201100110 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種水膠面膜（hydrogel mask pack)，特 別是指一種可變色之感溫水膠面膜及其製備方法。 【先前技術】201100110 VI. Description of the Invention: [Technical Field] The present invention relates to a hydrogel mask pack, and more particularly to a color-changing thermosensitive water gel mask and a preparation method thereof. [Prior Art]
目前市面上的面膜大多是不織布材質，而此種面膜的 製作方式是使調製好的精華液吸附或塗敷於面膜上，再進 行包裝封存，因此，在面膜被使用前，精華液是長時間處 於浸泡於水分中的狀態，容易氧化，且精華液往往是面膜 販售組合中價格成本最高的部分，而當取出面膜敷臉的同 時，精華液也容易沿著面膜的邊緣滴下並逐漸流失，不僅 造成使用者的不便與成本的浪費，亦使得其效果大為降低 。一般市售的不織布面膜敷臉的最佳時間為2〇至3()分鐘 ’倘右敷臉的時間太久，使用者由目視或手接觸面膜表面 往往還會保有濕潤度，但其實面膜敷料中的水分及營養分 都已兀全喪失，尤其是接觸到臉部肌膚那一面的部分則會 因為虹吸原理，將皮膚角質層中的水分再回收到面膜敷料 中，導致皮膚不但不會更加滋潤，嚴重者還有可能會因為 臉部水分的散失而產生刺激性皮膚炎等問題。 近年來，由於水膠之貼附性及吸水效果皆佳，便有一 些人將水膠應用來製作面膜，然：，目前已存在的水膠面膜 都未能有效地鎖住及控制精華液的釋放’或是不清楚其組 分為何，例如：TW 95218502 —案即揭示一種主要包括一 模片的類真皮水晶果床面膜結構，而由該案說明書可知它 201100110 .乍方式疋藉由膜層與肌膚貼觸時，藉由肌膚之體溫逐 漸將活n酵素溶解並單向滲人肌膚深層但是該案中對於 膜片的材質並沒有任何說明，僅提及該膜層主要係由⑽ 活性酵素成分所構成，因此，無法依照該案說明書内容製 備出其所述的水晶果凍面膜。 再者，wo 2008/072817 —案則是揭示一種用於製備水 膠面膜的組成物，該組成物係包含（wt%〜对%的絲心 蛋白（版。in)、〇·4 wt%〜4 wt%之任何—個選自於海薄酸: (alglnate)、纖維素或瓖脂等的天然質，及其餘為水。就該 案=明書中記載的實施例來看，其所揭示的水膠面膜具有 门3 X量好的濕潤效果和拉伸強度，對於肌膚亦有極仵 的服貼性，並可達7〇錢的使用時間而不產生心 ⑽祕喂），但同樣無法從外觀上目測面媒所含之精華液及 水分已釋放至何種程度’亦沒有控制釋放的機制。 【發明内容】 有鑑於習知面膜對於精華液成分的有效鎖住與控制釋 放無法二者兼顧’於是本案發明人結合材料特性的研發與 應用，以期改進面膜之功效並符合使用上的f求，―、 步降低製備之成本。 因此’本發明之第一目的，即在提供一種能適時地鎖 住精華液’且隨著溫度的升高而逐漸變色並調控精華 釋放的可變色之感溫水膠面膜。 ^ ^ 3 囬膜主 及-感溫釋放水膠，該面膜主體係由_包括—海藻酸鹽 201100110 ?二價金屬離子之鹽類化合物、-親水性單體、一化學 交聯劑及-起始劑的混合物經交聯及聚合反應得到之水膠 所構成的網狀結構，其中，該化學交聯劑可與該親水性單 體進行交聯，而該起始劑則用於起始該親水性單體之聚合 反應，而該感1釋放水膠係穿_地位於該面膜主 結構中，並且包括異丙基丙烯酿胺（肠opropylacr加ide， NIPAAm)所形成之水膠。 〇 冑成該面膜主體成分之-的海蒸酸鹽為-種天然的吸 水性高分子，其與鹽類化合物中的二價金屬離子進行交聯 (crosslinking)’可形成一具有網狀結構的水膠型錯化物，另 一成分為由親水性單體藉由化學交聯劑與起始劑的加入， 待進行交聯及聚合反應後，亦為一水膠產物，其作用除了 增強吸收水为與精華液之外，亦可加強海藻酸鹽錯化物的 網狀結構之機械強度與耐水解的穩定度。而異丙基丙烯醯 胺為一具有流動性之單體化合物，其化學式如下式⑴所示 0 ，異丙基丙烯醯胺可滲透進入上述之面膜主體的網狀結構 中，當/參入的異丙基丙烯酿胺進一步進行膠化反應後，便 形成一穿插於該網狀結構中的感溫性水膠，其相轉移溫度 (lower critical solution temperature，LCST)為 32〇C，即接近 LCST時，膠體會有不連續的相轉移發生，當溫度低於32。匸 時’異丙基丙烯酿胺膠體分子結構中的與_c=〇官能基 會與水及精華液之分子產生氫鍵結合，而使水膠吸收膨潤 並鎖住精華液分子；當溫度高於32°C時，所產生之氫鍵結 合力會消失，且異丙基丙烯醯胺膠體分子結構中的_Ch3疏 5 201100110 水性g能基所產生之疏水作用則變得明顯，此時水膠產生 相轉移而收縮（即去膨潤）且降低透光度，而由原本的透明水 朦轉變為乳白色’此相轉移;見象具有可逆性（reversible)，故 夂膠接觸之環丨兄溫度的升高與降低，可控制釋放所含之 精華液成分。 〇 CH2=C-C-S-C-CH3 (I)At present, most of the masks on the market are non-woven materials, and the mask is made by adsorbing or applying the prepared essence onto the mask, and then packaging and sealing. Therefore, the essence is long before the mask is used. It is easy to oxidize when it is immersed in water, and the essence is often the most expensive part of the mask sales combination. When the mask is taken out, the essence is easily dripped along the edge of the mask and gradually lost. Not only does the user's inconvenience and cost are wasted, but the effect is greatly reduced. The best time for a commercially available non-woven mask to apply face is 2〇 to 3() minutes. 'If the right face is applied for too long, the user will still have a moisturizing degree by visual or hand contact with the mask surface, but in fact, the mask dressing The water and nutrients in the skin have been completely lost. In particular, the part that touches the face of the face will reclaim the moisture in the stratum corneum into the mask dressing because of the siphon principle, which will not only moisturize the skin. In severe cases, there may be problems such as irritating dermatitis due to loss of facial moisture. In recent years, due to the adhesion of water gel and the water absorption effect, some people apply water gel to make masks. However, the existing water gel masks have not effectively locked and controlled the essence. Release 'or unclear about its composition, for example: TW 95218502 - the case reveals a dermis-like crystal bed structure mainly consisting of a die, and it is known from the description of the 201100110. When it is in contact with the skin, the skin's body temperature gradually dissolves the living enzyme and penetrates the skin deep into the skin. However, there is no explanation for the material of the film in this case. Only the film layer is mainly composed of (10) active enzyme. Since the composition is composed of the components, the crystal jelly mask described above cannot be prepared in accordance with the contents of the specification. Furthermore, WO 2008/072817 - The case is to disclose a composition for preparing a hydrogel mask comprising (wt% to % fibrin (in.), 〇·4 wt%~ Any one of 4 wt% is selected from the natural qualities of alginic acid, cellulose or blush, and the rest is water. As far as the case is described in the case of the case, it is disclosed. The water-based gel mask has a good moisturizing effect and tensile strength of the door 3 X. It also has a very good applicability to the skin, and can reach a life of 7 而不 without generating a heart (10) secret feeding), but it is also impossible From the appearance, it is visually determined to what extent the essence and moisture contained in the mask have been released, and there is no mechanism for controlling release. SUMMARY OF THE INVENTION In view of the fact that the mask is effective for locking and controlling the release of the essence component, the combination of the material characteristics of the inventor of the present invention is expected to improve the efficacy of the mask and meet the requirements of use. ―, step to reduce the cost of preparation. Therefore, the first object of the present invention is to provide a color-changing thermosensitive water-based gel mask which can lock the essence in a timely manner and gradually change color with an increase in temperature and regulate the release of the essence. ^ ^ 3 Membrane main and - temperature release water gel, the main system of the mask consists of _including - alginate 201100110 - salt compound of divalent metal ion, - hydrophilic monomer, a chemical crosslinker and a network structure formed by cross-linking and polymerization of a water-based gel obtained by crosslinking, wherein the chemical crosslinking agent can be cross-linked with the hydrophilic monomer, and the initiator is used to initiate the The polymerization of the hydrophilic monomer, and the sensation 1 release water gel is located in the main structure of the mask, and includes a water gel formed by isopropyl acrylamide (intestinal opropylacr plus ide, NIPAAm). The seawater acid salt which is a component of the main body of the mask is a natural water-absorbing polymer which crosslinks with a divalent metal ion in the salt compound to form a network having a network structure. The water-gel type is a compound, and the other component is a hydrophilic monomer which is added by a chemical crosslinking agent and a starter agent. After crosslinking and polymerization, it is also a hydrocolloid product, and its action is not only to enhance the absorption water. In addition to the essence, it is also possible to enhance the mechanical strength and hydrolysis stability of the network structure of the alginate complex. The isopropyl acrylamide is a monomer compound having fluidity, and the chemical formula is as shown in the following formula (1). 0, isopropyl acrylamide can penetrate into the network structure of the mask body, when/into After further gelation reaction of the isopropyl acrylamide, a temperature sensitive water gel interposed in the network structure is formed, and the lower critical solution temperature (LCST) is 32 〇C, that is, when it is close to the LCST. The colloid will have discontinuous phase transfer occurring when the temperature is below 32. The _c=〇 functional group in the molecular structure of the isopropyl acrylamide colloid will hydrogen bond with the molecules of water and essence, so that the water gel absorbs and swells and locks the essence molecules; when the temperature is high At 32 ° C, the hydrogen bonding force generated disappears, and the hydrophobic effect of the _Ch3 sparse 5 201100110 aqueous g-energy group in the molecular structure of the isopropyl acrylamide colloid becomes obvious. The glue produces phase transfer and shrinks (ie de-swells) and reduces the transmittance, while the original transparent water hydra is converted to milky white 'this phase transfer; seeing reversible, so the temperature of the ring contact The increase and decrease of the extract can control the release of the essence component contained. 〇 CH2=C-C-S-C-CH3 (I)
Η I ch3 特別說明的是，人體的體内的核心溫度（c〇re b〇dy 〇 temPerature)是維持在37〇c，但是人體的外圍部分（即體壁與 皮膚）的溫度大約為32。〇’恰好相近於異丙基丙稀酿水膠的 相轉移溫度。因此，本發明可變色之感溫水膠面膜於制 時與臉。P的肌膚貼合’至該面膜的溫度達到該感溫釋放水 膠之相轉移溫度時，便開始產生收縮並將精華液釋出，而 且該感溫水膠面膜會由透明逐漸變成乳白色，此時面膜主 體的水膠還含有分佈於其網狀結構中的精華液分子可提供 持續的釋放與潤澤，則該感溫水膠面膜不僅可以藉由面膜 外觀的顏色變化來判斷精華液釋放的情形，並且能持續保 有與肌膚接觸的滋潤，以提昇面膜控制釋放精華液的效果 〇 本發明之第二目的’即在提供一種上述可變色之感溫 水膠面膜的製備方法。 本發明可變色之感溫水膠面膜的製備方法係包含以下 步驟：⑷將一包括一海藻酸鹽、-親水性單體、一化學交 聯劑、-含二價金屬離子之鹽類化合物及—起始劑的混合 6 201100110 物注入一模具中；（b)以紫外光（uitravi〇iet，（jV)照射該步驟 (a)的模具，使其中的混合物經由交聯及聚合反應而得到— 具有網狀結構的水膠面膜主體；（c)使該步驟（b)的面膜主體 浸泡於一含有異丙基丙烯醯胺的溶液内；以及（d)以紫外光 照射該步驟（c)的溶液以使得滲入該面膜主體之網狀結構中 的異丙基丙烯醯胺進行膠化反應，並形成一穿插於該網狀 結構中的感溫釋放水膠，進而製得該可變色之感溫水膠面 〇 膜。 本發明之功效在於：本發明可變色感溫水膠面膜具有 高度的吸水性能完全鎖住精華液成分，使得精華液在保存 期間（即尚未被使用前的存放時間）能被保存於該面膜内而不 致於氧化或變質’當該可變色感溫水膠面膜被使用時，則 可元王貼附於肌膚’精華液更不易滴漏流失，且穿插於其 面膜主體中的感溫釋放水膠會因肌膚溫度的影響產生相轉 移而收縮，使得精華液分子能有效地隨著感溫釋放水膠的 〇 收縮被釋放出來，並使得該面膜變色，同時亦能保持面膜 主體的濕潤度與精華液分子的持續釋放，故確實能達到本 發明之功效。 【實施方式】 發明人跳脫以往的概念，利用溫度來控制精華液的釋 放量，也就是說，將一種會隨溫度改變其分子型態的感溫 釋放水膠穿插於具有網狀構造之水膠面膜主體中以組合成 一感溫型的水膠面膜。 較佳地，該可變色之感溫水膠面膜還包含一分佈於該 7 201100110 穿插有感溫釋放水膠之面膜主體的網狀結構中的精華液。 如^來’製得的面膜—方面能適時地鎖住精華液以降低 其流失的機率，一方面又能藉由溫度的改變使其中的精華 液在適當的時機下被釋放出來，並因組成水膠的特性之不 同而有控制釋放及持續滋潤的效果，而使用者更可由面膜 的顏色轉變判斷精華液釋放的情形，能更有效地掌握敷臉 的時間。 較佳地，該感溫釋放水膠還包括—聚氧乙稀_聚氧丙稀 聚氧乙烯三歲段共聚物’其中’該聚氧乙婦·聚氧丙浠-聚氧 乙稀二-嵌段共聚物亦為一感溫性高分子，其化學式如下式 所不（X、y、z皆為正整數），經紫外光照射後，該聚氧乙 烯-聚氧丙烯·聚氧乙婦三嵌段共聚物會形成膠狀並穿插於上 達之面膜主體的網狀結構中，在低溫環境下（如代冰箱 段時間’該共聚物之高分子鏈段中的聚氧乙烯、聚氧丙 烯嵌段會與水及精華液之分 生土虱鍵結合而呈現親水性 質，而當添加有該聚氧乙烯-聚氧丙稀.聚氧乙稀三後段丑聚 物的可變色之感溫水膠面膜貼附於人體肌膚上時，隨著田 度的增高’該共聚物分子鍵所產生之氣鍵結合力會消失-=氧丙稀嵌段中的偶疏水性官能基職現之疏水性質 貝1隨之明顯，使得所含之精華液分子亦同時釋放出來。 H- -〇CH2CH-Η I ch3 In particular, the core temperature of the human body (c〇re b〇dy 〇 temPerature) is maintained at 37〇c, but the temperature of the peripheral part of the human body (ie, the body wall and the skin) is approximately 32. 〇' is similar to the phase transfer temperature of isopropyl propylene styrene. Therefore, the color-sensitive warm water gel mask of the present invention is used in the preparation of the face and the face. P skin fits to the temperature of the mask reaches the phase transition temperature of the temperature-release gel, and begins to shrink and release the essence, and the warm water gel mask gradually turns from transparent to milky white. When the water gel of the mask main body also contains the essence molecules distributed in the mesh structure to provide continuous release and moisturization, the warm water gel mask can not only judge the release of the essence by the color change of the appearance of the mask. And the effect of continuously maintaining the moisturizing contact with the skin to enhance the effect of the mask control release essence. The second object of the present invention is to provide a method for preparing the above-mentioned color-changing thermosensitive water gel mask. The method for preparing a color-changing thermosensitive water gel mask of the present invention comprises the following steps: (4) comprising a sea alginate, a hydrophilic monomer, a chemical crosslinking agent, a salt compound containing a divalent metal ion, and - mixing of the initiator 6 201100110 into a mold; (b) irradiating the mold of step (a) with ultraviolet light (uitravi〇iet, (jV), the mixture is obtained by crosslinking and polymerization - a hydrogel mask body having a network structure; (c) immersing the mask body of the step (b) in a solution containing isopropyl acrylamide; and (d) irradiating the step (c) with ultraviolet light The solution is gelled by isopropyl acrylamide which is infiltrated into the network structure of the mask body, and forms a temperature-sensitive release water gel interspersed in the network structure, thereby preparing the color-changing temperature sensing The invention has the advantages that the color-changing warm water gel mask of the invention has high water absorption performance and completely locks the essence component, so that the essence can be stored during the storage period (ie, the storage time before being used) Saved in this In the film, it is not oxidized or deteriorated. When the color-changing warm water gel mask is used, it can be attached to the skin. The essence is less likely to leak and the temperature-sensing water interspersed in the mask body. The glue will shrink due to the phase change of the skin temperature, so that the essence molecules can be effectively released with the sputum shrinkage of the water-sensitive gel, and the mask is discolored, and the moisturization of the mask body can be maintained. The sustained release of the essence molecules can indeed achieve the efficacy of the present invention. [Embodiment] The inventor skips the previous concept and uses temperature to control the release of the essence, that is, a molecule that changes with temperature. The type of temperature-sensing release water gel is interspersed in the body of the water-repellent mask having a mesh structure to form a temperature-sensitive water-based gel mask. Preferably, the color-changing temperature-sensitive gel mask further comprises a distribution 7 201100110 The essence of the mesh structure of the mask body with the temperature-release gel is interspersed. If the mask is made, it can lock the essence in time to reduce it. The probability of loss, on the one hand, can be released by the temperature change at the right time, and has the effect of controlled release and continuous moisturization due to the different characteristics of the water gel, and the user is more The release of the essence can be judged by the color transition of the mask, and the time for applying the face can be more effectively grasped. Preferably, the temperature-releasing water gel further comprises - polyoxyethylene _ polyoxypropylene polyoxyethylene three years old The copolymer 'where' the polyoxymethylene-polyoxypropylene-polyoxyethylene di-block copolymer is also a temperature sensitive polymer, and its chemical formula is not as follows (X, y, z are positive) Integer), after irradiation with ultraviolet light, the polyoxyethylene-polyoxypropylene/polyoxyethylene triblock copolymer will form a gel and interspersed in the network structure of the upper mask body, in a low temperature environment (such as During the generation of the refrigerator, the polyoxyethylene and polyoxypropylene blocks in the polymer segment of the copolymer will be hydrophilically bonded to the metabodies of the water and the essence, and when the polyoxyethylene is added - Polyoxypropylene, polyoxyethylene, three-stage ugly polymer When the color-changing warm water gel mask is attached to human skin, as the field increases, the gas-bonding force generated by the molecular bond of the copolymer disappears - the even hydrophobic functional group in the oxypropylene block The hydrophobic nature of the job is evident, so that the essence molecules contained are also released at the same time. H- -〇CH2CH-
•〇CHCH2-t--〇CH2CH2 ch3 V ΌΗ (II) 平物 201100110 較佳地’適用於本案的聚氧乙烯-聚氧丙烯-聚氧乙烯三 嵌段共聚物的成膠濃度是介於20〜60 wt%之間，例如： BASF公司所生產的Pluronic® F-68(平均分子量為8350，成 膠濃度50~60以1%)、？1\11：〇11^?-1〇8(成膠濃度30贾1%)及•〇CHCH2-t--〇CH2CH2 ch3 V ΌΗ (II) Level 201100110 Preferably, the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer suitable for use in this case has a gelatinization concentration of 20 Between ~60 wt%, for example: Pluronic® F-68 produced by BASF (average molecular weight 8350, gelatinization concentration 50-60 to 1%), ? 1\11: 〇11^?-1〇8 (gelatinization concentration 30 Jia 1%) and
Pluronic® F-127(平均分子量為12600,成膠濃度20 wt%)皆 適用於本案。 較佳地’該混合物還包括一矽氧化物，可增加該面膜 Q 主體之韌性與光滑度，並增加使用時與肌膚的服貼程度。 更佳地，該矽氧化物為二氧化矽、矽橡膠或矽樹脂。 較佳地，該海藻酸鹽為海藻酸鈉或海藻酸鉀。 較佳地，該鹽類化合物所含的二價金屬離子可與該海 藻酸鹽相作用以形成一錯合物，且該金屬離子是選自於 Ca2+、Sr2+、Ba2+。 較佳地，該鹽類化合物是氯化鈣。 較佳地，該親水性單體是選自於丙浠酸（acrylic acid, ❹ AAc)、乙稀。比 b各烧酮（N-vinyl-2-pyrrolidone，VP)、乙二醇 (ethyleneglycol, EG、甲基丙稀酸-2-經基乙酯（2-hydroxyethyl methacrylate, 2-HEMA)、N，N-二甲基丙稀醯胺 (τνΆ-dimetyl acrylamide, DMAAm)、2-丙醢胺-2-甲基丙續酸 (2-Acrylamido-2-methylpropanesulfonic acid, AMPS)，或此 等之一組合。更佳地，該親水性單體是丙烯酸。 較佳地，該化學交聯劑是選自於Ν,Ν’-亞甲基雙丙烯醯 胺（A/jiV’-methylenebisacrylamide，ΝΜΒΑ)、16-二甲基♦氧燒 (platinum-divinyltetramethyldisiloxane，PDMS)、二甲基丙烯 9 201100110 酸乙二醋（ethyleneglycol dimethacrylate，EGDMA)，或此等 之一組合。更佳地，該化學交聯劑是N，N，·亞甲基雙丙稀醯 胺0 較佳地’該起始劑是過硫酸按（ammonium persulfate， APS)。但不應以此起始劑為限，只要是習知適用於此等聚 合反應的起始劑皆可。 較佳地，以構成該面膜主體的混合物中所含之海藻酸 鹽的重量為1重量分來計算，該鹽類化合物的含量範圍為 0_05〜0.3重量分、該親水性單體的含量範圍為i〜2 5重量分 、該化學交聯劑的含量範圍為0.05〜0.3重量分、該起始劑 的含量範圍為G.GG54G5重量分’以及組成該感溫釋放層 的異丙基丙烯醯胺之含量範圍為15〜8重量分。 "較佳地，以該海藻酸鹽的重量為丨重量分來計算，該 聚氧乙浠聚氧丙稀-聚氧乙嫌二祺in_ 邓一嵌奴共聚物的含量範圍為 3〜10重量分。 較佳地，以該海藻酸鹽的重量為1重量分來計算，拿 矽氧化物的含量範圍為1 5〜20重量分。 本發明可變色之感溫水膠面膜的大小或形狀沒有-篇 =，可以依照臉部不同部位的大小或形狀來製備適用 =同核的面膜，例如，眼袋面膜、鼻頭面膜和下巴面 π 1雯巴之感溫水膠之 步驟⑷的溶液更含有_聚氧乙.聚稀：: 共聚物。更佳地’該聚氧乙稀-聚氧 =席二飲 呵碲-聚氣乙烯三嵌段 10 201100110 聚物平均分子量是介於8350〜12600之間。 較佳地，該步驟⑷的混合物更包括一矽氧化物。更佳 地’抑氧化物為二氧化矽、石夕橡膠或秒樹脂。 較佳地，該纟驟（a)的海藻酸鹽為海藻酸納或海藻酸卸 〇 較佳地，該步驟（a)的鹽類化合物所含的二價金屬離子 疋選自於Ca 、Sr2+、Ba2+。更佳地，該鹽類化合物是氣化 〇 妈。 較佳地，該步驟（a)的親水性單體是選自於丙烯酸、乙 烯吡咯烷酮、乙二醇、甲基丙烯酸_2_羥基乙酯、N，N_二甲 基丙烯醯胺、2-丙醯胺-2-曱基丙磺酸，或此等之一組合。 更佳地，該親水性單體是丙烯酸。 較佳地’該步驟⑷的化學交聯劑是選自於N，N，_亞甲基 雙丙烯酿胺、翻-二曱基石夕氧烧、二甲基丙缚酸乙二酯，或 此等之一組合。更佳地，該化學交聯劑是N,N，_亞曱基雙丙 〇 烯醯胺。 較佳地’該步驟（a)的起始劑是過硫酸錄。 車父佳地’以s亥步驟（a)的混合物中所含之海藻酸鹽的重 量為1重量分來計算，該鹽類化合物的含量範圍為0 05~0 3 重量分、該親水性單體的含量範圍為1〜2.5重量分、該化學 交聯劑的含量範圍為0.05〜0.3重量分、該起始劑的含量範 圍為0.005〜〇.〇5重量分，以及組成該感溫釋放層的異丙基 丙烯醯胺之含量範圍為1·5〜8重量分。 較佳地’以該海藻酸鹽的重量為1重量分來計算，該 11 201100110 聚氧乙烯-聚氧丙烯-聚氧乙烯三嵌段共聚物的含量範圍為 3〜10重量分。 較佳地，以該海藻酸鹽的重量為1重量分來計算，該 矽氧化物的含量範圍為1.5〜20重量分。 較佳地，該步驟（d)還進一步將該面膜浸泡於一精華液 中，以製得一含有精華液的可變色感溫水膠面膜。 實施例 本發明將就以下實施例來作進一步說明，但應瞭解的 是，該等實施例僅為例示說明之用，而不應被解釋為本發 明實施之限制。 <儀器設備> 1. 均質機（homogenizer):購自於 Polytron，型號為 PT-MR2100。 2. 超音波震蘯機（ultrasonic cleaner):購自於Delta，型號為 DC400H。 <化學品來源> 1. 海藻酸鈉：購自於Sigma，型號為A2158。 2. 丙烯酸：購自於Fluka，型號為S5155281。 3. Ν,Ν’-亞甲基雙丙烯醯胺：購自於Fluka，型號為66670。 4. 過硫酸銨：購自於Wako，型號為012-03285。 5. 二氧化石夕：購自於日星化工，型號為snowtex-o。 6. 異丙基丙烯醯：購自於Wako，型號為099-03695。 7. 聚氧乙烯-聚氧丙烯-聚氧乙烯三嵌段共聚物：Pluronic® F- 12 201100110 127平均刀子量為12600，講自於sigma，型號為p2443 ，以下簡稱Pluronic。 8.玫瑰精華液：購自於美梭科技。 <實施例1> 如圖1所不’本發明可變色之感溫水膠面膜1之較佳 實施例包含一面膜主體u(其所具有之網狀結構以交錯之實 線表示）、一感溫釋放水膠j2(以虛線表示穿插於該網狀結構 中的水膠）以A精華液分+ 2(以點狀表示精華液分子被鎖住 並分佈於整個水膠面膜中）。 在製備本實施例可變色之感溫水膠面膜前，發明人先 配製下述三種溶液：⑴含碎水溶液：係藉由將5 g的二氧化 矽冷於50 mL的水中而製得；濃度為3 M的異丙基丙烯 醯水溶液：係藉由將13·56 g的異丙基丙烯醯胺溶於4〇紅 的水中而製得；及（iii)PIur〇nic溶液：係藉由在ι〇〇 ‘的 水中加入20 g的Plur〇nic，並將其放入的冰箱中靜置工 天，使其中的Pluronic完全溶解而製得。 本實施例的製備步驟如下： ()將0.308 g # n，N’-亞甲基雙丙埽酿胺及〇 〇46 g的 APS元全溶解於4〇 mL的水中，之後再加入名 的丙烯酸、0.333 g的CaCu 5〇址的二氧化石夕溶 液[溶液（i)]，以形成一第一溶液； ()將3 g的海藻g曼鈉加入】〇〇爪乙的水中，並用均質機 攪拌均勻（轉速為19〇〇〇 rpm)，以得到一二 (3)將步驟⑴的第一溶液倒入步驟（2)的第二溶液内，並 13 201100110 用均質機搜拌均勻（轉速為23000 rpm)，再用超音波 震盪機將氣泡趕掉並撈掉，使液體中完全沒有氣泡 ，以得到一第三溶液； (4) 利用針筒將步驟（3)的第三溶液打人—由發明人自行 製作的面膜模具（玻璃材質）中，再以紫外光照射30 分鐘’以製得一面膜主體11 ; (5) 將事先配好的異丙基丙烯醢水溶液[溶液⑴)]與 Pluronic溶液[溶液（m)]混合均勻成一第四溶液； (6) 將步驟（4)的面膜主體浸泡在該步驟（5)的第四溶液中 ，並在置於4〇c冰箱中浸泡1天後，以紫外光照射 3〇分鐘，，以形成一穿插於該面膜主體丨丨的感溫釋 放水膠12,此時面膜會因紫外光引發的膠化反應完 成後《L度隨之上升而呈現乳白色，故再將其放回冰 相中靜置1天以降溫，並使面膜回復透明無色的狀 態，進而製得本發明可變色之感溫水膠面膜J。 即以海藻酸鈉的重量為丨重量分來計算，本實施例用 以製備可變色之感溫水膠面膜之成分中量比例為： 海藻酸鈉：CaCh :丙烯酸：N，N’_亞甲基雙丙烯醯胺：Aps 氧化妙.異丙基丙稀醯：卩1111_〇1^=1:〇.1:2.3:〇.1: 0·〇1 : 1.7 : 4.5 : 6.7。 分別將實施例1製得的可變色之感溫水膠面膜丨與步 驟（4)所得之面膜主體裁成5x5 cm的大小，再同時乾燥並秤 重（W!)，於25。(：的溫度下浸泡於一玫魂精華液中，3〇分鐘 14 201100110 後可使得該可變色之感溫水膠面m !完整鎖住該精華液分 子2’將面膜榜起秤重（w2)，可得面膜之含水#，其計^ 而進一 75.8% 含水率（％)=(W2_Wi)/W2X i 〇〇 可得該面膜主體之含水率達93·3%，即吸水性極佳， 步製得之本發明可變色之感溫水膠面膜的含水率則為 ，亦達到良好的鎖水效果。Pluronic® F-127 (average molecular weight 12600, 20% gelatinization) is suitable for this case. Preferably, the mixture further comprises an antimony oxide which increases the toughness and smoothness of the mask Q body and increases the degree of conformation to the skin during use. More preferably, the cerium oxide is cerium oxide, cerium rubber or cerium resin. Preferably, the alginate is sodium alginate or potassium alginate. Preferably, the divalent metal ion contained in the salt compound interacts with the alginate to form a complex, and the metal ion is selected from the group consisting of Ca2+, Sr2+, and Ba2+. Preferably, the salt compound is calcium chloride. Preferably, the hydrophilic monomer is selected from the group consisting of acrylic acid (❹ AAc) and ethylene. N-vinyl-2-pyrrolidone (VP), ethylene glycol (ethyleneglycol, EG, 2-hydroxyethyl methacrylate, 2-HEMA), N, N-Dimethyl acetamide (DMAAm), 2-Acrylamido-2-methylpropanesulfonic acid (AMPS), or a combination of these More preferably, the hydrophilic monomer is acrylic acid. Preferably, the chemical crosslinking agent is selected from the group consisting of ruthenium, Ν'-methylenebisacrylamide (A/jiV'-methylenebisacrylamide, ΝΜΒΑ), 16 - platinum-divinyltetramethyldisiloxane (PDMS), dimethyl propylene 9 201100110 ethyleneglycol dimethacrylate (EGDMA), or a combination thereof. More preferably, the chemical crosslinking agent is N , N, · methylene diacrylamide 0 is preferably 'the initiator is ammonium persulfate (APS), but should not be limited to this initiator, as long as it is customary Preferably, the initiator of the polymerization reaction is acceptable. Preferably, the weight of the alginate contained in the mixture constituting the main body of the mask is 1. The content of the salt compound is in the range of 0_05 to 0.3 parts by weight, the content of the hydrophilic monomer is in the range of i to 25 parts by weight, and the content of the chemical crosslinking agent is in the range of 0.05 to 0.3 parts by weight. The content of the initiator is in the range of G.GG54G5 by weight 'and the content of isopropyl acrylamide constituting the temperature-sensing release layer is in the range of 15 to 8 parts by weight. " Preferably, the alginate is used. The weight is calculated as the weight fraction of the oxime, and the content of the polyoxyethylene propylene oxide-polyoxyethylene bismuth indole is in the range of 3 to 10 parts by weight. Preferably, the alginate is used. The weight is calculated as 1 part by weight, and the content of the lanthanum oxide is in the range of 15 to 20 parts by weight. The size or shape of the temperature-sensitive water-based gel mask of the present invention is not - the article can be according to different parts of the face. Size or shape to prepare a mask suitable for use with the same core, for example, the solution of the eye bag mask, the nose mask and the step (4) of the tempering water gel of the chin surface π 1 Wenba further contains a polyoxyethylene. More preferably 'the polyoxyethylene-polyoxygen=six two drink 碲 碲-polyethylene three The average molecular weight of the block 10 201100110 polymer is between 8350 and 12600. Preferably, the mixture of the step (4) further comprises a cerium oxide. More preferably, the oxidizing agent is cerium oxide, shisha rubber or a second resin. Preferably, the alginate of the step (a) is sodium alginate or alginic acid. Preferably, the divalent metal ion contained in the salt compound of the step (a) is selected from the group consisting of Ca and Sr2+. , Ba2+. More preferably, the salt compound is a gasification aunt. Preferably, the hydrophilic monomer of the step (a) is selected from the group consisting of acrylic acid, vinyl pyrrolidone, ethylene glycol, 2-hydroxyethyl methacrylate, N,N-dimethyl decylamine, 2- Propylamine-2-mercaptopropanesulfonic acid, or a combination of these. More preferably, the hydrophilic monomer is acrylic acid. Preferably, the chemical crosslinking agent of the step (4) is selected from the group consisting of N,N,_methylenebisacrylamide, fluorenyl fluorene, dimethyl dimethyl acrylate, or the like. One of the combinations. More preferably, the chemical crosslinking agent is N,N,-indenyl dipropenylamine. Preferably, the initiator of step (a) is persulfate. The car father's land is calculated by dividing the weight of the alginate contained in the mixture of the steps (a) by 1 part by weight, and the content of the salt compound is in the range of 0 05 to 0 3 by weight, the hydrophilic single The content of the body is in the range of 1 to 2.5 parts by weight, the content of the chemical crosslinking agent is in the range of 0.05 to 0.3 parts by weight, the content of the initiator is in the range of 0.005 to 〇. 5 parts by weight, and the temperature releasing layer is composed. The content of isopropyl acrylamide is in the range of 1.5 to 8 parts by weight. Preferably, the content of the 11 201100110 polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer is from 3 to 10 parts by weight based on 1 part by weight of the alginate. Preferably, the niobium oxide is contained in an amount ranging from 1.5 to 20 parts by weight based on 1 part by weight of the alginate. Preferably, in the step (d), the mask is further immersed in an essence to prepare a color-changing thermosensitive gel mask containing the essence. The present invention will be further illustrated by the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting. <Instrument Equipment> 1. Homogenizer: purchased from Polytron, model number PT-MR2100. 2. Ultrasonic cleaner: purchased from Delta, model DC400H. <Chemical Source> 1. Sodium Alginate: purchased from Sigma, model number A2158. 2. Acrylic: purchased from Fluka, model number S5155281. 3. Ν, Ν'-methylenebis acrylamide: purchased from Fluka, model number 66670. 4. Ammonium persulfate: purchased from Wako, model number 012-03285. 5. Dioxide Day: purchased from Sunstar Chemical, model is snowtex-o. 6. Isopropyl acrylonitrile: purchased from Wako, model number 099-03695. 7. Polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer: Pluronic® F- 12 201100110 127 The average knife volume is 12600, speaking from sigma, model p2443, hereinafter referred to as Pluronic. 8. Rose Essence: purchased from Meisuo Technology. <Example 1> A preferred embodiment of the thermosensitive hydrogel mask 1 of the present invention as shown in Fig. 1 comprises a membrane main body u (having a network structure represented by solid lines in a staggered manner), The temperature-sensing release glue j2 (showing the water glue interspersed in the mesh structure with a broken line) is divided into 2 by the A essence (in the form of dots, the essence molecules are locked and distributed throughout the water gel mask). Before preparing the thermosensitive water-sensitive gel mask of the present embodiment, the inventors first prepared the following three solutions: (1) Aqueous aqueous solution: obtained by cooling 5 g of ceria in 50 mL of water; concentration a 3 M aqueous solution of isopropyl acrylonitrile: obtained by dissolving 13.56 g of isopropyl acrylamide in 4 ruthenium water; and (iii) PIur〇nic solution: by 20 g of Plur〇nic was added to the water of ι〇〇', and it was placed in a refrigerator and allowed to stand for a long time to completely dissolve the Pluronic. The preparation steps of this example are as follows: () 0.308 g of # n,N'-methylenebispropionamide and 46 g of APS element are all dissolved in 4 mL of water, and then the name acrylic is added. 0.333 g of CaCu 5 site of a solution of cerium oxide [solution (i)] to form a first solution; () adding 3 g of seaweed g-sodium to the water of 〇〇 claw B, and using a homogenizer Stir well (19 rpm) to obtain one or two (3) pour the first solution of step (1) into the second solution of step (2), and 13 201100110 homogenize with a homogenizer (rotation speed is 23000 rpm), then use the ultrasonic oscillator to drive off the bubble and remove it, so that there is no bubble in the liquid to get a third solution; (4) use the syringe to beat the third solution of step (3) - In the mask mold (glass material) made by the inventor, ultraviolet light is irradiated for 30 minutes to obtain a one-sided film main body 11; (5) a previously prepared aqueous solution of isopropyl acrylonitrile [solution (1))] Pluronic solution [solution (m)] is uniformly mixed into a fourth solution; (6) immersing the mask body of step (4) in this step (4) in the fourth solution, and after being immersed in a 4 〇c refrigerator for 1 day, irradiated with ultraviolet light for 3 , minutes to form a temperature-sensing release water gel 12 interspersed in the mask body ,, At this time, the mask will be milky white after the gelation reaction caused by ultraviolet light is completed. Therefore, it is put back into the ice phase and allowed to stand for 1 day to cool down, and the mask is returned to a transparent and colorless state. The color-changing thermosensitive water gel mask J of the present invention is obtained. That is, the weight of sodium alginate is calculated as the weight fraction of strontium. The proportion of the components used in the preparation of the color-changing thermosensitive hydrogel mask of this embodiment is: sodium alginate: CaCh: acrylic acid: N, N'_ Bis-acrylamide: Aps Oxidation. Isopropyl propylene: 卩1111_〇1^=1: 〇.1:2.3:〇.1: 0·〇1 : 1.7 : 4.5 : 6.7. The color-changing thermosensitive hydrogel mask prepared in Example 1 and the mask body obtained in the step (4) were respectively cut into a size of 5 x 5 cm, and simultaneously dried and weighed (W!) at 25. (: The temperature is soaked in a rose essence, 3 〇 minutes 14 201100110 can make the color changeable warm water glue surface m! Completely lock the essence molecule 2' will weight the mask (w2 ), the moisture content of the mask can be obtained, and the moisture content (%) = (W2_Wi) / W2X i 〇〇 can obtain the moisture content of the mask main body is 93.3%, that is, the water absorption is excellent. The water content of the thermosensitive water-sensitive gel mask of the present invention obtained in the step is also a good water-locking effect.
水氣透過率測就 發明人依期刊Lamke L 0，如咖，1977, 3, ρ 159_165所 揭，的方法測財施例丨製得的可變色之感溫水膠面膜的 水氣透過率（water vapor transmissi〇n _，WVTR)，即將面 膜裁成相同克4(2.43 g)，然後置於瓶蓋上方，將瓶蓋鎖緊 以固疋面膜，瓶中添加去離子水，在適當的溫度及溼度下 ，進行水氣透過測試。測試結果為在37<3(：時，其MVTR為 5615±272 g/m2/day;在 25〇c 時，其 MVTR 為 2060 ±197 g/m /day，皆符合業界所要求的敷料之水氣透過率，亦顯示 以本發明之製備方法所得的可變色之感溫水膠面膜具有良 好的水氣透過率，不會使肌膚有缺氧的情形。 <實施例2 > 本實施例是將實施例丨製得的感溫水膠面膜置於一濃 度為10 vol°/。的經稀釋的玫瑰精華液中，在溫度25<dc下浸 泡3天’即可製得一含有玫瑰精華液的感溫水膠面膜。 精華液釋放的測Μ 15 201100110 將實施例2所得的含有精華液的可變色感溫水膠面膜 置於新鮮之40 mL麟酸緩衝液（phosphate buffered saline buffer，PBS buffer)中做釋放的測試，在不同時間點取出溶液 ’利用UV光譜儀分析精華液之含量，其結果如圖2所示， 可看出該測試之面膜分別在370C與25。(：下做不同溫度的 釋放曲線’主要因為感溫釋放水膠在高溫時會呈現較疏水 的情況’所以在37°C時釋放的速率會比25°C時快（即圖2 中之37 C測试結果之切線斜率高於250C之切線斜率）。另, 外，經過30分鐘後的速率急增，亦可合理推測當該面膜覆 蓋於臉上，相對地溫度會慢慢提高，因感溫釋放水膠的疏 水反應’所以精華液釋放的程度就更為增加。 綜上所述，本發明可變色之感溫水膠面膜利於吸收及 鎖住精華液之成分，並使得精華液在該面膜存放期間能不 致於氧化，且穿插於該面膜主體之網狀結構中的感溫釋放 水膠，會因溫度的不同而產生不同的親、疏水性，當使用 該面膜敷臉時，由於肌膚溫度高於該感溫釋放水膠之相轉f 移溫度而將精華液釋出，並且面膜主體結構中的精華液分 子可再持續釋放，進一步地，該感溫水膠面膜會由透明逐 漸變成乳白色，故使用者更可以由面膜外觀的顏色變化來 判斷精華液釋放的情形，故確實能達成本發明之目的。 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請專利 範圍及發明說明内容所作之簡單的等效變化與修飾皆仍 屬本發明專利涵蓋之範圍内。 16 201100110 【圖式簡單說明】 圖1是一剖面示意圖，說明本發明可變色之感溫水膠 面膜；及 圖2是一曲線圖，說明累積的玫瑰精華液釋放量（％)對 時間（min)做圖，其中，實心圓點代表實施例2之面膜於 37°C下，其中所含的玫瑰精華液的累積釋放量隨時間改變 的變化量，空心圓點代表實施例2之面膜於25〇c下，其中 〇 戶斤含的玫瑰精華液的累積釋放量隨時間改變的變化量。、 【主要元件符號說明】 1 .......可變色之感溫水膠面膜 11 ......面膜主體 12 ......感溫釋放水膠 2 .......精華液分子 〇 17The water vapor transmission rate is measured by the inventors according to the method of Lamke L 0, et al., 1977, 3, ρ 159_165, and the water vapor transmission rate of the discolorable thermosensitive water gel mask prepared by the method. Water vapor transmissi〇n _, WVTR), the mask is cut into the same gram 4 (2.43 g), then placed above the cap, the cap is locked to the solid mask, deionized water is added to the bottle at the appropriate temperature Under water and humidity, conduct a water vapor transmission test. The test result is MVTR of 5615±272 g/m2/day at 37<3 (when; MVTR is 2060 ± 197 g/m/day at 25 〇c, which meets the requirements of the industry for dressing water) The gas permeability also shows that the discolorable thermosensitive water gel mask obtained by the preparation method of the present invention has a good water vapor transmission rate and does not cause hypoxia in the skin. <Example 2> This embodiment The temperature sensitive water gel mask prepared in the example is placed in a diluted rose essence at a concentration of 10 vol /, and soaked at a temperature of 25 lt for 3 days to obtain a rose essence. Liquid temperature sensitive gel mask. Measurement of serum release 15 201100110 The gelatinous color sensitive gelatin gel mask obtained in Example 2 was placed in fresh 40 mL phosphate buffered saline buffer (PBS). The release test in buffer), the solution was taken at different time points. The content of the essence was analyzed by UV spectrometer. The results are shown in Fig. 2. It can be seen that the mask of the test is 370C and 25 respectively. The release curve of temperature is mainly due to the high temperature release of water gel at high temperature It will be more hydrophobic - so the rate of release at 37 ° C will be faster than at 25 ° C (ie, the tangent slope of the 37 C test results in Figure 2 is higher than the tangent slope of 250 C). After 30 minutes, the rate is sharply increased. It can be reasonably estimated that when the mask covers the face, the relative temperature will gradually increase, and the hydrophobic reaction of the water gel will be released due to the temperature sensing, so the degree of release of the essence is further increased. In summary, the color-changing thermosensitive water gel mask of the present invention is beneficial for absorbing and locking the components of the essence, and enables the essence to be oxidized during storage of the mask, and interspersed in the mesh structure of the mask body. The temperature-sensing release of water gel will produce different pro- and hydrophobic properties depending on the temperature. When the mask is applied to the face, the skin temperature is higher than the temperature-released water-gel phase. Released, and the essence molecules in the main structure of the mask can be continuously released. Further, the warm water gel mask will gradually change from transparent to milky white, so the user can judge the essence by the color change of the appearance of the mask. In the case of the present invention, it is possible to achieve the object of the present invention. The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the scope of the patent application according to the present invention is BRIEF DESCRIPTION OF THE DRAWINGS The simple equivalent changes and modifications made by the present invention are still within the scope of the present invention. 16 201100110 [Simplified Schematic] FIG. 1 is a schematic cross-sectional view showing a thermosensitive water-sensitive gel mask of the present invention; And Fig. 2 is a graph showing the cumulative amount of rose essence released (%) versus time (min), wherein the solid dots represent the mask of Example 2 at 37 ° C, which contains the rose essence The amount of change in the cumulative release of the liquid with time, the hollow dot represents the mask of Example 2 at 25 ° C, wherein the cumulative release of the rose essence contained in the Settlecler varies with time. , [Main component symbol description] 1 ....... can change the temperature of the water gel mask 11 ... mask body 12 ... temperature release water glue 2 ..... ..Essence molecule 〇17