JP2004315389A - External preparation for skin - Google Patents

Abstract

An object of the present invention is to stabilize a component which is unstable in an aqueous solution, a component having poor compatibility with water, and a component which easily reacts with other components and deteriorates, and for a long time. An object of the present invention is to provide a skin external preparation maintained in a skin external preparation.
SOLUTION: Sugars and sugar derivatives, amino acids, enzymes, vitamins, organic acids, plant extracts, herbal extracts, and other moisturizers, astringents, whitening agents, anti-inflammatory agents as active ingredients in advance And a skin (cell) activator, an antibacterial agent, an antioxidant, and a skin external preparation characterized by containing rice hull baked silica containing one or more components selected from ingredients used for fragrances and the like, which is more preferable. Is an external preparation for skin containing a polysaccharide produced by a bacterium, Alcaligenes L. strain B-16.
[Selection diagram] None

Description

【００４８】
本発明に使用される多糖類は、微生物産生の多糖類として得られるもので、一般に微生物は、２種以上の多糖類を産生することが多いために本発明に使用される多糖類の他に他の多糖類が含まれていても本発明の多糖類の効果を妨げるものでなければ、他の多糖類が含まれることを妨げるものではない。本発明に使用される多糖類を産生する微生物は、特に限定されるものではないが、例えば、アルカリゲネス レータスＢ−１６株細菌（ＦＥＲＭ ＢＰ−２０１５号）がある。
【００４９】
本発明に使用される多糖類の製造は、例えば、アルカリゲネス レータスＢ−１６株細菌の場合、次のように製造される。アルカリゲネス レータスＢ−１６株細菌は、通常の微生物の培養方法で培養され、例えば、炭素源にフラクトース、グルコース、シュークロースなどの単糖類、ヘミセルロース、デンプン、コーンスターチなどの天然高分子、オリーブ油脂などの油類を、窒素源に尿素、塩化アンモニウム、硝酸アンモニウム、硫酸アンモニウムなどの無機態窒素源、トリプトン、酵母エキス、肉エキス、ペプトン、麦芽エキスなどの有機態窒素源を、その他リン酸カリウム、硫酸マグネシウム、塩化ナトリウムなどの無機塩類を加えた培地を用いて、初発ｐＨが４〜１０、培養温度が１５〜４０℃で通気攪拌液体培養を３〜１０日間行なう。培養後、該培養液に約２倍量（容量）以上のアセトン、エタノール、イソプロピルアルコールなどの有機溶媒を入れ、培養産生物を不溶性の凝集物として回収する。
【００５０】
アルカリゲネス レータスＢ−１６株細菌の生産する多糖類（以下「Ｂ−１６多糖類」と記す）には、少なくとも２種の多糖類が含まれていることが確かめられており、一つは、本発明の多糖類である前記式（１）に示すようなグルコース、グルクロン酸、ラムノースからなる繰返し構造の主鎖中にある１つのグルコースに１つのフコースが分岐した構造を有する多糖類であり、分子量は１０^９程度の高分子成分である〔１９９８年度日本農芸化学会大会要旨集、３７１頁参照〕。他の一つは、実質的にフコースとマンノースを構成単糖とする構造の繰り返しの多糖類であり、分子量が１０^３〜１０^７の低分子成分である〔Ｙ．Ｎｏｈａｔａ、Ｊ．Ａｚｕｍａ、Ｒ．Ｋｕｒａｎｅ、Ｃａｒｂｏｈｙｄｒａｔｅ Ｒｅｓｅａｒｃｈ ２９３、（１９９６）２１３〜２２２参照〕。このＢ−１６多糖類は、アルカシーラン〔商品名、ＩＮＣＩｎａｍｅ：Ａｌｃａｌｉｇｅｎｅｓ Ｐｏｌｙｓａｃｃｈａｒｉｄｅｓ、伯東（株）製〕として市販されている。Ｂ−１６多糖類は、低い配合量においての分散物安定性、及び乳化物安定性に優れ、その効果は経時に対しても安定である。これら特性により、低い粘度でありながら、粉体の浮上や沈降が防止され均一に分散し、さっぱりとした使用感を有する製剤を得ることができる。
【００５１】
本発明の多糖類の配合量は、通常、乾燥固形分として０．０１〜０．５重量％（対全量）（以下、「重量％」を「％」で示す）であり、好ましくは０．０２〜０．２％、より好ましくは０．０５〜０．１％である。本発明の多糖類の配合量（含有量）が０．０１％より少ないと十分な効果が得られないことがあり、また、０．５％を超えて配合してもそれ以上の効果の増加は少なく、経済的メリットが少ないことがある。
【００５２】
本発明の多糖類とともに従来より使用された増粘剤およびゲル化剤等を併用してもなんら問題ない。具体的には、アラビアゴム、トラガカント、ガラクタン、キャロブガム、グアーガム、カラヤガム、カラギーナン、ペクチン、寒天、アルゲコロイド、フコイダン、トラントガム、ローカストビーンガム、ガラクトマンナン等の植物系高分子；キサンタンガム、カードラン、ジェランガム、フコゲル、デキストラン、サクシノグルカン、プルラン等の微生物系高分子；キトサン、カゼイン、アルブミン、ゼラチン等の動物系高分子；デンプン、カルボキシメチルデンプン、メチルヒドロキシプロピルデンプン等のデンプン系高分子；メチルセルロース、エチルセルロース、メチルヒドロキシプロピルセルロース、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシプロピルセルロース、ニトロセルロース、セルロース硫酸ナトリウム、カルボキシメチルセルロースナトリウム、結晶セルロース、セルロース末のセルロース系高分子；アルギン酸ナトリウム、アルギン酸プロピレングリコールエステル等のアルギン酸系高分子；ポリビニルメチルエーテル、カルボキシビニルポリマー、アルキル変性カルボキシビニルポリマー等のビニル系高分子；ポリオキシエチレン系高分子；ポリオキシエチレンポリオキシプロピレン共重合体系高分子；ポリアクリル酸ナトリウム、ポリエチルアクリレート、ポリアクリルアミド等のアクリル系高分子；ポリエチレンイミン等のカチオン性ポリマー；ベントナイト、ラポナイト、ヘクトライト等の無機系鉱物；Ｎ−ラウロイル−Ｌ−グルタミン酸、α、γ−ジ−ｎ−ブチルアミン等のアミノ酸誘導体；デキストリンパルミチン酸エステル、デキストリンステアリン酸エステル、デキストリン２−エチルヘキサン酸パルミチン酸エステル等のデキストリン脂肪酸エステル；ショ糖パルミチン酸エステル、ショ糖ステアリン酸エステル等のショ糖脂肪酸エステル；モノベンジリデンソルビトール、ジベンジリデンソルビトール等のソルビトールのベンジリデン誘導体；ジメチルベンジルドデシルアンモニウムモンモリロナイトクレー、ジメチルジオクタデシルアンモニウムモンモリロナイトクレー等の有機変性した無機系鉱物等が挙げられる。ポリビニルアルコールやポリビニルピロリドン等の皮膜形成剤も含まれる。これらの増粘剤・ゲル化剤の１種又は２種以上を適宜選択して配合することができ、その配合量は、増粘剤・ゲル化剤の種類により異なり、一律に決められないが、通常、皮膚外用剤に対して０．０５〜１０％である。
【００５３】
本発明の皮膚外用剤には、本発明の効果を損なわない範囲内で、一般に薬品類、医薬部外品類、化粧品類などに使用される有機基剤、油剤、シロキサン化合物、多価アルコール類、界面活性剤、色素、顔料、有機酸類、紫外線吸収剤、さらには籾殻焼成シリカに含有させる有効成分として記載した以外の酵素類、保湿剤、収斂剤、美白剤、抗炎症剤、皮膚（細胞）賦活化剤、抗菌剤、酸化防止剤、香料等も含めて、必要に応じて選択し、籾殻焼成シリカに含有させる、あるいは該皮膚外用剤に配合しても良い。以下、具体例を挙げる。
【００５４】
有機基剤（成分）としては、エタノール、アセトン、酢酸エチル、酢酸ブチル、１、３−ブチレングリコール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリ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、ブタノール、プロパノールなどがあげられ、適宜選択して配合することができ、その配合量は、有機基剤の種類により異なり、一律に決められないが、通常、皮膚外用剤に対して、１％〜５０％である。
【００５５】
油剤としては、炭化水素類、ロウ類、脂肪酸類、高級アルコール類、脂肪酸エステル類、有機酸エステル、グリセライド類、フッ化炭化水素類等がある。具体的には、炭化水素としてはスクワラン、スクワレン、セレシン、パラフィン、パラフィンワックス、流動パラフィン、プリスタン、ポリイソブチレン、マイクロクリスタリンワックス、ワセリン等があり、ロウ類としてはミツロウ、カルナウバロウ、キャンデリラロウ、鯨ロウ等があり、動物油類としては牛脂、牛脚脂、牛骨脂、硬化牛脂、硬化油、タートル油、豚脂、馬脂、ミンク油、肝油、卵黄油等があり、ラノリン誘導体としてはラノリン、液状ラノリン、還元ラノリン、ラノリンアルコール、硬質ラノリン、酢酸ラノリン、ラノリン脂肪酸イソプロピル、ＰＯＥラノリンアルコールエーテル、ＰＯＥラノリンアルコールアセテート、ラノリン脂肪酸ポリエチレングリコール、ＰＯＥ水素添加ラノリンアルコールエーテル等があり、脂肪酸類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、ベヘン酸、ウンデシレン酸、オレイン酸、アラキドン酸、ドコサヘキサエン酸（ＤＨＡ）、イソステアリン酸、１２−ヒドロキシステアリン酸等があり、高級アルコール類としてはラウリルアルコール、ミリスチルアルコール、パルミチルアルコール、ステアリルアルコール、ベヘニルアルコール、ヘキサデシルアルコール、オレイルアルコール、イソステアリルアルコール、ヘキシルドデカノール、オクチルドデカノール、セトステアリルアルコール、２−デシルテトラデシノール、コレステロール、フィトステロール、シトステロール、ラノステロール、ＰＯＥコレステロールエーテル、モノステアリルグリセリンエーテル（バチルアルコール）等があり、脂肪酸エステル類としてはアジピン酸ジイソブチル、アジピン酸−２−ヘキシルデシル、アジピン酸−ジ−２−ヘプチルウンデシル、モノイソステアリン酸−Ｎ−アルキルグリコール、イソステアリン酸イソセチル、トリイソステアリン酸トリメチロールプロパン、ジ−２−エチルヘキサン酸エチレングリコール、２−エチルヘキサン酸セチル、トリ−２−エチルヘキサン酸トリメチロールプロパン、テトラ−２−エチルヘキサン酸ペンタエリスリトール、オクタン酸セチル、オクチルドデシルガムエステル、オレイン酸オレイル、オレイン酸オクチルドデシル、オレイン酸デシル、ジカプリン酸ネオペンチルグリコール、クエン酸トリエチル、コハク酸−２−エチルヘキシル、酢酸アミル、酢酸エチル、酢酸ブチル、ステアリン酸イソセチル、ステアリン酸ブチル、セバシン酸ジイソプロピル、セバシン酸ジ−２−エチルヘキシル、乳酸セチル、乳酸ミリスチル、パルミチン酸イソプロピル、パルミチン酸−２−エチルヘキシル、パルミチン酸２−ヘキシルデシル、パルミチン酸２−ヘプチルウンデシル、１２−ヒドロキシステアリル酸コレステリル、ジペンタエリスリトール脂肪酸エステル、ミリスチン酸イソプロピル、ミリスチン酸オクチルドデシル、ミリスチン酸−２−ヘキシルデシル、ミリスチン酸ミリスチル、ジメチルオクタン酸ヘキシルデシル、ラウリン酸エチル、ラウリン酸ヘキシル等があり、アミノ酸エステルとしてはＮ−ラウロイル−Ｌ−グルタミン酸−２−オクチルドデシルエステル等があり、有機酸エステル類としてはリンゴ酸ジイソステアリル等があり、グリセライド類としてはアセトグリセライド、トリイソオクタン酸グリセライド、トリイソステアリン酸グリセライド、トリイソパルミチン酸グリセライド、トリ−２−エチルヘキサン酸グリセライド、モノステアリン酸グリセライド、ジ−２−ヘプチルウンデカン酸グリセライド、トリミリスチン酸グリセライド等があり、フッ素化炭化水素類としてはパーフルオロポリエーテル、パーフルオロデカリン、パーフルオロオクタン等があげられ、適宜選択して配合することができ、その配合量は、油剤の種類により異なり、一律に決められないが、通常、皮膚外用剤に対して、０．１％〜５０％である。
【００５６】
シロキサン化合物は、ジメチルポリシロキサン、エチルメチルポリシロキサン、ジエチルポリシロキサン、メチルハイドロジェンポリシロキサン、メチルフェニルポリシロキサン、ジメチルシロキサン−メチル（ポリオキシエチレン）シロキサン共重合体、ジメチルシロキサン−メチル（ポリオキシエチレン−ポリオキシプロピレン）シロキサン共重合体などのようなポリエーテル変性オルガノポリシロキサン、ジメチルシロキサン−アルコキシ（炭素数４〜１２）メチルシロキサン共重合体、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサンなどのような環状ジメチルポリシロキサン、フルオロメチルシロキサン・ジメチルシロキサン共重合体などのフッ素変性オルガノポリシロキサン、フルオロメチルシロキサン・ポリオキシエチレンメチルシロキサン共重合体やフルオロメチルメチルシロキサン・ポリオキシエチレンポリオキシプロピレンメチルシロキサン共重合体などのフルオロアルキル・ポリオキシアルキレン変性オルガノポリシロキサン、末端に水酸基を導入したジメチルポリシロキサン変性物や側鎖に部分的に水酸基を導入したヒドロキシメチルシロキサン・ジメチルポリシロキサン共重合体等の末端あるいは側鎖変性オルガノポリシロキサン、側鎖にジアルキルアミノアルキル基を持つジメチルアミノブチルメチルシロキサン・ジメチルシロキサン重合体などの変性アミノオルガノポリシロキサンがあげられる。これらのシリコーンオイルを皮膚用外用剤組成物に用いるには、通常、当該シリコーンオイルの粘度が１００、０００（ｍＰａ・ｓ：２５℃）以下のものが選ばれ、その配合量は通常、皮膚外用剤に対して０．１〜８０％、好ましくは０．５〜５０％である。
【００５７】
多価アルコール類としては、アントラセンジオール、キノリンジオール、グリオキシム、グリセルアルデヒド、アントラセノール、セドヘプチトール、プロパンジオール、イノシトール、ウスニン酸、ウルシオール、ウルソデオキシコール酸、エチルボロン酸、ジエタノールアミン、ジエチルプロパンジオール、ジエチレングリコール、ジエトキシプロパンジオール、シクロヘキサンジオール、シクロヘキサンジオン、シクロヘキサントリオール、ジヒドロキシオクタデカン酸、ジヒドロキシケイ皮酸、ジメチルシクロペンタンジオール、ジメチルプロパンジオール、ジメチルベンゼンジオール、酒石酸アミド、チオグリセリン、トリエチレングリコール、ニトロプロピルプロパンジオール、ブタンジオール、ブチンジオール、ヘキサンジオール、ペンタンジオール、ペンタントリオール、ペンタンペンタオール、酸化エチレン、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、酸化プロピレン、プロピレングリコール、ポリプロピレングリコール、１、３−ブチレングリコール、ペンチルグリコール、グリセリン、ペンタエリトリトール、トレイトール、アラビトール、キシリトール、リビトール、ガラクチトール、ソルビトール、マンニトール、ラクチトール、マルチトールル、メタンジオール、メチルブタンジオール、モノアセチン、ラムニトール等がある。これらの多価アルコール類は、１種又は２種以上を適宜選択して配合することができ、その含有量は、多価アルコール類の種類により異なり、一律に決められないが、通常、皮膚外用剤の０．０１〜５重量％である。
【００５８】
界面活性剤としては、非イオン界面活性剤、陰イオン界面活性剤、陽イオン界面活性剤、両性界面活性剤がある。非イオン性界面活性剤としては、ポリオキシアルキレンアルキルエーテル類、ポリオキシアルキレンアルキルフェニルエーテル類、ポリオキシアルキレン脂肪酸エステル類、ポリオキシアルキレンソルビタン脂肪酸エステル類、ソルビタン脂肪酸エステル類、ポリオキシアルキレングリセリン脂肪酸エステル類、グリセリン脂肪酸エステル類、ポリグリセリン脂肪酸エステル類、ポリオキシアルキレン硬化ヒマシ油類、ショ糖脂肪酸エステル類、ポリオキシアルキレンアルキルアミン類、エチレンオキシド・プロピレンオキシドブロック共重合体類などがあげられる。
【００５９】
上記非イオン性界面活性剤におけるポリオキシアルキレンは、ポリオキシエチレン（以下、「ＰＯＥ」とする）、ポリオキシプロピレン（以下、「ＰＯＰ」とする）、ポリオキシブチレン（以下、「ＰＯＢ」とする）の１種以上からなるものであり、ＰＯＥ、ＰＯＰ、ＰＯＢの重合モル数は目的とする界面活性剤の乳化特性により適宜、決定されるものであるが、通常、３〜２００である。また、ＰＯＥ、ＰＯＰ、ＰＯＢの重合モル比も目的とする界面活性剤の乳化特性により適宜、決定される。好ましくは、ポリオキシアルキレンがＰＯＥとＰＯＰからなり、ＰＯＥが２５モル％以上を占めるものである。炭素数２〜４のポリオキシアルキレンアルキルエーテル類は、炭素数８〜３０の直鎖あるいは分岐、飽和あるいは不飽和のアルコールにポリアルキレンオキシドを付加したものである。具体的には、ＰＯＥ（３モル）オクチルエーテル、ＰＯＥ（５モル）ドデシルエーテル、ＰＯＥ（１０モル）オレイルエーテル、ＰＯＥ（１５モル）ステアリルエーテル、ＰＯＥ（２０モル）ベヘニルエーテル、ＰＯＥ（１０モル）ＰＯＰ（１０モル）デシルエーテル、ＰＯＥ（１５モル）ＰＯＰ（２モル）イソステリルエーテル、ＰＯＥ（１０モル）コレスタノールエーテル、ＰＯＥ（５モル）ＰＯＰ（５モル）水添ラノリン類等がある。
【００６０】
ポリオキシアルキレンアルキルフェニルエーテル類は、炭素数１〜２２の直鎖あるいは分岐のアルキルフェノール、アルケニルフェノールにポリアルキレンオキシドを付加したものであり、具体的にはポリオキシエチレン（３モル）メチルフェニルエーテル、ＰＯＥ（５モル）オクチルフェニルエーテル、ＰＯＥ（１０モル）ノニルフェニルエーテル、ＰＯＥ（１５モル）ドデシルフェニルエーテル等がある。
【００６１】
ポリオキシアルキレン脂肪酸エステル類は、炭素数８〜２２の直鎖あるいは分岐の飽和脂肪酸又は不飽和脂肪酸にポリアルキレンオキシドを付加したものであり、具体的にはＰＯＥ（３モル）オクタン酸エステル、ＰＯＥ（５モル）デカン酸エステル、ＰＯＥ（１０モル）ドデカン酸エステル、ＰＯＥ（１５モル）ステアリン酸エステル、ＰＯＥ（２０モル）ベヘニル酸エステル、ＰＯＥ（１５モル）イソステアリン酸エステル、ＰＯＥ（１５モル）ＰＯＰ（５モル）オレイン酸エステル等がある。
【００６２】
ポリオキシエチレンソルビタン脂肪酸エステル類は、ソルビトールと炭素数８〜２２の直鎖あるいは分岐の飽和脂肪酸又は不飽和脂肪酸とポリアルキレンオキシドを付加したものであり、具体的にはＰＯＥ（５モル）ソルビタンモノラウレート、ＰＯＥ（２０モル）ソルビタントリラウレート、ＰＯＥ（２０モル）ソルビタンモノステアレート、ＰＯＥ（２０モル）ソルビタンセスキステアレート、ＰＯＥ（２０モル）ソルビタントリステアレート、ＰＯＥ（２０モル）ソルビタンモノオレエート等がある。
【００６３】
ソルビタン脂肪酸エステル類は、ソルビトールと炭素数８〜２２の直鎖あるいは分岐の飽和脂肪酸又は不飽和脂肪酸とのエステルであり、具体的にはソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノイソステアレート、ソルビタンモノオレエート、ソルビタンセスキオレエート、ソルビタントリオレエート、ペンタ−２−エルチヘキシル酸ジグリセロールソルビタン、テトラ−２−エチルヘキシル酸ジグリセロールソルビタン等がある。
【００６４】
ポリオキシエチレングリセリン脂肪酸エステル類は、グリセリンと炭素数８〜２２の直鎖あるいは分岐の飽和脂肪酸又は不飽和脂肪酸およびポリアルキレンオキシドの付加エステルである。具体的には、ＰＯＥ（５モル）グリセリンモノラウリレート、ＰＯＥ（１０モル）グリセリンモノステアレート、ＰＯＥ（１５モル）グリセリンジステアレート、ＰＯＥ（２０モル）ＰＯＰ（５モル）グリセリンジオレエート等がある。
【００６５】
グリセリン脂肪酸エステル類は、グリセリンと炭素数８〜２２の直鎖あるいは分岐の飽和脂肪酸又は不飽和脂肪酸のエステルであり、具体的にはモノラウリン酸グリセリン、セスキラウリン酸グリセリン、トリラウリン酸グリセリン、モノステアリン酸グリセリン、セスキステアリン酸グリセリン、トリステアリン酸グリセリン、モノオレイン酸グリセリン、セスキオレイン酸グリセリン、トリオレイン酸グリセリン、モノ綿実油脂肪酸グリセリン、モノエルカ酸グリセリン、α、α’−オレイン酸ピログルタミン酸グリセリン、炭素数８〜１２の飽和脂肪酸混合物とグリセリンのエステル、ステアリン酸とリンゴ酸とグリセリンのエステル等がある。
【００６６】
ポリグリセリン脂肪酸エステル類としては、縮合ヒドロキシステアリン酸ポリグリセリンエステル、縮合リシノレイン酸ポリグリセリンエステル等があり、ポリオキシエチレン硬化ヒマシ油類としては、ＰＯＥ（１０モル）ヒマシ油、ＰＯＥ（１５モル）硬化ヒマシ油、ＰＯＥ（１５モル）硬化ヒマシ油モノイソステアレート、ＰＯＥ（２０モル）硬化ヒマシ油トリイソステアレート、ＰＯＥ（２０モル）硬化ヒマシ油モノピログルタミン酸モノイソステアリン酸ジエステル、ＰＯＥ（２０モル）硬化ヒマシ油マレイン酸等がある。
ショ糖脂肪酸エステル類は、ショ糖と炭素数８〜２２の直鎖あるいは分岐の飽和脂肪酸又は不飽和脂肪酸のエステルであり、具体的にはショ糖べへニン酸エステル、ショ糖ステアリン酸エステル、ショ糖パルミチン酸エステル、ショ糖ミリスチン酸エステル、ショ糖ラウリン酸エステル、ショ糖エルカ酸エステル、ショ糖オレイン酸エステル等がある。
【００６７】
ポリオキシアルキレンアルキルアミン類は、炭素数３〜２２の１級ないし２級アミンとポリアルキレンオキシドを付加したものであり、具体的にはＰＯＥ（５モル）ジドデシルアミン、ジＰＯＥ（１０）ＰＯＰ（３）ドデシルアミン、ＰＯＥ（１０モル）ジステアリルアミン、ジＰＯＥ（１０モル）ステアリルアミン、ジＰＯＥ（１５モル）オレイルアミン、ジＰＯＥ（１７モル）ベヘニルアミン等がある。
【００６８】
エチレンオキシド・プロピレンオキシド共重合体類は、エチレンオキシドとプロピレンオキシドをモル比で１：９〜９：１の範囲で、分子量約５００〜５０、０００として重合して得られた共重合体である。
【００６９】
アニオン性界面活性剤としては、脂肪酸塩類、アルキル硫酸塩類及びアルケニル硫酸塩類、アルキルフェニル硫酸塩類及びアルケニルフェニル硫酸塩類、アルキルフェニルポリオキシアルキレンエーテル硫酸塩類及びアルキルフェニルポリオキシアルキレンエーテル硫酸塩類、（ジ）アルキルスルホコハク酸塩類、Ｎ−アシルアミノ酸塩類（アシル−Ｎ−メチルタウリン類）、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、ナフタレンスルホン酸塩のホルマリン重縮合物類等が挙げられる。金属塩はナトリウム塩、カリウム塩、アンモニウム塩が好ましい。
【００７０】
脂肪酸塩類は、炭素数８〜３０で直鎖あるいは分岐鎖、更には飽和あるいは不飽和の脂肪酸の金属塩類であり、具体的にはオクチル酸ナトリウム、デカン酸ナトリウム、ドデカン酸ナトリウム、テトラデカン酸ナトリウム、ステアリン酸ナトリウム、イソステアリン酸ナトリウム、オレイン酸ナトリウム、リノレン酸ナトリウム、エデト酸ナトリウム等がある。
【００７１】
アルキル硫酸塩類及びアルケニル硫酸塩類は、炭素数８〜３０で直鎖あるいは分岐鎖、更には飽和あるいは不飽和のアルキル硫酸塩類、アルケニル硫酸塩類であり、具体的にはオクチル硫酸ナトリウム、デシル硫酸ナトリウム、ドデシル硫酸ナトリウム、ヤシアルキル硫酸ナトリウム、ステアリル硫酸ナトリウム、イソステアリル硫酸カリウム、オレイル硫酸アンモニウム、ベヘニル硫酸アンモニウム等がある。
【００７２】
アルキルフェニルポリオキシアルキレンエーテル硫酸塩類及びアルキルフェニルポリオキシアルキレンエーテル硫酸塩類は、炭素数１〜２２で直鎖あるいは分岐鎖のアルキル基あるいはアルケニル基を持ったフェニル基と炭素数２〜４のポリオキシアルキレングリコールの付加物との硫酸エステル塩類である。具体的には、トシルＰＯＥ（３モル）硫酸ナトリウム、オクチルフェニルＰＯＥ（５モル）硫酸ナトリウム、ノニルフェニルＰＯＥ（１０モル）硫酸カリウム、デシルフェニルＰＯＥ（１０モル）硫酸ナトリウム、オクタデシルフェニルＰＯＥ（１５モル）硫酸カリウム、オクタデセニルフェニルＰＯＥ（１５モル）硫酸カリウム、イソオクタデシルフェニルＰＯＥ（１５モル）ＰＯＰ（５モル）硫酸カリウム等がある。
【００７３】
（ジ）アルキルスルホコハク酸塩類としては、ジオクチルスルホコハク酸ナトリウム、ジー２−エチルヘキシルスルホコハク酸ナトリウム、モノラウロイルモノエタノールアミドポリオキシエチレンスルホコハク酸ナトリウム、ラウリルポリプロピレングリコールスルホコハク酸ナトリウム等がある。
【００７４】
Ｎ−アシルアミノ酸塩類は、アシル−Ｎ−メチルタウリン類であり、具体的にはラウロイルサルコシンナトリウム、Ｎ−ミリストイル−Ｎ−メチルタウリンナトリウム、ヤシ油脂肪酸メチルタウリッドナトリウム、ラウリルメチルタウリッドナトリウム等の高級脂肪酸アミドスルホン酸塩、Ｎ−ラウロイルグルタミン酸モノナトリウム、Ｎ−ステアロイルグルタミン酸ジナトリウム、Ｎ−ミリストイル−Ｌ−グルタミン酸モノナトリウム等のＮ−アシルグルタミン酸塩等がある。
【００７５】
アルキルベンゼンスルホン酸塩類としては、ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸カリウム、ドデシルベンゼンスルホン酸アンモニウム等がある。これらの１種あるいは２種以上を組み合わせて用いることもできる。
【００７６】
カチオン性界面活性剤としては、アミノ酸類、アルキルアミン塩類、４級アンモニウム塩類、ピリジニウム塩類等が挙げられる。
【００７７】
アミノ酸類としては、卵黄あるいは大豆由来のレシチン、あるいはこれを水素添加した水添レシチンや水酸化レシチン等のレシチン誘導体等がある。
【００７８】
アルキルアミン塩類としては、炭素数３〜２２の１級ないし２級アミンと炭素数１〜２２のカルボン酸の塩、無機鉱酸の塩であり、具体的にはドデシルアミン酢酸塩、ドデシルアミン塩酸塩、ドデシルアミンステアリン酸塩、ジメチルアミンステアリン酸塩等がある。
【００７９】
４級アンモニウム塩類としては、炭素数３〜２２の４級アミンと炭素数１〜２２のカルボン酸の塩あるいは無機鉱酸の塩であり、具体的には塩化ステアリルトリメチルアンモニウム、塩化ラウリルトリメチルアンモニウム、塩化ジステアリルジメチルアンモニウム、塩化ベンザルコニウム、塩化ベンゼトニウム、臭化ヤシアルキル（炭素数１０〜１４）イソキノリニウム塩、塩化ドデシルイミダゾリウム塩等がある。
【００８０】
ピリジニウム塩類としては、塩化ポリ（Ｎ、Ｎ−ジメチル−３、５−メチレンピペリジニウム）、塩化セチルピリジニウム等がある。
【００８１】
その他、カチオン性界面活性剤として、ドデシルジメチルアミンオキシド等のアミンオキシド類、アクリル酸β−Ｎ−Ｎジメチル−Ｎ−エチルアンモニオエチル酸ビニルピロリドン共重合体等のカチオン性ポリマーなども使用できる。
【００８２】
両性界面活性剤としては、ベタイン類、ホスホベタイン類およびスルホベタイン類、グリシン系ベタイン類、イミダゾリウム系ベタイン類、アミンオキシド類等がある。具体的には、ベタイン類としてはドデシルジメチルアミノ酢酸ベタイン、ステアリルジメチル酢酸ベタイン、ドデカン酸アミドプロピルジメチルアミノ酢酸ベタイン等があり、ホスホベタイン類としては２−（ジメチルドデシルアンモニオ）プロピオホスフェート、２−（ジメチルドデシルアンモニオ）−２−ヒドロキシプロピオホスフェート等があり、スルホベタイン類としてはドデシルジメチルエチルアンモニウムエトサルフェート等があり、グリシン系ベタイン類としてはドデシルジ（アミノエチル）グリシン、イミダゾリウム系ベタイン類としては２−ウンデシル−Ｎ、Ｎ、Ｎ−（ヒドロキシエチルカルボキシメチル）−２−イミダゾリンナトリウム、２−ココイル−２−イミタゾリニウムヒドロキサイド−１−カルボキシエチロキシ２ナトリウム塩、２−ヘプタデシル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン等がある。
【００８３】
これらの中で好ましくは、界面活性剤であるショ糖脂肪酸エステル、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、レシチンおよびその誘導体であり、より好ましくはショ糖ステアリン酸エステル、ショ糖パルミチン酸エステル、ショ糖ミリスチン酸エステル、ショ糖ラウリン酸エステル、ショ糖エルカ酸エステル、ショ糖オレイン酸エステル、モノステアリン酸グリセリル、オレイン酸グリセリル、縮合ヒドロキシステアリン酸ポリグリセリンエステル、縮合リシノレイン酸ポリグリセリンエステル、レシチン、水添レシチン、水酸化レシチンであり、これらの１種あるいは２種以上を組み合わせて用いることもできる。その配合量は界面活性剤の種類により異なり、一律に決められないが、通常、皮膚外用剤に対して０．１〜１０重量％である。
【００８４】
本発明で用いられる色剤は、有機合成色素として、黄色５号、赤色５０５号などのアゾ系染料、赤色２１３号、赤色２３０号などのキサンテン系染料、黄色２０４号などのキノリン系染料、青色１号などのトリフェニルメテン系染料、緑色２０１号などのアンスラキノン系染料、インジゴ系染料などの染料、赤色２０２号、赤色２０８号などのレーキ顔料、赤色２２８号、赤色２２６号、青色４０４号などが、天然色素として、カロチン、カルサミン、コチニールなどがある。その配合量は色剤の種類により異なり、一律に決められないが、通常、皮膚外用剤に対して０．０１〜０．１重量％である。
【００８５】
本発明で用いられる顔料は、例えば、レーキ顔料、有機顔料、着色顔料、白色顔料、体質顔料等の無機顔料、真珠光沢顔料、金属光沢顔料、ガラスフレーク顔料、金属被覆無機顔料、樹脂顔料、高分子粉体、機能性顔料等があげられ、これらの１種以上が使用される。
【００８６】
レーキ顔料には２つの種類があり、１つは水に溶けやすい染料をカルシウム等の塩として水に不溶化した顔料で、例えば赤色２０２号、２０４号、２０６号、２０７号、２０８号、２２０号等がある。他の１つは、硫酸アルミニウム、硫酸ジルコニウム等で水不溶性にしてアルミナに吸着させた顔料で黄色５号、赤色２３０号等である。
【００８７】
有機顔料は、水、油や基剤に溶解しない有色粉末であり、着色力、耐光性に優れている。アゾ系顔料の赤色２２８号、インジゴ系顔料の赤色２２６号、フタロシアニン系顔料の青色４０４号等があげられる。
【００８８】
無機顔料は、ベンガラ、黄酸化鉄、黒酸化鉄等の色調の異なる酸化鉄、群青、紺青、酸化クロム、水酸化クロム、酸化マグネシウム、酸化コバルト、チタン酸コバルトカーボンブラック、マンガンバイオレット、コバルトバイオレット等があげられる。
【００８９】
白色顔料は、着色や被覆等の目的で用いられ、ニ酸化チタンと酸化亜鉛があげられる。
【００９０】
体質顔料は、着色よりも製品の形状維持や伸展性、付着性、光沢等の調節、色調の調整（希釈剤）に用いられ、例えば雲母（マイカ）、白雲母、合成雲母、金雲母、紅雲母、黒雲母、リチア雲母等の雲母系顔料、セリサイト、タルク、カオリン、モンモリロナイト、ゼオライト等の粘度鉱物、炭酸マグネシウム、炭酸カルシウム、ケイ酸、無水ケイ酸、ケイ酸アルミニウム、ケイ酸マグネシウム、ケイ酸アルミニウムマグネシウム、含硫ケイ酸アルミニウム、ケイ酸カルシウム、ケイ酸バリウム、ケイ酸ストロンチウム、酸化アルミニウム、硫酸バリウム等の合成無機粉体等があげられる。
【００９１】
真珠光沢顔料は、真珠光沢、あるいは虹彩色、メタリック感を与えるために使用される顔料であり、二酸化チタン被覆雲母、魚鱗箔、オキシ塩化ビヒマスなどが挙げられる。また、酸化チタンの代わりに酸化鉄で被覆した顔料、酸化チタンの被覆層の上に透明な異なった色の顔料を被覆させた顔料なども使用される。
【００９２】
金属光沢顔料としては、アルミニウム粉、真鍮粉、銅粉、錫粉、金粉、銀粉など、さらに、これらの金属粉を着色した着色金属粉顔料などが挙げられる。
【００９３】
ガラスフレーク顔料は、フレーク状ガラスが金属などで被覆されている。
【００９４】
金属被覆無機顔料は、金属蒸着などで金属、および／あるいは金属酸化物が被覆された無機顔料であり、例えば、酸化鉄被覆アルミニウム、酸化鉄被覆雲母、アルミニウム−マンガン被覆雲母状酸化鉄などがあげられる。
【００９５】
樹脂顔料としては、樹脂フィルムに着色し、裁断された薄片などがあり、例えば、ポリエステルフィルム末、ポリエチレンテレフタレート・アルミニウム・エポキシ積層フィルム末、ポリエチレンテレフタレート・ポリオレフィン積層フィルム末、ポリメタクリル酸メチル、ポリエチレンテレフタレート・ポリメチルメタクリレート積層末、ナイロンパウダー等などが挙げられる。
【００９６】
機能性顔料としては、窒化ホウ素、合成フッ素金雲母、フォトクロミック顔料、複合化微粒子粉体等があげられる。
【００９７】
本発明の光輝性顔料の形態は、特に限定されるものではなく、粒状、板状、棒状等、目的および使用顔料により適宜、選択されれば良い。また、顔料の大きさは、特に限定されるものではなく、目的および使用顔料により適宜、選択されれば良く、粒状の顔料であれば、通常、平均粒子径が０．０１μｍ〜５０００μｍのものが使用され、箔片状や棒状の粉体であれば、通常、長径が０．１〜５０００μｍのものが使用されている。その配合量は顔料の種類により異なり、一律に決められないが、通常、皮膚外用剤に対して０．１〜１０重量％である。
【００９８】
有機酸としては、具体的にはアセトキシプロピオン酸、イソ吉草酸、アミノ吉草酸、エトキシ酢酸、エトキシプロピオン酸、イソアミノ吉草酸、エポキシオレイン酸、エライジン酸、アミノ酪酸、エルカ酸、オキサロ酢酸、オレイン酸、アミノレブリン酸、２−アミノ４−グアニジノオキシ酪酸、アンゲリカ酸、ガラクツロン酸、カルバミン酸、イコサトリエン酸、ギ酸、ギ酸アリル、ギ酸イソブチル、イコサン酸、ギ酸イソペンチル、グルクロン酸、イズロン酸、クロトン酸、クロロイソクロトン酸、イソクロトン酸、酢酸、ジヒドロリポ酸、エチルクロトン酸、ジフェニル酢酸、ジメトキシフタル酸、エチルヒドロキシ酪酸、スクシンアミド酸、ステアリン酸、ステアロル酸、ソルビン酸、チグリン酸、チロキシン、デカン酸、トロパ酸、乳酸、ヒドロキシイソ酪酸、ヒドロキシ吉草酸、ピルビン酸、ブチル酢酸、ブチルヒドロペルオキシド、ブラシジン酸、プロピオル酸、ピロピオン酸、ブロモイソ吉草酸、ブロモイソ酪酸、ブロモプロピオン酸、ヘキサン酸、ヘキセン酸、ペトロセリン酸、ヘプタデカン酸、ヘプタン酸、アレアニル酸、マレアミド酸、マレアミド酸、ミコール酸、ミリスチン酸、メタクリル酸、メチル吉草酸、メチルチオ酢酸、メチル酪酸、メバロン酸、メリシン酸、メルカプト酢酸、ヨード酢酸、ラウリン酸、リシネライジン酸、リシノール酸、リノール酸、リノレン酸、アコニット酸、オキサロコハク酸、オキソグルタル酸、アジピン酸、カルセイン、カルボキシフェニル酢酸、アセトキシコハク酸、カルボキシコメロン酸、カンホロン酸、イソカンホロン酸、グルタコン酸、グルタル酸、イソクエン酸、クロセチン、コハク酸、フタル酸、フマル酸、イソシンコメロン酸、ジエチレントリアミン五酢酸、イソフタル酸、シトラマル酸、ジニコチン酸、イタコン酸、ジブロモコハク酸、ジクロロコハク酸、エチルマロン酸、ジメチルコハク酸、シュウ酸、酒石酸、シンコメロン酸、スルホニル二酢酸、セバシン酸、タルトロン酸、デソキサル酸、テトラクロロフタル酸、テトラヒドロキシコハク酸、テトラメチルコハク酸、テレフタル酸、トリメシン酸、トリメリト酸、ナフタル酸、ニトロフタル酸、ビキシン、ヒドロキシイソフタル酸、ヒドロキシフタル酸、プレーニト酸、ヒドロキシメチルペンタン二酸、ピロメリト酸、フェニルコハク酸、プロパントリカルボン酸、ブロモコハク酸、ブロモフマル酸、ブロモマレイン酸、ヘミメリト酸、ペラルゴン酸、ベルベロン酸、ベンゼンヘキサカルボン酸、ベンゼンペンタカルボン酸、マレイン酸、マロン酸、メサコン酸、メソ酒石酸、メソシュウ酸、メチルイソフタル酸、メチルコハク酸、メチルマロン酸、メルカプトコハク酸、メロファン酸、ペルオキシフタル酸、リンゴ酸、ルチジン酸、ロイコトリエン等の多価カルボン酸類、メチルアントラニル酸、メルカプト安息香酸、ヨード安息香酸、ベンジル安息香酸、ベンズアミド安息香酸、アセチル安息香酸、エチル安息香酸、オピアン酸、オルセリン酸、アセトアミド安息香酸、カルボキシオキサニル酸、アゾキシ二安息香酸、クロロ安息香酸、クロロ過安息香酸、アニス酸、ゲンチシン酸、ジアミノ安息香酸、シキミ酸、アミノ安息香酸、ジヒドロキシ安息香酸、ジブロモ安息香酸、ベンソイル安息香酸、アミノニトロ安息香酸、ジメチルアミノ安息香酸、ジメチル安息香酸、安息香酸、スルホ安息香酸、テレフタルアルデヒド酸、イソフタルアルデヒド酸、トリクロロ安息香酸、トリニトロ安息香酸、イソプロピル安息香酸、トリヒドロキシ安息香酸、トリメチル安息香酸、トルイル酸、トルオイル安息香酸、ニトロ安息香酸、バニリン酸、イドラゾ二安息香酸、ヒドロキシ安息香酸、ヒドロキシトルイル安息香酸、ピペロニル酸、フェノキシ安息香酸、フルオロ安息香酸、ベラトルム酸、プロトカテク酸、プロベネシド、ブロモ安息香酸、ブロモアントラニル酸、アミノケイ皮酸、イソプロピルケイ皮酸、オキサニル酸、アレカイジン、カルボキシケイ皮酸、ケイ皮酸、アロキサン酸、ケトシクロヘキサンカルボン酸、アントラキノンカルボン酸、シクロブタンカルボン酸、アントラセンカルボン酸、シクロプロパンカルボン酸、イソニコチン酸、シクロヘキサンカルボン酸、シクロプロパンカルボン酸、イソニコペンチン酸、シクロヘキサンジアミン四酢酸、シクロヘキサンジカルボン酸、イブプロフェン、シクロヘキセンジカルボン酸、シクロペンタンカルボン酸、インドメタシン、インドール酢酸、シクロペンタンジカルボン酸、ジメチルフランカルボン酸、シンコフェン、ガロイル没食子酸、トラネキサム酸、ニトロケイ皮酸、ヒドロキシケイ皮酸、メトキシケイ皮酸、ヒドロキシヒドロケイ皮酸、フェニルケイ皮酸、フェルラ酸、イソフェルラ酸、カフェー酸、クロロゲン酸、ブロモケイ皮酸、ヘスペリチン酸、没食子酸、メチルケイ皮酸等の芳香族カルボン酸類、その他、ウルソデオキシコール酸、エラグ酸、オロチジン、オロト酸、カンファン酸、キナ酸、ヒドロキシプロリン、エチオコラン酸、カウルモオグル酸、カルノシン、カルバゾール酢酸、キノリンカルボン酸、キノリン酸、キノリンジカルボン酸、クマリン酸、クロロフェノキシ酢酸、ケノデオキシコール酸、コラン酸、コール酸、サントニン酸、ジヒドロオルト酸、スクシニナル酸、チオフェンカルボン酸、テトラヒドロ葉酸、デヒドロコール酸、テルペニル酸、テレビン酸、ドイミノール酸、ドーパ、トロンボキサン、ナフチル酢酸、ナフトエ酸、ナリジクス酸、ニトロキナジル酸、ニトロフェニルプロピオール酸、ニコペチン酸、ルコナン酸、ドーパキノン、ヒオデオキシコール酸、ヒドロアトロパ酸、ヒドロキシイソプロピルトルイル酸、ヒドロキシシクロヘキサンカルボン酸、ヒドロキシピロンカルボン酸、ヒドロキシピロンジカルボン酸、ヒドロキシフェニル酢酸、ヒドロキシフェニルプロピオン酸、ビフェニルジカルボン酸、ピペコリン酸、ピペリン酸、ピマル酸、ピリジル酸、ピログルタミン酸、ピロールカルボン酸、ピロンカルボン酸、ピロンジカルボン酸、フェニルアントラニル酸、フェニルカルバミン酸、フェニルグリシド酸、フェニル酢酸、フェニルチオ酢酸、フェニル乳酸、フェニルピルビン酸、フェニルブテン酸、フェニルプロピオル酸、フェニル酪酸、フェニレン２酢酸、フェノールフタリン、フェンコル酸、フシジン酸、プロテロイン酸、フランカルボン酸、フランジカルボン酸、フリル酸、フルオレセイン、フルオロフェニル酢酸、プロスタグランジン、プロスタサイクリン、ブロモマンデル酸、ヘモピロールカルボン酸、ベンシジンカルボン酸、ベンジリデンマロン酸、ベンジル酸、ベンゾイルアクリル酸、ベンゾイルオキシ酢酸、ベンゾイルオキシプロピオン酸、ベンゾイルギ酸、ベンゾイル酢酸、ベンゾイルプロピオン酸、ベンゾフェノンカルボン酸、ベンゾフランカルボン酸、ポドカルピン酸、ホモゲンチシン酸、マンデル酸、ムリコール酸、メチルドーパ、メチルフェニル酢酸、メチルフランカルボン酸、メチルレッド、メフェナム酸、リセルグ酸、リトコール酸、リポ酸、レセルピン酸、レチノイン酸、レボピマル酸、グリコール酸、クエン酸、サルチル酸、等が挙げられる。これらの有機酸成分は、１種又は２種以上を適宜選択して配合することができ、その含有量は、有機酸の種類により異なり、一律に決められないが、通常、皮膚外用剤に対して０．０１〜５重量％である。
【００９９】
本発明で用いられる紫外線吸収剤としては、有機化合物系の紫外線吸収剤と無機化合物系の紫外線散乱剤があり、紫外線吸収剤には、パラアミノ安息香酸系紫外線吸収剤、ケイ皮酸系紫外線吸収剤、サリチル酸系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤などがあげられ、その１種以上が配合される。紫外線吸収剤のパラアミノ安息香酸系紫外線吸収剤には、パラアミノ安息香酸、パラアミノ安息香酸グリセリル、パラアミノ安息香酸エチルジヒドロプロピル、パラジメチルパラアミノ安息香酸アミル、パラメチルパラアミノ安息香酸オクチル、パラアミノ安息香酸エチル、パラアミノ安息香酸イソブチルなどがあり、ケイ皮酸系紫外線吸収剤としては、パラメトキシケイ皮酸イソプロピル、ジイソプロピルケイ皮酸エステル、メトキシケイ皮酸オクチル、ジパラメトキシケイ皮酸モノ、２−エチルへキサン酸グリセリルなどがあり、サリチル酸系紫外線吸収剤としては、サリチル酸ホモメンチル、サリチル酸オクチル、サリチル酸フェニル、サリチル酸鳥エタノールアミン、サリチル酸アミル、サリチル酸ベンジル、サリチル酸ｐ−ｔｅｒｔブチルフェニル、サリチル酸エチレングリコール、サリチル酸などがあり、ベンゾフェノン系紫外線吸収剤としては、ジヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、オキシベンゾン、オキシベンゾンスルホン酸、ヒドロキシメトキシベンゾフェノンスルホン酸ナトリウム、ジヒドロキシジメトキシベンゾフェノン、２−ヒドロキシクロロベンゾフェノン、ジオキシベンゾン、ジヒドロキシジメトキシベンゾフェノンジスルホン酸ナトリウム、２−ヒドロキシ−４−メトキシ−４’メチルベンゾフェノン、オクタベンゾンなどがあり、その他にもウロカニン酸、ウロカニン酸エチル、４−ｔｅｒｔ−４’−メトキシジベンゾイルメタン、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、アントラニル酸などがあげられる。紫外線散乱剤として用いられる無機化合物には、酸化チタン、酸化亜鉛、酸化セリウム、酸化ジルコニウム、酸化鉄などがあげられる。その配合量は紫外線吸収剤の種類により異なり、一律に決められないが、通常、皮膚外用剤に対して０．０１〜１重量％である。
【０１００】
本発明の皮膚外用剤の形態（剤型）は、特に限定されたものではなく、使用目的に応じて適宜、決定されれば良く、具体的には溶液状、懸濁分散状、ペースト状、ムース状、ゲル（ジェル）状、固体状、粉末状等任意の剤型をとることができる。
【０１０１】
本発明の皮膚外用剤の製造方法に特に制限はなく、従来から公知の方法を使用することができる。
【０１０２】
例えば、化粧水、乳液やクリーム等の水性物の場合、籾殻焼成シリカに含有させる成分を揮発性の有機溶剤であるエタノールに溶解し、該エタノール溶液に籾殻焼成シリカを浸漬して有効成分を含浸させた後、該籾殻焼成シリカからエタノールを除去する。次に水（精製水）に有効成分を含有させた籾殻焼成シリカ、その他の皮膚外用剤用の水溶性の有効成分、アルカシーラン等の多糖類及びその他の多糖類系増粘剤や水溶性高分子、界面活性剤、必要に応じて着色剤（色素）を加えて分散させて混合液１とし、他方、水溶性有機液体、例えばエタノール、エチレングリコ−ル等に、その他の皮膚外用剤用の非水溶性の有効成分、油剤、顔料等の色材、防腐剤、香料、エモリエント剤、界面活性剤、薬効成分及び機能成分を溶解し混合液２として、ホモミキサーを用いて混合液１に混合液２を混合し、エマルション化あるいは可溶化する。更に必要に応じて別途、色材（着色染料等）による調色を行った後、ろ過、容器への充てんを行なって化粧水乳液やクリーム等が調製される。乳化の温度は、目的とする化粧水、乳液やクリーム等の形態、物性を考慮して、適宜選択されれば良く、通常、４０〜７０℃である。また、乳化に使用される機器としては、マウントガウリングホモジナイザーやマイクロフルイダイザー、高圧ホモジナイザー、ナノマイザーなどが有り、目的とする化粧水、乳液やクリーム等の形態、物性を適宜選択して使用される。
【０１０３】
ペースト、ムース、ジェル等の調製は、水（精製水）にアルカシーランや増粘剤、保湿剤、界面活性剤等を加えて４０〜７０℃に加熱、攪拌して均一に調製し、これに有効成分を含有させた籾殻焼成シリカ、その他の皮膚外用剤用の有効成分、色材、防腐剤、香料、界面活性剤、薬効成分及び機能成分を溶解した混合液を、撹拌下、加えて乳化あるいは可溶化し、ペースト、ムース、ジェル等が得られる。また、必要に応じて更にロールミル等で混錬し、より均一に調製されても良い。
【０１０４】
ゼリー状のパックの調製は、精製水に保湿剤、緩衝剤を加え７０℃に加熱し、さらに攪拌下、増粘剤、皮膜形成剤を添加し、調製した混合液３に、撹拌下、エタノールに皮膚外用剤用の有効成分を含有した籾殻焼成シリカ、その他の皮膚外用剤の有効成分、防腐剤、香料、エモリエント剤、界面活性剤、薬効成分及び機能成分を溶解した混合液４を混合、乳化して、ゼリー状のパックが調製される。
【０１０５】
ベビーパウダーや粉白粉等の粉体皮膚外用剤の場合、皮膚外用剤用の有効成分を含有した籾殻焼成シリカ、その他の皮膚外用剤の有効成分、色材（特に顔料）並びに必要に応じてタルクや二酸化チタン等の無機鉱物や香料をブレンダーに入れて混合した後、ボールミル、ロールミル等でさらに均一に分散させて本発明のベビーパウダーや粉白粉等が得られる。また、ファンデーション等では、皮膚外用剤用の有効成分を含有した籾殻焼成シリカ、その他の皮膚外用剤の有効成分、色材（顔料等）、油剤、界面活性剤、アルカシーランあるいは他の多糖類、保湿剤、美白剤並びに必要に応じて香料、酵素類、ビタミン類をブレンダーに加えて混合し、均一にする。このとき場合によっては加熱溶融して混合する方法も用いられる。混合後、さらにコロイドミルで均一に分散にして、容器に入れて圧縮成型して本発明のファンデーション等が得られる。
【０１０６】
【実施例】
以下に実施例をあげて、本発明を詳細に説明するが、本発明はこれらによって何ら限定されるものではない。
【０１０７】
〔試験に用いた多糖類〕
（Ａ−１：アルカリゲネス レータスＢ−１６株細菌の産出多糖類（粗製品））
グルコース〔和光純薬工業（株）製、試薬〕４０．０ｇ、リン酸水素二カリウム〔和光純薬工業（株）製、試薬〕４．０ｇ、リン酸二水素カリウム〔和光純薬工業（株）製、試薬〕２．０ｇ、塩化ナトリウム〔和光純薬工業（株）製、試薬〕０．１ｇ、硫酸マグネシウム〔和光純薬工業（株）製、試薬〕０．２ｇ、硝酸カリウム〔和光純薬工業（株）製、試薬〕１．０ｇ、イーストエキストラクト〔オキソイド（ＯＸＯＩＤ）社製〕１．５ｇをイオン交換水に溶解し、水酸化ナトリウムあるいは硫酸を用いｐＨ６．５に調整し、全量を１リットルとした。この水溶液１５０ｍＬを５００ｍＬの三角フラスコに取り、オートクレーブにより加熱滅菌（１２１℃、１５分間）した後、室温まで戻し、アルカリゲネスレータスＢ−１６株（ＦＥＲＭ ＢＰ−２０１５号）を１白金耳接種し、３０℃にて６日間振とう培養（１８０ｒｐｍ）した。培養終了後、培養物に約３倍容量のイソプロピルアルコールを加えて攪拌混合し、析出した凝集物を濾過、回収、減圧下にて乾燥してアルカリゲネス レータスＢ−１６株細菌の産出多糖類（Ａ−１）を得た。この多糖類は、フコース、グルコース、グルクロン酸、ラムノースをモル比１：２：１：１で構成される多糖類を主成分とし、この他フコースとマンノースをモル比１：１で構成される多糖類を含み、その存在比は７：１（重量比）である。尚、構成単糖類は、多糖類を硫酸で加水分解した後高速液体クロマトグラフィー（ＨＰＬＣ）により分析した。
【０１０８】
（Ａ−２：上記Ａ−１の精製品）
多糖類：Ａ−１の０．５重量％水溶液を調製し、水酸化ナトリウム水溶液でｐＨを１２とした。この水溶液をイオン交換樹脂「ダイヤイオンＨＰＡ−７５（ＯＨ−）（商品名）」（日本錬水（株）製）のカラムを用いて８Ｒｕ以下で処理し、さらに濾過助剤「ラジオライトＲＬ７００」と５μｍメンブランフイルターで濾過し、タンパク質、核酸、微生物類を除去した。濾液を希塩酸にてｐＨが７にしてから減圧濃縮し、アセトンを投入して多糖類を沈澱させ、さらに１０倍量のアセトンで洗浄し、フコース：グルコース：グルクロン酸：ラムノース＝１：２：１：１で構成され、分子量が５，０００万の多糖類（Ａ−２）を得た。
【０１０９】
〔比較例で用いる多糖類〕
・Ｂ−１：キサンタンガム〔「ケルザンＴ」（商品名）、三晶（株）製〕
・Ｂ−２：ポリアクリル酸
・Ｂ−３：ポリビニルアルコール。
【０１１０】
〔本発明の籾殻焼成シリカの調製方法〕
未選別の籾殻２０ｇを１０メッシュのナイロン網にてふるいにかけ、稲茎と籾殻を分離選別した。５重量％濃度塩酸５００ｍＬに選別した籾殻を２時間、浸漬した。浸漬後、籾殻を水道水で十分に洗浄し、１０メッシュのナイロン網で水分を切り、屋内で自然乾燥させた。乾燥した籾殻を磁性ルツボに入れ、電気炉で５５０℃、１時間焼いた。次に電気炉の温度を８００℃の上げ、１時間焼成した。冷却後、約３ｇの籾殻焼成シリカを得た。これを篩いにかけて分級し、長径５０〜２５０μｍの籾殻焼成シリカ−１（以下、「焼成シリカ−１」とする）、２５０〜５００μｍの籾殻焼成シリカ−２（以下、「焼成シリカ−２」とする）を得た。
【０１１１】
（有効成分含有焼成シリカ−１：酢酸トコフェロール含有）
３００ｍＬステンレス容器に流動パラフィン５０．０ｇ、スクワラン４０．０ｇ、ミツロウ６．０ｇ、ワセリン３．５ｇ、酢酸トコフェロール０．５ｇを入れ、約８０℃に加熱し、撹拌下、焼成シリカ−１：２０ｇを添加し、均一に油相に浸漬した後、２００メッシュの金網でろ過し、焼成シリカ−１をろ別し、エタノールにて焼成シリカ−１の表面を簡単に洗浄した。次いでエタノールを乾燥、除去させて有効成分含有籾殻焼成シリカ−１を得た。
【０１１２】
（有効成分含有籾殻焼成シリカ−２：混合アミノ酸含有）
３００ｍＬステンレス容器にミツロウ２．０ｇ、ワセリン２．０ｇ、固形パラフィン３．０ｇ、オレイルアルコール３．０ｇ、流動パラフィン５０．０ｇ、ステアリン酸ソルビタン５．０ｇを約８０℃に加熱し、混合物１とした。一方、グリセリン１０．０ｇ、１、３−ブチレングリコール５．０ｇ、混合アミノ酸液〔「プロデュウ４００」（商品名、味の素（株）製）：グリシン、アラニン、プロリン、セリン、アルギニン、リジン、グルタミン酸の混合液〕１０．０ｇ、水１０．０ｇを約８０℃に加熱し、混合物２とした。混合物１をホモジナイザー〔「ＴＫホモミキサー Ｍ型」、特殊機化工業（株）製〕を５，０００ｒｐｍで撹拌させながら混合物２を添加し、油中水型乳化物−１を得た。約８０℃に保温した油中水型乳化物−１を撹拌下、焼成シリカ−２：２０ｇを添加し、籾殻焼成シリカ−２が均一に浸漬した後、２００メッシュの金網でろ過し、籾殻焼成シリカ−２をろ別し、エタノールにて洗浄した。次いで、次いでエタノールを乾燥、除去させて有効成分含有籾殻焼成シリカ−２を得た。
【０１１３】
（有効成分含有籾殻焼成シリカ−３：混合アミノ酸、ヒアルロン酸ナトリウム）
３００ｍＬステンレス容器に混合アミノ酸液１０．０ｇ、ヒアルロン酸ナトリウム１．０ｇ、寒天０．５ｇ、精製水８８．５ｇを撹拌、混合し、約７０℃に加熱して、焼成シリカ−１：２０ｇを添加した。焼成シリカが十分に浸漬した後、２００メッシュの金網でろ過し、焼成シリカ−１をろ別し、水にて焼成シリカ−１の表面を簡単に洗浄した。室温にて風乾し有効成分含有籾殻焼成シリカ−３を得た。
【０１１４】
（有効成分含有籾殻焼成シリカ−４：リパーゼ、プロテアーゼ含有）
３００ｍＬステンレス容器にスクワラン２０．０ｇ、ワセリン３．０ｇ、ステアリン酸１．０ｇ、モノステアリン酸グリセリル０．５ｇ、リパーゼ分散液（９９．５重量％のエタノールに０．５重量％のリパーゼを分散させリパーゼ分散液）５．０ｇ、プロテアーゼ分散液（９９．５重量％のエタノールに０．５重量％のプロテアーゼを分散させプロテアーゼ分散液）５．０ｇの混合液を「油相」とし、ポリオキシエチレン（２０モル付加）モノステアリン酸ソルビタン１．０ｇ、寒天０．５ｇ、精製水５８．５ｇの混合液を「水相」として水中油型乳化物を調製し、焼成シリカ−１：２０ｇを添加して有効成分含有籾殻焼成シリカ−４を得た。
【０１１５】
（有効成分含有籾殻焼成シリカ−５：リパーゼ、プロテアーゼ含有）
有効成分含有籾殻焼成シリカ−１の調製法と同様にして、焼成シリカ−１：２０ｇ、流動パラフィン３５．０ｇ、スクワラン４５．０ｇ、固形パラフィン５．０ｇ、ワセリン３．０ｇ、リパーゼ分散液（９９．５重量％のエタノールに０．５重量％のリパーゼを分散させてリパーゼ分散液とした。）６．０ｇ、プロテアーゼ分散液（９９．５重量％のエタノールに０．５重量％のプロテアーゼを分散させプロテアーゼ分散液とした。）６．０ｇから有効成分含有籾殻焼成シリカ−５を得た。
【０１１６】
（有効成分含有籾殻焼成シリカ−６：アスコルビン酸ステアレート）
有効成分含有籾殻焼成シリカ−１の調製法と同様にして、焼成シリカ−１：２０ｇ、ワセリン１．５ｇ、セチルアルコール１．５ｇ、ステアリン酸２．０ｇ、オレイン酸２０．０ｇ、流動パラフィン３０．０ｇ、スクワラン３５．０ｇ、アスコルビン酸ステアレート１０．０ｇから有効成分含有籾殻焼成シリカ−６を得た。
【０１１７】
（有効成分含有籾殻焼成シリカ−７：アスコルビン酸ジパルミテート）
有効成分含有籾殻焼成シリカ−１の調製法と同様にして、焼成シリカ−１：２０ｇ、ワセリン２．０ｇ、セチルアルコール１．５ｇ、ステアリン酸２．５ｇ、流動パラフィン３５．０ｇ、スクワラン４７．０ｇ、アスコルビン酸ジパルミテート１２．０ｇから有効成分含有籾殻焼成シリカ−７を得た。
【０１１８】
（有効成分含有籾殻焼成シリカ−８：アスコルビン酸リン酸マグネシウム含有）
３００ｍＬステンレス容器にセチルアルコール２．０ｇ、イソステアリン酸３．０ｇ、ワセリン１．０ｇ、ミリスチン酸イソプロピル１０．０ｇ、スクワラン１５．０ｇ、流動パラフィン８．０ｇ、モノオレイン酸ソルビタン１．５ｇ、モノステアリン酸グリセリン２．５ｇを入れて約８０℃に加熱し、均一に混合して「油相」とした。また、精製水２７．０ｇにクエン酸３．０ｇを溶解させ、順次、１、３−ブチレングリコール６．０ｇ、グリセリン６．０ｇ、アスコルビン酸リン酸マグネシウム１５．０ｇを添加して溶解し、水酸化ナトリウムにて中和して「水相」を調製した。油相および水相を約８０℃に加熱し、次いで油相をホモジナイザー〔「ＴＫホモミキサー Ｍ型」特殊機化工業（株）製〕を５０００ｒｐｍで撹拌させながら水相を添加し、油中水型乳化物−２を得た。約８０℃に保温した油中水型乳化物−２に焼成シリカ−１を添加し、焼成シリカ−１が浸漬した後、２００メッシュ金網にてろ過して、有効成分を含む焼成シリカ−１をろ別し、少量のエタノールにて洗浄した。次いで、エタノールを乾燥、除去させて有効成分含有籾殻焼成シリカ−８を得た。
【０１１９】
（有効成分含有籾殻焼成シリカ−９：アスコルビン酸ナトリウム）
３００ｍＬステンレス容器にアスコルビン酸ナトリウム２０．０ｇ、精製水６５．０ｇ、エタノール１５．０ｇを均一になるまで攪拌し、次いで焼成シリカ−１を添加し水相に浸漬した。均一に水相に浸漬した後、２００メッシュの金網でろ過し、焼成シリカ−１をろ別し、水にて焼成シリカ−１の表面を簡単に洗浄した。室温にて風乾し有効成分含有籾殻焼成シリカ−９を得た。
【０１２０】
（有効成分含有籾殻焼成シリカ−１０：アスコルビン酸ナトリウム、ビタミンＡパルミテート含有）
３００ｍＬステンレス容器にアスコルビン酸ナトリウム１０．０ｇ、ポリオキシエチレン（２０モル付加）モノステアリン酸ソルビタン１．０ｇ、精製水５８．５ｇ、エタノール１５．０ｇを約７０℃に加熱し、均一になるまで攪拌し、「水相」とした。同様に他の３００ｍＬステンレス容器にビタミンＡパルミテート２．０ｇ、スクワラン１２．０ｇ、ステアリン酸１．０ｇ、モノステアリン酸グリセリル０．５ｇを入れ、均一に撹拌混合して約７０℃に加熱し「油相」とした。水相をホモジナイザー〔「ＴＫホモミキサー Ｍ型」特殊機化工業（株）製〕を５０００ｒｐｍで撹拌させながら油相を添加し、水中油型乳化物−１を得た。約７０℃に保温した水中油型乳化物−１に焼成シリカ−２を添加し、焼成シリカ−２を十分に浸漬した後、２００メッシュの金網でろ過し、焼成シリカ−１をろ別し、水にて焼成シリカ−１の表面を簡単に洗浄した。室温にて風乾し、有効成分含有籾殻焼成シリカ−１０を得た。
【０１２１】
（有効成分含有籾殻焼成シリカ−１１：ビタミンＡパルミテート含有）
有効成分含有籾殻焼成シリカ−１の調製法と同様にして、焼成シリカ−１：２０ｇ、流動パラフィン３５．０ｇ、スクワラン４５．０ｇ、オレイルアルコール１０．０ｇ、ステアリルアルコール３．０ｇ、固形パラフィン５．０ｇ、ワセリン２．０ｇ、ビタミンＡパルミテート５．０ｇから有効成分含有籾殻焼成シリカ−１１を得た。
【０１２２】
（有効成分含有籾殻焼成シリカ−１２：オウバクエキス、カミツレエキス、アルブチン、コンドロイチン硫酸ナトリウム含有）
有効成分含有籾殻焼成シリカ−３と同様にして、オウバクエキス２．０ｇ、カミツレエキス３．０ｇ、アルブチン０．５ｇ、コンドロイチン硫酸ナトリウム２．０ｇ、寒天０．５ｇ、精製水９２．０ｇ、焼成シリカ−１：２０ｇから有効成分含有籾殻焼成シリカ−１２を得た。
【０１２３】
（有効成分含有籾殻焼成シリカ−１３：ビタミンＡパルミテート、酢酸トコフェロール）
有効成分含有籾殻焼成シリカ−１１と同様にして、ビタミンＡパルミテート２．０ｇ、酢酸トコフェロール１．０ｇ、ワセリン５．５ｇ、ステアリン酸１．０ｇ、モノステアリン酸グリセリル０．５ｇの混合液を「油相」とし、アスコルビン酸リン酸マグネシウム５．０ｇ、クエン酸１．０ｇ、中和に必要な適量の水酸化ナトリウム、ポリオキシエチレン（２０モル付加）モノステアリン酸ソルビタン１．０ｇ、アルカシーラン０．１ｇ、精製水８２．９ｇの混合液を「水相」として水中油型乳化物を調製し、焼成シリカ−１：２０ｇを添加して有効成分含有籾殻焼成シリカ−１３を得た。
【０１２４】
（有効成分含有籾殻焼成シリカ−１４：ヨーグルトエキス、ニコチン酸アミド、コウジ酸含有）
有効成分含有籾殻焼成シリカ−３と同様にして、ヨーグルトエキス５．０ｇ、ニコチン酸アミド１．０ｇ、コウジ酸０．５ｇ、ゼラチン０．５ｇ、精製水６５．０ｇ、焼成シリカ−１：２０ｇから有効成分含有籾殻焼成シリカ−１４を得た。
【０１２５】
（有効成分含有籾殻焼成シリカ−１５：ヨーグルトエキス、米糠エキス、混合アミノ酸、アルブチン含有）
有効成分含有籾殻焼成シリカ−３と同様にして、ヨーグルトエキス５．０ｇ、米糠エキス０．５ｇ、混合アミノ酸液１．０ｇ、アルブチン０．５ｇ、カードラン０．５ｇ、メチルパラベン０．２ｇ、精製水９２．３ｇ、焼成シリカ−１：２０ｇから有効成分含有籾殻焼成シリカ−１５を得た。
【０１２６】
（有効成分含有籾殻焼成シリカ−１６：ヨーグルトエキス、乳酸含有）
有効成分含有籾殻焼成シリカ−３と同様にして、ヨーグルトエキス５．０ｇ、乳酸０．５ｇ、カラギーナン０．２ｇ、アルカシーラン０．０４ｇ、メチルパラベン０．２ｇ、精製水９２．３ｇ、焼成シリカ−１：２０ｇから有効成分含有籾殻焼成シリカ−１６を得た。
【０１２７】
（有効成分含有籾殻焼成シリカ−１７：オウバクエキス、カミツレエキス、人参エキス含有）
有効成分含有籾殻焼成シリカ−３と同様にして、オウバクエキス５．０ｇ、カミツレエキス５．０ｇ、人参エキス３．０ｇ、寒天０．６ｇ、メチルパラベン０．２ｇ、精製水８６．２ｇ、焼成シリカ−１：２０ｇから有効成分含有籾殻焼成シリカ−１８を得た。
【０１２８】
（有効成分含有合成シリカ−１：酢酸トコフェロール含有）
有効成分含有籾殻焼成シリカ−１の調製方法に準じて、籾殻焼成シリカ−１：２０ｇを合成シリカ（商品名「サンスフェアＨ−２０１」、旭硝子（株）製）：２０ｇに置き換え、それ以外は有効成分含有籾殻焼成シリカ−１の配合と同様にして、有効成分含有合成シリカ−１を得た。
【０１２９】
以下同様にして、有効成分含有籾殻焼成シリカ−２〜１７の配合において、焼成シリカ−１あるいは焼成シリカ−２を合成シリカ〔商品名「サンスフェアＨ−２０１」、旭硝子（株）製〕に置き換え、それ以外の配合成分はそのままとして、有効成分含有合成シリカ−２〜１７を調製した。調製した有効成分含有焼成シリカおよび有効成分含有合成シリカを表１および表２に示した。
【０１３０】
【表１】

【０１３１】
【表２】

【０１３２】
〔有効成分含有シリカ配合の皮膚外用剤（水性ジェル状美容液）の安定性試験および官能試験−１〕
（水性ジェル状美容液−１の調製）
２００ｍＬビーカーにグリセリン１２ｇ（６重量％）、１，３−ブチレングリコール１２ｇ（６重量％）、アルカシーラン（Ａ−２）０．３ｇ（０．１５重量％）、精製水１００ｍＬ（５０重量％）を加えて、プロペラ型撹拌機により撹拌し、混合物３とした。一方、精製水５９．２８ｍＬ（２９．６４重量％）にエタノール１２ｇ（６重量％）、クエン酸０．０２ｇ（０．０１重量％）、クエン酸ナトリウム０．２ｇ（０．１重量％）、メチルパラベン０．２ｇ（０．１重量％）を加え、撹拌し、混合物４とした。混合物３を撹拌しながら混合物４を加え、さらに有効成分含有籾殻焼成シリカ−１：４．００ｇ（２重量％）を添加し、均一になるまで攪拌して水性ジェル状美容液−１を得た。
【０１３３】
（水性ジェル状美容液−２〜１６の調製）
水性ジェル状美容液−１の調製方法におけるアルカシーラン（Ａ−２）０．３ｇ（０．１５重量％）、精製水５９．２８ｍＬ（２９．６４重量％）、有効成分含有籾殻焼成シリカ−１：４．００ｇ（２重量％）を表３記載の配合組成に置き換えて、表３記載の水性ジェル状美容液−２〜１６を調製した。
【０１３４】
【表３】

【０１３５】
（安定性試験）
調製した水性ジェル状美容液Ｎｏ．１〜１４をふた付きの円筒状ガラス容器（高さ１３ｃｍ、内径５ｃｍ）の底から高さ１０ｃｍになるところまで入れ、４０℃に３ヶ月間静置した。３ヶ月間静置後、水性ジェル状美容液表面に浮上した有効成分含有シリカから流出した親油性有効成分の有無および水性ジェル状美容液の沈降分離の有無を以下のように目視評価した。水性ジェル状美容液表面に親油性有効成分が流出、浮上したものは好ましくなく、油水分離・沈降分離の生じたものも好ましくない。
・水性ジェル状美容液における親油性有効成分の流出、浮上の有無の評価
○：水性ジェル状美容液表面に流出、浮上した親油性有効成分がない。
×：水性ジェル状美容液表面に流出、浮上した親油性有効成分が有る。
・水性ジェル状美容液における沈降分離の有無の評価
○：水性ジェル状美容液に沈降・分離がない。
×：水性ジェル状美容液表面に沈降・分離が有る。
結果を表４に示した。
【０１３６】
（有効成分含有シリカを含む水性ジェル状美容液の皮膚官能試験）
パネル１０名を選出し、パネル１０名の各左手の甲に、調製後、３ヶ月間静置した水性ジェル状美容液０．５ｇを取り、手のひらで擦ったときの感触で評価した。「さらっと感じる」を「＋」、有効成分含有シリカから流出した親油性有効成分により「べたついた感じがする」を「−」として評価した。パネルの評価を以下の基準に従って判定した。水性ジェル状美容液の皮膚官能試験において、「さらっと感じる」パネルの数が多い方が好ましい。結果を表４に示した。
（判定基準）
○：８名以上が「＋」と感じる。
×：７名以下が「＋」と感じる。
【０１３７】
【表４】

【０１３８】
本発明の有効成分含有焼成シリカを添加した水性ジェル状美容液は、有効成分の流出が認められず、従来の合成シリカを使用した水性ジェル状美容液よりも安定であるこが確認された。また、アルカシーランを使用することで、有効成分含有焼成シリカを添加した水性ジェル状美容液の分離を防止することができた。その結果、水性ジェル状美容液の使用感は３ヶ月経ても変わることなく、「さらっと感じる」状態を維持することができた。
【０１３９】
〔有効成分含有シリカ配合の皮膚外用剤（クレンジングオイル）の安定性試験および官能試験−２〕
（クレンジングオイル−１の調製）
２００ｍＬビーカーにエタノール１６ｇ（８重量％）、およびショ糖ラウリン酸エステル６ｇ（３重量％）、トリイソステアリン酸ＰＯＥ（２０モル付加）グリセリル２０ｇ（１０重量％）、ブチルパラベン０．４ｇ（０．２重量％）を良く混合し、混合物５とし、約７０℃にした。一方、流動パラフィン６７．６ｇ（３３．８重量％）にオリーブオイル４０ｇ（２０重量％）、トリ２−エチルヘキサン酸グリセリル３０ｇ（１５重量％）を添加し、約７０℃に加熱、撹拌して混合物６とした。次いで、混合物５をプロペラ型撹拌機にて撹拌しながら混合物６を添加し、さらに有効成分含有焼成シリカ−１０を２０．００ｇ（１０重量％）添加し、均一になるまで攪拌してクレンジングオイル−１を得た。
【０１４０】
（クレンジングオイル−２〜１１の調製）
クレンジングオイル−１の調製方法における有効成分含有焼成シリカ−１０：２０．００ｇを表５記載の有効成分含有焼成シリカあるいは有効成分含有合成シリカに置き換えて、クレンジングオイル−１の調製方法と同様にしてクレンジングオイル−２〜２３を調製した。
【０１４１】
【表５】

【０１４２】
（安定性試験）
調製したクレンジングオイルＮｏ．１〜２３をふた付きの円筒状ガラス容器（高さ１３ｃｍ、内径５ｃｍ）の底から高さ１０ｃｍになるところまで入れ、４０℃に３ヶ月間静置した。３ヶ月間静置後、クレンジングオイル底部に沈降した有効成分含有シリカから流出した親水性有効成分の有無およびクレンジングオイルの沈降分離の有無を以下のように目視評価した。クレンジングオイル底部に親水性有効成分が流出、沈降・沈積したものは好ましくなく、油水分離・沈降分離の生じたものも好ましくない。
・クレンジングオイルにおける親水性有効成分の流出、沈降の有無の評価
○：クレンジングオイルに流出、沈降した親水性有効成分がない。
×：クレンジングオイルに流出、沈降した親水性有効成分が有る。
・クレンジングオイルにおける沈降分離の有無の評価
○：クレンジングオイルに沈降・分離がない。
×：クレンジングオイルに沈降・分離が有る。
結果を表６に示した。
【０１４３】
（有効成分含有シリカを含むクレンジングオイルの皮膚官能試験）
パネル１０名を選出し、パネル１０名の各左手の甲に、調製後、３ヶ月間静置したクレンジングオイル０．５ｇを取り、手のひらで擦ったときの感触で評価した。「さらっと感じる」を「＋」、有効成分含有シリカから流出した親水性有効成分により「べたついた感じがする」を「−」として評価した。パネルの評価を以下の基準に従って判定した。クレンジングオイルの皮膚官能試験において、「さらっと感じる」パネルの数が多い方が好ましい。結果を表６に示した。
（判定基準）
○：８名以上が「＋」と感じる。
×：７名以下が「＋」と感じる。
【０１４４】
【表６】

【０１４５】
本発明の有効成分含有焼成シリカを添加したクレンジングオイルは、有効成分の流出が認められず、従来の合成シリカを使用したクレンジングオイルよりも安定であるこが確認された。また、アルカシーランを使用することで、有効成分含有焼成シリカを添加したクレンジングオイルの分離を防止することができた。その結果、クレンジングオイルの使用感は３ヶ月経ても変わることなく、「さらっと感じる」状態を維持することができた。
【０１４６】
〔有効成分含有シリカ配合の皮膚外用剤の安定性試験および官能試験−３〕
（洗顔クリーム−１の調製）
（製法）
下記配合において、配合成分Ｎｏ．１〜３を約７０℃にて加熱溶融し、次いでＮｏ．４をＮｏ．１２：４０ｇに溶解させた水溶液を添加し、約７０℃に維持して混合物７とした。配合成分Ｎｏ．８、１０、１１、１２を約７０℃にて攪拌混合し、混合物８とした。混合物７をホモジナイザー〔「ＴＫホモミキサー Ｍ型」特殊機化工業（株）製〕を５０００ｒｐｍで攪拌しながら混合物８を添加し、エマルションを作り、さらに撹拌、冷却し、約４０℃にて配合成分Ｎｏ．５および６、９を添加し、洗顔クリーム−１を得た。
（配合）

（洗顔クリーム−２の調製）
洗顔クリーム−１の有効成分含有焼成シリカ−１：５．０重量％を有効成分含有合成シリカ−１：５．０重量％に、有効成分含有焼成シリカ−２：５．０重量％を有効成分含有合成シリカ−２：５．０重量％にそれぞれ置き換え、それ以外は洗顔クリーム−１と同様にして調製し、洗顔クリーム−２を得た。
【０１４７】
（クレンジングクリーム−１の調製）
（製法）
下記配合において、配合成分Ｎｏ．１〜４を約７０℃にて加熱溶解し、混合物９とした。また、配合成分Ｎｏ．５、６、１０、１１、１２を約７０℃にて攪拌混合し、混合物１０とした。混合物９をホモジナイザー〔「ＴＫホモミキサー Ｍ型」特殊機化工業（株）製〕を５０００ｒｐｍで攪拌しながら混合物１０を添加し、エマルションを調製した。さらに撹拌、冷却し、約４０℃にて配合成分Ｎｏ．７および８、９を添加し、クレンジングクリーム−１を得た。
（配合）

（クレンジングクリーム−２の調製）
クレンジングクリーム−１の有効成分含有焼成シリカ−２：５．０重量％を比較例−１のシリカ（５．０重量％）に、Ｎｏ．８：有効成分（親油性）含有焼成シリカ−４（５．０重量％）を比較例−２のシリカ（５．０重量％）に置き換え、それ以外はクレンジングクリーム−１と同様にして調製し、クレンジングクリーム−２を得た。
【０１４８】
（化粧水−１の調製）
（製法）
下記配合において、配合成分Ｎｏ．１をＮｏ．１０に添加し、均一に分散させ、次に攪拌下、Ｎｏ．２〜９を加え、均一になるまで攪拌し、化粧水−１を得た。
（配合）

（比較例３：化粧水−２）
化粧水−１の有効成分含有焼成シリカ−４：３．０重量％を有効成分含有合成シリカ−１：３．０重量％に、有効成分含有焼成シリカ−５：６．０重量％を有効成分含有合成シリカ−２：６．０重量％にそれぞれ置き換え、それ以外は化粧水−１と同様にして調製し、化粧水−２を得た。
【０１４９】
（乳液−１の調製）
（製法）
下記配合において、配合成分Ｎｏ．１６にＮｏ．８、９を加えて溶解後、７０℃に保ち混合物１１とした。また、Ｎｏ．１〜７及び１１を加熱混合し、７０℃に保ち混合物１２とし、混合物１１をホモジナイザー〔「ＴＫホモミキサー Ｍ型」特殊機化工業（株）製〕で５０００ｒｐｍに撹拌しながら混合物１２および配合成分Ｎｏ．１０を加え、乳化した。さらに約４０℃にまで撹拌冷却し、Ｎｏ．１２〜１４を加えて乳液−１を得た。
（配合）

（乳液−２の調製）
（製法）
下記配合において、配合成分Ｎｏ．１６にＮｏ．１５を加えて溶解後、Ｎｏ．７〜１０を加え均一に分散し、７０℃に保ち混合物１３とする。また、Ｎｏ．１〜６を加熱混合し、７０℃に保ち混合物１４とし、混合物１３をホモジナイザー〔「ＴＫホモミキサー Ｍ型」特殊機化工業（株）製〕で５０００ｒｐｍに撹拌しながら混合物１４を加え、乳化した。さらに約４０℃まで撹拌、冷却し、次いでＮｏ．１１〜１４を加えて乳液−２を得た。
（配合）

（乳液−３の調製）
乳液−１の有効成分含有焼成シリカ−８：３．０重量％を有効成分含有合成シリカ−１：３．０重量％に、有効成分含有焼成シリカ−９：３．０重量％を有効成分含有合成シリカ−２：３．０重量％にそれぞれ置き換え、それ以外は乳液−１と同様にして調製し、乳液−３を得た。
【０１５０】
（マッサージジェル−１の調製）
（製法）
下記配合において、配合成分Ｎｏ．１２にＮｏ．１〜３を添加し、均一に攪拌混合し、混合物１５とした。また、配合成分Ｎｏ．４〜９を攪拌混合し、混合物１６とする。混合物１５を小型ミキサーで撹拌しながら混合物１６を加え、均一になるまで攪拌し、Ｎｏ．１０および１１を加え攪拌してマッサージジェル−１を得た。
（配合）

（マッサージジェル−２の調製）
マッサージジェル−１の有効成分含有焼成シリカ−２：１０．０重量％を有効成分含有合成シリカ−１：１０．０重量％に、有効成分含有焼成シリカ−８：５．０重量％を有効成分含有焼成シリカ−比較例２：５．０重量％にそれぞれ置き換え、それ以外はマッサージジェル−１と同様にして調製し、マッサージジェル−２を得た。
【０１５１】
（有効成分含有シリカ配合の皮膚外用剤の安定性試験）
水性ジェル状美容液と同様に、上記の皮膚外用剤をふた付きの円筒状ガラス容器（高さ１３ｃｍ、内径５ｃｍ）の底から高さ１０ｃｍになるところまで入れ、４０℃に３ヶ月間静置し、有効成分含有シリカから流出した親油性有効成分の有無および水性ジェル状美容液の沈降分離の有無を目視評価した。有効成分含有シリカ配合の皮膚外用剤の表面に親油性有効成分が流出、浮上したものは好ましくなく、油水分離・沈降分離の生じたものも好ましくない。結果を表５に示した。
【０１５２】
（有効成分含有シリカ配合の皮膚外用剤の皮膚官能試験）
水性ジェル状美容液と同様に、パネル１０名を選出し、パネル１０名の各左手の甲に、調製直後の皮膚外用剤０．５ｇを取り、手のひらで擦ったときの感触で評価した。「さらっと感じる」を「＋」、有効成分含有シリカから流出した親油性有効成分により「べたついた感じがする」および親水性有効成分により「不均一感、冷ややかさを感じる」を「−」として評価した。同様に調製後に３ヶ月間静置した皮膚外用剤についても行ない、両者を比較して、以下のように判定した。
○：８人以上が、両者は同等の感触と感じた。
×：７人以下が、調製直後の皮膚外用剤の方が良いと感じた。
皮膚外用剤の皮膚官能試験において、「さらっと感じる」パネルの数が多い方が好ましい。結果を表７に示した。
【０１５３】
【表７】

【０１５４】
本発明の有効成分含有焼成シリカを配合した洗顔クリーム、クレンジングクリーム、化粧水、乳液、マッサージジェル等は、４０℃で３ヵ月間放置後でも当該シリカからの有効成分の流出がなく、その官能評価の結果は、調製直後と同様の感触を維持した。さらに特定の多糖類、例えばアルカシーランの使用により、皮膚用外用剤における有効成分含有焼成シリカの分離を防止し、安定性を向上させることがわかる。
【０１５５】
【発明の効果】
水溶液中あるいは低濃度では不安定な酵素類、ビタミン類、水と相溶性の悪い成分等の有効成分を籾殻焼成シリカに含有させ、これを皮膚外用剤に配合することにより、長期間、当該有効成分を安定な状態で皮膚外用剤中に維持することができ、製品品質の向上に大きく寄与する。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an external preparation for skin, characterized in that an active ingredient is previously contained in calcined rice hulls and blended with the active ingredient. More specifically, the present invention is a skin external preparation characterized in that an active ingredient which is affected by denaturation, deterioration, and the like upon contact with other components is previously contained in rice hull baked silica and is blended with the skin external preparation.
[0002]
[Prior art]
Cosmetic and quasi-drug skin external preparations are generally used for the purpose of cleansing face wash creams, cleansing creams, lotions, etc., products intended for skin conditioning such as serums, packs, massage creams, creams, Basic cosmetics for protection such as milky lotions, lip balms, etc., cosmetics for base makeup such as foundation, white powder, pressed cake, etc., and point makeup for lipstick, blusher, eyeshadow, eyeliner, mascara, etc. And cosmetics such as nail enamels and body cosmetics such as sun care, antiperspirant, deodorant, decolorization, hair removal, insect repellent, bath, etc. In addition, these skin external preparations are generally used to obtain the effects of moisturizing, preventing rough skin, preventing spots and freckles, tightening the skin, anti-inflammatory, promoting blood circulation, preventing skin deterioration due to aging, etc. Depending on the purpose of the active ingredient, for example, moisturizing ingredient, emollient ingredient, astringent ingredient, keratin softening ingredient, whitening ingredient, anti-inflammatory (anti-inflammatory) ingredient, Physiologically active components such as a component having an ultraviolet preventing property, a component having an antioxidant property, a component having a cell activating property, and a component having a blood circulation promoting property are blended.
[0003]
In recent years, importance has been placed on the usefulness of cosmetics. For example, in the case of a skin external preparation, various kinds of active ingredients have been incorporated into the skin external preparation. However, depending on the components, a change due to a chemical reaction between the components, precipitation / aggregation / precipitation, etc. occur, which is a great limitation in designing an external preparation for skin. For example, some enzymes, vitamins, etc. to be incorporated into external preparations for skin are extremely unstable in the preparation, and even a trace amount of water causes inactivation and / or decomposition, which causes quality deterioration. In many cases, its formulation was difficult. In addition, crude drug components containing tannins, flavonoids, and the like sometimes affect the physical properties of the preparation when blended in products such as cosmetics.
[0004]
Many methods have been proposed and implemented to solve these problems. For example, there is a method of immobilizing an unstable enzyme such as amylase, protease or lipase on hydroxyapatite and blending the same into cosmetics (for example, see Patent Document 1). However, this immobilization method can be used only for enzymes, and has a problem in that the three-dimensional structure is distorted due to the bond with hydroxyapatite, and the enzyme activity is reduced. In addition, a method has been proposed in which unstable components and incompatible components are blended in a compressible-disintegrable microcapsule (for example, see Patent Literatures 2 and 3). In some cases, it is difficult to adjust the strength of the microcapsules, for example, if the strength of the microcapsules is too high, the microcapsules cannot be disintegrated due to compression during use as expected.
[0005]
As a method of improving this, a method of stabilizing by containing in a pH-sensitive microcapsule which dissolves at pH 4 or more or pH 9 or less (for example, see Patent Documents 4 and 5) has been proposed. Alternatively, if it is 9 or more, the polysaccharide and the synthetic polymer to be incorporated in the external preparation for skin may be degraded under the influence of pH, and may cause deterioration in quality. As described above, various measures have been proposed to improve the stability when an active ingredient or a poorly compatible ingredient is blended in an external preparation for skin, but these have not always been satisfactory. .
[0006]
[Patent Document 1]
Japanese Patent Publication No. 8-764
[Patent Document 2]
JP-A-62-161712
[Patent Document 3]
Japanese Patent Publication No. 7-121850
[Patent Document 4]
JP-A-6-192035
[Patent Document 5]
JP-A-7-96166
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide an external preparation for skin for a long period of time, which is stable for components that are unstable in aqueous solution, components that are incompatible with water, and components that easily react with other components and deteriorate. It is an object of the present invention to provide a skin external preparation maintained inside.
[0008]
[Means for Solving the Problems]
The present inventors have conducted various studies to obtain an external preparation for skin that stably retains various active ingredients such as enzymes and vitamins and sufficiently exert their effects. By blending it with a skin external preparation, it was possible to stabilize the active ingredient, and it was further found that a specific polysaccharide was effective for dispersing baked rice hull silica, and thus completed the present invention.
[0009]
That is, the invention according to claim 1 is a skin external preparation characterized by containing rice hull baked silica previously containing an active ingredient.
[0010]
The invention according to claim 2 is the external preparation for skin according to claim 1, wherein the active ingredient is selected from sugars and sugar derivatives, amino acids, enzymes, vitamins, organic acids, plant extracts, and crude drug extracts. It is characterized by at least one kind.
[0011]
The invention according to claim 3 is the external preparation for skin according to claim 2, wherein the sugar and the sugar derivative are selected from xylitol, sorbitol, D-glucuronic acid, D-galacturonic acid, trehalose, raffinose, and sucrose stearate. It is characterized by at least one kind.
[0012]
The invention according to claim 4 is the skin external preparation according to claim 2, wherein the amino acids are selected from tryptophan, phenylalanine, proline, tyrosine, lysine, glycine, alanine, glutamine, serine, cysteine, aspartic acid, and glutamic acid. It is characterized by more than species.
[0013]
The invention according to claim 5 is the skin external preparation according to claim 2, wherein the enzymes are at least one selected from lipase, protease, and catalase.
[0014]
The invention according to claim 6 is the skin external preparation according to claim 2, wherein the vitamins are retinol, retinal, dehydroretinal, carotene, lycopene, tocopherol or a derivative thereof, ubiquinones, phytonadione, menaquinone, and magnesium ascorbate. , Sodium ascorbate, thiamine hydrochloride, thiamine sulfate, riboflavin, pyridoxine, cyanocobalamin, folate, nicotinic acid, pantothenic acid, and biotin.
[0015]
The invention according to claim 7 is the skin external preparation according to claim 2, wherein the organic acid is kojic acid, glycolic acid, citric acid, malic acid, lactic acid, salicylic acid, ferulic acid, isoferulic acid, caffeic acid, chlorogenic acid. And at least one member selected from the group consisting of:
[0016]
The invention according to claim 8 is the external preparation for skin according to any one of claims 1 to 7, characterized in that it contains at least a polysaccharide having glucose, fucose, glucuronic acid and rhamnose as constituent monosaccharides.
[0017]
The invention according to claim 9 is the external preparation for skin according to claim 8, characterized in that the polysaccharide is a polysaccharide produced by a bacterium of Alcaligenes stratus B-16 strain.
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention is an external preparation for skin, characterized in that an active ingredient is previously contained in calcined silica obtained by calcining rice hulls, and then the active ingredient is blended. Since many components are blended in skin external preparations, deterioration, complex formation, aggregation, precipitation, etc., occur due to chemical reactions between the various components used, and the original effects of the blended components are lost or exhibited May not be. In order to prevent this, an external preparation for skin is prepared by premixing husk-baked silica with a component which is susceptible to change or a component lacking stability among various components.
[0019]
The external preparation for skin of the present invention corresponds to cosmetics and quasi-drugs of the present invention, and its product form is aqueous solution, emulsion, suspension dispersion, cream, paste, mousse, gel, etc. More specifically, basic cosmetics such as face-washing cream, cleansing cream, lotion, serum, pack, massage cream, cream, milky lotion, lip balm, etc., base makeup cosmetics such as foundation, white powder, lipstick, blusher , Eye shadow, eye liner, point makeup cosmetics such as mascara, nail enamel, sun care, antiperspirant, deodorant, decolorization, hair removal, insect repellent, bath cosmetics, etc., shampoo, hair rinse, hair conditioner, Ointment, perfume, cologne, toothpaste, etc.
[0020]
The rice hull calcined silica of the present invention is obtained by selecting rice hulls to remove rice stalks and the like, and then adding the resultant to water or an aqueous solution of an inorganic acid having a concentration of 1 to 30% (hydrochloric acid, sulfuric acid, or nitric acid aqueous solution) for 30 minutes to 3 hours, preferably 5 to 10 hours. It is more desirable to immerse in a 1% aqueous solution of hydrochloric acid for 1 hour to 2 hours and to perform heating and boiling treatment. After performing the immersion treatment with an acid, washing with water to sufficiently remove the acid, draining the water, and then drying the rice husk, usually using an electric furnace or the like, in the presence of oxygen at 650 ° C to 1200 ° C. For 30 minutes to 6 hours, desirably at 800 ° C. to 920 ° C. for 1 hour to 4 hours.
[0021]
The rice husk is roughly composed of a woody layer, a silica layer, and a cuticle layer. By firing this, the woody layer and the cuticle layer are burned off, leaving a silica layer having a micro network structure and a macro network structure. The silica content in the rice hulls accounts for about 20% by weight of the total rice hulls, and is extremely porous with a maximum of 80% porosity. By pulverizing the calcined rice hull silica, the macro stitch structure is crushed, and calcined silica having a micro network structure and a large number of fine pores is obtained.
[0022]
The calcined silica of the present invention has a specific surface area of 250 to 800 m. ² / G, porosity is 50 to 80%, water absorption is 150 to 400 mL / silica 100 g, oil absorption is 100 to 400 mL / silica 100 g, and the specific surface area is preferably 300 to 600 m. ² / G, porosity is 55-75%, water absorption is 170-350 mL / silica 100 g, oil absorption is 120-350 mL / silica 100 g, and more preferably the specific surface area is 350-500 m. ² / G, porosity is 60-70%, water absorption is 180-300 mL / 100 g of silica, and oil absorption is 140-300 mL / 100 g of silica. Specific surface area is 250m ² / G, a porosity of less than 50%, a water absorption of less than 150 mL / 100 g of silica, and an oil absorption of less than 100 mL / 100 g of silica, the effect of the present invention may not be obtained in some cases. The specific surface area is 800m ² / G, a porosity of 80%, a water absorption of 400 mL / 100 g of silica, and an oil absorption of 400 mL / 100 g of silica, each of which is difficult to obtain and is not practical.
[0023]
The specific surface area of the rice hull calcined silica was measured by BET method using "Soltopmatic Series 1900" manufactured by Carlo Elba. The water absorption and oil absorption are measured in accordance with JIS K5101.
[0024]
The fired rice hull silica of the present invention is originally in the shape of a rugby ball, and is appropriately ground and used according to the intended use. The method of pulverizing the calcined silica is not particularly limited, and may be appropriately selected in consideration of the degree of pulverization and the size of the pulverized material, and is usually performed using a jet mill. The size of the calcined silica used after being pulverized is not particularly limited, and usually, the major axis is 100 to 0.1 μm, and preferably 20 to 0.5 μm.
[0025]
The method of removing the solvent in the calcined silica of the present invention is not particularly limited. For example, a method of removing the mixture of the calcined silica and the base from the bottom of the container through the solvent absorber from the top while filling the mixture, and the bottom surface is reticulated. The method of removing the mixture of the calcined silica and the base from the bottom while filling the mixture of the calcined silica and the base from the top of the container, filling the mixture of the calcined silica and the base in the vessel, and then removing the solvent by drying at room temperature or by heating. No.
[0026]
The active ingredient of the skin external preparation contained in the rice hull baked silica of the present invention includes sugar and sugar derivatives, amino acids, enzymes, vitamins, organic acids, plant extracts, herbal extracts, and moisturizing agents other than these. It is at least one selected from ingredients used for agents, astringents, whitening agents, anti-inflammatory agents, skin (cell) activators, antibacterial agents, antioxidants, fragrances and the like. Among them, sugars and sugar derivatives, amino acids, enzymes, vitamins, organic acids, plant extracts and herbal extracts are preferred.
[0027]
Examples of the sugar and the sugar derivative include sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch-degrading sugar, maltose, xylitol, starch-degrading sugar reducing alcohol, D-glyceryl aldehyde, Dihydroxyacetone, D-erythrose, D-erythrulose, D-threose, erythritol, etc.), L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose 2-deoxy, D-glucose, D-talose, D-busicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, aldheptose, heptrose and the like, octulose and the like. D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc., D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc., D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L-iduronic acid, etc., sucrose, gunthianose, umbelliferose, lactose, planteose, isoliqunoses, α, α-trehalose, raffinose, ricinose, umbilicin, stachyose verbascoses and the like. One or more of these sugar and sugar derivative components are appropriately selected and blended. The amount thereof varies depending on the type of sugar and sugar derivative and cannot be determined uniformly, but is usually 0.01 to 5% by weight of the external preparation for skin.
[0028]
Specific examples of amino acids include valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, glycine, alanine, asparagine, glutamine, serine, cysteine, cystine, tyrosine, proline, hydroxyproline, aspartic acid, and glutamic acid. , Hydroxylysine, arginine, ornithine, histidine, valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, glycine, alanine, asparagine, glutamine, serine, cysteine, cystine, tyrosine, proline, hydroxyproline, aspartic acid, Glutamic acid, hydroxylysine, arginine, ornithine, histidine, etc., and their sulfates, phosphates, nitrates, There are ene salt, or pyrrolidone carboxylic acid. One or more of these amino acids can be appropriately selected and blended, and the amount thereof varies depending on the type of amino acid and cannot be determined uniformly. % By weight.
[0029]
Enzymes are not particularly limited, regardless of the nature of natural products and industrial products produced by microorganisms. Specific examples thereof include lipase, protease, superoxide dismutase (SOD), lysozyme, alkaline phosphatase, and amylase. Lipases such as pancreatin, glutathione peroxidase and catalase, proteases and catalase. Preferred are lipase, protease and catalase. One or more of these enzymes can be appropriately selected and blended, and the amount of blending varies depending on the type of the enzyme and cannot be determined uniformly. 0.5% by weight.
[0030]
The vitamins are not particularly limited, regardless of the nature of natural products and microorganism-produced industrial products. For example, retinol, retinal (vitamin A1), dehydroretinal (vitamin A2), carotene, lycopene (pro Vitamin A), thiamine hydrochloride, thiamine sulfate (vitamin B1), riboflavin (vitamin B2), pyridoxine (vitamin B6), cyanocobalamin (vitamin B12), folic acids, nicotinic acids, pantothenic acids, biotins, choline, inositols , Vitamin C group: ascorbic acid and its derivatives, ergocalciferol (vitamin D2), cholecalciferol (vitamin D3), dihydrotaxerol, vitamin E group: tocopherol and its derivatives, ubiquinones, vitamin K group: phytonadione Vitamin K1), menaquinone (vitamin K2), menadione (vitamin K3), menadiol (vitamin K4), other essential fatty acids (vitamin F), carnitine, γ-oryzanol, orotic acid, vitamin Ps (rutin, eriocitrin, hesperidin) ), There is vitamin U. Desirably, retinol, retinal (vitamin A1), dehydroretinal (vitamin A2), carotene, lycopene (provitamin A), tocopherol or a derivative thereof, ubiquinones, vitamin K group: phytonadione (vitamin K1), menaquinone (vitamin K2) It is. One or two or more of these vitamins can be appropriately selected and blended, and the blending amount varies depending on the type of the vitamin and cannot be determined uniformly. 0.5% by weight.
[0031]
Organic acids include lactic acid, pyruvic acid, mevatilonic acid, succinic acid, glycolic acid, citric acid, salicylic acid, maleic acid, malic acid, ferulic acid, isoferulic acid, caffeic acid, chlorogenic acid, kojic acid, quinolinic acid, retinoin The amount of the acid varies depending on the type of the organic acid and cannot be uniformly determined, but is usually 0.1 to 20% by weight of the external preparation for skin.
[0032]
Specific examples of plant extracts include arnica, hawthorn, kina, salvia, bodaige, panax, ginseng, ginger, mannenrow, hypericum, ginkgo, melissa, ononis, malonier, assembly, garlic, chamomile, thyme, mentha, nettle, capsicum. , Ginger, hops, horse chestnuts, lavender, carrots, mustard, kay, pine, senkyu, elderberry, yamaseri, hashidokoro, button, bayberry, dokudami, kohone, shibugaki, tokinsenka, gujinsin, gentian, grape, hamabou, daidai, , Shobu, Natsumikan, Hamamerisu, Merryloth, Fennel, Sansho, Peony, Eucalyptus, Artemisia, Emmeiso, Rice, Clara, Shokyo, Clove, etc. Or two or more may be used. The compounding amount is usually preferably 0.001 to 5% by weight, particularly preferably 0.01 to 3% by weight of the external preparation for skin. However, any component soluble in water, alcohol, or polyhydric alcohol may be used, and is not limited thereto.
[0033]
Crude herbal extracts include walnut leaves, gourd, sage, hops, rosemary, hypericum, peppermint, chamomile, pheasant, oren, huangbai, huangling, heavy duty medicine, cinnamon, carrot, peonies, toushin, propolis, taxia Tannin, hamamelis, button, birch tar, royal jelly, lycopodium extract and the like. One or more of these can be used, and usually 0.001 to 5% by weight of the external preparation for skin.
[0034]
Examples of the humectant used in the present invention include alkaline simple hot spring water, deep water, hyaluronic acid, chondroitin sulfate, dermatan sulfate, heparan sulfate, mucopolysaccharides such as heparin and keratan sulfate or salts thereof, collagen, elastin, keratin and the like. Or their derivatives and their salts, soybean and egg-derived phospholipids, glycolipids, ceramides, mucins, honey, erythritol, maltose, maltitol, xylitol, xylose, pentaerythritol, fructose, dextrin and derivatives thereof, mannitol , Sorbitol, inositol, trehalose, sugars such as glucose, urea, asparagine, aspartic acid, alanine, arginine, isoleucine, ortinine, glutamine, glycine, glutamic acid and its derivatives Body and salts thereof, amino acids such as cysteine, cystine, citrulline, threonine, serine, tyrosine, tryptophan, theanine, valine, histidine, hydroxylysine, hydroxyproline, pyrrolidonecarboxylic acid and salts thereof, proline, phenylalanine, methionine, lysine and the like. Derivatives or salts thereof, D-panthenol, and plant extracts are included.
[0035]
The plant extracts used for the moisturizer include avocado extract, almond oil, carob extract, rice extract, strawberry extract, fennel extract, usnia oyster extract, spinach extract, olive oil, olive oil extract, cacao Fats, oat extract, kizuta extract, kumazasa extract, gardenia extract, grapefruit extract, genoshoko extract, gentian extract, burdock extract, kobotdul extract, sesame extract, cactus extract, sabonso extract, Ginger extract, Geo extract, Shea butter, Spiraea extract, Senkyu extract, Genio extract, Tachija extract, Camellia extract, Maize extract, Eucommia extract, Tormentilla extract, Dokudami extract, Bakumondou extract Stuff, housepea extract, Bean extract, peppermint extract, green peppermint extract, mint extract, parsley extract, rose extract, sunflower extract, hinoki extract, loofah extract, prune extract, butchers bloom extract, borage oil, button Extract, jojoba oil, bodaille extract, hop extract, pine extract, maronier extract, macadamia nut oil, quince extract, murasaki extract, meadow home oil, melissa extract, cornflower extract, lily extract, yuzu An extract, a lime extract, a lavender extract, a gentian extract, a potato extract, an apple extract and the like can be mentioned. Yeast metabolites, yeast extract, rice fermented extract, rice bran fermented extract, euglena extract, lactic acid fermented product of raw milk and skim milk powder and trehalose or its derivatives such as alcohols and polyhydric alcohols such as ethanol, isopyropanol, and lauryl alcohol Natural alcohols such as, cetanol, stearyl alcohol, oleyl alcohol, lanolin alcohol, cholesterol, and phytosterol; and synthetic alcohols such as 2-hexyldecanol, isostearyl alcohol, and 2-octyldodecanol. Ethylene oxide, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, polyethylene glycol, propylene oxide, propylene glycol, polypropylene glycol, 1,3-butylene glycol , Glycerin, pentaerythritol, sorbitol, mannitol and the like. One or more of these moisturizing components are appropriately selected and blended, and the amount of the moisturizing component varies depending on the type of the moisturizing component and is not uniformly determined. -20% by weight.
[0036]
Astringents (components) used in the present invention include zinc sulfocarbonate, sodium sulfocarbonate, and plant extracts. Examples of plant extracts include arnica, hawthorn, kina, salvia, bodaiju, panax ginseng, ginger, mannenrou, hypericum, ginkgo, melissa, ononis, malonier, assembly, garlic, chamomile, thyme, peppermint, nettle, capsicum, ginger, hop. , Western horse chestnut, lavender, carrot, mustard, kei, pine, senkyu, elderberry, yamaseri, hashidokoro, button, yamamomo, dokudami, kohone, shibugaki, tokinsenka, gubijinsou, gentian, grape, hamabofu, daidai, yuzu, shobu , Hamamelis, Mary Roth, Fennel, Sansho, Peonies, Eucalyptus, Artemisia, Emmeiso, Rice, Clara, Ginger, Clove, Walnut leaf, Ogon, Sage, Ho , Rosemary, hypericum, peppermint, chamomile, pheasant bird, orchid, huangkashi, yellowling, heavy duty medicine, skin, ginseng, peonies, tousin, propolis, taxia, tannin, hamamelis, button, birch tar, royal jelly, kobo extract And other plant extracts. As the astringent, one or more of these can be used in combination. The use amount is usually 0.001 to 5% by weight based on the external preparation for skin.
[0037]
Examples of the whitening agent (component) used in the present invention include a tyrosinase inhibitor, an endothelin antagonist, an α-MSH inhibitor, glabridine, glabrene, liquiritin, isoliquiritin, ellagic acid and its salts and derivatives, kojic acid and its salts. Are vitamins such as derivatives thereof, arbutin and salts thereof, and derivatives thereof, cysteine and salts thereof, and derivatives thereof, ascorbic acid, sodium ascorbate, ascorbyl stearate, ascorbyl palmitate, ascorbyl dipalmitate, and magnesium ascorbate. Cs and their salts and derivatives thereof, glutathione and its salts and derivatives thereof, resorcin and its salts and derivatives thereof, lucinol, neoagarobiose, agarose oligosaccharide, plant extraction Kind it is raised.
[0038]
Plant extracts used as whitening agents (components) include asparagus extract, Altea extract, Ibukitranoo extract, chinko extract, pea extract, oedum extract, gongon extract, ononis extract, Seaweed extract, fire spike extract, liquorice extract, raspberry extract, kujin extract, brown sugar extract, calyx extract, gokahi extract, wheat germ extract, saishin extract, hawthorn extract, sunpenz extract , Peony extract, White lily extract, Sengokuka extract, Soybean extract, Soybean extract, Placenta extract, Taranoki extract, Tea extract, Touki extract, Molasses extract, Noibara extract, Byakuren extract, Grapes Seed extract, beech tree extract, flow de manita extract, hop extract, silkworm extract, mocca extract, yukino Data extract, Coix extract, etc. may be mentioned. Swingle extract is formulated by selecting the one or more appropriate. The amount of the whitening agent is usually 0.01 to 10% by weight based on the external preparation for skin. When a plant extract or the like is used as it is as an extract, it is an amount in terms of dry solid content.
[0039]
Examples of the anti-inflammatory agent used in the present invention include zinc oxide, sulfur and derivatives thereof, glycyrrhizic acid, dipotassium glycyrrhizinate, glycyrrhizic acid and its derivatives such as monoammonium glycyrrhizinate and salts thereof, β-glycyrrhetinic acid and stearyl glycyrrhetinate. , Glycyrrhetinic acid and its derivatives such as disodium 3-succinyloxyglycyrrhetinate and salts thereof, tranexamic acid, chondroitin sulfate, mefenamic acid, phenylbutazone, indomethacin, ibuprofen, ketoprofen, allantoin, guaiazulene and derivatives thereof and their derivatives Salts, extracts of various microorganisms, animals and plants, and the like. The amount of the compound varies depending on the type of the anti-inflammatory agent and cannot be determined uniformly, but is usually 0.01 to 1% by weight based on the external preparation for skin.
[0040]
Examples of the skin (cell) activator (component) that can be used in the present invention include deoxyribonucleic acid and salts thereof, adenylic acid derivatives such as adenosine triphosphate and adenosine monophosphate and salts thereof, ribonucleic acid and salts thereof , Cyclic AMP, cyclic GMP, flavin adenine nucleotide, guanine, adenine, cytosine, thymine, xanthine and derivatives thereof, caffeine, theopherin and its salts, retinol and retinol palmitate, retinol derivatives such as retinol acetate, retinal and Retinal derivatives such as dehydroretinal, carotenoids such as carotene and vitamin A, thiamine and thiamine hydrochloride, thiamine salts such as thiamine sulfate, riboflavin salts such as riboflavin and riboflavin acetate, pyridoxine Pyridoxine hydrochloride, pyridoxine hydrochloride, pyridoxine dioctanoate and other pyridoxine salts, flavin adenine nucleotides, cyanocobalamin, folic acids, nicotinic acid and nicotinamide, nicotinic acid derivatives such as benzyl nicotinate, vitamin Bs such as choline, γ- Linolenic acid and its derivatives, eicosapentaenoic acid and its derivatives, estradiol and its derivatives and their salts, organic acids such as glycolic acid, succinic acid, lactic acid and salicylic acid and their derivatives and their salts and the like. The amount thereof varies depending on the type of the skin (cell) activator and cannot be determined uniformly, but is usually 0.01 to 1% by weight based on the external preparation for skin.
[0041]
Antibacterial agents (components) used in the present invention include benzoic acid, sodium benzoate, carboxylic acid, sorbic acid, potassium sorbate, paraoxybenzoate, parachloromethcresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, Trichlorocarbanilide, photosensitizer, bis (2-pyridylthio-1-oxide) zinc, phenoxyethanol and thiantol, isopropylmethylphenol and the like. The amount is different depending on the type of the antibacterial agent and cannot be determined uniformly, but is usually 0.01 to 1% by weight based on the external preparation for skin.
[0042]
Antioxidants (components) used in the present invention include vitamin A such as retinol, dehydroretinol, retinol acetate, retinol palmitate, retinal, retinoic acid, vitamin A oil and derivatives thereof, and salts thereof, α- Carotenoids such as carotene, β-carotene, γ-carotene, cryptoxanthin, astaxanthin, fucoxanthin and derivatives thereof, pyridoxine, pyridoxal, pyridoxal-5-phosphate, vitamin Bs such as pyridoxamine, derivatives thereof and their derivatives Vitamin Cs such as salts, ascorbic acid, sodium ascorbate, ascorbyl stearate, ascorbyl palmitate, ascorbyl dipalmitate, magnesium phosphate ascorbate, derivatives thereof and their derivatives Vitamin Ds such as ergocalciferol, cholecalciferol, 1,2,5-dihydroxy-cholecalciferol, derivatives and salts thereof, α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, Vitamin E such as α-tocotrienol, β-tocotrienol, γ-tocotrienol, δ-tocotrienol, tocopherol acetate, tocopherol nicotinate, derivatives thereof and salts thereof, trolox, derivatives thereof and salts thereof, dihydroxytoluene, butyl Hydroxytoluene, butylhydroxyanisole, dibutylhydroxytoluene, α-lipoic acid, dehydrolipoic acid, glutathione, derivatives thereof and salts thereof, uric acid, erythorbic acid, sodium erysorbate, etc. Sorbic acid, its derivatives and their salts, gallic acid, gallic acids such as propyl gallate, their derivatives and their salts, rutin, rutin such as α-glycosyl-rutin, its derivatives and their salts, tryptophan and its derivatives And salts thereof, histidine, derivatives thereof and salts thereof, cysteine derivatives such as N-acetylcysteine, N-acetylhomocysteine, N-octanoylcysteine, N-acetylcysteine methyl ester and salts thereof, N, N ′ -Diacetylcystine dimethyl ester, N, N'-dioctanoylcystine dimethyl ester, N, N'-dioctanoyl homocystine dimethyl ester and other cystine derivatives and their salts, carnosine and its derivatives and their salts, homocarnosine and Derivatives and them Salt, anserine and its derivatives and their salts, calcinin and its derivatives and their salts, histidine and / or tryptophan and / or histamine-containing dipeptide or tripeptide derivatives and their salts, flavanone, flavone, anthocyanin, anthocyanidin, flavonol Flavonoids such as quercetin, quercitrin, myricetin, fisetin, hammerittannin, catechin, epicatechin, gallocatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, tannic acid, caffeic acid, ferulic acid, protocatechuic acid, chalcone , Oryzanol, carnosol, sesamol, sesamin, sesamolin, zingerone, curcumin, tetrahydrocurcumin, clobamide, deoxyclobamide, show All, capsaicin, vanillylamide, ellagic acid, bromophenol, flavoglasin, melanoidin, riboflavin, riboflavin butyrate, flavin mononucleotide, flavin adenine nucleotide, ubiquinone, ubiquinol, mannitol, bilirubin, cholesterol, ebselen, selenomethionine, celluloplasmin, transferrin Lactoferrin, albumin, bilirubin, superoxide dismutase, catalase, glutathione peroxidase, metallothionein, O-phosphono-pyridoxylidene rhodamine, and N- (2-hydroxybenzyl) amino acids described in U.S. Pat. No. 5,594,012; Derivatives and salts thereof, and N- (4-pyridoxymethylene) amino acid, and derivatives and derivatives thereof And the salts thereof. The content of the antioxidant component varies depending on the type of the antioxidant component and cannot be determined uniformly, but is usually 0.01 to 10% by weight based on the external preparation for skin. is there. When a plant extract or the like is used as it is as an extract, it is an amount in terms of dry solid content.
[0043]
Flavors (components) used in the present invention include natural flavors and synthetic flavors. Natural flavors include rose oil, jasmine oil, neroli oil, lavender oil, tuberose oil, ylang ylang oil, clary sage oil, clove oil and peppermint. Oil, geranium oil, patchouli oil, sandalwood oil, cinnamon oil, coriander oil, nutmeg oil, pine oil, vanilla oil, Peruvian balsam oil, banana oil, apple oil, fennel oil, tonka beans oil, pepper oil, lemon oil, Vegetable flavors such as orange oil, bergamot oil, opponox oil, vetiver oil, oris oil, oak moss oil, anise oil, and boad rose oil; and animal flavors such as musk oil, civet oil, castorium oil and ambergris oil. Examples of the synthetic fragrance include hydrocarbons such as limonene and β-caryophyllin, cis-3-hexenol, linalool, farnesol, β-phenylethyl alcohol, geraniol, citronellol, alcohols such as terpineol, menthol, santalol, bacdanol, and bramanol. , Aldehydes such as lilanol, lylial, 2,6-nonadienal, citral, α-hexylcinnamic aldehyde, β-ionone, l-carvone, cyclopentadecanone, damascon, methylionone, iron, isoesuper, acetylcell Ketones such as drain and muscone, esters such as benzyl acetate, methyl dihydrojasmonate, methyl jasmonate, linalyl acetate and benzyl benzoate, γ-undecalact Lactones such as ton, jasmine lactone, cyclopentadecanolid, ethylene brassate, oxides such as galact solid, ambroxane, and rose oxide; phenols such as eugenol; nitrogen-containing compounds such as indole; phenylacetaldehyde dimethyl acetal Acetals and Schiff bases such as Auranchiol. Generally, fragrances are rarely used alone, and are used as a compounded fragrance in which a plurality of fragrances are combined depending on the purpose.
[0044]
Sugar and sugar derivatives, amino acids, enzymes, vitamins, organic acids, plant and seaweed extracts, herbal extracts, humectants, astringents, whitening agents, anti-inflammatory agents, skin (cell) activators, antibacterial The mixing ratio of the agent, antioxidant, perfume and the like is not particularly limited, and may be appropriately determined according to the intended skin external preparation.
[0045]
The method for incorporating the active ingredient into the rice hull baked silica of the present invention is not particularly limited, but a method in which the active ingredient is dissolved in a solvent and the rice hull baked silica is immersed therein, the active ingredient is dissolved in the solvent, and There are a method of spraying on silica, a method of preparing the active ingredient as an aqueous or oily emulsion, and immersing or spraying the baked rice hull silica, and any of them may be used. Generally, a method of dissolving an active ingredient in a solvent and immersing baked rice hull silica in the solvent is generally used. Examples of the solvent include ethanol, isopropyl alcohol, water, hexane, volatile silicone, volatile hydrocarbon, and the like, and a mixture of two or more thereof is used. Among them, ethanol and water are preferred from the viewpoint of easy recovery of the solvent.
[0046]
The polysaccharide used in the external preparation for skin of the present invention is used for dispersion of silica hulls and other active ingredients in powder external preparations, and rice hulls in liquid skin external preparations. A polysaccharide used for stabilizing the dispersion of silica and other active ingredients, and for imparting a suitable viscosity to the external preparation for skin, and is a polysaccharide containing at least fucose, glucose, glucuronic acid, and rhamnose as constituent monosaccharides. is there. Preferably, a polysaccharide having a main chain having a repeating structure comprising glucose, glucuronic acid, and rhamnose as represented by the following formula (1), and having a structure in which one fucose is branched from one glucose in the main chain. is there.
[0047]
Embedded image

[0048]
The polysaccharide used in the present invention is obtained as a polysaccharide produced by a microorganism. Generally, microorganisms often produce two or more polysaccharides, and thus, besides the polysaccharide used in the present invention, Even if other polysaccharides are contained, they do not prevent other polysaccharides from being contained as long as they do not prevent the effect of the polysaccharide of the present invention. Microorganisms that produce the polysaccharide used in the present invention are not particularly limited, but include, for example, Alcaligenes L. strain B-16 bacteria (FERM BP-2015).
[0049]
The polysaccharide used in the present invention is produced, for example, in the case of Alcaligenes strain B-16 strain bacteria, as follows. Alcaligenes latus B-16 strain bacterium is cultured by a usual microorganism culture method, and includes, for example, fructose, glucose, monosaccharides such as sucrose, hemicellulose, starch, natural polymers such as corn starch, olive oil and the like. Oils, nitrogen sources such as urea, ammonium chloride, ammonium nitrate, inorganic nitrogen sources such as ammonium sulfate, tryptone, yeast extract, meat extract, peptone, malt extract, and other organic nitrogen sources, other potassium phosphate, magnesium sulfate, Using a medium to which inorganic salts such as sodium chloride are added, a liquid culture with aeration and stirring at an initial pH of 4 to 10 and a culture temperature of 15 to 40 ° C. is performed for 3 to 10 days. After the culturing, about twice (volume) or more of an organic solvent such as acetone, ethanol, or isopropyl alcohol is added to the culture solution, and the culture product is collected as insoluble aggregates.
[0050]
It has been confirmed that at least two types of polysaccharides are contained in polysaccharides (hereinafter referred to as "B-16 polysaccharides") produced by Alcaligenes latus B-16 strain bacteria. A polysaccharide having a structure in which one fucose is branched into one glucose in a main chain of a repeating structure comprising glucose, glucuronic acid, and rhamnose as shown in the above formula (1), which is a polysaccharide of the invention, and has a molecular weight of Is 10 ⁹ It is a high molecular component (see the 1998 Annual Meeting of the Japanese Society of Agricultural Chemistry, p. 371). The other is a polysaccharide having a repeating structure substantially composed of fucose and mannose as constituent monosaccharides, and having a molecular weight of 10%. ³ -10 ⁷ [Y. Nohata, J .; Azuma, R.A. Kurane, Carbohydrate Research 293 , (1996) 213-222]. The B-16 polysaccharide is commercially available as Alkasylan [trade name, INCIname: Alcaligenes Polysaccharides, manufactured by Hakuto Co., Ltd.]. B-16 polysaccharide is excellent in dispersion stability and emulsion stability in a low blending amount, and its effect is stable over time. Due to these properties, it is possible to obtain a formulation having a low viscosity, which prevents the powder from floating or settling, is uniformly dispersed, and has a refreshing feeling in use.
[0051]
The compounding amount of the polysaccharide of the present invention is usually 0.01 to 0.5% by weight (to the total amount) as a dry solid content (hereinafter, "% by weight" is indicated by "%"), and preferably 0.1% by weight. 02-0.2%, more preferably 0.05-0.1%. If the compounding amount (content) of the polysaccharide of the present invention is less than 0.01%, a sufficient effect may not be obtained, and if the compounding amount exceeds 0.5%, the effect is further increased. May be less and have less economic merit.
[0052]
There is no problem if a thickener, a gelling agent and the like conventionally used are used together with the polysaccharide of the present invention. Specifically, plant polymers such as gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, algae colloid, fucoidan, trant gum, locust bean gum, galactomannan, etc .; xanthan gum, curdlan, gellan gum , Fucogel, dextran, succinoglucan, pullulan and the like; macromolecules such as chitosan, casein, albumin and gelatin; starch-based polymers such as starch, carboxymethyl starch and methylhydroxypropyl starch; methylcellulose; Ethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, cellulose sulfate Cellulose polymers such as sodium, sodium carboxymethylcellulose, crystalline cellulose and cellulose powder; alginic acid polymers such as sodium alginate and propylene glycol alginate; vinyl polymers such as polyvinyl methyl ether, carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer Polyoxyethylene-based polymers; polyoxyethylene polyoxypropylene copolymer-based polymers; acrylic polymers such as sodium polyacrylate, polyethyl acrylate, and polyacrylamide; cationic polymers such as polyethylene imine; bentonite, laponite, Inorganic minerals such as hectorite; amino acid derivatives such as N-lauroyl-L-glutamic acid, α, γ-di-n-butylamine; dextrin palmitin Dextrin fatty acid esters such as esters, dextrin stearate, dextrin 2-ethylhexanoate palmitate; sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol Organically modified inorganic minerals such as dimethylbenzyl dodecylammonium montmorillonite clay and dimethyldioctadecyl ammonium montmorillonite clay. Film forming agents such as polyvinyl alcohol and polyvinyl pyrrolidone are also included. One or more of these thickeners / gelling agents can be appropriately selected and blended, and the blending amount varies depending on the type of the thickener / gelling agent and cannot be determined uniformly. , Usually 0.05 to 10% based on the external preparation for skin.
[0053]
The external preparation for skin of the present invention includes organic bases, oils, siloxane compounds, polyhydric alcohols generally used in medicines, quasi-drugs, cosmetics, etc., as long as the effects of the present invention are not impaired. Surfactants, pigments, pigments, organic acids, ultraviolet absorbers, and enzymes other than those described as active ingredients to be contained in rice hull baked silica, humectants, astringents, whitening agents, anti-inflammatory agents, skin (cells) An activator, an antibacterial agent, an antioxidant, a fragrance, and the like may be selected as necessary, and may be contained in the baked rice husk silica or may be blended with the external preparation for skin. Hereinafter, specific examples will be described.
[0054]
Organic bases (components) include ethanol, acetone, ethyl acetate, butyl acetate, 1,3-butylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, butanol, and propanol. And the like, and can be appropriately selected and blended. The blending amount varies depending on the type of the organic base and cannot be uniformly determined, but is usually 1% to 50% with respect to the skin external preparation. is there.
[0055]
Examples of the oil include hydrocarbons, waxes, fatty acids, higher alcohols, fatty acid esters, organic acid esters, glycerides, fluorinated hydrocarbons, and the like. Specifically, examples of the hydrocarbon include squalane, squalene, ceresin, paraffin, paraffin wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax, and petrolatum, and waxes include beeswax, carnauba wax, candelilla wax, and whale There are waxes and the like, and animal oils include beef tallow, beef tallow, beef bone fat, hardened tallow, hardened oil, turtle oil, lard, horse fat, mink oil, liver oil, egg yolk oil, and the like. , Liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether and the like. Fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, arachidonic acid, docosahexaenoic acid (DHA), isostearic acid, 12-hydroxystearic acid, and the like. Is lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol, There are sitosterol, lanosterol, POE cholesterol ether, monostearyl glycerin ether (bacyl alcohol), etc. Examples of the fatty acid esters include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, Ethylene glycol 2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyldodecyl gum ester, oleyl oleate, Octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate Butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, 12 Cholesteryl hydroxystearylate, dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, and the like, Examples of the amino acid ester include N-lauroyl-L-glutamic acid-2-octyldodecyl ester, and examples of the organic acid esters include diisostearyl malate and the like. Glycerides such as acetoglyceride, glyceride triisooctanoate, glyceride triisostearate, glyceride triisopalmitate, glyceride tri-2-ethylhexanoate, glyceride monostearate, glyceride di-2-heptylundecanoate, and glyceride trimyristate And fluorinated hydrocarbons such as perfluoropolyether, perfluorodecalin, perfluorooctane, etc., which can be appropriately selected and blended. The blending amount varies depending on the type of oil agent, and is uniform. However, it is usually 0.1% to 50% with respect to the external preparation for skin.
[0056]
The siloxane compound includes dimethylpolysiloxane, ethylmethylpolysiloxane, diethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, dimethylsiloxane-methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxyethylene). Polyether-modified organopolysiloxane such as polyoxypropylene) siloxane copolymer, dimethylsiloxane-alkoxy (C4-12) methylsiloxane copolymer, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodeca Cyclic dimethylpolysiloxane such as methylcyclohexasiloxane, and fluorine-modified organopodium such as fluoromethylsiloxane / dimethylsiloxane copolymer Fluoroalkyl / polyoxyalkylene-modified organopolysiloxanes such as siloxane, fluoromethylsiloxane / polyoxyethylenemethylsiloxane copolymer and fluoromethylmethylsiloxane / polyoxyethylene polyoxypropylenemethylsiloxane copolymer, with hydroxyl groups introduced at the terminals Terminal or side chain-modified organopolysiloxanes such as modified dimethylpolysiloxane or hydroxymethylsiloxane / dimethylpolysiloxane copolymer with a partial introduction of hydroxyl groups in the side chain, dimethylaminobutylmethyl having a dialkylaminoalkyl group in the side chain A modified aminoorganopolysiloxane such as a siloxane / dimethylsiloxane polymer can be used. In order to use these silicone oils in the external preparation composition for skin, those having a viscosity of 100,000 (mPa · s: 25 ° C.) or less are usually selected, and the amount of the silicone oil is usually in the range of It is 0.1 to 80%, preferably 0.5 to 50%, based on the amount of the agent.
[0057]
Examples of polyhydric alcohols include anthracene diol, quinoline diol, glyoxime, glyceraldehyde, anthracenol, sedheptitol, propanediol, inositol, usnic acid, urushiol, ursodeoxycholic acid, ethylboronic acid, diethanolamine, diethylpropanediol, Diethylene glycol, diethoxypropanediol, cyclohexanediol, cyclohexanedione, cyclohexanetriol, dihydroxyoctadecanoic acid, dihydroxycinnamic acid, dimethylcyclopentanediol, dimethylpropanediol, dimethylbenzenediol, tartaramide, thioglycerin, triethylene glycol, nitropropyl Propanediol, butanediol, butynediol, hexanediol Pentanediol, pentanetriol, pentanepentol, ethylene oxide, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene oxide, propylene glycol, polypropylene glycol, 1,3-butylene glycol, pentyl glycol, glycerin, pentaerythritol , Threitol, arabitol, xylitol, ribitol, galactitol, sorbitol, mannitol, lactitol, maltitol, methanediol, methylbutanediol, monoacetin, rhamnitol and the like. One or more of these polyhydric alcohols can be appropriately selected and blended, and the content thereof varies depending on the type of the polyhydric alcohol and cannot be determined uniformly, but is usually used for skin external use. 0.01 to 5% by weight of the agent.
[0058]
Surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. As nonionic surfactants, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyoxyalkylene glycerin fatty acid esters Glycerin fatty acid esters, polyglycerin fatty acid esters, polyoxyalkylene hydrogenated castor oils, sucrose fatty acid esters, polyoxyalkylene alkylamines, ethylene oxide / propylene oxide block copolymers, and the like.
[0059]
The polyoxyalkylene in the nonionic surfactant is polyoxyethylene (hereinafter, referred to as “POE”), polyoxypropylene (hereinafter, referred to as “POP”), or polyoxybutylene (hereinafter, referred to as “POB”). ), And the number of moles of POE, POP, and POB to be polymerized is appropriately determined depending on the emulsifying properties of the target surfactant, and is usually from 3 to 200. In addition, the polymerization molar ratio of POE, POP, and POB is appropriately determined depending on the emulsifying properties of the target surfactant. Preferably, the polyoxyalkylene is composed of POE and POP, wherein POE accounts for 25 mol% or more. Polyoxyalkylene alkyl ethers having 2 to 4 carbon atoms are obtained by adding a polyalkylene oxide to a linear or branched, saturated or unsaturated alcohol having 8 to 30 carbon atoms. Specifically, POE (3 mol) octyl ether, POE (5 mol) dodecyl ether, POE (10 mol) oleyl ether, POE (15 mol) stearyl ether, POE (20 mol) behenyl ether, POE (10 mol) POP (10 mol) decyl ether, POE (15 mol) POP (2 mol) isosteryl ether, POE (10 mol) cholestanol ether, POE (5 mol) POP (5 mol) hydrogenated lanolins and the like.
[0060]
The polyoxyalkylene alkyl phenyl ethers are obtained by adding a polyalkylene oxide to a linear or branched alkyl phenol or alkenyl phenol having 1 to 22 carbon atoms, specifically, polyoxyethylene (3 mol) methyl phenyl ether, POE (5 mol) octyl phenyl ether, POE (10 mol) nonyl phenyl ether, POE (15 mol) dodecyl phenyl ether, and the like.
[0061]
Polyoxyalkylene fatty acid esters are obtained by adding a polyalkylene oxide to a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms, and specifically include POE (3 mol) octanoic acid ester, POE (5 mol) decanoate, POE (10 mol) dodecanoate, POE (15 mol) stearate, POE (20 mol) behenylate, POE (15 mol) isostearate, POE (15 mol) POP (5 mol) oleate and the like.
[0062]
Polyoxyethylene sorbitan fatty acid esters are obtained by adding sorbitol, a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms and a polyalkylene oxide, and specifically, POE (5 mol) sorbitan monoester. Laurate, POE (20 mol) sorbitan trilaurate, POE (20 mol) sorbitan monostearate, POE (20 mol) sorbitan sesquistearate, POE (20 mol) sorbitan tristearate, POE (20 mol) sorbitan mono There are oleates.
[0063]
Sorbitan fatty acid esters are esters of sorbitol and a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms, specifically, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, Sorbitan monoisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, penta-2-erthyhexyl diglycerol sorbitan, tetra-2-ethylhexyl diglycerol sorbitan, and the like.
[0064]
Polyoxyethylene glycerin fatty acid esters are addition esters of glycerin with a straight or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms and a polyalkylene oxide. Specifically, POE (5 mol) glycerin monolaurate, POE (10 mol) glycerin monostearate, POE (15 mol) glycerin distearate, POE (20 mol) POP (5 mol) glycerin dioleate, etc. There is.
[0065]
The glycerin fatty acid ester is an ester of glycerin and a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms, specifically, glyceryl monolaurate, glyceryl sesquilaurate, glyceryl trilaurate, and monostearic acid. Glycerin, glycerin sesquistearate, glyceryl tristearate, glycerin monooleate, glycerin sesquioleate, glycerin trioleate, glycerin mono-cottonseed oil, glycerin monoerucate, glycerin monoerucate, α, α'-glycerol pyroglutamate, carbon number 8 And glycerin esters, and stearic acid, malic acid, and glycerin esters.
[0066]
Polyglycerin fatty acid esters include condensed hydroxystearic acid polyglycerin ester and condensed ricinoleic acid polyglycerin ester. Polyoxyethylene-cured castor oils include POE (10 mol) castor oil and POE (15 mol) cured. Castor oil, POE (15 mol) hydrogenated castor oil monoisostearate, POE (20 mol) hydrogenated castor oil triisostearate, POE (20 mol) hydrogenated castor oil monopyroglutamic acid monoisostearate diester, POE (20 mol) Hardened castor oil and maleic acid.
The sucrose fatty acid esters are esters of sucrose and a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms, specifically, sucrose behenate, sucrose stearate, Sucrose palmitate, sucrose myristate, sucrose laurate, sucrose erucate, sucrose oleate, and the like.
[0067]
The polyoxyalkylene alkylamines are obtained by adding a primary or secondary amine having 3 to 22 carbon atoms and a polyalkylene oxide. Specifically, POE (5 mol) didodecylamine, diPOE (10) POP (3) Dodecylamine, POE (10 mol) distearylamine, diPOE (10 mol) stearylamine, diPOE (15 mol) oleylamine, diPOE (17 mol) behenylamine and the like.
[0068]
Ethylene oxide / propylene oxide copolymers are copolymers obtained by polymerizing ethylene oxide and propylene oxide in a molar ratio of 1: 9 to 9: 1 with a molecular weight of about 500 to 50,000.
[0069]
Examples of the anionic surfactant include fatty acid salts, alkyl sulfates and alkenyl sulfates, alkylphenyl sulfates and alkenylphenyl sulfates, alkylphenyl polyoxyalkylene ether sulfates and alkylphenyl polyoxyalkylene ether sulfates, and (di). Examples include alkylsulfosuccinates, N-acylamino acid salts (acyl-N-methyltaurines), alkylbenzenesulfonates, alkylnaphthalenesulfonates, and formalin polycondensates of naphthalenesulfonates. The metal salt is preferably a sodium salt, a potassium salt, or an ammonium salt.
[0070]
Fatty acid salts are metal salts of straight or branched chain fatty acids having 8 to 30 carbon atoms, and further, saturated or unsaturated fatty acids, specifically, sodium octylate, sodium decanoate, sodium dodecanoate, sodium tetradecanoate, Examples include sodium stearate, sodium isostearate, sodium oleate, sodium linolenate, and sodium edetate.
[0071]
Alkyl sulfates and alkenyl sulfates are straight-chain or branched and further saturated or unsaturated alkyl sulfates and alkenyl sulfates having 8 to 30 carbon atoms, specifically, sodium octyl sulfate, sodium decyl sulfate, Examples include sodium dodecyl sulfate, sodium cocoalkyl sulfate, sodium stearyl sulfate, potassium isostearyl sulfate, ammonium oleyl sulfate, and ammonium behenyl sulfate.
[0072]
Alkyl phenyl polyoxyalkylene ether sulfates and alkyl phenyl polyoxyalkylene ether sulfates are a phenyl group having 1 to 22 carbon atoms and having a linear or branched alkyl group or alkenyl group and a polyoxy group having 2 to 4 carbon atoms. Sulfates with alkylene glycol adducts. Specifically, sodium tosyl POE (3 mol) sulfate, octylphenyl POE (5 mol) sodium sulfate, potassium nonylphenyl POE (10 mol) potassium sulfate, sodium decylphenyl POE (10 mol) sodium sulfate, octadecylphenyl POE (15 mol) ) Potassium sulfate, potassium octadecenylphenyl POE (15 mol), potassium isooctadecylphenyl POE (15 mol), POP (5 mol), and the like.
[0073]
(Di) alkyl sulfosuccinates include sodium dioctyl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, and the like.
[0074]
N-acyl amino acid salts are acyl-N-methyl taurines, and specifically include sodium lauroyl sarcosine, N-myristoyl-N-methyl taurine sodium, coconut oil fatty acid methyl tauride sodium, sodium lauryl methyl tauride, and the like. N-acyl glutamates such as higher fatty acid amide sulfonates, monosodium N-lauroylglutamate, disodium N-stearoylglutamate, monosodium N-myristoyl-L-glutamate and the like.
[0075]
Examples of the alkylbenzene sulfonates include sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, and ammonium dodecylbenzenesulfonate. These may be used alone or in combination of two or more.
[0076]
Examples of the cationic surfactant include amino acids, alkylamine salts, quaternary ammonium salts, and pyridinium salts.
[0077]
Examples of the amino acids include lecithin derived from egg yolk or soybean, and hydrogenated lecithin or lecithin derivatives such as hydroxylated lecithin.
[0078]
Examples of the alkylamine salts include salts of a primary or secondary amine having 3 to 22 carbon atoms and a carboxylic acid having 1 to 22 carbon atoms, and salts of inorganic mineral acids, and specifically, dodecylamine acetate, dodecylamine hydrochloride. Salts, dodecylamine stearate, dimethylamine stearate and the like.
[0079]
The quaternary ammonium salts are salts of a quaternary amine having 3 to 22 carbon atoms and a carboxylic acid having 1 to 22 carbon atoms or salts of inorganic mineral acids. Specifically, stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, Distearyl dimethyl ammonium chloride, benzalkonium chloride, benzethonium chloride, cocoalkyl bromide (10-14 carbon atoms) isoquinolinium salt, dodecyl imidazolium chloride and the like.
[0080]
Examples of the pyridinium salts include poly (N, N-dimethyl-3,5-methylenepiperidinium) chloride and cetylpyridinium chloride.
[0081]
In addition, as the cationic surfactant, amine oxides such as dodecyldimethylamine oxide, and cationic polymers such as vinylpyrrolidone acrylic acid β-NN-dimethyl-N-ethylammonioethylate copolymer can be used.
[0082]
Examples of the amphoteric surfactant include betaines, phosphobetaines and sulfobetaines, glycine betaines, imidazolium betaines, and amine oxides. Specifically, betaines include dodecyldimethylaminoacetate betaine, stearyldimethylacetate betaine, and betaine dodecanoate dimethyldimethylaminoacetate betaine, and phosphobetaines include 2- (dimethyldodecylammonio) propiophosphate, -(Dimethyldodecylammonio) -2-hydroxypropiophosphate and the like, sulfobetaines include dodecyldimethylethylammonium ethosulfate, and glycine betaines include dodecyldi (aminoethyl) glycine and imidazolium betaine. Examples include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imitazolinium hydroxide-1-carboxyethyloxy. Disodium salt, 2-heptadecyl -N- carboxymethyl -N- hydroxyethyl imidazolinium betaine.
[0083]
Among these, surfactants such as sucrose fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, lecithin and derivatives thereof are preferable, and sucrose stearate, sucrose palmitate and sucrose are more preferable. Myristate, sucrose laurate, sucrose erucate, sucrose oleate, glyceryl monostearate, glyceryl oleate, polyglycerin condensed hydroxystearate, polyglycerin condensed ricinoleate, lecithin, hydrogenated Lecithin and hydroxylated lecithin, and these can be used alone or in combination of two or more. The compounding amount varies depending on the type of the surfactant and cannot be determined uniformly, but is usually 0.1 to 10% by weight based on the external preparation for skin.
[0084]
The coloring agent used in the present invention includes, as organic synthetic dyes, azo dyes such as Yellow No. 5 and Red No. 505; xanthene dyes such as Red No. 213 and Red No. 230; quinoline dyes such as Yellow No. 204; No. 1; triphenylmethene dyes such as No. 1; anthraquinone dyes such as Green No. 201; dyes such as indigo dyes; lake pigments such as Red No. 202 and Red No. 208; Red No. 228, Red No. 226, Blue No. 404 And carotene, calsamine, cochineal and the like as natural pigments. The amount of the compound varies depending on the type of the coloring agent and cannot be determined uniformly, but is usually 0.01 to 0.1% by weight based on the external preparation for skin.
[0085]
Pigments used in the present invention include, for example, lake pigments, organic pigments, coloring pigments, white pigments, inorganic pigments such as extender pigments, pearlescent pigments, metallic glossy pigments, glass flake pigments, metal-coated inorganic pigments, resin pigments, and the like. Molecular powders, functional pigments and the like are used, and one or more of these are used.
[0086]
There are two types of lake pigments, one of which is a pigment in which a water-soluble dye is insolubilized in water as a salt such as calcium, for example, red 202, 204, 206, 207, 208, 220 Etc. The other is a pigment which is made water-insoluble with aluminum sulfate, zirconium sulfate or the like and adsorbed on alumina, such as Yellow No. 5 and Red No. 230.
[0087]
Organic pigments are colored powders that do not dissolve in water, oil or base, and have excellent coloring power and light resistance. Azo-based pigment Red No. 228, indigo-based pigment Red No. 226, phthalocyanine-based pigment Blue No. 404, and the like.
[0088]
Inorganic pigments include iron oxides with different colors such as red iron oxide, yellow iron oxide, black iron oxide, ultramarine, navy blue, chromium oxide, chromium hydroxide, magnesium oxide, cobalt oxide, cobalt titanate carbon black, manganese violet, cobalt violet, etc. Is raised.
[0089]
The white pigment is used for the purpose of coloring or coating, and examples thereof include titanium dioxide and zinc oxide.
[0090]
The extender pigment is used for maintaining the shape of the product, adjusting the extensibility, adhesion, gloss, etc., and adjusting the color tone (diluent) rather than coloring. For example, mica, mica, synthetic mica, phlogopite, red Mica pigments such as mica, biotite, and lithia mica; viscous minerals such as sericite, talc, kaolin, montmorillonite, and zeolite; magnesium carbonate, calcium carbonate, silicic acid, silicic anhydride, aluminum silicate, magnesium silicate, and silica Examples include synthetic inorganic powders such as aluminum magnesium silicate, sulfur-containing aluminum silicate, calcium silicate, barium silicate, strontium silicate, aluminum oxide, and barium sulfate.
[0091]
The pearlescent pigment is a pigment used to give a pearly luster, an iris color, and a metallic feeling, and examples thereof include titanium dioxide-coated mica, fish scale foil, and bihemous oxychloride. In addition, pigments coated with iron oxide instead of titanium oxide, pigments in which transparent pigments of different colors are coated on a coating layer of titanium oxide, and the like are also used.
[0092]
Examples of the metallic luster pigment include aluminum powder, brass powder, copper powder, tin powder, gold powder, silver powder, and the like, and further, a colored metal powder pigment obtained by coloring these metal powders.
[0093]
The glass flake pigment is formed by coating a flaky glass with a metal or the like.
[0094]
The metal-coated inorganic pigment is an inorganic pigment coated with a metal and / or a metal oxide by metal vapor deposition or the like, and examples thereof include iron oxide-coated aluminum, iron oxide-coated mica, and aluminum-manganese-coated mica-like iron oxide. Can be
[0095]
Examples of the resin pigment include resin film colored and cut flakes.For example, polyester film powder, polyethylene terephthalate / aluminum / epoxy laminated film powder, polyethylene terephthalate / polyolefin laminated film powder, polymethyl methacrylate, polyethylene terephthalate -Polymethyl methacrylate laminated powder, nylon powder and the like.
[0096]
Examples of the functional pigment include boron nitride, synthetic fluorophlogopite, photochromic pigment, and composite fine particle powder.
[0097]
The form of the brilliant pigment of the present invention is not particularly limited, and may be appropriately selected depending on the purpose and the pigment to be used, such as granules, plates and rods. The size of the pigment is not particularly limited, and may be appropriately selected depending on the purpose and the pigment to be used. If the pigment is a granular pigment, the pigment usually has an average particle diameter of 0.01 μm to 5000 μm. As long as it is used, if it is a foil-shaped or rod-shaped powder, a powder having a major axis of 0.1 to 5000 μm is usually used. The compounding amount varies depending on the type of the pigment and cannot be determined uniformly, but is usually 0.1 to 10% by weight based on the external preparation for skin.
[0098]
Specific examples of the organic acid include acetoxypropionic acid, isovaleric acid, aminovaleric acid, ethoxyacetic acid, ethoxypropionic acid, isoaminovaleric acid, epoxy oleic acid, elaidic acid, aminobutyric acid, erucic acid, oxaloacetic acid, and oleic acid. , Aminolevulinic acid, 2-amino-4-guanidinooxybutyric acid, angelic acid, galacturonic acid, carbamic acid, icosatrienoic acid, formic acid, allyl formate, isobutyl formate, icosanoic acid, isopentyl formate, glucuronic acid, iduronic acid, crotonic acid, chlorotonic acid, chloroisoic acid Crotonic acid, isocrotonic acid, acetic acid, dihydrolipoic acid, ethyl crotonic acid, diphenylacetic acid, dimethoxyphthalic acid, ethylhydroxybutyric acid, succinamic acid, stearic acid, stearic acid, sorbic acid, tiglic acid, thyroxine, decanoic acid, tropic acid Lactic acid, hydroxyisobutyric acid, hydroxyvaleric acid, pyruvic acid, butylacetic acid, butylhydroperoxide, brassic acid, propiolic acid, pyropionic acid, bromoisovaleric acid, bromoisobutyric acid, bromopropionic acid, hexanoic acid, hexenoic acid, petroselinic acid, heptadecane Acid, heptanoic acid, areanilic acid, maleamic acid, maleamic acid, mycolic acid, myristic acid, methacrylic acid, methylvaleric acid, methylthioacetic acid, methylbutyric acid, mevalonic acid, melicic acid, mercaptoacetic acid, iodoacetic acid, lauric acid, ricineraidic acid , Ricinoleic acid, linoleic acid, linolenic acid, aconitic acid, oxalosuccinic acid, oxoglutaric acid, adipic acid, calcein, carboxyphenylacetic acid, acetoxysuccinic acid, carboxycomeronic acid, camphoronic acid, isocan Lonic acid, glutaconic acid, glutaric acid, isocitric acid, crocetin, succinic acid, phthalic acid, fumaric acid, isosincomomeronic acid, diethylenetriaminepentaacetic acid, isophthalic acid, citramalic acid, dinicotinic acid, itaconic acid, dibromosuccinic acid, dichlorosuccinic acid Acid, ethylmalonic acid, dimethylsuccinic acid, oxalic acid, tartaric acid, cinchomeronic acid, sulfonyldiacetic acid, sebacic acid, tartronic acid, desoxalic acid, tetrachlorophthalic acid, tetrahydroxysuccinic acid, tetramethylsuccinic acid, terephthalic acid, trimesin Acid, trimellitic acid, naphthalic acid, nitrophthalic acid, bixin, hydroxyisophthalic acid, hydroxyphthalic acid, planitic acid, hydroxymethylpentanedioic acid, pyromellitic acid, phenylsuccinic acid, propanetricarboxylic acid, bromosuccinic acid, Lomofumaric acid, bromomaleic acid, hemimellitic acid, pelargonic acid, berberic acid, benzenehexacarboxylic acid, benzenepentacarboxylic acid, maleic acid, malonic acid, mesaconic acid, mesotartaric acid, mesooxalic acid, methylisophthalic acid, methylsuccinic acid, methylmalon Polycarboxylic acids such as acid, mercaptosuccinic acid, melophanic acid, peroxyphthalic acid, malic acid, lutidic acid, leukotriene, methylanthranilic acid, mercaptobenzoic acid, iodobenzoic acid, benzylbenzoic acid, benzamide benzoic acid, and acetylbenzoic acid , Ethylbenzoic acid, opianic acid, orseric acid, acetamidobenzoic acid, carboxyoxanilic acid, azoxydibenzoic acid, chlorobenzoic acid, chloroperbenzoic acid, anisic acid, gentisic acid, diaminobenzoic acid, shikimic acid, amino Benzoic acid, dihydroxybenzoic acid, dibromobenzoic acid, benzoylbenzoic acid, aminonitrobenzoic acid, dimethylaminobenzoic acid, dimethylbenzoic acid, benzoic acid, sulfobenzoic acid, terephthalaldehyde acid, isophthalaldehyde acid, trichlorobenzoic acid, trinitro Benzoic acid, isopropylbenzoic acid, trihydroxybenzoic acid, trimethylbenzoic acid, toluic acid, toluoylbenzoic acid, nitrobenzoic acid, vanillic acid, idrazodibenzoic acid, hydroxybenzoic acid, hydroxytoluylbenzoic acid, piperonylic acid, phenoxybenzoic acid , Fluorobenzoic acid, veratric acid, protocatechuic acid, probenecid, bromobenzoic acid, bromoanthranilic acid, aminocinnamic acid, isopropylcinnamic acid, oxanilic acid, arecaidine, carboxycinnamic acid, silica Acid, alloxanic acid, ketocyclohexanecarboxylic acid, anthraquinonecarboxylic acid, cyclobutanecarboxylic acid, anthracenecarboxylic acid, cyclopropanecarboxylic acid, isonicotinic acid, cyclohexanecarboxylic acid, cyclopropanecarboxylic acid, isonicopentic acid, cyclohexanediaminetetraacetic acid, cyclohexanedicarboxylic acid Acid, ibuprofen, cyclohexenedicarboxylic acid, cyclopentanecarboxylic acid, indomethacin, indoleacetic acid, cyclopentanedicarboxylic acid, dimethylfurancarboxylic acid, cincophen, galloyl gallic acid, tranexamic acid, nitrocinnamic acid, hydroxycinnamic acid, methoxycinnamic acid , Hydroxyhydrocinnamic acid, phenylcinnamic acid, ferulic acid, isoferulic acid, caffeic acid, chlorogenic acid, bromocinnamic acid, Aromatic carboxylic acids such as hesperitic acid, gallic acid, methylcinnamic acid, and others, ursodeoxycholic acid, ellagic acid, orotidine, orotic acid, camphanic acid, quinic acid, hydroxyproline, ethicholanic acid, caulmoogluric acid, carnosine, carbazole Acetic acid, quinoline carboxylic acid, quinolinic acid, quinoline dicarboxylic acid, coumaric acid, chlorophenoxyacetic acid, chenodeoxycholic acid, cholanic acid, cholic acid, santonic acid, dihydroorthoic acid, succininal acid, thiophenecarboxylic acid, tetrahydrofolate, dehydrocholic acid, Terpenylic acid, terenic acid, dominoleic acid, dopa, thromboxane, naphthylacetic acid, naphthoic acid, nalidixic acid, nitroquinadylic acid, nitrophenylpropiolic acid, nicopetinic acid, ruconanic acid, dopaquinone, Deoxycholic acid, hydroatropic acid, hydroxyisopropyltoluic acid, hydroxycyclohexanecarboxylic acid, hydroxypyronecarboxylic acid, hydroxypyronedicarboxylic acid, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, biphenyldicarboxylic acid, pipecolic acid, piperic acid, pimaric acid, pyridyl Acid, pyroglutamic acid, pyrrolecarboxylic acid, pyronecarboxylic acid, pyronedicarboxylic acid, phenylanthranilic acid, phenylcarbamic acid, phenylglycidic acid, phenylacetic acid, phenylthioacetic acid, phenyllactic acid, phenylpyruvic acid, phenylbutenoic acid, phenylpropiolic acid , Phenylbutyric acid, phenylene diacetic acid, phenolphthalein, phencoric acid, fusidic acid, proteroic acid, furancarboxylic acid, frangicar Acid, furic acid, fluorescein, fluorophenylacetic acid, prostaglandin, prostacyclin, bromomandelic acid, hemopyrrole carboxylic acid, benzidine carboxylic acid, benzylidene malonic acid, benzyl acid, benzoyl acrylic acid, benzoyloxy acetic acid, benzoyloxy Propionic acid, benzoylformic acid, benzoylacetic acid, benzoylpropionic acid, benzophenonecarboxylic acid, benzofurancarboxylic acid, podocarpinic acid, homogentisic acid, mandelic acid, muricholic acid, methyldopa, methylphenylacetic acid, methylfurancarboxylic acid, methylred, mefenamic acid, Examples include risergic acid, lithocholic acid, lipoic acid, reserpic acid, retinoic acid, levopimaric acid, glycolic acid, citric acid, and salicylic acid. One or more of these organic acid components can be appropriately selected and blended, and the content thereof varies depending on the type of the organic acid and cannot be determined uniformly, but is usually determined with respect to a skin external preparation. 0.01 to 5% by weight.
[0099]
As the ultraviolet absorber used in the present invention, there are an organic compound-based ultraviolet absorber and an inorganic compound-based ultraviolet scattering agent, and the ultraviolet absorber includes a paraaminobenzoic acid-based ultraviolet absorber and a cinnamic acid-based ultraviolet absorber. And a salicylic acid-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and the like, and one or more of them are blended. Para-aminobenzoic acid-based ultraviolet absorbers of the ultraviolet absorber include para-aminobenzoic acid, glyceryl para-aminobenzoate, ethyl dihydropropyl para-aminobenzoate, amyl para-dimethyl para-amino benzoate, octyl para-methyl para-amino benzoate, ethyl para-amino benzoate, and para-amino benzoate. There are isobutyl benzoate and the like, and as cinnamate UV absorbers, isopropyl paramethoxycinnamate, diisopropylcinnamate, octyl methoxycinnamate, monodiparamethoxycinnamate, 2-ethylhexanoic acid Glyceryl and the like, and as a salicylic acid-based ultraviolet absorber, homomenthyl salicylate, octyl salicylate, phenyl salicylate, ethanolamine bird salicylate, amyl salicylate, benzyl salicylate, p-ter salicylate There are butylphenyl, ethylene glycol salicylate, salicylic acid, and the like, and benzophenone-based ultraviolet absorbers include dihydroxybenzophenone, tetrahydroxybenzophenone, oxybenzone, oxybenzonesulfonic acid, sodium hydroxymethoxybenzophenonesulfonate, dihydroxydimethoxybenzophenone, 2-hydroxychlorobenzophenone, There are dioxybenzone, dihydroxydimethoxybenzophenone disulfonate sodium, 2-hydroxy-4-methoxy-4′methylbenzophenone, octabenzone and the like, and also urocanic acid, ethyl urocanate, 4-tert-4′-methoxydibenzoylmethane, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, anthranilic acid And the like. Examples of the inorganic compound used as the ultraviolet light scattering agent include titanium oxide, zinc oxide, cerium oxide, zirconium oxide, and iron oxide. The amount of the compound varies depending on the type of the ultraviolet absorbent and cannot be determined uniformly, but is usually 0.01 to 1% by weight based on the external preparation for skin.
[0100]
The form (dosage form) of the external preparation for skin of the present invention is not particularly limited, and may be appropriately determined depending on the purpose of use. Specifically, a solution form, a suspension dispersion form, a paste form, Any dosage form such as mousse, gel (gel), solid, and powder can be used.
[0101]
The method for producing the external preparation for skin of the present invention is not particularly limited, and a conventionally known method can be used.
[0102]
For example, in the case of an aqueous substance such as a lotion, an emulsion or a cream, the components to be contained in the chaff baked silica are dissolved in ethanol, which is a volatile organic solvent, and the husk baked silica is immersed in the ethanol solution to impregnate the active ingredient. After that, ethanol is removed from the chaff calcined silica. Next, rice husk baked silica containing an active ingredient in water (purified water), a water-soluble active ingredient for other skin external preparations, polysaccharides such as alkacylan, and other polysaccharide thickeners and water-soluble thickeners Molecules, surfactants and, if necessary, a coloring agent (dye) are added and dispersed to form a mixture 1. On the other hand, water-soluble organic liquids such as ethanol, ethylene glycol, etc. A water-insoluble active ingredient, a coloring material such as an oil agent and a pigment, a preservative, a fragrance, an emollient, a surfactant, a medicinal component and a functional component are dissolved and mixed as a mixture 2 with a mixture 1 using a homomixer. The liquid 2 is mixed and made into an emulsion or solubilized. Further, if necessary, the toner is separately toned with a coloring material (a coloring dye or the like), and then filtered and filled into a container to prepare a lotion or a cream. The temperature of the emulsification may be appropriately selected in consideration of the form and physical properties of the intended lotion, milky lotion, cream and the like, and is usually 40 to 70 ° C. The equipment used for emulsification includes a mount gouring homogenizer, a microfluidizer, a high-pressure homogenizer, a nanomizer, and the like.The intended lotion, the form of a milky lotion or a cream, and the like are appropriately selected and used. .
[0103]
Preparation of paste, mousse, gel, etc. is performed by adding alkacylan, thickener, humectant, surfactant, etc. to water (purified water), heating to 40-70 ° C, stirring, and preparing uniformly. Emulsify by adding, with stirring, a mixed solution of rice hull baked silica containing active ingredients, other active ingredients for skin external preparations, coloring materials, preservatives, fragrances, surfactants, medicinal ingredients and functional ingredients. Alternatively, it is solubilized to obtain a paste, mousse, gel or the like. Further, if necessary, the mixture may be further kneaded with a roll mill or the like to be prepared more uniformly.
[0104]
To prepare a jelly-like pack, add a humectant and a buffer to purified water, heat to 70 ° C., add a thickener and a film-forming agent under stirring, and add ethanol to the prepared mixture 3 under stirring. Mix the mixed liquid 4 in which the chaff calcined silica containing the active ingredient for the external preparation for the skin, the active ingredient of the other external preparation for the skin, the preservative, the fragrance, the emollient, the surfactant, the medicinal ingredient and the functional ingredient are dissolved. After emulsification, a jelly-like pack is prepared.
[0105]
In the case of powdered skin external preparations such as baby powder or white powder, rice hull baked silica containing active ingredients for skin external preparations, other active ingredients for skin external preparations, coloring materials (especially pigments), and talc if necessary After blending inorganic minerals and fragrances such as titanium dioxide and titanium dioxide in a blender, and further dispersing them evenly with a ball mill, a roll mill or the like, the baby powder, white powder, etc. of the present invention can be obtained. In addition, in foundations and the like, rice hull baked silica containing an active ingredient for skin external preparations, active ingredients of other skin external preparations, coloring materials (eg, pigments), oils, surfactants, alkacylan or other polysaccharides, Add moisturizer, whitening agent and, if necessary, fragrance, enzymes and vitamins to the blender and mix to make uniform. At this time, a method of mixing by heating and melting depending on the case is also used. After mixing, the mixture is further uniformly dispersed by a colloid mill, and placed in a container and compression-molded to obtain the foundation of the present invention.
[0106]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
[0107]
[Polysaccharide used for test]
(A-1: Polysaccharides (Crude Product) Produced by Alcaligenes Laertus B-16 Bacteria)
40.0 g of glucose [manufactured by Wako Pure Chemical Industries, Ltd.], 4.0 g of dipotassium hydrogen phosphate [manufactured by Wako Pure Chemical Industries, Ltd.], potassium dihydrogen phosphate [manufactured by Wako Pure Chemical Industries, Ltd.] ), Reagent] 2.0 g, sodium chloride [manufactured by Wako Pure Chemical Industries, Ltd.] 0.1 g, magnesium sulfate [manufactured by Wako Pure Chemical Industries, Ltd., reagent] 0.2 g, potassium nitrate [Wako Pure Chemical Industries, Ltd.] 1.0 g of yeast extract [manufactured by Kogyo Co., Ltd.] and 1.5 g of yeast extract [manufactured by OXOID] are dissolved in ion-exchanged water, and adjusted to pH 6.5 with sodium hydroxide or sulfuric acid. It was 1 liter. 150 mL of this aqueous solution was placed in a 500 mL Erlenmeyer flask, sterilized by heating in an autoclave (121 ° C., 15 minutes), returned to room temperature, and one loopful of alkaligenestraus B-16 strain (FERM BP-2015) was inoculated. Shaking culture (180 rpm) was performed at 30 ° C. for 6 days. After completion of the culture, about 3 times the volume of isopropyl alcohol was added to the culture, and the mixture was stirred and mixed. The precipitated aggregate was filtered, collected, dried under reduced pressure, and dried under reduced pressure to produce the polysaccharide (A) produced by the Alcaligenes strain B-16 strain bacteria. -1) was obtained. This polysaccharide is mainly composed of a polysaccharide composed of fucose, glucose, glucuronic acid and rhamnose in a molar ratio of 1: 2: 1: 1, and a polysaccharide composed of fucose and mannose in a molar ratio of 1: 1. It contains saccharides and its abundance is 7: 1 (weight ratio). The constituent monosaccharides were analyzed by high performance liquid chromatography (HPLC) after hydrolyzing polysaccharides with sulfuric acid.
[0108]
(A-2: purified product of A-1)
A 0.5% by weight aqueous solution of polysaccharide: A-1 was prepared, and the pH was adjusted to 12 with an aqueous sodium hydroxide solution. This aqueous solution is treated with a column of ion exchange resin "Diaion HPA-75 (OH-) (trade name)" (manufactured by Nippon Rensui Co., Ltd.) at 8 Ru or less, and further, a filter aid "Radiolite RL700" And a 5 μm membrane filter to remove proteins, nucleic acids, and microorganisms. The filtrate was concentrated to a pH of 7 with dilute hydrochloric acid and concentrated under reduced pressure. Acetone was added to precipitate a polysaccharide, which was further washed with 10 times the volume of acetone, and fucose: glucose: glucuronic acid: rhamnose = 1: 2: 1. : 1 and a polysaccharide (A-2) having a molecular weight of 50,000,000 was obtained.
[0109]
(Polysaccharide used in Comparative Example)
B-1: Xanthan gum ["Kelzan T" (trade name), manufactured by Sanseki Co., Ltd.]
-B-2: polyacrylic acid
B-3: polyvinyl alcohol.
[0110]
(Preparation method of chaff calcined silica of the present invention)
20 g of unsorted rice hulls were sieved through a 10 mesh nylon net to separate and sort rice stalks and rice husks. Rice husks selected in 500 mL of 5% by weight hydrochloric acid were immersed for 2 hours. After immersion, the rice husks were sufficiently washed with tap water, water was removed with a 10-mesh nylon net, and air-dried indoors. The dried chaff was put in a magnetic crucible and baked at 550 ° C. for 1 hour in an electric furnace. Next, the temperature of the electric furnace was raised to 800 ° C., and firing was performed for 1 hour. After cooling, about 3 g of rice hull calcined silica was obtained. This is sieved and classified, and rice hull baked silica-1 (hereinafter, referred to as “calcined silica-1”) having a major axis of 50 to 250 μm, and rice hull baked silica-2 (hereinafter, referred to as “calcined silica-2”) having a diameter of 250 to 500 μm are used. ) Got.
[0111]
(Fused silica containing active ingredient-1: containing tocopherol acetate)
50.0 g of liquid paraffin, 40.0 g of squalane, 6.0 g of beeswax, 3.5 g of petrolatum, and 0.5 g of tocopherol acetate were placed in a 300 mL stainless steel container, heated to about 80 ° C., and stirred, and calcined silica-1: 20 g was added. After being added and uniformly immersed in the oil phase, the mixture was filtered through a 200-mesh wire gauze, the calcined silica-1 was separated by filtration, and the surface of the calcined silica-1 was easily washed with ethanol. Then, ethanol was dried and removed to obtain fired rice hull silica containing active ingredient-1.
[0112]
(Active ingredient-containing rice hull calcined silica-2: containing mixed amino acids)
In a 300 mL stainless steel container, 2.0 g of beeswax, 2.0 g of petrolatum, 3.0 g of solid paraffin, 3.0 g of oleyl alcohol, 50.0 g of liquid paraffin, and 5.0 g of sorbitan stearate were heated to about 80 ° C. to obtain a mixture 1. . On the other hand, 10.0 g of glycerin, 5.0 g of 1,3-butylene glycol, and a mixed amino acid solution ["Prodeu 400" (trade name, manufactured by Ajinomoto Co., Inc.): glycine, alanine, proline, serine, arginine, lysine, glutamic acid 10.0 g of water and 10.0 g of water were heated to about 80 ° C. to obtain a mixture 2. The mixture 2 was added to the mixture 1 while stirring the mixture 1 with a homogenizer (“TK homomixer M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5,000 rpm, to obtain a water-in-oil emulsion-1. While stirring the water-in-oil emulsion-1 kept at about 80 ° C., 20 g of calcined silica-2 was added, and the rice hull calcined silica-2 was uniformly immersed. Silica-2 was separated by filtration and washed with ethanol. Then, the ethanol was then dried and removed to obtain fired rice hulls-containing silica-2 containing the active ingredient.
[0113]
(Rice hull silica containing active ingredient-3: mixed amino acid, sodium hyaluronate)
In a 300 mL stainless steel container, 10.0 g of the mixed amino acid solution, 1.0 g of sodium hyaluronate, 0.5 g of agar, and 88.5 g of purified water are stirred and mixed, heated to about 70 ° C., and baked silica-1: 20 g is added. did. After the calcined silica was sufficiently immersed, it was filtered through a 200-mesh wire net, the calcined silica-1 was filtered off, and the surface of the calcined silica-1 was easily washed with water. It was air-dried at room temperature to obtain rice hull calcined silica-3 containing the active ingredient.
[0114]
(Rice hull silica containing active ingredient-4: containing lipase and protease)
In a 300 mL stainless steel container, 20.0 g of squalane, 3.0 g of petrolatum, 1.0 g of stearic acid, 0.5 g of glyceryl monostearate, and a lipase dispersion (0.5% by weight of lipase dispersed in 99.5% by weight of ethanol) A mixture of 5.0 g of a lipase dispersion) and 5.0 g of a protease dispersion (a protease dispersion in which 0.5% by weight of a protease was dispersed in 99.5% by weight of ethanol) was used as an “oil phase”, and polyoxyethylene was used. (20 mol addition) An oil-in-water emulsion was prepared using a mixture of 1.0 g of sorbitan monostearate, 0.5 g of agar, and 58.5 g of purified water as an “aqueous phase”, and calcined silica-1: 20 g was added. Thus, fired rice hull silica-4 containing the active ingredient was obtained.
[0115]
(Rice hull calcined silica-5 containing active ingredient: contains lipase and protease)
In the same manner as in the preparation method of the rice hulls containing the active ingredient, calcined silica-1: 20 g, liquid paraffin 35.0 g, squalane 45.0 g, solid paraffin 5.0 g, petrolatum 3.0 g, lipase dispersion (99 6.0 g of a protease dispersion liquid (dispersion of 0.5% by weight of protease in 99.5% by weight of ethanol) was performed by dispersing 0.5% by weight of lipase in 0.5% by weight of ethanol to obtain a lipase dispersion. This yielded a protease dispersion.) 6.0 g of rice hull-baked silica-5 containing an active ingredient was obtained.
[0116]
(Active ingredient-containing chaff calcined silica-6: ascorbic acid stearate)
In the same manner as in the preparation method of calcined silica-1 containing the active ingredient, calcined silica-1: 20 g, vaseline 1.5 g, cetyl alcohol 1.5 g, stearic acid 2.0 g, oleic acid 20.0 g, liquid paraffin 30. From 0 g, 35.0 g of squalane, and 10.0 g of ascorbic acid stearate, fired rice hull silica containing active ingredient was obtained.
[0117]
(Active ingredient-containing chaff calcined silica-7: ascorbic acid dipalmitate)
In the same manner as in the preparation method of the active ingredient-containing rice husk calcined silica-1, calcined silica-1: 20 g, petrolatum 2.0 g, cetyl alcohol 1.5 g, stearic acid 2.5 g, liquid paraffin 35.0 g, squalane 47.0 g Then, from 12.0 g of ascorbic acid dipalmitate, calcined rice hulls containing active ingredient were obtained.
[0118]
(Rice hull calcined silica-8 containing active ingredient: contains magnesium phosphate ascorbate)
Cetyl alcohol 2.0 g, isostearic acid 3.0 g, petrolatum 1.0 g, isopropyl myristate 10.0 g, squalane 15.0 g, liquid paraffin 8.0 g, sorbitan monooleate 1.5 g, monostearic acid in a 300 mL stainless steel container 2.5 g of glycerin was added, heated to about 80 ° C., and uniformly mixed to obtain an “oil phase”. Further, 3.0 g of citric acid was dissolved in 27.0 g of purified water, and 6.0 g of 1,3-butylene glycol, 6.0 g of glycerin, and 15.0 g of magnesium ascorbate were sequentially added and dissolved. The “aqueous phase” was prepared by neutralizing with sodium oxide. The oil phase and the aqueous phase are heated to about 80 ° C., and then the oil phase is added while stirring the homogenizer (“TK homomixer M type” manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm. Emulsion-2 was obtained. The calcined silica-1 is added to the water-in-oil emulsion-2 kept at a temperature of about 80 ° C., and the calcined silica-1 is immersed. It was separated by filtration and washed with a small amount of ethanol. Next, the ethanol was dried and removed to obtain fired rice hulls containing active ingredient silica-8.
[0119]
(Active ingredient-containing chaff calcined silica-9: sodium ascorbate)
In a 300 mL stainless steel container, 20.0 g of sodium ascorbate, 65.0 g of purified water, and 15.0 g of ethanol were stirred until uniform, then calcined silica-1 was added and immersed in the aqueous phase. After being uniformly immersed in the aqueous phase, the mixture was filtered through a 200-mesh wire gauze, and the calcined silica-1 was separated by filtration. The surface of the calcined silica-1 was easily washed with water. It was air-dried at room temperature to obtain fired rice husk silica-9 containing the active ingredient.
[0120]
(Active ingredient-containing rice hull calcined silica-10: containing sodium ascorbate and vitamin A palmitate)
In a 300 mL stainless steel container, 10.0 g of sodium ascorbate, 1.0 g of polyoxyethylene (addition of 20 mol) sorbitan monostearate, 58.5 g of purified water, and 15.0 g of ethanol are heated to about 70 ° C. and stirred until uniform. And the "water phase". Similarly, 2.0 g of vitamin A palmitate, 12.0 g of squalane, 1.0 g of stearic acid, and 0.5 g of glyceryl monostearate are placed in another 300 mL stainless steel container, uniformly stirred and mixed, and heated to about 70 ° C. Phase. " The oil phase was added to the aqueous phase while stirring the homogenizer (“TK homomixer M type” manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm to obtain an oil-in-water emulsion-1. The calcined silica-2 was added to the oil-in-water emulsion-1 kept at about 70 ° C., and the calcined silica-2 was sufficiently immersed. Then, the calcined silica-2 was filtered through a 200-mesh wire net, and the calcined silica-1 was separated by filtration. The surface of calcined silica-1 was easily washed with water. It air-dried at room temperature, and obtained the rice hull calcined silica-10 containing an active ingredient.
[0121]
(Active ingredient-containing chaff calcined silica-11: Vitamin A palmitate contained)
In the same manner as in the preparation method of the active ingredient-containing rice husk calcined silica-1, calcined silica-1: 20 g, liquid paraffin 35.0 g, squalane 45.0 g, oleyl alcohol 10.0 g, stearyl alcohol 3.0 g, solid paraffin 5. The active ingredient-containing chaff calcined silica-11 was obtained from 0 g, vaseline 2.0 g, and vitamin A palmitate 5.0 g.
[0122]
(Active ingredient-containing chaff baked silica-12: oak extract, chamomile extract, arbutin, containing chondroitin sodium sulfate)
As in the case of the active ingredient-containing rice hull calcined silica-3, 2.0 g of oak extract, 3.0 g of chamomile extract, 0.5 g of arbutin, 2.0 g of chondroitin sulfate sodium, 0.5 g of agar, 92.0 g of purified water, and calcined silica -1: From 20 g of the active ingredient-containing chaff calcined silica-12 was obtained.
[0123]
(Active ingredient-containing chaff calcined silica-13: Vitamin A palmitate, tocopherol acetate)
In the same manner as in the active ingredient-containing chaff baked silica-11, 2.0 g of vitamin A palmitate, 1.0 g of tocopherol acetate, 5.5 g of petrolatum, 1.0 g of stearic acid, and 0.5 g of glyceryl monostearate were mixed in an oil. Phase, 5.0 g of magnesium phosphate ascorbate, 1.0 g of citric acid, an appropriate amount of sodium hydroxide required for neutralization, 1.0 g of polyoxyethylene (20 mole addition) sorbitan monostearate, 0.1 g of alkacylan. An oil-in-water emulsion was prepared by using a mixed solution of 1 g and 82.9 g of purified water as an “aqueous phase”, and calcined silica-1: 20 g was added to obtain calcined chaff silica-13 containing the active ingredient.
[0124]
(Active ingredient-containing chaff calcined silica-14: containing yogurt extract, nicotinamide, and kojic acid)
As in the case of the active ingredient-containing rice husk calcined silica-3, from 5.0 g of yogurt extract, 1.0 g of nicotinamide, 0.5 g of kojic acid, 0.5 g of gelatin, 65.0 g of purified water, and 20 g of calcined silica-1 An active ingredient-containing chaff calcined silica-14 was obtained.
[0125]
(Active ingredient-containing chaff calcined silica-15: Yogurt extract, rice bran extract, mixed amino acid, arbutin-containing)
As in the case of the active ingredient-containing chaff-silica-3, yogurt extract 5.0 g, rice bran extract 0.5 g, mixed amino acid solution 1.0 g, arbutin 0.5 g, curdlan 0.5 g, methyl paraben 0.2 g, purified water 92.3 g and calcined silica-1: 20 g of calcined rice hull containing active ingredient was obtained from 20 g.
[0126]
(Active ingredient-containing chaff baked silica-16: Yogurt extract, lactic acid-containing)
As in the case of the active ingredient-containing chaff calcined silica-3, 5.0 g of yogurt extract, 0.5 g of lactic acid, 0.2 g of carrageenan, 0.04 g of alkasylan, 0.2 g of methylparaben, 92.3 g of purified water, and calcined silica-1 : From 20 g, an active ingredient-containing chaff calcined silica-16 was obtained.
[0127]
(Active ingredient-containing rice hull baked silica-17: Oubaku extract, chamomile extract, carrot extract contained)
In the same manner as the active ingredient-containing rice hull baked silica-3, 5.0 g of oak extract, 5.0 g of chamomile extract, 3.0 g of ginseng extract, 0.6 g of agar, 0.2 g of methylparaben, 86.2 g of purified water, and baked silica- From 1: 20 g, an active ingredient-containing chaff baked silica-18 was obtained.
[0128]
(Active ingredient-containing synthetic silica-1: containing tocopherol acetate)
According to the method for preparing the active ingredient-containing chaff calcined silica-1, 20 g of chaff calcined silica-1 was replaced with 20 g of synthetic silica (trade name "Sunsphere H-201", manufactured by Asahi Glass Co., Ltd.), and otherwise Synthetic silica-1 containing the active ingredient was obtained in the same manner as the composition of the fired silica-1 containing the active ingredient.
[0129]
In the same manner, in the same manner, in the blending of the active ingredient-containing chaff baked silica-2 to 17, baked silica-1 or baked silica-2 was replaced with synthetic silica (trade name "Sunsphere H-201", manufactured by Asahi Glass Co., Ltd.). The active ingredient-containing synthetic silicas 2 to 17 were prepared while keeping the other components as they were. Tables 1 and 2 show the prepared active component-containing calcined silica and active component-containing synthetic silica.
[0130]
[Table 1]

[0131]
[Table 2]

[0132]
[Stability test and sensory test-1 of skin external preparation (aqueous gel-like serum) containing silica containing active ingredient]
(Preparation of Aqueous Gel Essence-1)
Glycerin 12g (6% by weight), 1,3-butylene glycol 12g (6% by weight), Alkasylan (A-2) 0.3g (0.15% by weight), 100 mL of purified water (50% by weight) in a 200 mL beaker Was added and stirred with a propeller-type stirrer to obtain a mixture 3. Meanwhile, 12 g (6 wt%) of ethanol, 0.02 g (0.01 wt%) of citric acid, 0.2 g (0.1 wt%) of sodium citrate were added to 59.28 mL (29.64 wt%) of purified water. 0.2 g (0.1% by weight) of methylparaben was added, and the mixture was stirred to obtain a mixture 4. While stirring the mixture 3, the mixture 4 was added, and further, 4.00 g (2% by weight) of the active ingredient-containing chaff calcined silica-1 was added, and the mixture was stirred until it became uniform to obtain an aqueous gel-type beauty serum-1. .
[0133]
(Preparation of aqueous gel-like serum -2 to 16)
0.3 g (0.15% by weight) of Alkasylan (A-2), 59.28 mL (29.64% by weight) of purified water, and rice hull-baked silica-1 containing an active ingredient in the preparation method of aqueous gel-like beauty liquid-1 : 4.00 g (2% by weight) was replaced with the composition shown in Table 3 to prepare aqueous gel serums-2 to 16 shown in Table 3.
[0134]
[Table 3]

[0135]
(Stability test)
The prepared aqueous gel-like beauty liquid No. 1 to 14 were put to a height of 10 cm from the bottom of a cylindrical glass container with a lid (height: 13 cm, inner diameter: 5 cm), and allowed to stand at 40 ° C. for 3 months. After standing for 3 months, the presence or absence of the lipophilic active ingredient which flowed out from the active ingredient-containing silica floating on the surface of the aqueous gel cosmetic liquid and the presence or absence of sedimentation and separation of the aqueous gel cosmetic liquid were visually evaluated as follows. It is not preferable that the lipophilic active ingredient flows out and floats on the surface of the aqueous gel-like serum, and that the oil-water separation / sedimentation occurs is not preferable.
・ Evaluation of efflux and floating of lipophilic active ingredient in aqueous gel serum
：: There is no lipophilic active ingredient which has flowed out and floated on the surface of the aqueous gel serum.
×: There are lipophilic active ingredients which have flowed out and floated on the surface of the aqueous gel-like serum.
・ Evaluation of sedimentation separation in aqueous gel serum
：: No sedimentation / separation of the aqueous gel serum.
X: There is sedimentation / separation on the surface of the aqueous gel-like serum.
The results are shown in Table 4.
[0136]
(Skin sensory test of aqueous gel-like serum containing active ingredient-containing silica)
Ten panelists were selected, and 0.5 g of an aqueous gel-like essence, which had been allowed to stand for three months after preparation, was taken on the back of each left hand of each of the ten panels, and evaluated by feeling when rubbed with the palm. “Smooth” was evaluated as “+”, and “feeling sticky” due to the lipophilic active ingredient flowing out of the active ingredient-containing silica was evaluated as “−”. The panel was evaluated according to the following criteria. In the skin sensory test of the aqueous gel-like serum, it is preferable that the number of panels "feeling dry" is large. The results are shown in Table 4.
(Judgment criteria)
：: 8 or more people feel “+”.
×: 7 or less felt “+”.
[0137]
[Table 4]

[0138]
The aqueous gel serum added with the calcined silica containing the active ingredient of the present invention showed no outflow of the active ingredient and was confirmed to be more stable than the aqueous gel serum using the conventional synthetic silica. In addition, the use of Alkasylan was able to prevent the separation of the aqueous gel-like serum added with the calcined silica containing the active ingredient. As a result, the feeling of use of the aqueous gel-like serum did not change even after 3 months, and the state of "feeling dry" could be maintained.
[0139]
[Stability test and sensory test-2 of skin external preparation (cleansing oil) containing silica containing active ingredient]
(Preparation of cleansing oil-1)
In a 200 mL beaker, 16 g (8% by weight) of ethanol, 6 g (3% by weight) of sucrose laurate, 20 g (10% by weight) of glyceryl triisostearate POE (20 mol addition), 0.4 g (0.2%) of butyl paraben % By weight) to obtain a mixture 5, which was heated to about 70 ° C. On the other hand, 40 g (20% by weight) of olive oil and 30 g (15% by weight) of glyceryl tri-2-ethylhexanoate were added to 67.6 g (33.8% by weight) of liquid paraffin, and the mixture was heated and stirred at about 70 ° C. Mixture 6 was obtained. Next, the mixture 6 was added to the mixture 5 while stirring the mixture 5 with a propeller-type stirrer. Further, 20.00 g (10% by weight) of the calcined silica-10 containing the active ingredient was added thereto, and the mixture was stirred until it became uniform to obtain a cleansing oil. 1 was obtained.
[0140]
(Preparation of cleansing oil-2 to 11)
The method for preparing cleansing oil-1 was the same as that for preparing cleansing oil-1, except that the active ingredient-containing calcined silica-10: 20.00 g in the method for preparing cleansing oil-1 was replaced with calcined silica containing active ingredient or synthetic silica containing active ingredient shown in Table 5. Cleansing oils-2 to 23 were prepared.
[0141]
[Table 5]

[0142]
(Stability test)
The prepared cleansing oil No. 1 to 23 were put to a height of 10 cm from the bottom of a cylindrical glass container with a lid (height: 13 cm, inner diameter: 5 cm) and allowed to stand at 40 ° C. for 3 months. After standing for 3 months, the presence or absence of the hydrophilic active ingredient which had flowed out from the silica containing the active ingredient settled on the bottom of the cleansing oil and the presence or absence of sedimentation and separation of the cleansing oil were visually evaluated as follows. It is not preferable that the hydrophilic active ingredient has flowed out, settled, or settled on the bottom of the cleansing oil, and it is not preferable that oily water separation or sedimentation occurred.
・ Evaluation of outflow and sedimentation of hydrophilic active ingredient in cleansing oil
：: No hydrophilic active ingredient which flowed out and settled in the cleansing oil.
×: There is a hydrophilic active ingredient which has flowed out and settled in the cleansing oil.
・ Evaluation of sedimentation / separation in cleansing oil
：: No sedimentation or separation of cleansing oil.
X: The cleansing oil has sedimentation / separation.
The results are shown in Table 6.
[0143]
(Skin sensory test of cleansing oil containing silica containing active ingredient)
Ten panelists were selected, and 0.5 g of cleansing oil that had been allowed to stand for three months after preparation was taken on the back of each left hand of the ten panelists, and evaluated by feeling when rubbed with the palm. "Smooth feeling" was evaluated as "+", and "feeling sticky" due to the hydrophilic active ingredient flowing out of the active ingredient-containing silica was evaluated as "-". The panel was evaluated according to the following criteria. In the skin sensory test of the cleansing oil, it is preferable that the number of panels "feeling dry" is large. The results are shown in Table 6.
(Judgment criteria)
：: 8 or more people feel “+”.
×: 7 or less felt “+”.
[0144]
[Table 6]

[0145]
The cleansing oil to which the active ingredient-containing calcined silica of the present invention was added showed no outflow of the active ingredient, and was confirmed to be more stable than the cleansing oil using the conventional synthetic silica. In addition, the use of Alkasylan could prevent the separation of the cleansing oil to which the calcined silica containing the active ingredient was added. As a result, the feeling of use of the cleansing oil did not change even after 3 months, and it was possible to maintain a “dry feel” state.
[0146]
[Stability test and sensory test-3 of skin external preparation containing active ingredient-containing silica]
(Preparation of facial cleansing cream-1)
(Production method)
In the following formulation, the formulation component No. No. 1 to 3 were heated and melted at about 70 ° C. 4 as No. 4. An aqueous solution dissolved at 12:40 g was added, and the mixture was maintained at about 70 ° C. to obtain a mixture 7. Ingredient No. 8, 10, 11, and 12 were stirred and mixed at about 70 ° C. to obtain a mixture 8. The mixture 7 was added to the homogenizer (“TK homomixer M type” manufactured by Tokushu Kika Kogyo Co., Ltd.) while stirring at 5000 rpm to form an emulsion, which was further stirred and cooled. No. 5 and 6, 9 were added to obtain facial cleansing cream-1.
(Combination)

(Preparation of facial cleansing cream-2)
Effective component-containing calcined silica-1: 5.0% by weight of active component-containing synthetic silica-1: 5.0% by weight, and active component-containing calcined silica-2: 5.0% by weight of facial cleanser-1 Synthetic silica-2 contained: Replaced with 5.0% by weight, and otherwise prepared in the same manner as facial cleanser-1 to obtain facial cleanser-2.
[0147]
(Preparation of Cleansing Cream-1)
(Production method)
In the following formulation, the formulation component No. 1 to 4 were heated and melted at about 70 ° C. to obtain a mixture 9. In addition, the mixing component No. 5, 6, 10, 11, and 12 were stirred and mixed at about 70 ° C. to obtain a mixture 10. The mixture 9 was added to the mixture 9 while stirring the mixture 9 with a homogenizer (“TK homomixer M type” manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm to prepare an emulsion. After further stirring and cooling, at about 40 ° C., 7 and 8, 9 were added to obtain Cleansing Cream-1.
(Combination)

(Preparation of Cleansing Cream-2)
The active ingredient-containing calcined silica-2 of cleansing cream-1: 5.0% by weight was added to the silica of Comparative Example-1 (5.0% by weight). 8: Prepared similarly to Cleansing Cream-1 except that the active ingredient (lipophilic) -containing calcined silica-4 (5.0% by weight) was replaced with the silica of Comparative Example-2 (5.0% by weight). , Cleansing cream-2.
[0148]
(Preparation of lotion-1)
(Production method)
In the following formulation, the formulation component No. No. 1 is No. No. 10 and uniformly dispersed, and then, with stirring, 2 to 9 were added, and the mixture was stirred until the mixture became uniform to obtain lotion-1.
(Combination)

(Comparative Example 3: Lotion-2)
Active ingredient-containing calcined silica-4: 3.0% by weight of active ingredient-containing synthetic silica-1: 3.0% by weight and active ingredient-containing calcined silica-5: 6.0% by weight of active ingredient-1 Synthetic silica-2 contained: Replaced with 6.0% by weight, and otherwise prepared in the same manner as lotion-1 to obtain lotion-2.
[0149]
(Preparation of emulsion-1)
(Production method)
In the following formulation, the formulation component No. No. 16 After adding and dissolving 8 and 9, the mixture was maintained at 70 ° C. to obtain a mixture 11. No. 1 to 7 and 11 were heated and mixed at 70 ° C. to obtain a mixture 12, and the mixture 12 and the blending components were mixed with a homogenizer (“TK Homomixer M type” manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm. No. 10 was added and emulsified. Further, the mixture was stirred and cooled to about 40 ° C. Emulsion-1 was obtained by adding 12-14.
(Combination)

(Preparation of emulsion-2)
(Production method)
In the following formulation, the formulation component No. No. 16 No. 15 was added and dissolved. Add 7 to 10 and uniformly disperse the mixture. No. 1 to 6 were heated and mixed at 70 ° C. to obtain a mixture 14, and the mixture 13 was added to the mixture 14 while stirring at 5000 rpm with a homogenizer (“TK homomixer M type” manufactured by Tokushu Kika Kogyo Co., Ltd.) to emulsify. . Further, the mixture was stirred and cooled to about 40 ° C. Emulsion-2 was obtained by adding 11 to 14.
(Combination)

(Preparation of emulsion-3)
Emulsion-1 containing active ingredient-containing fused silica-8: 3.0% by weight to active ingredient-containing synthetic silica-1: 3.0% by weight and active ingredient-containing fused silica-9: 3.0% by weight containing active ingredient Synthetic silica-2 was replaced with 3.0% by weight, and otherwise prepared in the same manner as in Emulsion-1 to obtain Emulsion-3.
[0150]
(Preparation of Massage Gel-1)
(Production method)
In the following formulation, the formulation component No. No. 12 1 to 3 were added, and the mixture was uniformly stirred and mixed to obtain a mixture 15. In addition, the mixing component No. 4 to 9 are stirred and mixed to obtain a mixture 16. While stirring the mixture 15 with a small mixer, the mixture 16 was added and stirred until it became uniform. 10 and 11 were added and stirred to obtain Massage Gel-1.
(Combination)

(Preparation of Massage Gel-2)
Calcined silica-2 containing active ingredient of massage gel-1: 10.0% by weight of synthetic silica-1 containing active ingredient: 10.0% by weight, and calcined silica-8 containing active ingredient-8: 5.0% by weight as active ingredient. Containing calcined silica-Comparative Example 2: each was replaced with 5.0% by weight, and otherwise prepared in the same manner as massage gel-1 to obtain massage gel-2.
[0151]
(Stability test of skin external preparation containing silica containing active ingredient)
As in the case of the aqueous gel serum, the above external preparation for skin is put into a cylindrical glass container with a lid (height: 13 cm, inner diameter: 5 cm) from the bottom to a height of 10 cm, and left at 40 ° C. for 3 months. Then, the presence or absence of the lipophilic active ingredient which had flowed out from the silica containing the active ingredient and the presence or absence of sedimentation and separation of the aqueous gel-like serum were visually evaluated. It is not preferable that the lipophilic active ingredient flows out and floats on the surface of the skin external preparation containing the active ingredient-containing silica, and that the oil-water separation / sedimentation occurs is not preferable. Table 5 shows the results.
[0152]
(Skin organoleptic test of skin external preparation containing silica containing active ingredient)
As in the case of the aqueous gel serum, 10 panelists were selected, and 0.5 g of the skin external preparation immediately after preparation was placed on the back of each left hand of the 10 panelists and evaluated by feeling when rubbed with the palm. "+" For "feeling dry" and "-" for "feeling sticky" due to the lipophilic active ingredient escaping from the active ingredient-containing silica and "feeling uneven and cool" due to the hydrophilic active ingredient evaluated. Similarly, an external preparation for skin which had been allowed to stand for 3 months after preparation was also performed, and the two were compared and judged as follows.
：: Eight or more felt the same feeling.
×: 7 or less felt that the external preparation for skin immediately after preparation was better.
In the skin sensory test of the external preparation for skin, it is preferable that the number of panels "feeling dry" is large. The results are shown in Table 7.
[0153]
[Table 7]

[0154]
The facial cleansing cream, cleansing cream, lotion, milky lotion, massage gel, etc. containing the active ingredient-containing baked silica of the present invention have no outflow of the active ingredient from the silica even after being left at 40 ° C. for 3 months, and their sensory evaluation As a result, the same feeling as that immediately after the preparation was maintained. Furthermore, it is found that the use of a specific polysaccharide, for example, alkacylan, prevents separation of the active ingredient-containing calcined silica in the external preparation for skin and improves the stability.
[0155]
【The invention's effect】
Active ingredients such as enzymes, vitamins, and water-incompatible ingredients that are unstable in aqueous solutions or at low concentrations are contained in baked rice husk silica, and blended in an external preparation for skin for a long period of time, The components can be maintained in the external preparation for skin in a stable state, which greatly contributes to improvement of product quality.

Claims (9)

An external preparation for skin, characterized by containing rice hull calcined silica containing an active ingredient in advance. The external preparation for skin according to claim 1, wherein the active ingredient is at least one selected from sugars and sugar derivatives, amino acids, enzymes, vitamins, organic acids, plant extracts, and crude drug extracts. 3. The external preparation for skin according to claim 2, wherein the sugar and the sugar derivative are at least one selected from xylitol, sorbitol, D-glucuronic acid, D-galacturonic acid, trehalose, raffinose, and sucrose stearate. 3. The external preparation for skin according to claim 2, wherein the amino acids are one or more selected from tryptophan, phenylalanine, proline, tyrosine, lysine, glycine, alanine, glutamine, serine, cysteine, aspartic acid, and glutamic acid. The skin external preparation according to claim 2, wherein the enzymes are at least one selected from lipase, protease, and catalase. Vitamins are retinol, retinal, dehydroretinal, carotene, lycopene, tocopherol or derivatives thereof, ubiquinones, phytonadione, menaquinone, magnesium ascorbate phosphate, sodium ascorbate phosphate, thiamine hydrochloride, thiamine sulfate, riboflavin, pyridoxine, The external preparation for skin according to claim 2, which is at least one selected from cyanocobalamin, folic acids, nicotinic acids, pantothenic acids, and biotins. The skin external preparation according to claim 2, wherein the organic acid is at least one selected from kojic acid, glycolic acid, citric acid, malic acid, lactic acid, salicylic acid, ferulic acid, isoferulic acid, caffeic acid, and chlorogenic acid. The external preparation for skin according to any one of claims 1 to 7, comprising at least a polysaccharide having glucose, fucose, glucuronic acid, and rhamnose as constituent monosaccharides. 9. The external preparation for skin according to claim 8, wherein the polysaccharide is a polysaccharide produced by Alcaligenes latus B-16 strain bacteria.