201033324 六、發明說明： 【發明所屬之技術領域】 溫度顯現黏著力之感溫性 本發明係有關一種在預定 黏著劑及感溫性黏著膠帶。 【先前技術】 至今’做為可藉由熱來可逆地控制黏著力之黏著劑係 有感溫性黏著劑（例如參照專利文獻…該感溫性黏劑 ❹ 係含有側鏈結晶性聚合物1加熱處理至該侧鏈結晶性聚 合物之融點以上的溫度，則因前述侧鏈結晶性聚合物顯示 流動性而顯現黏著力。 前述感溫性黏著劑之-使用形態之感溫性黏著膜帶 可使用於例如製造專利文獻2中所記载之液晶顯示裝置、 有機發光顯示裝置等平板顯示裝置。具體而言，首先，透 過於基材薄膜之兩面設置由感溫性黏著劑所構成之黏著劑 層而成之感溫性黏著膠帶，將可撓性基板固定於支撐體 上此固疋係經由將前述黏著劑層加熱至側鏈結晶性聚合 物之融點以上的溫度使黏著力顯現來進行^ 接著，於經固定之可撓性基板之表面形成預定之薄膜 圖案。最後’將前述黏著劑層冷卻至未達側鏈結晶性聚合 物融點的溫度使黏著力降低後，將可撓性基板從支撐體剝 離。 ' ^ 另—方面’如專利文獻1中所記載之習知之感溫性黏 著劑’係具有在高溫環境下（例如l5(rc附近）黏著力會 降低之問續。因此，使用習知之感溫性黏著劑之感溫性黏 3 321806 201033324 著膠帶，在高溫環境下之步驟中，無法對應於因可撓性基 板與支撐體之熱膨脹差所造成之彎曲、或因黏著劑層中之 水分/殘留溶劑等揮發所造成之彎曲、浮起應力等，而在 黏著劑層與可撓性基板之間發生剝離。因此，期望有即使 在高溫環境下仍可維持高黏著力之耐熱性優良的感溫性黏 著劑及感溫性黏著膠帶。 〔專利文獻1〕曰本特開平9 —251923號公報 〔專利文獻2〕日本特開2006 — 337983號公報 【發明内容】 ❹ (發明欲解決的課題） 本發明之課題係提供一種具有高耐熱性之感溫性黏 著劑及感溫性黏著膠帶。 (解決課題的手段） 本發明人等係為了解決上述課題而屢次致力研究 後，結果發現下述技術思想。換言之，只要在使構成侧鏈 結晶性聚合物之單體進行聚合後加入交聯劑進行交聯反 0 應，即可提高感溫性黏著劑之耐熱性。 然而，若為形成共價鍵之一般的交聯反應，則側鏈結 晶性聚合物變硬，故柔軟性降低。其結果，即使將該聚合 物加熱至融點以上的溫度，也難以顯示流動性，而難以顯 現黏著力。 雖若將侧鏈結晶性聚合物低分子量化、或減少交聯劑 量等來減少共價鍵，則柔軟性會提高而顯現黏著力，但相 反地凝聚力會降低，而在實際使用時發生凝聚破壞，而發 4 321806 201033324 生所謂糊劑碎裂、殘留之不良情形。 另一方面，若採用金屬鉗合化合物做為交聯劑，則侧 鏈結晶性聚合物與金屬钳合化合物形成配位鍵。該配位鍵 係自由度較共價鍵更高，且容易流動。此傾向係在高溫環 境下更顯著。 流動性係有助於側鏈結晶性聚合物之硬度，而硬度有 助於黏著力。通常，越柔軟的侧鏈結晶性聚合物，則黏著 ^ 力越高，因此以金屬钳合化合物進行交聯之侧鏈結晶性聚 〇 合物可顯現充分的黏著力。而且，若藉由配位鍵，則不會 低分子量化、或因減少共價鍵等交聯鍵結造成凝聚力降 低，而可得到高耐熱性。 本發明係依據此等技術思想而完成者。 本發明之感溫性黏著劑係包含側鏈結晶性聚合物，且 在該側鏈結晶性聚合物之融點以上的溫度顯現黏著力。前 述側鏈結晶性聚合物係由在該側鏈結晶性聚合物中加入金 Ο 屬鉗合化合物進行交聯反應而得之交聯聚合物所構成。 本發明之感溫性黏著膠帶，係將由前述感溫性黏著劑 所構成之黏著劑層設置於基材薄膜之單面或兩面而成。 (發明的效果） 根據本發明，由於可顯示高耐熱性，故即使在高溫環 境下將物品加工時受到任何應力（例如因外部應力、固定 構件/零件等之熱變形所產生之應力），也難以剝離，而可 將零件確實地固定。而且，在從零件剝離時，由於只要將 感溫性黏著劑或黏著劑層冷卻至未達前述側鏈結晶性聚合 5 321806 201033324 物融點的溫度，即可降低黏著力，故可簡單地剝離。 【實施方式】 本發明之黏著劑係感溫性黏著劑。所謂該感溫性黏著 、 劑，係指對應於溫度變化而黏著力產生變化之黏著劑。本 發明之感溫性黏著劑係包含側鍵結晶性聚合物。該侧鍵結 晶性聚合物係在未達融點的溫度結晶化，且在融點以上的 溫度相轉移而顯示流動性。換言之，前述側鏈結晶性聚合 物會對應於溫度變化而可逆地產生結晶狀態與流動狀態。 前述感溫性黏著劑係以在前述侧鏈結晶性聚合物在 ❹ 融點以上的溫度顯示流動性時會顯現黏著力之比例含有側 鏈結晶性聚合物。換言之，前述感溫性黏著劑係含有前述 側鍵結晶性聚合物做為主成分。藉此，在將零件等固定時， 只要將感溫性黏著劑或黏著劑層加熱至前述侧賴晶性聚 合物之融點以上的溫度’則會因前述側鍵結晶性聚合物顯 示流動性而顯現黏著力。此外，在從零件剝離時，只要將 前述感溫性黏著劑冷卻至未達前述侧鍵結晶性聚合物之融 點的溫度’則因前述侧鏈結晶性聚合物結晶化而使黏著力 降低。 所謂前述融點’係意指藉由某種平衡程序使最初整合 成有秩序排狀聚合物特定部分成為無秩序狀態的溫度。 前述融點宜為2代以上，且以2〇至6〇〇c為佳。此外“士 晶化溫度（剝離溫度）以融點―吹以下為佳。前述融點 及結晶化*度係藉由示差熱掃描熱量相邮/分鐘之 測定條件進行測定而得之值。使前述融點及結晶化溫度成 321806 6 201033324 為預定溫度係可經由改變侧鏈結晶性聚合物之組成等來任 意進行。 前述側鏈結晶性聚合物之組成，以例如使具有碳數16 以上之直鏈狀烷基之（甲基）丙烯酸酯、具有碳數1至6 之院基之（甲基）丙烯酸酯、與極性單體（交聯成分）進 行聚合而得之共聚物等為佳。聚合比例以例如具有碳數16 以上之直鏈狀烷基之（曱基）丙烯酸酯為20至80重量份、 具有碳數1至6之烷基之（甲基）丙烯酸酯為20至80重 量份、與極性單體為1至10重量份為隹。 前述具有碳數16以上之直鏈狀烷基之（曱基）丙烯 酸酯可舉例如：（曱基）丙烯酸鯨蠟酯、（甲基）丙烯酸硬 脂酯、（甲基）丙烯酸二十烷酯、（曱基）丙烯酸二十二烷 酯等具有碳數16至22之線狀烷基之（曱基）丙烯酸酯， 前述具有碳數1至6之烷基之（甲基）丙烯酸酯可舉例如： (甲基）丙烯酸曱酯、（曱基）丙烯酸乙酯、（曱基）丙烯 ❹酸丁酯、（甲基）丙烯酸己酯等，前述極性單體可舉例如： 丙烯酸、甲基丙烯酸、巴豆酸、伊康酸、馬來酸、畲馬酸 等含有羧基之乙烯性不飽和單體；（曱基）丙烯酸2-羥基 乙酯、（曱基）丙烯酸2-羥基丙酯、（曱基）丙烯酸2-羥基 己酯等具有羥基之乙烯性不飽和單體等，此等可使用1種 或混合2種以上使用。 前述侧鏈結晶性聚合物之具體的組成可舉例如：使丙 烯酸硬脂酯30至50重量份、丙烯酸曱酯50至70重量份、 與丙烯酸1至10重量份聚合而得之共聚物；使丙烯酸二十 7 321806 201033324 二烷酯30至50重量份、丙烯酸曱酯50至70重量份、與 丙烯酸1至10重量份聚合而得之共聚物等。 聚合方法並無特別限定，可舉例如：溶液聚合法、塊 狀聚合法、懸浮聚合法、乳化聚合法等。例如當採用溶液 聚合法時，可經由將前述所例示之單體與溶劑混合，並在 40至90°C左右攪拌2至6小時左右，使前述單體聚合。 前述側鏈結晶性聚合物之重量平均分子量宜為 200,000 至 1,000,000，且以 400,000 至 800,000 為佳。若前 述重量平均分子量過小，則在將感溫性黏著劑從零件剝離 ® 時，有該黏著劑殘留在零件上之所謂糊劑殘留變多之虞。 此外，若前述重量平均分子量過大，則由於即使將側鏈結 晶性聚合物加熱至融點以上的温度也難以顯示流動性，故 難以顯現黏著力。前述重量平均分子量係藉由凝膠滲透層 析法（GPC)測定側鏈結晶性聚合物後，將所得之測定值 換算成聚苯乙烯而得之值。 在此，本發明之侧鏈結晶性聚合物係由在該側鏈結晶 0 性聚合物中加入金屬甜合化合物進行交聯反應而得之交聯 聚合物所構成。藉此，由於侧鏈結晶性聚合物與金屬鉗合 化合物形成配位鍵，故即使在高溫環境下仍可維持高黏著 力，而可顯示優良的财熱性。 前述金屬钳合化合物可舉例如：多價金屬之乙醯丙酮 配位化合物、多價金屬之乙醯乙酸S旨配位化合物，前述多 價金屬可舉例如··銘、鎳、鉻、鐵、鈦、鋅、銘、猛、錯 等，此等可使用1種或混合2種以上使用。特別是，在本 8 321806 201033324 乙酿乙酸酯配位化 發明中’以鋁之乙醯丙酮配位化合物或 &物為佳’宜為參（乙醯丙酮）鋁。 相對於前述侧鏈結晶性聚合物之總 ，合物之添加量宜為…重量％，且以 過少’則交聯不充分，凝聚力降低， 剝離時發生_殘留之虞。此外4前述添加量過多， 則，屬钳合化合物之反應部位較前述極性單體之反應部位 更多，而有未反應之金屬鉗合化合物析出之虞。 刖述交聯反應可例如以下述方式進行。首先，使構成 侧鏈結晶性聚合物之前述單體進行聚合而得到共聚物後， 在此共聚物中加人溶劑，而得到絲物溶液。接著，只要 在此共聚物溶液中加入金屬鉗合化合物後加熱乾燥即可。 該加熱乾燥之條件係溫度為90至110t左右，時間為/分 鐘至20分鐘左右。 ❽ 本發明之感溫性黏者劑之使用形態並無特別限定。例 如.將添加有金屬鉗合化合物之前述共聚物溶液塗佈於基 材薄膜之單面或兩面並加熱乾燥。藉此，可將由前述感溫 性黏著劑所構成之黏著劑層設置於基材薄膜之單面或兩 面，可將前述感溫性黏著劑製作成感溫性黏著膠帶使用。 此外’亦可為將前述共聚物溶液直接塗佈至被著體並加熱 乾燥之方式。將前述共聚物溶液塗佈於經矽或氟等實施表 面離型處理之基材薄膜之表面並加熱乾燥，而形成感溫性 黏著劑層。只要在使用該感溫性黏著劑層時從前述基材薄 膜剥離’即可將前述感溫性黏著劑製作成無基材之感溫性 9 321806 201033324 黏著劑層使用。 前述基材薄膜可舉例如：聚乙烯、聚對酞酸乙二g旨、 聚丙稀、聚醋、聚醢胺、聚酿亞胺、聚碳酸g旨、乙稀—乙 酸乙嫦酯共聚物、乙稀一丙稀酸乙酯共聚物、乙烯—聚丙 烯共聚物、聚氯乙烯等合成樹脂薄膜。此外，該薄膜可為 由單層鱧或此等之複層體所構成者，厚度通常為25至250 左右。為了提高對於黏著劑層之密著性，也可對前述 基材薄膜之表面實施例如電暈處理、電漿處理、鼓風處理、 化學钱刻處理、底漆處理等表面處理。此外，為了得到無 ❹ 基材之感渴性黏著劑層’也可對基材薄膜之表面實施例如 矽處理、氟處理等表面離型處理。 前述塗佈一般可藉由刮刀塗佈器、輥塗佈器、壓延塗 佈器、刮刀式塗佈器（comma coater)等。此外，依塗佈 厚度或前述共聚物溶液之黏度，也可藉由凹版塗佈器、棒 塗佈器等來進行。包含無基材者之前述感溫性黏著劑層之 厚度宜為5至60"m，且以5至50/zm為佳、以5至40 ❹ "m較佳。 其次’列舉前述製造平板顯示裝置之例子說明本發明 之感溫性黏者膠帶之一使用例。首先，透過將由本發明之 感温性黏著劑所構成之黏著劑層設置於基材薄膜之兩面而 成之感溫性黏著膠帶，將可撓性基板固定於支撐體上。此 固定係使用加熱器等加熱手段將環境溫度加熱至侧鏈結晶 性聚合物之融點以上的溫度來進行。藉此，由於前述側鏈 結晶性聚合物顯示流動性因此使黏著劑層顯現黏著力，故 10 321806 201033324 可透t感溫性黏著膠帶將可撓性基板固定在支樓體上。 材斜撓性基板係財可撓性。構成該可撓性基板之 酉/田β列如·聚碳酸醋、聚對醜酸乙二醋、聚甲基丙稀 广甲酯、聚醯亞胺、聚萘二甲酸乙二酯、聚關 P〇lyethersulfone)、薄膜破璃、金屬箔等。構成前述支撐 體之材料可舉例如玻璃。 ~在將可撓性基板固定後，於該可撓性基板之表面形成 ®預定之薄膜圖案。在形成此薄顧案時，有時環境溫度會 $為高溫。前述感溫性黏著膠帶之黏著劑層由於具有側鏈 二晶性聚合物與金屬鉗合化合物形成配位鍵而成之交聯聚 〇物，故即使在高溫環境下仍可顯示優良的耐熱性。 具體而言，在15〇。〇之環境温度中，對於不鏽鋼之18〇。 韌離強度通常為3N/25mm以上，且以3炱7N/25mm為 隹。因此，只要藉由前述感溫性黏著膠帶，即可充分地對 ❾應於因可撓性基板與支撐體之熱膨脹差所造成之彎曲、或 因黎著劑層中之水分/殘留溶劑等揮發所造成之彎曲、浮 起應力等’而可持續地將可撓性基板固定在支撐體上。 另一方面’取代前述侧鏈結晶性聚合物，而在一般的 内烯酸系黏著劑中添加金屬鉗合化合物製作丙烯酸系黏著 膠帶時，具有以下之問題。換言之，若使该丙烯酸系黏著 膠帶以貼著於被著體之狀態暴露於高溫環境下，則黏著劑 層變柔軟。結果’對於被著體表面之黏著剩層之沾濕性提 高，使黏著劑層經常跟隨存在於被著體表面之凹凸形狀， 而_現所謂定錨效應（anchor effect)。因此’前述丙稀酸 11 321806 201033324 黏著膠帶係在環境溫度降低時黏著力較初期黏著力更高， 而經常發生剝離缺陷。 本發明之感溫性黏著膠帶由於包含侧鍵結晶性节人 物，故即使暴露於高溫環境下而使黏著力較初期黏著力^ 高’只要將環境溫度冷卻至未達側鏈結晶性聚合物之融點 的溫度，則因前述側鏈結晶性聚合物結晶化而使黏著力 (千 低0 因此，在形成薄膜圖案後，由於只要使用風扇等冷卻 手段將環境溫度冷卻至未達前述侧鏈結晶性聚合物之融點 的溫度，則黏著劑層之黏著力降低，故可簡單地將可撓性 基板從支撐體剝離。 再者，則述平板顯示裝置之製造也可使用前述感溫性 黏著劑’取代前述感溫性黏著膠帶來進行。此外，在前述 使用例巾係朗將本發明之感溫性黏著劑及n〖生勘 膠帶使用於製造平板顯示装置之情形，但本發明並不限於 ❹ :’且在如例如半導髅、積層陶瓷電感器、電阻器、鐵氧 體（f—)、偵測器元件、熱阻（th一^ 陶变電子科衫切驗之錢+制。 、下】舉σ成例及實施例 明:不僅限於以下之合成例及實施例。再者，在以下3 明中，「份」係意指重量份。 Β (合成例1) 以丙婦酸硬脂醋（ 本觸媒公司製）.65份、201033324 VI. Description of the Invention: [Technical Field of the Invention] Temperature Sensitivity of Temperature Appearance The present invention relates to a predetermined adhesive and temperature sensitive adhesive tape. [Prior Art] As the adhesive which can reversibly control the adhesion by heat, there is a temperature sensitive adhesive (for example, refer to the patent document... The temperature sensitive adhesive contains a side chain crystalline polymer 1 When the temperature is increased to a temperature higher than the melting point of the side chain crystalline polymer, the side chain crystalline polymer exhibits fluidity to exhibit an adhesive force. The temperature sensitive adhesive is a temperature sensitive adhesive film using a form. The tape can be used, for example, to manufacture a flat panel display device such as a liquid crystal display device or an organic light-emitting display device described in Patent Document 2. Specifically, first, a temperature sensitive adhesive is provided on both surfaces of a base film. a temperature-sensitive adhesive tape made of an adhesive layer, and the flexible substrate is fixed to the support. The solid-state adhesive system exhibits adhesive force by heating the adhesive layer to a temperature above the melting point of the side chain crystalline polymer. Then, a predetermined film pattern is formed on the surface of the fixed flexible substrate. Finally, the adhesive layer is cooled to a temperature at which the melting point of the side chain crystalline polymer is not reached. After the adhesive force is lowered, the flexible substrate is peeled off from the support. ' ^ Other aspects of the conventional temperature sensitive adhesive described in Patent Document 1 are in a high temperature environment (for example, near l5 (rc) The adhesion will be reduced. Therefore, using the temperature sensitive adhesive of the conventional temperature sensitive adhesive 3 321806 201033324 tape, in the high temperature environment, can not correspond to the thermal expansion of the flexible substrate and the support The bending caused by the difference, or the bending or floating stress caused by the volatilization of the moisture/residual solvent in the adhesive layer, etc., causes peeling between the adhesive layer and the flexible substrate. Therefore, it is desirable to have A temperature-sensitive adhesive and a temperature-sensitive adhesive tape which are excellent in heat resistance and high heat-resistance in a high-temperature environment. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-251923 (Patent Document 2) JP-A-2006- 337 983 337 ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ 337 337 ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ In order to solve the above problems, the inventors of the present invention have repeatedly made efforts to study the following technical ideas. In other words, as long as the monomers constituting the side chain crystalline polymer are polymerized, a crosslinking agent is added to carry out cross-linking. The heat resistance of the temperature sensitive adhesive can be improved. However, in the case of a general crosslinking reaction for forming a covalent bond, the side chain crystalline polymer becomes hard, so that the flexibility is lowered. When the polymer is heated to a temperature higher than the melting point, it is difficult to exhibit fluidity, and it is difficult to exhibit adhesiveness. When the side chain crystalline polymer is reduced in molecular weight or the amount of the crosslinking agent is decreased to reduce covalent bonds, flexibility is obtained. It will increase and show adhesion, but on the contrary, the cohesive force will decrease, and in the actual use, cohesive failure will occur, and the hair is broken and the residual condition is caused by the 4321806 201033324. On the other hand, when a metal nip compound is used as the crosslinking agent, the side chain crystalline polymer forms a coordinate bond with the metal cleavage compound. The coordination bond has a higher degree of freedom than the covalent bond and is easy to flow. This tendency is more pronounced in high temperature environments. The fluidity contributes to the hardness of the side chain crystalline polymer, and the hardness contributes to the adhesion. In general, the softer side chain crystalline polymer has a higher adhesive force, so that the side chain crystalline polymer which is crosslinked by the metal nip compound exhibits sufficient adhesion. Further, when the coordination bond is used, high heat resistance can be obtained without lowering the molecular weight or reducing the cohesive force by reducing the cross-linking bond such as a covalent bond. The present invention has been completed in accordance with these technical ideas. The temperature sensitive adhesive of the present invention contains a side chain crystalline polymer and exhibits an adhesive force at a temperature higher than a melting point of the side chain crystalline polymer. The side chain crystalline polymer is composed of a crosslinked polymer obtained by adding a metal ruthenium compound to the side chain crystalline polymer to carry out a crosslinking reaction. In the temperature-sensitive adhesive tape of the present invention, the pressure-sensitive adhesive layer comprising the temperature sensitive adhesive is provided on one or both sides of the base film. (Effect of the Invention) According to the present invention, since high heat resistance can be exhibited, even if the article is subjected to any stress during processing in a high temperature environment (for example, stress due to external stress, thermal deformation of a fixing member/part, etc.), It is difficult to peel off, and the part can be fixed securely. Further, when peeling off from the part, since the temperature sensitive adhesive or the adhesive layer is cooled to a temperature that does not reach the melting point of the side chain crystalline polymerization 5 321806 201033324, the adhesive force can be lowered, so that the adhesive can be easily peeled off. . [Embodiment] The adhesive of the present invention is a temperature sensitive adhesive. The term "temperature sensitive adhesive" refers to an adhesive that changes in adhesion depending on temperature changes. The temperature sensitive adhesive of the present invention comprises a side bond crystalline polymer. The side bond crystalline polymer crystallizes at a temperature that does not reach the melting point, and exhibits fluidity at a temperature phase above the melting point. In other words, the aforementioned side chain crystalline polymer reversibly produces a crystalline state and a flowing state in response to a change in temperature. The temperature-sensitive adhesive contains a side chain crystalline polymer in a ratio at which the adhesiveness is exhibited when the side chain crystalline polymer exhibits fluidity at a temperature higher than the melting point of the side chain. In other words, the temperature sensitive adhesive contains the above-mentioned side bond crystalline polymer as a main component. Therefore, when the component or the like is fixed, if the temperature sensitive adhesive or the adhesive layer is heated to a temperature higher than the melting point of the side lyotropic polymer, the side bond crystalline polymer exhibits fluidity. And it shows adhesion. Further, when the temperature sensitive adhesive is cooled to a temperature at which the melting point of the side-bond crystalline polymer is not removed, the adhesion of the side chain crystalline polymer is lowered to lower the adhesive force. The aforementioned melting point means a temperature at which the initial integration into a disordered state of a specific portion of the ordered polymer is stabilized by a certain balancing procedure. The melting point is preferably 2 generations or more, and preferably 2 to 6 inches. In addition, it is preferable that the melting temperature and the crystallization degree are measured by the measurement conditions of the differential heat scanning calorimeter/minute. The melting point and the crystallization temperature are 321806 6 201033324. The predetermined temperature can be arbitrarily changed by changing the composition of the side chain crystalline polymer, etc. The composition of the aforementioned side chain crystalline polymer is, for example, such that the carbon number is 16 or more. Preferably, the chain alkyl group (meth) acrylate, the (meth) acrylate having a carbon number of 1 to 6 and the copolymer obtained by polymerizing a polar monomer (crosslinking component) are preferred. The ratio is, for example, 20 to 80 parts by weight of a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, and 20 to 80 parts by weight of a (meth) acrylate having an alkyl group having 1 to 6 carbon atoms. And 1 to 10 parts by weight of the polar monomer is ruthenium. The (fluorenyl) acrylate having a linear alkyl group having 16 or more carbon atoms may, for example, be cetyl (meth) acrylate, (methyl) Stearyl acrylate, (meth)acrylic acid a (meth) acrylate having a linear alkyl group having a carbon number of 16 to 22, such as an ester, behenyl (mercapto) acrylate, or the like (meth) acrylate having an alkyl group having 1 to 6 carbon atoms. For example, (meth)acrylic acid acrylate, (mercapto)ethyl acrylate, (decyl) butyl acrylate, hexyl (meth) acrylate, etc., the polar monomer may be, for example, acrylic acid, methyl a carboxyl group-containing ethylenically unsaturated monomer such as acrylic acid, crotonic acid, itaconic acid, maleic acid or humic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, In the above-mentioned side chain crystalline polymer, for example, the specific composition of the side chain crystalline polymer can be used, for example, in the case of an ethylenically unsaturated monomer having a hydroxyl group such as 2-hydroxyhexyl acrylate. a copolymer obtained by polymerizing 30 to 50 parts by weight of stearyl acrylate, 50 to 70 parts by weight of decyl acrylate, and 1 to 10 parts by weight of acrylic acid; and making 30 to 50 parts by weight of acrylic acid with acrylic acid 20 7 321806 201033324 dialkyl ester 50 to 70 parts by weight of decyl ester and 1 to 10 parts by weight with acrylic acid The copolymerization method is not particularly limited, and examples thereof include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method. For example, when the solution polymerization method is employed, the above-mentioned The exemplified monomer is mixed with a solvent and stirred for about 2 to 6 hours at about 40 to 90 ° C to polymerize the monomer. The weight average molecular weight of the aforementioned side chain crystalline polymer is preferably 200,000 to 1,000,000, and is 400,000 to 800,000 is preferable. If the weight average molecular weight is too small, when the temperature sensitive adhesive is peeled off from the part, the so-called paste residue remaining on the part of the adhesive becomes large. Further, if the weight average molecular weight is as described above When the amount is too large, it is difficult to exhibit the fluidity even if the side chain crystalline polymer is heated to a temperature higher than the melting point. The weight average molecular weight is a value obtained by measuring a side chain crystalline polymer by a gel permeation chromatography (GPC) and converting the obtained measurement value into polystyrene. Here, the side chain crystalline polymer of the present invention is composed of a crosslinked polymer obtained by adding a metal sweet compound to the side chain crystalline oligomeric polymer to carry out a crosslinking reaction. Thereby, since the side chain crystalline polymer forms a coordinate bond with the metal entangled compound, high adhesion can be maintained even in a high temperature environment, and excellent heat retention can be exhibited. The metal chelating compound may, for example, be an acetoacetone complex of a polyvalent metal or a ruthenium acetate S complex of a polyvalent metal, and the polyvalent metal may be, for example, nickel, chromium, or iron. Titanium, zinc, Ming, Meng, and the like may be used alone or in combination of two or more. In particular, in the invention of the present invention, it is preferred that the aluminum acetoacetate coordination compound or & is preferably ginseng (acetonitrile) aluminum. The amount of the compound added is preferably 5% by weight based on the total amount of the side chain crystalline polymer, and if the amount is too small, the crosslinking is insufficient, the cohesive force is lowered, and the enthalpy is left at the time of peeling. Further, if the amount of addition is too large, the reaction site of the conjugated compound is more than the reaction site of the polar monomer, and the unreacted metal chelating compound is precipitated. The cross-linking reaction can be carried out, for example, in the following manner. First, after the monomer constituting the side chain crystalline polymer is polymerized to obtain a copolymer, a solvent is added to the copolymer to obtain a filament solution. Next, as long as a metal nip compound is added to the copolymer solution, it is dried by heating. The heat drying condition is a temperature of about 90 to 110 t and a time of from /minute to about 20 minutes. The form of use of the thermosensitive adhesive of the present invention is not particularly limited. For example, the aforementioned copolymer solution to which a metal nip compound is added is applied to one side or both sides of a substrate film and dried by heating. Thereby, the pressure-sensitive adhesive layer composed of the temperature sensitive adhesive can be provided on one side or both sides of the base film, and the temperature sensitive adhesive can be used as a temperature sensitive adhesive tape. Further, it may be a method in which the aforementioned copolymer solution is directly applied to a subject and dried by heating. The copolymer solution is applied to the surface of a substrate film subjected to surface release treatment such as ruthenium or fluorine, and dried by heating to form a temperature sensitive adhesive layer. The temperature sensitive adhesive can be made into a substrate-free temperature sensitive property by peeling off from the base film when the temperature sensitive adhesive layer is used. 9 321806 201033324 The adhesive layer is used. The base material film may, for example, be polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamine, polyaniline, polycarbonate, ethylene-acetate copolymer, A synthetic resin film such as ethyl ethacrylate copolymer, ethylene-polypropylene copolymer or polyvinyl chloride. Further, the film may be composed of a single layer of tantalum or a laminate of these, and has a thickness of usually about 25 to 250. In order to improve the adhesion to the adhesive layer, the surface of the base film may be subjected to surface treatment such as corona treatment, plasma treatment, blast treatment, chemical etching treatment, primer treatment or the like. Further, in order to obtain the thirsty adhesive layer of the base material, the surface of the base film may be subjected to surface release treatment such as hydrazine treatment or fluorine treatment. The aforementioned coating can be generally carried out by a knife coater, a roll coater, a calender coater, a comma coater or the like. Further, depending on the coating thickness or the viscosity of the copolymer solution, it may be carried out by a gravure coater, a bar coater or the like. The thickness of the aforementioned temperature sensitive adhesive layer comprising no substrate is preferably from 5 to 60 " m, preferably from 5 to 50/zm, preferably from 5 to 40 Å " m. Next, an example of use of the temperature sensitive adhesive tape of the present invention will be described by way of an example in which the above-described flat panel display device is manufactured. First, a flexible substrate is fixed to a support by a pressure sensitive adhesive tape formed by providing an adhesive layer composed of the temperature sensitive adhesive of the present invention on both surfaces of a base film. This fixing is carried out by heating the ambient temperature to a temperature equal to or higher than the melting point of the side chain crystalline polymer by a heating means such as a heater. Thereby, since the side chain crystalline polymer exhibits fluidity and thus the adhesive layer exhibits adhesive force, 10 321806 201033324 can be used to fix the flexible substrate to the support body through the t-temperature sensitive adhesive tape. The material oblique flexible substrate is flexible. The 酉/田β column of the flexible substrate, such as polycarbonate, polyacetic acid, ethylene glycol dimethacrylate, polymethyl methacrylate, polyethylenimine, polyethylene naphthalate, poly P〇lyethersulfone), film broken glass, metal foil, etc. The material constituting the support may be, for example, glass. After the flexible substrate is fixed, a predetermined thin film pattern is formed on the surface of the flexible substrate. In the formation of this thin film, sometimes the ambient temperature will be high. The adhesive layer of the temperature sensitive adhesive tape exhibits excellent heat resistance even in a high temperature environment because of a crosslinked polycondensate formed by a side chain dimorphic polymer forming a coordination bond with a metal clamp compound. . Specifically, at 15〇. In the ambient temperature of 〇, 18〇 for stainless steel. The toughness is usually 3N/25mm or more, and is 3炱7N/25mm. Therefore, as long as the temperature sensitive adhesive tape is used, the bending due to the difference in thermal expansion between the flexible substrate and the support or the evaporation of moisture/residual solvent in the coating layer can be sufficiently performed. The resulting bending, floating stress, etc.' can be used to securely fix the flexible substrate to the support. On the other hand, when the acrylic resin adhesive tape is added to a general internal acid-based adhesive to form an acrylic pressure-sensitive adhesive, the following problems are caused. In other words, when the acrylic pressure-sensitive adhesive tape is exposed to a high temperature environment in a state of being attached to the object, the pressure-sensitive adhesive layer is soft. As a result, the wettability of the adhesive remaining layer on the surface of the body is increased, so that the adhesive layer often follows the uneven shape existing on the surface of the object, and the so-called anchor effect. Therefore, the aforementioned acrylic acid 11 321806 201033324 adhesive tape has a higher adhesive force than the initial adhesive when the ambient temperature is lowered, and peeling defects often occur. Since the temperature sensitive adhesive tape of the present invention contains a side bond crystalline section, the adhesion is higher than the initial adhesion even when exposed to a high temperature environment, as long as the ambient temperature is cooled to a side chain crystalline polymer. When the temperature of the melting point is crystallization due to the crystallization of the side chain crystalline polymer (the thousand is low), after the film pattern is formed, the ambient temperature is cooled to a temperature below the side chain by using a cooling means such as a fan. When the temperature of the melting point of the polymer is lowered, the adhesive force of the adhesive layer is lowered, so that the flexible substrate can be easily peeled off from the support. Further, the above-described temperature-sensitive adhesive can be used for the manufacture of the flat display device. The agent is used in place of the above-mentioned temperature-sensitive adhesive tape. In addition, in the above-mentioned use case, the temperature sensitive adhesive of the present invention and the n-ray tape are used in the manufacture of a flat panel display device, but the present invention does not Limited to ❹ : ' and in such as, for example, semi-conducting germanium, laminated ceramic inductors, resistors, ferrites (f-), detector components, thermal resistance (th ^ ^ ceramic electronic shirt test money + system . The following is a description of the following examples and examples. In the following, "parts" means parts by weight. Β (Synthesis Example 1) Stearic acid (made by the company). 65 parts,
曰油公司製）3〇份、丙烯酸曱酯 丙缚酸5份及pERBUtyl ND a 曰 321806 12 201033324 • . 油公司製）0_2份之比例分別加入至乙酸乙酯23〇份中並 混合後，在55 C攪拌4小時使此等單體聚合。所得之共聚 物（側鏈結晶性聚合物）之重量平均分子量為6〇萬，融點 為25°C，結晶化溫度為1〇。〇。 (合成例2)3 parts by oyster sauce company, 5 parts of decyl acrylate acid and pERBUtyl ND a 曰 321806 12 201033324 • The ratio of 0_2 parts of the oil company is added to 23 parts of ethyl acetate and mixed, after The monomer was polymerized by stirring at 55 C for 4 hours. The obtained copolymer (side chain crystalline polymer) had a weight average molecular weight of 60,000, a melting point of 25 ° C, and a crystallization temperature of 1 Torr. Hey. (Synthesis Example 2)
以丙烯酸二十二烷酯（日油公司製）45份、丙烯酸甲 醋（日本觸媒公司製）5〇份、丙稀酸5份及pERBUTYL ND ❽（日油公司製）〇.2份之比例分別加入至乙酸乙酯230份 中並混合後，在55°C攪拌4小時使此等單體聚合。所得之 共聚物（側鏈結晶性聚合物）之重量平均分子量為6〇萬， 融點為55°C，結晶化溫度為4〇。(：。 合成例1、2之共聚物如表1所示。再者，前述重量 平均分子量像藉由GPC測定共聚物後，將所得之測定值換 鼻成聚苯乙烯而得之值。此外，融點及結晶化溫度係藉由 DSC以10°C/分鐘之測定條件進行測定。 ❹[表1] 單體之調配 —_ 重量平均 融點 結晶化溫 組成U 比例 .分子量 (°C) 度(°c) 合成例1 C18A/C1A/AA 30/65/5 6〇萬 25 10 合成例2 C22A/C1A/AA 45/50/5 60萬 55 40 1) C18A :丙烯酸硬脂酯，C22A :丙烯酸二十二院醋， C1A :丙烯酸甲酯，AA，·丙烯酸 (實施例1) 321806 13 201033324 <感溫性黏著膠帶之製作> 首先，使用乙酸乙酯，將前述合成例1中所得之共聚 物溶液以使固形份成為30重量％之方式稀釋。接著，以相 對於經乙酸乙醋稀釋之共聚物溶液之固形份之總量為1重 量％之比例添加參（乙酿丙酮）紹（川研Fine Chemicals 公司製）。 接著，將此共聚物溶液塗佈於厚度l〇0//ln之聚對酞 酸乙二醋薄膜之單面’並在1 〇〇°C加熱1 〇小時使其進行交 聯反應，而製作形成有厚度20/zm之黏著劑層之感溫性黏 著膠帶。 <評估> 將所得之感溫性黏著膠帶在4〇°C之環境溫度貼著於 不鑛鋼板，並依序將環境溫度調整成40、150°C及5°C 後，依據JIS Z0237測定在各環境溫度中保持2〇分鐘後之 180°剝離強度。180°剝離係使用荷重元（I〇ad cdl)以 300mm/分鐘之速度進行。結果如表2所示。 再者，在5 C之環境溫度中之測定係藉由下述之判定 基準進行官能評估。 (1 ) ··易剝離至（5 ):剝離困難 (比較例1) 除了使用氡丙啶（aziridine)化合物（日本觸媒公司 製之商品名「PZ—33」）（U重量％，取代金屬甜合化合物 之前述參（乙醯丙酮）鋁丨重量％做為交聯劑以外，其餘 與前述實施例1同樣進行，而製作形成有厚度20 之黏 321806 14 201033324 著劑層之感溫性黏著膠帶。對於所得之感溫性黏著膠帶， 與前述實施例1同樣進行，測定在各環境溫度中之180°剝 離強度。結果如表2所示。 (比較例2) 首先，以相對於丙烯酸系黏著劑（東洋油墨公司製之 「Oribain BPS5448」）之固形份之總量為1重量％之比例 添加參（乙酿丙酮）铭（川研Fine Chemicals公司製）。接 著，將此丙烯酸系黏著劑塗佈於厚度100/zm之聚對酞酸 ® 乙二酯薄膜之單面，並在100°C加熱10分鐘使其進行交聯 反應，而製作形成有厚度20# m之黏著劑層之丙烯酸系黏 著膠帶。對於所得之丙烯酸系黏著膠帶，與前述實施例1 同樣進行，測定在各環境温度中之180°剝離強度。結果如 表2所示。 (實施例2) 除了使用前述合成例2中所得之共聚物溶液，取代前 ❹述合成例1中所得之共聚物溶液以外，其餘與前述實施例 1同樣進行，而製作形成有厚度20#m之黏著劑層之感溫 性黏著膠帶。對於所得之感溫性黏著膠帶，除了將測定環 境溫度變更為80°C、150°C及23°C，取代40°C、150°C及5 °C以外，其餘與前述實施例1同樣進行，測定在各環境溫 度中之180°剝離強度。結果如表3所示。再者，在23°C之 環境溫度中之測定係藉由與前述在5 °C之環境溫度中之測 定相同的判定基準進行官能評估。 [表2] 15 321806 201033324 黏著劑層 交聯劑 180°剝離強度 (N/25mm) 40°C 150°C 5°C 實施例1 合成例1 金屬甜合化合物 1重量％ 9 6 (1) 比較例1 合成例1 氮丙唆化合物 0.1重量％ 10 2 ⑴ 比較例2 丙烯酸系 金屬鉗合化合物 1重量％ 6 1 (5) [表3] 180°剝離強度 黏著劑層 交聯劑 (N/25mm) 80°C 150°C 23〇C 實施例2 合成例2 金屬鈿合化合物 1重量％ 5 3.5 (1) 由表2、3明顯得知’實施例1、2之感溫性黏著膠帶 係因在150。(：之環境溫度中對於不鏽鋼之丨80°剝離強度為 3N/25mm以上，所以即使在高溫環境下仍維持高黏著 力，而财熱性優良。此外’由在5°C、23°C之壞境溫度中 測定結果得知，若冷卻至未達側鏈結晶性聚合物之融點的 温度，則黏著力充分降低。 16 321806 201033324 相對地，於交聯劑使用氮丙唆化合物之比較例1、及 於丙嫦酸系黏著劑使用金屬钳合化合物之比較例2係，任 一者在150°C之環境溫度中之180°剝離強度皆未達3N/ 25mm，而顯示耐熱性不良之結果。此外，比較例2係因在 5°C之環境溫度中之180°剝離強度為（5)，所以得知發生 剝離缺陷。 【圖式簡單說明】 無。 ® 【主要元件符號說明】 •fe 〇 Μ、、 17 32180645 parts of behenyl acrylate (manufactured by Nippon Oil Co., Ltd.), 5 parts of methyl vinegar (manufactured by Nippon Shokubai Co., Ltd.), 5 parts of acrylic acid, and pERBUTYL ND 制 (made by Nippon Oil Co., Ltd.). The ratios were respectively added to 230 parts of ethyl acetate and mixed, and the mixture was stirred at 55 ° C for 4 hours to polymerize the monomers. The obtained copolymer (side chain crystalline polymer) had a weight average molecular weight of 60,000, a melting point of 55 ° C, and a crystallization temperature of 4 Å. (: The copolymers of Synthesis Examples 1 and 2 are shown in Table 1. Further, the weight average molecular weight is obtained by measuring the copolymer by GPC and then changing the obtained measured value into polystyrene. The melting point and crystallization temperature were determined by DSC at 10 ° C / min. ❹ [Table 1] Monomer blending - _ Weight average melting point crystallization temperature composition U ratio. Molecular weight (°C) Degree (°c) Synthesis Example 1 C18A/C1A/AA 30/65/5 6 million 25 Synthesis Example 2 C22A/C1A/AA 45/50/5 600,000 55 40 1) C18A: stearyl acrylate, C22A : Acrylic twenty-two yard vinegar, C1A: methyl acrylate, AA, · acrylic acid (Example 1) 321806 13 201033324 <Preparation of temperature sensitive adhesive tape> First, using ethyl acetate, the above Synthesis Example 1 The obtained copolymer solution was diluted so that the solid content became 30% by weight. Next, ginseng (acetone) was added in a ratio of 1% by weight based on the total amount of the solid solution of the copolymer solution diluted with ethyl acetate to make (Kawasei Fine Chemicals Co., Ltd.). Next, the copolymer solution is applied to a single side of a film of polyethylene terephthalate film having a thickness of l〇0//ln and heated at 1 ° C for 1 hour to cause a crosslinking reaction. A temperature sensitive adhesive tape having an adhesive layer having a thickness of 20/zm was formed. <Evaluation> The obtained temperature-sensitive adhesive tape is attached to the non-mineral steel sheet at an ambient temperature of 4 ° C, and the ambient temperature is adjusted to 40, 150 ° C and 5 ° C in sequence, according to JIS Z0237. The 180° peel strength after 2 minutes of each ambient temperature was measured. The 180° peeling was carried out using a load cell (I〇ad cdl) at a speed of 300 mm/min. The results are shown in Table 2. Further, the measurement in the ambient temperature of 5 C was evaluated by the following criteria. (1) · Easy peeling to (5): difficulty in peeling (Comparative Example 1) In addition to the use of aziridine compound (trade name "PZ-33" manufactured by Nippon Shokubai Co., Ltd.) (U% by weight, substituted metal) The weight of the above-mentioned ginseng (acetamidineacetone) aluminum ruthenium as the crosslinking agent was carried out in the same manner as in the above-mentioned Example 1, and the temperature-sensitive adhesive of the 321806 14 201033324 coating layer having the thickness of 20 was formed. The obtained temperature-sensitive adhesive tape was measured in the same manner as in Example 1 above, and the 180° peel strength at each ambient temperature was measured. The results are shown in Table 2. (Comparative Example 2) First, relative to the acrylic system A total amount of the solid content of the adhesive ("Oribain BPS5448" manufactured by Toyo Ink Co., Ltd.) was added in a ratio of 1% by weight to the base (Ethylene Acetone) (manufactured by Kasei Fine Chemicals Co., Ltd.). Next, the acrylic adhesive was added. It was coated on one side of a 100/zm polyparaxamic acid ethyl acrylate film and heated at 100 ° C for 10 minutes to carry out a crosslinking reaction to prepare an acrylic layer having an adhesive layer having a thickness of 20 # m. Adhesive tape. For The obtained acrylic pressure-sensitive adhesive tape was measured in the same manner as in Example 1 above, and the 180° peel strength at each ambient temperature was measured. The results are shown in Table 2. (Example 2) The copolymer obtained in the above Synthesis Example 2 was used. The solution was prepared in the same manner as in the above Example 1 except that the copolymer solution obtained in Synthesis Example 1 was replaced, and a temperature-sensitive adhesive tape having an adhesive layer having a thickness of 20 #m was produced. The adhesive tape was measured in the same manner as in the above Example 1 except that the measurement ambient temperature was changed to 80 ° C, 150 ° C, and 23 ° C instead of 40 ° C, 150 ° C, and 5 ° C. 180° peel strength at temperature. The results are shown in Table 3. Further, the measurement at ambient temperature of 23 ° C was carried out by the same evaluation criteria as the above determination at an ambient temperature of 5 ° C. [Table 2] 15 321806 201033324 Adhesive layer cross-linking agent 180° peel strength (N/25 mm) 40° C. 150° C. 5° C. Example 1 Synthesis Example 1 Metal-sweet compound 1% by weight 9 6 (1) Comparative Example 1 Synthesis Example 1 Aziridine compound 0.1% by weight 10 2 (1) Comparative Example 2 Acrylic metal compound compound 1% by weight 6 1 (5) [Table 3] 180° peel strength Adhesive layer crosslinking agent (N/25 mm) 80 ° C 150 ° C 23 ° C Example 2 Synthesis Example 2 Metal chelating compound 1% by weight 5 3.5 (1) It is apparent from Tables 2 and 3 that the temperature-sensitive adhesive tapes of Examples 1 and 2 are at 150. (In the ambient temperature, the 80° peel strength for stainless steel is 3N/25mm or more, so it maintains high adhesion even in a high temperature environment, and the heat is excellent. In addition, it is bad at 5°C and 23°C. As a result of measurement in the ambient temperature, it was found that the adhesion was sufficiently lowered if it was cooled to a temperature at which the melting point of the side chain crystalline polymer was not reached. 16 321 806 201033324 In contrast, Comparative Example 1 using an aziridine compound for a crosslinking agent And Comparative Example 2 using a metal-clamping compound for a propionic acid-based adhesive, the 180° peel strength at any of the ambient temperatures of 150 ° C was less than 3 N / 25 mm, and the result of poor heat resistance was exhibited. Further, in Comparative Example 2, since the 180° peel strength at the ambient temperature of 5 ° C was (5), it was found that a peeling defect occurred. [Simple description of the drawing] None. [Main component symbol description] • fe 〇Μ,, 17 321806