TW200920414A - Gel sheet and sheet-like cosmetic material using the same - Google Patents

Gel sheet and sheet-like cosmetic material using the same Download PDF

Info

Publication number
TW200920414A
TW200920414A TW97135734A TW97135734A TW200920414A TW 200920414 A TW200920414 A TW 200920414A TW 97135734 A TW97135734 A TW 97135734A TW 97135734 A TW97135734 A TW 97135734A TW 200920414 A TW200920414 A TW 200920414A
Authority
TW
Taiwan
Prior art keywords
gel sheet
gel
sheet
hydrogel
extract
Prior art date
Application number
TW97135734A
Other languages
Chinese (zh)
Inventor
Shigetomo Tsujihata
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of TW200920414A publication Critical patent/TW200920414A/en

Links

Abstract

The invention provides the gel sheet comprising a hydrogel which comprises an ether-based temperature-sensitive polymer, and at least one of collagen or decomposition products of collagen; and the sheet-like cosmetic material using the gel sheet described above.

Description

200920414 九、發明說明: 【發明所屬之技術領域】 本發明系關於一種藥物、類藥品、化妝品、衛生保健 材料及各種物品領域之凝膠片,及一種使用凝膠片之近似 片狀化妝品材料。 【先前技術】 凝膠片被用於面膜材料,且黏著劑用於美容及臉部處 理及皮膚治療;例如皮膚可滲透成分、消炎止痛劑之活性 成分的載劑;以保護傷口或固定藥物爲目的之活體用膠 布;及用於一種傷口覆蓋藥劑。這些凝膠片經由,黏貼於皮 膚表面而保護皮膚表面,提供皮膚表面保水性,並含有各 種成分於該凝膠片,因此,給予皮膚水含量(保水性),並 控制皮膚溫度,或呈現供應凝膠片活性成分於活體之功 能。尤其是,由於活性成分滲透至皮膚中,增加皮膚之溫 度及水分可促進活性成分之移動。 已知具有上述功能之凝膠片含有膠原蛋白及多醣 類,例如幾丁質、甲殻素、褐藻酸及纖維素爲構成成分(例 如詳見日本專利申請案特開(JP-Α)第3-81213號)。 同時,關於一種溫度敏感性狀態變化水凝膠組成物, 爲一種已知技術,其當水凝膠接觸皮膚時,因爲藉由體溫 而由凝膠轉變成可流動狀態之狀態改變,掺入水凝膠中之 藥物進入皮膚中(例如,詳見專利申請案(JP-T)第 200920414 2007-502269號之PCT國際公開案的公開日文翻譯版)。此 外,已知有含有溫度敏感性聚合物之黏著片具有4至34°C 之移轉溫度及黏性聚合物(例如’詳見JP-A第5 - 1 8 46 5 7 號),及一種由特定聚醚酯形成之溫度敏感性水凝膠所認可 溫度敏感性凝膠片(例如,詳見JP-A第1 1 -92 5 54號)。 然而,這些凝膠片並不能充分快速地投與凝膠中之活 性成分等至皮膚,且在許多情況中,該薄片在操作性上是 較不足的。 【發明內容】 有鑑於上述情況,本發明之百的係提供一種凝膠片, 其具有在所接觸例如表皮等之黏附體上改良關於水或活 性成分之滲透性,與優異之操作性,及提供一種使用該凝 膠片之近似片狀化妝品材料。 本發明之第一態樣係提供一種含水凝膠之凝膠片,該 水凝膠包含醚系(ether-based)溫度敏感性聚合物,及至少 一種膠原蛋白或膠原蛋白之分解產物。 本發明之第二態樣爲提供一種使用上述任一種凝膠 片之近似片狀化妝品材料。 本發明可提供一種凝膠片及使用該之凝膠片近似片 狀化妝品材料’具有在所接觸例如表皮等之黏附體上改良 凝膠片所攜帶之水或活性成分之滲透性,與優異之操作 性。 200920414 【實施方式】 實施本發明之最佳方式 本發明凝膠片含有一種醚系溫度敏感性聚合物’及至 少一種膠原蛋白及其分解產物。 上述凝膠片之醚系溫度敏感性聚合物較佳爲選自聚 醚類、聚乙烯醚類及烷基化多酿衍生物所組成群組之至少 一者,更佳爲含聚氧化乙烯及聚氧化丙烯之嵌段聚合物。 凝膠片可含有0/W型乳液,且0/W型乳液可含類胡 蘿蔔素。 再者,本發明凝膠片較佳者爲凝膠片之膠體脫水液體 含有o/w型乳液之乳化顆粒。 本發明凝膠片較佳地含有水凝膠層,其含水凝膠及供 於水凝膠層或鄰接於水凝膠層之近似片狀基層。 本發明敘述如下。 本發明中表示數字範圍的任何標記係表示經由包含 最小値與最大値所界定之範圍。 在本發明中,"凝膠片"包含用於面膜材料凝膠片及用 於美化及臉部處理及皮膚治療之黏著劑、用於例如皮膚滲 透成分、消炎止痛劑之活性成分的載劑、與用於活體傷口 保護、藥物固定目的之膠帶、及傷口覆蓋劑,及與保留活 性成分或水份相關之薄片’且以滲透保留之成分至黏附體 爲目的直接使用該薄片黏附於黏附體。凝膠片使用作爲化 200920414 妝品材料,例如用於黏附於皮膚上之面膜劑以提供皮膚水 分或活性成分。 [凝膠片] 本發明之凝膠片含有含醚系溫度敏感性聚合物之凝 膠片,及至少一種膠原蛋白及其分解產物。 本發明所使用之醚系溫度敏感性聚合物在增加溫度 會引起脫水,另一方面,膠原蛋白或明膠(一種膠原蛋白之 分解產物)之型態隨著溫度增加而變化。合倂使用醚系溫度 敏感性聚合物與具有能控制釋放活性成分(例如醫藥性質) 數量之性質的膠原蛋白或其分解產物包含於水凝膠,且維 持水凝膠之適當外型強度。因此,含水凝膠之凝膠片用於 近似片狀化妝品材料,以提供保濕性質及滲透活性成分至 皮膚。 (水凝膠) <醚系溫度敏感性聚合物> 用於本發明之水凝膠含醚系溫度敏感性聚合物。 本發明之醚系溫度敏感性聚合物係指一種於某一溫 度以下,於水存在下水合之聚合物,且當超過此溫度,會 脫水並因此進行型態變化。這些起因於溫度變化的微小改 變顯現出例如體積變化、親水性-疏水性變化、光學變化、 膨脹-收縮變化等微小改變。 "某一溫度”意指較低臨界共溶溫度之溫度,且由增加 200920414 貼凝膠片於活 :30°C 。 具有上述溫度 用任何聚合物 之安定性的觀 量平均分子量 g 500,000 c 之親和性的觀 醚類、乙烯醚 且其之實例包 丙烯、聚氧化 聚氧化丙烯/聚 、聚乙基乙烯 :乙烯醚等,可 :素、羥丙基纖 乙基纖維素、 水分或活性成分之皮膚滲透性的觀點,當黏 體時,溫度較佳爲20至40°C,更佳爲25至 用於本發明之醚系溫度敏感性聚合物: 敏感性特性,且只要聚合物具有醚鍵,可使 而不需限制。由溫度反應之適合性及儲存 點,醚系溫度敏感性聚合物較佳地具有重 (Mw)5,000 至 1,〇〇〇,〇〇〇,且較佳爲 1 0,000 三 尤其是,由活體溫度回應及與基層材料 點,至少一種醚系溫度敏感性聚合物選自聚 類及烷基化多醣衍生物所組成之群組較佳, 括下列化合物: 關於聚醚類,例如聚氧化乙烯、聚氧化 乙烯/聚氧化丙烯嵌段共聚物、聚氧化乙烯/ 氧化乙烯嵌段共聚物等,可爲較佳之範例。 關於聚乙烯醚類,例如聚甲基乙烯醚 醚、聚甲氧基乙基乙烯醚、聚乙氧基乙基莠 爲較佳之範例。 關於烷基化多醣衍生物,例如甲基纖雑 維素、羥乙基纖維素、羥丙基甲基纖維素、 羥丙基甲殼素等,可爲較佳之範例。 再者,由活體溫度回應及與基層材料之親和性的觀 點’該聚醚類、聚乙烯醚類及烷基化多醣衍生物較佳具有 200920414 至少一或多個官能基,其選自羥伸乙基、羥伸丙基、甲氧 基及乙氧基所組成之群組,且上述實例中’較佳爲聚氧化 乙烯/聚氧化丙烯嵌段共聚物、聚氧化乙烯/聚氧化丙烯/聚 氧化乙烯嵌段共聚物、聚甲基乙烯醚、甲基纖維素等。 關於本發明之醚系溫度敏感性聚合物,含聚氧化乙稀 及聚氧化丙烯之嵌段聚合物爲特佳,且更明確而言’聚氧 化乙烯/聚氧化丙烯嵌段共聚物(下文簡稱MpE〇-ppo嵌段 聚合物")、或聚氧化乙烯/聚氧化丙烯/聚氧化乙烯嵌段共 聚物(下文簡稱,'PEO-PPO-PEO嵌段聚合物")是令人滿意 的。這些聚醚類已知爲普羅沙姆(Poloxamer)’且可易於獲 得商業產品(商品名"PLURONIC”及” LUTROL(二者皆爲 BASF A. G.製造)、NEWPOL(Sanyo Chemical Industries, Ltd.製造)、及 EPAN(Dai-Ichi Kogyo Seiyaku Co·, Ltd.製 造)、PRONON (Nippon Oil & Fats Co.,Ltd.製造)等。上述 醚系溫度敏感性聚合物可單獨使用’或可使用二種或多種 之混合物。 在本發明所使用之水凝膠中’醚系溫度敏感性聚合物 之含量較佳爲0.05至20質量%,更佳爲0.1至10質量。/。, 且特佳爲0.2至5質量%。 當醚系溫度敏感性聚合物之含量爲〇.〇5質量%或以 上,添加於水凝膠之活性成分滲透至皮膚的增加效果可充 分達成,且當含量爲20質量%或以下,可避免在水凝膠儲 -10- 200920414 存性上顯著的降低。 <膠原蛋白及分解產物> 用於本發明之水凝膠包括膠原蛋白及其分解產物。 本文之膠原蛋白並不受特別限制,且包括各種膠原蛋 白萃取物。可使用已知技術之含膠原蛋白原料進行萃取, 例如酸溶解、鹼溶解、中性鹽類溶解及酶溶解。就材料包 含膠原蛋白而言,可使用任何材料,且皮膚、魚鱗、骨、 軟骨、腱及脊椎(例如牛、豬、沙丁魚、鯊魚等)可爲實例, 而就高含量膠原蛋白之觀點,可適當使用骨、軟骨、皮膚、 或魚鱗、腱及胎盤等。尤其是,適於本發明使用之髎原蛋 白較佳爲水溶性膠原蛋白。可經由以例如膠原蛋白酶、 胰蛋白酶、及凝乳蛋白酶等蛋白水解酶分解膠原蛋白、或 經由酸或鹼水解、或經由熱變性而獲得本發明之膠原蛋白 分解產物。 膠原蛋白分解產物,例如,酸處理明膠、鹼處理明膠、 酶分解明膠、膠原蛋白三肽、膠原蛋白二肽、及胺基酸(甘 胺酸、脯氨酸、羥基脯氨酸、乙醯基羥基脯氨酸等)爲例示。 於本發明中’由釋放活性成分之觀點而言,於膠原蛋 白及膠原蛋白分解產物中較佳者爲至少一種明膠或明膠 衍生物。 明膠爲一種膠原蛋白之水解蛋白質,明膠之製造方法 並不受特別限制,且該明膠一般以牛骨、牛皮、豬皮及魚 11 - 200920414 鱗等爲原料,經由酸處理或鹼處理製造,但可經由酵素方 法製造。 再者,作爲明膠衍生物,可使用已知衍生物,例如明 膠之酸酐加成物(例如、酞酸化明膠、琥珀酸化明膠、偏苯 三甲酸化明膠等)、內酯加成物(葡萄糖酸-δ-內酯加成物明 膠等)、醯化明膠(乙醯化明膠等)、酯化明膠(甲酯化明膠 等)、明膠之有機酸鹽(乙酸鹽明膠、硬脂酸鹽明膠、苯甲 酸鹽明膠)等爲例示。 作爲本發明凝膠片所使用之明膠及其衍生物,由與活 體之親和性及釋放活性成分之性質,之觀點,源自豬皮之明 膠、源自魚之明膠、琥珀酸化明膠、酞酸化明膠及偏苯三 甲酸化明膠是所欲的。 關於明膠及其衍生物,明膠可單獨使用,或可使用二 或多種明膠之組合,明膠衍生物可單獨使用,或可使用二 或多種明膠衍生物之組合,或可使用明膠及明膠衍生物之 混合物。 此外,當重量平均分子量以凝膠滲透層析(GPC)量測 時,於本發明中明膠及明膠衍生物之重量平均分子量較佳 爲 5,000 至 1,〇〇〇,〇〇〇,更佳爲 5,〇〇〇 至 300,000,特佳爲 10,〇〇〇 至 3 0 0,000。 於本發明水凝膠中所含之膠原蛋白及膠原蛋白分解 產物的含量較佳爲0.05至20質量%,更佳爲0.1至10質 -12- 200920414 量%,特佳爲〇. 2至5質量%。〇 . 〇 5質量%或以上之膠原蛋 白及膠原蛋白分解產物含量可有效將水凝膠中活性成分 滲透入皮膚內’且當含量爲20質量%或以下,操作性變好。 再者,由活性成分滲透入皮膚內之觀點,醚系溫度敏 感性聚合物與膠原蛋白及其分解產物之質量比例(醚系溫 度敏感性聚合物:膠原蛋白及其分解產物)較佳爲1:50 至50:1’更佳爲1:10至10:1,且特佳爲1:5至5:1。 爲了發揮不同功能,本發明凝膠片較佳地在水凝膠中 進一步含有其他成分,例如多元醇化合物、0 / W型乳液、 及多醣類。此外,如果需要,亦可含有親水性聚合物等。 <多元醇化合物> 由活性成分滲透入皮膚內及儲存性之觀點,本發明凝 膠片較佳地進一步含有多元醇化合物。 多元醇化合物特別包括甘油類(甘油、二甘油等);二 醇類(例如二乙二醇、三乙二醇、四乙二醇、聚乙二醇、1,2-丙二醇丙二醇、1,3-丙二醇、伸二丙基二醇、1,2-丁二醇、 1,3-丁二醇、ΐ,2-戊二醇、l,2-己二醇、1,2_辛二醇等)、醣 類(葡萄糖、果糖、甘露糖、半乳糖、木糖、阿拉伯糖 '葡 萄糖胺、Ν-乙醯基葡萄糖胺、蔗糖、乳糖、麥芽糖、異麥 芽糖、海藻糖、纖維二糖、麴二糖、槐醣、麥芽三糖、棉 子糖、菜豆糖等)、糖醇(甘油、蘇糖醇、赤藻醇、阿拉伯 糖醇、木糖醇、核糖醇、甘露醇、山梨醇、半乳糖醇、肌 -13- 200920414 醇等)爲例示。上述多元醇化合物可單獨使用,或使用二或 多種之混合物。 其中’本發明凝膠片中較佳使用甘油類或二醇類’特 別是’甘油、1,2 -丙二醇、1,2 -丁二醇、1,2 -戊二醇、1,2- 己二醇、及1,3 -丁二醇更令人滿意。此外,特佳爲使用甘 油、丨,2·丙二醇、1,3-丁二醇、及1,2-己二醇。 於本發明中水凝膠所含之多元醇化合物比例較佳爲 5 0質量%或以下,特佳爲1至2 0質量°/。。 於本發明中水凝膠所含之多元醇化合物比例較佳爲 50 ’質量%或以下,因此可避免凝膠強度之降低,及改善操 作性。 <o/w型乳液> 本發明凝膠片較佳含有o/w型乳液,特別是,較佳爲 含有脂溶性活性成分及藥效性質之0/W型乳液。在此方法 中’ 0/W型乳液之成分可被施用於黏附體,以便各成分之 功能(例如使皮膚美化)藉由皮膚滲透而增強。 關於脂溶性活性成分,更令人滿意的爲例如脂溶性維 生素及其相關物質(生育酚、生育三烯醇、視黃醇、視黃醛、 鈣化醇等)、固醇類(膽固醇、植物固醇等)、輔酶Q(CoQ10 等)、及神經脂質、神經醯胺、米糠醇、鯊烯、鯊烷、類胡 蘿蔔素等及其衍生物,且於本發明中,類胡蘿蔔素爲特佳。 作爲類胡蘿蔔素,海葵赤藻醇(actinioerythrol)、蝦紅 -14 - 200920414 素、紅木素(bixin)、角黃素(cantaxanthin)、辣椒紅素 (capsorbin)、β-8’ -阿樸-胡蘿荀酸(P-8’-apo-cartenal)、 β-12’-阿樸-胡蘿蔔醛、α-胡蘿蔔素、β-胡蘿蔔素、γ-胡蘿 蔔素、β-玉米黃質(β-cryptoxanthin)、葉黃素、茄紅素、 董菜黃質(violaxantin)、玉米黃素(zeaxanthin)、岩藻黃質 (fucoxanthin)及其衍生物爲例示。 其中,更令人滿意的爲蝦紅素、葉黃素、玉米黃素及 β-玉米黃質,且抗氧化效果、抗發炎效果、抗老化皮膚保 護效果及美白效果已被證實之蝦紅素特別令人滿意。 此外,其他成分可以一般使用量包含於0/W型乳液組 成物中,例如乳化劑,其通常可包含於乳液之各相中。此 類其他成分中’包括其他成分,例如發明說明中所述之多 元醇。 0 / W型乳液之乳化顆粒的體積平均粒徑較佳爲1至 200 nm ’更佳爲1至150 nm,特佳爲inm至1〇〇nm。 體積平均直徑顆粒可以商業顆粒尺寸分布分析儀等 量測。關於乳液之顆粒尺寸量測方法,已知有光學顯微鏡 法、共焦雷射掃瞄顯微鏡法、電子顯微鏡法、原子力顯微 鏡法、靜態光散射光譜法、及雷射繞射法、動態光散射法、 離心沉澱法、電脈衝量測法、層析法、超音波阻尼法等, 且對應於各別原理之裝置爲商業上可獲得的。 由本發明中體積平均直徑的範圍及容易測量的觀 -15- 200920414 點,本發明乳液之體積平均粒徑量測以動態光散射法較令 人滿意。關於使用動態光散射之商業量測裝置,例示如 NANOTRAC UPA (Nikkiso Co.,Ltd.)、及動態光散射顆粒 尺寸分布分析儀LB-5 5 0 (Horiba,Ltd.)、稠化系統顆粒尺 寸分析儀 FPAR-1000 (Otsuka Electronics Co_,Ltd.)等。 在本發明中’以稠化系統顆粒尺寸分析儀F P A R -1 0 0 0 (Otsuka Electronics Co., Ltd.製)於 25°C 量測被採用作爲 Ο/W型乳液體積平均粒徑之値。 在量測體積平均粒徑之方法中,以純水稀釋使油相成 分之濃度可在〇 · 1至1質量%之範圍內的方式,以量測用 玻璃試管進行量測體積平均粒徑。當分散介質折射指數設 定爲 1.3313(純水),且分散介質黏度設定爲 0.8 846 mP a. s (純水),體積平均粒徑可獲得一累積(50%)値。 製備Ο/W型乳液的方法並不受特別限制,例如,可使 用揭示於JP-A第2005-75817號之方法。或者是,Ο/W型 乳液較佳以包含下列步驟之方法製造:a)將水溶性乳化劑 溶於水性介質中製備以形成一水相,b)經由混合並溶解類 胡蘿蔔素、生育酚、卵磷脂及視所需之其他油類及脂類, 形成一油相,及Ο在攪拌下混合及乳化水相及油相。 當乳化時,特佳爲使用一般利用剪切作用之乳化設備 的方法進行乳化,例如攪拌器、葉片攪拌器、均質機及連 續流動型剪切設備,然後通過高壓均質機等,因此可合倂 -16 - 200920414 使用二或多種乳化設備。經由使用高壓均質機,可獲得含 更均勻細微顆粒之液體微滴的乳液。 由效果及活性成分滲透入皮膚之觀點,本發明水凝膠 中0/W型乳液之含量較佳爲0.001至10質量%,更佳爲 0.0 5至1質量%。 此外,本發明水凝膠中脂溶性活性成分含量較佳爲 0.000 1至10質量%,更佳爲0.05至5質量%,然而脂溶性 活性成分之含量依活性成分種類而變化。 本發明水凝膠之類胡蘿蔔素含量較佳爲0.0001至0.5 質量%,更佳爲0.0005至0.1質量%,且特佳爲0.001至 0.05質量%。當類胡蘿蔔素含量爲0·0001質量%或更多, 則在本發明凝膠片黏貼至皮膚後,可感覺到效果(皮膚-美 化效果等)。若含量爲0.5質量%或更少,因爲抑制著色至 皮膚而幾乎不會產生的不舒適感。 <多醣類> . 另人滿意的是,添加多醣類至本發明凝膠片以改善其 之操作性。 可使用於本發明之多醣類包括上述醚系溫度敏感性 聚合物以外之多醣類,例如中性多醣類(例如,纖維素、澱 粉醣、支鏈澱粉、瓊脂糖、葡聚糖、聚三葡萄糖、菊澱粉、 聚半乳糖、聚甘露糖、樹膠質、聚阿拉伯糖、聚葡甘露糖、 聚半乳甘露糖等),及陰離子多醣類(果膠酸、褐藻酸、瓊 -17- 200920414 脂、鹿角菜膠、褐藻糖膠、玻糖醛酸、硫酸軟骨膠、肝素、 結冷膠、天然結冷膠、黃原膠、羧基甲基纖維素等),及陽 離子多醣類(幾丁質、甲殻素、陽離子化纖維素等)。 其中’具有高增稠膠凝作用之多醣類更佳,且以聚葡 甘露糖、聚半乳甘露糖、瓊脂、鹿角菜膠、結冷膠、天然 結冷膠、及黃原膠特佳。爲了增加膠凝作用,二或多種此 多醣類可合倂使用。 本發明水凝膠中多醣類含量較佳爲0.01至5質量%, 更佳爲〇 . 1至4質量%,且特佳爲〇. 2至2質量%。 當多醣類之含量爲〇.〇1質量%或>以上,凝膠強度之不 足可被抑制,使操作性變佳,且當多醣類含量爲5質量% 或以下,可避免皮膚滲透下降。 <親水性聚合物> 爲了改善保濕性質等目的,已知親水性聚合物可添加 至本發明所使用之凝膠片的水凝膠,除非在黏附凝膠片至 皮膚時的凝膠之可溶性被減弱。再者,親水性聚合物亦可 用於增改善凝膠片形狀之安定性。 可於本發明中使用之親水性聚合物可爲上述醚系溫 度敏感性聚合物及多醣類以外之聚合物化合物,且可爲合 成或天然聚合物化合物,只要聚合物化合物具有親水性官 能基(例如羥基、羧基、磺酸基、磷酸基、胺甲醯基、胺基、 銨基及伸乙氧基),此等聚合物化合物可單獨使用或可使用 -18- 200920414 其之二或多種的混合物。 作爲適於本發明之具有親水性基之合成聚合物化合 物,例如陰離子聚合物化合物,諸如乙烯醇(共)聚合物、 2-羥乙基丙烯酸酯(共)聚合物、丙烯酸(共)聚合物、甲基丙 烯酸(共)聚合物、順丁烯二酸(共)聚合物、伊康酸(共)聚合 物、對乙烯基苯甲酸(共)聚合物、2-丙烯醯胺基-2-甲基-1-丙烷磺酸(共)聚合物及苯乙烯磺酸(共)聚合物、與丙烯醯 胺(共)聚合物、丙烯醯基嗎啉(共)聚合物、N-乙烯基吡咯 酮(共)聚合物、乙烯基胺(共)聚合物、Ν,Ν-二甲基二丙烯 基銨氯(共)聚合物、2-甲基丙烯醯氧基乙基銨氯(共)聚合 物、聚乙二醇甲基丙烯酸酯(共)聚合物、及聚伸乙亞胺等 爲例示。 由保濕性的觀點,上述親水性聚合物之重量平均分子 量較佳具有1,000至500,000,更佳爲5,000至100,000。 此外,由保濕性及操作性的觀點,在水凝膠中親水性 聚合物之含量較佳爲0.05至5質量%,更佳爲0.1至3質 量%。 <賦形劑> 爲了進一步改善凝膠片外形之安定性目的,在本發明 水凝膠中較佳可添加賦形劑。作爲賦形劑,可適當使用有 機或無機之細微顆粒。作爲有機顆粒,技術中已知之聚苯 乙烯顆粒、聚甲基丙烯酸酯顆粒、及微晶纖維素爲較佳。 -19- 200920414 另外’作爲無機細微顆粒,以二氧化矽、礬土、碳酸銘、 问領土、黏土礦物、氧化鈦等較令人滿意。其中,以二氧 化砂或黏土礦物較佳。特別是,具有2〇〇 nm或以下之平 均粒徑的氣相法二氧化矽及合成彭潤土爲特佳。 在本發明中水凝膠所含賦形劑之比例較佳爲1 〇質量 °/。或以下’且特佳爲1至5質量。/。。 <香料> 爲了增加舒緩的效果,可添加香料於本發明水凝膠。 作爲香料’其例示爲醇系香料香料、酚系香料、羧酸系香 料 '胺系香料等。作爲醇系香料,其例示爲葉醇、3 _辛稀 醇、9·癸烯醇、沈香醇、香葉醇、橙花醇、香茅醇、玫瑰 醇、二甲基辛醇、羥基香茅醇、四氫沈香醇、薰衣草醇、 別羅勒烯醇、月桂烯醇、香油腦、1 -薄荷腦(L-薄荷腦)、 龍腦、異蒲勒醇、四氫鈴蘭醇、冰片基甲氧基環己醇、諾 波醇(η 〇 b ο 1 )、法尼醇、橙花三級醇、檀香醇、檀香腦、 柏木腦、岩蘭草醇、虎尾草醇、苯甲基醇、β -苯基乙基醇、 γ -苯基丙基醇' 肉桂醇、大茴香醇、α -戊烷基肉桂醇、二 甲基苯甲基甲醇、甲基苯基甲醇、二甲基苯基甲醇、β_苯 基乙基二甲基甲醇、β-苯基乙基甲基乙基甲醇、苯氧基乙 基醇、苯基乙二醇、第三丁基環己醇等。 此外,作爲酚系香料,其例示爲丁香油酚、香草醛、 扁柏硫醇,作爲羧酸系香料,其例示爲肉桂酸、苯基乙酸、 -20- 200920414 氫基肉桂酸等,及作爲胺系香料,其例示爲吲哚、糞臭素、 2 -甲基四氫喹啉、6 -甲基唾啉等。 <防腐劑> 爲了量測因微生物引起之腐敗的目的,本發明凝膠片 較佳地進一步包含防腐劑。該防腐劑包含例如酚、苯甲酸 及其鹽類、水楊酸及其鹽類、對羥基苯甲酸酯類(對羥苯甲 酸甲酯、對羥苯甲酸乙酯、對羥苯甲酸丙酯、對羥苯甲酸 丁酯)、2-苯氧基乙醇、去水乙酸及其鹽類、山梨酸及其鹽 類、院基胺基乙基甘胺酸氯、二氯沙(triclosan)、氯化苯 二甲經錢(benzalkonium chloride)、乙醇、丙醇、丁 醇等。 這些化合物可單獨使用,但較佳爲合併使用。其中,以對 羥基羥基苯甲酸酯類及苯氧基乙醇特佳。 於本發明中防腐劑之含量較佳爲0.01至0.5質量%, 更佳爲0.02至0.3質量%,且特佳爲〇.〇3至0.2質量%。 <有機酸> 由控制pH値之觀點,本發明水凝膠亦可進一步包含 有機酸。具體而言,有機酸包括乙酸、α -羥基酸(例如檸檬 酸、乳酸、葡萄糖酸、蘋果酸、琥珀酸等)、抗壞血酸、η比 咯陡酮竣酸等。這些化合物可單獨使用,或可合倂二或多 種使用。這些化合物在水凝膠中之含量較佳爲0.01至5質 量%,且更佳爲〇.〇5至2質量%。 <其他活性成分> -21 - 200920414 本發明凝膠片可根據表格中所欲之用途進—步包含 各種活性成分或添加劑。關於此活性成分或添加劑,下列 化合物爲其例示: 抗氧化劑(生育酚、二丁基羥基甲苯、丁基淫基苯甲 醚、沒食子酸鹽、類黃酮、單寧、木脂素(lignan)及皂甘 (saponin)等); 紫外光吸收劑(P-甲氧基肉桂酸、P-甲氧基肉桂酸辛 酯、2-甲氧基-2-羥基苯甲酮、2-乙基己基-p_二甲基胺基苯 甲酸酯等); p Η調節劑(緩衝劑,例如乳酸-乳酸鈉、檸檬酸-檸檬 酸鈉、琥珀酸-琥珀酸鈉等); 螯合劑(六磷酸肌醇、乙二胺四乙酸等); 界面活性劑(聚甘油脂肪酸酯、蔗糖脂肪酸酯、卵磷脂 等): 維生素(維生素人、81、82、86、(:、0、£及其衍生物、 泛酸、生物素、煙鹼醯胺及維生素C酯等); 胺基酸(甘胺酸、三甲基甘胺酸、吡略啶酮羧酸、絲胺 酸、肉鹼、γ-胺基丁酸、牛礦酸、蘇胺酸、天冬醯胺、麩 醯胺酸、酪胺酸、離胺酸、組胺酸、精胺酸、天冬胺酸、 麩氨酸、鳥胺酸、纈胺酸、白胺酸等); 消炎劑(甘草苷酸衍生物、甘草酸衍生物、水楊酸衍生 物、扁柏硫醇、氧化鋅 '尿囊素等); -22- 200920414 保濕劑(尿素、酪蛋白、大豆胜肽、乳酸菌發酵代謝產 物、酵母發酵代謝產物'蜂蜜、乳鐵蛋白、白蛋白、水解 彈力蛋白、水解角質素、水解蠶絲、α-羥基酸鹽類(例如乳 酸鈉、乳酸鉀及葡萄糖酸鉀等)、吡咯啶酮羧酸鈉、三甲甘 胺酸及乳清等); 美白劑(抗壞血酸葡萄糖苷、3-0-乙基抗壞血酸、熊果 素、對苯一酸、麵酸(kojic acid)、盧辛諾(lucinol)、傳明 酸、隣酸腺苷-1-鈉、厚樸木脂素(magnolignan)、鞋花酸、 維他命A酸(retinoid)、芸香苷、間-苯二酣(resolcinol)、 半胱胺酸、穀胱甘肽(glutathione)、亞麻油酸等); · 各種萃取物(例如明日葉(angelica keiskei)萃取物、酪 梨(persea gratissima ; avocado)果實萃取物、粗齒繡球 (hydrangea serrata)葉萃取物、藥蜀葵(althea)萃取物、山 金車(arnica)萃取物、蘆薈(aloe)萃取物、杏桃(prunus armeniaca; apricot)萃取物、杏桃核仁萃取物、銀杏(ginkgo biloba)萃取物、甜茵香(foeniculum vulgare; fennel)萃取物、 薑黃根(turmeric)萃取物、烏龍茶(oolong tea)萃取物、玫瑰 果(rose fruit)萃取物、狹葉松果菊(echinacea angustifolia) 葉萃取物、黃等(scutellaria baicalensis)根部萃取物、黃柏 (phellodendron bark)萃取物、日本白樺樹(coptis japonica) 根部萃取物、大麥(h o r d e u m v u 1 g a r e)種子萃取物、金絲桃 (hypericum perforatum)萃取物、短柄野芝麻(lamium album) -23- 200920414 萃取物、西洋菜(nasturtium officinale)萃取物、甜橙(citrus aurantium dulcis ; orange)果實萃取物、脫水海水、海藻萃 取物、水解彈性蛋白、水解麥粉、水解蠶絲、德國洋甘菊 (chamomilla recutita ; matricaria)萃耳又物、古月蘿蔔(daucus carota sativa ; carrot)根部萃取物、茵藤蒿(artemisia capillaries)花萃取物、甘草(glycyrrhiza)萃取物、木槿茶 (hibiscus tea)萃取物、火刺木(pyracantha fortuneana)果實 萃取物、奇異果(kiwi)果實萃取物、金雞納樹(cinchona)萃 取物、小黃瓜(cucumis sativus; cucumber)果實萃取物、鳥 音(guanosine)、山黃梔(gardenia florida)萃取物、粽葉(sasa veitchii)萃取物、苦參(sophora angustifolia)根部萃取物、 核桃殼萃取物、柚子(citrus grandis ;葡萄柚)果實萃取物、 鐵線蓮(clematis vitalba)葉萃取物、小球藻屬綠藻 (chlorella vulgaris)萃取物、桑樹(morus alba)葉萃取物、 龍膽草(gentiana lutea)萃取物、紅茶萃取物、酵母萃取物、 牛蒡(arctium lappa)根部萃取物、發酵米糠(fe rmented rice bran)萃取物、米胚芽油、聚合草(Symphyturn officinal^ 葉卒取物、越橘葉卒取物、細辛(asiasarum)根部萃取物、 柴胡(bupleurum)科萃取物、臍帶(UInbilical cord)萃取物、 肥巷草(saponaria officinalis)萃取物、竹萃取物、山楂 (crataegus cuneata)果實萃取物、花椒(zanth〇xylum)果實萃 取物、冬菇(corthellus shiitake ; mushroom)萃取物、熟地 -24- 200920414 黃(rehmania)根部萃取物、紫草(lithospermum erythrorhizone)根部萃取物、紫蘇(perilla herb)萃取物、菩 提樹(linden)花萃取物、榆繡線菊(spiraea ulmaria)花萃取 物,牡丹根部萃取物、菖蒲(acorus calamus)根部萃取物、 樺樹萃取物、問荆(equisetum arvense)萃取物、常春藤 (hedera helix ; ivy)萃取物、山楂(crataegus oxyacantha) 萃取物、接骨木(sambucus nigra)花萃取物、洋蓍草 (achillea millefolium)萃取物、金沙薄荷(mentha piperita ; peppermint)葉萃取物、鼠尾草(salvia officinalis; sage)葉萃取物、錦葵(malva sylvestri s ; mallow) 萃取物、日本川号(cnidium officinale)根部萃取物、日本 猜牙菜(swertiajaponica)萃取物、野大豆(glycine soja;大 _&)種子萃取物、棗樹果實萃取物、百里香(thymus vulgaris; thyme)萃取物,綠茶萃取物、丁香(eugenia caryophyllus; clove)花萃取物、白茅(Imperata cylindrical) 萃取物、溫州蜜柑(citrus unshiu)果皮萃取物、日本當歸 (Japanese angelica)根部萃取物、金盞花(calendula officinalis)花萃取物、核桃仁萃取物、苦橙(bitter orange) 果皮萃取物、魚腥草(houttuynia cordata)萃取物、番前 (solanum lycopersicum)萃取物、發酵大豆萃取物、人參 (panax ginseng)根部萃取物、大蒜(allium sativum)萃取 物、野玫瑰卒取物、木槿萃取物、麥門冬(ophiopogonis -25- 200920414 tuber)萃取物、荷蘭序(carum petroselinum; parsley)萃取 物、蜂蜜、金縷梅(hamamelis virginiana ; witch hazel)萃 取物、牆草(pari et aria officinal is)萃取物、夏枯草(iso donis japonicus)萃取物、金菊油(bisabolol)、枇杷(eriobotrya japonica)萃取物、款冬(coltsfoot)萃取物、紫蜂鬥葉 (butterbur)芽萃取物、茯茶(poria cocos)萃取物、假葉樹 (ruscus aculeatus)根部萃取物、葡萄(vitis vinifera)果實萃 取物、蜂膠、絲瓜(luffa cylindrical)果實萃取物、紅花 (carthamus tinctorius; safflower)花萃取物、薄荷萃取物、 大葉殿(tilia platyphyllos)花萃取物、牡丹(paeonia suffruticosa)根部萃取物、啤酒花(humulus lupulus; hops) 萃取物、歐洲赤松(pinus sylvestris)毯果萃取物、七葉樹 (aesculus hippocastanum ; horse chestnut)萃取物、水色蕉 (lysichiton camtschatcense)萃取物、無患子(sapindus mukurossi)果皮萃取物、香蜂花(melissa officinalis;芳香 薄荷)葉萃取物、桃樹(prunus persica)葉萃取物、矢車草 (centaurea cyanus)花萃取物、尤加利葉萃取物、虎尾草 (saxifraga sarmentosa)萃取物、柚子萃取物、薏仁(c〇ix seed)萃取物、艾蒿(mugwort)萃取物、薰衣草(lavandula angustifolia; lavender)萃取物、蘋果(pyrusmalus)果實萃 取物、高音(lactuca scariola sativa; lettuce)萃取物、檸檬 (citrus medica limonum; lemon)萃取物、紫雲英(astragalus -26- 200920414 sinicus)萃取物、保加利亞玫瑰(rosa centifolia)花萃取物、 西班牙迷迭香(rosamarinus officinalis; rosemary)葉萃取 物、羅馬洋甘菊(anthemis nobilis)花萃取物、蜂王乳萃取 物、蝴蝶花萃取物、聖母百合(lilium candidum)球莖萃取 物、番紅花(crocus sativus)花萃取物、生蔓根萃取物、辣 椒萃取物、胎盤萃取物、薏米(coix lachryma-jobi ; Job's tears)子萃取物、香橙(citrus junos)子萃取物、葡萄(vitis vinifera ; grape)子萃取物、西洋水芽萃取物、曇花 (epiphyllum oxpetalum)花萃取物、白羽扇丑花萃取物、雞 冠萃取物等; 活化劑(例如蜂王乳、敏化劑、膽固醇衍生物等); 血液循環促進劑(例如壬酸香草醯胺、菸鹼酸苯甲基 酯、菸鹼酸β -丁氧基乙基酯、唐辛子、薑油酮(zingerone)、 斑蝥 ST (cantharis tincture)、魚石脂(ichthammol)、單寧 酸、α-龍腦、生育酣薛鹼酸酯、六蔽鹼酸肌醇、環扁桃酯 (cyclandelate)、星納利淨(cinnarizine)、查諾林 (trazoline)、乙醯基膽鹼、維拉帕米(verapamil)、千金藤 驗(cepharanthine)、γ-穀維醇(orizanol)等; 抗皮脂漏劑(例如硫、二甲硫蔥等), 消炎劑(例如傳明酸、硫代牛磺酸、次牛磺酸、ε-胺基 己酸、甘草酸(glycyrrhizic acid)、β -甘草酸、氯化溶菌酶、 愈創奧(guaiazulene)、氫氧可體素(hydrocortisone)等); -27- 200920414 活性成分(例如二異丙基胺二氯乙酸鹽、4-胺基甲基 環己烷羧酸等);及 又,鹽酸維他命B6、菸鹼酸、菸鹼酸衍生物、泛酸鈣、 D-泛醇、乙醯基泛酸基乙醚、異丙基甲酚、雌二醇、乙炔 基雌二醇、卡普氯鞍(capronium chloride)、鹽酸苯海拉明 (diphenhydramine)、塔卡納(takanal)、棒腦、香草醯胺壬 酯、香草醯胺壬酯、Pirocton-Olamin、甘油十五烷酸酯、 1 -薄荷醇、單硝基癒創木酚、樹脂酚、氯化苯銨松寧 (benzethonium chloride)' 鹽酸美西律(mexiletine)、生長 素、雌激素、斑蝥酊、環孢菌素、氫化可體松、聚氧乙烯 山梨醇酐單硬脂酸酯、及薄荷油。 此外,若醫藥成分能經由皮膚滲入而投與活體,則亦 可添加,例如止痛藥、鎭定劑、抗高血壓劑、抗生素、抗 組織胺劑及抗菌物質。 依據凝膠片所欲之用途,可單獨使用一種或合倂二或 多種這些活性成分。包含於水凝膠中之活性成分根據本發 明可進一步包含下列成分。因爲這些活性成分及醫藥性質 根據物質本身在有效劑量上相異,成分含量及醫藥性質一 般並不能特定,但一般較佳爲關於水凝膠總量之0.001至 1 0質量%,且更佳爲0.0 5至5質量%。此外,相同地,在 保濕劑之情況,其之含量一般較佳爲關於水凝膠總量之0.1 至1 0質量%,且更佳爲0.5至5質量%。 -28- 200920414 [凝膠片之結構] 如上所述,在本發明凝膠片中,水凝膠可形成單層結 構,或亦可與其它層體形成多層結構。此外,可提供多層 水凝膠層。以上所述各成分可包含於水凝膠層,或是如果 可能,可包含於其他層體中。再者,當形成多層水凝膠層 時,各成分可被包含於相同之水凝膠層,或可分別包含於 多層之中。因此,當本發明凝膠片被形成多層水凝膠層 時,上述成分之含量爲組成凝膠片之所有水凝膠層中所含 之數量。 <近似片狀基質> · 爲了強化水凝膠層及改善凝膠片操作性之目的,近似 片狀基質可被提供於水凝膠層或鄰接於水凝膠層。 由本發明凝膠片之形狀穩定性及操作性之觀點,較佳 爲提供此近似片狀結構。水凝膠層以外之其他層體的實例 可爲支撐層及保護薄片。 由本發明凝膠片之形狀穩定性及操作性之觀點,較佳 爲提供一支撐層,且由使用凝膠片前保護水凝膠層表面之 觀點’較佳提供保護薄片。 關於支撐層,較佳使用已知之近似片狀材料,例如不 織布布料、紡織布料及塑膠薄膜、交聯凝膠(明膠/戊二醒 交聯凝膠、聚丙烯酸/多價金屬離子交聯凝膠等)、天然凝 膠(瓊脂糖凝膠、K-鹿角菜膠凝膠等)、及由親水性聚合物 -29- 200920414 所形成之非水溶性薄膜(甲殼素薄膜、玻璃紙、κ-鹿角菜膠 流延薄膜等)等等。 其中,就形狀之穩定性及凝膠片之操作性的觀點,在 本發明凝膠片中,較佳爲使用具有厚度1 00 μιη或以下之 透明薄膜。特別是,由親水性聚合物所形成之非水溶性薄 膜較佳,例如甲殼素薄膜、玻璃紙、由親水性聚合物所形 成之κ-鹿角菜膠流延薄膜等。 此外,關於保護薄片,較佳使用聚乙烯薄膜、聚丙烯 薄膜、PET薄膜等。特別是,較佳使用具有厚度5 00 μιη 或以下之聚乙烯薄膜。 * 當活凝膠片僅由水凝膠層構成時,就形狀之保持性及 操作性的觀點,一般而言,凝膠片之厚度較佳爲0.4至3 mm,更佳爲0.5至2 mm。 此外,雖然支撐層及保護薄片之厚度如前所述時,在 由水凝膠層及支撐層及/或保護薄片所構成之多層結構凝 膠片的情況下,支撐層之厚度係更佳爲5至80 μιη,且保 護薄片之厚度更佳爲50至5 00 μπι。在此多層結構之情況, 水凝膠之厚度可調整至等於前述水凝膠之厚度,或者是, 可適當地調整,以便使凝膠片之全部厚度在0.4至3 mm 範圍內。 [高膠體脫水(syneresis)凝膠片] 由包含上述成分之水凝膠中,當本發明凝膠片包括合 -30- 200920414 倂Ο/W型乳液(其包括具有1至I50nm之平均直徑之乳化 顆粒)及作爲醚系溫度敏感性聚合物之聚醚化合物(聚醚類) 所形成之水凝膠與至少選自膠原蛋白凝膠或其分解產物 之一者時,其可形成具有特別優異膠體脫水之凝膠片。 爲了快速供給凝膠片中所含之水分或活性成分至目 標區域,除了凝膠片之保水性外,供應保留於凝膠片中之 水分或類似物至鄰近黏附體之預定區域的膠體脫水性質 亦爲重要。然而,已知技術(例如JP-A第200 5 -225 8 3 7號 中所述技術,及JP-A第2003 - 1 8 3147號中所述技術)在保 持皮膚表面之保濕性質時·,對於水凝膠中所含之活性成分 快速且有效滲透至皮膚呈現不足之膠體脫水。 如上所述,經由形成凝膠片,該凝膠片包含合倂含具 有1至150nm之平均直徑之乳化顆粒之Ο/W型乳液、聚 醚化合物、及膠原蛋白及/或其分解產物所形成的水凝膠, 當此一凝膠片接觸例如皮膚之吸水性物體(黏附體)時,含 脂溶性活性成分之Ο/W型乳液有效地被釋放,供應水含量 至角質層同時增加,且可得到活性成分之滲透至黏附體。 此外,高膠體脫水凝膠片,除了高膠體脫水之外,片 體爲可彎曲的且容易以壓力而形變,且因爲表面爲潮濕狀 態,亦可增強黏著於黏附體。 於本發明中,膠體脫水意指由於凝膠片與黏附體之接 觸,滲出水凝膠中所含之液體成分(膠體脫水之水分)的功 -31 - 200920414 能,及將膠體脫水之水分移至鄰近黏附體之活體或可吸收 之生物體。除了存在水凝膠之乳液中的水分及水相成分之 外,本發明凝膠片之膠體脫水之水含有脂溶性成分或細微 固體顆粒,其不僅在水相,亦在乳液顆粒中,以溶解或分 散於液體成分而存在。結果,凝膠片中各種活性成分可經 由凝膠片與黏附體接觸而有效供給至鄰近的黏附體。 此外,在此說明書中,凝膠片可被指爲一種"高膠體脫 水凝膠片",特別是當凝膠片在上下文之膠體脫水中被指出 時。 本發明中高膠體脫水凝膠片可呈現較佳爲40質量% 或以上及90質量%或以下之膠體脫水率,更佳爲45質量% 或以上及85質量%或以下,且特佳爲50質量%或以上及 80質量%或以下。 本發明中膠體脫水率以下述方式獲得:將凝膠片剪成 3cm><3cm之大小而形成樣本凝膠片,將這些樣本凝膠片放 入Advantec MSF. Inc.製之具有9cm直徑之2號濾紙(二種 JIS P3 80 1規定之定性濾紙( 1 995版):125g/m2及厚度 0.2 6 m m ;排水時間:8 0秒;水吸收力:8 0 c m)之間,以便 將兩片濾紙夾住樣本凝膠片之各上下端,並當保持在周圍 溫度25 °C及相對溼度50± 10% 10分鐘下,量測濾紙質量 變化。膠體脫水率經由使用獲得之量測値以下式(1)計算。 膠體脫水率(質量%)=(濾紙所吸收液體之質量/凝膠 -32- 200920414 起始質量)Χ100 (1) 在上述式(1)中,"凝膠起始質量"爲樣本凝膠片測試片 質量減去支撐材料質量所得之値。 量測膠體脫水率之方法可參照例如20 07年6月發行 之"香料雜誌"Fragrance Journal,,第9 5 - 1 02頁中所述之方 法。 在本發明凝膠片構成例如用於活體之凝膠片的情 況’基於作爲水吸收性黏附體之濾紙的液體吸收量,評估 凝膠片之膠體脫水率可爲一種各成分(例如水及水凝膠所 保留之功能性成分)是否可經由凝膠片與黏附體(例如表皮) 接觸帶入而有效地滲入皮膚的指數。當膠體脫水率少於40 質量% ’水或類似物滲透至皮膚可能變得不足,且當膠體 脫水率超過9 0質量%,凝膠片儲存時之安定性可能下降。 此外,在膠體脫水液體中之0/W型乳液顆粒之濃度較 佳爲0.001至2倍之濃度,更佳爲0.01至1.5倍,且最佳 爲0.1至1倍水凝膠中0/W型乳液顆粒之濃度。 在此點上,膠體脫水液體中乳液顆粒之濃度可使用量 測膠體脫水率中所使用之濾紙,由比色計所量測之濃度粗 略估計。此外,在乳液所含之乳液或脂溶性成分由使用於 量測膠體脫水率的濾紙提取後,膠體脫水液體中乳液顆粒 之濃度可以分光光度計、HP LC等粗略估計。 上述關於各種成分,包括各種脂溶性活性成分及其他 -33- 200920414 添加劑,及其含量 '製造o/w型乳液之方法無須修正而適 於高膠體脫水凝膠片所含之〇/w型乳液。此外’相似地, 除非各成分之主要用途減損,乳液各油相及水相中所含的 其他成分可被包含於〇/w型乳液各項中。 高膠體脫水凝膠片在膠體脫水液體中可含有高濃度 之含脂溶性活性成分之細微顆粒乳液,因此,活性成分可 有效供應至黏附體。 作爲於聚醚化合物,其可包含於高膠體脫水凝膠片 中,例如聚氧化乙烯、聚氧化丙烯、聚氧化乙烯/聚氧化丙 烯嵌段共聚物、聚氧化乙烯/聚氧化丙烯/聚氧化乙烯嵌段 共聚物等可爲較佳例示,且含聚氧化乙烯及聚氧化丙烯之 嵌段聚合物特別合適,且更佳爲,聚氧化乙烯/聚氧化丙嫌 嵌段共聚物(下文簡稱"PEO-PPO嵌段聚合物"),或聚氧化 乙烯/聚氧化丙烯/聚氧化乙烯嵌段共聚物(下文簡稱 "PEO-PPO-PEO嵌段聚合物")特別合適。這些聚醚類已知 如普羅沙姆(poloxamer),且可在商業產品上易於取得’商 品名爲"PLURONICn 及,1LUTROL (二者皆由 BASF A.G•製 造)、NEWPOL (Sanyo Chemical Industries,Ltd.製造)、 及 EPAN (Dai-Ichi Kogyo Seiyaku Co., Ltd.製 is )、 PRONON (Nippon Oil & Fats Co.,Ltd.製造)等。 在此情況,聚醚類之重量平均分子量(M w)較佳爲 1,000 至 1,000,000,且更佳爲 5,000 至 500,000。 -34- 200920414 在高膠體脫水凝膠片中,水凝膠中所含之聚醚含量較 佳爲〇 · 〇 5至2 0質量%,更佳爲〇. 1至1 0質量%,且特佳 爲0.2至5質量%。在上述範圍內,當聚醚含量爲0.05質 量%或以上,膠體脫水可完全提升,且水凝膠所添加之活 性成分滲透至皮膚的效率可充分達成,且當含量爲20質 量%或以下,可有效地避免儲存力明顯下降。 可包含於高膠體脫水凝膠片中之膠原蛋白並不受特 別限制,可包括各種膠原蛋白萃取物。可使用含膠原蛋白 之粗原料經已知技術進行萃取,例如酸溶解、鹼溶解中性 鹽溶解及酵素溶解。只要原料含有膠原蛋白,任何含膠原 蛋白原料皆可使用,且脊椎動物(例如牛、豬、沙丁魚、鯊 魚等)之皮、魚鱗、骨、軟骨、腱、器官等可爲例示,就高 含量膠原蛋白之觀點,可適當使用骨、軟骨、皮或魚鱗、 腱、胎盤等。特別是,適於本發明所使用之膠原蛋白較佳 爲水溶性膠原蛋白。 可包含於高膠體脫水凝膠片中之膠原蛋白分解產物 可經由以蛋白質水解酶(例如膠原蛋白酶、胰蛋白酶、及凝 乳蛋白)分解膠原蛋白而獲得,或經由酸或鹼水解、或經由 熱變性。 作爲膠原蛋白分解產物’例如酸處理明膠、鹼處理明 膠、酶分解明膠、膠原蛋白三胜肽、膠原蛋白二胜肽及胺 基酸(甘胺酸、脯氨酸、羥基脯氨酸、乙醯基羥基脯氨酸等) -35- 200920414 爲例示。 高膠體脫水凝膠片中水凝膠的膠原蛋白或膠原蛋白 分解產物之含量較佳爲0.05至20質量%,更佳爲0.1至 10質量%,且特佳爲0.2至5質量%。當含量爲0.05質量 %或以上,經由貼附凝膠片至表皮可達到保溼效果,當含 量爲20質量%或以下,操作性變得較佳。 由改善膠體脫水性質之觀點,高膠體脫水凝膠片所含 之水凝膠較佳爲一種使用陰離子聚合物及水溶性二價金 屬鹽類所形成之水凝膠,且相對於1 00質量份之陰離子聚 合物化合物,水溶性二價金屬鹽之含量比例' 特佳爲5質量 份或以上。 <水溶性二價金屬鹽> 本發明凝膠片之水凝膠較佳含有水溶性二價金屬 鹽。於本文中,水溶解度於本發明中意指於2YC至少可 溶解0.1質量%於純水之溶解度。 作爲用於形成水溶性二價金屬鹽之二價金屬,以週期 表第II族之鎂、鈣、緦及鋇或過渡金屬Cu2+、Fe2+、Zn2 + 及Mn2 +爲例示,且較佳爲鎂及鈣。 水溶性鹽類可爲任何無機鹽及有機酸鹽類,並無特別 限制’例如,無機鹽例如爲鹽酸鹽、硝酸鹽、硫酸鹽、磷 酸鹽、碳酸鹽等,且有機酸鹽例如爲檸檬酸鹽、乳酸鹽、 蘋果酸鹽、琥珀酸鹽、抗壞血酸鹽、葡萄糖酸鹽,及有機 -36- 200920414 及無機復合鹽類,例如抗壞血酸基磷酸鹽爲例示。 其中,以氯化鎂、氯化鈣、乳酸鎂、蘋果酸鎂、檸檬 酸鎂、檸檬酸鈣、抗壞血酸鎂、抗壞血酸鈣、抗壞血酸基 磷酸鎂、葡萄糖酸鎂及葡萄糖酸鈣較適當,特別是氯化鎂 及抗壞血酸基磷酸鎂較佳。 高膠體脫水凝膠片中水溶性二價金屬鹽之混合量,相 對於1 〇〇質量份陰離子聚合物化合物(後述),必須爲50質 量份或以上(在本說明書中,”質量份”可被指爲”份"),且 由效果之觀點,較佳爲50份至1,000份,更佳爲70份至 5 00份,特佳爲80份至3 00份。 此外,在用於形成水凝膠之混合液體中的水溶性二價 金屬鹽之含量較佳爲0.1至5質量%,更佳爲0·2至4質量 %,且特佳爲0.5至2質量%。當水溶性金屬鹽之比率在此 範圍內,水凝膠之膠體脫水可被改善,可獲得優異操作性 之凝膠片。 在由陰離子聚合物及水溶性二價金屬鹽所形成之水 凝膠中,水溶性二價金屬鹽用於形成凝膠,且並不必定以 ”鹽”之狀態存在。然而,在所形成之水凝膠中,可經由量 測組成金屬鹽之金屬量,並經由轉換所獲得之量而獲得水 溶性二價金屬鹽或由金屬鹽所衍生之化合物的含量。g 此,’’水凝膠中水溶性二價金屬鹽之含量”意指依此方法幸專 換之値。根據此方法,甚至在水凝膠形成後,能偵測出水 -37- 200920414 溶性二價金屬鹽含量是否在上述範圍內。 <陰離子聚合物化合物> 可用於高膠體脫水凝膠片之陰離子聚合物化合物並 不受特別限制,且可使用合成聚合物及天然聚合物,只要 聚合物化合物在分子中含有陰離子基,其選自例如羧基、 礦基、隣基%。 可單獨使用一種些類陰離子聚合物化合物,或是二或 多種之混合物於水凝膠。 陰離子合成聚合物化合物包括丙烯酸(共)聚合物、甲 基丙烯酸(共)聚合物、馬來酸(共)聚合物、伊康酸(共)聚合 物、P-乙烯基苯甲酸(共)聚合物、2_丙烯醯胺-2-甲基-1-丙 烷磺酸(共)聚合物及苯乙烯磺酸(共)聚合物。 此外,陰離子天然聚合物化合物包括果膠酸、褐藻 酸、瓊脂、鹿角菜膠、褐藻糖膠、玻糖醛酸、硫酸軟骨膠、 肝素、結冷膠、天然結冷膠、黃原膠、羧基甲基纖維素、 羧基甲基澱粉、羧基甲基葡聚糖、聚麩胺酸、及DN A、RN A 等。 其中,較佳爲丙烯酸(共)聚合物、褐藻酸、瓊脂、鹿 角菜膠、結冷膠、天然結冷膠、黃原膠、羧基甲基纖維素、 羧基甲基澱粉、羧基甲基葡聚糖、聚麩胺酸、及DN A、 RNA。 特別是,關於陰離子聚合物化合物,由保水性與凝膠 -38- 200920414 強度之相容性之觀點,較佳爲丙烯酸(共)聚合物、褐藻酸、 瓊脂、鹿角菜膠、玻糖醛酸、結冷膠、天然結冷膠、黃原 膠、羧基甲基纖維素,特別是,以瓊脂、鹿角菜膠、結冷 膠、天然結冷膠、黃原膠更佳。 由凝膠強度之觀點,陰離子聚合物化合物之分子量較 佳爲10, 〇〇〇至 5,000,000之範圍內,更佳爲20,000至 2,000,000之範圍內。 在高膠體脫水凝膠片中,水凝膠中陰離子聚合物化合 物之含量較佳爲0 · 0 1至1 0質量%,更佳爲0 · 1至8質量%, 且特佳爲〇 _ 2至4質量%。當含量位於這些範圍內時,可 獲得具有充分膠體脫水之水凝膠,同時達到高凝膠強度與 優異之操作性。 經由一起使用陰離子聚合物及二價金屬水溶性鹽之 組合’形成一種具有弱交聯結構形成於水凝膠系統之立體 網狀結構,因此認爲改良了充足的液體保留性及優異的膠 體脫水。 儘管水凝膠中所含之陰離子聚合物化合物及水溶性 二價金屬鹽可依據所欲用途適當的組合,由凝膠強度與膠 體脫水之相容性之觀點’水溶性二價金屬鹽/陰離子聚合物 化合物之組合可如以下較佳實例所示,但該組合不受這些 實例所限制: 抗壞血酸磷酸鎂/鹿角菜膠; -39- 200920414 抗壞血酸磷酸鎂/結冷膠; 抗壞血酸磷酸鎂/瓊脂; 抗壞血酸磷酸鎂/黃原膠; 抗壞血酸磷酸鎂/丙烯酸(共)聚合物; 抗壞血酸磷酸鎂/羧基甲基纖維素 氯化鎂/鹿角菜膠, 氯化鎂/結冷膠; 氯化鎂/丙烯酸(共)聚合物; 乳酸鎂/鹿角菜膠; 乳酸鎂/瓊脂; 乳酸鈣/結冷膠; 抗壞血酸鈣/鹿角菜膠;及 葡萄糖酸鈣/結冷膠。 <具有三價或以上之多價金屬鹽> 由用於形成水凝膠混合溶液中預防減少膠體脫水之 觀點’在高膠體脫水凝膠片之水凝膠中具有三價或以上之 多價金屬鹽之含量較佳爲0.1質量%或以下。 作爲具有三價或以上之多價金屬鹽,含例如Al3+、 Fe3+、Ti3+' Ti4+、In3+、Zr4+、Ta5 +等之多價金屬陽離子之 鹽爲例示’更明確而言,鉀明礬、銨明礬、鐵明礬、硫酸 鋁、聚氯化鋁、合成矽酸鋁、氫氧化鋁、硬脂酸鋁、乙酸 鋁、硫酸鐵、氫氧化鐵、乳酸鈦 '乙酸鍩等爲例示。 -40- 200920414 高膠體脫水凝膠片之水凝膠中’用於形成水凝膠混合 溶液中具有三價或以上之多價金屬鹽含量較佳爲ο·1質量 %或以下’更佳爲0 ·0 5質量%或以下’特佳爲0 ·01質量% 或以下,且最佳爲除了不可避免之雜質外’水凝膠並不含 此類多價金屬鹽。當三價金屬鹽之含量超過0·1質量%’ 膠體脫水有惡化的可能。 <多醣類> 爲了改善操作性質,在高膠體脫水凝膠片中,除了如 上述陰離子聚合物化合物實例所述之陰離子多醣類’較佳 爲添加多醣類至水凝膠。 爲此目的,作爲可含於高膠體脫水凝膠片之多醣類, 例如中性多醣類(例如纖維素、澱粉醣、支鏈澱粉、葡聚糖、 聚三葡萄糖、菊澱粉、聚半乳糖、聚甘露糖、樹膠質、聚 阿拉伯糖、聚葡甘露糖、聚半乳甘露糖、瓊脂糖、甲基纖 維素、羥丙基纖維素、卡特蘭多醣、木糖葡聚醣等),及陽 離子多醣類(幾丁質、甲殼素、陽離子化纖維素、陽離子 化澱粉、陽離子化葡聚糖等)爲例示。 其中,以高稠化膠凝作用之多醣類爲更佳,且特佳爲 聚葡甘露糖、聚半乳甘露糖、瓊脂糖、甲基纖維素、羥丙 基纖維素。爲了更增加膠凝性,可組合使用—或多種此類 多醣類。 高膠體脫水凝膠片之水凝膠中多醣類之含量較佳爲 -41 - 200920414 0.01至5質量%,更佳爲0.1至4質量%,且特佳爲0.2至 2質量%。若多醣類之含量在上述範圍內,凝膠強度達到 改善效果,且操作性優異,可預防膠體脫水及皮膚滲透力 的降低。 <親水性聚合物> 在高膠體脫水凝膠片中,爲了增加保濕性,除了凝膠 溶解度在貼附凝膠片至皮膚時被減弱之外,可添加已知之 親水性聚合物至水凝膠。再者,親水性聚合物亦可用於改 善高膠體脫水凝膠片之形狀安定性。 作爲可含於高膠體脫水凝膠片之親水性聚合物,上述 陰離子聚合物化合物及多醣類以外之聚合物化合物可爲 合成或天然聚合物化合物,只要聚合物化合物具有親水性 官能基(例如羥基、胺甲醯基、胺基、銨基及伸乙氧基等)。 這些聚合物化合物可單獨使用或可使用其之二或多種的 混合物。 作爲具有此親水性基之合成聚合物化合物,例如乙烯 醇(共)聚合物、2-羥乙基丙烯酸酯(共)聚合物、丙烯醯胺(共) 聚合物、丙烯醯基嗎啉(共)聚合物、N-乙烯基吡咯啶酮(共) 聚合物、乙烯基胺(共)聚合物、氯化N,N-二甲基二烯丙基 銨(共)聚合物、氯化2 -甲基丙烯醯氧基甲基銨(共)聚合 物、聚乙二醇甲基丙烯酸酯(共)聚合物、聚伸乙亞胺等爲 例示。 -42- 200920414 由保濕性的觀點,上述親水性聚合物 量較佳爲1,〇〇〇至5〇〇 〇〇〇,更佳爲5,000 再者’由保濕性及操作性的觀點,親 凝膠中之含量較佳爲〇.〇5至5質量%,更 量%。 依所欲用途亦可混合各種活性成分2 體脫水凝膠片。作爲此類活性成分及添加 臉部治療與皮膚治療爲目的之醫藥性, 劑、增稠劑、香料、色素、安定劑、抗氧 收劑、增黏劑、Ρ Η調整劑、螯合劑、表面 及抗菌劑等爲例示。關於這些項目,可不 文所述。 <近似片狀材料> 在高膠體脫水凝膠片中,爲了增強水 膠片之操作性之目的,可提供一種近似片 層或鄰接於水凝膠層。由增進高膠體脫水 定性及操作性之觀點,較佳提供一種近似 在高膠體脫水凝膠片中,當近似片狀 種支撐層時,可使用已知之近似片狀基質 布布料、紡織布料及塑膠薄膜。 形成不織布布料或紡織布料之材料並 使用一般所使用之布料,且以天然布料, 之重量平均分子 至 100,000° 水性聚合物在水 佳爲〇. 1至3質 之添加劑至高膠 劑,爲了美化及 [可以例如保濕 化劑、紫外線吸 活化劑、殺菌劑 經修改而應用前 凝膠層及增進凝 狀基質於水凝膠 凝膠片之形狀安 片狀基質。 基質使用作爲一 材料,例如不織 無特別限制,可 例如纖維素、絲 -43- 200920414 蛋白等’回收布料,例如人造纖維等,合成布料例如尼龍、 聚酯、聚乙烯、聚丙烯、丙烯酸樹脂'聚乳酸'聚胺甲酸 酯等爲例示’且可適用纖維素、尼龍及聚酯。 適用於高膠體脫水凝膠片之紡織布料或不織布布料 具有之基重較佳爲3g/m2至100g/m2之範圍,更佳爲5g/m2 至70g/m2’且特佳爲5g/m2至5〇g/rn2。在此基重之範圍內, 近似片狀基質具有較佳操作性之強度,同時,凝膠片之撓 性並無劣化’且在貼附時凝膠片之黏附性並不降低。 當使用塑膠膜時,塑膠膜可爲液體不通透性單層體或 多層塑膠薄片’’或可爲多孔性薄片或網狀薄片。 由操作性之觀點,近似片狀基質之厚度較佳約爲 0.01mm至1mm。再者,當用於化妝品材料或類似物時, 如本說明書中所述之具有高透明度之薄片較佳。 當近似片狀用於水凝膠層,較佳爲液體可通透薄片, 例如紡織布料、不織布布料、多孔性薄片、網狀薄片等。 但,當使用作爲水凝膠層之一表面上的支撐層時,可使用 液體不通透性薄片或厚的紡織布料、不織布布料等。 再者,當使用近似片狀基質作爲水凝膠層之補強層 時’可使用例如具有高破裂強度之聚合物凝膠片的基質, 及親水性聚合物薄膜,例如交聯凝膠(明膠/戊二醛交聯凝 膠、聚丙烯酸/多價金屬離子交聯凝膠等),及天然凝膠(瓊 脂糖凝膠、κ-鹿角菜膠凝膠等),及由親水性聚合物所形成 -44- 200920414 之非水溶性薄膜(甲殻素薄膜、玻璃紙、K-鹿角菜膝流延 膜等)等。 其中’以具有主3C由水凝膨及紡織布料或不織布布料 形成之結構的高膠體脫水凝膠片特別令人滿意。於此,$ 要所形成之結構意指一種將例如紡織布料、不織布布 ~ 之基質薄片疊於水凝膠層之至少一表面上的結構,且基胃 薄片及水凝膠層相互黏合,以致於在操作時無法相g分 離,或爲一種將基質薄片完全及不可分地包含於水凝龄層 的結構,且水凝膠層置於基質薄片之二表面上。 爲了維持直到使用凝膠片時活性成分或保水性的目 的,較佳於高膠體脫水凝膠片施用於活體的凝膠片表面上 設置保護薄片。 作爲保護薄片,較佳使用聚乙烯薄膜、聚丙烯薄膜、 PET薄膜等。特別是,較佳使用具有厚度500 μηι或以下 之聚乙烯薄膜,且更佳爲20μιη至400μπι。 由形狀保持性及操作性之觀點,一般而言,無論支撐 物是否存在’高膠體脫水凝膠片中水凝膠層之厚度較佳爲 0.4mm 至 2mm,且特佳爲 〇.5mm 至 l_5mm。 [凝膠片之製造方法] 本發明凝膠片可根據一般所使用之方法製造。 例如當凝膠片僅以水凝膠形成時,凝膠片可根據製造 水凝膠之通常方法製造,更明確地,在加熱並混合成份以 -45- 200920414 製備混合液體(用於形成水凝膠之混合液體)後,以例如刮 刀等之塗覆機器的方式形成凝膠片。然後,將凝膠片冷卻 至完全凝結,因而獲得凝膠片。 在具有支撐層之凝膠片之情況,凝膠片可經下述方式 易於獲得,例如塗覆前述水凝膠之成分的混合水溶液於近 似片狀支撐基質上而疊合。 此外,在製造水凝膠之程序中可分別或一起添加多元 醇、0/W型乳液及多醣類,或在製造水凝膠後分別或一起 添加。 再者,當保護薄片形成時,在僅由水凝膠層形成凝膠 片之情況,凝膠片之一表面或二表面可以保護薄片覆蓋, 且在近似片狀基質與水凝膠層所形成之層狀結構的情 況,保護層被疊合於無形成近似片狀基質之凝膠層表面 上。 [凝膠片之物理性質] 由當其貼附於皮膚時減少外觀上之不舒適感的觀 點,較佳爲本發明凝膠片係爲高透明。 此外,當凝膠片需要高透明度時,理想上爲選擇近似 片狀基質等,其可一起與水凝膠層使用,且具有高透光 度,例如尼龍篩網、透明樹脂薄膜。 可基於波長600 nm之分光光度計所度量之透射率値 來評估本發明中之透明度。前述透明度理想上爲一種經由 -46- 200920414 評估方法所量測之對於蒸餾水的透射率較佳爲60%或 上,且更佳爲98%或以上。 當透射率爲60%或以上時,其使得易於檢測皮膚於 附下之狀況。然而,當其施用於不需考慮外觀之使用部 時,凝膠片並不當然需要是透明的。 本發明凝膠片中水凝膠之水含量理想上爲70質量 或以上,及9 5質量%或以下。當水含量在此範圍中時, 性成分由水凝膠之釋放效果不僅增進,且可降低貼附凝 片時對於表皮之刺激性。 水凝膠之水含量較佳爲70質量%或以上及95質J 或以下,更佳爲75質量%或以上及95質量。/。或以下,且 佳爲8 0質量%或以上及9 0質量%或以下。當水含量少 7 〇質量%,成份之皮膚通透性可降低,且當水含量超過 質量%,由於減少水凝膠之強度,操作性可能劣化。 特別是,在上述膠體脫水凝膠片之情況,由於膠體 水優異,經由含有各種活性成分於在較佳水含量範圍之 凝膠中,此活性成分可有效地滲入黏附體之預定標的 置’例如活體等。因此,本發明凝膠片可適用作爲一種 性成分或化妝物質之持續釋放載體。 更明確而言,由凝膠片取出lg水凝膠,在減壓 25°C乾燥直至不再觀測到樣本之質量變化,且上述水 根據下式(2)所計算出之値獲得: 以 貼 位 :% 活 膠 :% 特 於 95 脫 水 位 活 於 量 -47- 200920414 水含量(%)=[(起始質量-乾燥後質量)/起始質量]x 100 (2) 由於熱乾燥或減壓乾燥’水凝膠之水含量可由水凝膠 質量之減少比率量測。或者是,水凝膠之水含量可以卡爾 費雪(Carl Fischer )型、紅外線型或電阻型測水儀量測。 此外,當水凝膠混合液自身膠凝時,水之混合率可被視爲 凝膠之水含量。 雖然本發明凝膠片之型式並不特別限定,該型式可爲 捲繞成膠帶之成卷型狀,或其可爲各自獨立之分離薄片。 在分離薄片之情況,其可爲任何型式,且依據所’欲使用之 身體位置而適當地選擇,例如橢圓形、圓形、心形、半圓 形、半橢圓形、方形、長方形、梯形、三角形、或其之組 合等爲例示。此外,可適當設計沿著身體施用部位之形 狀,或可最恰當地貼附至所欲使用之身體位置的形狀。 例如,當使用凝膠片作爲活體之黏附薄片時,依具體 實施例可呈現爲,凸面部份或凹面部分形成於凝膠片中央 部份或周圍部分,用於定位凝膠片等之目的,或根據使用 部位之外型形成截斷部位或挖空部位,以便具體實施例之 黏附薄片能增加操作性,及增加黏附體與薄片在所欲區域 接觸的黏附力。 本發明凝膠片所施用之活體之身體部位包括可爲臉 部(唇、頰 '眼部、眼之上下區域、鼻、前額、全臉)、手 -48- 200920414 臂、腿、胸、腹、背、頸等。 當本發明凝膠片使用做爲活體用黏附薄片時,不僅可 根據身體位置調整上述型式,而且亦可調整面積、厚度、 水凝膠層外表面之黏性等。而且,包含於凝膠片之活性成 分種類及含量亦可適當之調整。 例如,當活體用黏附薄片之施用部位爲整臉時,對於 所施用之黏附薄片,較佳調整薄片形成一種眼及口所對應 之部位已移除且對應於鼻之部位已切開的形狀,再者,增 加黏著層之黏著力或降低凝膠片厚度以適於所欲黏附之 較大區域。此外,用於臉部之黏*附薄片可被分成二部分, 即上部分施用於前額、眼部及鼻子周圍,而下部分施用於 嘴部周圍及下巴。 爲了避免水含量或活性成分隨時間降低,這些凝膠片 可在使用前被密封於由不透氣材料所製之包裝材料中。 例如,在凝膠片爲連續性膠帶型之情況,凝膠片可儲 存於不透氣容器中,例如由不透氣薄片所形成之具有拉錬 之包裝袋,或由不透氣塑膠所形成之具有可開啓或關閉之 蓋子的容器。再者’在一片片各自分離的薄片之情況,個 別之薄片可密封於由不透氣薄片所形成之可開的個別包 裝袋中。在儲存及配給至使用凝膠片之期間,可維持水含 量及活性成分於適當狀態。 由上述所構成之本發明凝膠片具有優異的活性成分 -49- 200920414 等之黏附體滲透性及優異的操作性,且經由選擇包含於水 凝膠層之成分的種類或數量、水凝膠層之厚度、及凝膠片 之劑量形式,其可使用作爲提供經皮膚吸收藥物之載體的 黏著劑,供投藥於活體;近似片狀化妝品材料,例如用於 美容及臉部治療之及皮膚治療的包裝組;用於例如皮膚可 滲透成分、消炎止痛劑之活性成分之載體;用於活體作爲 傷口保護或藥物固定,及傷口覆蓋劑之目的的黏附膠帶。 因爲高膠體脫水凝膠片在黏附於活體、保濕性及活性 成分之膠體脫水上十分優異,且呈現良好之操作性,水或 活性成分在黏附·時可特別有效地供應於黏附體,因此高膠 體脫水凝膠片適用於所有需要持續供應水或活性成分之 用途,且在生物相容性及安全性上十分優異,因此在藉由 施用凝膠片而供應水或活性成分至活體之用途上,效果是 顯著的,並可適當地使用作爲一種活性成分之持續釋放載 體及化妝品材料。 [近似片狀化妝品材料] 本發明之近似片狀化妝品材料可包括本發明凝膠片。 即’可由本發明凝膠片保持如活性成分、保濕成分、 皮膚美白成分、收斂成分等,以形成一種化妝品材料。經 由使水凝膠層表面與皮膚接觸而使用此近似片狀化妝品 材料。 因爲本發明活體用黏附凝膠片在活性成分等滲透至 -50- 200920414 皮膚、及操作性上十分優異’本發明近似片狀化妝品材料 特別適用於作爲近似片狀化妝品材料,用於經由貼附該材 料於臉部而濕潤皮膚或提供皮膚醫療性質。 [實施例] 下文本發明進一步參照以下實施例說明,但本發明並 不受限於該等實施例。此外,除另有特定外,“份”與“ %,, 分別意指“質量份”及“質量%”。 [實施例1] 將下列成分於50 °C加熱攪拌1小時,獲得溶膠態溶 液1。 酸處理明膠(源自豬皮來源) 3.0g 1,3-丁二醇 5.0g PLURONIC F-127 (PEO-PPO-PEO 嵌段聚合物:BASF A.G_ 製備) 〇.5g 純水 4 1 . 5 g 在聚苯乙稀製之盒(尺寸65mm X 95mm)中,將溶膠 溶液1歷經流延以形成1 mm之厚度,於4°c冷卻1 6小時, 獲得水凝膠用於實施例1。該水凝膠稱爲實施例1凝膠片。 使用分光光度計,於波長6 OOnrn之凝膠片透射率爲85%。 [實施例2] 除了 PLURONIC F-127以聚甲基乙烯醚置換外,經由 相似於實施例1之水凝膠製造方法獲得實施例2之水凝 -51 - 200920414 膠,且實施例2之水凝膠稱爲實施例2凝膠片。使用分光 光度計,於波長600nm之凝膠片透射率爲72%。 [實施例3 ] 除了 PLURONICF-127以甲基纖維素置換外,經由相 似於實施例1之水凝膠製造方法獲得實施例3之水凝膠, 且實施例3之水凝膠稱爲實施例3凝膠片。使用分光光度 計,於波長600nm之凝膠片透射率爲84%。 [實施例4] <含類胡蘿蔔素乳液之製備> 經由在7 0 ° C加熱一小時以溶解下列成分,而獲得水 相組成物。 蔗糖油酸酯 1 3 g 單油酸十甘油酯 2 5 g 甘油 500g 純水 322g 經由在7 0 ° C加熱一小時以溶解下列成分,而獲得油 相組成物。 雨生紅球藻(Haematococcus Pluvialis)萃取物(暇紅素 含量=20質量%) 40g 混合生育酣 1 0 g 卵磷脂(來自大豆) 90g 經由以均質器(於1〇,〇〇〇 rpm)攪拌水相組成物,添加 -52- 200920414 油相組成物於其中,同時保持於70°C,而獲得含類胡蘿蔔 素乳液。使用 Ultimizer HJP-25 005 (Sugino Machine Ltd. 製),在200 MPa壓力下將所產生之含類胡蘿蔔素乳液進 行高壓乳化,以增稠系統顆粒尺寸分析儀 FPAR-1 000(0tsuka Electronics Co., Ltd.製)於 25 °C量測所 產生之乳液之體積平均粒徑,獲得體積平均粒徑9 0 nm。 <水凝膠之製備> 於8 0 °C加熱並捏製下列成分而獲得溶膠態產物2。 κ-鹿角菜膠 〇.2g 聚葡甘露糖(衍生自象根) 〇.2g 酸處理明膠(衍生自豬皮) 〇.5g PLURONIC F-127 (PEO-PPO-PEO 嵌段聚合物:BASF A.G.製) 0.5g 1,3-丁二醇 5.0g 純水 4 3 . 1 g 將此溶膠態產物2冷卻至60°C後,添加0.5g之含類 胡蘿蔔素乳液,並均勻攪拌混合物而獲得一溶液。在聚苯 乙烯製之盒(尺寸65mm X 95mm)中,將溶膠溶液歷經流 延以形成1 mm之厚度,於4°C冷卻16小時,獲得實施例 4用之水凝膠。該水凝膠稱爲實施例4凝膠片。使用分光 光度計,於波長6 0 0 n m之凝膠片透射率爲8 0 %。 [比較實施例1] -53- 200920414 在5 0 ° C加熱下攪拌下列成分一小時,而獲得溶膠態 溶液3。 3 · 〇 g 5 .〇g 42.0g 酸處理明膠(衍生自豬皮) 1,3-丁二醇 純水 f 在聚苯乙燒製之盒(尺寸65mm χ 95mm)中,將溶膠溶 液3歷經流延以形成1 m m之厚度,於4。C冷卻1 6小時, 獲得水凝膠。該水凝膠稱爲比較實施例1凝膠片。 [比較實施例2] 於80°C加熱並捏製下列成分而獲得溶膠態產物4。 κ-鹿角菜膠 0.2g 聚葡甘露糖(來自象根) 0.2g PLURONIC F-1 27 (PEO-PPO-PEO 嵌段聚合物:BASF A.G·製) 〇.5g 1,3-丁二醇 5.0g 純水 4 4.1 g 在聚苯乙烯製之盒(尺寸65 mm χ 95mm)中,將溶膠溶 液4歷經流延以形成1 mm之厚度,於4。C冷卻1 6小時, 獲得水凝膠。該水凝膠稱爲比較實施例2凝膠片。 [比較實施例3] 將聚乙二醇-共聚萘二甲酸丁二酯溶於THF,以便使濃 度成爲10質量%,在尺寸5cm X 5cm TEFLON (註冊商標) -54- 200920414 製之淺盤上將溶液歷經流延,並於一般溫度及壓力下乾燥 形成薄膜,將薄膜浸入1 〇〇ml純水中,獲得水凝膠。該水 凝膠稱爲比較實施例3凝膠片。 [比較實施例4] 除了 PLURONIC F-127以聚(N-異丙基丙烯醯胺)置換 外,經由相似於實施例1之水凝膠製造方法獲得水凝膠, 該水凝膠稱爲比較實施例4凝膠片。 -凝膠片之評估- 實施例1至4及比較實施例1至4之凝膠片實施於評 分員,使凝膠片黏附於各評分員臉部(各評分員於洗臉後將 凝膠片黏附於眼睛部份1 5分鐘),根據下列方法及標準進 行評估,評估結果顯示於下表1。以五位評分員評估結果 之平均値顯示評估結果。 (1) 操作性 根據下列方法進行評估,當凝膠片黏附於臉部上時, 凝膠片易於黏附而無黏在評分員指頭上的情況,該凝膠片 評爲A ;因黏在評分員指頭上而多花時間黏附的情況,該 凝膠片評爲B ;而當凝膠片容易破裂且難以黏附的情況, 該凝膠片評爲C。 (2) 黏附感 在上述操作”(1 )操作性,,中’根據下列方法進行評估黏 附感’當凝膠片黏附於臉部上達到與臉表面密接的情況, -55- 200920414 該凝膠片評爲A;當凝膠片一部分脫落的情況,該凝膠片 評爲B ;而當凝膠片皴褶且凝膠片許多部分剝落的情況, 該凝膠片評爲C。 (3) 保濕性 將凝膠片黏附1 5分鐘,並剝下凝膠片後,3 0分鐘過 後以角質層水份測量儀(Asahibiomed製)量測角質層之水 含量’根據下列方法進行評估保濕性,當五位評分員評估 値之平均値的水含量增加1 0 %或以上的情況,該凝膠片評 爲A ;當水含量增加2%至1 0%的情況,該凝膠片評爲B ; 而當水含量增加少’於2%的情況,該凝膠片評爲C。 (4) 皮膚阻隔性 爲了評估粗糙乾燥皮膚之改善功能,以下列方法量測 經皮膚水分流失量(TEWL)。 即,將凝膠片定期貼附每日15分鐘,連續三天,在 第三日剝下凝膠片後立即以經皮膚水分流失量分析儀 (Asahibiomed製)測量經皮膚水分流失量(TEWL)。以下列 方法量測皮膚阻隔性,當TEWL値與測試前之値比較而下 降5 %或以上的情況,該凝膠片評爲A ;當下降1至4 %的 情況,該凝膠片評爲B ;而當TEWL並無變化的情況,該 凝膠片評爲C。 -56- 200920414200920414 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a gel sheet for medicines, medicines, cosmetics, health care materials, and various articles, and an approximate sheet cosmetic material using a gel sheet. [Prior Art] Gel sheets are used for mask materials, and adhesives are used for cosmetic and facial treatments and skin treatments; for example, carriers for skin permeable components, active ingredients of anti-inflammatory analgesics; for protecting wounds or fixing drugs The purpose of the living body with a tape; and for a wound covering agent. These gel sheets protect the surface of the skin by adhering to the surface of the skin, provide water retention on the surface of the skin, and contain various ingredients on the gel sheet, thereby giving the skin water content (water retention), controlling the skin temperature, or presenting the supply. The function of the gel tablet active ingredient in living organisms. In particular, since the active ingredient penetrates into the skin, increasing the temperature and moisture of the skin promotes the movement of the active ingredient. It is known that a gel sheet having the above functions contains collagen and a polysaccharide such as chitin, chitin, alginic acid, and cellulose as constituent components (for example, see Japanese Patent Application Laid-Open (JP-Α) No. 3 -81213). Meanwhile, with respect to a temperature-sensitive state-changing hydrogel composition, it is a known technique in which when a hydrogel contacts a skin, it is incorporated into water due to a state change from a gel to a flowable state by body temperature. The drug in the gel enters the skin (for example, see the published Japanese translation of the PCT International Publication No. 200920414 2007-502269 for the patent application (JP-T). Further, it is known that an adhesive sheet containing a temperature-sensitive polymer has a transfer temperature of 4 to 34 ° C and a viscous polymer (for example, 'see JP-A No. 5 - 1 8 4 457 7), and a type A temperature-sensitive gel sheet approved by a temperature-sensitive hydrogel formed of a specific polyether ester (for example, see JP-A No. 11-92 5 54). However, these gel pieces do not sufficiently sufficiently transfer the active ingredients in the gel to the skin, and in many cases, the sheets are insufficient in operability. SUMMARY OF THE INVENTION In view of the above circumstances, the present invention provides a gel sheet which has improved permeability to water or an active ingredient on an adherend such as a skin or the like, and excellent operability, and An approximate sheet cosmetic material using the gel sheet is provided. The first aspect of the present invention provides a gel sheet of an aqueous gel comprising an ether-based temperature-sensitive polymer and at least one decomposition product of collagen or collagen. A second aspect of the present invention provides an approximate sheet cosmetic material using any of the above gel sheets. The present invention can provide a gel sheet and a gel sheet which is similar to a sheet-like cosmetic material having an improved permeability of water or an active ingredient carried by the gel sheet on an adherent such as a skin or the like. Operational. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The gel sheet of the present invention contains an ether-based temperature-sensitive polymer' and at least one collagen and a decomposition product thereof. The ether-based temperature-sensitive polymer of the above gel sheet is preferably at least one selected from the group consisting of polyethers, polyvinyl ethers, and alkylated multi-flavored derivatives, more preferably polyoxyethylene and A block polymer of polyoxypropylene. The gel sheet may contain a 0/W type emulsion, and the 0/W type emulsion may contain a carotenoid. Further, the gel sheet of the present invention is preferably a colloidal dehydrated liquid of a gel sheet containing emulsified particles of an o/w type emulsion. The gel sheet of the present invention preferably contains a hydrogel layer having a hydrogel and an approximate sheet-like base layer for or adjacent to the hydrogel layer. The invention is described below. Any reference sign indicating a numerical range in the present invention means a range defined by including a minimum 値 and a maximum 値. In the present invention, "gel sheet" includes an adhesive for a mask material and an adhesive for beautification and facial treatment and skin treatment, and an active ingredient for use in, for example, a skin infiltrating component and an anti-inflammatory analgesic agent. The agent, the tape for the purpose of live wound protection, drug fixation, and the wound covering agent, and the sheet associated with retaining the active ingredient or moisture', and directly adhere to the adhesive for the purpose of infiltrating the retained component to the adhesive. body. The gel sheet is used as a makeup material for 200920414, for example, a masking agent for adhering to the skin to provide skin moisture or active ingredients. [Gel Sheet] The gel sheet of the present invention contains a gel film containing an ether-based temperature-sensitive polymer, and at least one collagen and a decomposition product thereof. The ether-based temperature-sensitive polymer used in the present invention causes dehydration at an increased temperature, and on the other hand, the form of collagen or gelatin (a decomposition product of collagen) changes with an increase in temperature. The use of an ether-based temperature-sensitive polymer in combination with a collagen having a property of controlling the amount of the active ingredient (e.g., medicinal properties) or a decomposition product thereof is contained in the hydrogel, and the proper appearance strength of the hydrogel is maintained. Thus, gel sheets of aqueous gels are used to approximate sheet cosmetic materials to provide moisturizing properties and to penetrate the active ingredients to the skin. (Hydrogels) <Ether-based temperature-sensitive polymer> The hydrogel used in the present invention contains an ether-based temperature-sensitive polymer. The ether-based temperature-sensitive polymer of the present invention refers to a polymer which hydrates in the presence of water below a certain temperature, and when it exceeds this temperature, it dehydrates and thus undergoes a form change. These small changes due to temperature changes show small changes such as volume change, hydrophilic-hydrophobic change, optical change, expansion-shrinkage change, and the like. "A certain temperature" means the temperature of the lower critical co-solvation temperature, and is increased by adding 200920414 to the gel sheet at a temperature of 30 ° C. The observed average molecular weight g 500,000 c with the stability of any polymer at the above temperature. Affinity of ethers, vinyl ethers and examples thereof include propylene, polyoxypropylene oxide/poly, polyethylethylene: vinyl ether, etc., which can be: ketone, hydroxypropyl cellulose, water or active From the viewpoint of skin permeability of the component, when the viscosity is a viscosity, the temperature is preferably from 20 to 40 ° C, more preferably from 25 to the ether-based temperature-sensitive polymer used in the present invention: sensitivity characteristics, and as long as the polymer has The ether linkage can be made without limitation. The ether temperature sensitive polymer preferably has a weight (Mw) of 5,000 to 1, 〇〇〇, 〇〇〇, and preferably, from the suitability and storage point of the temperature reaction. In particular, it is preferably a group consisting of clusters and alkylated polysaccharide derivatives selected from the group consisting of clusters and alkylated polysaccharide derivatives, in response to the temperature of the living body and the point of contact with the substrate material, including the following compounds: Polyethers, such as polyethylene oxide A polyoxyethylene/polyoxypropylene block copolymer, a polyethylene oxide/ethylene oxide block copolymer, etc. may be preferred examples. Regarding polyvinyl ethers, such as polymethyl vinyl ether ether, polymethoxy B. A vinyl ether or a polyethoxyethyl hydrazine is a preferred example. Regarding alkylated polysaccharide derivatives, such as methyl saponin, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl carapace Further, it may be a preferred example. Further, from the viewpoint of the temperature response of the living body and the affinity with the base material, the polyether, the polyvinyl ether and the alkylated polysaccharide derivative preferably have at least one or more of 200920414. a functional group selected from the group consisting of hydroxyethyl, hydroxypropyl, methoxy and ethoxy, and in the above examples 'preferably a polyoxyethylene/polyoxypropylene block copolymer, Polyethylene oxide/polyoxypropylene/polyoxyethylene block copolymer, polymethyl vinyl ether, methyl cellulose, etc. Regarding the ether-based temperature-sensitive polymer of the present invention, it contains polyethylene oxide and polypropylene oxide. Block polymers are particularly good and more specific 'Polyethylene oxide/polyoxypropylene block copolymer (hereinafter referred to as MpE〇-ppo block polymer "), or polyethylene oxide/polyoxypropylene/polyoxyethylene block copolymer (hereinafter referred to as ' PEO-PPO-PEO block polymers ") are satisfactory. These polyethers are known as Poloxamer' and are readily available in commercial products (trade name "PLURONIC" and "LUTROL (2 All manufactured by BASF AG), NEWPOL (manufactured by Sanyo Chemical Industries, Ltd.), and EPAN (manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.), PRONON (manufactured by Nippon Oil & Fats Co., Ltd.), etc. . The above ether-based temperature-sensitive polymers may be used singly or a mixture of two or more kinds may be used. The content of the 'ether-based temperature-sensitive polymer in the hydrogel used in the present invention is preferably from 0.05 to 20% by mass, more preferably from 0.1 to 10% by mass. /. And particularly preferably from 0.2 to 5% by mass. When the content of the ether-based temperature-sensitive polymer is 〇.〇5 mass% or more, the effect of the penetration of the active ingredient added to the hydrogel into the skin can be sufficiently achieved, and when the content is 20% by mass or less, it can be avoided. Significant reduction in the retention of hydrogel storage-10-200920414. <Collagen and Decomposition Products> The hydrogel used in the present invention includes collagen and its decomposition products. The collagen herein is not particularly limited and includes various collagen protein extracts. Extraction may be carried out using a collagen-containing material of a known technique, such as acid dissolution, alkali dissolution, neutral salt dissolution, and enzyme dissolution. As far as the material contains collagen, any material can be used, and skin, fish scales, bones, cartilage, tendons and spines (such as cattle, pigs, sardines, sharks, etc.) can be exemplified, and from the viewpoint of high content of collagen, Proper use of bone, cartilage, skin, or scales, tendons, and placenta. In particular, the prion protein suitable for use in the present invention is preferably water-soluble collagen. The collagen decomposition product of the present invention can be obtained by decomposing collagen with a proteolytic enzyme such as collagenase, trypsin, and chymotrypsin, or by acid or base hydrolysis, or by thermal denaturation. Collagen decomposition products, for example, acid-treated gelatin, alkali-treated gelatin, enzymatically decomposed gelatin, collagen tripeptide, collagen dipeptide, and amino acid (glycine, proline, hydroxyproline, ethyl thiol) Hydroxyproline or the like is exemplified. In the present invention, at least one gelatin or gelatin derivative is preferred among the collagen protein and the collagen decomposition product from the viewpoint of releasing the active ingredient. Gelatin is a hydrolyzed protein of collagen. The method for producing gelatin is not particularly limited, and the gelatin is generally produced by using an acid treatment or an alkali treatment using bovine bone, cowhide, pig skin and fish 11 - 200920414 scales. It can be produced by an enzyme method. Further, as the gelatin derivative, a known derivative such as an acid anhydride adduct of gelatin (for example, capric acid gelatin, succinated gelatin, trimellitized gelatin or the like) or a lactone adduct (gluconic acid- Δ-lactone adduct gelatin, etc.), bismuth gelatin (acetylated gelatin, etc.), esterified gelatin (methylated gelatin, etc.), gelatin organic acid salt (acetate gelatin, stearate gelatin, benzene Formate gelatin) and the like are exemplified. The gelatin and its derivative used in the gel sheet of the present invention are derived from pig skin gelatin, gelatin derived from fish, succinated gelatin, and citric acid from the viewpoints of affinity with a living body and properties of an active ingredient. Gelatin and trimellitic acid gelatin are desirable. As the gelatin and its derivatives, gelatin may be used singly or in combination of two or more gelatins, and the gelatin derivative may be used singly or in combination of two or more gelatin derivatives, or gelatin and gelatin derivatives may be used. mixture. Further, when the weight average molecular weight is measured by gel permeation chromatography (GPC), the weight average molecular weight of the gelatin and the gelatin derivative in the present invention is preferably 5,000 to 1, 〇〇〇, 〇〇〇, more Good for 5, 〇〇〇 to 300,000, especially good for 10, 〇〇〇 to 30,000. The content of the collagen and collagen decomposition products contained in the hydrogel of the present invention is preferably from 0.05 to 20% by mass, more preferably from 0.1 to 10, and from -12 to 200920414%, particularly preferably from 2 to 5. quality%. 〇 〇 5 mass% or more of collagen protein and collagen decomposition product content can effectively penetrate the active ingredient in the hydrogel into the skin' and when the content is 20% by mass or less, the workability is improved. Further, from the viewpoint of penetration of the active ingredient into the skin, the mass ratio of the ether-based temperature-sensitive polymer to the collagen and its decomposition product (ether-based temperature-sensitive polymer: collagen and its decomposition product) is preferably 1 : 50 to 50:1' is preferably 1:10 to 10:1, and particularly preferably 1:5 to 5:1. In order to exert different functions, the gel sheet of the present invention preferably further contains other components such as a polyol compound, a 0/W type emulsion, and a polysaccharide in the hydrogel. Further, if necessary, a hydrophilic polymer or the like may be contained. <Polyol compound> The gel film of the present invention preferably further contains a polyol compound from the viewpoint of penetration of the active ingredient into the skin and storage. The polyol compound particularly includes glycerin (glycerin, diglycerin, etc.); glycols (for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,2-propylene glycol propylene glycol, 1, 3) -propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, hydrazine, 2-pentanediol, 1,2-hexanediol, 1,2-octanediol, etc.) , sugar (glucose, fructose, mannose, galactose, xylose, arabinose 'glucosamine, guanidine-glycosyl glucosamine, sucrose, lactose, maltose, isomaltose, trehalose, cellobiose, bismuthose , sugar, maltose, raffinose, kidney bean, etc.), sugar alcohol (glycerol, threitol, erythritol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactose Alcohol, muscle-13-200920414 alcohol, etc.) are exemplified. The above polyol compounds may be used singly or in combination of two or more. Among them, it is preferred to use glycerin or glycol in the gel sheet of the present invention, particularly 'glycerin, 1,2-propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexene Glycols, and 1,3-butanediol are more desirable. Further, it is particularly preferred to use glycerin, hydrazine, 2. propylene glycol, 1,3-butylene glycol, and 1,2-hexane diol. The proportion of the polyol compound contained in the hydrogel in the present invention is preferably 50% by mass or less, particularly preferably 1 to 20% by mass. . In the present invention, the proportion of the polyol compound contained in the hydrogel is preferably 50% by mass or less, so that the decrease in gel strength and the improvement in workability can be avoided. <o/w type emulsion> The gel sheet of the present invention preferably contains an o/w type emulsion, and particularly preferably a 0/W type emulsion containing a fat-soluble active ingredient and a pharmacological property. In this method, the ingredients of the '0/W type emulsion can be applied to the adherent so that the function of each ingredient (e.g., beautifying the skin) is enhanced by skin penetration. With regard to the fat-soluble active ingredient, more desirable are, for example, fat-soluble vitamins and related substances (tocopherol, tocotrienol, retinol, retinal, calciferol, etc.), sterols (cholesterol, plant solids) Alcohol, etc., Coenzyme Q (CoQ10, etc.), and neurolipids, neuropterin, rice sterol, squalene, squalane, carotenoids and the like, and derivatives thereof, and carotenoids are particularly preferred in the present invention. As carotenoids, sea cucumber, actinioerythrol, shrimp red-14 - 200920414, erythroic acid (bixin), cantaxanthin, capsorbin, beta-8' - apo P-8'-apo-cartenal, β-12'-apo-carotenoid, α-carotene, β-carotene, γ-carotene, β-zeaxanthin (β-cryptoxanthin) ), lutein, lycopene, violaxantin, zeaxanthin, fucoxanthin and derivatives thereof are exemplified. Among them, more satisfactory are astaxanthin, lutein, zeaxanthin and β-zeaxanthin, and anti-oxidation effect, anti-inflammatory effect, anti-aging skin protection effect and whitening effect have been confirmed as astaxanthin Particularly satisfactory. In addition, other ingredients may be included in the 0/W type emulsion composition in a usual amount, such as an emulsifier, which may generally be included in each phase of the emulsion. Among other ingredients of this type are included other ingredients such as the polyols described in the description of the invention. The volume average particle diameter of the emulsified particles of the 0 / W type emulsion is preferably from 1 to 200 nm', more preferably from 1 to 150 nm, particularly preferably from inm to 1 〇〇 nm. The volume average diameter particles can be measured by a commercial particle size distribution analyzer or the like. Regarding the particle size measurement method of the emulsion, optical microscopy, confocal laser scanning microscopy, electron microscopy, atomic force microscopy, static light scattering spectroscopy, laser diffraction, dynamic light scattering, Centrifugal sedimentation, electric pulse measurement, chromatography, ultrasonic damping, etc., and devices corresponding to the respective principles are commercially available. From the range of the volume average diameter in the present invention and the point of easy measurement -15-200920414, the volume average particle diameter measurement of the emulsion of the present invention is more satisfactory by the dynamic light scattering method. Regarding a commercial measuring device using dynamic light scattering, exemplified by NANOTRAC UPA (Nikkiso Co., Ltd.), and dynamic light scattering particle size distribution analyzer LB-5 5 0 (Horiba, Ltd.), thickened system particle size Analyzer FPAR-1000 (Otsuka Electronics Co., Ltd.) and the like. In the present invention, the thickened system particle size analyzer F P A R -1 0 0 0 (manufactured by Otsuka Electronics Co., Ltd.) was measured at 25 ° C to be used as the volume average particle diameter of the Ο/W type emulsion. In the method of measuring the volume average particle diameter, the volume average particle diameter is measured by measuring in a glass test tube by diluting with pure water so that the concentration of the oil phase component can be in the range of 〇·1 to 1% by mass. When the refractive index of the dispersion medium is set to 1.3313 (pure water) and the viscosity of the dispersion medium is set to 0.8 846 mP a.s (pure water), a cumulative (50%) 値 can be obtained for the volume average particle diameter. The method of preparing the Ο/W type emulsion is not particularly limited, and for example, the method disclosed in JP-A No. 2005-75817 can be used. Alternatively, the Ο/W emulsion is preferably produced by a process comprising the steps of: a) dissolving a water soluble emulsifier in an aqueous medium to form an aqueous phase, b) mixing and dissolving carotenoids, tocopherol, Lecithin and other oils and lipids as needed form an oil phase, and the mixture mixes and emulsifies the aqueous phase and the oil phase under stirring. When emulsified, it is particularly preferred to use an emulsification apparatus which generally utilizes a shearing action, such as a stirrer, a blade stirrer, a homogenizer, and a continuous flow type shearing apparatus, and then a high pressure homogenizer, etc., so that it can be combined. -16 - 200920414 Use two or more emulsifying equipment. By using a high pressure homogenizer, an emulsion containing liquid droplets of more uniform fine particles can be obtained. The content of the 0/W type emulsion in the hydrogel of the present invention is preferably from 0.001 to 10% by mass, more preferably from 0.05 to 1% by mass, from the viewpoint of the effect and penetration of the active ingredient into the skin. Further, the content of the fat-soluble active ingredient in the hydrogel of the present invention is preferably from 0.000 to 10% by mass, more preferably from 0.05 to 5% by mass, whereas the content of the fat-soluble active ingredient varies depending on the kind of the active ingredient. The carotenoid content of the hydrogel of the present invention is preferably 0.0001 to 0.5% by mass, more preferably 0.0005 to 0.1% by mass, and particularly preferably 0.001 to 0.05% by mass. When the carotenoid content is 0.0001 mass% or more, the effect can be felt after the gel sheet of the present invention is applied to the skin (skin-beautifying effect, etc.). If the content is 0.5% by mass or less, the discomfort which is hardly generated by coloring to the skin is suppressed. <Polysaccharide>. It is also satisfactory to add a polysaccharide to the gel sheet of the present invention to improve the workability thereof. The polysaccharide which can be used in the present invention includes polysaccharides other than the above ether-based temperature-sensitive polymers, such as neutral polysaccharides (for example, cellulose, starch sugar, amylopectin, agarose, dextran, Polytriglucose, inulin starch, polygalactose, polymannose, gum, polyarabinose, polyglucomannan, polygalactomannan, etc., and anionic polysaccharides (pectic acid, alginic acid, joan) 17- 200920414 Fat, carrageenan, fucoidan, hyaluronic acid, chondroitin sulfate, heparin, gellan gum, natural gellan gum, xanthan gum, carboxymethylcellulose, etc., and cationic polysaccharides (chitin, chitin, cationized cellulose, etc.). Among them, 'the polysaccharide with high thickening gelation is better, and it is made of polyglucomannan, polygalactomannan, agar, carrageenan, gellan gum, natural gellan gum, and xanthan gum. . In order to increase the gelation effect, two or more of these polysaccharides may be used in combination. The content of the polysaccharide in the hydrogel of the present invention is preferably from 0.01 to 5% by mass, more preferably from 1 to 4% by mass, and particularly preferably from 2 to 2% by mass. When the content of the polysaccharide is 〇.〇1% by mass or more, the insufficient gel strength can be suppressed, the workability is improved, and when the polysaccharide content is 5% by mass or less, skin penetration can be prevented. decline. <Hydrophilic polymer> For the purpose of improving moisturizing properties and the like, it is known that a hydrophilic polymer can be added to the hydrogel of the gel sheet used in the present invention unless the gel is adhered to the skin of the gel sheet to the skin. The solubility is weakened. Further, the hydrophilic polymer can also be used to improve the stability of the shape of the gel sheet. The hydrophilic polymer which can be used in the present invention may be a polymer compound other than the above ether-based temperature-sensitive polymer and polysaccharide, and may be a synthetic or natural polymer compound as long as the polymer compound has a hydrophilic functional group. (e.g., hydroxy, carboxyl, sulfonate, phosphate, amine, mercapto, amine, ammonium, and ethoxy), these polymer compounds may be used alone or may be used -18-200920414 two or more mixture. As a synthetic polymer compound having a hydrophilic group suitable for the present invention, for example, an anionic polymer compound such as a vinyl alcohol (co)polymer, a 2-hydroxyethyl acrylate (co)polymer, an acrylic (co)polymer , methacrylic acid (co)polymer, maleic acid (co)polymer, itaconic acid (co)polymer, p-vinylbenzoic acid (co)polymer, 2-acrylamido-2- Methyl-1-propanesulfonic acid (co)polymer and styrenesulfonic acid (co)polymer, with acrylamide (co)polymer, acryloylmorpholine (co)polymer, N-vinylpyrrole Ketone (co)polymer, vinylamine (co)polymer, ruthenium, osmium-dimethyldipropenyl ammonium chloride (co)polymer, 2-methylpropenyloxyethylammonium chloride (co)polymerization Examples, polyethylene glycol methacrylate (co)polymer, and polyethylenimine are exemplified. The weight average molecular weight of the above hydrophilic polymer is preferably from 1,000 to 500,000, more preferably from 5,000 to 100,000, from the viewpoint of moisture retention. Further, the content of the hydrophilic polymer in the hydrogel is preferably from 0.05 to 5% by mass, more preferably from 0.1 to 3% by mass, from the viewpoint of moisture retention and handling properties. <Excipient> In order to further improve the stability of the shape of the gel sheet, an excipient is preferably added to the hydrogel of the present invention. As the excipient, organic or inorganic fine particles can be suitably used. As the organic particles, polystyrene particles, polymethacrylate particles, and microcrystalline cellulose which are known in the art are preferred. -19- 200920414 In addition, as inorganic fine particles, it is more satisfactory to use cerium oxide, alumina, carbonic acid, territories, clay minerals, and titanium oxide. Among them, silica sand or clay minerals are preferred. In particular, gas phase ruthenium dioxide having a mean particle diameter of 2 〇〇 nm or less and synthetic Peng Run soil are particularly preferable. The proportion of the excipient contained in the hydrogel in the present invention is preferably 1 〇 mass ° /. Or below and particularly preferably from 1 to 5 mass. /. . <Spices> In order to increase the soothing effect, a perfume may be added to the hydrogel of the present invention. The perfume is exemplified by an alcohol-based perfume, a phenol-based fragrance, a carboxylic acid-based fragrance, an amine-based fragrance, and the like. As the alcohol-based flavor, it is exemplified by leaf alcohol, 3 - octanol, 9 · decenol, linalool, geraniol, nerol, citronellol, rose alcohol, dimethyl octanol, hydroxy citronella Alcohol, tetrahydrofurfuryl alcohol, lavender alcohol, bellerolol, myrcenol, sesame oil brain, 1-menthol (L-menthol), borneol, isopulegol, tetrahydropyranyl alcohol, borneol-based methoxy Cyclohexanol, nopolol (η 〇b ο 1 ), farnesol, nerolitriol, sandalwood, sandalwood, cypress, zephyrin, chlorfen, benzyl alcohol, beta -phenylethyl alcohol, γ-phenylpropyl alcohol 'cinnamyl alcohol, anisyl alcohol, α-pentyl cinnamyl alcohol, dimethylbenzyl alcohol, methyl phenyl methanol, dimethyl phenyl methanol , β-phenylethyldimethylmethanol, β-phenylethylmethylethylmethanol, phenoxyethyl alcohol, phenylethylene glycol, t-butylcyclohexanol, and the like. Further, examples of the phenolic flavor are eugenol, vanillin, and cedar thiol, and carboxylic acid-based flavors are exemplified by cinnamic acid, phenylacetic acid, -20-200920414 hydrogen cinnamic acid, and the like. A flavoring agent, which is exemplified by hydrazine, skatole, 2-methyltetrahydroquinoline, 6-methylsaliline or the like. <Preservative> The gel sheet of the present invention preferably further contains a preservative for the purpose of measuring the spoilage caused by microorganisms. The preservative comprises, for example, phenol, benzoic acid and salts thereof, salicylic acid and salts thereof, p-hydroxybenzoic acid esters (methyl paraben, ethyl paraben, propyl paraben, Butyl p-hydroxybenzoate), 2-phenoxyethanol, dehydrated acetic acid and its salts, sorbic acid and its salts, amphoteric aminoglycolic acid chloride, triclosan, chlorination Benzalkonium chloride, ethanol, propanol, butanol, etc. These compounds may be used singly, but are preferably used in combination. Among them, p-hydroxy hydroxybenzoate and phenoxyethanol are particularly preferred. The content of the preservative in the present invention is preferably from 0.01 to 0.5% by mass, more preferably from 0.02 to 0.3% by mass, and particularly preferably from 0.3 to 0.2% by mass. <Organic Acid> The hydrogel of the present invention may further contain an organic acid from the viewpoint of controlling pH. Specifically, the organic acid includes acetic acid, an α-hydroxy acid (e.g., citric acid, lactic acid, gluconic acid, malic acid, succinic acid, etc.), ascorbic acid, η-pyrroic acid, and the like. These compounds may be used singly or in combination of two or more. The content of these compounds in the hydrogel is preferably from 0.01 to 5% by mass, and more preferably from 5 to 2% by mass. <Other Active Ingredient> -21 - 200920414 The gel sheet of the present invention can further comprise various active ingredients or additives according to the intended use in the table. For the active ingredient or additive, the following compounds are exemplified: Antioxidants (tocopherol, dibutylhydroxytoluene, butyl benzyl anisole, gallate, flavonoids, tannins, lignans (lignan) ) and saponin, etc.; ultraviolet light absorber (P-methoxycinnamic acid, octyl p-methoxycinnamate, 2-methoxy-2-hydroxybenzophenone, 2-ethylhexyl) -p_dimethylamino benzoate, etc.); p Η modulator (buffer, such as lactic acid - sodium lactate, citric acid - sodium citrate, succinic acid - sodium succinate, etc.); chelating agent (hexaphosphate muscle) Alcohol, ethylenediaminetetraacetic acid, etc.); surfactant (polyglycerol fatty acid ester, sucrose fatty acid ester, lecithin, etc.): vitamins (vitamins, 81, 82, 86, (:, 0, £ and its derivatives) , pantothenic acid, biotin, nicotinamide and vitamin C esters; amino acid (glycine, trimethylglycine, pyrrolidone carboxylic acid, serine, carnitine, γ-amine Butyric acid, bovine acid, sulphate, aspartame, glutamic acid, tyrosine, lysine, histidine, arginine, aspartic acid , glutamic acid, ornithine, valine, leucine, etc.; anti-inflammatory agents (glycyrrhizin derivatives, glycyrrhizic acid derivatives, salicylic acid derivatives, cypress thiol, zinc oxide 'allantoin, etc. -22- 200920414 Moisturizer (urea, casein, soybean peptide, lactic acid bacteria fermentation metabolite, yeast fermentation metabolite 'honey, lactoferrin, albumin, hydrolyzed elastin, hydrolyzed keratin, hydrolyzed silk, α- Hydroxy acid salts (such as sodium lactate, potassium lactate and potassium gluconate, etc.), sodium pyrrolidonecarboxylate, trimethylglycine and whey, etc.; whitening agents (ascorbyl glucoside, 3-0-ethylascorbic acid, arbutin) , p-benzoic acid, kojic acid, lucinol, tranexamic acid, adenosine-1-sodium, magnolignan, shoe acid, vitamin A acid Retinoid), rutin, resolcinol, cysteine, glutathione, linoleic acid, etc.; · various extracts (eg angelica keiskei extract, cheese) Pear (persea gratissima; avocado) fruit extract Hydrangea serrata leaf extract, hollyhock extract, arnica extract, aloe extract, apricot extract (prunus armeniaca; apricot) extract, apricot Nucleolus extract, ginkgo biloba extract, foeniculum vulgare; fennel extract, turmeric extract, oolong tea extract, rose fruit extract, Echinacea angustifolia leaf extract, root extract of scutellaria baicalensis, phellodendron bark extract, coptis japonica root extract, barley (hordeumvu 1 gare) seed extract , hypericum perforatum extract, lamium album -23- 200920414 extract, nasturtium officinale extract, citrus aurantium dulcis; orange fruit extract, dehydration Seawater, seaweed extract, hydrolyzed elastin, hydrolyzed wheat flour, hydrolyzed silk, German chamomile (chamomilla recutita; matr Icaria) extract of ear, radish (daucus carota sativa; carrot) root extract, artemisia capillaries flower extract, glycyrrhiza extract, hibiscus tea extract, spur Wood (pyracantha fortuneana) fruit extract, kiwi fruit extract, cinchona extract, cucumber (cucumis sativus; cucumber) fruit extract, bird vocal (guanosine), sassafras (gardenia) Florida) extract, sasa veitchii extract, sophora angustifolia root extract, walnut shell extract, grapefruit (citrus grandis; grapefruit) fruit extract, clematis vitalba leaf extract , Chlorella vulgaris extract, morus alba leaf extract, gentiana lutea extract, black tea extract, yeast extract, arctium lappa root extract Fermented rice bran extract, rice germ oil, polymer grass (Symphyturn officinal^ leaf extract, bilberry leaf extract, asarum (a Siasarum) root extract, bupleurum extract, UInbilical cord extract, saponaria officinalis extract, bamboo extract, crataegus cuneata fruit extract, pepper (zanth〇) Xylum) fruit extract, mushroom (corthellus shiitake; mushroom) extract, rehmannia-24- 200920414 yellow (rehmania) root extract, lithospermum erythrorhizone root extract, perilla herb extract, linden Flower extract, spiraea ulmaria flower extract, peony root extract, acorus calamus root extract, birch extract, equietum arvense extract, hedera helix ; ivy) extract, crataegus oxyacantha extract, sambucus nigra flower extract, achillea millefolium extract, mentha piperita; peppermint leaf extract, sage ( Salvia officinalis; sage) leaf extract, mallow (malva sylvestri s; mallow) extract, Japanese chuan (cni Ddium officinale) root extract, switziajaponica extract, wild soy (glycine soja; large _&) seed extract, jujube fruit extract, thymus vulgaris; thyme extract, green tea extract , clove (eugenia caryophyllus; clove) flower extract, Imperata cylindrical extract, citrus unshiu peel extract, Japanese angelica root extract, calendula officinalis flower extract, Walnut kernel extract, bitter orange peel extract, houttuynia cordata extract, solanum lycopersicum extract, fermented soybean extract, ginseng (panax ginseng) root extract, garlic ( Allium sativum) extract, wild rose extract, hibiscus extract, maiden (ophiopogonis -25- 200920414 tuber) extract, Dutch order (carum petroselinum; parsley) extract, honey, witch hazel (hamamelis virginiana; Witch hazel) extract, pari et aria officinal is extract, prunella (iso donis) Japonicus) extract, bisabolol, eriobotrya japonica extract, coltsfoot extract, butterbur bud extract, poria cocos extract, false leaf tree ( Ruscus aculeatus) root extract, vitis vinifera fruit extract, propolis, luffa cylindrical fruit extract, safflower flower extract, peppermint extract, tilia platyphyllos flower extract Root extract of paeonia suffruticosa, humulus lupulus (hops) extract, European pine (pinus sylvestris) carpet extract, aesculus hippocastanum; horse chestnut extract, watery banana (lysichiton camtschatcense) Extract, sapindus mukurossi peel extract, melissa officinalis (aromatic mint) leaf extract, peach tree (prunus persica) leaf extract, centaurea cyanus flower extract, eucalyptus leaves Extract, saxifraga sarmentosa extract, grapefruit extract, hazelnut (c〇ix seed) extract, mugwort extract, lavenderula angustifolia; lavender extract, apple (pyrusmalus) fruit extract, lacing (lactuca scariola sativa; lettuce) extract, lemon (citrus medica Limonum; lemon) extract, extract of Chinese milk vetch (astragalus -26- 200920414 sinicus), flower extract of rosa centifolia, rosemary (rosamarinus officinalis; rosemary), extract of Roman chamomile (anthemis nobilis) Extract, Royal Jelly Extract, Pansy Extract, Lilium candidum bulb extract, crocus (crocus sativus) flower extract, raw vine root extract, capsicum extract, placenta extract, glutinous rice (coix Lachryma-jobi ; Job's tears) fruit extract, citrus junos extract, grape (vitis vinifera; grape) fruit extract, western water bud extract, epiphyllum oxpetalum flower extract, white feather fan Flower extract, cockscomb extract, etc.; activator (eg royal jelly, sensitizer, cholesterol derivative) Blood circulation promoter (eg vanillyl citrate, benzyl nicotinic acid, β-butoxyethyl nicotinic acid, tangsin, zingerone, cantharis tincture, Fish stone fat (ichthammol), tannic acid, α-borneol, fertility sylvestreate, hexaerythritol inositol, cyclandelate, cinnarizine, trazoline, Acetylcholine, verapamil, cepharanthine, orizanol, etc.; anti-serum leaking agents (eg sulfur, dimethyl sulphate, etc.), anti-inflammatory agents (eg Tranexamic acid, thiotaurine, hypotaurine, ε-aminocaproic acid, glycyrrhizic acid, β-glycyrrhizic acid, chlorinated lysozyme, guaiazulene, oxyhydrogen Hydrocortisone, etc.; -27- 200920414 active ingredients (eg diisopropylamine dichloroacetate, 4-aminomethylcyclohexanecarboxylic acid, etc.); and, further, vitamin B6, nicotinic acid, Nicotinic acid derivatives, calcium pantothenate, D-panthenol, ethyl ethenyl pantothenate, isopropyl cresol, female , ethinyl estradiol, capronium chloride, diphenhydramine hydrochloride, takanal, rod brain, vanillyl decyl ester, vanillyl decyl ester, Pirocton-Olamin , glycerol pentadecanoate, 1-menthol, mononitroguaiacol, resin phenol, benzethonium chloride' mexiletine, auxin, estrogen, cantharidin Anthraquinone, cyclosporin, hydrocortisone, polyoxyethylene sorbitan monostearate, and peppermint oil. Further, if the pharmaceutical ingredient can be administered to the living body through skin penetration, for example, an analgesic, a sputum, an antihypertensive agent, an antibiotic, an antihistamine, and an antibacterial substance may be added. One or a combination of two or more of these active ingredients may be used singly depending on the intended use of the gel sheet. The active ingredient contained in the hydrogel may further comprise the following ingredients in accordance with the present invention. Since these active ingredients and medicinal properties differ depending on the effective amount of the substance itself, the ingredient content and the medicinal properties are generally not specified, but it is generally preferably from 0.001 to 10% by mass based on the total amount of the hydrogel, and more preferably 0.0 5 to 5 mass%. Further, in the same manner, in the case of the humectant, the content thereof is generally preferably from 0.1 to 10% by mass, and more preferably from 0.5 to 5% by mass based on the total amount of the hydrogel. -28- 200920414 [Structure of Gel Sheet] As described above, in the gel sheet of the present invention, the hydrogel may form a single layer structure, or may form a multilayer structure with other layer bodies. In addition, a multilayer hydrogel layer can be provided. The ingredients described above may be included in the hydrogel layer or, if possible, in other layers. Further, when the multilayer hydrogel layer is formed, the components may be contained in the same hydrogel layer, or may be contained in the plurality of layers, respectively. Therefore, when the gel sheet of the present invention is formed into a multilayer hydrogel layer, the content of the above components is the amount contained in all of the hydrogel layers constituting the gel sheet. <Approximate sheet-like substrate> • For the purpose of strengthening the hydrogel layer and improving the workability of the gel sheet, the approximate sheet-like substrate may be provided to the hydrogel layer or adjacent to the hydrogel layer. From the viewpoint of shape stability and workability of the gel sheet of the present invention, it is preferred to provide the approximate sheet structure. Examples of other layers other than the hydrogel layer may be a support layer and a protective sheet. From the viewpoint of shape stability and workability of the gel sheet of the present invention, it is preferred to provide a support layer, and it is preferable to provide a protective sheet from the viewpoint of protecting the surface of the hydrogel layer before using the gel sheet. As the support layer, it is preferred to use a known sheet-like material such as a non-woven fabric, a woven fabric and a plastic film, a crosslinked gel (gelatin/penta-clear crosslinked gel, polyacrylic acid/polyvalent metal ion crosslinked gel). Etc.), natural gel (agarose gel, K-carrageenan gel, etc.), and water-insoluble film formed from hydrophilic polymer -29-200920414 (chitin film, cellophane, kappa-carrageen Glue cast film, etc.) and so on. Among them, from the viewpoint of the stability of the shape and the handleability of the gel sheet, in the gel sheet of the present invention, a transparent film having a thickness of 100 μm or less is preferably used. In particular, a water-insoluble film formed of a hydrophilic polymer is preferable, for example, a chitin film, cellophane, a kappa-carrageenan cast film formed of a hydrophilic polymer, or the like. Further, as the protective sheet, a polyethylene film, a polypropylene film, a PET film or the like is preferably used. In particular, a polyethylene film having a thickness of 500 μm or less is preferably used. * When the living gel sheet is composed only of the hydrogel layer, in general, the thickness of the gel sheet is preferably from 0.4 to 3 mm, more preferably from 0.5 to 2 mm, from the viewpoint of shape retention and workability. . Further, in the case where the thickness of the support layer and the protective sheet is as described above, in the case of a multilayered gel sheet composed of a hydrogel layer and a support layer and/or a protective sheet, the thickness of the support layer is more preferably 5 to 80 μm, and the thickness of the protective sheet is more preferably 50 to 500 μm. In the case of this multilayer structure, the thickness of the hydrogel can be adjusted to be equal to the thickness of the aforementioned hydrogel, or can be appropriately adjusted so that the entire thickness of the gel sheet is in the range of 0.4 to 3 mm. [High Colloidal Synthetic Gel Sheet] From the hydrogel comprising the above ingredients, when the gel sheet of the present invention comprises a -30-200920414 倂Ο/W type emulsion (which includes an average diameter of 1 to 19 nm) Emulsified particles) and a hydrogel formed of a polyether compound (polyether) as an ether-based temperature-sensitive polymer, which is particularly excellent when formed from at least one selected from the group consisting of collagen gels or decomposition products thereof Colloidal dehydrated gel tablets. In order to rapidly supply the moisture or active ingredient contained in the gel sheet to the target area, in addition to the water retention of the gel sheet, the colloidal dehydration property of the moisture or the like remaining in the gel sheet to a predetermined region adjacent to the adhesive body is supplied. It is also important. However, the known technique (for example, the technique described in JP-A No. 200 5 - 225 837, and the technique described in JP-A No. 2003 - 1 8 3147) maintains the moisturizing property of the skin surface, A colloidal dehydration that exhibits rapid and effective penetration of the active ingredients contained in the hydrogel into the skin. As described above, by forming a gel sheet comprising a Ο/W type emulsion containing a emulsified particle having an average diameter of 1 to 150 nm, a polyether compound, and collagen and/or a decomposition product thereof a hydrogel, when the gel sheet contacts a water-absorbing object (adhesive body) such as a skin, the Ο/W type emulsion containing the fat-soluble active ingredient is effectively released, and the supply of water to the stratum corneum is simultaneously increased, and The penetration of the active ingredient into the adherent can be obtained. In addition, the high colloidal dehydrated gel sheet, in addition to the high colloidal dehydration, is flexible and easily deformed by pressure, and because the surface is wet, it can also be adhered to the adherend. In the present invention, the colloidal dehydration means that the liquid component (the water of the colloidal dehydration) contained in the hydrogel is exuded by the contact of the gel sheet with the adherent, and the water of the colloid is dehydrated. To a living organism or an absorbable organism adjacent to the adherent. In addition to the moisture and water phase components in the emulsion of the hydrogel, the colloidal dehydrated water of the gel sheet of the present invention contains a fat-soluble component or fine solid particles which are dissolved not only in the aqueous phase but also in the emulsion particles. Or exist in dispersion in liquid ingredients. As a result, the various active ingredients in the gel sheet can be efficiently supplied to the adjacent adherend via contact of the gel sheet with the adherend. Further, in this specification, the gel sheet can be referred to as a "high colloidal dehydrated gel sheet", particularly when the gel sheet is indicated in the context of colloidal dehydration. In the present invention, the high-gel dehydrated gel sheet may exhibit a colloidal dehydration ratio of preferably 40% by mass or more and 90% by mass or less, more preferably 45% by mass or more and 85% by mass or less, and particularly preferably 50% by mass. % or more and 80% by mass or less. The colloidal dehydration rate in the present invention is obtained in the following manner: cutting the gel sheet into 3 cm><3 cm in size to form sample gel pieces, which were placed in a No. 2 filter paper of 9 cm diameter manufactured by Advantec MSF. Inc. (two kinds of qualitative filter papers according to JIS P3 80 1 (version 995)) : 125g / m2 and thickness of 0.2 6 mm; drainage time: 80 seconds; water absorption: 80 cm), so that two pieces of filter paper are clamped to the upper and lower ends of the sample gel sheet, and when kept at ambient temperature The quality of the filter paper was measured at 25 ° C and relative humidity of 50 ± 10% for 10 minutes. The colloidal dehydration rate was calculated by using the amount obtained by using the following formula (1). Colloidal dehydration rate (% by mass) = (mass of liquid absorbed by filter paper / gel - 32 - 200920414 starting mass) Χ 100 (1) In the above formula (1), "gel initiation mass" The quality of the film test piece minus the quality of the support material. The method for measuring the rate of dehydration of the colloid can be referred to, for example, the method described in the June 20, 2007 issue of "Fragrance Journal", pages 5-10-1. In the case where the gel sheet of the present invention constitutes, for example, a gel sheet for a living body, 'the liquid absorption amount based on the filter paper as the water-absorbent adhesive body, the colloidal dehydration rate of the gel sheet can be evaluated as a component (for example, water and water). Whether the functional component retained by the gel) can be effectively infiltrated into the skin by the contact of the gel sheet with the adherent (e.g., the epidermis). When the colloidal dehydration rate is less than 40% by mass, water or the like may become insufficient to penetrate into the skin, and when the colloidal dehydration rate exceeds 90% by mass, the stability of the gel sheet during storage may be lowered. Further, the concentration of the 0/W type emulsion particles in the colloidal dehydrating liquid is preferably 0.001 to 2 times, more preferably 0.01 to 1.5 times, and most preferably 0.1 to 1 times of the 0/W type in the hydrogel. The concentration of the emulsion particles. At this point, the concentration of the emulsion particles in the colloidal dehydrating liquid can be roughly estimated from the concentration measured by the colorimeter using the filter paper used in the measurement of the colloidal dehydration rate. Further, after the emulsion or the fat-soluble component contained in the emulsion is extracted from the filter paper for measuring the dehydration rate of the colloid, the concentration of the emulsion particles in the colloidal dehydration liquid can be roughly estimated by a spectrophotometer, HP LC or the like. The above-mentioned various ingredients, including various fat-soluble active ingredients and other -33-200920414 additives, and their contents 'method for making o/w type emulsions are suitable for the 〇/w type emulsion contained in the high colloidal dehydrated gel sheet without modification. . Further, similarly, unless the main use of each component is impaired, the other components contained in the oil phase and the aqueous phase of the emulsion may be contained in the 〇/w type emulsion. The high colloidal dehydrated gel sheet may contain a high concentration of a fine particle emulsion containing a fat-soluble active ingredient in the colloidal dehydrating liquid, so that the active ingredient can be efficiently supplied to the adherend. As a polyether compound, it may be contained in a high colloidal dehydrated gel sheet such as polyethylene oxide, polypropylene oxide, polyethylene oxide/polyoxypropylene block copolymer, polyethylene oxide/polyoxypropylene/polyethylene oxide. A block copolymer or the like may be preferably exemplified, and a block polymer containing polyethylene oxide and polypropylene oxide is particularly suitable, and more preferably, a polyethylene oxide/polyoxypropylene block copolymer (hereinafter referred to as " PEO-PPO block polymer "), or polyethylene oxide/polyoxypropylene/polyoxyethylene block copolymer (hereinafter referred to as "PEO-PPO-PEO block polymer") is particularly suitable. These polyethers are known, for example, as poloxamers, and are readily available on commercial products as 'commercial name' PLURONICn and 1LUTROL (both manufactured by BASF AG), NEWPOL (Sanyo Chemical Industries, Ltd) . Manufactured, and EPAN (is manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.), PRONON (manufactured by Nippon Oil & Fats Co., Ltd.), and the like. In this case, the weight average molecular weight (M w ) of the polyether is preferably from 1,000 to 1,000,000, and more preferably from 5,000 to 500,000. -34- 200920414 In the high colloidal dehydrated gel sheet, the content of the polyether contained in the hydrogel is preferably 〇· 〇 5 to 20% by mass, more preferably 〇. 1 to 10% by mass, and Preferably, it is 0.2 to 5% by mass. In the above range, when the content of the polyether is 0.05% by mass or more, the colloidal dehydration can be completely improved, and the efficiency of penetration of the active ingredient added by the hydrogel into the skin can be sufficiently achieved, and when the content is 20% by mass or less, It can effectively avoid a significant drop in storage capacity. Collagen which may be contained in the high colloidal dehydrated gel sheet is not particularly limited and may include various collagen extracts. The crude raw material containing collagen can be extracted by a known technique such as acid dissolution, alkali dissolution neutral salt dissolution, and enzyme dissolution. As long as the raw material contains collagen, any collagen-containing raw material can be used, and the skin, scales, bones, cartilage, tendons, organs, etc. of vertebrates (such as cattle, pigs, sardines, sharks, etc.) can be exemplified, and high-content collagen is used. From the viewpoint of protein, bone, cartilage, skin or fish scales, sputum, placenta, and the like can be suitably used. Particularly, the collagen suitable for use in the present invention is preferably water-soluble collagen. The collagen decomposition product which can be contained in the high colloidal dehydrated gel sheet can be obtained by decomposing collagen with a protein hydrolase such as collagenase, trypsin, and curd protein, or by acid or base hydrolysis, or via heat. transsexual. As a collagen decomposition product, such as acid-treated gelatin, alkali-treated gelatin, enzymatic decomposition gelatin, collagen tripeptide, collagen dipeptide and amino acid (glycine, proline, hydroxyproline, acetamidine) Hydroxyproline, etc.) -35- 200920414 is shown as an example. The content of the collagen or collagen decomposition product of the hydrogel in the high colloidal dehydrated gel sheet is preferably from 0.05 to 20% by mass, more preferably from 0.1 to 10% by mass, and particularly preferably from 0.2 to 5% by mass. When the content is 0.05% by mass or more, the moisturizing effect can be attained by attaching the gel sheet to the epidermis, and when the content is 20% by mass or less, the workability becomes better. From the viewpoint of improving the colloidal dehydration property, the hydrogel contained in the high colloidal dehydrated gel sheet is preferably a hydrogel formed using an anionic polymer and a water-soluble divalent metal salt, and is relative to 100 parts by mass. The content ratio of the anionic polymer compound to the water-soluble divalent metal salt is particularly preferably 5 parts by mass or more. <Water-soluble divalent metal salt> The hydrogel of the gel sheet of the present invention preferably contains a water-soluble divalent metal salt. Herein, the water solubility in the present invention means that 2YC can dissolve at least 0.1% by mass of the solubility in pure water. As the divalent metal for forming the water-soluble divalent metal salt, magnesium, calcium, strontium and barium or transition metals Cu2+, Fe2+, Zn2+ and Mn2+ of Group II of the periodic table are exemplified, and magnesium and calcium. The water-soluble salt may be any inorganic salt or organic acid salt, and is not particularly limited. For example, the inorganic salt is, for example, a hydrochloride, a nitrate, a sulfate, a phosphate, a carbonate, or the like, and the organic acid salt is, for example, a lemon. Acid salts, lactate, malate, succinate, ascorbate, gluconate, and organic-36-200920414 and inorganic complex salts such as ascorbyl phosphate are exemplified. Among them, magnesium chloride, calcium chloride, magnesium lactate, magnesium malate, magnesium citrate, calcium citrate, magnesium ascorbate, calcium ascorbate, magnesium ascorbyl phosphate, magnesium gluconate and calcium gluconate are more suitable, especially magnesium chloride and ascorbic acid. Magnesium phosphate is preferred. The amount of the water-soluble divalent metal salt in the high-gel dehydrated gel sheet must be 50 parts by mass or more based on 1 part by mass of the anionic polymer compound (described later) (in the present specification, "parts by mass" may be used. It is referred to as "parts" and, from the viewpoint of effect, preferably from 50 parts to 1,000 parts, more preferably from 70 parts to 500 parts, and particularly preferably from 80 parts to 30,000 parts. The content of the water-soluble divalent metal salt in the mixed liquid of the hydrogel is preferably from 0.1 to 5% by mass, more preferably from 0.2 to 4% by mass, and particularly preferably from 0.5 to 2% by mass. When the ratio of the salt is within this range, the gelatin dehydration of the hydrogel can be improved, and a gel sheet having excellent handleability can be obtained. In the hydrogel formed of an anionic polymer and a water-soluble divalent metal salt, water solubility The divalent metal salt is used to form a gel and does not have to be in a "salt" state. However, in the formed hydrogel, the amount of metal constituting the metal salt can be measured and obtained by conversion. To obtain a water-soluble divalent metal salt or a compound derived from a metal salt .G this content, '' a hydrogel of a water soluble divalent metal salt content "means Zhi designed so change the method of Koda. According to this method, even after the formation of the hydrogel, it is possible to detect whether or not the content of the soluble divalent metal salt of water - 37 - 200920414 is within the above range. <Anionic Polymer Compound> The anionic polymer compound which can be used for the high colloidal dehydrated gel sheet is not particularly limited, and a synthetic polymer and a natural polymer can be used as long as the polymer compound contains an anionic group in the molecule, It is selected, for example, from a carboxyl group, a mineral group, or a % of a neighboring group. One type of anionic polymer compound may be used alone, or a mixture of two or more kinds may be used in the hydrogel. Anionic synthetic polymer compounds include acrylic (co)polymers, methacrylic (co)polymers, maleic acid (co)polymers, itaconic acid (co)polymers, P-vinylbenzoic acid (co)polymerization , 2_ acrylamide-2-methyl-1-propane sulfonic acid (co)polymer and styrene sulfonic acid (co)polymer. In addition, anionic natural polymer compounds include pectic acid, alginic acid, agar, carrageenan, fucoidan, hyaluronic acid, chondroitin sulfate, heparin, gellan gum, natural gellan gum, xanthan gum, carboxyl Methylcellulose, carboxymethyl starch, carboxymethyldextran, polyglutamic acid, and DN A, RN A, and the like. Among them, preferred are acrylic (co)polymer, alginic acid, agar, carrageenan, gellan gum, natural gellan gum, xanthan gum, carboxymethylcellulose, carboxymethyl starch, carboxymethyl glucoside Sugar, polyglutamic acid, and DN A, RNA. In particular, with respect to the anionic polymer compound, from the viewpoint of compatibility of water retention with the strength of the gel-38-200920414, acrylic acid (co)polymer, alginic acid, agar, carrageenan, and hyaluronan are preferred. , gellan gum, natural gellan gum, xanthan gum, carboxymethyl cellulose, in particular, agar, carrageenan, gellan gum, natural gellan gum, xanthan gum is better. The molecular weight of the anionic polymer compound is preferably from 10, 〇〇〇 to 5,000,000, more preferably from 20,000 to 2,000,000, from the viewpoint of gel strength. In the high colloidal dehydrated gel sheet, the content of the anionic polymer compound in the hydrogel is preferably from 0. 01 to 10% by mass, more preferably from 0.1 to 8% by mass, and particularly preferably 〇_ 2 Up to 4% by mass. When the content is within these ranges, a hydrogel having sufficient colloidal dehydration can be obtained while achieving high gel strength and excellent handleability. By using a combination of an anionic polymer and a divalent metal water-soluble salt together to form a three-dimensional network structure having a weakly crosslinked structure formed in a hydrogel system, it is considered that sufficient liquid retention and excellent colloidal dehydration are improved. . Although the anionic polymer compound and the water-soluble divalent metal salt contained in the hydrogel can be appropriately combined according to the intended use, from the viewpoint of compatibility of gel strength with colloidal dehydration, 'water-soluble divalent metal salt/anion The combination of polymer compounds can be as shown in the following preferred examples, but the combination is not limited by these examples: magnesium ascorbyl phosphate / carrageenan; -39- 200920414 magnesium ascorbyl phosphate / gellan gum; magnesium ascorbyl phosphate / agar; Magnesium ascorbyl phosphate/xanthan gum; magnesium ascorbyl phosphate/acrylic acid (co)polymer; magnesium ascorbyl phosphate/carboxymethylcellulose magnesium chloride/carrageenan, magnesium chloride/gellan gum; magnesium chloride/acrylic acid (co)polymer; lactic acid Magnesium / carrageenan; magnesium lactate / agar; calcium lactate / gellan gum; calcium ascorbate / carrageenan; and calcium gluconate / gellan gum. <Multivalent metal salt having a trivalent or higher content> From the viewpoint of preventing the reduction of colloidal dehydration in the formation of a hydrogel mixed solution, 'there is a trivalent or more in the hydrogel of the high colloidal dehydrated gel sheet The content of the valence metal salt is preferably 0.1% by mass or less. As a polyvalent metal salt having a trivalent or higher value, a salt containing a polyvalent metal cation such as Al3+, Fe3+, Ti3+'Ti4+, In3+, Zr4+, Ta5+ or the like is exemplified as 'more specifically, potassium alum, ammonium alum, Iron alum, aluminum sulfate, polyaluminum chloride, synthetic aluminum citrate, aluminum hydroxide, aluminum stearate, aluminum acetate, iron sulfate, iron hydroxide, titanium lactate 'acetate acetate, and the like are exemplified. -40- 200920414 In the hydrogel of the high colloidal dehydrated gel sheet, the content of the polyvalent metal salt having a trivalent or higher content in the hydrogel mixed solution is preferably ο·1 mass% or less, more preferably 0 · 0 5 mass % or less 'excellently 0 · 01% by mass or less, and optimally except for unavoidable impurities 'hydrogel does not contain such polyvalent metal salts. When the content of the trivalent metal salt exceeds 0.1 mass%, the colloid dehydration may deteriorate. <Polysaccharide> In order to improve handling properties, in the high colloidal dehydrated gel sheet, the anionic polysaccharides described in the above examples of the anionic polymer compound are preferably added with a polysaccharide to a hydrogel. For this purpose, as a polysaccharide which can be contained in a high colloidal dehydrated gel sheet, such as a neutral polysaccharide (for example, cellulose, starch sugar, amylopectin, dextran, polytriglucose, inulin starch, polyhalf Lactose, polymannose, gum, polyarabinose, polyglucomannan, polygalactomannose, agarose, methylcellulose, hydroxypropylcellulose, cartein, xyloglucan, etc.) And cationic polysaccharides (chitin, chitin, cationized cellulose, cationized starch, cationized dextran, etc.) are exemplified. Among them, polysaccharides having a highly thick gelation effect are more preferable, and particularly preferred are polyglucomannan, polygalactomannose, agarose, methylcellulose, hydroxypropylcellulose. In order to further increase the gelation property, a plurality of such polysaccharides may be used in combination. The content of the polysaccharide in the hydrogel of the high colloidal dehydrated gel sheet is preferably from -41 to 200920414 0.01 to 5% by mass, more preferably from 0.1 to 4% by mass, and particularly preferably from 0.2 to 2% by mass. When the content of the polysaccharide is within the above range, the gel strength is improved, and the handleability is excellent, and colloid dehydration and skin penetration can be prevented from being lowered. <Hydrophilic polymer> In the high colloidal dehydrated gel sheet, in order to increase the moisturizing property, in addition to the gel solubility being weakened when the gel sheet is attached to the skin, a known hydrophilic polymer may be added to the water. gel. Further, the hydrophilic polymer can also be used to improve the shape stability of the high colloidal dehydrated gel sheet. As the hydrophilic polymer which may be contained in the high colloidal dehydrated gel sheet, the above anionic polymer compound and the polymer compound other than the polysaccharide may be a synthetic or natural polymer compound as long as the polymer compound has a hydrophilic functional group (for example) Hydroxy, amine, mercapto, amine, ammonium, and ethoxy, etc.). These polymer compounds may be used singly or as a mixture of two or more thereof. As a synthetic polymer compound having such a hydrophilic group, for example, a vinyl alcohol (co)polymer, a 2-hydroxyethyl acrylate (co)polymer, an acrylamide (co)polymer, and an acryloyl morpholine (total ) polymer, N-vinylpyrrolidone (co)polymer, vinylamine (co)polymer, N,N-dimethyldiallylammonium chloride (co)polymer, chlorination 2 - A methacryloxymethylammonium (co)polymer, a polyethylene glycol methacrylate (co)polymer, a polyethylenimine or the like is exemplified. -42- 200920414 From the viewpoint of moisture retention, the amount of the above hydrophilic polymer is preferably from 1, 〇〇〇 to 5 〇〇〇〇〇, more preferably 5,000. Further, from the viewpoint of moisture retention and handling properties, pro-gel The content in the middle is preferably from 5% to 5% by mass, more by weight. A variety of active ingredient 2-body dehydrated gel tablets can also be mixed as desired. As such an active ingredient and a pharmaceutical, a thickener, a fragrance, a pigment, a stabilizer, an antioxidant, a tackifier, a sputum adjuster, a chelating agent, a surface for the purpose of adding a face treatment and a skin treatment And antibacterial agents and the like are exemplified. Regarding these items, it is not mentioned in the text. <Approximate sheet material> In the high colloidal dehydrated gel sheet, in order to enhance the operability of the water film, an approximate sheet layer or a layer adjacent to the hydrogel layer can be provided. From the viewpoint of improving the qualitative and operability of high colloidal dehydration, it is preferred to provide an approximation in a high colloidal dehydrated gel sheet. When approximating the sheet-like support layer, a known sheet-like matrix cloth, textile fabric and plastic can be used. film. Form the material of non-woven fabric or textile fabric and use the fabric generally used, and the natural fabric, the weight average molecular weight to 100,000 °, the water-based polymer in water is good. 1 to 3 additives to high glue, in order to beautify and [For example, the moisturizing agent, the ultraviolet absorbing activator, and the bactericide may be modified to apply the front gel layer and to enhance the shape of the condensed matrix in the shape of the hydrogel gel sheet. The substrate is used as a material, for example, non-woven is not particularly limited, and may be, for example, cellulose, silk-43-200920414 protein, etc., such as recycled fabrics, such as rayon, synthetic fabrics such as nylon, polyester, polyethylene, polypropylene, acrylic. 'Polylactic acid' polyurethane or the like is exemplified' and cellulose, nylon and polyester are applicable. The textile fabric or non-woven fabric suitable for the high colloidal dehydrated gel sheet has a basis weight of preferably from 3 g/m2 to 100 g/m2, more preferably from 5 g/m2 to 70 g/m2' and particularly preferably from 5 g/m2 to 5〇g/rn2. Within the range of the basis weight, the sheet-like substrate has a preferable handle strength, and at the same time, the flexibility of the gel sheet does not deteriorate' and the adhesion of the gel sheet does not decrease at the time of attachment. When a plastic film is used, the plastic film may be a liquid impermeable single layer or a multilayer plastic sheet' or may be a porous sheet or a web sheet. From the viewpoint of operability, the thickness of the sheet-like substrate is preferably about 0.01 mm to 1 mm. Further, when used for a cosmetic material or the like, a sheet having high transparency as described in the present specification is preferable. When the sheet is approximately used for the hydrogel layer, it is preferably a liquid permeable sheet such as a woven fabric, a non-woven fabric, a porous sheet, a mesh sheet or the like. However, when a support layer on the surface of one of the hydrogel layers is used, a liquid impervious sheet or a thick woven fabric, a non-woven fabric or the like can be used. Further, when an approximate sheet-like substrate is used as the reinforcing layer of the hydrogel layer, 'for example, a matrix of a polymer gel sheet having a high breaking strength, and a hydrophilic polymer film such as a crosslinked gel (gelatin/ Glutaraldehyde crosslinked gel, polyacrylic acid/polyvalent metal ion crosslinked gel, etc., and natural gel (agarose gel, kappa-carrageenan gel, etc.), and formed by a hydrophilic polymer -44- 200920414 Non-water soluble film (chitin film, cellophane, K-carrageenan cast film, etc.). Among them, a high-colloid dehydrated gel sheet having a structure in which the main 3C is formed by water-condensing and woven or non-woven fabric is particularly satisfactory. Herein, the structure to be formed means a structure in which a substrate sheet such as a woven fabric or a non-woven fabric is laminated on at least one surface of the hydrogel layer, and the base stomach sheet and the hydrogel layer are bonded to each other. It is not capable of phase separation during operation, or a structure in which the matrix sheet is completely and indivisibly contained in the hydrous age layer, and the hydrogel layer is placed on both surfaces of the matrix sheet. In order to maintain the effect of the active ingredient or water retention up to the use of the gel sheet, it is preferred that the high colloidal dehydrated gel sheet is applied to the surface of the living gel sheet to provide a protective sheet. As the protective sheet, a polyethylene film, a polypropylene film, a PET film or the like is preferably used. In particular, a polyethylene film having a thickness of 500 μm or less is preferably used, and more preferably 20 μm to 400 μm. From the viewpoint of shape retention and workability, in general, the thickness of the hydrogel layer in the high colloidal dehydrated gel sheet is preferably 0.4 mm to 2 mm regardless of the presence or absence of the support, and particularly preferably 〇5 mm to l_5 mm. . [Method for Producing Gel Sheet] The gel sheet of the present invention can be produced according to a method generally used. For example, when the gel sheet is formed only of a hydrogel, the gel sheet can be produced according to a usual method for producing a hydrogel, and more specifically, a mixed liquid is prepared by heating and mixing the ingredients at -45 to 200920414 (for forming a hydrogel) After the mixed liquid of the glue, the gel sheet is formed in the form of a coating machine such as a doctor blade. Then, the gel sheet was cooled to complete coagulation, thereby obtaining a gel sheet. In the case of a gel sheet having a support layer, the gel sheet can be easily obtained by, for example, coating a mixed aqueous solution of the components of the aforementioned hydrogel on a similar sheet-like support substrate. Further, a polyol, a 0/W type emulsion, and a polysaccharide may be added separately or together in the procedure for producing the hydrogel, or may be added separately or together after the hydrogel is produced. Furthermore, when the protective sheet is formed, in the case where the gel sheet is formed only of the hydrogel layer, one or both surfaces of the gel sheet can protect the sheet covering, and form a sheet-like matrix and a hydrogel layer. In the case of a layered structure, the protective layer is laminated on the surface of the gel layer which does not form an approximately sheet-like substrate. [Physical Properties of Gel Sheet] It is preferred that the gel sheet of the present invention is highly transparent from the viewpoint of reducing the uncomfortable appearance when it is attached to the skin. Further, when the gel sheet requires high transparency, it is desirable to select an approximate sheet-like substrate or the like which can be used together with the hydrogel layer and has high light transmittance such as a nylon mesh or a transparent resin film. The transparency in the present invention can be evaluated based on the transmittance 値 measured by a spectrophotometer having a wavelength of 600 nm. The aforementioned transparency is desirably a transmittance of distilled water of preferably 60% or more, and more preferably 98% or more, measured by the evaluation method of -46-200920414. When the transmittance is 60% or more, it makes it easy to detect the condition in which the skin is attached. However, the gel sheet does not necessarily need to be transparent when it is applied to the use portion which does not require consideration of the appearance. The water content of the hydrogel in the gel sheet of the present invention is desirably 70 mass% or more, and 95 mass% or less. When the water content is in this range, the release effect of the sexual component by the hydrogel is not only enhanced, but also the irritation to the epidermis when the coagulation patch is attached. The water content of the hydrogel is preferably 70% by mass or more and 95% by mass or less, more preferably 75% by mass or more and 95% by mass. /. Or less, and preferably 80% by mass or more and 90% by mass or less. When the water content is less than 7% by mass, the skin permeability of the component can be lowered, and when the water content exceeds the mass%, the workability may be deteriorated by reducing the strength of the hydrogel. In particular, in the case of the above-mentioned colloidal dehydrated gel sheet, since the colloidal water is excellent, the active ingredient can be effectively infiltrated into the predetermined target of the adherend by containing various active ingredients in a gel having a preferred water content range, for example. Living body, etc. Therefore, the gel sheet of the present invention can be suitably used as a sustained release carrier for a sexual ingredient or a cosmetic substance. More specifically, the lg hydrogel was taken out from the gel piece and dried under reduced pressure at 25 ° C until the mass change of the sample was no longer observed, and the above water was obtained according to the following formula (2): Bit: % Activated rubber: % Specially in 95 Dehydration level in the amount -47- 200920414 Water content (%) = [(starting mass - mass after drying) / starting mass] x 100 (2) Due to heat drying or subtraction The water content of the pressed dry 'hydrogel' can be measured by the reduction ratio of the hydrogel quality. Alternatively, the water content of the hydrogel can be measured by a Carl Fischer type, an infrared type or a resistive type water meter. Further, when the hydrogel mixture gels itself, the mixing ratio of water can be regarded as the water content of the gel. Although the form of the gel sheet of the present invention is not particularly limited, the pattern may be in the form of a roll wound into a tape, or it may be a separate separate sheet. In the case of separating the sheets, they may be of any type and are appropriately selected depending on the position of the body to be used, such as an ellipse, a circle, a heart, a semicircle, a semi-ellipse, a square, a rectangle, a trapezoid, Triangles, combinations thereof, and the like are exemplified. Further, the shape along the body application site or the shape which can be most appropriately attached to the body position to be used can be appropriately designed. For example, when a gel sheet is used as the adhesive sheet of the living body, according to a specific embodiment, a convex portion or a concave portion may be formed at a central portion or a peripheral portion of the gel sheet for positioning a gel sheet or the like. Or, the cut portion or the hollow portion may be formed according to the shape of the use portion, so that the adhesive sheet of the specific embodiment can increase the operability and increase the adhesion of the adhesive body to the contact area of the sheet in the desired area. The body part of the living body to which the gel sheet of the present invention is applied may include a face (lip, cheek 'eye, upper eye area, nose, forehead, full face), hand-48-200920414 arm, leg, chest, Belly, back, neck, etc. When the gel sheet of the present invention is used as a cohesive sheet for living body, the above type can be adjusted not only according to the position of the body but also the area, the thickness, the viscosity of the outer surface of the hydrogel layer, and the like. Further, the type and content of the active ingredient contained in the gel sheet can be appropriately adjusted. For example, when the application site of the living body with the adhesive sheet is a full face, it is preferable to adjust the sheet to form a shape in which the eye and the mouth corresponding to the portion have been removed and correspond to the shape in which the nose portion has been cut, and then Increase the adhesion of the adhesive layer or reduce the thickness of the gel sheet to suit the larger area to be adhered. Further, the adhesive sheet for the face can be divided into two parts, that is, the upper portion is applied to the forehead, the eyes, and the nose, and the lower portion is applied around the mouth and the chin. In order to avoid a decrease in water content or active ingredient over time, these gel sheets may be sealed in a packaging material made of a gas impermeable material prior to use. For example, in the case where the gel sheet is of a continuous tape type, the gel sheet may be stored in an airtight container, such as a bag having a pull tab formed of a gas impermeable sheet, or formed of a gas impermeable plastic. A container that opens or closes the lid. Further, in the case of sheets which are separated from each other, individual sheets can be sealed in openable individual bags formed of air-impermeable sheets. The water content and the active ingredient are maintained in an appropriate state during storage and dispensing until the gel piece is used. The gel sheet of the present invention composed of the above has excellent adhesive body permeability and excellent handleability of the active ingredient -49-200920414, etc., and the type or amount of the component contained in the hydrogel layer, hydrogel is selected. The thickness of the layer, and the dosage form of the gel sheet, which can be used as an adhesive for providing a drug for absorbing the skin for administration in a living body; similar to a sheet cosmetic material, for example, for cosmetic and facial treatments and skin treatment a packaging group; a carrier for an active ingredient such as a skin permeable component, an anti-inflammatory analgesic; an adhesive tape for living body as a wound protection or drug fixation, and a wound covering agent. Since the high-colloid dehydrated gel sheet is excellent in adhesion to the colloidal dehydration of the living body, the moisturizing property, and the active ingredient, and exhibits good handleability, the water or the active ingredient can be particularly efficiently supplied to the adherent during adhesion, and thus is high. The colloidal dehydrated gel sheet is suitable for all applications requiring continuous supply of water or active ingredients, and is excellent in biocompatibility and safety, so that it is used for supplying water or active ingredients to a living body by applying a gel sheet. The effect is remarkable, and a sustained release carrier and a cosmetic material as an active ingredient can be suitably used. [Approximate sheet cosmetic material] The approximate sheet cosmetic material of the present invention may comprise the gel sheet of the present invention. Namely, the gel sheet of the present invention can be maintained as an active ingredient, a moisturizing ingredient, a skin whitening component, astringent component or the like to form a cosmetic material. This approximate sheet cosmetic material is used by contacting the surface of the hydrogel layer with the skin. Since the living body adhered to the gel sheet in the living body, the active ingredient or the like penetrates into the skin of -50 to 200920414, and is excellent in handling property. The approximate sheet-like cosmetic material of the present invention is particularly suitable for use as an approximate sheet-like cosmetic material for attachment via a patch. The material moisturizes the skin on the face or provides medical properties to the skin. [Embodiment] The following text is further explained with reference to the following examples, but the present invention is not limited to the embodiments. Further, "parts" and "%," mean "parts by mass" and "% by mass", respectively, unless otherwise specified. [Example 1] The following ingredients were heated and stirred at 50 ° C for 1 hour to obtain a sol-state solution. 1. Acid-treated gelatin (from pig skin source) 3.0g 1,3-butanediol 5.0g PLURONIC F-127 (PEO-PPO-PEO block polymer: BASF A.G_ preparation) 〇.5g pure water 4 1.5 g In a polystyrene box (size 65 mm X 95 mm), the sol solution 1 was cast to form a thickness of 1 mm, and cooled at 4 ° C for 16 hours to obtain a hydrogel for implementation. Example 1. The hydrogel was referred to as the gel sheet of Example 1. Using a spectrophotometer, the gel sheet transmittance at a wavelength of 6 OOnrn was 85%. [Example 2] In addition to PLURONIC F-127, polymethylethylene In addition to the ether replacement, the hydrogel-51 - 200920414 gel of Example 2 was obtained via a hydrogel manufacturing method similar to that of Example 1, and the hydrogel of Example 2 was referred to as the gel piece of Example 2. Using a spectrophotometer The gel sheet transmittance at a wavelength of 600 nm was 72%. [Example 3] Except that PLURONICF-127 was replaced with methyl cellulose, similarly to implementation The hydrogel production method of 1 obtained the hydrogel of Example 3, and the hydrogel of Example 3 was referred to as the gel piece of Example 3. The transmittance of the gel sheet at a wavelength of 600 nm was 84% using a spectrophotometer. [Embodiment 4] <Preparation of carotenoid-containing emulsion> An aqueous phase composition was obtained by heating at 70 ° C for one hour to dissolve the following components. Sucrose oleate 1 3 g Decaglyceryl monooleate 2 5 g Glycerol 500 g Pure water 322 g An oil phase composition was obtained by heating at 70 ° C for one hour to dissolve the following components. Haematococcus Pluvialis extract (asperin content = 20% by mass) 40g Mixed fertility 酣 10 g Lecithin (from soybean) 90g Stirred by homogenizer (at 1 〇, 〇〇〇 rpm) The aqueous phase composition was added with -52-200920414 oil phase composition while maintaining at 70 ° C to obtain a carotenoid-containing emulsion. Using a Ultimizer HJP-25 005 (manufactured by Sugino Machine Ltd.), the resulting carotenoid-containing emulsion was subjected to high-pressure emulsification under a pressure of 200 MPa to thicken the system particle size analyzer FPAR-1 000 (0tsuka Electronics Co., The volume average particle diameter of the emulsion produced was measured at 25 ° C to obtain a volume average particle diameter of 90 nm. <Preparation of hydrogel> The following components were heated and kneaded at 80 ° C to obtain a sol-form product 2. κ-Carrageenan gum. 2g Polyglucomannan (derived from elephant root) 〇.2g Acid-treated gelatin (derived from pig skin) 〇.5g PLURONIC F-127 (PEO-PPO-PEO Block polymer: BASF AG 0.5 g 1,3-butanediol 5.0 g pure water 4 3 . 1 g After cooling the sol-form product 2 to 60 ° C, 0.5 g of a carotenoid-containing emulsion is added, and the mixture is uniformly stirred to obtain a Solution. The sol solution was cast in a polystyrene container (dimension 65 mm X 95 mm) to form a thickness of 1 mm, and cooled at 4 ° C for 16 hours to obtain a hydrogel for Example 4. This hydrogel was referred to as the gel piece of Example 4. Using a spectrophotometer, the transmittance of the gel sheet at a wavelength of 60 nm is 80%. [Comparative Example 1] -53- 200920414 The following components were stirred under heating at 50 ° C for one hour to obtain a sol-state solution 3. 3 · 〇g 5 .〇g 42.0g Acid-treated gelatin (derived from pig skin) 1,3-butanediol pure water f In a polystyrene-fired box (size 65mm χ 95mm), the sol solution 3 goes through Cast to a thickness of 1 mm at 4. C was cooled for 16 hours to obtain a hydrogel. This hydrogel was referred to as Comparative Example 1 gel sheet. [Comparative Example 2] The following components were heated and kneaded at 80 ° C to obtain a sol-form product 4. κ-Carrageenan 0.2g Polyglucomannan (from elephant root) 0.2g PLURONIC F-1 27 (PEO-PPO-PEO block polymer: manufactured by BASF AG) 〇.5g 1,3-butanediol 5.0 g Pure water 4 4.1 g In a box made of polystyrene (size 65 mm χ 95 mm), the sol solution 4 was cast to form a thickness of 1 mm at 4. C was cooled for 16 hours to obtain a hydrogel. This hydrogel was referred to as Comparative Example 2 gel sheet. [Comparative Example 3] Polyethylene glycol-polybutylene naphthalate was dissolved in THF so as to have a concentration of 10% by mass on a shallow plate of a size of 5 cm X 5 cm TEFLON (registered trademark) -54-200920414 The solution was cast and dried to form a film under normal temperature and pressure, and the film was immersed in 1 〇〇 ml of pure water to obtain a hydrogel. This hydrogel was referred to as Comparative Example 3 gel sheet. [Comparative Example 4] A hydrogel was obtained via a hydrogel production method similar to that of Example 1, except that PLURONIC F-127 was replaced with poly(N-isopropylacrylamide), which is called comparison Example 4 Gel sheet. - Evaluation of gel pieces - The gel pieces of Examples 1 to 4 and Comparative Examples 1 to 4 were applied to a scorer to adhere the gel pieces to the face of each scorer (each scorer will apply the gel pieces after washing the face) Adhere to the eye part for 15 minutes) and evaluate according to the following methods and standards. The results of the evaluation are shown in Table 1 below. The average of the results of the five scorers is used to display the results of the assessment. (1) The operability was evaluated according to the following method. When the gel sheet adhered to the face, the gel sheet was easy to adhere without sticking to the scorer's finger, and the gel piece was rated as A; In the case where the finger is on the head and spends more time adhering, the gel piece is rated as B; and when the gel piece is easily broken and difficult to adhere, the gel piece is rated as C. (2) Adhesive feeling in the above operation "(1) operability, in 'evaluation of adhesion feeling according to the following method'" when the gel sheet adheres to the face to reach the surface of the face, -55- 200920414 The sheet was rated as A; when the gel sheet was partially peeled off, the gel sheet was rated as B; and when the gel sheet was pleated and many portions of the gel sheet were peeled off, the gel sheet was rated as C. (3) Moisture retention The gel sheet was adhered for 15 minutes, and after peeling off the gel sheet, the water content of the stratum corneum was measured by a stratum corneum moisture meter (made by Asahibiomed) after 30 minutes. 'The moisture retention was evaluated according to the following method. When the five scorers evaluated that the average water content of the cockroach increased by 10% or more, the gel piece was rated A; when the water content increased by 2% to 10%, the gel piece was rated B. And when the water content increase is less than 2%, the gel piece is rated as C. (4) Skin barrier property In order to evaluate the improved function of rough and dry skin, the amount of transepidermal water loss (TEWL) is measured by the following method. That is, the gel piece is regularly attached for 15 minutes per day for three consecutive days, peeling off on the third day. The skin moisture loss (TEWL) was measured immediately after filming using a skin moisture loss analyzer (Asahibiomed). The skin barrier was measured by the following method, and the TEWL was decreased by 5% or more when compared with the test before the test. In the case, the gel piece was rated as A; when the decrease was 1 to 4%, the gel piece was rated as B; and when the TEWL was not changed, the gel piece was evaluated as C. -56- 200920414

表1 操作性 緊密貼合感 保濕性 皮膚阻隔性 實施例1 A A A B 實施例2 A A A B 實施例3 A A A B 實施例4 A A A A 比較實施例1 C A B B 比較實施例2 A B C C 比較實施例3 B B B C 比較實施例4 C A B C 如表1所示,清楚可見實施例1 -4中所有凝膠片在操 作性、緊密貼合感、保濕性及皮膚阻隔性上皆十分優異。 因此,清楚地,該具有優異效果之凝膠片作爲近似片狀化 妝品材料亦可十分優異。 實施例5 <〇/W型乳液之製備> 將下列成分在70°C加熱下溶解1小時,而獲得水相 組成物。 蔗糖油酸酯 15g 單油酸十甘油酯 23g 甘油 5〇〇g 純水 322g -57- 200920414 此外,將下列成分在70°C加熱下溶解1小時’而獲 得油相組成物。 雨生紅球藻萃取物(蝦紅素含量=20質量%) 4〇g 混合生育酚 1 〇 g 卵磷脂(來自大豆) 90g 經由以均質器(1 0,000 r pm)攪拌,同時保持於7〇°C’ 添加水相組成物於油相組成物中而獲得乳液。使用 Ultimizer HJP-2 5005 (Sugino Machine Ltd.製),在 200 MPa 壓力下將所產生之乳液進行高壓乳化,以纖維-光學顆粒尺 寸分析儀 FPAR-1000(Otsuka Electronics Co.,Ltd.製),於 2 5 ° C量測所產生之乳液,獲得體積平均粒徑9 0 nm。 <水凝膠之製備> 除了表2中於乳液所述成分之外,將成分連續添加至 水中’並於80°C加熱並捏製,獲得溶膠態產物。 將此溶膠態產物冷卻至60°C後,添加上述0/W型乳 液至溶膠產物,並均勻攪拌。以刮刀延展所產生之水凝膠 以形成〇.8mm之厚度後,水凝膠以具有基重20 g/m2之網 狀尼龍纖維覆蓋,並置於25。C 30分鐘,因此獲得實施例 5之具有尼龍網狀薄片作爲近似片狀基質之凝膠片,於基 質兩面上具有水凝膠層,水凝膠層總厚度爲〇.8 mm。 此外’表2中成分量所示之數値表示質量份。 [實施例6 · 8及比較實施例5 _ 8 ] -58- 200920414 如表2所示,各成分使用於實施例5類似方法,根據 實施例5-8及比較實施例5-8獲得活體用黏附凝膠片。 (活體用黏附凝凝膠片之評估) 使用實施例5-8及比較實施例5-8之活體用黏附凝膠 片,進行下列評估且評估結果顯示於下表2。此外,使用 實施例5-8及比較實施例5-8之凝膠片,黏附性、保濕性、 皮膚阻隔性及皮膚美化效果之各功能評估由十位評分員 做成(黏附於臉上),評估結果之平均値顯示於表2。 (1) 膠體脫水率 將實施例5 - 8及比較實施例5 - 8之活體用黏附凝凝膠 片剪成3cmx3cm之大小而形成樣本凝膠片,並將這些樣本 凝膠片放入Advantec MSF. Inc.製之2號濾紙,以便使兩 片濾紙位於樣本凝膠片之各上下端,並當保持在周圍溫度 25°C及相對溼度55% 10分鐘下,量測濾紙質量變化。膠 體脫水率經由使用獲得之量測値以下式計算。反覆測試五 次,且其平均値顯示於下表2。 膠體脫水率(質量%) = (濾紙所吸收液體之質量/凝膠 起始質量)X 100 在此點上,"凝膠起始質量”經由爲樣本凝膠片測試片 質量減去做爲薄片基層之尼龍網之質量獲得。 (2) 膠體脫水液之著色 在膠體脫水率評估中,估計液體吸收濾紙之著色程 -59- 200920414 度。 當清楚觀察由類胡蘿蔔素引起之著色,該樣本評爲 A,當觀察到輕微著色,該樣本評爲B,而當無法以視覺 判斷著色,該樣本評爲C。 (3) 膠體脫水液中乳液之含有率 含於濾紙之蝦紅素以下列方法萃取,在膠體脫水率之 評估中,在液體吸收濾紙中將5質量份之水及4質量份之 丙酮加入一質量份吸收液。爲了比較,5質量份水及4質 量份丙酮加入一質量份用於形成水凝膠之混合液,且所產 生之萃取液在473nm吸光率以分光光度計(V-630: JASCO Corporation製)量測,而膠體脫水液中乳液含有率根據下 式計算: 膠體脫水液中乳液含有率=膠體脫水液萃取液於 473nm之吸光率/用於形成水凝膠之混合液於473nm之吸 光率 (4) 水含量 各由實施例5 - 8及比較實施例5 - 8凝膠片取出一克之 水凝膠層在減壓下於25°C乾燥,持續乾燥直至未觀察到 樣本之質量變化,且水含量根據下式計算:Table 1 operative close-fitting moisturizing skin barrier properties Example 1 AAAB Example 2 AAAB Example 3 AAAB Example 4 AAAA Comparative Example 1 CABB Comparative Example 2 ABCC Comparative Example 3 BBBC Comparative Example 4 CABC As shown in Table 1, it is clear that all of the gel sheets of Examples 1 to 4 are excellent in workability, close adhesion, moisture retention, and skin barrier properties. Therefore, it is clear that the gel sheet having excellent effects can be excellent as an approximate sheet-like cosmetic material. Example 5 <Preparation of 〇/W type emulsion> The following ingredients were dissolved by heating at 70 ° C for 1 hour to obtain an aqueous phase composition. Sucrose oleate 15 g Decaglyceryl monooleate 23 g Glycerol 5 〇〇 g Pure water 322 g -57- 200920414 Further, the following components were dissolved by heating at 70 ° C for 1 hour to obtain an oil phase composition. Haematococcus pluvialis extract (astaxanthin content = 20% by mass) 4〇g Mixed tocopherol 1 〇g Lecithin (from soybean) 90g Stirred with a homogenizer (1 0,000 r pm) while remaining at 7〇 °C' The aqueous phase composition is added to the oil phase composition to obtain an emulsion. The emulsion produced was subjected to high-pressure emulsification under a pressure of 200 MPa using an Ultimizer HJP-2 5005 (manufactured by Sugino Machine Ltd.), and a fiber-optic particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). The resulting emulsion was measured at 25 ° C to obtain a volume average particle diameter of 90 nm. <Preparation of hydrogel> The components were continuously added to water in addition to the components of the emulsion in Table 2 and heated and kneaded at 80 ° C to obtain a sol-form product. After cooling the sol-form product to 60 ° C, the above 0/W type emulsion was added to the sol product, and uniformly stirred. After the hydrogel produced by the doctor blade was stretched to have a thickness of 〇8 mm, the hydrogel was covered with a mesh nylon fiber having a basis weight of 20 g/m2 and placed at 25. C 30 minutes, thus obtaining a gel sheet having a nylon mesh sheet as an approximate sheet-like substrate of Example 5, having a hydrogel layer on both sides of the substrate, the total thickness of the hydrogel layer being 〇.8 mm. Further, the number 値 indicated by the amount of the ingredients in Table 2 indicates the parts by mass. [Example 6·8 and Comparative Example 5 _ 8 ] -58- 200920414 As shown in Table 2, each component was used in a similar manner to Example 5, and the living body was obtained according to Examples 5-8 and Comparative Examples 5-8. Adhesive gel pieces. (Evaluation of the adhesive patch for living body use) Using the adhesive gel sheets for living bodies of Examples 5-8 and Comparative Examples 5-8, the following evaluations were carried out and the evaluation results are shown in Table 2 below. In addition, using the gel sheets of Examples 5-8 and Comparative Examples 5-8, the evaluation of the functions of adhesion, moisturization, skin barrier and skin beautification was made by ten scorers (adhered to the face). The average value of the evaluation results is shown in Table 2. (1) Colloidal dehydration rate The living gels of Examples 5 - 8 and Comparative Examples 5 - 8 were cut into 3 cm x 3 cm pieces to form sample gel pieces, and these sample pieces were placed in Advantec MSF. Inc. No. 2 filter paper was prepared so that the two pieces of filter paper were placed at the upper and lower ends of the sample gel sheet, and the quality of the filter paper was measured while maintaining the ambient temperature at 25 ° C and the relative humidity of 55% for 10 minutes. The gel dehydration rate was calculated by using the amount obtained by the following formula. The test was repeated five times and the average 値 is shown in Table 2 below. Colloidal dehydration rate (% by mass) = (mass of liquid absorbed by filter paper / initial mass of gel) X 100 At this point, "gel initiation mass" is determined by subtracting the mass of the test piece from the sample gel The quality of the nylon mesh of the base layer is obtained. (2) The color of the colloidal dehydration solution In the evaluation of the colloidal dehydration rate, the color distance of the liquid-absorbent filter paper is estimated to be -59-200920414 degrees. When the coloration caused by carotenoids is clearly observed, the sample Graded as A, when a slight coloration was observed, the sample was rated as B, and when it was not possible to visually judge the coloration, the sample was rated as C. (3) The content of the emulsion in the colloidal dehydration solution was contained in the filter paper as follows. Method extraction, in the evaluation of the colloidal dehydration rate, 5 parts by mass of water and 4 parts by mass of acetone are added to one part by mass of the absorption liquid in the liquid absorption filter paper. For comparison, 5 parts by mass of water and 4 parts by mass of acetone are added to one mass. The mixture is used to form a hydrogel mixture, and the resulting extract is measured at a 473 nm absorbance by a spectrophotometer (V-630: manufactured by JASCO Corporation), and the emulsion content in the colloidal dehydration solution is calculated according to the following formula. The emulsion content in the colloidal dehydration solution = the absorbance of the colloidal dehydration solution at 473 nm / the absorbance of the mixture for forming the hydrogel at 473 nm (4) The water content of each of Examples 5 - 8 and Comparative Example 5 - 8 gel pieces One gram of the hydrogel layer was taken out and dried at 25 ° C under reduced pressure, and dried until no mass change of the sample was observed, and the water content was calculated according to the following formula:

水含量(%)=[(起始質量-乾燥後質量)/起始質量]X 上述量測試驗重複5次,且其平均値被評爲水含量。 -60 - 100 200920414 (5) 黏附感 根據下列方法進行評估黏附感,當凝膠片黏附於臉部 上達到與臉表面密接的情況,該凝膠片評爲A ;當凝膠片 一部分脫落的情況,該凝膠片評爲B ;而當凝膠片皺褶且 凝膠片許多部分剝落的情況,該凝膠片評爲C。 (6) 保濕性 在凝膠片黏附前,對於1 0位評分員臉部眼部區域之 角質層水含量以角質層水份測量儀(Asahibiomed製)量 測,並根據傳導値評估。此後,將凝膠片黏附1 5分鐘, 並剝下凝膠片後,3 0分鐘過後以角質層水份測量儀 (Asahibiomed製)量測角質層之水含量作爲傳導値。比較 1 0位評分員所作成之黏附前及黏附後之値,且當傳導之平 均値增加1 〇%或以上時,該凝膠片評爲AA,當觀察到增 加2%至1 〇%時,該凝膠片評爲B,而當增加少於2%的情 況,該凝膠片評爲C。 (7 )皮膚阻隔性 爲了評估粗糙乾燥皮膚之改善功能,以下列方法量測 經皮膚水分流失量(TEWL)。 即,將凝膠片定期貼附每日1 5分鐘,連續三天,在 第三日剝下凝膠片後立即以經皮膚水分流失量分析儀 (A s a h i b i 〇 m e d製)測量經皮膚水分流失量(T E W L)。以下歹U 方法量測皮膚阻隔性,當TEWL値與測試前之値比較而下 -61 - 200920414 降5 %或以上的情況,該凝膠片評爲A ;當下降1至4%時, 該凝膠片評爲B;而當TEWL觀察到並無變化時,該凝膠 片評爲C。 (8)功能評估 當將貼附凝膠片定期貼附每日1 5分鐘,連續三天, 且在第三日撕下活體用黏附凝膠片後立刻評估有關皮膚 外表印象。當清楚獲得皮膚肌理改善的感覺之情況,該凝 膠片評估爲A ;當輕微獲得皮膚肌理改善的感覺之情況, 該凝膠片評估爲B ;當無感覺皮膚肌理改善時,該凝膠片 評估爲C。 ’ -62- 200920414 表2 比 比 比 比 實 實 實 實 較 較 較 較 施 施 施 施 實 實 實 實 例 例 例 例 施 施 施 施 &lt;ι 00 例 例 例 例 〇\ 00 wo乳液 0.2 0.2 0.2 0.2 0.2 0.2 聚葡甘露糖 0.4 0.4 0.4 0.4 0.4 0.4 κ-鹿角菜膠 0.5 0.5 0.5 0.5 0.6 0.6 聚丙烯酸鈉 12 12 酸處理明膠 (衍生自豬皮) 1 1 1 1 1 1 PLURONIC F-127 1 1 1 1 膠原蛋白三 胜肽* 0.1 抗壞血酸磷 酸鎂 1 1 氯化鎂 0.4 合成矽酸鋁 2 2 1,3-丁二醇 10 10 10 10 10 10 10 10 水 86.9 85.9 85.8 86.5 88 88 76 76 (評估) 膠體脫水率 45 62 60 49 35 32 16 17 膠體脫水液 之著色 A A A A C C C C 膠體脫水液 中乳液含量 0.82 0.98 0.96 0.92 n.d. n.d n.d. n.d 水含量(質量 %) 84 82 83 84 86 84 73 72 黏附感 A A A A B B A A 保濕性 A A AA A B B C C 皮膚阻隔性 A A A A C C C C 功能評估 A A A A C C c c n.d.:未被測得 -63- 200920414 根據表2之結果,明顯地,實施例5 - 8中活體用黏附凝 膠片爲高的膠體脫水率,且0/W型乳液顆粒被包含於膠體 脫水液中。此外,更明顯的是,保濕性、皮膚阻隔性及皮膚 肌理之改善效果十分優異。 另一方面,關於比較實施例5-8之活體用黏附凝膠片’ 膠體脫水液之料較小,且乳液並不包含於膠體脫水液中,並 不能獲得改善之確實感,特別是在功能性評估,且保溼效果 亦不足。 日本專利申請案2007-244489之揭示於本文一倂作爲參 考。 若本說明書中所述之個別之刊物、專利申請案、或技術 標準具體且各別地被指出作爲參考,則這些所有刊物、專利 申請案、及技術標準以相同範疇於本文一倂作爲參考。對於 熟悉技術者而言,明顯地有許多變化可實施於上述本發明之 較佳具體實施例的詳細敘述,本發明之範圍意圖以下列申請 專利範圍及其等效物界定。 【圖式簡單說明】 •fnr 那0 【主要元件符號說明】 4πτ 無。 -64-Water content (%) = [(starting mass - mass after drying) / initial mass] X The above measurement test was repeated 5 times, and the average enthalpy was evaluated as the water content. -60 - 100 200920414 (5) Adhesion sensation The adhesion was evaluated according to the following method. When the gel sheet adhered to the face to reach the surface of the face, the gel piece was rated as A; when the gel piece partially fell off In the case, the gel piece was rated as B; and when the gel piece was wrinkled and many parts of the gel piece were peeled off, the gel piece was rated as C. (6) Moisturizing property Before the gel sheet was adhered, the stratum corneum water content of the face of the face of the 10 scorer was measured by a stratum corneum moisture meter (Asahibiomed) and evaluated based on the conduction enthalpy. Thereafter, the gel sheet was adhered for 15 minutes, and after the gel sheet was peeled off, the water content of the stratum corneum was measured as a conductive enthalpy by a stratum corneum moisture meter (manufactured by Asahibiomed) after 30 minutes. Compare the scores made by the 10 scorers before and after the adhesion, and when the average value of conduction increased by 1% or more, the gel was rated AA, when an increase of 2% to 1% was observed. The gel piece was rated as B, and when the increase was less than 2%, the gel piece was rated as C. (7) Skin barrier property In order to evaluate the improvement function of rough and dry skin, the amount of skin water loss (TEWL) was measured by the following method. That is, the gel sheet was periodically attached for 15 minutes a day for three consecutive days, and after peeling off the gel sheet on the third day, the skin moisture loss was measured by the skin moisture loss analyzer (A sahibi 〇med). Quantity (TEWL). The following 歹U method measures the skin barrier property. When the TEWL値 is compared with the 前 before the test, the gel is evaluated as A when the temperature is decreased by 5% or more from -61 to 200920414; when it is decreased by 1 to 4%, The gel piece was rated as B; and when the TEWL was observed to be unchanged, the gel piece was rated as C. (8) Functional evaluation When the attached gel sheet was periodically attached for 15 minutes for three consecutive days, and the adhesive gel sheet for living body was peeled off on the third day, the skin appearance impression was immediately evaluated. The gel piece was evaluated as A when the feeling of skin texture improvement was clearly obtained; the gel piece was evaluated as B when the feeling of skin texture improvement was slightly obtained, and the gel piece was evaluated when no sensory skin texture was improved. The assessment is C. '-62- 200920414 Table 2 Bibibi ratio is more practical than the implementation of practical examples. Application example lt ι 00 Example 〇 00 wo lotion 0.2 0.2 0.2 0.2 0.2 0.2 Polyglucomannose 0.4 0.4 0.4 0.4 0.4 0.4 κ-carrageenan 0.5 0.5 0.5 0.5 0.6 0.6 Sodium polyacrylate 12 12 Acid-treated gelatin (derived from pigskin) 1 1 1 1 1 1 PLURONIC F-127 1 1 1 1 Collagen tripeptide * 0.1 Magnesium ascorbyl phosphate 1 1 Magnesium chloride 0.4 Synthetic aluminum citrate 2 2 1,3-butanediol 10 10 10 10 10 10 10 10 Water 86.9 85.9 85.8 86.5 88 88 76 76 (Evaluation) Colloidal dehydration rate 45 62 60 49 35 32 16 17 Coloring of colloidal dehydration solution AAAACCCC Colloidal dehydration solution Emulsion content 0.82 0.98 0.96 0.92 ndnd ndnd Water content (% by mass) 84 82 83 84 86 84 73 72 Adhesive AAAABBAA Moisture-proof AA AA ABBCC Skin barrier AAAACCCC function evaluation AAAACC cc nd: not measured -63- 200920414 According to the conclusion of Table 2 As a result, it is apparent that in Example 5-8, the living body adhered to the coagulation film as a high colloidal dehydration rate, and the 0/W type emulsion particles were contained in the colloidal dehydration solution. Further, it is more remarkable that the moisturizing property, the skin barrier property, and the skin texture are excellent. On the other hand, the adhesive gel sheet for colloidal gels of Comparative Examples 5-8 was smaller, and the emulsion was not contained in the colloidal dehydration solution, and the improvement of the sense of solidity was not obtained, especially in the function. Sexual assessment, and moisturizing effect is not enough. The disclosure of Japanese Patent Application No. 2007-244489 is incorporated herein by reference. If individual publications, patent applications, or technical standards described herein are specifically and individually indicated as a reference, all such publications, patent applications, and technical standards are hereby incorporated by reference. It will be apparent to those skilled in the art that <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; [Simple description of the diagram] • fnr 0 [Main component symbol description] 4πτ None. -64-

Claims (1)

200920414 十、申請專利範圍: 1 · 一種包含水凝膠之凝膠片,該水凝膠包含醚系溫度敏感性 聚合物,及至少一種膠原蛋白或膠原蛋白之分解產物。 2 .如申請專利範圍第1項之凝膠片,其中醚系溫度敏感性聚 合物爲選自由聚醚類、聚乙烯醚類、及烷基化多醣衍生物 所組成之群組中至少一者。 3. 如申請專利範圍第2項之凝膠片,其中聚醚類、聚乙烯醚 類、及烷基化多醣衍生物之具有至少一種官能基係選自羥 伸乙基、羥伸丙基、甲氧基及乙氧基所組成之群組。 4. 如申請專利範圍第1至3項中任一項之凝膠片,其中醚系 聚合物爲含聚氧化乙烯及聚氧化丙烯之嵌段聚合物。 5. 如申請專利範圍第1至4項中任一項之凝膠片,其中凝膠 片進一步包含0/W型乳液。 6 ·如申請專利範圍第5項之凝膠片,其中〇 / W型乳液包含類 胡蘿蔔素。 7 ·如申請專利範圍第5或第6項之凝膠片,其中〇 / W型乳液 之乳化顆粒的平均粒徑爲1 - 1 50nm。 8 .如申請專利範圍第5至7項中任一項之凝膠片,其中〇 / w 型乳液之乳化顆粒被包含於凝膠片之膠體脫水液。 9 ·如申請專利範圍第丨至8項中任一項之凝膠片,其中凝膠 片包含使用陰離子聚合物化合物及水溶性二價金屬鹽所 形成之水凝膠。 1 0 .如申請專利範圍第1至9項中任一項之凝膠片,其中凝 膠片進一步包含多醣類。 -65- 200920414 1 1 .如申請專利範圍第1至1 〇項中任一項之凝膠片,其中凝 膠片進一步包含多元醇化合物。 . 1 2 .如申請專利範圍第1至1 1項中任一項之凝膠片,其中凝 膠片之水含量爲70質量%至95質量%。 1 3 ·如申請專利範圍第丨至丨2項中任一項之凝膠片,其中凝 膠片含有包含水凝膠之水凝膠層及設置於水凝膠層或鄰 接於水凝膠層之近似片狀基層。 1 4 .如申請專利範圍第1至1 3項中任一項之凝膠片,其中凝 膠片之厚度爲0.4mro至2πιπι。 1 5 . —種近似片狀化妝品材料,其使用如申請專利範圍第1 至14項中任一項之凝膠片。 -66- 200920414 七、指定代表圖: (一) 本案指定代表圖為:無。 (二) 本代表圖之元件符號簡單說明: 4FR1 〇 y\\\ 八、本案若有化學式時,請揭示最能顯示發明特徵的化學式:200920414 X. Patent Application Range: 1 · A hydrogel-containing gel sheet comprising an ether-based temperature-sensitive polymer and at least one collagen or collagen decomposition product. 2. The gel sheet of claim 1, wherein the ether temperature sensitive polymer is at least one selected from the group consisting of polyethers, polyvinyl ethers, and alkylated polysaccharide derivatives. . 3. The gel sheet of claim 2, wherein the polyether, the polyvinyl ether, and the alkylated polysaccharide derivative have at least one functional group selected from the group consisting of hydroxyethyl, hydroxypropyl, a group consisting of methoxy and ethoxy groups. 4. The gel sheet of any one of claims 1 to 3 wherein the ether polymer is a block polymer comprising polyethylene oxide and polypropylene oxide. 5. The gel sheet of any one of claims 1 to 4, wherein the gel sheet further comprises a 0/W type emulsion. 6. The gel sheet of claim 5, wherein the 〇/W emulsion contains carotenoids. 7. The gel sheet of claim 5 or 6, wherein the emulsified particles of the 〇 / W type emulsion have an average particle diameter of from 1 to 150 nm. The gel sheet according to any one of claims 5 to 7, wherein the emulsified particles of the 〇 / w type emulsion are contained in a colloidal dehydration liquid of the gel sheet. The gel sheet according to any one of the preceding claims, wherein the gel sheet comprises a hydrogel formed using an anionic polymer compound and a water-soluble divalent metal salt. The gel sheet of any one of claims 1 to 9, wherein the gel film further comprises a polysaccharide. The gel sheet of any one of claims 1 to 1 wherein the gel film further comprises a polyol compound. The gel sheet of any one of claims 1 to 11, wherein the water content of the film is from 70% by mass to 95% by mass. A gel sheet according to any one of claims 2 to 2, wherein the gel sheet contains a hydrogel layer comprising a hydrogel and is disposed on or adjacent to the hydrogel layer It approximates the sheet base layer. The gel sheet of any one of claims 1 to 13 wherein the thickness of the film is from 0.4 mro to 2πιπι. An approximate sheet-like cosmetic material using the gel sheet of any one of claims 1 to 14. -66- 200920414 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 4FR1 〇 y\\\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
TW97135734A 2007-09-20 2008-09-18 Gel sheet and sheet-like cosmetic material using the same TW200920414A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007244489 2007-09-20
JP2007284508A JP5653573B2 (en) 2007-09-20 2007-10-31 Gel sheet and sheet cosmetic using the same

Publications (1)

Publication Number Publication Date
TW200920414A true TW200920414A (en) 2009-05-16

Family

ID=40663675

Family Applications (1)

Application Number Title Priority Date Filing Date
TW97135734A TW200920414A (en) 2007-09-20 2008-09-18 Gel sheet and sheet-like cosmetic material using the same

Country Status (2)

Country Link
JP (1) JP5653573B2 (en)
TW (1) TW200920414A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108601748A (en) * 2016-01-20 2018-09-28 Lts勒曼治疗系统股份公司 It controls from the water release in the Aquo-composition of form stable

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5737607B2 (en) * 2011-01-14 2015-06-17 国立大学法人富山大学 Functional sheet and manufacturing method thereof
JP6044104B2 (en) * 2012-04-23 2016-12-14 大日本印刷株式会社 Articles for sheet application
JP6430128B2 (en) 2014-02-17 2018-11-28 コスメディ製薬株式会社 Cosmetic gel sheet and method for producing the same
JP6853994B2 (en) 2016-04-28 2021-04-07 コスメディ製薬株式会社 Cosmetic alcogel sheet and its manufacturing method
CN111700905A (en) * 2020-06-29 2020-09-25 湛江千护宝生物有限公司 Chitosan and preparation method thereof
CN113057928B (en) * 2021-03-29 2022-10-21 烟台鲁量新材料科技有限公司 Gel matrix containing aloe extract, nano zinc oxide antibacterial gel and preparation method thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2761936B2 (en) * 1989-08-24 1998-06-04 株式会社コーセー Packing agent
JP3002733B2 (en) * 1990-07-19 2000-01-24 テイカ製薬株式会社 Indomethacin-containing patch
JP2003183147A (en) * 2001-12-18 2003-07-03 Sekisui Plastics Co Ltd Hydrogel sheet
KR100506543B1 (en) * 2003-08-14 2005-08-05 주식회사 제닉 Temperature Sensitive State-Changing Hydrogel Composition and Method for their Preparation
JP2005103421A (en) * 2003-09-30 2005-04-21 Shiseido Co Ltd Micronized emulsion and its preparing method
JP4128521B2 (en) * 2003-12-19 2008-07-30 信越化学工業株式会社 Gel sheet and method for producing the same
JP2005225837A (en) * 2004-02-16 2005-08-25 Shiseido Co Ltd Sheet-like cosmetic
JP4726497B2 (en) * 2005-01-13 2011-07-20 ポーラ化成工業株式会社 Cosmetics
JP4162680B2 (en) * 2005-10-21 2008-10-08 花王株式会社 Sheet-like composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108601748A (en) * 2016-01-20 2018-09-28 Lts勒曼治疗系统股份公司 It controls from the water release in the Aquo-composition of form stable

Also Published As

Publication number Publication date
JP2009091342A (en) 2009-04-30
JP5653573B2 (en) 2015-01-14

Similar Documents

Publication Publication Date Title
US20100239621A1 (en) Gel sheet and cosmetic preparation in sheet form using the same
JP5600005B2 (en) Water-soluble electrospun sheet
US20100221306A1 (en) Adhesive gel sheet for living organisms and sheet form cosmetics comprising the same
CN101889958B (en) Freeze-dried composition
KR102098427B1 (en) Hyaluronic acid gel and method for producing same
TW200920414A (en) Gel sheet and sheet-like cosmetic material using the same
TWI453035B (en) Gel sheet for cosmetic patching
WO2012063947A1 (en) Gel sheet comprising lipidic peptide type gelling agent and polymeric compound
CN105664223A (en) Cosmetic and external skin preparation, and medical instrument
EP2921164A1 (en) Sticky hydrogel cosmetic composition
JP5089165B2 (en) Antibacterial substance
JP2009536647A (en) Water dispersible patch containing active agent for skin delivery
JP2008137970A (en) Pressure-sensitive adhesive gel sheet for living body and sheet-like cosmetic using the same
JP4230221B2 (en) Manufacturing method of biomedical adhesive gel sheet
JP2021080302A (en) Cosmetic alcogel sheet and method for producing the same
JP2008285461A (en) Self-adhesive gel sheet for living organism and sheet-like cosmetic comprising the same
KR20190122641A (en) Skin application method of cellulose membrane, cosmetic for application
WO2009038030A1 (en) Gel sheet and sheet-like cosmetic material using the same
JP2016014060A (en) Foamable external skin preparation
JP2009108006A (en) Method for producing gel sheet, gel sheet and sheet-like cosmetic
CN115006265A (en) Separated gel mask
JP2009108008A (en) Gel sheet and sheet-like cosmetic using the same
JP2009108005A (en) Gel sheet and sheet-like cosmetic
JP2010215553A (en) Hydrogel external preparation
JP2022020844A (en) Foamable external preparation for skin