、例えばエチレングリコール、プロピレングリコール、ジプロピレングリコール、グリセリン、ジグリセリン、ポリグリセリン、１，３−ブチレングリコール、ポリエチレングリコール、ソルビトール等の多価アルコールまたはそれら多価アルコールの酢酸、硫酸、燐酸、脂肪酸等の部分エステル化合物であり、好ましくは多価アルコールまたはその脂肪酸の部分エステル化合物である。
【００１７】
本発明のａ．成分である木通の抽出エキスは組成物全量中に乾燥残留物として０．００００５〜２重量％であり、好ましくは０．０００１〜１．５重量％、更に好ましくは０．０００５〜１重量％である。０．００００５重量％未満では保湿効果の持続性、肌荒れ改善効果、しわとり効果が弱くなり、２重量％を超えると経時安定性に問題を生じるだけでなくコスト的に不利である。ただし、本発明でいう乾燥残留物とは通常抽出エキスを１０５℃で乾燥して溶媒を除去した時の残留物である溶質を指すが、抽出溶媒が不揮発性の場合にはガスクロマトグラフや高速液体クロマトグラフ等により溶媒量を定量した値から溶質量を計算値として求め、乾燥残留物量と見なす。
【００１８】
本発明のｂ．成分であるＰＣポリマーは組成物全量中に０．００１〜１０重量％であり、好ましくは０．００５〜７重量％、更に好ましくは０．０１〜５重量％である。０．００１重量％未満では肌荒れ改善効果および肌にはりを与える効果が弱くなるとともに水洗いした後の保湿性が弱くなり、１０重量％を超えるとぬめりやべたつきを有して感触が悪くなる。
【００１９】
一方、本発明においては皮膚化粧料の性能および使用感の更なる向上の為にｃ．成分である多価アルコールまたはその部分エステル化合物を組成物全量中に０．１〜３０重量％配合することが好ましく、更に好ましくは１〜２０重量％である。すなわち、０．１％以上配合すると肌にはりを与える効果および肌荒れ改善効果が向上するが、３０重量％を超えると使用時の感触が悪くなるとともにべたつきを有する。
【００２０】
なお、本発明の皮膚化粧料には、化粧料に常用されている添加剤を本発明の性能を損なわない範囲で配合することができる。例えばエタノール、イソプロピルアルコール等の低級アルコール、流動パラフィン、流動イソパラフィン、スクワラン、ワセリン、固形パラフィン等の炭化水素系油、牛脂、豚脂、魚油等の天然油脂、トリ２−エチルヘキサン酸グリセリル等の合成トリグリセライド、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、パルミチン酸セチル、オレイン酸エチル、オレイン酸オレイル、ミリスチン酸オクチルドデシル等のエステル油、ミツロウ、カルナバロウ等のロウ、直鎖および環状のジメチルポリシロキサン、ポリエーテル変性ジメチルポリシロキサン、アミノ変性ジメチルポリシロキサン等のシリコーン誘導体、セラミド、コレステロール、蛋白誘導体、ラノリン、ラノリン誘導体、レシチン等の油性基剤、せっけん、アシルメチルタウリン塩、アミドエーテル硫酸エステル塩等の陰イオン性界面活性剤、アミドアミノ酸塩、アミドプロピルジメチルアミノ酢酸ベタイン等の両性界面活性剤、ポリオキシエチレンアルキルエーテル、アルキルポリグルコシド、アルカノールアミド等の非イオン性界面活性剤、塩化アルキルトリメチルアンモニウム等の陽イオン性界面活性剤、アルキルジメチルアミンオキシド等の半極性界面活性剤、アルギン酸、カルボキシビニルポリマー、カルボキシメチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシエチルセルロース、ヒアルロン酸、キサンタンガム等の水溶性高分子、ピロリドンカルボン酸塩、クエン酸塩、リンゴ酸塩、食塩等の有機または無機塩、ｐＨ調製剤である酸およびアルカリ、殺菌剤、キレート剤、抗酸化剤、紫外線吸収剤、動植物由来の天然エキス、色素および香料等を配合できる。
【００２１】
【実施例】
次に実施例によって本発明を更に詳細に説明する。
実施例１〜７および比較例１〜７
表１〜表２に示す透明または半透明化粧水である皮膚化粧料を調整し、下記の方法により評価を行なった。ただし、添加成分として表３に示す４成分を共通添加成分Ａとして使用した。結果を表１〜２に示す。
また、使用した木通抽出エキスは次のようにして調製した。すなわち、木通の茎乾燥後粉砕物３０ｇに３００ｍｌの水を加えて７０℃に加熱し、還流しながら３時間温浸した後濾過して木通抽出エキスを得た。なお、該エキスを１０５℃で乾燥させた時の乾燥残留物は１．３％であった。一方、レンゲソウ抽出エキスは一丸ファルコス（株）製「ファルコレックスレンゲソウ」を使用した。そして、該エキスを１０５℃で乾燥させた時の乾燥残留物は１．１％であった。
【００２２】
【表１】
１）ＭＰＣ８０重量％、メタクリル酸ブチル２０重量％の構成単位で重量平均分子量約７０万の共重合体
２）ＭＰＣ７０重量％、メタクリル酸ブチル３０重量％の構成単位で重量平均分子量約１００万の共重合体
３）ＭＰＣ６０重量％、メタクリル酸プロピル３０重量％、酢酸ビニル１０重量％の構成単位で重量平均分子量約８０万の共重合体
４）ＭＰＣ１００重量％の構成単位で重量平均分子量約１００万の共重合体
５）ＭＰＣ５重量％、メタクリル酸ブチル９５重量％の構成単位で重量平均分子量約７０万の共重合体
６）紀文フードケミファ（株）製 「ヒアルロン酸ナトリウム ＦＣＨ−２００」
【００２４】
【表２】
１）ＭＰＣ８０重量％、メタクリル酸ブチル２０重量％の構成単位で重量平均分子量約７０万の共重合体
２）ＭＰＣ７０重量％、メタクリル酸ブチル３０重量％の構成単位で重量平均分子量約１００万の共重合体
３）ＭＰＣ６０重量％、メタクリル酸プロピル３０重量％、酢酸ビニル１０重量％の構成単位で重量平均分子量約８０万の共重合体
４）ＭＰＣ１００重量％の構成単位で重量平均分子量約１００万の共重合体
５）ＭＰＣ５重量％、メタクリル酸ブチル９５重量％の構成単位で重量平均分子量約７０万の共重合体
６）紀文フードケミファ（株）製 「ヒアルロン酸ナトリウム ＦＣＨ−２００」
【００２６】
【表３】
（１）使用時の感触
２０名の女性（２０才〜３５才）をパネラーとし、洗顔した後に皮膚化粧料を使用した時の感触について下記のように判定し、２０名の平均値を求めて、平均値１．５点以上を使用時の感触の軽い化粧料であると評価した。
２点：使用時ののびが良く、ひっかからずに軽い感触であると感じた場合。
１点：使用時ののびがやや悪く、ややひっかかると感じた場合。
０点：使用時ののびが悪く、ひっかかり重い感触であると感じた場合。
【００２８】
（２）使用後のべたつき
２０名の女性（２０才〜３５才）をパネラーとし、洗顔した後に皮膚化粧料を使用して１０分後の肌の感触について下記のように判定し、２０名の平均値を求めて、平均値１．５点以上を使用後にべたつきがない化粧料であると評価した。２点：肌がべたつきが無いと感じた場合。
１点：肌がややべたつくと感じた場合。
０点：肌が非常にべたつくと感じた場合。
【００２９】
（３）保湿効果の持続性
２０名の女性（２０才〜３５才）をパネラーとし、洗顔した後に皮膚化粧料を使用し、２時間後の肌のうるおいについて下記のように判定し、２０名の平均値を求めて、平均値１．５点以上を保湿効果の持続性の良好な化粧料であると評価した。
２点：使用直後と変わらず肌が十分うるおっていると感じた場合。
１点：使用直後と比べてやや肌のうるおいが足りないと感じた場合。
０点：使用直後と比べて明らかに肌のうるおいが足りないと感じた場合。
【００３０】
（４）水洗い後の保湿効果
２０名の女性（２０才〜３５才）をパネラーとし、洗顔した後に化粧料を使用してから１０分後に水のみで再度洗顔し、更に１０分後の肌のうるおいについて下記のように判定し、２０名の平均値を求めて、平均値１．５点以上を水洗い後の保湿効果の良好な化粧料であると評価した。
２点：肌が十分うるおっていると感じた場合。
１点：やや肌がうるおっていると感じた場合。
０点：肌のうるおいが足りないと感じた場合。
【００３１】
（５）肌荒れ改善効果
肌荒れを生じた１０名の女性（２４才〜３３才）をパネラーとし、皮膚化粧料を一日２回ずつ連続２週間使用した時の肌の状態について下記のように判定し、２０名の平均値を求めて、平均値１．５点以上を肌荒れ改善効果のある化粧料であると評価した。
２点：肌荒れが明らかに治ってきたと感じた場合。
１点：肌荒れがやや治ってきたと感じた場合。
０点：肌荒れ改善効果が全く見られないと感じた場合。
【００３２】
（６）しわとり効果
２０名の女性（２０才〜３５才）をパネラーとし、皮膚化粧料を一日２回ずつ連続２週間使用した時の肌の状態について官能で下記のように判定し、２０名の平均値を求めて、平均値１．５点以上をしわとり効果のある化粧料であると評価した。
２点：しわが明らかに目立たなくなったと感じた場合。
１点：しわがやや目立たなくなったと感じた場合。
０点：しわとり効果が全く無いと感じた場合。
【００３３】
（７）肌のはり
２０名の女性（２０才〜３５才）をパネラーとし、皮膚化粧料を一日２回ずつ連続２週間使用した時の肌の状態について官能で下記のように判定し、２０名の平均値を求めて、平均値１．５点以上を肌にはりを与える効果のある化粧料であると評価した。
２点：明らかに肌にはりがでたと感じた場合。
１点：やや肌にはりがでたと感じた場合。
０点：肌にはりがでないと感じた場合。
【００３４】
（８）経時安定性
化粧料を透明ガラス容器に密封して０℃、２５℃および４０℃で３ヶ月間保存し、その外観を観察して、下に示す３段階で評価した。
○：安定性良好（いずれの温度でも外観の変化がない。）
△：安定性やや不良（いずれかの温度において若干おり、沈殿を生じるかまたは若干着色を生じる。）
×：安定性不良（いずれかの温度においており、沈殿を生じるかまたは分離する。もしくは着色が著しい。）
【００３５】
実施例１〜７より、本発明の成分を用いた化粧水はいずれも使用時の感触が軽く使用後もべたつかず、保湿効果の持続性および水洗い後の保湿効果に優れ、肌荒れ改善効果、しわとり効果に優れるとともに肌にはりを与え、経時安定性にも優れていた。
一方、比較例１〜７では十分な性能が得られていない。つまり、比較例１ではａ．成分が配合されていないことから保湿効果の持続性が悪くなるとともに肌荒れ改善効果およびしわとり効果が弱くなっており、比較例２ではｂ．成分が配合されていないことから肌荒れ改善効果、肌にはりを与える効果が弱くなるとともに水洗い後の保湿効果が弱くなっている。また、比較例３ではｂ．成分が本発明の範囲を超えて配合されていることから、使用時ののびが極端に悪くなっており、比較例４、比較例５ではｂ．成分の構成比が本発明の範囲を外れていることから保湿効果の持続性、肌荒れ改善効果および水洗い後の保湿効果が悪くなっている。さらに、比較例６、比較例７ではｂ．成分に変えてムコ多糖類であるヒアルロン酸ナトリウムが配合されていることから使用後のべたつき、肌荒れ改善効果、肌にはりを与える効果が弱くなるとともに水洗い後の保湿効果が弱くなっている。
【００３６】
実施例８〜１０
表４に示す水中油型乳液である皮膚化粧料を調整し、実施例１〜７と同様の方法により評価を行なった。ただし、添加成分として表５に示す１１成分を共通添加成分Ｂとして使用し、木通抽出エキス、レンゲソウ抽出エキスには実施例１〜７と同じものを使用した。結果を表４に示す。
【００３７】
【表４】
１）ＭＰＣ８０重量％、メタクリル酸ブチル２０重量％の構成単位で重量平均分子量約７０万の共重合体
２）ＭＰＣ７０重量％、メタクリル酸ブチル３０重量％の構成単位で重量平均分子量約１００万の共重合体
３）分子量１５４０
４）分子量４０００
【００３９】
【表５】
実施例８〜１０より、本発明の乳液はいずれも使用時の感触が軽く使用後もべたつかず、保湿効果の持続性および水洗い後の保湿効果に優れ、肌荒れ改善効果、しわとり効果に優れるとともに肌にはりを与え、経時安定性にも優れていた。
【００４１】
実施例１１〜１２
表４に示す水中油型乳化クリームである皮膚化粧料を調整し、評価方法については（１）〜（７）は実施例１〜７の方法により、（８）経時安定性については下記の方法により評価を行なった。ただし、添加成分として表６に示す９成分を共通添加成分Ｃとして使用し、木通抽出エキス、レンゲソウ抽出には実施例１〜７と同じのものを使用した。結果を表４に示す。
【００４２】
【表６】
（８）経時安定性
化粧料を透明ガラス容器に密封して−５℃、２５℃および４５℃で１ヶ月間保存したときの状態を調査し、下に示す３段階で評価した。
○：安定性良好（外観の変化がなくブツ等も生じない。）
△：安定性やや不良（僅かに沈殿を生じるか僅かに分離が見られる。または僅かにブツ、ダマを生じている。）
×：安定性不良（明らかに沈殿を生じるか分離する。またはブツやダマを生じる。）
【００４４】
実施例１１〜１２より、本発明のクリームはいずれも使用時の感触が軽く使用後もべたつかず、保湿効果の持続性および水洗い後の保湿効果に優れ、肌荒れ改善効果、しわとり効果に優れるとともに肌にはりを与え、経時安定性にも優れていた。
【００４５】
実施例１３〜１４
表４に示す油中水型乳化クリームである皮膚化粧料を調整し、実施例１１〜１２の方法により評価を行なった。ただし、添加成分として表７に示す１０成分を共通添加成分Ｄとして使用し、木通抽出エキス、レンゲソウ抽出エキスには実施例１〜７と同じのものを使用した。結果を表４に示す。
【００４６】
【表７】
実施例１３〜１４より、本発明のクリームはいずれも使用時の感触が軽く使用後もべたつかず、保湿効果の持続性および水洗い後の保湿効果に優れ、肌荒れ改善効果、しわとり効果に優れるとともに肌にはりを与え、経時安定性にも優れていた。
【００４８】
【発明の効果】
本発明の皮膚化粧料は使用時の感触が軽く使用後もべたつかず、保湿効果の持続性および水洗い後の保湿効果に優れ、肌荒れ改善効果、しわとり効果に優れるとともに肌にはりを与え、経時安定性にも優れていた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to skin cosmetics such as lotions, emulsions, creams, packs, and the like. More specifically, the touch during use is light and non-sticky after use, has excellent moisturizing effect and excellent moisturizing effect after washing and rough skin. The present invention relates to a skin cosmetic that is excellent in an improving effect and a wrinkle removing effect, gives skin to the skin, and is excellent in stability over time.
[0002]
[Prior art]
Usually, the surface of human skin is covered with a sebum film, and the transpiration of water is moderately suppressed. Keeping the skin moisture within an appropriate range is very important from the viewpoint of skin health. If the moisture is insufficient, rough skin or the like is likely to occur. If you wash your face or take a bath, the sebum film will be temporarily removed and it will be easy to lose the moisture of your skin, so it is necessary to supplement the moisture with moisturizing cosmetics such as lotion, milky lotion, cream, and beauty serum. .
Here, generally, cosmetics are blended with polyhydric alcohols such as glycerin, 1,3-butylene glycol, sorbitol, and pyrrolidone carboxylates as moisturizers. Although it was excellent, there was difficulty in moisture retention under low humidity, and the moisture retention effect could not be maintained.
[0003]
Therefore, in recent years, various substances such as chitin, chitosan and their derivatives, protein hydrolysates, acidic mucopolysaccharides such as hyaluronic acid, plant extracts and the like have been studied as moisturizing components having high water retention ability at low humidity. However, these moisturizing components having high moisturizing power have an unpleasant stickiness and have a drawback that the feel becomes heavy. Moreover, since these components are generally water-soluble, they can be easily washed away by washing with water after use, and the moisturizing effect cannot be obtained unless they are used again. Among them, Mokutsu is a herbal medicine that has been used as a component of traditional Chinese medicine since the vine stems of akebi or other related plants were collected, cut into slices, and dried. Generation prevention effect {Drug 95, 1179 (1975)}, diuretic action {Chem. Phar. Bull. 27, 1464 (1979)}, known to have an anti-inflammatory action {Abstracts Presented at the 90th Annual Meeting of the Pharmaceutical Society of Japan (1970)}. JP-A-64-42411 and JP-A-8-133958 show that the extract has a high whitening effect, and a cosmetic or external skin having a high whitening effect using the extract. Agents have been proposed. Furthermore, in Japanese Patent Application Laid-Open No. 10-7581, it has been shown that the extract of Mokutsu has a function of enhancing the skin moisturizing ability, and a skin external preparation having a high moisturizing effect containing the extract is proposed. ing. Further, forsythia is a leguminous biennial plant, and it has been found that this extract also has high moisturizing action, whitening action, cell activation action and the like. JP-A 1-1117814 proposes a cosmetic using this extract. However, cosmetics and topical skin preparations containing these tree extract and lotus extract extract are not only unstable due to coloring and precipitation over time, but also have a little stickiness and feel bad. It was easy, and the effect of improving rough skin and the effect of giving skin was weak. Furthermore, the moisturizing effect was impaired when washed with water after use.
[0004]
On the other hand, 2-methacryloyloxyethyl phosphorylcholine (hereinafter referred to as MPC) is a monomer having the same structure as the polar group of phospholipid (phosphatidylcholine), which is a main component of biological membranes, and its homopolymer and other hydrophobic monomers Copolymers with hydrophilic monomers have been reported to have high moisturizing action and film-forming ability. However, these MPC-containing polymers have a high moisturizing action and a film-forming ability, and therefore, when applied to the skin, there is a drawback in that they are caught by moisture evaporation and the spread becomes worse. Cosmetics using MPC-containing polymers include cosmetics described in JP-A-5-70321, JP-A-6-157269, JP-A-6-157270 and JP-A-6-157271. In addition, not only did the spread during use worse, but the effect of giving the skin and the effect of wrinkle were weak.
[0005]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems, feels light during use, is not sticky after use, has excellent moisturizing effect and moisturizing effect after washing with water, is excellent in roughening effect on skin and wrinkle, and gives skin elasticity. An object of the present invention is to provide a skin cosmetic that is also excellent in stability over time.
[0006]
[Means for Solving the Problems]
That is, the present invention relates to a. 0.00005 to 2% by weight of an extract of Mokutsu or Astragalus as a dry residue, b. 0.001 to 10% by weight of a polymer obtained by polymerizing a monomer containing 60 to 100% by weight of the compound represented by formula (I) and (meth) acrylic acid alkyl ester in a weight ratio of 100/0 to 10/90 % Skin cosmetic, characterized by further containing c. A skin cosmetic comprising 0.1 to 30% by weight of a polyhydric alcohol or a partial ester compound thereof.
[0007]
[Chemical 2]
(R 1 is a hydrogen atom or a methyl group, R 2 , R 3 and R 4 are alkyl groups having 1 to 8 carbon atoms, and n is 2 to 4)
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The extract from the tree used in the present invention is one or two or more selected from hydrocarbons, esters, ketones, ethers, halogenated hydrocarbons, alcohols and water, after the vine vine stems are dried or dried. It is obtained by heating under reflux or immersion, preferably extracted with water or one or more of alcohols such as ethanol, propyl alcohol, isopropyl alcohol, butanol, and more preferably extracted with water. .
[0010]
In addition, the extract of Astragalus used in the present invention is one or two selected from hydrocarbons, esters, ketones, ethers, halogenated hydrocarbons, alcohols, and water after the whole legumes or seeds of legumes or after drying. It is obtained by heating under reflux or immersion with more than one species, preferably extracted with water or one or more of alcohols such as ethanol, propyl alcohol, isopropyl alcohol, 1,3-butylene glycol, more preferably Extracted with one or a mixture of two or more of water, ethanol and 1,3-butylene glycol.
The tree extract of the present invention or the extract of Astragalus refers to the extraction solution itself or a concentrate thereof.
[0011]
In the compound represented by the formula (I) used in the present invention, R 1 is a hydrogen atom or a methyl group, R 2 , R 3 and R 4 are alkyl groups having 1 to 8 carbon atoms, and n is 2 to 2 4. Among them, 2-methacryloyloxyethyl phosphorylcholine (MPC) represented by the formula (II) is preferable.
[0012]
[Chemical 3]
b. The polymer as a component contains the compound represented by formula (I) and the alkyl (meth) acrylate as a constituent ratio of 100/0 to 10/90 by weight, preferably 100/0 to 30/70, Preferably, it is a polymer (hereinafter referred to as a PC polymer) contained as a constituent ratio of 95/5 to 50/50. The total amount of the compound represented by formula (I) and the alkyl (meth) acrylate in the PC polymer is 60 to 100% by weight, preferably 70 to 100% by weight, more preferably 80 to 100% by weight. %. If it is out of the above range, the sustainability of the moisturizing effect, the moisturizing effect after washing with water, and the effect of improving rough skin are deteriorated.
The weight average molecular weight of the PC polymer is preferably 10,000 to 10,000,000, more preferably 50,000 to 1,000,000.
[0014]
When the compound represented by the formula (I) and the alkyl (meth) acrylate are not 100% by weight, the compound represented by the formula (I) and the alkyl (meth) acrylate are copolymerized with other monomers. Can be made.
The compound represented by the formula (I) and the other monomer copolymerizable with the (meth) acrylic acid alkyl ester are compounds having a double bond capable of addition polymerization, and do not impair the effects of the present invention. For example, olefinic hydrocarbons such as ethylene, propylene, butene, isobutene, and styrene and isomerized olefins, multimerized olefins, or olefinic compounds obtained by introducing various derivatives thereof; acrylic acid, methacrylic acid, vinyl Acetic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and other ethylenically unsaturated carboxylic acids and their multimers, anhydrides, esters with alcohols other than monohydric alcohols having 1 to 6 carbon atoms, or carbonyl Derived from ethylenically unsaturated carboxylic acid with amino group, amino group, cyano group, nitrile group, etc. Vinyl alcohol and esters thereof with various carboxylic acids, ethers with various alcohols, or ethylenically unsaturated carboxylic acid derivatives having vinyl, carbonyl, amino, cyano or nitrile groups introduced therein, vinyl alcohol and the like Examples thereof include esters with various carboxylic acids, ethers with various alcohols, and vinyl alcohol derivatives in which a carbonyl group, an amino group, a cyano group, a nitrile group, or the like is introduced.
[0015]
The alcohol constituting the (meth) acrylic acid alkyl ester is an alcohol having 1 to 18 carbon atoms such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, tert-butyl alcohol, and preferably has a carbon number. It is a C2-C12 alcohol, More preferably, it is a C3-C4 alcohol.
[0016]
C. Used in the present invention. The components include, for example, polyhydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, polyglycerin, 1,3-butylene glycol, polyethylene glycol, sorbitol, or acetic acid, sulfuric acid, phosphoric acid of these polyhydric alcohols, A partial ester compound such as a fatty acid, preferably a polyhydric alcohol or a partial ester compound of the fatty acid.
[0017]
A. The extract of the woody extract as a component is 0.00005 to 2% by weight, preferably 0.0001 to 1.5% by weight, more preferably 0.0005 to 1% by weight as a dry residue in the total amount of the composition. It is. If it is less than 0.00005% by weight, the durability of the moisturizing effect, the rough skin improving effect, and the wrinkle removing effect are weakened, and if it exceeds 2% by weight, not only does it cause problems in stability over time, but it is also disadvantageous in terms of cost. However, the dry residue as used in the present invention refers to a solute that is a residue when the extract is usually dried at 105 ° C. to remove the solvent, but when the extract solvent is non-volatile, a gas chromatograph or a high-performance liquid is used. The dissolved mass is obtained as a calculated value from the value obtained by quantifying the amount of solvent by a chromatograph or the like, and is regarded as the dry residue amount.
[0018]
B. The PC polymer as a component is 0.001 to 10% by weight, preferably 0.005 to 7% by weight, and more preferably 0.01 to 5% by weight in the total amount of the composition. If the amount is less than 0.001% by weight, the effect of improving rough skin and the effect of giving the skin are weakened, and the moisture retention after washing with water is weakened. If the amount exceeds 10% by weight, the skin feels sticky and sticky.
[0019]
On the other hand, in the present invention, in order to further improve the performance and usability of the skin cosmetic, c. The component polyhydric alcohol or a partial ester compound thereof is preferably blended in an amount of 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the total amount of the composition. That is, when 0.1% or more is blended, the effect of giving the skin to the skin and the effect of improving the rough skin are improved, but when it exceeds 30% by weight, the feeling at the time of use becomes worse and the stickiness is obtained.
[0020]
In addition, the skin cosmetics of the present invention can be blended with additives commonly used in cosmetics as long as the performance of the present invention is not impaired. For example, synthesis of lower alcohols such as ethanol and isopropyl alcohol, hydrocarbon oils such as liquid paraffin, liquid isoparaffin, squalane, petrolatum and solid paraffin, natural fats and oils such as beef tallow, lard and fish oil, glyceryl tri-2-ethylhexanoate, etc. Triglyceride, isopropyl myristate, isopropyl palmitate, cetyl palmitate, ethyl oleate, oleyl oleate, octyldodecyl myristate, etc. wax, beeswax, carnauba wax, etc., linear and cyclic dimethylpolysiloxane, polyether modified Silicone derivatives such as dimethylpolysiloxane and amino-modified dimethylpolysiloxane, ceramide, cholesterol, protein derivatives, lanolin, lanolin derivatives, oily bases such as lecithin, soap, acylmethy Anionic surfactants such as taurine salt and amide ether sulfate ester salt, amphoteric surfactants such as amide amino acid salt, amidopropyldimethylaminoacetic acid betaine, nonionics such as polyoxyethylene alkyl ether, alkylpolyglucoside, alkanolamide Surfactants, cationic surfactants such as alkyltrimethylammonium chloride, semipolar surfactants such as alkyldimethylamine oxide, alginic acid, carboxyvinyl polymer, carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, hyaluronic acid, xanthan gum Water-soluble polymers such as pyrrolidone carboxylate, citrate, malate, salt or other organic or inorganic salts, pH adjusters such as acids and alkalis, bactericides, chelating agents, Oxidants, UV absorbers, natural extracts derived from animals and plants, a dye and flavoring such as can be incorporated.
[0021]
【Example】
Next, the present invention will be described in more detail by way of examples.
Examples 1-7 and Comparative Examples 1-7
Skin cosmetics that are transparent or translucent lotions shown in Tables 1 and 2 were prepared and evaluated by the following methods. However, the four components shown in Table 3 were used as the additive component A as additive components. The results are shown in Tables 1-2.
Moreover, the used tree extract was prepared as follows. That is, after drying the tree stalk, 300 ml of water was added to 30 g of the pulverized product, heated to 70 ° C., digested for 3 hours while refluxing, and then filtered to obtain a tree extract. When the extract was dried at 105 ° C., the dry residue was 1.3%. On the other hand, “Falco rex lotus” manufactured by Ichimaru Falcos Co., Ltd. was used as the extract of lotus root. And when this extract was dried at 105 degreeC, the dry residue was 1.1%.
[0022]
[Table 1]
1) Copolymer with 80% by weight of MPC and 20% by weight of butyl methacrylate and having a weight average molecular weight of about 700,000 2) Copolymer with 70% by weight of MPC and 30% by weight of butyl methacrylate having a weight average molecular weight of about 1 million Polymer 3) Copolymer having 60% by weight of MPC, 30% by weight of propyl methacrylate and 10% by weight of vinyl acetate and having a weight average molecular weight of about 800,000 4) Copolymer having 100% by weight of MPC and having a weight average molecular weight of about 1 million Copolymer 5) Copolymer having 5 wt% MPC and 95 wt% butyl methacrylate and having a weight average molecular weight of about 700,000 6) “Sodium Hyaluronate FCH-200” manufactured by Kibun Food Chemifa Co., Ltd.
[0024]
[Table 2]
1) Copolymer with 80% by weight of MPC and 20% by weight of butyl methacrylate and having a weight average molecular weight of about 700,000 2) Copolymer with 70% by weight of MPC and 30% by weight of butyl methacrylate having a weight average molecular weight of about 1 million Polymer 3) Copolymer having 60% by weight of MPC, 30% by weight of propyl methacrylate and 10% by weight of vinyl acetate and having a weight average molecular weight of about 800,000 4) Copolymer having 100% by weight of MPC and having a weight average molecular weight of about 1 million Copolymer 5) Copolymer having 5 wt% MPC and 95 wt% butyl methacrylate and having a weight average molecular weight of about 700,000 6) “Sodium Hyaluronate FCH-200” manufactured by Kibun Food Chemifa Co., Ltd.
[0026]
[Table 3]
(1) Feel at the time of use 20 women (20 to 35 years old) are panelists, and the skin feel is used after the face is washed and the skin feel is used as follows. The average value of 1.5 points or more was evaluated as a light-weight cosmetic when used.
2 points: When the feel of use is good and it feels light without touching.
1 point: When the feel of use is slightly bad and it feels a little stuck.
0 point: When it feels that it has a bad feel during use, and has a heavy feel.
[0028]
(2) Twenty women (20 to 35 years old) with stickiness after use were panelists, and after washing their skin, using skin cosmetics, the skin feel after 10 minutes was determined as follows. An average value was obtained, and an average value of 1.5 points or more was evaluated as a cosmetic without stickiness after use. 2 points: When the skin feels non-sticky.
1 point: When the skin feels somewhat sticky.
0 points: When the skin feels very sticky.
[0029]
(3) Sustainability of moisturizing effect 20 females (20-35 years old) are panelists, use skin cosmetics after washing their face, and determine the moisture content of the skin after 2 hours as follows. The average value of 1.5 was evaluated as a cosmetic material having a good moisturizing effect.
2 points: When the skin feels sufficiently moistened just after use.
1 point: When feeling that the moisture of the skin is slightly insufficient compared with immediately after use.
0 point: When it feels that the moisture of the skin is clearly insufficient compared with immediately after use.
[0030]
(4) Moisturizing effect after washing with water 20 females (20 to 35 years old) are panelists, and after washing their face, they are washed again with water only 10 minutes after using cosmetics, and after 10 minutes, Moisture was determined as follows, the average value of 20 people was obtained, and an average value of 1.5 points or more was evaluated as a cosmetic with a good moisturizing effect after washing with water.
2 points: When the skin feels moist enough.
1 point: When the skin feels slightly moist.
0 point: When it feels that the moisture of the skin is insufficient.
[0031]
(5) Skin roughening effect 10 skinny females (24 to 33 years old) are panelists, and the skin condition when skin cosmetics are used twice a day for two consecutive weeks is determined as follows. Then, the average value of 20 people was obtained, and an average value of 1.5 points or more was evaluated as a cosmetic having an effect of improving skin roughness.
2 points: When it is felt that rough skin has been cured.
1 point: When it feels that the rough skin has been cured somewhat.
0 point: When it feels that the rough skin improvement effect is not seen at all.
[0032]
(6) Wrinkle removal effect 20 females (20-35 years old) are panelists, and the skin condition when using skin cosmetics twice a day for two consecutive weeks is determined sensorially as follows: An average value of 20 people was obtained, and an average value of 1.5 points or more was evaluated as a cosmetic with a wrinkle effect.
2 points: When wrinkles are clearly inconspicuous.
1 point: When wrinkles are slightly inconspicuous.
0 point: When it is felt that there is no wrinkle removal effect.
[0033]
(7) Skin skin 20 females (20-35 years old) are panelists, and the skin condition when skin cosmetics are used twice a day for two consecutive weeks is determined sensuously as follows: An average value of 20 people was obtained, and an average value of 1.5 points or more was evaluated as a cosmetic having an effect of giving a skin tone.
2 points: When the skin is clearly felt.
1 point: When it feels that the skin has a little bit.
0 points: When the skin feels non-sticky.
[0034]
(8) Stability over time The cosmetic was sealed in a transparent glass container and stored at 0 ° C., 25 ° C. and 40 ° C. for 3 months. The appearance was observed and evaluated in the following three stages.
○: Good stability (no change in appearance at any temperature)
Δ: Slightly poor (slightly at any temperature, causing precipitation or slight coloration)
×: Stability failure (at any temperature, precipitation occurs or separates, or coloring is significant)
[0035]
From Examples 1 to 7, all of the lotions using the ingredients of the present invention have a light touch during use and are not sticky after use, have excellent moisturizing effect and moisturizing effect after washing with water, rough skin improving effect, wrinkle In addition to its excellent removal effect, it gave a skin tone and was excellent in stability over time.
On the other hand, in Comparative Examples 1-7, sufficient performance is not obtained. That is, in Comparative Example 1, a. Since the ingredients are not blended, the persistence of the moisturizing effect is deteriorated and the rough skin improving effect and the wrinkle removing effect are weakened. Since the ingredients are not blended, the effect of improving rough skin and the effect of giving skin are weakened and the moisturizing effect after washing with water is weakened. In Comparative Example 3, b. Since the components are blended beyond the scope of the present invention, the spread during use is extremely poor. In Comparative Examples 4 and 5, b. Since the component ratio is out of the range of the present invention, the durability of the moisturizing effect, the effect of improving the rough skin, and the moisturizing effect after washing with water are deteriorated. Further, in Comparative Examples 6 and 7, b. Because it contains sodium hyaluronate which is a mucopolysaccharide in place of the ingredients, the stickiness after use, the effect of improving rough skin, the effect of giving the skin becomes weak and the moisturizing effect after washing with water are weakened.
[0036]
Examples 8-10
Skin cosmetics that are oil-in-water emulsions shown in Table 4 were prepared and evaluated by the same methods as in Examples 1-7. However, 11 components shown in Table 5 as additive components were used as the common additive component B, and the same extracts as in Examples 1 to 7 were used as the extract from the tree extract and the extract from Astragalus. The results are shown in Table 4.
[0037]
[Table 4]
1) Copolymer with 80% by weight of MPC and 20% by weight of butyl methacrylate and having a weight average molecular weight of about 700,000 2) Copolymer with 70% by weight of MPC and 30% by weight of butyl methacrylate having a weight average molecular weight of about 1 million Polymer 3) Molecular weight 1540
4) Molecular weight 4000
[0039]
[Table 5]
From Examples 8 to 10, all of the emulsions of the present invention have a light touch during use and are not sticky after use, have excellent moisturizing effect and moisturizing effect after washing with water, and are excellent in rough skin improvement effect and wrinkle removing effect. It gave skin elasticity and was excellent in stability over time.
[0041]
Examples 11-12
Skin cosmetics that are oil-in-water emulsified creams shown in Table 4 were prepared, and (1) to (7) were evaluated by the methods of Examples 1 to 7 for the evaluation method, and (8) the following method for stability over time. Evaluation was carried out. However, the nine components shown in Table 6 were used as the additive component C as the additive component, and the same extract as in Examples 1 to 7 was used for the extraction through the tree extract and the spinach extract. The results are shown in Table 4.
[0042]
[Table 6]
(8) Stability over time The cosmetics were sealed in a transparent glass container, and the state when stored at -5 ° C, 25 ° C and 45 ° C for 1 month was investigated and evaluated in the following three stages.
◯: Good stability (no change in appearance and no flaws, etc.)
Δ: Slightly poor (slight precipitation or slight separation, or slight lumps and lumps)
X: poor stability (clearly precipitate or separate.
[0044]
From Examples 11 to 12, the cream of the present invention has a light touch during use and is not sticky after use, has excellent moisturizing effect and moisturizing effect after washing with water, is excellent in rough skin improvement effect, and wrinkle removing effect. It gave skin elasticity and was excellent in stability over time.
[0045]
Examples 13-14
Skin cosmetics that are water-in-oil emulsified creams shown in Table 4 were prepared and evaluated by the methods of Examples 11-12. However, 10 components shown in Table 7 as additive components were used as the common additive component D, and the same extract as in Examples 1 to 7 was used for the tree-extract extract and the lotus extract. The results are shown in Table 4.
[0046]
[Table 7]
From Examples 13 to 14, all of the creams of the present invention have a light touch during use and are not sticky after use, have excellent moisturizing effect and moisturizing effect after washing with water, and have excellent skin roughening effect and wrinkle removing effect. It gave skin elasticity and was excellent in stability over time.
[0048]
【The invention's effect】
The skin cosmetic of the present invention has a light touch during use and is not sticky after use, has excellent moisture retention effect and moisturizing effect after washing with water, is excellent in rough skin improvement effect, wrinkle removal effect and gives skin firmness. Excellent stability.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26186499A JP4126819B2 (en) | 1999-06-23 | 1999-09-16 | Skin cosmetics |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-176475 | 1999-06-23 | ||
| JP17647599 | 1999-06-23 | ||
| JP26186499A JP4126819B2 (en) | 1999-06-23 | 1999-09-16 | Skin cosmetics |
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| Publication Number | Publication Date |
|---|---|
| JP2001064151A JP2001064151A (en) | 2001-03-13 |
| JP4126819B2 true JP4126819B2 (en) | 2008-07-30 |
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| JP26186499A Expired - Fee Related JP4126819B2 (en) | 1999-06-23 | 1999-09-16 | Skin cosmetics |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE60223472T2 (en) * | 2001-09-20 | 2008-09-18 | Kao Corp. | Cosmetic procedure for hair removal |
| FR2846555B1 (en) * | 2002-10-31 | 2006-08-11 | NOVEL MOISTURIZING AND ANTI-IRRITATING DERMATOLOGICAL AND / OR COSMETOLOGICAL COMPOSITIONS | |
| JP2005179326A (en) * | 2003-12-15 | 2005-07-07 | Iona International Corp | Cosmetic |
| JP5311704B2 (en) | 2004-11-25 | 2013-10-09 | 日油株式会社 | Skin cosmetics |
| JP4808445B2 (en) * | 2005-07-25 | 2011-11-02 | 日本メナード化粧品株式会社 | W / O type emulsion composition |
| JP4846300B2 (en) * | 2005-08-18 | 2011-12-28 | フマキラー株式会社 | Pest repellent for human body |
| JP6149682B2 (en) * | 2013-10-17 | 2017-06-21 | 日油株式会社 | Gastric ulcer prophylactic agent |
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1999
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