201031699 六、發明說明： 【發明所屬之技術領域】 本發明疋關於熱感應性雨分子凝膠及將其成為薄膜狀 而成的熱感應性高分子凝膠薄膜，特別是關於藉由熱刺激 而發生膨潤度的變化、或發生表面的水滴接觸角的變化之 熱感應性高分子凝膝及熱感應性高分子凝膠薄膜。 【先前技術】 ® 近年來’有人提出藉由熱刺激而發生膨潤度、體積等 的變化之熱感應性高分子凝膠。例如在專利文獻1中，揭 露了一種機能性高分子凝膠，其特徵在於為了具有足夠的 膨潤度變化量，作為交聯點的微粒子呈現均一分散的狀 態；在專利文獻2中’其揭露了感應到外部刺激而產生體 積變化之嶄新的高分子凝膠組合物，其特徵在於此高分子 凝勝組合物具有因彼此的相互作用而形成高分子複合體之 二種高分子化合物及液體，這些高分子化合物的丈中一種 9 是形成立體交聯體、另一種是具有離子性官能基而在溶解 於上述液體之時而包含於立體交聯體的内部；在專利文獻 3中’其揭露了一種高分子凝膠組合物，其特徵在於具有 因液體的吸收•釋出而發生體積變化的刺激感應性高分子 凝膠、與用於分散•固定刺激感應性高分子凝膠的高分子 凝膠固定用樹脂組合物，此高分子凝膠固定用樹脂組合物 含有重量平均分子量為100,000以上的交聯性高分子、與 交聯劑；在專利文獻4中’揭露了一種刺激感應性高分子 3 201031699 水凝膠’其因為吸收水而膨潤而凝膠化、並因刺激而發生 膨潤度、體積等的變化，此刺激感應性高分子水凝膠的特 徵在於因相分離構造而含有非水溶性高分子。 【先行技術文獻】 【專利文獻】 【專利文獻1】特開2006-3681 1號公報 【專利文獻2】特開2006-249 258號公報 【專利文獻3】特開20 07-146 000號公報 【專利文獻4】特開2005-264046號公報 【發明内容】 【發明所欲解決的問題】 上述習知的熱感應性高分子凝膠，會因為熱刺激而發 生膨潤度、體積等的變化，但*代表其變化速度很快。而 上述專利文獻中，是揭露了為熱刺激而發生膨潤度、體積 等的變化，但無關於其變化速度的記載或暗示。也就是習 知技術完全未著眼於膨潤度、體積等的變化速度的相關技 術’而對提昇其速度的努力並未作任何嘗試。 另外’上述習知的熱感應性高分子凝膠，會因為熱刺 激而發生膨潤度、體積等的變化，但凝膠表面的水滴接觸 角幾乎不會變化，或是即使有變化但是其變化量極小。而 上述各專利文獻中，關於因熱刺激而導致_表面的水滴 接觸角的變化，並未作任何揭示、也未作任何暗示。 另一方面，上述專利文獻1〜3所揭露的^子凝膠， 201031699 是將其完全微粒子化而分散於液體中，因此若未封入歹 專利文獻2或3所揭露的封裝構件等，則無法保有這 分子凝膠。因此，高分子凝膠的體積變化受到封裝構件@ 限制；另外’關於受到微粒子化而分散於液體中的高分子 凝膠，是無法將其薄膜化。 有鑑於此，本發明是提供一種熱感應性高分子凝膠及 熱感應性高分子凝膠薄膜，其藉由熱刺激而快速地發生膨 潤度的變化或發生凝膠表面的水滴接觸角的大幅變化。 【用以解決問題的手段】 為了達成上述目的，首先本發明是提供一種熱感應性 高分子凝膠’其特徵在於：藉由熱刺激，其質量在300秒 以内從最大含水狀態；咸少為最大含水狀態@ 2〇%以下；或 在熱刺激的前後的表面水滴接觸角差為2〇β以上（發明 1) ° 、在上述發明（發8月D中，上述熱刺激的溫度較好為室 Φ 溫以上、1 〇 〇 °c以下（發明2〉。 在上述發明（發明卜2)中，上述熱感應性高分子凝膠 較好為含有10質量％以上的水分（發明3)。 在上述發明（發明卜3)中，較好為含有輪烷構造 (rotaxane structure)(發明 4)。 、：上述發明(發日月4)中，較好為含有高分子交聯體， 上述同刀子父聯體是經由高分子交聯前驅體的直鏈狀分子 ^聚口 基而使上述直鏈狀分子與熱感應性成分共聚 口而彳于上述间分子交聯前驅體是由混合具有二個以上的 201031699 環狀部分的聚合物及上述直鏈狀分子而得，上述直鍵狀分 子在-侧的末端具有嵌段㈤心）基、另—端具有聚合性= 能基’且上述直鏈狀分子得以與上述聚合物形成包接錯入 物（發明5)。 " 在上述發明（發日月5)中，上述聚合物的環狀部分㈣ 是選自環糊精（a_cycl〇dextrin)、万—環糊精及 環糊精所組成之族群中的最少—種或是選自環狀聚喊 (poiyether)、環狀聚醋（p〇lyester)、環狀聚 _ 胺 (polyetheramine)及環狀聚胺（p〇lyamine)所組成之族群 中的最少一種（發明6)。 在上述發明（發明5、6)中，上述熱感應性成分是具有 N —異丙基醯胺（N-isopropylainide)基的聚合性化合物（發 明7)。 其次，本發明是提供一種熱感應性高分子凝膠，其是 將上述熱感應性高分子凝膠（發明卜7)形成為薄膜狀而成 (發明8)。 【發明效果】 若使用本發明，可以得到藉由熱刺激而快速地發生膨 潤度的變化或發生凝膠表面的水滴接觸角的大幅 感應性高分子凝膠及熱感應性高分子凝膠薄膜。 【實施方式】 【用以實施發明的最佳形態】 以下，針對本發明的實施形態來作說明。 201031699 本發明相關的熱感應性高分子凝膠是： (1) 藉由熱刺激，其質量在300秒以内從最大含水狀態 減少為最大含水狀態的20%以下、較好為在秒以内減 少至15%以下或1〇〇秒内減少至20%以下；或 (2) 在熱刺激的前後的表面水滴接觸角差為2〇。以 上、較好為30。以上、更好為40。以上。 在此處，熱刺激的溫度較好為室溫以上、i 〇(rc以下； 特別較好為4 0 ~ 10 〇 °C、更好為6 01：。 (1)的特性疋規把熱感應性高分子凝膠的膨潤度的變 化速度。另外，藉由此膨潤度的變化（減少），熱感應性高 分子凝膠是釋出水分而收縮，因此（1)的特性是規範熱感應 性高分子凝膠的收縮速度。 最大含水狀態，是指使此熱感應性高分子凝膠在室溫 下（較好為23。〇使其實質上無法再含有更多的水的時候的 3水狀態。具體而言’是指將乾燥狀態的熱感應性高分子 鲁凝膠在至温下（較好為23°C)浸於水中，而根據其膨濁速度 而可以判斷膨潤停止的狀態。例如在本實施形態中，是以 在室溫下（較好為23°C)浸於水中，膨潤度的變化在30分 鐘内未達5%的狀態作為最大含水狀態。 習技術不知道如⑴—般膨调度的變化速度（收縮速 度）快得熱感應性高分子凝膠。另外，習知技術連這樣的特 性也未者眼，對提昇熱刺激所造成的變化速度（收縮速度） 的努力並未作任何嘗試。 另方面’（2)的特性是可以顯示熱感應性高分子凝膠 7 201031699 的親水性〜疏水性的變化程度。例如在本實施形態中，藉由 對熱感應性高分子凝膠施加加熱的刺激，會使水滴接觸角 變大’故水滴接觸角的差’是由熱刺激後的水滴接觸角減 掉熱刺激前的水滴接觸角來計算出來。而「熱刺激的前 後」’是由熱感應性高分子凝膠的感應溫度及含水量來作 適當決定’但是只要將對熱刺激發生感應的溫度置中來比 較低溫側的任意溫度與高溫側的任意溫度即可，且在任意 的可能潛在的含水量中，只要是滿足上述既定的水滴接觸 角差即可。例如在本實施形態中，關於以含水量為2〇質量 %的熱感應性高分子凝膠（較好為熱感應性高分子凝膠薄 膜）較好為在23C與60C之下的表面的水滴接觸角的差 成為上述既定的範圍。 當然，本實施形態相關的熱感應性高分子凝膠亦可同 時滿足（1)及（2)的特性。 本實施形態相關的熱感應性高分子凝膠，是含有熱感 應性的高分子成分與水分，而熱感應性高分子凝膠中的含 水量較好為10質量％以上、特別好為15〜100質量％、更好 為20〜90質量％。藉由熱感應性高分子凝膠中的含水量為 10質量％以上，會有效地發揮上述（2)的特性、後文所述的 其他特性等。 作為本實施形態相關的熱感應性高分子凝膠所含有的 熱感應性高分子成分的物質，是根據第i圖模式性所示的 方法來製造的熱感應性高分子交聯體（E)。以下說明熱感應 性高分子交聯體（E)的製造方法。 201031699 首先準備/、有2個以上環狀部分的聚合物（以下稱之 為「聚合物（A)」）與在—側的末端具有嵌段（block)基、另 一側的末端具有聚合性官能基的直鏈狀分子（以下稱之為 「直鏈狀分子（B)」）（請參考第1圖）。 聚合物（A)的環狀部分可以包接直鏈狀分子（B)，在此 狀態下可以在此直鏈狀分子（B)上移動。而在本說明書中， 「環狀部分」&「環狀」的意義是實質上的「環狀」，只 要可以在直鏈狀分子（B)上移動，環狀部分可以是未完全閉 鎖的環狀’例如可以是螺旋構造。另外，聚合物⑴是如後 文所述，是以分子量相對較大的環狀分子作為構成部份的 多量體，即使聚合度少，其本身的分子量仍巨大。聚合物 (A)是由於此原因而制定的權宜名稱，亦包含2〜1〇個單體 左右的募聚物的聚合物的物質。 作為構成環狀部分的分子（環狀分子）者，較好為 環糊精（a -cyclodextrin)環糊精、環糊精等的環 鲁糊精，或是環狀聚醚（p〇lyether)、環狀聚酯（p〇lyester)、 環狀聚醚胺（polyetheramine)及環狀聚胺（polyamine)、環 苋（cyclophane)等的環狀分子，亦可以在聚合物（A)或後文 所述的局分子交聯前驅體（C)或是後文所述的熱感應性高 分子交聯體（E)中混有二種以上的上述環狀分子。 在上述環狀分子為環糊精的情況中，亦可以在環糊精 的氫氧基導入可提昇聚合物（A)之對於直鏈狀分子（β)的溶 解性的高分子鍊及/或置換基。可列舉出作為上述高分子鍊 的有氧化乙烯（oxyethylene)鍊、烷基（311^1)鍊、丙烯酸 201031699 醋（acmicester)鍊等。另一方面，可列舉出作為上述置 換基的有乙醯基、烧基、三苯甲基（trityl)'甲苯確酿基 (tosyl)、三甲基矽烷基、笨基等。 可列舉出作為上述環狀分子的環糊精以外的具體例子 的有冠醚（crown ether)或其衍生物、環狀内酯⑽elk lactone)或其衍生物、芳杯（caHxarene)或其衍生物、氮 雜環番（aZaCyCl〇phane)或其衍生物、噻環玢 (thiaCyci〇phane)或其衍生物、大環胺醚或其 衍生物等。 八 作為環狀分子者，較好是α -環糊精、万-環糊精、τ _ 環糊精、及冠醚，因為直鏈狀分子容易貫通而成串；特別 好為α -環糊精、yg _環糊精、及了 _環糊精，因為在水中 谷易與鍊狀分子形成包接錯合物。 聚合物（Α)中的環狀分子的個數為2個以上、較好為 3〜50個、特別好為3〜5個，藉由環狀分子為2個以上，可 以包接複數個直鍵狀分子（Β)，藉由使這些直鏈狀分子（Β) 聚合’具有直鏈狀分子（Β)作為·構成單位的複數個（共）聚合 物則經由聚合物（Α)而相互連結，而構成交聯構造。環狀分 子若為3個以上，則交聯構造變密，因此不會對所完成的 熱感應性高分子交聯體（Ε)的應力緩和性造成阻礙，而可以 提昇強度，故更佳。 作為聚合物（A)的構造者’較好是以連結部分將2個以 上的環狀分子連結的構造。作為連結部分的原料化合物（連 結分子），較好為不會或難以與環狀分子形成包接錯合物的 201031699 分子。藉由使用這樣的連結分子，在合成聚合物⑴之時， 不會將環狀分子的開口部封閉，而可以連結環狀分子。 作為上述連結分子者，可以是直鍵狀、也可以是具有 分支的鏈狀’較好為具有某種程度魔大的側鍵。例如，上 述環狀分子為α-環糊精的情況中’較好為具有比甲基還 龐大的側鏈。也就是從與上述環狀分子不會成為包接錯合 物的觀點，可列舉出作為較佳的連結分子的有聚丙二醇 (polypropylene glycol)、聚丙烯酸醋（p〇lyacryHc 攀eSter)、聚雙甲基石夕氧院（p〇lydimethyisU㈣此）、聚異 戊二烯（p〇lyisoprene)等，其中特別好為聚丙二醇。 一個連結分子的數量平均分子量（Mn)較好為 100 100000、特別較好為500〜10Q01若連結分子的數量 平均分子量不滿100 ’所形成的聚合物（4)的環狀分子的開 口部彼此過於接近，而難以獲得交聯構造，又會有未充分 發揮基於聯鎖（inter lock)構造所得效果之虞。另外，若連 • 結分子的數量平均分子量若超過1 00000,與直鏈狀分子（B) 等的相溶性會惡化，而有難以形成交聯構造之虞。 而聯鎖構造是指未利用非共價鍵及共價鍵的機械性的 鍵結構造。本實施形態的聯鎖構造是將具有以直鏈狀分子 (B)為構成單位的二個不同的聚合體的各自的直鏈狀分子 的本體部分（在後文中詳述），各自貫通聚合物以^的至少二 個環狀分子的開口部，上述本體部分的末端側是受到嵌段 基的保護，而藉此成為無法將本體部分從上述開口部拔出 的結構（輪烷結構（rotaxane structure))，藉此成為上述 11 201031699 二個聚合物無法分離的構造。藉由此連鎖構造，聚合物（a) 可沿著上述聚合物的直鏈狀分子（B)的本體部分而通過環 狀分子的開口部而移動，但因為嵌段基而無法拔出，因此 上述二個聚合物與習知以共價鍵所得到的交聯結構相比， 交聯部分的自由度大而仍具有與共價鍵的交聯結構相同程 度直鏈狀分子（B)的強度的鍵結性。 聚合物（A)的質量平均分子量會受到環狀分子的 種類的影響，但通常較好為1〇〇〇~1〇〇〇〇〇〇、特別較好為 3000〜100000。聚合物（A)的質量平均分子量若不滿1〇〇〇， ^ 則多會有環狀分子不滿二個的情況，而會有無法形成聯鎖 構造之虞，另外即使可以形成聯鎖構造，由於交聯構造非 常接近，會有未充分發揮基於聯鎖構造所得效果之虞。另 一方面，若聚合物U)的質量平均分子量超過1〇〇〇〇〇〇 ,與 直鏈狀分子（B)等的相溶性會惡化，而有難以形成交聯構造 之虞。 聚合物（A)可藉由一般方法來合成。例如，藉由使具有 官能基的環狀分子、與在末端具有可與此環狀分子的官能 〇 基反應的反應性基的環狀分子發生反應，則得到聚合物 (A)。具體而言，合成環狀分子為α _環糊精、連結分子為 聚丙二醇的聚合物（Α)的情況，將α_環糊精與末端具有反 應性基的聚丙二醇混合，加入所需要的觸媒而使二者反 應，藉此而得到聚合物（Α)。 作為與連結分子結合的環狀分子的官能基者，較好為 例如羥基、羧基、胺基、硫醇（thiol)基等；作為連結分子 12 201031699 的末端的反應基者，較好為例如異氰酸S旨（i socyanat e ) 基、環氧基、氮丙咬（aziridine)基等。作為連結分子者， 可使用在末端具有下列分子的物質，例如：亞二甲苯 氰酸酯（xylylene diisocyanate)、六亞曱二異氰酸酯 (hexamethy1ene di i socyanate)、甲苯二異氰酸酯 (tolylene diisocyanate)、異佛爾酮二異氰酸酯 (isophorone diisocyanate)等的異氰酸酯系化合物；乙二 醇二環氧丙基醚（ethylene glycol diglycidyl ether)、 丙二醇二環氧丙基醚（pr〇pylene glyc〇1 diglycidyl ether)、1，6-己二醇二縮水甘油醚（1，6—hexanedi〇1 glycidyl ether)等的環氧系化合物；n，N -六甲婦-1，6_ 雙（卜氮丙啶醯胺）（N, N-hexamethylene-1, 6-1^3(&2 11^(^1^031'1)(^31^(^))等的氮丙啶系化合物。 直鏈狀分子（B)是受到聚合物（a)的環狀分子的包接， 不是共價鍵等的化學鍵，而是可以以機械性的鍵結而一體 化的直鏈狀的分子或物質，且一側的末端具有嵌段基、另 一側的末端具有聚合性官能基。而在本說明書中，「直鏈 狀分子」的「直鏈」的意思是實質上的「直鏈」。也就是 只要是聚合物(A)的環狀分子可以在直鏈狀分子⑻上移 動，直鏈狀分子（B)亦可以具有分支鏈。 作為相當於直鏈狀分子⑻的二末端的嵌段基與聚合 性官能基以外的部分（本體部分）的構成分子，只要是大小 可以貫通上述聚合物(A)的環狀分子的開口部的分子即 可。例如上述聚合物⑴的環狀分子為環糊精的情況， 13 201031699 則較好為聚乙二醇（polyethylene glyc〇1)、聚四氫呋喃 (polytetrahydrofuran)、聚乙烯（p〇lyethylene)、聚己内 酯（polycaprolactone)等，亦可以在高分子交聯前驅體（c) 或熱感應性高分子交聯體（E)中混有二種以上的具有由這 些刀子所構成的本體部分的直鍵狀分子（B )。 直鏈狀分子（B)的本體部分的構成分子的數量平均分 子量（Μη)較好是1〇〇〜300000、特別較好是2〇〇~2000〇〇、更 好是30(Μ〇〇〇〇〇。若數量平均分子量不滿1〇〇，則環狀分 子之在直鏈狀分子（Β)上的移動量變小，而會有所得到的熱❿ 感應性高分子交聯體（Ε)中未得到足夠的柔軟性之虞。另 外若數量平均分子量超過300000，則會有溶解至溶劑的 溶解性惡化之虞。 嵌段基，若是包接直鏈狀分子（…的狀態的聚合物（Α) 的環狀分子不會脫離、而可以保持包接錯合物的形態，則 無特別限定。可列舉出作為這些官能基的有巨大基團 (bulky group)、離子性官能基等。 作為嵌段基者，較好為例如二烷基苯基 . (dialkylphenyl)類、二硝苯基（dinitrophenyn 類、環糊 精類、金剛烷（adamantane)類、三苯甲基（trityl)類、螢 光素（fluorescein)類、祐（pyrene)類、蒽（anthracene) 類等’亦可以在包接錯合物或高分子交聯體中混有二種以 上的這些嵌段基。作為與直鏈狀分子（B)的單一末端結合而 形成嵌段基的封端劑（capping agent)者，可適用例如二甲 基笨基異氰酸酯（dimethylphenyl isocyanate)、三苯甲某 14 201031699 本基異氰酸酯（trityl phenyl isocyanate)、2，4-二石肖氣 苯（2， 4-dinitrofluorobenzene)、金剛胺（adamantane amine)等。 聚合性官能基，只要是可經由此聚合性官能基而使直 鏈狀分子（B)與後文所述的熱感應性成分（D)共聚合者，並 無特別限定。作為上述聚合性官能基者’較好為（甲基）丙 稀醯基（（meth)acry loy 1)、乙烯基、環氧基、乙块基、氧 雜環丁基（oxetanyl)等。 ® 直鏈狀分子（B)可藉由一般方法來合成。例如使在一側 的末端具有聚合性官能基的直鏈狀分子、或是在二側的末 端具有不同的聚合性官能基的直鏈狀分子與嵌段基的用封 端劑反應，而在一側的末端留下上述聚合性官能基、在另 一側的末端附加嵌段基，藉此而可以得到直鏈狀分子（B)。 以下作為一例：將在一侧的末端具有羥基、在另一側 的末端具有（甲基）丙烯醯基的直鏈狀分子，與具有異氰酸 φ 酯基的二烷基苯基類混合，並根據需求添加觸媒，而使二 者反應，藉此得到在一側的末端具有二烷基苯基來作為嵌 段基、在另一側的末端具有（甲基）丙烯醯基來作為聚合性 官能基的直鏈狀分子（B)。 準備了以上說明的聚合物（A)與直鏈狀分子（β)之後， 混合聚合物（A)及直鏈狀分子（B)，藉由將其全部或一部分 形成包接錯合物而製造高分子交聯前驅體（c)。也就是，以 直鏈狀分子（B)貫通聚合物（A)的環狀分子的一個開口部而 成串，且以另一個直鏈狀分子貫通聚合物的環狀分 15 201031699 子的剩下的開口部中的至少-個，而製造具有上述2個以 上的直鏈狀刀子（β)受到同一個聚合物（A)的複數個環狀分 子的包接的構造之高分子交聯前驅體（c)(請參考第^圖）。 而高分子交聯前驅體（C)的特徵在於具有由上述的包 接錯口物所开）成的構造’但是不需要聚合物⑴的環狀分子 卩的開口邠都成為這樣的狀態。也就是在作為混合物 的聚合物⑷中’亦可以是僅在此環狀分子的開π部的-個 又到直鏈狀分子⑻的貫通而成串的構造、或是亦可具有直 鍵狀刀子⑻並未完全貫通聚合物（A)的環狀分子的開口部 而成串的構造、或是亦可含有作為未受到聚合物α)的包接 的混合物之直鏈狀分子（β)。 物⑴上述般的高分子交聯前驅體(c)的製造，可以使聚告 納水鏈狀分子⑻成為存在於㈣巾例如水、氫氧化 二二二甲基甲酿胺(―一 IMF)與水 的混^谷液、甲醇與水的混合溶 合物⑷的溶液添加直鏈狀八子㈤中的㈣(例如在聚 進行。高分子交聯前:二由㈣此溶液來 上升來判斷。 體(C)的-成’可藉由溶液的黏度的 關於攪拌方法並無特別限制’可 的溫度下’以機械性的授拌處理、超音波==备控， ㈣，特別是較好為以超音波處理來‘處==方法; 為以數分鐘]小時的條件來進 ，間較:¾ 並無:別限制，較好為…kHz的頻=照射條， 上所迷製造高分子交聯前驅體⑹之後，經由受到驾 201031699 合物（A)的環狀分子包接的直鍵狀分子⑻的聚合性官能 基，將此直鏈狀分子（B)與熱感應性成分⑻共聚合，而得 到熱感應性高分子交聯體⑻（請參考第ig)。此熱感應性 高分子交聯體（E)是含有作為聯鎖結構的輪燒結構。 作為熱感應性成分⑻者，是選擇顯示上述⑴或⑵ 的熱感應性而經由直鏈狀分子⑻的聚合性官能基而可以 與直鏈狀分子⑻共聚合的單體、寡聚物或聚合物。 作為較佳的熱感應性成分⑻者，可列舉出較好為具有 N-異丙基醯胺基（N-is_pylamide)的聚合性化合物。作 為此聚合性化合物者，可以是單體、而只要是具有聚合性 官能基而亦可以是募聚物、聚合物等。此聚合性化合物為 聚合物的情況的質量平均分子量⑹較㈣刪_以 下、特別好為loom以下。質量平均分子量㈣若過大， 則與其他成分的互溶性會變·差而會發生聚合性的降低、製 媒性的降低等’也會有降低刺激感應速度之虞。 另外’此聚合性化合物的聚合性官能基，只要是與直 鍵狀分子⑻發生共聚合者，則無特駭^料上述聚合 :官能基者’可列舉出例如為(甲基)丙烯醯基、乙烯基、 衣氧基乙块基、氧雜環丁基（〇xetanyl)等，若考慮到聚 合速度的快速、取得的容易度，則特別較好為（甲基）丙烯 醯基、乙烯基。 若考慮到以上事項，作為熱感應性成分（D)者，最好為 N 異丙基丙烯醯胺（N_is〇pr〇pylacryiamide)。 使用具有上述N-異丙基醯胺基的聚合性化合物（較好 17 201031699 為N-異丙基丙烯醯胺）來作為熱感應性成分（d)的熱感應性 高分子交聯體（E)，使此熱感應性高分子交聯體（e)含水而 成為熱感應性高分子凝膠，此熱感應性高分子凝膠是滿足 上述（1)及（2)的特性，另外亦顯示因熱刺激而從透明或半 透明顯著地變成白色的特性。此時，在熱刺激前後的全光 線穿透率的差較好為50%以上、特別好為7〇%以上。201031699 VI. Description of the Invention: [Technical Field] The present invention relates to a heat-sensitive rain molecular gel and a heat-sensitive polymer gel film which is formed into a film shape, in particular, by thermal stimulation A thermally induced polymer knee and a heat-sensitive polymer gel film which undergo a change in the degree of swelling or a change in the contact angle of the water droplets on the surface. [Prior Art] ® In recent years, a heat-sensitive polymer gel having undergone a change in swelling degree, volume, or the like by thermal stimulation has been proposed. For example, Patent Document 1 discloses a functional polymer gel characterized in that a fine particle as a crosslinking point exhibits a uniform dispersion state in order to have a sufficient amount of swelling degree change; in Patent Document 2, it discloses A novel polymer gel composition which induces a change in volume by external stimulation, and is characterized in that the polymer composition has two polymer compounds and a liquid which form a polymer composite due to interaction with each other. One of the polymer compounds is one which forms a three-dimensional crosslinked body and another which has an ionic functional group and is contained in the three-dimensional crosslinked body when dissolved in the liquid; in Patent Document 3, it discloses A polymer gel composition characterized by a stimulating inductive polymer gel having a volume change due to absorption and release of a liquid, and a polymer gel for dispersing and fixing a stimulating inductive polymer gel The fixing resin composition containing a crosslinkable high molecular weight having a weight average molecular weight of 100,000 or more In the patent document 4, a stimuli-inducing polymer 3 201031699 hydrogel is swelled by absorbing water and gelled, and changes in swelling degree, volume, and the like due to stimulation. This stimulating inductive polymer hydrogel is characterized by containing a water-insoluble polymer due to a phase separation structure. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2006-249 No. 258 [Patent Document 2] JP-A-2006-249 No. [Problem to be Solved by the Invention] The above-described conventional thermally sensitive polymer gel undergoes a change in swelling degree, volume, and the like due to thermal stimulation, but * Represents its rapid change. Further, in the above-mentioned patent documents, changes in swelling degree, volume, and the like occur for thermal stimulation, but there is no description or suggestion regarding the rate of change. That is, the prior art has not focused on the speed of change in swelling degree, volume, etc., and has not attempted to increase its speed. Further, the above-mentioned conventional thermally sensitive polymer gel undergoes a change in swelling degree, volume, and the like due to thermal stimulation, but the contact angle of the water droplet on the surface of the gel hardly changes, or changes even if there is a change. Very small. Further, in each of the above-mentioned patent documents, the change in the contact angle of the water droplets on the surface due to thermal stimulation is not disclosed or implied. On the other hand, the gel of the above-mentioned Patent Document 1 to 3, 201031699, is completely microparticulated and dispersed in a liquid. Therefore, if the package member disclosed in Patent Document 2 or 3 is not enclosed, it cannot be This molecule gel is retained. Therefore, the volume change of the polymer gel is limited by the package member@, and the polymer gel which is dispersed in the liquid by the microparticles cannot be thinned. In view of the above, the present invention provides a heat-sensitive polymer gel and a heat-sensitive polymer gel film which rapidly undergo a change in swelling degree by thermal stimulation or a large contact angle of a water droplet on a gel surface. Variety. [Means for Solving the Problem] In order to achieve the above object, the present invention firstly provides a heat-sensitive polymer gel which is characterized in that its mass is within a maximum water content within 300 seconds by thermal stimulation; The maximum water content is @2〇% or less; or the contact angle difference of the surface water droplets before and after the thermal stimulation is 2〇β or more (Invention 1) °, in the above invention (in August D, the temperature of the above thermal stimulation is preferably In the above invention (Invention 2), the heat-sensitive polymer gel preferably contains 10% by mass or more of water (Invention 3). In the above invention (Invention 3), it is preferred to contain a rotaxane structure (Invention 4). In the above invention (Daily Moon 4), it is preferred to contain a polymer crosslinked body, and the same knife is used. The parent complex is obtained by copolymerizing the linear molecule with the heat-sensitive component via a linear molecule of a polymer cross-linking precursor, and the precursor is crosslinked by the intermediate molecular cross-linking precursor. Polymerization of the above 201031699 ring portion And the linear molecule having the above-mentioned linear bond molecule having a block (five) core group at the end on the - side and a polymerizable = energy group at the other end and the linear molecule is formed with the above polymer Inclusion of the misplaced material (Invention 5). " In the above invention (Day 5), the cyclic portion (4) of the above polymer is selected from the group consisting of cyclodextrin (a_cycl〇dextrin), 10,000-cyclodextrin and ring The least of the groups consisting of dextrin is selected from the group consisting of a circular poiyether, a plylyester, a polyetheramine, and a cyclic polyamine (p〇lyamine). In the above invention (Inventions 5 and 6), the heat-sensitive component is a polymerizable compound having an N-isopropylainide group ( Inventive 7) The present invention provides a heat-sensitive polymer gel obtained by forming the heat-sensitive polymer gel (Invention 7) into a film form (Invention 8). If the present invention is used, it is possible to obtain a rapid change in swelling degree by thermal stimulation. A large-sized inductive polymer gel and a thermally sensitive polymer gel film which have a contact angle of water droplets on the surface of the gel. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the embodiment of the present invention is 201031699 The heat-sensitive polymer gel according to the present invention is: (1) by thermal stimulation, the mass is reduced from the maximum water state to less than 20% of the maximum water state within 300 seconds, preferably within seconds Reduced to less than 15% or reduced to less than 20% within 1 second; or (2) The surface water contact angle difference before and after thermal stimulation is 2〇. Above, preferably 30. Above, better is 40. the above. Here, the temperature of the heat stimulation is preferably room temperature or more, i 〇 (rc or less; particularly preferably 40 to 10 〇 ° C, more preferably 6 01: (1) characteristics of the thermal conductivity The rate of change of the degree of swelling of the polymer gel. Further, the change (suppression) of the degree of swelling causes the heat-sensitive polymer gel to release moisture and shrink. Therefore, the characteristic of (1) is the specification of heat sensitivity. The shrinkage rate of the polymer gel. The maximum water content refers to the state of the water in the case where the heat-sensitive polymer gel is at room temperature (preferably 23 〇 makes it substantially impossible to contain more water). Specifically, it means that the heat-sensitive polymer gel in a dry state is immersed in water at a temperature (preferably 23 ° C), and the state in which swelling is stopped can be judged based on the swelling speed. In the present embodiment, the immersion in water at room temperature (preferably 23 ° C) causes the change in the degree of swelling to be less than 5% within 30 minutes as the maximum water content. The technique is not known as (1) - The rate of change (shrinkage speed) of the general expansion schedule is as fast as the heat-sensitive polymer gel. The conventional technology has no such characteristics, and no attempt has been made to improve the speed of change (shrinkage speed) caused by thermal stimulation. In addition, the characteristic of (2) is that it can display a thermally sensitive polymer. The degree of change from the hydrophilicity to the hydrophobicity of the gel 7 201031699. For example, in the present embodiment, by applying a heating stimulus to the heat-sensitive polymer gel, the contact angle of the water droplets becomes large. 'It is calculated from the contact angle of water droplets after thermal stimulation minus the contact angle of water droplets before thermal stimulation. The "before and after thermal stimulation" is determined by the induction temperature and water content of the thermally sensitive polymer gel. 'But as long as the temperature at which the thermal stimulus is induced is centered, the arbitrary temperature on the low temperature side and any temperature on the high temperature side can be compared, and in any possible potential water content, as long as the above-mentioned predetermined water droplet contact angle difference is satisfied For example, in the present embodiment, the heat-sensitive polymer gel (preferably a heat-sensitive polymer gel film) having a water content of 2% by mass is preferably used. The difference in the contact angle of the water droplets on the surface under the conditions of 23C and 60C is within the above-described predetermined range. Of course, the heat-sensitive polymer gel according to the present embodiment can satisfy the characteristics of (1) and (2) at the same time. The heat-sensitive polymer gel according to the form contains a heat-sensitive polymer component and water, and the water content in the heat-sensitive polymer gel is preferably 10% by mass or more, particularly preferably 15 to 100% by mass. %, more preferably 20 to 90% by mass. The water content in the heat-sensitive polymer gel is 10% by mass or more, and the characteristics of the above (2), other characteristics described later, and the like are effectively exhibited. The heat-sensitive polymer component contained in the heat-sensitive polymer gel according to the present embodiment is a heat-sensitive polymer crosslinked body (E) produced by the method schematically shown in Fig. i. . The method for producing the thermally inductive polymer crosslinked body (E) will be described below. 201031699 First, a polymer having two or more cyclic portions (hereinafter referred to as "polymer (A)") has a block group at the end on the side, and a polymerizable terminal at the other end. A linear molecule of a functional group (hereinafter referred to as "linear molecule (B)") (refer to Fig. 1). The cyclic portion of the polymer (A) may surround the linear molecule (B), and in this state, it can move on the linear molecule (B). In the present specification, the meaning of "annular portion" & "ring" is a substantially "ring", and as long as it can move on the linear molecule (B), the annular portion may be incompletely blocked. The ring shape 'for example may be a spiral structure. Further, the polymer (1) is a multi-component having a relatively large molecular weight cyclic molecule as a constituent portion as described later, and its molecular weight itself is large even if the degree of polymerization is small. The polymer (A) is an expedient name established for this reason, and also contains a polymer of a polymer of about 2 to 1 monomer. As the molecule (cyclic molecule) constituting the cyclic portion, cyclodextrin such as cyclodextrin or cyclodextrin, or cyclic polyether (p〇lyether) is preferred. , cyclic polyester (p〇lyester), cyclic polyetheramine (polyetheramine), cyclic polyamine (polyamine), cyclophane (cyclophane) and other cyclic molecules, can also be in polymer (A) or later The local molecular crosslinking precursor (C) or the heat-sensitive polymer crosslinked body (E) described later is mixed with two or more kinds of the above cyclic molecules. In the case where the above cyclic molecule is a cyclodextrin, a hydroxyl chain of a cyclodextrin may be introduced into a polymer chain which enhances the solubility of the polymer (A) with respect to the linear molecule (β) and/or Substituent. Examples of the polymer chain include an oxyethylene chain, an alkyl (311^1) chain, and an acrylic 201031699 acmicester chain. On the other hand, examples of the above-mentioned substituent include an ethyl fluorenyl group, an alkyl group, a trityl 'tosyl group, a trimethyl decyl group, and a stupid group. A crown ether or a derivative thereof, a cyclic lactone (10) elk lactone or a derivative thereof, a caffe cup (caHxarene) or a derivative thereof, which is a specific example other than the cyclodextrin of the above cyclic molecule, may be mentioned. , aZaCyCl〇phane or a derivative thereof, thiaCyci〇phane or a derivative thereof, a macrocyclic amine ether or a derivative thereof, and the like. As a cyclic molecule, it is preferably α-cyclodextrin, 10,000-cyclodextrin, τ _ cyclodextrin, and crown ether, because linear molecules are easily penetrated into a string; particularly preferably α-cyclodextrin Fine, yg _ cyclodextrin, and _ cyclodextrin, because in the water valley easy to form a inclusion complex with chain molecules. The number of the cyclic molecules in the polymer (Α) is 2 or more, preferably 3 to 50, particularly preferably 3 to 5, and the number of the cyclic molecules is two or more, and a plurality of straight A key molecule (Β) is obtained by polymerizing these linear molecules (Β), and a plurality of (co)polymers having a linear molecule (Β) as a constituent unit are connected to each other via a polymer (Α) And constitute a crosslinked structure. When the number of the cyclic molecules is three or more, the crosslinked structure is dense, and therefore the stress relaxation property of the completed heat-sensitive polymer crosslinked body (Ε) is not hindered, and the strength can be improved, which is more preferable. The structure of the polymer (A) is preferably a structure in which two or more cyclic molecules are linked by a linking portion. The starting compound (linking molecule) as the linking moiety is preferably a molecule of 201031699 which does not or is difficult to form a complex with a cyclic molecule. By using such a linking molecule, when the polymer (1) is synthesized, the opening of the cyclic molecule is not blocked, and the cyclic molecule can be linked. The linker may be a straight bond or a branched chain, which is preferably a side bond having a certain degree of magic. For example, in the case where the above cyclic molecule is α-cyclodextrin, it is preferable to have a side chain which is larger than a methyl group. That is, from the viewpoint that the above-mentioned cyclic molecule does not become a inclusion complex, polypropylene glycol (polypropylene glycol), polyacrylic acid vinegar (p〇lyacryHc climbing eSter), poly-double is preferable as a preferred linking molecule. Methyl oxalate (p〇lydimethyis U (4)), polyisoprene (p〇lyisoprene), etc., among which polypropylene glycol is particularly preferred. The number average molecular weight (Mn) of one of the linking molecules is preferably 100 100000, particularly preferably 500 to 10 Q01. If the number average molecular weight of the linking molecules is less than 100 Å, the openings of the cyclic molecules of the polymer (4) formed are too far apart. When it is close, it is difficult to obtain a crosslinked structure, and the effect obtained by the interlocking structure may not be fully exerted. In addition, when the number average molecular weight of the ligated molecule exceeds 100,000, the compatibility with the linear molecule (B) or the like is deteriorated, and it is difficult to form a crosslinked structure. The interlocking structure refers to a mechanical bond structure that does not utilize non-covalent bonds and covalent bonds. The interlocking structure of the present embodiment is a main portion of a linear molecule having two different polymers having a linear molecule (B) as a constituent unit (described later in detail), and each of them penetrates the polymer. In the opening of at least two cyclic molecules of the ^, the end side of the main body portion is protected by the block base, thereby making it impossible to extract the main body portion from the opening portion (rotaxane structure) )), thereby becoming the above-mentioned 11 201031699 two polymers can not be separated structure. By this interlocking structure, the polymer (a) can move through the opening of the cyclic molecule along the bulk portion of the linear molecule (B) of the above polymer, but cannot be pulled out due to the block group. The above two polymers have a higher degree of freedom in the crosslinked portion than the crosslinked structure obtained by covalent bonding, and still have the same degree of linear structure as the crosslinked structure of the covalent bond (B). Bonding. The mass average molecular weight of the polymer (A) is affected by the kind of the cyclic molecule, but it is usually preferably from 1 Torr to 1 Torr, particularly preferably from 3,000 to 100,000. If the mass average molecular weight of the polymer (A) is less than 1 〇〇〇, ^ there are cases where the cyclic molecule is less than two, and there is a possibility that the interlocking structure cannot be formed, and even if an interlocking structure can be formed, The cross-linking structure is very close, and there is a possibility that the effect based on the interlocking structure is not sufficiently exerted. On the other hand, when the mass average molecular weight of the polymer U) exceeds 1 Å, the compatibility with the linear molecule (B) or the like is deteriorated, and it is difficult to form a crosslinked structure. The polymer (A) can be synthesized by a general method. For example, a polymer (A) is obtained by reacting a cyclic molecule having a functional group with a cyclic molecule having a reactive group reactive with a functional thiol group of the cyclic molecule at the terminal. Specifically, in the case where the synthetic cyclic molecule is α-cyclodextrin and the linking molecule is a polypropylene glycol polymer, the α-cyclodextrin is mixed with the polypropylene glycol having a reactive group at the terminal, and is added as needed. The catalyst is reacted to cause the two to react, thereby obtaining a polymer (Α). The functional group of the cyclic molecule to which the linking molecule is bonded is preferably, for example, a hydroxyl group, a carboxyl group, an amine group, a thiol group or the like; and as a reactive group at the terminal of the linking molecule 12 201031699, it is preferably, for example, different The cyanic acid S is an (i socyanat e ) group, an epoxy group, an aziridine group or the like. As the linking molecule, a substance having the following molecules at the terminal can be used, for example, xylylene diisocyanate, hexamethy 1ene di i socyanate, tolylene diisocyanate, and isophora. Isocyanate compound such as isophorone diisocyanate; ethylene glycol diglycidyl ether, pr〇pylene glyc〇1 diglycidyl ether, 1, An epoxy compound such as 6-hexanediol diglycidyl ether; n,N-hexamethyl-1,6-bis(aziziridine) (N, N Aziridine-based compound such as -hexamethylene-1, 6-1^3 (& 2 11^(^1^031'1)(^31^(^)). The linear molecule (B) is subjected to polymerization. The inclusion of the cyclic molecule of the substance (a) is not a chemical bond such as a covalent bond, but a linear molecule or substance which can be integrated by mechanical bonding, and has a block group at one end. The other end has a polymerizable functional group. In the present specification, "Linear" means "substantially linear", that is, as long as the cyclic molecule of the polymer (A) can move on the linear molecule (8), the linear molecule (B) The constituent molecule corresponding to the block base corresponding to the two ends of the linear molecule (8) and the moiety (bulk portion) other than the polymerizable functional group may be a ring that penetrates the polymer (A) in size. The molecule of the opening of the molecule may be. For example, when the cyclic molecule of the above polymer (1) is a cyclodextrin, 13 201031699 is preferably polyethylene glycol (polyethylene glyc 〇 1), polytetrahydrofuran (polytetrahydrofuran), polyethylene. (p〇lyethylene), polycaprolactone, etc., may be mixed in the polymer crosslinked precursor (c) or the thermally inductive polymer crosslinked body (E) by two or more kinds of knives. The linear bond molecule (B) of the bulk portion formed. The number average molecular weight (?η) of the constituent molecules of the bulk portion of the linear molecule (B) is preferably from 1 3 to 300,000, particularly preferably 2 〇〇. ~2000〇〇, more preferably 30 (Μ〇〇〇〇〇. If the number average molecular weight is less than 1 〇〇, the amount of movement of the cyclic molecule on the linear molecule (Β) becomes smaller, and the obtained enthalpy-induced polymer cross-linking is obtained. There is not enough flexibility in the body (Ε). Further, if the number average molecular weight exceeds 300,000, the solubility in the solvent is deteriorated. The block group is not particularly limited as long as it is a form in which a ring-shaped molecule of a polymer (Α) in a state in which a linear molecule is encapsulated is not detached, and the inclusion of a complex compound can be retained. The functional group has a bulky group, an ionic functional group, etc. As the block group, it is preferably, for example, a dialkylphenyl group, a dinitrophenyl group (dinitrophenyn type, a cyclodextrin). Classes, adamantanes, trityls, fluoresceins, pyrenes, anthracenes, etc. can also be incorporated into complexes or polymers. Two or more of these block groups are mixed in the crosslinked body. As a capping agent which forms a block group in combination with a single terminal of the linear molecule (B), for example, dimethyl stupid is applicable. Dimethylphenyl isocyanate, triphenylmethyl 14 201031699 trityl phenyl isocyanate, 2,4-dinitrofluorobenzene, adamantane amine, etc. Polymeric functional Base, as long as it is available The linear functional group (B) is copolymerized with the heat-sensitive component (D) described later, and is not particularly limited. The polymerizable functional group is preferably (meth). Acryl (meth) acry loy 1 (vinyl), epoxy, ethyl bromide, oxetanyl, etc. ® Linear molecules (B) can be synthesized by a general method. For example, a linear molecule having a polymerizable functional group at one end or a linear molecule having a different polymerizable functional group at the terminal on both sides is reacted with a blocking agent for a block group, and The polymerizable functional group is left at one end and the block group is added to the other end, whereby a linear molecule (B) can be obtained. Hereinafter, as an example, a hydroxyl group is provided at one end. a linear molecule having a (meth)acryl fluorenyl group at the other end, mixed with a dialkylphenyl group having a φ ester group of isocyanate, and a catalyst is added as needed to cause the two to react. This results in a dialkylphenyl group at the end of one side as a block group, at the end of the other side. a linear molecule (B) having a (meth) acrylonitrile group as a polymerizable functional group. After preparing the polymer (A) and the linear molecule (β) described above, the polymer (A) is mixed. And the linear molecule (B), the polymer cross-linked precursor (c) is produced by forming all or part of the inclusion complex, that is, the linear molecule (B) penetrates the polymer (A) One of the openings of the cyclic molecule is formed in a series, and at least one of the remaining openings of the ring-shaped group 15 201031699 of the polymer is passed through the other linear polymer to have the above two or more The linear cross-linking precursor (c) of the linear knives (β) which is surrounded by a plurality of cyclic molecules of the same polymer (A) (refer to Fig. 2). On the other hand, the polymer cross-linking precursor (C) is characterized by having a structure in which the above-mentioned inclusion of the erroneous substance is formed, but the opening 邠 of the cyclic molecule 不需要 which does not require the polymer (1) is in such a state. That is, in the polymer (4) as a mixture, it may be a structure in which only the π-end of the cyclic molecule is connected to the linear molecule (8), or may have a straight bond shape. The knife (8) does not completely penetrate the opening of the cyclic molecule of the polymer (A), or may contain a linear molecule (β) which is a mixture which is not surrounded by the polymer α). (1) The above-mentioned polymer cross-linking precursor (c) can be produced so that the polyfluorene water-chain-like molecule (8) can be present in a (four) towel such as water or didimethyl dimethylamine (--IMF). The solution of the mixed solution of water and the mixed solvent of methanol and water (4) is added to (4) of the linear octa (5) (for example, in the polymerization. Before the crosslinking of the polymer: 2), the solution is raised by (4). The mixing method of the body (C) can be made by the viscosity of the solution. There is no particular limitation on the stirring method. The mechanical mixing treatment, ultrasonic wave == preparation, (4), especially preferably Ultrasonic processing to 'where == method; for a few minutes> hours to enter, between: 3⁄4 No: not limited, preferably ... kHz frequency = illuminating strip, the above-mentioned manufacturing of polymer After the precursor (6), the linear molecule (B) is copolymerized with the heat-sensitive component (8) via a polymerizable functional group of the linear bond molecule (8) which is surrounded by a cyclic molecule of the compound 201031699 (A). And obtaining a heat-sensitive polymer crosslinked body (8) (refer to ig). The heat-sensitive polymer crosslinked body (E) is contained In the case of the heat-sensitive component (8), the heat-sensitive property of (1) or (2) is selected to be compatible with the linear molecule (8) via the polymerizable functional group of the linear molecule (8). Polymerized monomer, oligomer or polymer. Preferred examples of the heat-sensitive component (8) include a polymerizable compound having N-isopropyl-pylamide. The polymerizable compound may be a monomer, and may be a polymerizable functional group, or may be a polymer, a polymer, etc. When the polymerizable compound is a polymer, the mass average molecular weight (6) is lower than (4) In particular, when the mass average molecular weight (4) is too large, the mutual solubility with other components may become poor, and the decrease in polymerizability and the decrease in the medianability may be reduced. The polymerizable functional group of the polymerizable compound is not particularly limited as long as it is copolymerized with the linear compound (8). The polymerization: the functional group is, for example, a (meth) acrylonitrile group. B The base, the oxyethylidene group, the oxetanyl group, and the like are particularly preferably a (meth) acrylonitrile group or a vinyl group in consideration of the rapid polymerization rate and ease of availability. In view of the above, as the heat-sensitive component (D), N-isopyrylpyramine (N_is〇pr〇pylacryiamide) is preferred. The polymerizable compound having the above N-isopropylamine group is used. Good 17 201031699 is N-isopropyl acrylamide as the heat-sensitive polymer crosslinked body (E) of the heat-sensitive component (d), and the heat-sensitive polymer crosslinked body (e) is made to contain water. It is a heat-sensitive polymer gel which satisfies the characteristics (1) and (2) above, and also exhibits a characteristic that it changes from transparent or translucent to white significantly due to thermal stimulation. At this time, the difference in the total light transmittance before and after the thermal stimulation is preferably 50% or more, particularly preferably 7% by weight or more.
使用N-異丙基丙烯醯胺來作為熱感應性成分（d)的熱 感應性高分子交聯體（E)的一例是模式性地示於第2圖。但 疋本發明的熱感應性高分子凝膠並未受限於第2圖的樣 態。在第2圖所示的熱感應性高分子交聯體（E)中，是由聚 合物BD!、及Αχ所構成，其中聚合物BDi、BD2是藉由直 鏈狀分子（B)及作為熱感應性成分（1))的卜異丙基丙烯醯胺 的共聚合而得到，聚合物Ax是以連結分子來結合二個以上 的環狀分子而成。而作為聚合物BDi、的直鏈狀分子的 來源的Βχ及By’是分別貫通聚合物Αχ的不同的環狀分子的 開口部，且成為藉由存在於匕及1的末端的嵌段基而無法 拔出的構造（聯鎖構造）。而在第2圖中，是以熱感應性成 刀（D)被排入在聚合物BDl、BD2的主鏈的狀態來作圖示，但 其亦可以存在於聚合物BDl、BL的側鏈、亦可以存在於聚 合物Αχ中。 聚合反應可以藉由一般的方法來進行，通常是藉由自 由基聚合（radical p〇iymerizati〇n)來使其反應。例如在 含高分子交聯前驅體（C)及熱感應性成分（1))的溶液中，添 加所需的光聚合開始劑並照射紫外線、或是添加熱聚合開 18 201031699 始劑並加熱’藉此將直鏈狀分子（幻與熱感應性成分（D)共 聚合。 作為光聚合開始劑者，只要是一般所使用的物質，並 無特別限制’例如可使用二苯基酮（benzophenone)、苯乙 酮（acetophenone)、安息香（benzoin)、安息香曱醚 (benzoin methyl ether)、安息香乙醚、安息香異丙醚、 安息香異丁醚、安息香苯甲酸（benzoin benzoic acid)、 安息香苯甲酸甲醋（benzoin methyl benzoate)、安息香丙 酮（匕6112〇111(1111161:11丫11^七31)、2，4-二乙基嘆吨酮（2,4-diethylthioxanthone)、1-羥基環己基苯基甲酮（1-hydroxycyclohexyl phenyl ketone)、节基二苯硫（benzyl diphenyl sulfide)、 一 硫化四 甲 硫醯胺 (tetramethylthiuram monosulfide)、偶氮雙異丁腈 (azobi si sobutyroni tr i le)、二苯基乙二酮（benzil)、1，2-二苯乙烧（dibenzil 或 dibenzyl 或聯苄）、聯乙醯 (diacetyl)、/3 -氣蒽酿（/S -chi oroanthraqui none)、4-(2-羥乙氧）-苯基（2-羥基-2-丙基）酮、膦氧化（2，4，6-三甲 基苄基二苯基）（（2， 4， 6-trimethylbenzyldiphenyl) phosphine oxide)、2 -苯并嘆嗤-N，N-二乙二硫胺曱酸酯 (2-benzothiazol-N， N-diethyldithiocarbamate)等。而 光聚合開始劑可使用單獨一種、也可以併用二種以上。 上述紫外線可以藉由高壓水銀燈、熔融Η燈（fusion Η lamp)、氣氣燈（xenon lamp)等來取得，照射量通常為 100~500mJ/cm2 ° 19 201031699 另一方面，作為熱聚合開始劑者，只要是一般所使用 的物質，並無特別限制，例如可使用過氧化笨甲醯（WnzoO Peroxide)、偶氮雙異丁腈（az〇bisis〇butyr〇nitri aibn) 等。使用熱聚合開始劑的情況的加熱溫度，可根據熱聚合 開始劑的分解溫度來作適當選擇，通常為〇~13〇。〇左右。 熱感應性高分子交聯體（E)的精製可根據一般方法來 進行，例如以水、四氫呋喃（tetrahydr〇furan)及二甲基曱 酿胺（dimethylformamide)依序洗淨即可。 。若藉由以上的方法，不經過準輪烷（pseud〇r〇taxane)❿ 的單離精製而僅藉由混合擾拌聚合物（A)與直鏈狀分子 (B) ’而可以簡便地製造高分子交聯前驅體，再將所得 到的高分子交聯前驅體(C)的直鏈狀分子(B)與熱感應性成 分〇>)共聚合’藉此可以簡便地製造包含具聯鎖構造的輪烷 結構的熱感應性高分子交聯體（E)。 藉由使所彳于到的熱感應性高分子交聯體邙）含有例如 上述劑定量的水’而可以得到滿足上述⑴及/或⑺的特性 的熱=應性高分子凝膠。另外’關於所得到的熱感應性冑© 刀子父聯體⑻為薄膜狀的情況中’藉由同樣地使其含水 =’而可以得到滿^上述⑴及/或⑺的特性的熱感應性高 、膠薄膜jt匕熱感應性南分子凝膠薄膜不但滿足上述 )的特|·生，亦顯示藉由熱刺激而從透明或半透明顯 著地變成白色的特性。 •’ 為了取得本實施形態相關的熱感應性高分子凝膠 膜，例如將上述高分子交聯前驅體⑹與熱感應性成分⑻ 20 201031699 ‘混合並流入鑄模、或是以捲轴式（r〇11 t〇 r〇⑴的方式塗 佈在基材上，之後藉由加熱或紫外線照射使其共聚合而藉 此形成薄膜狀的熱感應性高分子交聯體（Ε )，亦可以使所得 到的薄膜含水。 薄膜的厚度通常為50〜5000叫、較好為1〇〇〜2〇〇〇⑽、 特別好為150~1500μπΐβ 上述熱感應性高分子凝膠及熱感應性高分子凝膠薄 ❹膜，可期望將其用於熱感應器、醫療用材料、感溫性黏著 劑、溫度調整薄膜、熱感應性遮光薄膜等廣泛的領域中。 、以上所說明的實施形態，是為了容易理解本發明所記 載者，而非為了限定本發明所記載者。因此上述實施形 態所揭露的各個要素，其主要内容亦包含屬於本發明的技 術性範圍的全部的設計變更、均等物等。 【實施例】 以下’藉由實施例等來更具體地說明本發明，但是本 _ 發明的範圍並未受到這些實施例等的限定。 [實施例1 ] (1)聚合物（Α)的合成 使5g的環糊精（NACALAI TESQUE，INC.製）溶解於 50ml的一甲基甲酿胺（dimethyif〇rmamide)中，在此溶液 中加入3. 4g的甲苯2， 4-二異氰酸酯末端聚丙二醇 (Aldrich公司製，Μη: 1000)與200mg的作為錫觸媒的二 月桂酸一丁錫（dibutyltin dilaurate)(東京化成公司 製），在室溫下攪拌一個晚上。 21 201031699 將上述反應溶液注入乙醚中使其沉澱，將回收的固體 乾燥後，以水洗淨並再度乾燥’而得到4.6g的具有α —環 糊精來作為環狀分子、聚丙二醇來作為連結分子、並經由 連結分子連接3〜5個環狀分子的聚合物（Α)。 (2) 直鏈狀分子（Β)的合成 使5g的聚乙二醇（和光純藥工業公司製；Μη: 1〇〇〇) 溶解於50ml的氣化曱烷（methylene chl〇ride)，在此溶液 加入1.6g的3, 5-二甲基苯基異氰酸酯 (3,5-dimethylphenyl isocyanate)(Aldrich 公司製）與 ❹ 2〇〇mg的作為錫觸媒的二月桂酸二丁錫（dibutyitin di laurate)(東京化成公司製），在室溫下攪拌一個晚上。 接下來，在上述溶液加入1.7g的2-曱基丙烯酿氧乙 基異氰酸酯（2-methacryl〇yi〇xyethyl is〇cyanate)(昭和 電工么司製，Karenz MOI)與i〇〇mg的作為錫觸媒的二月 桂酸一丁錫（dibutyltin di laurate)(東京化成公司製）， 在室溫下授拌一個晚上。 將所得到的溶液濃縮之後，注入已冷卻至—乃^的二乙❹ 醚（diethyl ether)中，藉此使其沉澱，並回收此沉澱物。 藉此得到3. 8g之在一側的末端具有3，5_二甲基苯基所構 成的嵌段基、在另一側的末端具有甲基丙烯醯基的聚乙二 醇（ΜΑ-PEG-DPI ;直鏈狀分子（B))。 (3) 高分子交聯前驅體（c)的製造 使300mg的聚合物（A)溶解於lml的〇 4wt%的氫氧化 鈉水溶液，將112mg的直鏈狀分子（B)加入此溶液，一面作 22 201031699 機械性的攪拌、一面進行300秒的超音波照射（35Hz)時， 洛液呈白濁、黏性上升。認為此黏度上升的白濁物，就是 聚合物（A)的環狀分子包接直鏈狀分子（6)而成的高分子交 聯前驅體（C)。 (4)熱感應性馬分子交聯體（e)的製造 將作為熱感應性成分（D)的2. Og的N-異丙基丙烯醯胺 加入被認為是高分子交聯前驅體（C)的上述白濁物，攪拌至An example of the thermally inductive polymer crosslinked body (E) using N-isopropylacrylamide as the heat-sensitive component (d) is schematically shown in Fig. 2 . However, the heat-sensitive polymer gel of the present invention is not limited to the form of Fig. 2. The heat-sensitive polymer crosslinked body (E) shown in Fig. 2 is composed of a polymer BD! and Αχ, wherein the polymers BDi and BD2 are made of a linear molecule (B) and The heat-sensitive component (1)) is obtained by copolymerization of isopropyl acrylamide, and the polymer Ax is obtained by bonding two or more cyclic molecules by linking molecules. On the other hand, ruthenium and By' which are sources of the linear molecule of the polymer BDi are openings of different cyclic molecules which penetrate the polymer oxime, and are formed by block groups existing at the ends of ruthenium and 1 Unable to pull out the structure (interlocking structure). In the second drawing, the thermally inductive forming tool (D) is discharged into the main chain of the polymers BD1 and BD2, but it may be present in the side chains of the polymers BD1 and BL. It may also be present in the polymer crucible. The polymerization can be carried out by a usual method, usually by radical polymerization (radical p〇iymerizati〇n). For example, in a solution containing a polymer cross-linking precursor (C) and a heat-sensitive component (1), a desired photopolymerization initiator is added and irradiated with ultraviolet rays, or a thermal polymerization is added to open the catalyst and heat. In this way, the linear molecule (the sensation is combined with the heat-sensitive component (D). The photopolymerization initiator is not particularly limited as long as it is generally used. For example, benzophenone can be used. , acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl vinegar ( Benzoin methyl benzoate), benzoin acetone (匕6112〇111 (1111161:11丫11^7 31), 2,4-diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone (1-hydroxycyclohexyl phenyl ketone), benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobi si sobutyroni tr i le, diphenyl Benzil, 1,2-diphenylethylidene (dibenzil or dibenzyl or bibenzyl), diacetyl, /3 -qi oroanthraqui none, 4-( 2-(hydroxyethyl)-phenyl(2-hydroxy-2-propyl)one, (2,4,6-trimethylbenzyldiphenyl) phosphine Oxide), 2-benzothiazol-N, N-diethyldithiocarbamate, etc. The photopolymerization initiator may be used alone or in combination of two. The above ultraviolet rays can be obtained by a high pressure mercury lamp, a fusion Η lamp, a xenon lamp, or the like, and the irradiation amount is usually 100 to 500 mJ/cm 2 ° 19 201031699 On the other hand, as a thermal polymerization start The agent is not particularly limited as long as it is generally used, and for example, WnzoO Peroxide, azobisbisisobutyronitrile (az〇bisis〇butyr〇nitri aibn), or the like can be used. The heating temperature in the case of using a thermal polymerization initiator can be appropriately selected depending on the decomposition temperature of the thermal polymerization initiator, and is usually 〇13〇. Hey around. The heat-sensitive polymer crosslinked product (E) can be purified by a general method, for example, by washing with water, tetrahydrofurfuran, and dimethylformamide in this order. . According to the above method, it is possible to easily manufacture only by mixing the polymer (A) and the linear molecule (B) ' without mixing by the separation of pseudo-rhodiumtaxane. The polymer cross-linking precursor and the linear polymer (B) of the obtained polymer cross-linking precursor (C) are copolymerized with the heat-sensitive component 〇>), whereby the conjugate can be easily produced. A thermally inductive polymer crosslinked body (E) of a rotaxane structure of a lock structure. A heat-reactive polymer gel satisfying the characteristics of the above (1) and/or (7) can be obtained by containing, for example, the heat-sensitive polymer crosslinked body 邙). In addition, in the case where the obtained heat-sensitive 胄© knife-to-female joint (8) is in the form of a film, the heat resistance of the above (1) and/or (7) is high by the same water content. The film jt 匕 heat-sensitive southern molecular gel film not only satisfies the above-mentioned characteristics, but also exhibits a characteristic of being significantly changed from transparent or translucent to white by thermal stimulation. In order to obtain the heat-sensitive polymer gel film according to the present embodiment, for example, the polymer cross-linked precursor (6) is mixed with the heat-sensitive component (8) 20 201031699 and flows into a mold or a reel type (r 〇11 t〇r〇(1) is applied to a substrate, and then copolymerized by heating or ultraviolet irradiation to form a film-like heat-sensitive polymer crosslinked body (Ε), which can also be used. The obtained film contains water. The thickness of the film is usually 50 to 5000, preferably 1 to 2 〇〇〇 (10), particularly preferably 150 to 1500 π ΐ β, the above-mentioned heat-sensitive polymer gel and heat-sensitive polymer gel. The thin film can be expected to be used in a wide range of fields such as a heat sensor, a medical material, a temperature sensitive adhesive, a temperature-adjusting film, and a heat-sensitive light-shielding film. The embodiment described above is for ease of use. The present invention is not limited to the description of the present invention. Therefore, the main elements disclosed in the above embodiments also include all design changes belonging to the technical scope of the present invention. [Embodiment] The present invention will be described more specifically by way of Examples and the like, but the scope of the invention is not limited by the examples and the like. [Example 1] (1) Polymer ( 5克的甲醇2, 4-二。 The synthesis of 5g of cyclodextrin (NACALAI TESQUE, INC.) was dissolved in 50ml of methyridine (dimethyif〇rmamide), the solution was added 3. 4g of toluene 2, 4- Isocyanate-terminated polypropylene glycol (Μη: 1000, manufactured by Aldrich Co., Ltd.) and 200 mg of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a tin catalyst, and stirred at room temperature for one night. 21 201031699 The reaction solution was poured into diethyl ether to precipitate, and the recovered solid was dried, washed with water and dried again to obtain 4.6 g of α-cyclodextrin as a cyclic molecule or polypropylene glycol as a linking molecule. A polymer (Α) in which 3 to 5 cyclic molecules are linked by a molecule. (2) Synthesis of a linear molecule (Β) 5 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.; Μη: 1〇〇〇) Dissolved in 50ml of vaporized decane (methyle) Ne chl〇ride), 1.6 g of 3,5-dimethylphenyl isocyanate (manufactured by Aldrich Co., Ltd.) and 〇〇 2 〇〇 mg of dilauric acid as a tin catalyst were added to the solution. Dibutyitin di laurate (manufactured by Tokyo Chemical Industry Co., Ltd.), stirred at room temperature for one night. Next, 1.7 g of 2-mercaptopropene oxyethyl isocyanate (2-methacryl〇yi) was added to the above solution. 〇xyethyl is〇cyanate) (Karenz MOI by Showa Denko, Karenz MOI) and dibutyltin di laurate (made by Tokyo Chemical Industry Co., Ltd.) as a tin catalyst of i〇〇mg, given at room temperature Mix for one night. After the obtained solution was concentrated, it was poured into diethyl ether which had been cooled to -, to precipitate it, and the precipitate was recovered. Thus, 3.8 g of a block group having a block group of 3,5-dimethylphenyl group at one end and a methacryl fluorenyl group at the other end is obtained (ΜΑ-PEG) -DPI; linear molecule (B)). (3) Production of polymer cross-linking precursor (c) 300 mg of the polymer (A) was dissolved in 1 ml of a 4 wt% aqueous sodium hydroxide solution, and 112 mg of a linear molecule (B) was added to the solution. 22 201031699 When mechanically stirred and subjected to ultrasonic irradiation (35 Hz) for 300 seconds, the Lok solution becomes cloudy and viscous. The white turbidity in which the viscosity is increased is a polymer crosslinked precursor (C) in which a cyclic molecule of the polymer (A) is surrounded by a linear molecule (6). (4) Production of heat-sensitive horse molecular crosslinked body (e) The addition of 2.0 g of N-isopropyl acrylamide as the heat-sensitive component (D) is considered to be a polymer cross-linking precursor (C) The above white turbidity, stir until
均勻為止。接下來，加入作為光聚合開始劑的4〇以1的卜 羥基-環己基-苯基—甲酮（卜hydr〇xy_cycl〇hexyl ketone)及二笨基酮（benz〇phen〇ne)的ι:ι共融混合物 (Ciba Specialty Chemicals Inc.製；iruGACURE 500)， 授掉後’在真空泵進行脫氣。之後，&第5圖所示，將藉 述操作所得到的混合溶液，流入玻璃板上的聚矽氧橡 / I的模具（厚度lmm)的内側’蓋上玻璃板而使空氣不要 進=藉由照射紫外線3分鐘（照射條件：照度& MW/cm2、 光量30〇mJ/cm2)，得到凝膠狀的薄膜。 ^所得到的凝膠狀薄膜，被認為是經由上述高分子交聯 引驅體(C)中的直鏈狀分子⑻的聚合性官能基(甲基丙烯 酿基），由直鏈狀分子⑻與熱感應性成分⑻共聚合而成的 '、、、感應陡同分子交聯體（E)(在末端具有嵌段基的高分子的 ^鏈受到聚合物（A)的環狀分子的包接，而由熱感應性成分 的聚合物構成此高分子的主鏈之熱感應性高分子交聯 由所得到的凝膠狀的薄膜所構成的熱感應性高分子交 23 201031699 聯體（E)，是藉由拆卸第5圖所示的上側的玻璃板而取出， 將其依序在水、四氫呋喃、二甲基曱醯胺中浸潰並洗淨， 之後使其乾燥而得到透明的熱感應性高分子交聯體薄膜 (厚度：1. Omm ;非延伸）。 再者，對於此熱感應性高分子交聯體薄膜，藉由使其 含水而成為室溫下（23°C )、含水量為20質量％，而得到透 明的熱感應性高分子凝膠薄膜。 [比較例1] 使用44mg的聚乙二醇二丙稀酸酿（polyethylene 參 glycol di acrylate)(相當於交聯劑）來取代實施例1中的 聚合物（A)之外，與實施例1同樣地製作熱感應性高分子交 聯體薄膜（厚度：1. ;非延伸）^再者’對於此熱感應性 兩分子交聯體薄膜，藉由使其含水而成為室溫下（23°c )、 含水量為20質量％，而得到透明的熱感應性高分子凝膠薄 膜。 [試驗1 ](膨潤率的測定） 將實施例及比較例所得到的熱感應性高分子凝膠薄膜❹ 浸潰於水，確認30分鐘之間的膨潤度的變化為5%以下， 再使水溫從室溫以rc/min的升溫速度上升5〇。匸。此時’ >、J疋在各,皿度下的熱感應性南分子交聯體薄膜的質量，計 算出膨潤率。 膨潤率是從乾燥的薄膜的質量D與膨潤後的薄膜 的質量（Wswell)的差而求得。計算式如下。 膨潤率[%] = {(Wsweu_Wdry)/Uxi〇〇 24 201031699 藉此而得到的溫度與膨潤率的關係示於第3圖的曲線 圖。 藉由第3圖的圖表，瞭解到實施例的熱感應性高分子 凝膠薄膜，是從室溫（23°C)下膨潤率為15〇〇%的狀態，變 化成在達到40Ό的時間點的膨潤率為2〇%以下。相對於 此，比較例的熱感應性尚分子凝膠薄膜，是在室溫（2 3。〇) 下膨潤率為大於600% ;另一方面，即使在4〇t的膨潤率仍 為300%。也就是瞭解到實施例的熱感應性高分子凝膠薄膜 ® 疋與比較例者相比，顯示出對應於溫度的非常大的膨潤· 收縮行為。 [試驗例2 ](收縮行為的評量） 將實施例及比較例所得到的熱感應性高分子凝膠薄膜 (至恤.2 3 C )浸潰於5 0。(：的水，經時性地測定膨潤率 s(t) ’而計算出收縮率Sn。 收縮率Sn是由下式所求得。 • 收縮率Sn=時間（ΐ)時的膨潤率S(t)/最大含水狀態下 的膨潤率S(max) 、藉此所得到的時間與收縮率Sn的關係（收縮行為）示 =第4圖的曲線圖。而最大含水狀態是指在室溫（23°C )中 於水時的膨潤度的變化在3〇分鐘之間不滿5%的狀態。 藉由第4圖的圖表’瞭解到實施例的熱感應性高分子 凝膠薄, β & 、疋與比較例的熱感應性高分子凝膠薄膜比較， 對於溫a ^, ''文的收縮速度顯著較快，而滿足本發明的要件。 [試驗例3](水滴接觸角的測定） 25 201031699 (至皿）及60C (加熱），使用接觸角計（〇uss 公司製；脱⑽）來測定實施例及比較例所得到的熱感應性 高分子交聯體薄膜的表面之對純水的接觸角。結果示於表 1 〇 表1】Evenly. Next, as a photopolymerization initiator, 4 〇 hydroxy-cyclohexyl-phenyl ketone (Bu 〇 〇 _ _ _ yl yl yl 及 及 及 及 及 及 及 及 ben ben ben ben ben ben ben ben ben ben ben : :: The ι eutectic mixture (manufactured by Ciba Specialty Chemicals Inc.; iruGACURE 500) was subjected to degassing under vacuum pumping. After that, as shown in Fig. 5, the mixed solution obtained by the operation will be introduced into the inner side of the mold (thickness lmm) of the polyfluorene rubber/I on the glass plate to cover the glass plate so that the air does not enter. A gel-like film was obtained by irradiating ultraviolet rays for 3 minutes (irradiation conditions: illuminance & MW/cm2, light amount: 30 〇 mJ/cm2). The obtained gel-like film is considered to be a polymerizable functional group (methacrylic acid) of a linear molecule (8) in the above-mentioned polymer crosslinked lead (C), and is composed of a linear molecule (8). ',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The heat-sensitive polymer crosslinked by the polymer of the heat-sensitive component constituting the main chain of the polymer is a heat-sensitive polymer composed of the obtained gel-like film 23 201031699 (E It is taken out by disassembling the upper glass plate shown in Fig. 5, and it is immersed in water, tetrahydrofuran, and dimethyl decylamine, and washed, and then dried to obtain transparent heat. Inductive polymer crosslinked film (thickness: 1. Omm; non-extension). Further, the heat-sensitive polymer crosslinked film is made to have a water content at room temperature (23 ° C). The water content was 20% by mass to obtain a transparent heat-sensitive polymer gel film. [Comparative Example 1] Using 44 m Thermal inductivity was produced in the same manner as in Example 1 except that polyethylene (glycol di acrylate) (corresponding to a crosslinking agent) of g was used instead of the polymer (A) in Example 1. Polymer crosslinked film (thickness: 1.; non-extension) ^ Again, for this thermally inductive two-molecular crosslinked film, by making it watery, it becomes room temperature (23 °c), and the water content is 20% by mass, a transparent heat-sensitive polymer gel film was obtained. [Test 1] (Measurement of swelling ratio) The heat-sensitive polymer gel film obtained in the examples and the comparative examples was immersed in water. It was confirmed that the change in the degree of swelling between 30 minutes was 5% or less, and the temperature of the water was increased from room temperature by a temperature increase rate of rc/min by 5 Torr. At this time, '>, J疋 at each, the degree of the dish The swelling ratio is calculated from the mass of the heat-sensitive southern molecular crosslinked film. The swelling ratio is obtained from the difference between the mass D of the dried film and the mass (Wswell) of the film after swelling. The calculation formula is as follows. %] = {(Wsweu_Wdry)/Uxi〇〇24 201031699 The relationship between the temperature and the swelling rate obtained is shown in 3 is a graph of the heat-sensitive polymer gel film of the example, which is changed from a room temperature (23 ° C) to a swelling ratio of 15% by weight. The swelling ratio at a time point of 40 Å was 2% or less. On the other hand, the heat-sensitive molecular gel film of the comparative example had a swelling ratio of more than 600% at room temperature (23 〇); On the one hand, even if the swelling ratio at 4 〇t is still 300%, it is understood that the heat-sensitive polymer gel film 疋 of the embodiment shows a very large swelling corresponding to the temperature as compared with the comparative example. · Contraction behavior. [Test Example 2] (Evaluation of Shrinkage Behavior) The heat-sensitive polymer gel film (to the shirt. 2 3 C ) obtained in the examples and the comparative examples was impregnated at 50. (: water, the swelling ratio s(t)' was measured over time to calculate the shrinkage ratio Sn. The shrinkage ratio Sn was obtained by the following formula: • Shrinkage ratio Sn = time (ΐ) when the swelling ratio S ( t) / swelling ratio S (max) in the maximum water state, the relationship between the time obtained by this and the shrinkage ratio Sn (shrinkage behavior) is shown in the graph of Fig. 4. The maximum water state is at room temperature ( The change in the degree of swelling in water at 23 ° C is less than 5% between 3 minutes. The heat-sensitive polymer gel of the example is understood by the graph of Fig. 4, β & Compared with the heat-sensitive polymer gel film of the comparative example, the shrinkage speed of the text is significantly faster for the temperature, and the requirements of the present invention are satisfied. [Test Example 3] (Measurement of contact angle of water droplets) 25 201031699 (to the dish) and 60C (heating), the surface of the heat-sensitive polymer crosslinked film obtained in the examples and the comparative examples was measured using a contact angle meter (manufactured by 〇uss Co., Ltd.; Contact angle. The results are shown in Table 1 〇 Table 1]
❹ 一藉由表卜瞭解到與比較例相比，實施例的熱感應性 回分子凝膠薄膜中，藉由加熱的接觸角差達40。以上，表 面狀態從親水性到疏水性而大幅地變化，而滿足本發明的 要件。 【產業上的可利用性】 本發明相關的熱感應性高分子凝膠及熱感應性高分子 凝膠薄膜’可期望將其用於熱感應器、醫療用材料、感溫 性黏著劑、溫度調整薄膜、熱感應性遮光薄膜等廣泛的領 域中。 【圖式簡單說明】 第i圖為一模式圖，係顯示本發明的—實施形態相關 之熱感應性高分子交聯體的製造步驟。 26 201031699 第2圖為一模式圖，係顯示本發明的一實施形態相關 之熱感應性高分子交聯體的構造。 第3圖為一曲線圖，係顯示熱感應性高分子薄膜的溫 度與膨潤率的關係。 第4圖為一曲線圖，係顯示熱感應性高分子薄膜的時 間與收縮率的關係。 第5圖是說明實施例中的熱感應性高分子交聯體（E) 的凝膠狀薄膜的製造方法。 【主要元件符號說明】 無 27藉 It is understood from the table that the difference in contact angle by heating is 40 in the thermally sensitive molecular gel film of the embodiment as compared with the comparative example. From the above, the surface state largely changes from hydrophilic to hydrophobic, and satisfies the requirements of the present invention. [Industrial Applicability] The heat-sensitive polymer gel and the heat-sensitive polymer gel film of the present invention can be expected to be used for a heat sensor, a medical material, a temperature sensitive adhesive, and a temperature. Adjusting films, heat-sensitive light-shielding films and other fields. BRIEF DESCRIPTION OF THE DRAWINGS Fig. i is a schematic view showing the steps of producing a thermally inductive polymer crosslinked body according to an embodiment of the present invention. 26 201031699 Fig. 2 is a schematic view showing the structure of a heat-sensitive polymer crosslinked body according to an embodiment of the present invention. Fig. 3 is a graph showing the relationship between the temperature of the heat-sensitive polymer film and the swelling ratio. Fig. 4 is a graph showing the relationship between the time of the heat-sensitive polymer film and the shrinkage ratio. Fig. 5 is a view showing a method of producing a gel-like film of the thermally inductive polymer crosslinked body (E) in the examples. [Main component symbol description] None 27