TWI293031B

TWI293031B - Composition for percutaneous absortion of carbon dioxide

Info

Publication number: TWI293031B
Application number: TW90123837A
Authority: TW
Inventors: Takashi Ishihara; Yoshikazu Fujinaga
Priority date: 2000-09-28
Filing date: 2001-09-27
Publication date: 2008-02-01

Description

1293031 B7 五、發明說明（j) 發明之詳細說明【發明所屬之技術領域】本發明係關於含有高濃度溶解性二氧化碳之水溶性組成物，特別是關於謀求與人體皮膚接觸而通過皮膚使二氧化碳有效地被人體吸收，以促進皮膚血液循環之碳酸經皮吸收用組成物、使用上述組成物的化粧水、由該組成物與片狀支持體所複合形成的碳酸經皮吸收用片狀物、以及該等之使用方法。【習知技術】自古以來，含有二氧化碳的水具有促進人體血液循環的作用被廣爲熟知，特別是爲使全身血液循環良好而以碳酸泉水沐浴的習慣自古有之。一般認爲，此乃因二氧化碳滲入皮膚後’引起毛細血管增加與擴張，因而促進皮膚血液循環。因此，已有將上述二氧化碳的特點，應用在化粧水、生髮育髮料、或面膜劑的生產製造。日本專利特公平3-14284號公報中，揭示了含有一定量二氧化碳，其pH値爲5-6.5的化粧水。此外，特開昭 60-215606號公報或特開平U-228334號公報中，揭示了含有二氧化碳的面膜劑或高黏度化粧料。【發明欲解決之課題】溶解在化粧料或面膜劑（本發明將之稱爲碳酸經皮吸收用組成物）中的二氧化碳濃度愈高，其血液循環促進效 3 _____________ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂---------線,· 1293031 A7 ^______B7___ 五、發明說明（^ ) 果將愈大。不過，若僅使二氧化碳溶解於水中，其pH値雖因該水酸鹼度而有所變化，如圖1所示其pH値將漸趨降低。而此pH値較低的水溶液對於皮膚具有強烈刺激性將難以做爲化粧品原料使用。儘管低PH値可藉由添加PH 値調整劑使pH値上升至5以上，但在化粧水等敏感用途上使用添加劑可能引發不良效果。本發明以尋找即使在低pH値的條件下，對於皮膚仍較不具刺激性之安全性添加劑爲首要課題。至於次要課題，乃針對一般含有高濃度二氧化碳水溶液在保存過程中，其一氧化碳常通過容器向外界空氣逸散，抑或在常壓下使用時，水溶液中的二氧化碳常立即向空氣中逸散等缺點提出解決之道。有關第2課題過去所使用的技術，儘管如特開平11-228834號公報中有所揭不，迄今爲止仍尙未完備。【發明所欲解決之課題】本發明之一爲一種碳酸經皮吸收用組成物，其特徵在於，係由：含有300ppm以上的遊離碳酸，且以海藻糖 (trehalose)爲必需成分之實質上不含氣泡狀二氧化碳之水溶液所構成。本發明之二爲一種碳酸經皮吸收用組成物，係至少由水、水溶性高分子、游離碳酸所構成的組成物，且該組成物的游離碳酸濃度在300ppm以上，實質上不以氣泡狀存在，而處於溶解狀態；其特徵在於，前述組成物具有溶膠一凝膠轉移或凝膠一溶膠轉移（以下簡稱爲「相轉移」） 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ——— II—,----ΜΎ (請先閱讀背面之注意事項再填寫本頁) ----訂---------線00^ · 1293031 B7 五、發明說明（77 ) 性質，且該轉移溫度範圍爲〇°C〜未滿45°c。 IJ——ΊΙΙΙΛΎ {請先閱讀背面之注意事項再填寫本頁) 本發明之三爲一種凝膠狀碳酸經皮吸收用組成物，係至少由水、水溶性高分子、游離碳酸所構成的組成物，且該組成物的游離碳酸濃度在300ppm以上，實質上不以氣泡狀存在，而處於溶解狀態之凝膠狀。第2、第3發明中，以含有海藻糖爲必需成分之碳酸經皮吸收用組成物爲最佳。本發明之四爲上述碳酸經皮吸收用組成物含浸或/及塗佈在片狀支持體所形成的碳酸經皮吸收用片狀物。本發明之五爲一種碳酸經皮吸收用組成物之使用方法，其特徵在於，在使用時係使該組成物發生相轉移，來讓組成物黏度發生變化。在此使用方法中，以藉由溫度或/及添加劑使組成物發生相轉移爲最佳。【發明之實施形態】線二氧化碳（C02)在20°c、一大氣壓下，對於水的溶解度爲〇.88(ml/ml水）（化學大事典）。溶解於水中的二氧化碳與水反應產生碳酸（H2C03)，而水中氫離子濃度（pH)超過6以上時，pH値愈高，碳酸將進一步解離成碳酸氫離子與碳酸離子。本發明所謂游離碳酸係指二氧化碳溶解於水中後，以二氧化碳及碳酸的狀態存在。儘管水的酸鹼度將對此產生影響，pH値6以下的條件下，大部分二氧化碳將形成游離碳酸而存在於水中。血液循環促進效果未見於碳酸氫離子與碳酸離子，而 5 本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公釐） 1293031 A7 ___B7__ 五、發明說明（f ) 必須以二氧化碳的狀態存在。如前文所述，1大氣壓的二氧化碳約0.88ml可溶解於lg的水中，不過，將該二氧化碳量換算成質量則約等於〇.〇〇16g。即約1600ppm (質量基準）。本發明雖以ppm表示溶解於碳酸經皮吸收用組成物的游離碳酸質量，惟由於該組成物大部分爲水，故視爲近似溶解於構成該組成物之水中的游離碳酸亦不爲過。本發明之含有一定量游離碳酸的碳酸經皮吸收用組成物製造方法將在下文中詳述，不過，實際上即以加壓方式直接將二氧化碳溶解於構成組成物之水中或組成物水溶液中。因此，與過去沐浴劑利用碳酸鹽與有機酸反應產生二氧化碳，藉由二氧化碳氣泡所產生的刺激作用，以及部分溶解於水中的二氧化碳具有血液循環促進效果所使用的技術具有本質上的差異。經由上述化學反應雖可使二氧化碳溶解於水中，但反應生成物殘存於水中，故一般認爲使用在如化粧水等針對肌膚敏感用途並不合適。爲了與此類技術區別，本組成物水溶液實質上不含氣泡狀二氧化碳。所謂「實質上」係指溶解在水或水溶液中的游離碳酸，因攪拌作用、氣溫、壓力變化’造成二氧化碳溶解度發生變化所產生的氣泡亦包含在本發明之範圍內。本發明之碳酸經皮吸收用組成物的血液循環促進作用可依據如下方法檢測得知。在肌膚呈白色的部位，例如手腕內側陽光較不易照射到的部位或足部膝關節部位，黏貼充分含漬碳酸經皮吸收用組成物的脫脂棉或紗布5或10分 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） (請先閱讀背面之注意事項再填寫本頁) 訂---------線Φ---r 1293031 a7 ______B7 _ 五、發明說明（f ) 鐘，並觀察其前後皮膚的狀態。而做爲比較之用，同時在接鄰部位黏貼含浸純水或自來水的脫脂棉或紗布。經過一定時間後，將所黏貼的脫脂棉等撕下並觀察皮膚的狀態。由於具有血液循環促進作用的碳酸經皮吸收用組成物將使得黏貼部位的皮膚變紅，而對照組部分與黏貼前的狀態相同，故容易加以區分。意即本發明所謂血液循環促進作用係指上述測試中造成膚色變紅的現象。據此檢測血液循環促進作用時發現，當組成物中的游離碳酸濃度在300ppm以上，最好在 500ppm以上即表現有血液循環促進作用。此外，有關游離碳酸濃度的上限，由於碳酸經皮吸收用組成物多在大氣壓下使用，雖受使用時溫度影響，其上限約2000ppm左右。將數大氣壓之二氧化碳壓入水溶液時，依據亨利定律含量在2000ppm以下的二氧化碳應可溶解於水溶液中，不過，因使用時多在常壓下之故，該水溶液在與空氣接觸的同時將產生氣泡，使得過飽和的二氧化碳立刻逸散於空氣中。圖1爲將二氧化碳溶解於自來水後所得之碳酸水中二氧化碳濃度與pH値間的關係。二氧化碳濃度係以二氧化碳電極測定得之。此圖顯示含有300ppm二氧化碳的碳酸水其pH値爲4.95。因此’爲使本發明產生血液循環促進作用，如前所述游離碳酸濃度必須在300ppm以上。也因此必須使碳酸水的PH値在5以下，最好在4.9以下。另一方面瞭解到由於碳酸水具有溶解人體皮脂的作用，故以pH 値5以下的碳酸水做爲化粧水之用時，將因皮脂溶解造成 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ^--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) _ A7 1293031 ___B7^_____ 五、發明說明（l ) 臉部刺痛而無法使用。爲消除以上缺點’本發明人等對於現今化粧品使用之添加劑進行了各項檢討，其中發現海藻糖十分具效果。碳酸水與海藻糖之組合何以較具優點其原因雖不甚明瞭，目前據推測可能與海藻糖可保有2水分子爲結晶水，使其具有特殊的吸濕特性有關。此外，海藻糖具有抑制脂質腐敗的作用，因此可能也具有防止年齡老化或體臭的效果，以此觀點視之，使用在化粧水中亦爲良好的添加劑。應使炭酸經皮吸收用組成物中的海藻糖含量至少在O.lwt%以上，較好爲0.5 wt%以上，最佳爲1 wt%以上。而上限以使用時不黏腻爲考量基準，最高爲10wt%以下，最好在7wt%以下。當以含有300ppm以上的游離碳酸與海藻糖之pH値未滿 5的碳酸經皮吸收用組成物做爲化粧水時發現，因其弱酸性對於皮膚產生收斂作用的同時可促進血液循環，並與海藻糖之特殊作用產生互補作用，故可得到對於皮膚刺激性小並具有濕潤感或美白等多重良好效果的化粧水。本發明之化粧水中除海藻糖外，亦可合倂使用眾所周知之保濕成分與角質軟化劑。保濕成分中包括乙二醇、甘油、丙二醇、二甘醇、1，3-丁二醇、1，2-戊二醇、聚乙二醇、聚丙二醇、山梨糖醇等多元醇類、前述多元醇類之脂肪酸酯類、木糖醇等多糖類、氨基酸類、透明質酸、彈性蛋白、膠原蛋白、幾丁質、殻聚糖衍生物等列舉如上。其中，就使用經驗而言，以如甘油、絲氨酸或谷氨酸鈉等氨基酸或氨基酸鹽、透明質酸或其鹽類爲較佳的保濕 8 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----*·---^----------— ---------線 (請先閱讀背面之注意事項再填寫本頁) _ 1293031 A7 ___B7___ 五、發明說明（7 ) 成分，此外，上述保濕成分可單獨或至少2種混合使用。而角質軟化劑除氨基酸、焦谷氨酸、乳酸、尿素、鹼金屬等天然保濕因子外、亦可使用乳酸鹽、三乙醇胺、α -羥基酸等列舉如上。本發明之碳酸經皮吸收用組成物及化粧水，如前文所述，雖以游離碳酸與海藻糖爲其必需成分，除上述保濕成分與角質軟化劑外，亦可依其目的添加眾所周知之添加劑成分。此類添加劑包含橄攬油、鯨蠟醇、羊毛脂、硬脂醇等柔軟劑，礦物質、各種營養劑，蘆薈或甘草等藥草之植物萃取成份，小球藻萃取物、海藻萃取物、迷迭香萃取物、加密列萃取物、薰衣草萃取物等之藥草，各種香料、熊果苷、維他命C、曲酸等美白劑列舉如上。此外，可依其不同用途，添加適量可能具有促進皮膚新陳代謝改善皺紋效果的視黃酸、維他命a、r-氨基丁酸等。依使用目的亦可添加如甘草酸之抗發炎劑而使其具有療效。此外，使用時若欲使其具有清涼感，亦可添加少量乙醇等。本發明之化粧水本身雖因含有游離碳酸而具有防腐效果，不過，爲使之可長時間保存於高溫下等使用於嚴苛的條件下，可添加對羥苯甲酸或檸檬酸等防腐劑或抗氧化劑。關於上述添加劑的添加量，由於本發明的目的爲提供柔順肌膚之化粧水，意即提供添加劑含量少的化粧水，故儘可能少量添加爲宜。以下針對第2發明、第3發明之碳酸經皮吸收用組成 9 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公釐） ___I Ί---V-------11---訂·-------- (請先閱讀背面之注意事項再填寫本頁) _ 1293031 A7 ____B7 ____ 五、發明說明（^ ) 物及有關其使用方法之第5發明，以及其較佳之實施形態加以說明。而與上述第1發明重複之構成要件則省略說明。此發明之含有游離碳酸的組成物，以用來塗抹或黏貼於人體局部部位爲其主要目的，因此，應依據其使用形態適當選擇其黏度。但另一方面，由於二氧化碳經由擴散作用逸散於空氣中的速度與組成物的黏度成反比，故以較高黏度爲佳。室溫下至少應爲5dPa_s、取好在1 OdPa.s以上爲佳。上述黏度的調整，可藉由改變高分子的種類、聚合度及其在水溶液中的濃度達成。有時藉由在高分子水溶液中添加有機或無機低分子鹽亦可能使黏度發生變化。本發明中所謂凝膠係指在黏度處於無限大的狀態下所呈現的無流動性狀態，使組成物中之水溶性高分子因分子間相互作用形成3次元網狀結構而出現膠化。處於凝膠狀態時因黏度無限大使得二氧化碳自組成物逸散遲緩對於組成物的保存較爲合適。不過，使用時因缺少流動性造成塗抹等發生困難，故以溶膠化後再使用爲佳。本發明中之凝膠如前文所述係處於非流動性的狀態而使得黏度無法測定，故與一般化粧品所謂膠凍爲不同物質。化粧品中將黏度高可以指尖挖取的狀態稱爲膠凍，此膠凍可測定其黏度，而本發明中將具有流動性的狀態定義爲溶膠，故所謂膠凍在本發明中乃歸屬於溶膠之範疇。本發明中將溶膠轉移爲凝膠的過程稱爲溶膠一凝膠轉移，反之稱爲凝膠一溶膠轉移，而此類轉移統稱爲相轉移 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----M.---------------^--------- (請先閱讀背面之注意事項再填寫本頁) _ 1293031 B7 五、發明說明（^ ) 。本發明中此相轉移係由水溶性高分子之分子間相互作用的變化所引起，不過，分子間相互作用的變化乃藉由加諸該水溶液中之物理與化學作用所引發。物理作用中以使溫度變化爲佳。藉由溫度變化引起轉移，意即轉移溫度可經由使用DSC或NMR等分析儀器正確得之，但本發明以下列簡易方法求得。膠化或溶膠化時，因整體黏度發生變化導致流動性喪失或回復，故一般須經一段時間移轉方可完全完成。化學作用中可利用加入添加劑改變水溶性高分子之溶解性。本發明中之添加劑以易溶於水溶液之低分子鹽爲佳。此時需保持水溶液在一定溫度下，並在加入一定量添加劑後放置短暫時間，再以上述試管法即可確認究竟爲膠化或溶膠化。由於轉移溫度隨添加劑的量而有所不同，故含有一定量添加劑之水溶液的轉移溫度可利用上述方法求得。有關本發明之碳酸經皮吸收用組成物的轉移溫度，以使用在人體的觀點視之，應爲0°C以上、未滿45°C，最好在〇-40°C之間。即該組成物在此溫度範圍內具有溶膠一凝膠轉移，亦所謂熱膠化特性。本發明之組成物係將水溶性高分子溶解於碳酸水或將二氧化碳溶於高分子水溶液而成 ’但無論採用何種方法製造，由於溫度愈低二氧化碳對於水的溶解度愈大，故必須在低溫下進行。此外，水溶液的情況下，以其黏度愈低二氧化碳對於水的擴散速率愈快爲佳。因此’低溫下呈現溶膠狀態且黏度低的高分子水溶液可使高濃度二氧化碳溶解於組成物中。另一方面，當欲保 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐） --------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1293031 7 A7 __B7____ 五、發明說明（ρ ) 存組成物時，若以防止二氧化碳逸散的觀點視之，應以黏度較大而呈現凝膠狀者爲佳。此外，使用時以在溶膠狀態下而能適當調節其黏度者爲佳。上述相轉移以能簡易進行爲佳，故本發明採用改變溫度或加入低分子鹽添加劑或二者相互組合的方法。轉移溫度愈高，爲得到適合使用的黏度，必須提高組成物溫度，這將導致二氧化碳容易自組成物逸散的不良現象發生。以此觀點視之，轉移溫度亦以未滿45°C爲佳，更好爲40°C以下，最好組成物的轉移溫度在37t附近，當以溶膠狀態塗抹於人體時，可藉由體溫使膠化作用發生，使二氧化碳不易逸散於空氣中。其下限溫度若以實用的觀點考量，最好在保存於冰箱的溫度即容易發生膠化或溶膠化作用，故以〇°C以上爲宜。具有凝膠一溶膠轉移作用之組成物的情況亦相同，故組成物於調製階段時，亦即將二氧化碳溶於水溶液時必須在溶膠狀態下進行，.且以低溫爲佳，轉移溫度以35°C以下爲佳。本發明之組成物中的水溶性高分子，使用合成高分子、天然高分子、以天然高分子爲材料所衍生之半合成高分子皆可，合成高分子包括聚丙烯醯胺、聚（甲基）丙烯酸及其鹽類、聚環氧乙烷、聚乙烯醇、聚乙烯毗咯酮等，天然高分子包括明膠、水解膠原蛋白、洋菜、角叉菜膠、瓜爾豆膠、果膠、聚葡萄糖、透明質酸、澱粉等，而半合成高分子可使用甲基纖維素、乙基纖維素、羧甲基纖維素、 12 ----^ ^ (請先閱讀背面之注意事項再填寫本頁) 訂---------. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 1293031 ___B7__ 五、發明說明（) 羥基甲基乙基纖維素、羥基丙基纖維素等纖維素衍生物。不過，因直接接觸人體，故以天然高分子、半合成高分子爲佳。或將至少2種則述之水溶性高分子混合使用亦可。組成物中水溶性高分子濃度範圍以0.5-5wt%爲佳。具有低溫時呈溶膠狀，高溫時成凝膠狀特性之水溶性高分子而爲人所熟知者爲甲基纖維素。此外，合成高分子中聚-N-異丙基丙烯醯胺、聚乙烯基乙烯醯胺、聚-N-乙烯基異丁醯胺、N-乙烯基異丁醯胺與N-乙烯基乙烯醯胺等之共聚物等亦廣爲所知。不過，因使用於人體，故以半合成之甲基纖維素爲佳。當使用甲基纖維素時，其2wt%水溶液的轉移溫度經本發明之方法測定爲45°C，爲使轉移溫度未滿45°C以添加低分子鹽爲佳。此類鹽類有氯化鈉、硫酸鈉、碳酸鈉、碳酸氫鈉、檸檬酸鈉等鈉鹽列舉如上。本發明較佳之實施形態爲使用具有熱凝膠特性之水溶性高分子，在低溫下使二氧化碳充分溶解於水溶液後保存於密閉容器中，必要時可放置於冰箱內，使用時經由將前述密閉容器置於30-40°C的環境下，使組成物在膠化的同時增加其黏度，待調節至容易塗抹的黏度後再將容器開封並塗抹於人體局部部位。伴隨膠化而產生的增黏作用，在使用（組成物）時仍可添加上述低分子鹽。採用此方法的同時，爲使鹽類得以均勻溶解於碳酸經皮吸收用組成物中必須予以攪拌，此時則須避免溶解在組成物中的二氧化碳逸散。經採用易溶之鹽類或縮短攪拌時間且於低溫下進行操作，將可使二氧化 13 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂--------- A7 1293031 ___B7___1293031 B7 V. INSTRUCTION DESCRIPTION (j) DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a water-soluble composition containing a high concentration of dissolved carbon dioxide, particularly for making carbon dioxide effective through skin through contact with human skin. a composition for percutaneous absorption of carbonic acid which is absorbed by the human body, which promotes blood circulation of the skin, a lotion using the above composition, a sheet for transdermal absorption of carbonic acid formed by combining the composition with a sheet-like support, and The method of use. [Prior Art] Since ancient times, water containing carbon dioxide has been widely known to promote blood circulation in humans, and in particular, the habit of bathing with carbonic acid springs for the good circulation of the whole body has been known since ancient times. It is generally believed that this is caused by the increase and expansion of capillaries due to the infiltration of carbon dioxide into the skin, thereby promoting skin blood circulation. Therefore, the characteristics of the above carbon dioxide have been applied to the production of lotions, raw hair growth materials, or masking agents. Japanese Patent Publication No. Hei 3-14284 discloses a lotion containing a certain amount of carbon dioxide and having a pH of 5-6.5. Further, a masking agent containing carbon dioxide or a high-viscosity cosmetic is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. [Problem to be Solved by the Invention] The higher the concentration of carbon dioxide dissolved in a cosmetic or a masking agent (which is referred to as a composition for percutaneous absorption of carbonic acid in the present invention), the blood circulation promoting effect 3 _____________ The paper scale applies to the Chinese national standard (CNS) A4 size (210 X 297 mm) (Please read the note on the back and fill out this page) Order ---------Line, · 1293031 A7 ^______B7___ V. Invention Description (^) The bigger it will be. However, if only carbon dioxide is dissolved in water, the pH 有所 varies depending on the pH of the water, and as shown in Fig. 1, the pH 渐 will gradually decrease. However, this aqueous solution having a lower pH 对于 is strongly irritating to the skin and is difficult to use as a cosmetic raw material. Although a low pH 値 can increase the pH 至 to 5 or more by adding a pH 値 adjusting agent, the use of an additive in a sensitive use such as a lotion may cause an adverse effect. The present invention is aimed at finding a safety additive which is less irritating to the skin even under conditions of low pH 値. As for the secondary issue, it is aimed at the high concentration of carbon dioxide aqueous solution in the preservation process, the carbon monoxide often escapes to the outside air through the container, or when used under normal pressure, the carbon dioxide in the aqueous solution often escapes to the air immediately. Propose the solution. The technique used in the past for the second problem has not been completed until now, as disclosed in Japanese Laid-Open Patent Publication No. Hei 11-228834. [Problem to be Solved by the Invention] One of the present invention is a composition for percutaneous absorption of carbonic acid, which comprises: 300 ppm or more of free carbonic acid, and trehalose as an essential component. It is composed of an aqueous solution containing bubble-like carbon dioxide. The second aspect of the present invention is a composition for percutaneous absorption of carbonic acid, which is a composition comprising at least water, a water-soluble polymer, and free carbonic acid, and the composition has a free carbonic acid concentration of 300 ppm or more, and is substantially not in the form of bubbles. Exist, but in a dissolved state; characterized in that the composition has a sol-gel transfer or a gel-sol transfer (hereinafter referred to as "phase transfer"). 4 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210). X 297 mm) ——— II—,----ΜΎ (Please read the notes on the back and fill out this page) ----Book---------Line00^ · 1293031 B7 Five The invention (77) is characterized in that the transfer temperature ranges from 〇 ° C to less than 45 ° c. IJ——ΊΙΙΙΛΎ {Please read the precautions on the back and fill out this page.) The third aspect of the present invention is a composition for gelatinous carbonic acid percutaneous absorption, which is composed of at least water, a water-soluble polymer, and free carbonic acid. The composition has a free carbonic acid concentration of 300 ppm or more, and does not substantially exist in the form of bubbles, but is in a gel state in a dissolved state. In the second and third inventions, a composition for percutaneous absorption of carbonic acid containing trehalose as an essential component is preferred. The fourth aspect of the present invention is a sheet for percutaneous absorption of carbonic acid formed by impregnating or/or coating the composition for percutaneous carbonic acid absorption on a sheet-like support. The fifth aspect of the present invention is a method for using a composition for percutaneous absorption of carbonic acid, which is characterized in that, when used, the composition is phase-transferred to change the viscosity of the composition. In this method of use, it is preferred to phase shift the composition by temperature or/and additives. [Embodiment of the Invention] The carbon dioxide (C02) has a solubility in water of 〇.88 (ml/ml water) at 20 ° C and an atmospheric pressure (Chemical Events). The carbon dioxide dissolved in water reacts with water to produce carbonic acid (H2C03), and when the concentration of hydrogen ions (pH) in the water exceeds 6 or more, the higher the pH, the further dissociation of carbonic acid into hydrogen carbonate ions and carbonate ions. The term "free carbonic acid" as used in the present invention means that carbon dioxide is dissolved in water and then exists in the state of carbon dioxide and carbonic acid. Although the pH of the water will affect this, most of the carbon dioxide will form free carbonic acid and will be present in the water below pH 値6. The blood circulation promoting effect is not seen in bicarbonate ions and carbonate ions, and the 5 paper scales are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1293031 A7 ___B7__ V. Invention description (f) must exist in the state of carbon dioxide . As described above, about 0.88 ml of carbon dioxide at 1 atm is soluble in lg of water, but the amount of carbon dioxide converted to mass is approximately equal to g.〇〇16g. That is about 1600ppm (mass standard). In the present invention, the mass of free carbonic acid dissolved in the carbonic acid percutaneous absorption composition is expressed in ppm. However, since most of the composition is water, it is considered that the free carbonic acid which is dissolved in the water constituting the composition is not excessive. The method for producing a carbonic acid percutaneous absorption composition containing a certain amount of free carbonic acid of the present invention will be described later in detail, but actually, carbon dioxide is directly dissolved in water or a composition liquid solution which constitutes the composition by pressurization. Therefore, the technology used in the past bathing agent to produce carbon dioxide by reacting carbonate with an organic acid, the stimulating effect by carbon dioxide bubbles, and the carbon dioxide partially dissolved in water having a blood circulation promoting effect are substantially different. Although the carbon dioxide is dissolved in water by the above chemical reaction, the reaction product remains in the water, and it is generally considered to be inappropriate for use in sensitive skin such as lotion. In order to distinguish from such techniques, the aqueous solution of the composition is substantially free of bubble-like carbon dioxide. The term "substantially" means free carbonic acid dissolved in water or an aqueous solution, and bubbles generated by changes in the solubility of carbon dioxide due to agitation, temperature, and pressure change are also included in the scope of the present invention. The blood circulation promoting action of the carbonic acid percutaneous absorption composition of the present invention can be detected by the following method. In areas where the skin is white, such as the part of the wrist where the sunlight is less likely to be irradiated or the part of the foot and knee, adhere to the absorbent cotton or gauze containing the composition of the percutaneous absorption of carbonic acid. 5 or 10 minutes. Standard (CNS) A4 specification (210 X 297 public) (Please read the note on the back and fill out this page) Order---------Line Φ---r 1293031 a7 ______B7 _ V. Invention description (f) Clock and observe the state of the skin before and after it. For comparison purposes, adhesive cotton or gauze impregnated with pure water or tap water is applied to the adjacent parts. After a certain period of time, the adhered absorbent cotton or the like is peeled off and the state of the skin is observed. Since the carbonic acid percutaneous absorption composition having a blood circulation promoting action causes the skin of the adhesive site to become red, and the control portion has the same state as before the pasting, it is easy to distinguish. That is, the so-called blood circulation promoting action of the present invention means a phenomenon in which the skin color becomes red in the above test. According to this, when the blood circulation promoting action is detected, it is found that when the free carbonic acid concentration in the composition is 300 ppm or more, preferably 500 ppm or more, blood circulation promoting action is exhibited. Further, regarding the upper limit of the free carbonic acid concentration, since the carbonic acid percutaneous absorption composition is used at a large atmospheric pressure, the upper limit is about 2000 ppm depending on the temperature at the time of use. When a few atmospheres of carbon dioxide is pressed into an aqueous solution, carbon dioxide in accordance with Henry's law content of 2000 ppm or less should be soluble in the aqueous solution. However, since it is often used under normal pressure, the aqueous solution will generate bubbles while being in contact with air. So that the supersaturated carbon dioxide immediately escapes into the air. Fig. 1 is a graph showing the relationship between the concentration of carbon dioxide in carbonated water obtained by dissolving carbon dioxide in tap water and pH 値. The carbon dioxide concentration was measured by a carbon dioxide electrode. This figure shows that carbonated water containing 300 ppm of carbon dioxide has a pH of 4.95. Therefore, in order to cause the blood circulation promoting action of the present invention, the free carbonic acid concentration must be 300 ppm or more as described above. Therefore, it is necessary to make the pH of the carbonated water below 5, preferably below 4.9. On the other hand, it is understood that since carbonated water has the function of dissolving human sebum, when carbonated water having a pH of 値5 or less is used as a lotion, it will be dissolved due to sebum. 7 paper scales are applicable to China National Standard (CNS) A4 specifications. (210 X 297 mm) ^--------Book---------Line (please read the notes on the back and fill out this page) _ A7 1293031 ___B7^_____ V. Invention Description (l) The face is stinging and cannot be used. In order to eliminate the above disadvantages, the present inventors conducted various reviews on the additives used in cosmetics today, and found that trehalose is very effective. Although the combination of carbonic acid water and trehalose is more advantageous, the reason is not clear. It is speculated that it may be related to trehalose to retain 2 water molecules as crystal water, which has a special hygroscopic property. Further, trehalose has an effect of suppressing lipid spoilage, and therefore may also have an effect of preventing ageing or body odor, and as such, it is also a good additive for use in lotion. The trehalose content in the carbonic acid percutaneous absorption composition is at least 0.1% by weight or more, preferably 0.5% by weight or more, and most preferably 1% by weight or more. The upper limit is based on the non-stickiness when used, and the upper limit is 10% by weight or less, preferably 7% by weight or less. When the composition for percutaneous absorption of carbonic acid containing 300 ppm or more of free carbonic acid and trehalose has a pH of less than 5, it is found that the weak acidity promotes blood circulation and promotes blood circulation due to its astringent effect on the skin. The special action of trehalose produces a complementary effect, so that a lotion which is less irritating to the skin and has multiple effects such as moist feeling or whitening can be obtained. In addition to trehalose, the lotion of the present invention may be combined with a well-known moisturizing ingredient and a keratolytic agent. The moisturizing ingredients include glycols such as ethylene glycol, glycerin, propylene glycol, diethylene glycol, 1,3-butylene glycol, 1,2-pentanediol, polyethylene glycol, polypropylene glycol, sorbitol, and the like. Examples of the fatty acid esters of alcohols, polysaccharides such as xylitol, amino acids, hyaluronic acid, elastin, collagen, chitin, and chitosan derivatives are as described above. Among them, in terms of experience, amino acid or amino acid salts such as glycerol, serine or sodium glutamate, hyaluronic acid or a salt thereof are preferred. The paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) -----*·---^---------------- --------- Line (please read the notes on the back and fill out this page) _ 1293031 A7 ___B7___ V. Inventive Note (7) Ingredients, the above-mentioned moisturizing ingredients may be used singly or in combination of at least two. The keratolytic agent may be, in addition to the natural moisturizing factors such as amino acid, pyroglutamic acid, lactic acid, urea, and alkali metal, lactated acid, triethanolamine, or α-hydroxy acid, and the like. In the carbonic acid percutaneous absorption composition and the lotion of the present invention, as described above, free carbonic acid and trehalose are essential components, and in addition to the above-mentioned moisturizing component and keratolytic agent, a well-known additive may be added depending on the purpose. ingredient. Such additives include softeners such as olive oil, cetyl alcohol, lanolin, stearyl alcohol, minerals, various nutrients, plant extracts of herbs such as aloe or licorice, chlorella extract, seaweed extract, fans Herbs such as rosemary extract, encrypted extract, lavender extract, and the like, various whitening agents such as various flavors, arbutin, vitamin C, and kojic acid are listed above. In addition, depending on the application, an appropriate amount of retinoic acid, vitamin A, r-aminobutyric acid, etc., which may promote skin metabolism and improve wrinkles, may be added. An anti-inflammatory agent such as glycyrrhizin may also be added for the purpose of use. In addition, if you want to make it feel cool, you can add a small amount of ethanol. Although the lotion itself of the present invention has a preservative effect by containing free carbonic acid, it may be added to a preservative such as p-hydroxybenzoic acid or citric acid in order to be stored under high temperature conditions for a long period of time or the like. Antioxidants. Regarding the amount of the above-mentioned additive to be added, since the object of the present invention is to provide a lotion which is soft to the skin, that is, to provide a lotion having a small additive content, it is preferable to add it as little as possible. In the following, the carbonic acid percutaneous absorption composition of the second invention and the third invention is applicable to the Chinese National Standard (CNS) A4 specification (21〇x 297 mm) ___I Ί---V------- 11---Book·------- (Please read the note on the back and fill out this page) _ 1293031 A7 ____B7 ____ V. Invention Description (^) and the fifth invention of its use, And preferred embodiments thereof will be described. The constituent elements that are the same as the above-described first invention are not described. The composition containing free carbonic acid of the present invention is mainly used for application or adhesion to a part of a human body, and therefore, its viscosity should be appropriately selected depending on its use form. On the other hand, since the rate at which carbon dioxide escapes into the air via diffusion is inversely proportional to the viscosity of the composition, a higher viscosity is preferred. It should be at least 5dPa_s at room temperature and preferably at least 1 OdPa.s. The above viscosity adjustment can be achieved by changing the type of the polymer, the degree of polymerization, and the concentration in the aqueous solution. Sometimes, the viscosity may be changed by adding an organic or inorganic low molecular salt to an aqueous polymer solution. The term "gel" as used in the present invention means a non-flowing state which is exhibited in a state where the viscosity is infinite, and the water-soluble polymer in the composition is gelatinized by the intermolecular interaction to form a three-dimensional network structure. In the gel state, due to the infinite viscosity, the slow escape of carbon dioxide from the composition is suitable for the preservation of the composition. However, it is difficult to apply smear due to lack of fluidity during use, so it is preferable to use it after solification. The gel of the present invention is in a non-flowing state as described above, so that the viscosity cannot be measured, so it is different from the so-called jelly of a general cosmetic. The state in which the viscosity is high in the cosmetic can be referred to as jelly, and the jelly can measure the viscosity thereof, and in the present invention, the state having fluidity is defined as a sol, so the so-called jelly is attributed to the present invention. The scope of the sol. The process of transferring a sol into a gel in the present invention is called sol-gel transfer, and vice versa is a gel-sol transfer, and such transfer is collectively referred to as phase transfer. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) -----M.---------------^--------- (Please read the notes on the back and fill out this page. ) _ 1293031 B7 V. Description of invention (^). This phase transfer in the present invention is caused by a change in the intermolecular interaction of the water-soluble polymer, but the change in the intermolecular interaction is caused by the physical and chemical action added to the aqueous solution. Physical effects are preferred to make temperature changes. The transfer is caused by a temperature change, i.e., the transfer temperature can be correctly obtained by using an analytical instrument such as DSC or NMR, but the present invention is obtained by the following simple method. In the case of gelation or solification, the fluidity is lost or recovered due to changes in the overall viscosity, so it usually takes a period of time to complete the conversion. In the chemical action, the addition of an additive can be used to change the solubility of the water-soluble polymer. The additive of the present invention is preferably a low molecular salt which is easily soluble in an aqueous solution. At this time, it is necessary to keep the aqueous solution at a certain temperature and leave it for a short time after adding a certain amount of the additive, and then confirm the gelation or solification by the above-mentioned test tube method. Since the transfer temperature varies depending on the amount of the additive, the transfer temperature of the aqueous solution containing a certain amount of the additive can be obtained by the above method. The transition temperature of the carbonic acid percutaneous absorption composition of the present invention should be 0 ° C or more, less than 45 ° C, preferably 〇 - 40 ° C from the viewpoint of use in the human body. That is, the composition has a sol-gel transfer in this temperature range, and is also called a thermogelling property. The composition of the present invention dissolves the water-soluble polymer in carbonated water or dissolves carbon dioxide in the aqueous polymer solution. However, no matter what method is used, the lower the temperature, the greater the solubility of carbon dioxide in water, so it must be at a low temperature. Go on. Further, in the case of an aqueous solution, the lower the viscosity, the faster the diffusion rate of carbon dioxide to water. Therefore, an aqueous polymer solution exhibiting a sol state at a low temperature and having a low viscosity allows a high concentration of carbon dioxide to be dissolved in the composition. On the other hand, when you want to protect 11 paper scales, apply Chinese National Standard (CNS) A4 specifications (210 X 297 public meals) -------- order --------- line (please read first) Precautions on the back side Fill in this page.) 1293031 7 A7 __B7____ V. INSTRUCTIONS (ρ) When storing a composition, it is preferable to use a gel with a large viscosity to prevent carbon dioxide from escaping. Further, it is preferred that the viscosity can be appropriately adjusted in the sol state during use. The above phase transfer is preferably carried out simply, and the present invention employs a method of changing the temperature or adding a low molecular salt additive or a combination of the two. The higher the transfer temperature, the higher the temperature of the composition must be in order to obtain a viscosity suitable for use, which will cause the carbon dioxide to easily escape from the composition. From this point of view, the transfer temperature is preferably less than 45 ° C, more preferably below 40 ° C, preferably the composition of the transfer temperature is around 37 t, when applied to the human body in the sol state, by body temperature The gelation occurs so that carbon dioxide does not easily escape into the air. When the lower limit temperature is considered from a practical viewpoint, it is preferable to carry out gelation or solification at a temperature stored in a refrigerator, so that it is preferably 〇 ° C or more. The composition of the composition having the gel-sol transfer effect is also the same. Therefore, when the composition is in the preparation stage, the carbon dioxide must be dissolved in the aqueous solution in the sol state, and the low temperature is preferred, and the transfer temperature is 35 ° C. The following is better. The water-soluble polymer in the composition of the present invention may be a synthetic polymer, a natural polymer, or a semi-synthetic polymer derived from a natural polymer, and the synthetic polymer includes polyacrylamide, poly(methyl). Acrylic acid and its salts, polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, etc. Natural polymers include gelatin, hydrolyzed collagen, Chinese cabbage, carrageenan, guar gum, pectin, Polydextrose, hyaluronic acid, starch, etc., and semi-synthetic polymer can use methyl cellulose, ethyl cellulose, carboxymethyl cellulose, 12 ----^ ^ (please read the precautions on the back and fill in This page) Order ---------. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) A7 1293031 ___B7__ V. Description of invention () hydroxymethyl ethyl cellulose, A cellulose derivative such as hydroxypropylcellulose. However, due to direct contact with the human body, natural polymers and semi-synthetic high molecules are preferred. Alternatively, at least two kinds of water-soluble polymers described above may be used in combination. The concentration of the water-soluble polymer in the composition is preferably in the range of 0.5 to 5% by weight. It is a water-soluble polymer which has a sol-like state at a low temperature and a gel-like property at a high temperature, and is known as methyl cellulose. In addition, in the synthetic polymer, poly-N-isopropylacrylamide, polyvinylvinylamine, poly-N-vinylisobutylamine, N-vinylisobutylamine and N-vinylvinylhydrazine Copolymers such as amines and the like are also widely known. However, since it is used in the human body, it is preferred to use semi-synthetic methyl cellulose. When methyl cellulose is used, the transfer temperature of the 2 wt% aqueous solution is determined to be 45 ° C by the method of the present invention, and it is preferred to add a low molecular salt so that the transfer temperature is less than 45 ° C. Such salts are, for example, sodium chloride, sodium sulfate, sodium carbonate, sodium hydrogencarbonate or sodium citrate. In a preferred embodiment of the present invention, a water-soluble polymer having thermogel properties is used, and carbon dioxide is sufficiently dissolved in an aqueous solution at a low temperature, and then stored in a sealed container, and if necessary, placed in a refrigerator, and the sealed container is used in use. The solution is placed in an environment of 30-40 ° C to increase the viscosity of the composition while being gelatinized. After the viscosity is easily applied, the container is opened and applied to a part of the human body. The above-mentioned low molecular salt can be added while using (composition) with the viscosity-increasing effect caused by gelation. At the same time as this method, in order to uniformly dissolve the salt in the carbonic acid percutaneous absorption composition, it is necessary to stir, and at this time, the carbon dioxide dissolved in the composition must be avoided. By using readily soluble salts or shortening the mixing time and operating at low temperatures, the 13-gauge paper size can be applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back note first) Matters fill out this page) Order --------- A7 1293031 ___B7___

五、發明說明（I 碳逸散在最小限度下，達成經由組成物相轉移所引發的黏度變化。另一方面，低溫下呈凝膠狀態，高溫下呈溶膠狀態之碳酸經皮吸收用組成物，因可保存在凝膠狀態下，使二氧化碳自組成物逸散得以在最小限度內亦爲較佳之實施形態。例如由明膠所構成之碳酸經皮吸收用組成物，雖因明膠濃度不同而有所改變，其2wt%水溶液約在25°C以下產生膠化作用。因此，使二氧化碳溶解在25-30°C之範圍內的溶膠狀態下，再保存於25°C以下，例如冰箱，即可得到二氧化碳幾乎不逸散之碳酸經皮吸收用組成物。有許多諸如上述隨著溫度上升而具有凝膠一溶膠轉移作用之水溶性高分子爲人所熟知。具有高溫溶解性的水溶性高分子包括澱粉、洋菜、瓊脂糖、瓜爾豆膠、洋槐膠、黃原膠、角叉菜膠、果膠、甘露聚糖、聚葡萄糖等天然高分子，羥基丙基纖維素、羥基乙基甲基纖維素、羧甲基纖維等半合成高分子，聚乙烯吡咯酮、聚（甲基)丙烯酸及其鹽類、聚丙烯醯胺或其部分水解產物、聚環氧乙烷等合成高分子列舉如上，不過，其轉移溫度隨水溶液中高分子之聚合度或濃度而有所變化。一般而言，聚合度愈高濃度愈高，相轉移溫度也愈高。有關本發明中第2、第3發明之組成物，由於含有 300ppm以上的二氧化碳，故其pH値可能低於5以下。此時除水、游離碳酸、水溶性高分子外，如第1發明中之說明，可經由添加海藻糖得到pH値低但使用感良好之碳酸 14 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) tr---------線辦· 1293031 A7 ______B7_____ 五、發明說明（G) 經皮吸收用組成物。如有進一步需要，可如第1發明中之說明，依其使用目的添加各種保濕成分、角質軟化劑、藥劑等。本發明之碳酸經皮吸收用組成物含有高濃度的二氧化碳，並且如稍後實施例中所述，當黏貼於人體局部部位時，30分鐘後因皮膚仍呈現紅化現象而被證實具有血液循環促進作用，而二氧化碳逸散速度緩慢，其血液循環促進作用可經由黏貼在必要患部以達到治癒之效果。接著針對第4本發明加以說明。黏度低塗抹於人體即造成流失的組成物或反之在室溫下即呈現膠化的組成物，皆難以直接塗抹於人體局部部位。此時，可將處於溶膠狀態下的組成物含浸或塗佈於片狀的支持物，再將含有組成物之片狀支持物黏貼於人體局部部位。做爲支持體之用者，可使用以纖維編織而成，具柔軟性之布料、編織物、不織布、毛氈狀物、高分子製成之膠膜等。此外，爲防止黏貼於人體局部部位後二氧化碳逸散，或防止組成物外滲，亦可使用由具有組成物含浸層機能之支持體與高分子膠膜等氣體阻斷機能之支持體所複合而成之複合支持體。就使用性而言，片狀支持物的厚度以 5mm以下爲佳。最後再針對本發明之碳酸經皮吸收用組成物的製造方法加以說明。過去使用的製造技術係將所謂化粧水或洗液等化粧品原液裝入耐壓容器內，再以二氧化碳加壓而製造出含有二氧化碳之化粧品原料。以製造法而言，此方法雖看似簡便，爲使加壓注入容器內之二氧化碳溶於容器內之 15 (請先閱讀背面之注意事項再填寫本頁) 訂--------- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1293031 A7 ------- B7 五、發明說明（/产）水或酒精以生產含有一定量二氧化碳之化粧品原料，須使高濃度二氧化碳溶解，故必須提高二氧化碳的壓力。因此，所使用的容器必須具有充分之耐壓構造。此外，因=氧化碳溶解僅發生於與氣體接觸之液體表面，必須經長時間方可使高濃度二氧化碳溶解。有關時間問題，一般認爲若將二氧化碳加壓注入後，放置在密閉狀態下，溶解作用將自動緩慢進行，故溶解作用於產品保存過程亦將持續進行。不過，爲達此目的，必須充分確保二氧化碳在容器內所佔的空間。如此必然造成谷益內化粧品原料所佔的量因而變少。梦與本發明之多位發明人爲消除上述缺點，發明了將一氧化碳溶解於組成物之製程與經上述製程所得之含有二氧化碳的組成物充塡於容器內之製程予以分開之碳酸經皮吸收用組成物的製造方法。使二氧化碳溶解於組成物中之溶解製程最好採取單一製程，即將不含二氧化碳之組成物原料水溶液予以調整後，使該水溶液與二氧化碳接觸。此曰寸最好事則使原料水丨谷液脫氣。此外，由於二氧化碳對於水等液體之溶解度將因低溫而增大，故應在3(rc以下，最好在25°C以下使其溶解於原料水溶液。此外，以使用加大二氧化碳與原料水溶液接觸面積之裝置爲佳。原料水溶液的黏度較低時，發現可使用膜式二氧化碳溶解器在短時間內使二氧化碳溶解於原料水溶液。上述膜式二氧化碳溶解器，以例如特許2810694號公報或特開= 號公報所揭示之使用中空系膜，可加大氣體與液體 16 本紙張尺度適用中ϋ國家標準（CNS)A4規格（210 X 297公髮)~ ------- (請先閱讀背面之注意事項再填寫本頁) tr---------線, 1293031 A7 _____ B7 _ 五、發明說明（丨f) 接觸面積而具效率者爲佳。使用膜式二氧化碳溶解器時，因其前段或後段連續裝設有精密過濾裝置，故經由過濾細菌或異物即可輕易得到呈現無菌狀態之碳酸經皮吸收用組成物。另一方面，含有水溶性高分子而黏度較大的原料組成物的情況，可將水溶液裝入具備攪拌裝置之高壓鍋等加壓容器中，一邊攪拌使水溶液脫氣，再加壓二氧化碳即可使之溶解於水溶液中。採用二氧化碳幫浦供給二氧化碳雖較爲便利，惟亦可先將固態二氧化碳（乾冰）與水溶液一起裝入局壓鍋再使之密閉。此外，在可連續性使二氧化碳溶解於高黏度水溶液的裝置，如於濕壁裝置或靜力攪拌器內導入二氧化碳，使之與水溶液接觸或一邊混合使之溶解於水溶液後，再將組成物取出等方法亦爲較佳的製造方法。二氧化碳的壓力範圍以0.1-0.5MPa爲佳。經由上述方法所得之溶解有300ppm以上二氧化碳的組成物，將依個別目的密閉於各種容器收納保存。收納容器以二氧化碳不易通過容器器壁而逸散者爲佳，若爲塑膠製品，以聚對苯二甲酸乙二醇酯（PET)或氯乙腈、丙烯腈聚合物等氣體通透性低的材料較佳。此外，與鋁等金屬類製成箔狀之包裝材料或黏度較低時金屬製噴霧器亦爲較佳之容器。若組成物中含有具熱膠化特性之水溶性高分子，最好使高分子在其膠化溫度以上的條件下分散於水或含有海藻糖或低分子鹽類之水溶液中。因爲在膠化溫度以下高分子 17 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂--------線 1293031 A7 ___B7 ____ 五、發明說明（ίί ) 的溶解速度快，即使水溶液黏度上升數％的濃度，高分子亦難以均勻溶解。另一方面，在膠化溫度以上使高分子分散於溶液時，因高分子不發生溶解，造成溶液黏度低，故可得到均勻之分散溶液。而在膠化溫度以下的溫度下一邊攪拌該分散溶液並使之冷卻，即可得到均勻的高分子水溶液。因愈低溫二氧化碳的溶解度愈大，若在冷卻狀態下將上述均勻溶液充塡於二氧化碳溶解裝置，二氧化碳將可溶解於溶液中。不過，最好採一邊冷卻低黏度之分散溶液並使二氧化碳溶解其中的方法。冷卻溫度爲30°C、較好爲25 °C以下、最好爲20°C以下。經上述方法調整後之組成物中的二氧化碳濃度可藉由以下幾種方法求得。二氧化碳電極法或利用標準試劑之化學滴定法對於自來水或低黏度液體有效，但無法使用在高黍占度組成物。含有水溶性高分子之高黏度組成物在本發明中係利用二氧化碳溶解製程中所吸收之二氧化碳質量以及該組成物之血液循環促進作用，以定性方式判斷其濃度。本發明之碳酸經皮吸收用組成物，做爲利用血液循環促進作用以保持臉部肌膚之健康、美容所使用之基礎化粧水’具體而言，具有保持肌膚滋潤、改善黑班雀斑、改善青春痘、改善日曬後皮膚、美白效果、改善皺紋等效果。此外’因二氧化碳具有血液循環效果，故可做爲用於頭皮 β育髮劑，或用於身體腳踵或手肘等角質層較發達部位之角質柔軟劑之用。此外，亦可能治癒一般認爲係由皮膚乾 18 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---—— —I —訂- -------· (請先閱讀背面之注意事項再填寫本頁) 1293031 B7 五、發明說明（7 ) 燥所引起之異位性皮膚炎。此外，高黏度之碳酸經皮吸收用組成物除做爲瘦身用品具有上述作用效果之外，可經由塗抹或黏貼於血行不良之患部，例如長期臥病在床患者之褥瘡患部等，促進患部血液循環而達到治癒效果。以下將以實施例、參考例及比較例進一步說明本發明 ’但本發明之技術範疇將不以此處之實施例爲限。參考例1 在中空糸膜式二氧化碳溶解器中使用自來水調製成含有不同濃度二氧化碳之碳酸水。二氧化碳的濃度係以改變自來水流量及供給二氧化碳溶解器之二氧化碳流量進行調節。而碳酸水中所含之游離碳酸濃度以二氧化碳電極（ ORION RESEARCH公司製造）測量。該碳酸水之二氧化碳濃度與pH値的關係如圖1所示。表1海藻糖含量與碳酸化粧水的效果（實施例1) 化粧水編號海藻糖含量 (wt%) 刺激性受試者之評價（人數）皮膚的滋潤程度_ 美白 1 0.1 10 12 10 2 0.5 6 14 14 3 1.0 4 15 14 4 2.0 3 16 15 5 (比較例） 0 18 5 8 實施例1 19 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）請先閱讀背面之注意事項再填寫本頁V. INSTRUCTION OF THE INVENTION (I. The carbon scatter is minimized, and the viscosity change caused by the phase transition of the composition is achieved. On the other hand, the carbonic acid percutaneous absorption composition is in a gel state at a low temperature and is in a sol state at a high temperature. It is also preferred to minimize the escape of carbon dioxide from the composition because it can be stored in a gel state. For example, a composition for percutaneous absorption of carbonic acid composed of gelatin may be different depending on the gelatin concentration. Change, the 2wt% aqueous solution produces gelation at about 25 ° C. Therefore, the carbon dioxide is dissolved in the sol state in the range of 25-30 ° C, and then stored at 25 ° C or less, such as a refrigerator, can be obtained A carbonic acid permeation-absorbing composition in which carbon dioxide hardly escapes. There are many water-soluble polymers having a gel-sol transfer effect as the temperature rises as described above. Water-soluble polymers having high-temperature solubility include Natural polymers such as starch, agar, agarose, guar gum, artichoke gum, xanthan gum, carrageenan, pectin, mannan, polydextrose, etc. Semi-synthetic polymer such as propyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl fiber, polyvinylpyrrolidone, poly(meth)acrylic acid and its salts, polyacrylamide or its partial hydrolyzate, poly The synthetic polymer such as ethylene oxide is as described above, but the transfer temperature varies depending on the degree of polymerization or concentration of the polymer in the aqueous solution. Generally, the higher the degree of polymerization, the higher the concentration and the higher the phase transition temperature. Since the composition of the second and third inventions of the present invention contains carbon dioxide of 300 ppm or more, the pH 値 may be less than 5 or less. In this case, in addition to water, free carbonic acid, and a water-soluble polymer, the first invention is It is indicated that carbon dioxide with low pH but good use can be obtained by adding trehalose. 14 The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) Tr---------Line Office 1293031 A7 ___B7_____ V. INSTRUCTION DESCRIPTION (G) Composition for percutaneous absorption. If necessary, as described in the first invention, various types may be added depending on the purpose of use. Moisturizing , a keratin softening agent, a pharmaceutical agent, etc. The carbonic acid percutaneous absorption composition of the present invention contains a high concentration of carbon dioxide, and as described in later embodiments, when adhered to a local part of the human body, the skin is still red after 30 minutes. It has been confirmed to have a blood circulation promoting effect, and the carbon dioxide escape rate is slow, and the blood circulation promoting action can be cured by adhering to the affected part to achieve the healing effect. Next, the fourth invention will be described. The viscosity is low and applied to the human body. The composition causing the loss or the composition which is gelled at room temperature is difficult to apply directly to a part of the human body. At this time, the composition in the sol state can be impregnated or coated on the sheet-like support. Then, the sheet-like support containing the composition is adhered to a local part of the human body. As the supporter, a fabric made of fiber, a soft fabric, a woven fabric, a non-woven fabric, a felt, or a polymer film can be used. In addition, in order to prevent the carbon dioxide from escaping after being adhered to a local part of the human body, or to prevent the composition from being extravasated, it may be compounded by a support having a function of the impregnation layer of the composition and a gas blocking function such as a polymer film. Become a composite support. In terms of usability, the thickness of the sheet-like support is preferably 5 mm or less. Finally, a method for producing the carbonic acid percutaneous absorption composition of the present invention will be described. In the manufacturing technique used in the past, a cosmetic stock solution such as a lotion or a lotion is placed in a pressure-resistant container, and then pressurized with carbon dioxide to produce a cosmetic material containing carbon dioxide. In terms of manufacturing method, although this method seems to be simple, in order to dissolve the carbon dioxide injected into the container into the container (please read the note on the back and fill in the page) ------------- - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1293031 A7 ------- B7 V. Description of invention (/production) Water or alcohol to produce cosmetic raw materials containing a certain amount of carbon dioxide The high concentration of carbon dioxide must be dissolved, so the pressure of carbon dioxide must be increased. Therefore, the container used must have a sufficient pressure resistant construction. Further, since the dissolution of the carbon oxide occurs only on the surface of the liquid in contact with the gas, it is necessary to dissolve the high concentration of carbon dioxide over a long period of time. Regarding the time problem, it is generally believed that if the carbon dioxide is injected under pressure and placed in a closed state, the dissolution will automatically proceed slowly, so the dissolution for the product preservation process will continue. However, in order to achieve this, it is necessary to fully ensure the space occupied by carbon dioxide in the container. This inevitably leads to a decrease in the amount of cosmetic raw materials in Guyi. In order to eliminate the above disadvantages, the inventors of the present invention have invented a process for dissolving carbon monoxide in a process of dissolving carbon monoxide in a composition and a process in which a carbon dioxide-containing composition obtained by the above process is filled in a container. A method of producing a composition. The dissolution process for dissolving carbon dioxide in the composition is preferably carried out in a single process in which the aqueous solution of the carbon dioxide-free composition is adjusted to bring the aqueous solution into contact with carbon dioxide. The best thing about this is to degas the raw water glutinous solution. In addition, since the solubility of carbon dioxide in liquids such as water increases due to low temperature, it should be dissolved in the raw material aqueous solution at 3 or less, preferably at 25 ° C or lower. In addition, the use of increased carbon dioxide is in contact with the aqueous raw material solution. The device of the area is preferred. When the viscosity of the aqueous solution of the raw material is low, it is found that the carbon dioxide dissolver can be used to dissolve the carbon dioxide in the raw material aqueous solution in a short time. The above-mentioned membrane type carbon dioxide dissolver is exemplified by, for example, Japanese Patent No. 2810694 or special open = The hollow film used in the bulletin can increase the gas and liquid. 16 The paper size is applicable to the China National Standard (CNS) A4 specification (210 X 297 mil) ~ ------- (please read the back first) Note: Please fill out this page) tr---------Line, 1293031 A7 _____ B7 _ V. Invention description (丨f) It is better to have contact area and efficiency. When using membrane carbon dioxide dissolver, Since the front or rear section is continuously provided with a precision filtering device, it is possible to easily obtain a sterilized composition for percutaneous absorption of carbonic acid by filtering bacteria or foreign matter. On the other hand, it contains high water solubility. In the case of a raw material composition having a large viscosity, the aqueous solution may be placed in a pressurized container such as a pressure cooker equipped with a stirring device, and the aqueous solution may be degassed while stirring, and then the carbon dioxide may be pressurized to dissolve it in the aqueous solution. Although it is convenient to supply carbon dioxide to the pump, it is also possible to first put the solid carbon dioxide (dry ice) together with the aqueous solution into the local pressure cooker and then seal it. In addition, in the device which can continuously dissolve carbon dioxide in the high viscosity aqueous solution, for example, It is also preferred to introduce carbon dioxide into the wet wall device or the static stirrer to make it contact with the aqueous solution or to dissolve it in the aqueous solution, and then take out the composition. The pressure range of carbon dioxide is 0.1-0.5. MPa is preferable. The composition obtained by the above method and having 300 ppm or more of carbon dioxide dissolved therein is sealed and stored in various containers for individual purposes. The storage container preferably disperses carbon dioxide through the wall of the container, and is a plastic product. With polyethylene terephthalate (PET) or chloroacetonitrile, acrylonitrile polymer A material having low permeability is preferred. In addition, a metal sprayer is also a preferred container when a metal such as aluminum is formed into a foil-like packaging material or a low viscosity. If the composition contains water-soluble properties with thermal gelation properties. The polymer is preferably dispersed in water or an aqueous solution containing trehalose or a low molecular salt at a gelation temperature or higher, because the polymer is below the gelatinization temperature and the paper size is applicable to the Chinese national standard ( CNS)A4 specification (210 X 297 mm) (Please read the note on the back and fill out this page) Order--------Line 1293031 A7 ___B7 ____ V. The invention description (ίί) dissolves quickly. Even if the viscosity of the aqueous solution rises by several %, it is difficult for the polymer to be uniformly dissolved. On the other hand, when the polymer is dispersed in the solution at a gelation temperature or higher, since the polymer does not dissolve, the viscosity of the solution is low, so that a uniform dispersion solution can be obtained. Further, the dispersion solution is stirred and cooled at a temperature lower than the gelation temperature to obtain a uniform aqueous polymer solution. The higher the solubility of the lower temperature carbon dioxide, the more the above homogeneous solution is charged to the carbon dioxide dissolving device under cooling, the carbon dioxide will be dissolved in the solution. However, it is preferable to use a method of cooling a low-viscosity dispersion solution and dissolving carbon dioxide therein. The cooling temperature is 30 ° C, preferably 25 ° C or less, preferably 20 ° C or less. The concentration of carbon dioxide in the composition adjusted by the above method can be obtained by the following methods. The carbon dioxide electrode method or chemical titration using standard reagents is effective for tap water or low viscosity liquids, but cannot be used in high enthalpy composition. In the present invention, the high-viscosity composition containing a water-soluble polymer utilizes the mass of carbon dioxide absorbed in the carbon dioxide dissolution process and the blood circulation promoting action of the composition to determine its concentration qualitatively. The composition for percutaneous absorption of carbonic acid of the present invention is used as a foundation lotion for utilizing blood circulation promoting action to maintain the health of the facial skin and for beauty. Specifically, it maintains skin moisture, improves black spot freckles, and improves youth. Acne, improve the skin after sun exposure, whitening effect, improve wrinkles and other effects. In addition, because carbon dioxide has a blood circulation effect, it can be used as a keratin β hair growth agent, or as a keratin softener for a more developed part of the stratum corneum of the body ankle or elbow. In addition, it is also possible that the cure is generally considered to be by the skin dryness. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -----I-book-------- (Please read the precautions on the back and fill out this page) 1293031 B7 V. INSTRUCTIONS (7) Atopic dermatitis caused by dryness. In addition, the high-viscosity carbonic acid percutaneous absorption composition has the above-mentioned effects in addition to being used as a slimming article, and can be promoted or affixed to the affected part of the bloodstream, such as the acne affected part of the bed patient for a long time, thereby promoting blood circulation of the affected part. And achieve a healing effect. The present invention will be further described by the following examples, reference examples and comparative examples, but the technical scope of the present invention is not limited to the examples herein. Reference Example 1 Tap water was used in a hollow helium film type carbon dioxide dissolver to prepare carbonated water containing carbon dioxide at different concentrations. The concentration of carbon dioxide is adjusted by varying the flow rate of tap water and the flow of carbon dioxide supplied to the carbon dioxide dissolver. The free carbonic acid concentration contained in the carbonated water was measured by a carbon dioxide electrode (manufactured by ORION RESEARCH). The relationship between the carbon dioxide concentration of the carbonated water and the pH 如图 is shown in Fig. 1. Table 1 Effect of trehalose content and carbonated lotion (Example 1) Lotion number trehalose content (wt%) Evaluation of irritating subjects (number of people) Degree of moisturization of skin _ Whitening 1 0.1 10 12 10 2 0.5 6 14 14 3 1.0 4 15 14 4 2.0 3 16 15 5 (Comparative example) 0 18 5 8 Example 1 19 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Please read the back note first. Please fill out this page again

I I 4 A7 1293031 ____B7_______ 五、發明說明（/7 ) 使用離子交換水（DI水）並以參考例1之相同方法調製含有ΙΟΟΟρρηι游離碳酸的碳酸水。再於該碳酸水中，如表1所示含量，添加海藻糖製成化粧水。該化粧水pH値爲4.6。之後，將該化粧水與做爲對照之用不含海藻糖之碳. 酸水使用在自認肌膚乾燥之受試女子20名（年齡：23-53 歲），每日早晚各一次使用於臉部，進行爲期20天的試用測試。評估項目針對了抱怨其臉部刺痛等「對於皮膚具有刺激性」的人數，以及就「皮膚滋潤」、「美白」兩項相較於使用前認爲具有改善效果的人數進行調查。其結果彙整於表1。結果顯示本發明之含有海藻糖與二氧化碳的化粧水，雖然pH値偏低僅4.6，但刺激性小，且具有滋潤皮膚與美白效果。比較例1 在與實施例1相同之含有l〇〇〇PPm游離碳酸的DI水中，添加表2所列之保濕劑2wt%製成化粧水。不過，透明質酸鈉溶液因其增黏效果較大’故在水溶液中添加 3wt%。調製而成的化粧水pH値均爲4.6。針對各化粧水，與實施例1相同，使用在20名女性受試者的臉部，進行爲期1週的試用測試’評估項目則只針對「皮膚刺激性」進行調查。其結果彙整於表2。表2保濕劑與皮膚的刺激性（比較例1 ) 20 ________- (請先閱讀背面之注音？事項再填寫本頁) -J · tl--------- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 1293031 _____ B7___ 五、發明說明（^ ) sssm 保濕劑種類抱怨具刺激性人數 " ϊ "Ίϊΐ 14 2 1，3-丁二醇 15 3 二甘醇 15 4 山梨糖醇 14 5 透明質酸鈉 14 實施例2 以參考例1之相同方法在DI水中溶解濃度各異的二氧化碳製成碳酸水。之後，在各碳酸水中溶解海藻糖使其最終濃度爲2wt%而得到碳酸經皮吸收用組成物。再使此組成物充分滲入長3cm、寬1.5cm、厚3mm的脫脂棉片後，黏貼於手腕內側之白色皮膚5分鐘並觀察皮膚狀態。其結果彙整於表3。表3二氧化碳濃度與皮膚紅化程度（實施例2) 組成物編號二氧化碳濃度 (ppm) 組成物pH値皮膚紅化程度 1 1000 4.6 大 2 500 4.8 中 3 300 4.9 小 4 (比較例） 250 5.0 dfirt： Μ 大、中、小爲紅化程度，無爲無紅化現象。皆以目視判斷。本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） %------ (請先閱讀背面之注意事項再填寫本頁) 訂---------^9! 21 1293031 A7 __— B7____ 五、發明說明（^) 實施例3 以參考例1之相同方法調製含有lOOOppm游離碳酸的碳酸水，再添加下列化合物調製成化粧水。甘油 2wt% 海澡糖 0.5wt% 透明質酸鈉 0.03wt% 檸檬酸 0.05wt% 將此化粧水使用在具有油性肌膚的女性受試者（年齡 20-35歲）10名，每日早晚各一次塗抹於臉部並觀察肌膚改善之情況。其結果爲2週後起有8名受試者認爲可改善青春痘等膿庖。實施例4 以實施例1之相同方法調製含有l〇〇〇PPm游離碳酸的碳酸水，再添加下列化合物調製成化粧水。甘油 5wt% 海藻糖 0.5wt% 透明質酸鈉 0.03wt°/〇檸檬酸 0.05wt% 曲酸 0.5wt% 將此化粧水使用在抱怨臉部缺少光澤的女1'生< 年齢30-50歲）10名，每日早晚各一次塗抹於臉部並針對 22 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 (請先閱讀背面之注意事項再填寫本頁)I I 4 A7 1293031 ____B7_______ V. Description of the Invention (/7) Carbonated water containing ΙΟΟΟρρηι free carbonic acid was prepared by using ion-exchanged water (DI water) in the same manner as in Reference Example 1. Further, in the carbonated water, as shown in Table 1, trehalose was added to prepare a lotion. The lotion has a pH of 4.6. After that, the lotion is used as a control with carbon containing no trehalose. The sour water is used in 20 women (aged: 23-53 years old) who are self-identifying dry skin, and used once a day in the morning and evening. , for a 20-day trial test. The evaluation project was conducted to investigate the number of people who were "irritating to the skin" such as tingling their faces, and the number of people who thought that they had improved effects compared with "skin moisturizing" and "whitening". The results are summarized in Table 1. As a result, it was revealed that the makeup water containing trehalose and carbon dioxide of the present invention has a low pH of 4.6, but is less irritating and has a moisturizing effect on the skin and whitening. Comparative Example 1 In the same DI water containing l〇〇〇PPm free carbonic acid as in Example 1, 2% by weight of the humectant listed in Table 2 was added to prepare a lotion. However, the sodium hyaluronate solution has a large viscosity-increasing effect, so 3 wt% is added to the aqueous solution. The pH of the prepared lotion was 4.6. For each lotion, in the same manner as in the first embodiment, the face of 20 female subjects was used for a one-week trial test. The evaluation item was only investigated for "skin irritation". The results are summarized in Table 2. Table 2 Humectant and skin irritation (Comparative Example 1) 20 ________- (Please read the phonetic transcription on the back side and then fill out this page) -J · tl--------- This paper size applies to China Standard (CNS) A4 specification (210 X 297 mm) A7 1293031 _____ B7___ V. Description of invention (^) sssm Type of humectant complains of irritating number " ϊ "Ίϊΐ 14 2 1,3-butanediol 15 3 Diethylene glycol 15 4 Sorbitol 14 5 Sodium hyaluronate 14 Example 2 Carbon dioxide water was prepared by dissolving carbon dioxide of various concentrations in DI water in the same manner as in Reference Example 1. Thereafter, trehalose was dissolved in each of the carbonated water to a final concentration of 2% by weight to obtain a composition for percutaneous absorption of carbonic acid. Then, the composition was sufficiently infiltrated into a cotton pad having a length of 3 cm, a width of 1.5 cm, and a thickness of 3 mm, and then adhered to the white skin on the inner side of the wrist for 5 minutes and the skin condition was observed. The results are summarized in Table 3. Table 3 Carbon dioxide concentration and degree of skin redness (Example 2) Composition number Carbon dioxide concentration (ppm) Composition pH 値 Skin redness degree 1 1000 4.6 Large 2 500 4.8 Medium 3 300 4.9 Small 4 (Comparative example) 250 5.0 dfirt : Μ Large, medium and small are the degree of redness, and there is no redness. They are judged by visual inspection. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) %------ (Please read the note on the back and fill out this page) Order ---------^ 9: 21 1293031 A7 __- B7____ V. Description of Invention (^) Example 3 Carbonated water containing 1000 ppm of free carbonic acid was prepared in the same manner as in Reference Example 1, and the following compound was added to prepare a lotion. Glycerin 2wt% Sea Bath Sugar 0.5wt% Sodium Hyaluronate 0.03wt% Citric Acid 0.05wt% Apply this lotion to 10 female subjects (aged 20-35 years old) with oily skin, once a day in the morning and evening. Apply to the face and observe the improvement of the skin. As a result, 8 subjects thought that it could improve purulent sputum such as acne after 2 weeks. Example 4 Carbonated water containing l〇〇〇PPm free carbonic acid was prepared in the same manner as in Example 1, and the following compound was added to prepare a lotion. Glycerin 5wt% trehalose 0.5wt% sodium hyaluronate 0.03wt ° / citric acid 0.05wt% kojic acid 0.5wt% This lotion is used in women who complain of lack of luster on the face 1 'sheng < 30-50 years old 10 people, apply once a day to face and apply Chinese National Standard (CNS) A4 size (210 X 297 mm) for 22 paper sizes (please read the back note and fill out this page)

A7 1293031 五、發明說明（>^ ) 缺少光澤的改善效果進行調查。其結果爲2週後起有7名受試者認爲可改善臉部缺少光澤。實施例5 調製含有下列組成物之DI水1Kg做爲化粧水原水。海藻糖 lwt% 甘油 2.5wt% L-絲氨酸 lwt% 鹽鹵液（30%溶液） 3wt% 再將此化粧水原水分別通過精密過濾器，以及與參考例1之二氧化碳溶解器相連之裝置，以同時進行異物過濾與溶解二氧化碳。所得之化粧水中溶解了 1000ppm的二氧化碳（以二氧化碳供給量計算），pH値爲4.8。針對此化粧水，以實施例2之相同方法，進行皮膚紅化測試時皮膚呈現了紅化現象。此外，以實施例1之相同方法，針對女性受試者進行皮膚刺激性測試，結果20名中抱怨有刺激感的女性有3名。實施例6 以實施例5之相同方法調製含有下列成分之碳酸經皮吸收用組成物。海藻糖 2Wt% 甘油 2.5wt% 23 本紙張尺度適用中國國家標準（CNS)A4規格（2l〇 X 297公爱） ___Ί4—V----------II 訂---------—·· (請先閱讀背面之注意事項再填寫本頁) __ 1293031 B7 五、發明說明（IV) 尿素 5wt°/〇游離碳酸 15〇〇p PH 4.5 (請先閱讀背面之注意事項再填寫本頁) 將此組成物使用在腳踵乾燥且龜裂嚴重之受試者（男性，59歲），每天早晨塗抹於右側腳踵並觀察夜晚沐浴後腳鍾龜裂之改善情形。約1週時間即可觀察到龜裂之改善。實施例7 DI水lKg中溶解硫酸鈉並使其最終濃度爲3wt%。將此水溶液加熱至50-60°C後，使甲基纖維素（2wt%水溶液黏度之型錄値爲1500mPa.s)分散其中。再將該分散溶液冷卻至30°C (此狀態下聚合物不發生溶解而呈現分散狀態 )並充塡配備有1.5L攪拌機之高壓鍋內且密閉之。在此狀態下一邊攪拌並以真空幫浦脫氣30分鐘後，將高壓鍋冷卻至15°C。再將真空管線切換至二氧化碳供給管線，經由二氧化碳幫浦供給高壓鍋〇.2MPa的二氧化碳。隨著時間推移，二氧化碳溶解於水溶液將使得高壓鍋壓力降低，此時供給適量之二氧化碳使壓力回復至0.2MPa。圖2所示爲由高壓鍋之氣體空間容積與壓力變化所求得之水溶液所吸收之二氧化碳質量與時間的關係。數據顯示30分鐘可溶解4g以上的二氧化碳。使二氧化碳溶解4 小時後將高壓鍋開封並將水溶液收納於保特瓶。水溶液於高壓鍋開封的同時將明顯發生氣泡，此時聚合物尙未完全本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1293031 A7 _ B7_ 五、發明說明（1) 溶解而呈現半透明狀態。若將保特瓶保存於冰箱一夜，聚合物將持續溶解而呈現透明狀溶液。取該溶液之一部份置於試管內，再放置在恆溫水槽中一邊升溫並考察其增黏情形。結果顯示自30°C左右起出現急速增黏現象，故以30°C 爲溶膠一凝膠轉移溫度。實施例8 將實施例7中所調製的碳酸經皮吸收用組成物40ml 平鋪於培養皿（開放面積56.7cm2)後，在室溫（約18它 )下置於空氣中並追蹤其pH値的變化。做爲比較之用，在相同條件下，亦針對碳酸水與自來水（空白測試）進行考察。其結果如表4所示。結果顯示本發明之碳酸經皮吸收用組成物與碳酸水相較之下，其pH値變化小而二氧化碳的逸散速度慢。表4放置時間與pH値間的變化（實施例8) 試劑室溫下的放置時間（分) 0 20 60 90 150 本發明之組成物 4.5 4.6 4.8 4.8 4.9 碳酸水 4.4 4.6 4.8 4.9 5.2 自來水 6.6 6.6 6.6 6.6 6.6 實施例9 以實施例7之相同方法調製碳酸經皮吸收用組成物。 25 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----I J---v------------^--------- (請先閱讀背面之注意事項再填寫本頁) 1293031 B7 ____ 五、發明說明（β 不過，本實驗在除硫酸鈉外另添加2wt%海藻糖的水溶液中，以實施例7之相同方法，使甲基纖維素分散其中且二氧化碳亦溶解其中。所得二氧化碳溶解曲線與實施例7大致相同。此外，該溶液之溶膠一凝膠轉移濃度爲30 C ’ pH 値爲4.5。之後，將保存於冰箱中之該碳酸經皮吸收用組成物在30°C的環境下放置半天使其黏度增加，再以實施例2 之相同方法進行皮膚紅化測試。做爲比較之用’亦針對碳酸水進行測試。該實驗中黏貼皮膚的時間分別爲5、10、 20、30分鐘並觀察各時間的效果。結果如表5所示。根據測試結果，以碳酸水爲例，隨著時間推移，因二氧化碳逸散紅化現象將消失，而本發明之碳酸經皮吸收用組成物即使經過30分鐘仍可見到紅化現象。表5皮膚紅化測試（實施例9 ) 試劑 5 皮膚黏貼時間（分） 10 20 30 本發明之組成物中大大大碳酸水（pH値= 大大小 Μ j\\\ 4.4) 大 '中、小爲紅化程度，無爲無紅化現象。皆以目視判斷實施例10 以碳酸氫鈉取代硫酸鈉調製成5wt%水溶性，再以實 26A7 1293031 V. INSTRUCTIONS (>^) The lack of gloss improvement effect was investigated. As a result, 7 subjects thought that it could improve the lack of luster of the face from 2 weeks later. Example 5 1 kg of DI water containing the following composition was prepared as a lotion raw water. Trehalose lwt% glycerin 2.5 wt% L-serine lwt% salt brine (30% solution) 3 wt% The makeup water raw water was passed through a precision filter and a device connected to the carbon dioxide dissolver of Reference Example 1 at the same time. Foreign matter filters and dissolves carbon dioxide. The obtained lotion was dissolved with 1000 ppm of carbon dioxide (calculated as the amount of carbon dioxide supplied), and the pH was 4.8. With respect to this makeup water, in the same manner as in Example 2, the skin was reddened when the skin redness test was performed. Further, skin irritation test was conducted on female subjects in the same manner as in Example 1, and as a result, 3 out of 20 women complained of irritation. Example 6 A carbonic acid percutaneous absorption composition containing the following components was prepared in the same manner as in Example 5. Trehalose 2Wt% Glycerin 2.5wt% 23 This paper scale applies to China National Standard (CNS) A4 specification (2l〇X 297 public) ___Ί4—V----------II ------ ----·· (Please read the notes on the back and fill out this page) __ 1293031 B7 V. INSTRUCTIONS (IV) Urea 5wt°/〇 free carbonic acid 15〇〇p PH 4.5 (Please read the notes on the back first) Fill in this page again. Use this composition on subjects with dry ankles and severely cracked (male, 59 years old), apply to the right ankle every morning and observe the improvement of the foot clock crack after bathing at night. An improvement in cracking was observed in about 1 week. Example 7 Sodium sulfate was dissolved in 1 kg of DI water and brought to a final concentration of 3 wt%. After heating the aqueous solution to 50-60 ° C, methyl cellulose (having a viscosity of 2 wt% aqueous solution of 1500 mPa·s) was dispersed therein. The dispersion solution was further cooled to 30 ° C (in this state, the polymer did not dissolve to exhibit a dispersed state) and was filled in an autoclave equipped with a 1.5 L stirrer and sealed. After stirring in this state and degassing with a vacuum pump for 30 minutes, the autoclave was cooled to 15 °C. The vacuum line was switched to a carbon dioxide supply line, and a carbon dioxide pump was supplied to the autoclave at a pressure of 2 MPa of carbon dioxide. Over time, carbon dioxide dissolved in the aqueous solution will reduce the pressure in the autoclave, at which point an appropriate amount of carbon dioxide is supplied to restore the pressure to 0.2 MPa. Figure 2 shows the relationship between the mass of carbon dioxide absorbed by the aqueous solution obtained from the gas space volume and pressure change of the autoclave and time. The data shows that more than 4 g of carbon dioxide can be dissolved in 30 minutes. After dissolving the carbon dioxide for 4 hours, the autoclave was opened and the aqueous solution was stored in a PET bottle. When the aqueous solution is opened in the autoclave, bubbles will obviously appear. At this time, the polymer is not completely in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1293031 A7 _ B7_ V. Description of the invention (1) Dissolution Renders a semi-transparent state. If the PET bottle is stored in the refrigerator overnight, the polymer will continue to dissolve and present a clear solution. One part of the solution was placed in a test tube, and placed in a constant temperature water bath while warming up and examining the viscosity-increasing condition. The results showed that the rapid viscosity increase occurred from about 30 ° C, so the temperature of the sol-gel transfer was 30 ° C. Example 8 40 ml of the carbonic acid percutaneous absorption composition prepared in Example 7 was spread on a Petri dish (open area: 56.7 cm 2 ), and then placed in the air at room temperature (about 18 Å) and the pH was traced. The change. For comparison purposes, carbonated water and tap water (blank test) were also examined under the same conditions. The results are shown in Table 4. As a result, it was revealed that the carbonic acid percutaneous absorption composition of the present invention has a small change in pH 而 and a slow rate of diffusion of carbon dioxide as compared with carbonated water. Table 4 Changes in settling time and pH ( (Example 8) Retention time of reagent at room temperature (minutes) 0 20 60 90 150 Composition of the present invention 4.5 4.6 4.8 4.8 4.9 Carbonated water 4.4 4.6 4.8 4.9 5.2 Tap water 6.6 6.6 6.6 6.6 6.6 Example 9 A carbonic acid percutaneous absorption composition was prepared in the same manner as in Example 7. 25 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----I J---v------------^------- -- (Please read the precautions on the back and fill out this page) 1293031 B7 ____ V. Inventive Note (β However, this experiment is the same as in Example 7 except that an additional 2 wt% trehalose is added to the solution except sodium sulfate. Methylcellulose was dispersed therein and carbon dioxide was also dissolved therein. The obtained carbon dioxide dissolution profile was substantially the same as in Example 7. Further, the solution had a sol-gel transfer concentration of 30 C 'pH 値 of 4.5. Thereafter, it was stored in The carbonic acid percutaneous absorption composition in the refrigerator was placed in a 30 ° C environment to increase the viscosity of the half angel, and the skin redness test was carried out in the same manner as in Example 2. For comparison, 'also for carbonated water Test. The time of sticking to the skin in this experiment was 5, 10, 20, 30 minutes, respectively, and the effect of each time was observed. The results are shown in Table 5. According to the test results, taking carbonated water as an example, with time, due to carbon dioxide The phenomenon of reddening redness will disappear, and the carbonic acid percutaneous of the present invention The reddening phenomenon was observed even after 30 minutes of the composition. Table 5 Skin redness test (Example 9) Reagent 5 Skin adhesion time (minutes) 10 20 30 Large carbonic acid water (pH値) in the composition of the present invention = Large size Μ j\\\ 4.4) Large 'medium and small are reddening degree, no redness. Nothing is visually judged. Example 10 is prepared by substituting sodium bicarbonate for sodium sulphate to prepare 5 wt% water-soluble. 26

本紙張尺度綱中國國家標準（CNS)A4規格（210 X 297公楚Y (請先閱讀背面之注意事項再填寫本頁) 1!1111 4 1293031 a7 _________B7_____ 五、發明說明（/) 施例7之相同方法，調製甲基纖維素之分散溶液並使二氧化碳溶解其中。所得二氧化碳溶解曲線如圖2所示。由圖 2得知二氧化碳在30分鐘內可溶解於水溶液中5g以上。經4小時溶解後，溶液將成半透明狀態而伴隨高壓鍋的開放出現明顯的氣泡。若以實施例7之相同方法將水溶液裝入保特瓶中並置於冰箱保存一夜可得到透明的溶液。此溶液pH値爲7.3。溶膠一凝膠轉移溫度爲32°C。若將保存於冰箱內的溶液置於35°C的環境下半天使其黏度增加，再以實施例9之相同方法進行紅化測試，可在5-30分鐘的黏貼時間內確認皮膚產生紅化現象。實施例11 以料理用市售明膠調製成2wt%的水溶液lKg。將此水溶液裝入高壓鍋，在30°C下一邊攪拌並於30分鐘減壓狀態下保存於真空幫浦。接著以幫浦將0.2 MPa的二氧化碳導入其中並加壓1小時。其間，由於二氧化碳被明膠水溶液吸收之故，隨著高壓鍋的壓力降低，壓力將回復爲 0.2MPa。藉由計算高壓鍋的空間與二氧化碳的減壓度，得知被明膠水溶液所吸收的全部二氧化碳量爲800ppm。此外，該明膠水溶液的pH値爲5.5。而該明膠水溶液放置在室溫（約20°C )下將產生膠化現象。若將該明膠水溶液含浸於30°C的溫水，使其呈現溶膠狀態，再以實施例2之相同方法進行皮膚的紅化測試，其結果顯示儘管分別改變黏貼於皮膚的時間爲5分、10分、20分，各時間皆可確認皮膚 27 __________ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1------—訂--------- (請先閱讀背面之注意事項再填寫本頁) _ 1293031 A7 ______Β7___ 五、發明說明（％) 產生紅化現象。實施例12 將實施例Π中所調製之溶解有二氧化碳的明膠水溶液放置在室溫（約20°C )下使其產生膠化現象後，先以杓刮取並平鋪於培養皿中，再置於空氣中並經由pH値變化考察二氧化碳的逸散速度。做爲比較之用，在相同條件下亦針對碳酸水進行考察。其結果如表6所示，當處於凝膠狀態時，與碳酸水相較，其pH値變化小，而二氧化碳逸散速度亦小。表6放置時間與pH値間的變化（實施例12) 試劑 0 室溫下之放置時間（分） 20 50 110 190 本發明之組成 5.5 5.5 5.5 5.6 5.7 物碳酸水 4.4 4.6 4.8 5.0 5.4 實施例13 以實施例11之相同方法使明膠水溶液吸收二氧化碳。不過，此實驗中以2小時加壓供給0.2MPa的二氧化碳，使水溶液中吸收1500ppm的二氧化碳而pH値爲4.8。之後，將該溶解有二氧化碳的明膠水溶液在溶膠狀態下塗佈於 100 mm四方、厚3mm的氈墊布狀片上。並在溶膠浸透於 28 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）This paper scales the Chinese National Standard (CNS) A4 specification (210 X 297 public Chu Y (please read the back note first and then fill this page) 1!1111 4 1293031 a7 _________B7_____ V. Invention Description (/) Example 7 In the same way, a dispersion solution of methyl cellulose is prepared and carbon dioxide is dissolved therein. The obtained carbon dioxide dissolution curve is shown in Fig. 2. It can be seen from Fig. 2 that carbon dioxide can be dissolved in an aqueous solution of 5 g or more in 30 minutes. The solution will be in a translucent state with obvious air bubbles accompanying the opening of the autoclave. If the aqueous solution is placed in a PET bottle in the same manner as in Example 7 and stored in a refrigerator overnight, a clear solution can be obtained. The pH of the solution is 7.3. The sol-gel transfer temperature is 32 ° C. If the solution stored in the refrigerator is placed in a 35 ° C environment, the viscosity of the half angel increases, and then the red test is performed in the same manner as in Example 9, which can be performed at 5 The skin was confirmed to have a reddening effect within a -30 minute pasting time. Example 11 A vegetable solution of commercially available gelatin was used to prepare a 2 wt% aqueous solution of 1 kg. This aqueous solution was placed in an autoclave at 30 ° C. While stirring, the vacuum pump was stored under reduced pressure for 30 minutes. Then, 0.2 MPa of carbon dioxide was introduced into the pump and pressurized for 1 hour. During this time, as the carbon dioxide was absorbed by the gelatin aqueous solution, the pressure of the pressure cooker was lowered. The pressure will return to 0.2 MPa. By calculating the space of the autoclave and the degree of decompression of carbon dioxide, it is found that the total amount of carbon dioxide absorbed by the aqueous gelatin solution is 800 ppm. Further, the pH of the aqueous gelatin solution is 5.5. When it is placed at room temperature (about 20 ° C), gelation occurs. If the gelatin aqueous solution is impregnated with warm water at 30 ° C to give a sol state, the skin reddening is carried out in the same manner as in Example 2. The results of the test showed that although the time to adhere to the skin was changed to 5, 10, and 20, the skin was confirmed at each time. 27 __________ This paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1-------book--------- (please read the notes on the back and fill out this page) _ 1293031 A7 ______Β7___ V. Invention description (%) Redness occurs. Example 12 The gelatin solution prepared by dissolving carbon dioxide prepared in the Example 放置 was placed at room temperature (about 20 ° C) to cause gelation, and then scraped and smeared in a Petri dish. It was placed in the air and the rate of escape of carbon dioxide was examined via pH 。. For comparison purposes, carbonated water was also examined under the same conditions. The results are shown in Table 6, when in the gel state, with carbonic acid. Compared with the aqueous phase, the pH 値 change is small, and the carbon dioxide escaping speed is also small. Table 6 The change between the standing time and the pH ( (Example 12) Reagent 0 The standing time at room temperature (minutes) 20 50 110 190 The present invention Composition 5.5 5.5 5.5 5.6 5.7 Carbonic acid water 4.4 4.6 4.8 5.0 5.4 Example 13 An aqueous gelatin solution was subjected to carbon dioxide absorption in the same manner as in Example 11. However, in this experiment, 0.2 MPa of carbon dioxide was supplied under pressure for 2 hours, and 1500 ppm of carbon dioxide was absorbed in the aqueous solution to have a pH of 4.8. Thereafter, the gelatin solution in which carbon dioxide was dissolved was applied to a 100 mm square and 3 mm thick felt cloth sheet in a sol state. And in the sol soaked on 28 paper scales, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable.

I績 ί請先閱讀背面之注意事項再填寫本頁) 訂--- 1293031 a7 _ __B7__ 五、發明說明（/^) 賣毛墊布內部但表面仍有2 mm左右溶液殘留的狀態下’立即保存於2°C的冰箱中使其產生膠化現象。膠化後’片狀物將成爲容易使用並可以剪刀裁成任意尺寸的物品。再以剪刀裁成寬15 mm、長30mm後’黏貼於手腕內側皮膚並觀察皮膚紅化程度。黏貼時間分別爲5、10、20分鐘。結果顯示5分鐘內雖未出現紅化現象，自1〇分鐘後起即可觀察到皮膚產生紅化現象。【發明效果】由本發明之碳酸經皮吸收用組成物所製成的化粧水，雖因含有高濃度二氧化碳而pH値較低，但在海藻糖的作用下，除可減緩其刺激性外，在二氧化碳之血液循環促進作用下，亦可達成促進臉部皮膚健康、美容（肌膚水嫩、美白、消除青春痘等膿庖）、改善粗糙皮膚的效果。此外，利用水溶性高分子的相轉移現象所得之含有高濃度二氧化碳，且使用時二氧化碳較少逸散於空氣中的碳酸經皮吸收用組成物’將可能用於塗袜或黏貼於人體患部，藉以促進血液循環，達到治癒的效果。 [圖式之簡單說明] 圖1爲參考例之一 ’用以袠示碳酸水之二氧化碳濃度與pH値間的關係圖。圖2爲使用高壓鍋時二氧化碳對於水溶液的溶解曲線。本紙張尺度適用中國國家標準（CNS)A4規格 ,!ιβ!!ιαψ (請先閱讀背面之注意事項再填寫本頁) 訂--- 考I. Please read the notes on the back and fill out this page. Order--- 1293031 a7 _ __B7__ V. Invention description (/^) Selling the inside of the felt pad but the surface still has about 2 mm of residual solution. Store in a refrigerator at 2 ° C to cause gelation. After gelatinization, the sheet will be easy to use and can be cut into any size by scissors. Then cut into a width of 15 mm and a length of 30 mm with a pair of scissors, and then adhere to the inner side of the wrist and observe the degree of redness of the skin. The bonding time is 5, 10, 20 minutes respectively. The results showed that although redness did not occur within 5 minutes, redness of the skin was observed from 1 minute later. [Effect of the Invention] The lotion prepared by the carbonic acid percutaneous absorption composition of the present invention has a low pH due to the high concentration of carbon dioxide, but in addition to stimulating the irritating property under the action of trehalose, Under the promotion of blood circulation of carbon dioxide, it can also achieve the effect of promoting facial skin health, beauty (skin tenderness, whitening, elimination of purulent acne, etc.) and improving rough skin. In addition, the carbonic acid percutaneous absorption composition obtained by the phase transfer phenomenon of the water-soluble polymer and containing a high concentration of carbon dioxide, and the carbon dioxide is less likely to escape in the air during use, may be used for applying socks or sticking to the affected part of the human body. In order to promote blood circulation, to achieve a healing effect. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing the relationship between the carbon dioxide concentration of carbonated water and pH 之一. Figure 2 is a graph showing the dissolution profile of carbon dioxide for an aqueous solution when using an autoclave. This paper scale applies to China National Standard (CNS) A4 specifications, !ιβ!!ιαψ (please read the notes on the back and fill out this page) Order---

Claims

Β8 C8 D8 1293031 Patent Application No. 1 A composition for percutaneous absorption of carbonic acid, characterized in that it contains: free carbonic acid of 300 Ppm or more, and the essence of trehalose o.iwt% to l〇wt% is an essential component It is composed of an aqueous solution containing no bubble-like carbon dioxide, and has a pH 値 (hydrogen ion concentration) of less than 5. 2. The composition for percutaneous absorption of carbonic acid according to item 1 of the patent application is applicable to lotions. 3. A composition for percutaneous absorption of carbonic acid, which is a composition comprising at least 0.5 wt% to 5 wt% of water, a water-soluble polymer, and free carbonic acid, and the free carbonic acid concentration in the composition is 300 ppm or more, substantially Is not in the form of bubbles and is in a dissolved state; characterized in that the composition has a sol-gel transfer or a gel-sol transfer (phase transfer) property, and the transfer temperature ranges from 〇 ° C to less than 45 ° C. 4. The composition for percutaneous absorption of carbonic acid according to item 3 of the patent application, wherein the trehalose is an essential component. A sheet for percutaneous absorption of carbonic acid, which is obtained by impregnating or/or coating a composition for percutaneous absorption of carbonic acid according to any one of claims 1 to 4 to a sheet-like support. L paper home standard (CNS) Α 4 specifications (210 X 297 mm)