200846439 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種再剝離用黏著片，其係於黏貼在黏 附物之後，可再剝離。 【先前技術】 以進行商品或服務之廣告宣傳爲目的，在化妝品、化 妝用品、飮料及食品等之包裝容器、設置在自動販賣機及 自動剪票機等公共場所之設備、或是電車及汽車等公共場 所所利用之車輛等，黏貼已印刷文字或影像之黏著片。針 對此等之黏著片，尋求於一定期間黏貼之後，黏著劑不會 殘留於黏附物上，且基材片不會被切斷，完美地予以剝離 之再剝離性。但是，爲了顯現再剝離性，一般而言，必須 設計減弱黏著力，黏附於具有凹凸之黏附物或彎曲面等之 情形下，會有隨時間經過而發生剝離之問題。 另一方面，以商品之品名表示，或是爲了使用者或修 理員等之操作說明書或零件替換程序爲目的，在複印機、 印表機、傳真機、個人電腦、電視、空氣調節器、冰箱及 洗衣機等之各種電器製品；大多採行碳粉匣或墨水匣等再 使用之各種關聯性製品；或構成汽車、機車及建築材料等 各種內外裝飾零件等之上，黏貼黏著片。由於此等黏著片 係長期被黏貼後而使用，因此特別要求黏貼於黏附物之期 間，黏著片與黏附物之間，並無浮動之發生或剝離之發生 (以下，將有稱爲浮動剝離之情形。），強化黏著力等之 不容易剝離黏著片的對策爲一般所施行的。 200846439 然而近年來，基於對自然環境之關懷，強烈期望循環 使用過之製品、或構成此等製品之零件的一部分或全部。 例如，藉由熱可塑性樹脂來構成各種電器製品之零件或構 件、此等各種關聯性製品之零件或構件等，以進行循環等。 具體而言，利用碎解機以將使用過之零件或構件或是超過 耐用年數之零件或構件碎解成九粒狀，將其予以加熱熔 融，再作成某些零件或構件後而予以成形，再度使用如此 之再循環成形品。於粉碎此等零件等之時，黏著片貼附於 零件等，於黏貼此黏著片之零件等與黏著片無相熔性之情 形，爲了使利用加熱熔融而不相熔之不純物所再循環的零 件強度得以不降低，將有去除黏著片之必要。因此，習知 利用吹風機加熱黏著片後而予以剝離，或利用硏磨機予以 刮除，之後，將此零件等碎裂成九粒狀，再將其熔融後而 得到再循環成形品。然而，從零件等剝離黏著片之作業係 一種既費事又費時之極爲麻煩的作業，藉此，不可避免零 Φ 件之再循環成本將上升的缺點，因此，於剝離黏著片之際， 要求黏著劑不殘留於黏附物，且基材片不會被切斷，能夠 容易地再剝離。 但是，若僅重視再剝離性的話，在各種電器製品等’ 黏貼於已實施所觀察到的壓紋加工之具有凹凸的表面之情 形，或黏貼於彎曲的黏附物之情形下，將有黏著片發生浮 動剝離的問題。另外，由於從構成各種電器製品等之熱可 塑性樹脂發生的氣體釋出，將發生於暫時所黏貼t ^著1片 200846439 與熱可塑性樹脂之間積存氣泡的問題。 爲了解決如此問題之技術，於專利文獻1中揭示一種 丙烯酸系黏著劑組成物，其特徵在於：相對於（甲基）丙 烯酸烷酯單體成分74.999〜99.9質量％、與（甲基）丙讎 酸烷酯單體成分可進行共聚合之含有羧基的單體〇〜〇〇〇1 質量％、與（甲基）丙烯酸烷酯單體成分可進行共聚合之 含有羥基的單體0.1〜5質量％、及與其他可進行共聚合之 _ 單體〇〜20質量％的單體成分進行自由基共聚合後所得的 丙烯酸系共聚物1 00重量份，含有異氰酸酯系交聯劑〇 . i 〜5重量份而成的丙烯酸系黏著劑組成物，該黏著劑組成 物乾燥皮膜的動態黏彈性光譜測定中之於1 20 °C的儲存彈 性率爲2xl05〜7xl05dyn/cm2及損失正切（tanS)爲〇.〇5 〜0.4，並且於0°C的儲存彈性率爲lxlO5〜4xl06dyn/cm2。 但是，於上述專利文獻1所揭示之黏著加工製品之情 形，雖然再剝離性爲優異的，但是於複印機、印表機、傳 • 真機或此等複合機等之影像形成裝置，或是各種電器製品 等之電子機器具有實施壓紋加工之凹凸表面，黏著力不 足，一旦黏貼後經過長期時，將有被剝離之問題點。 另外，已知一種再剝離用黏著膜（參照專利文獻2 )， 其特徵在於：相對於聚甲基丙烯酸甲酯板之1 80度撕剝黏 著力爲〇.2N/25mm〜5.0N/25mm，固定載重剝離測定法中之 3〇分鐘後的剝離長度爲50mm以下，並且將黏著膜貼於聚 甲基丙烯酸甲酯板，於常溫下放置1小時後，將撕剝速度 200846439 1 m/分鐘、撕剝角度1 8 0度撕剝時之黏著力設爲p 1，於6 0 °C放置24小時後，將撕剝速度lm/分鐘、撕剝角度180度 撕剝時之黏著力設爲P2時的P1與P2之比（P1/P2)爲1.4 〜〇·7。該技術係關於一種再剝離用黏著膜，其係具有優越 之黏接性，不會發生浮動剝離等，另外，於剝離時，黏著 劑將不會污染黏附物而具優越之再剝離性。 再者，已知一種再剝離性黏著膜（參照專利文獻3 )， _ 其係於使聚苯乙烯系膜基材、黏著劑層與剝離片予以積層 之黏著膜中，相對於聚苯乙烯系黏附物之隨時間經過的黏 接力’剝離速度 5mm/分鐘下爲2·0〜4.0N/25mm，並且剝 離速度300mm /分鐘下爲8.0〜12.0 N/25mm;及一種再剝離 型水性黏著劑組成物（參照專利文獻4 )，其特徵在於： 其係由含有聚合物粒子〔X〕與肼衍生物〔Y〕而成的水性 黏著劑組成物，其中，聚合物粒子〔X〕係由含有羰基與羧 基的酸價爲3〜30之聚合物所構成的平均粒徑爲3 00nm以 馨下者，肼衍生物〔Y〕係於分子中具有至少二個肼基，由該 再剝離型水性黏著劑組成物所形成的皮膜，其玻璃轉移溫 度爲-25 °C以下，凝膠分率爲80質量％以上，並且水萃取 物量爲2質量％以下。此等技術係關於一種具優越之黏著 性’並且貼附於黏附物後，即使於長時間放置後，也能夠 容易地從黏附物表面剝離之技術，尤其後者係有關使用乳 液型黏著劑之技術。 然而，於上述專利文獻2〜4中，針對在壓紋加工等之 200846439 表面上黏貼已實施凹凸的粗糖面情形的問題，則無任何之 記載，事實上，若黏貼於壓紋加工面等之粗糙面，經過長 期的話，黏著膜容易剝離。 另外，於專利文獻5中，已知一種容易從複印機、印 表機等之影像形成裝置或各種電子機器之零件去除黏著片 之方法，係於黏貼黏著片之區域形成溝與溝交叉的凹處， 當再循環時，利用用於分解之工具等’沿著溝而切開黏著 片，將凹處作爲記號而剝離黏著片之方法。 但是，已揭示於上述專利文獻5之方法中，於黏貼之 零件中必須實施形成凹處之加工，另外，爲了切開剝離黏 著片，若使用黏著力強的黏著片時，擔憂於剝離途中，基 材將斷裂，或黏著劑殘留於黏附物，將有剝離作業效率變 差之情形。 專利文獻1 :日本專利特開平1 1 - 1 5 8 4 5 3號公報 專利文獻2:日本專利特開20〇4-315775號公報 專利文獻3 :日本專利特開2 0 0 3 - 1 8 3 6 0 4號公報 專利文獻4 :日本專利特開2 0 0 4 - 2 7 7 7 1 1號公報 * 專利文獻5:日本專利特開2003-308020號公報 【發明內容】 發明所欲解決之技術問題 因而，本發明提供一種再剝離用黏著片，不僅是黏附 物之平滑面，對於具有壓紋加工等凹凸之粗糙面，也具有 優越之黏接性的同時’一旦完成黏著片之貼附時，黏著片 200846439 之浮動剝離等將長期不容易發生，另外，於剝離黏著片之 際’具優越之再剝離性，不容易發生因黏著劑而造成黏附 物污染。 尤其’本發明之其他目的係在於提供一種再剝離用黏 著片’對於藉由以聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、 聚苯乙嫌、聚苯醚、AB S、聚碳酸酯及此等之複合材料爲 主要成分之熱可塑性樹脂所構成的平滑表面及粗糙面，顯 | 示優越之黏著性及再剝離性，長期將不會發生浮動剝離。 再者’本發明之其他目的係在於提供一種再剝離用黏著 片’對於具有以丙烯酸系樹脂爲主要成分之表面層的平滑 表面及粗糙面，顯示優越之黏著性及再剝離性，長期將不 會發生浮動剝離。再者，本發明之其他目的係在於提供一 種再剝離用黏著片，解決上述課題，並且對於上述各被黏 著物質之彎曲面’也顯示優越之黏著性及再剝離性，長期 浮動剝離將不會發生。 • 再者，本發明之其他目的係在於提供一種黏著片，即 使從被黏接物質之熱可塑性樹脂發生氣體釋出，也不會發 生氣泡積存於黏著片與熱可塑性樹脂之間。 解」决問穎之技術丰跺 爲了解決上述課題，進行鑽硏之結果，得知使用一種 保持適度彈性與黏性均衡之黏著劑的黏著片能夠達成本發 明之目的。而且，發現長期黏貼後之浮動剝離及再剝離性 係藉由測定動態黏彈性光譜中之高溫區域的損失正切而能 -10- .200846439 夠預見，使本發明得以完成。 亦即’本發明係提供一種再剝離用黏著片，其係於基 材之至少一面具備黏著劑層的再剝離用黏著片，其特徵係 於該黏著劑層之頻率1 Η z、- 5 0〜1 5 0 °C中之動態黏彈性光 譜的損失正切爲： (a )於-2 0 C以下之低溫區域，上方具有凸的波峰； (b)於10〜40 °C之中溫區域，下方具有凸的波峰； I (c)於70C之損失正切爲〇_38〜0.57。 發明之效果 本發明之黏著片，不僅是對於黏附物之平滑面，對於 具有凹凸之粗糙面或對彎曲面也具有優越之黏著性的同 時，一旦完成黏著片之貼附時，黏著片之浮動剝離等將不 會長期發生，另外，於剝離黏著片之際，不會因黏著劑而 污染黏附物或基材片破裂。因而，適合於以下列爲前提之 用途：爲了以進行商品或服務之廣告宣傳爲目的，在化妝 • 品、化妝用品、飮料及食品等之包裝容器、自動販賣機及 自動剪票機等公共場所所設置之設備、或是電車及汽車等 公共場所所利用之車輛等，或是表示爲了使用者或修理員 等之操作說明書或零件替換程序之文字及圖案等各種影像 資訊，黏貼在複印機、印表機、傳真機、個人電腦、電視、 空氣調節器、冰箱及洗衣機等之各種電器製品；大多採行 再使用之碳粉匣、或墨水匣等各種關聯性製品·，或構成汽 車、機車及建築材料等之各種內外裝飾零件等’於一定期 -11- 200846439 間黏貼後而予以剝離。 尤其，因爲本發明之黏著片即使對於藉由以聚乙烯、 聚丙烯、聚對苯二甲酸乙二酯、聚苯乙烯、改性聚苯醚' ABS、聚碳酸酯及此等之複合材料爲主要成分之熱可塑性 樹脂所構成的平滑表面及粗糙面或彎曲面，具有優越之黏 接性的同時，也具有優越之剝離性，於再循環貼附本發明 黏著片的電器製品之情形下，於剝離黏著片之際，不會發 0 生因黏著劑而污染黏附物，或基材片被切斷，另外，因爲 剝離作業也爲容易的，作爲優越之黏著片而黏貼於以再循 環爲目的之電器製品等構件。 再者，本發明之黏著片，即使從熱可塑性樹脂發生氣 體釋出，也能夠防止於黏著片與熱可塑性樹脂之間發生氣 泡積存。尤其，於複印機、印表機、電視等之各種家電製 品中，於製品完成後，以手貼予以貼附的標籤之情形下， 較宜爲厚的標籤，若根據本發明之黏著片，由於厚的基材， φ 排斥力爲強的，因此即使爲氣泡不容易排出之厚度，也能 夠作成具有良好之再剝離性與剝離承受性，不容易發生氣 泡積存之標籤。 再者，對於具有以丙烯酸系樹脂爲主要成分之表面層 的平滑表面及粗糙面或彎曲面，因爲本發明之黏著片係顯 示優越之黏接性及再剝離性，作爲化妝品、化妝用品等之 包裝容器所使用之管子，或作爲黏貼於自動販賣機彎曲面 之再剝離用黏著片也爲優異的。 -12- 200846439 【實施方式】 實施發明之最佳形態 以下’基於其構造要件，更詳細說明本發明之再剝離 用黏著片。還有，於本專利說明書中，所謂（甲基）丙烯 酸，係指丙烯酸或甲基丙烯酸，針對丙烯酸或甲基丙烯酸 之衍生物也爲相同的。另外，所謂循環係指將使用過之製 品作爲同種或別種之製品原材料而加以再利用之情形，將 I 使用過之製品，於原狀態下或修整一部分後而再使用（rouse) 之二種情形。 (再剝離用黏著片之構造） 本發明之再剝離用黏著片係將黏著劑積層於基材片之 至少一面而成物作爲基本構造，以單面黏著片或雙面黏著 片之形式予以形成，必要時將剝離片設置於黏著劑層上。 於任一種之情形下，積層於基材片之黏著劑，可以積層在 基材片之至少一面的整面，也可以爲一部分。 • 另外’單面黏著片之情形，也可以在黏著劑層與相反 側之基材片表面進行印刷。再者，以保護其印刷面，或提 高創意性或美觀性爲目的，也可以透過黏著劑層或黏接劑 層，將透明膜或消光色調之半透明膜積層於印刷面。 (黏著劑層之動態黏彈性特性的規定方法） 構成本發明之再剝離用黏著片之黏著劑層的動態黏彈 性特性，其係根據特定頻率及特定溫度之動態黏彈性光譜 的損失正切，或根據損失正切及儲存彈性率而加以規定， -13- 200846439 再者，顯示特定頻率之動態黏彈性光譜的損失正切波峰之 溫度，或損失正切之波峰値而加以規定。於動態黏彈性之 測定中，使用黏彈性試驗機（Rheometrics公司製之商品 名：Ares 2KSTD )，於相同試驗機之測定部位的平行圓盤 之間夾入試驗片，測定於頻率1 Hz、從-5 0 °C至1 5 0 °C爲止 之儲存彈性率（G’）與損失彈性率（G”）。試驗片也可以 單獨將厚度〇·5〜2.5mm之黏著劑夾入於平行圓盤之間。還 0 有，後者之情形係僅使黏著劑之厚度成爲該範圍之方式來 加以調整。本發明人等已確認若將作爲黏著劑之厚度調整 成爲上述範圍時，即使基材被夾持於中間，對於黏著劑之 動態黏彈性光譜也不會造成影響。 構成本發明之再剝離用黏著片之黏著劑層，於頻率 1Hz下之- 5 0°C〜150°C範圍的損失正切，於- 20°C以下之低 溫區域，上方具有凸狀的波峰，從低溫區域至中溫區域減 少，於1 0〜4 0 °C之中溫區域，下方具有凸的波峰，從中溫 # 區域上升至高溫區域，採取於7 0 特定範圍內之値。 藉由將損失正切設爲上述各範圍，將適度之流動性賦 與黏著劑。具體而言，即使於黏附物表面之微小凹凸內也 發現能夠滲透之流動性的同時，由於並非過度流動，也能 夠抑制黏接力之過度上升。再者，藉由黏著劑適度流動之 性質，能夠緩和施加於黏著劑之應力。其結果，隨時間經 過或高溫環境下予以曝露後，再剝離黏貼於黏附物的黏著 片之作業中，不會發生使欲剝離之基材變得容易破裂、黏 -14- 200846439 著劑變成容易殘留於黏附物。另外’即使隨時間經過或高 溫環境下，曝露已貼附於黏附物的黏著片時’也不容易發 生黏著片之浮動剝離。再者，將黏著片黏貼於熱可塑性樹 脂之情形下，即使從熱可塑性樹脂發生氣體釋出，於黏著 片與熱可塑性樹脂之間，氣泡積存也將變得不容易發生。 (高溫區域中之黏著劑層的損失正切） 於5 0〜1 2 0 °C之高溫領域中，構成本發明之再剝離用 I 黏著片之黏著劑層在頻率1Hz、70°C的損失正切爲0.38〜 0.57。於70 °C的損失正切適宜爲0·43〜0.55，更佳爲0.46 〜〇 · 5 4。另外，於5 0 °C的損失正切適宜爲0 · 3 8〜0 · 5 3，更 佳爲0.40〜0.51。另外，於100 °C的損失正切適宜爲0.40 〜0.65，更佳爲0.44〜0.65，尤以0.50〜0.60特別理想。 再者，於120°C之損失正切適宜爲0.40〜0.66,更佳爲0.45 〜0·66。其中，尤以0.51〜0.62特別理想。 (中溫區域中之黏著劑層的損失正切） # 於頻率1Hz、10°C〜60°C之間，構成本發明再剝離用 黏著片之黏著劑層的損失正切係於下方具有凸的波峰。再 者’其波峰値適宜爲〇·35〜0.51，更佳爲0.4〜0.51。 (顯示低溫區域中之損失正切曲線的凸波峰之溫度） 於頻率1 Hz，構成本發明之再剝離用黏著片之黏著劑 層，顯示其損失正切曲線的凸波峰之溫度適宜爲_ 2 〇 t以 下，更佳爲-25 °C以下，尤以-30 °C以下特別理想。若爲此 車巷圍內’於黏貼時，黏著劑層將容易於壓紋面等之凹凸面 -15- 200846439 充分流動，其結果，與黏附物之黏接力變得足夠，隨時間 經過，浮動剝離不容易發生。另外，於進行再剝離時，不 容易顯現間斷性抗拒感，或嘎啦嘎啦之剝離聲音，能夠進 行順利的剝離作業。 (低溫區域中之損失正切的凸波峰値） 構成本發明之再剝離用黏著片之黏著劑層，其損失正 切之波峰値較宜爲1 . 3〜1 . 0以下。 (黏著劑層之貯藏彈性率） 於頻率1Hz，構成本發明之再剝離用黏著片的黏著劑 層，其於70 °C之儲存彈性率較宜爲6.0x1 04〜2.1 xl 05( Pa)。 另外，於50°C之儲存彈性率較宜爲7.0χ104〜2.4x1 05( Pa)。 另外，於 1 0 0 °C之儲存彈性率較宜爲 3.0 X 1 0 4〜1.6 X 1 0 5 (Pa)。另外，於120 °C之儲存彈性率較宜爲2.ΟχΙΟ4〜1.4 xlO5 ( Pa)。再者，於-4 0 °C之儲存彈性率較宜爲5.0x1 〇6 〜5.〇xl〇7(Pa) 〇 φ (初期黏著力） 本發明之再剝離用黏著片的初期黏著力F a較宜爲3.0 〜9.0(N/25mm)。另外，初期黏著力Fa較宜爲3.0〜8.0 (N/25mm )，其中，更佳爲 3.0 〜7.0(N/25mm)。還有， 初期黏著力Fa係以相對於依照JIS B 〇6012()()1所定義之輪 廓曲線的算術平均高度R a ( 3 )爲〇〜〇 · 1 μ m之聚苯乙燒板 成9 〇度撕剝黏接力所定義之値，該9 0度撕剝黏接力係根 據JIS Z 023 7，於壓黏速度5mm/s、壓黏次數1次來回， -16- 200846439 將貼上試驗片之試驗板，於溫度23±2°C、相對濕度50土5 %之氣體環境中放置24小時後，拉伸速度50m m/m in之條 件下所測定的値。 若初期黏著力Fa爲上述範圍時，於黏貼黏著片之期 間，剝離不容易發生。另外，於進行剝離之際，黏著劑將 殘留於黏附物，或是基材片從破壞之黏附物的剝離變得困 難也不容易發生。 0 另外，於本發明之再剝離用黏著片中，將相對於該Ra (3)爲 6.8〜7·2μιη之聚苯乙烯板的初期黏著力設爲Fb (N/25mm)時，該Fa與該Fb之關係較宜符合式（1): 0.30<Fb/Fa<l .00 ( 1 ) 初期黏著力Fb係相對於該Ra ( 3 )爲6.8〜7.2卞111之聚 苯乙烯板成90度撕剝黏接力所定義之値，90度撕剝黏接 力係根據JIS Z 02 3 7，於壓黏速度5mm/s、壓黏次數1次 來回，將貼上試驗片之試驗板，於溫度23 ±2 °C、相對濕度 • 5 0±5%之氣體環境中放置24小時後，拉伸速度50mm/min 之條件下所測定的値。還有，Fb/Fa之値更佳爲符合下式 (2)，最好爲符合下式（3 )。該Fb與Fa之關係於此範 圍內，其係意指黏著片不僅對黏附物之平滑面，即使對具 有凹凸的粗糙面也具有優越之黏接性。若Fb/Fa之値爲此 範圍時，可以得到相對於具有凹凸面的粗糙面之良好黏著 力，浮動剝離不容易發生。 0.40<Fb/Fa<l .00 ( 2 ) -17- 200846439 0.50<Fb/Fa<l .00 ( 3 ) (基材片） 使用於本發明之再剝離用黏著片的基材片，不應該爲 予以特別限定之物，例如，可列舉：塑膠系薄膜、纖維素 系薄膜、不織布、紙、布或金屬箔等。 塑膠系薄膜可列舉：聚烯烴（例如，聚丙烯、聚乙烯）、 聚酯（例如，聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯）、 聚苯乙烯、ABS、聚碳酸酯、聚醯亞胺薄膜、聚氯乙烯、 耐綸、聚乙烯醇等；纖維素系薄膜可列舉：賽珞凡 (cellophane)、二醋酸纖維素、三醋酸纖維素等。另外，不 織布可列舉：紙漿、螺縈、馬尼拉麻、丙烯腈、耐綸、聚 酯等；紙可列舉··高級紙、樹脂塗布紙等。尤其，單面黏 著片之情形，爲了於防止再剝離時基材片之切斷，較宜將 塑膠系薄膜作爲基材片使用。另外，關於上述材料，能夠 m II獨成分爲主要成分，也能夠使用此等之複合材料。再 # 者’以改質基材片之目的下，也可以少量添加其他成分。 例如’將聚苯乙烯使用於基材片之情形，較宜使用將聚丁 =烯少量摻合於主要成分之聚苯乙烯中，使柔軟性得以提 高之高衝擊聚苯乙烯（HIPS )，再者，以耐光性爲必要之 1青M T ’較宜使用甲基丙烯酸甲酯-苯乙烯共聚合樹脂（MS 樹脂）或丙烯腈-苯乙烯-丙烯酸共聚合樹脂（ASA樹脂） 胃t胃丙烯酸系單體的共聚合樹脂或摻合丙烯酸系樹脂之 基材片。 -18- 200846439 另外，將再剝離用黏著片使用於再循環構件的標籤等 之情形下，也較宜將使用於再剝離用黏著片之基材主要成 分作成與黏附對象之再循環構件主要成分可進行相同的再 循環處理之基材，尤以作成與黏附對象之再循環構件相同 的基材特別理想。例如，適用於黏貼在具備由以聚丙烯、 聚乙烯、聚苯乙烯、聚苯醚、AB S、聚碳酸酯及此等之複 合材料爲主要成分之熱可塑性樹脂所形成的構件之電器製 0 品等該構件的用途之情形，藉由將與該構件的主要成分相 同性質之聚丙烯、聚乙烯、聚苯乙烯、聚苯醚、AB S、聚 碳酸酯作爲基材片之主要成分，由於與該構件之相溶性將 提高，必要時不予以再剝離，黏貼黏著片之狀態下，直接 連同該構件進行材料再循環也變得可能，能夠進一步提高 再循環適合性。 例如，該構件之主要成分爲聚丙烯之情形，期望使用 聚丙烯作爲基材片之主要成分；該構件之主要成分爲聚乙 # 烯之情形，期望使用聚乙烯作爲基材片之主要成分；該構 件之主要成分爲聚苯乙烯之情形，期望使用聚苯乙烯作爲 基材片之主要成分；該構件之主要成分爲聚苯醚之情形， 期望使用聚苯醚作爲基材片之主要成分；該構件之主要成 分爲ABS之情形，期望使用ABS作爲基材片之主要成分； 該構件之主要成分爲聚碳酸酯之情形，期望使用聚碳酸酯 作爲基材片之主要成分；該構件之主要成分爲聚碳酸酯與 AB S的複合材料之情形，期望使用以聚碳酸酯、A b S、或 -19- 200846439 聚碳酸酯與abs之複合材料爲主要成分之熱可塑性樹脂所 構成的基材片。 另外，爲了抑制因來自熱可塑性樹脂之氣體釋出所造 成之黏著片與熱可塑性樹脂之間的氣泡積存，期望使用氣 體透過性優越之基材。例如，可列舉：聚丙烯、聚乙烯、 聚苯乙烯等。_ HIPS基材片之情形，拉伸斷裂強度MD較宜爲20MPa 0 以上、TD較宜爲15MPa以上。若爲上述範圍的話，進行 再剝離之際，基材並未被切斷而進行剝離將成爲可能。再 者，拉伸斷裂伸度係MD與TD較宜均爲30〜60%。若爲 上述範圍，爲了賦與適度之剛性與柔軟性，薄膜變得不容 易斷裂的同時，也變得不容易拉伸，再剝離性將進一步提 高。 基材片之拉伸斷裂強度及拉伸斷裂伸度係於溫度23 土2 °C、相對濕度50±5%之氣體環境中，在拉伸速度200mm/min # 之條件下，拉伸基材片，依基材斷裂時之強度與伸度而加 以規定。於規定之時，依基材片之流動方向（MD )、寬度 方向（TD )而加以規定。於測定之時，雖然基材片較宜單 獨測定，但是，本發明人等確認：即使黏著劑層予以積層 之狀態下，也不會對拉伸斷裂強度及拉伸斷裂伸度造成影 響。 著色基材之情形，能夠添加利用與基材片相同的樹脂 以攪拌氧化鈦等之無機顏料的著色劑（母煉膠）。相對於 -20- 200846439 成爲薄膜基底之樹脂100質量份，添加量適宜摻合5〜20 質量份之含有5 0質量％氧化鈦的母煉膠，更佳爲1 0〜1 5 質量份。藉由設爲5質量份以上，基材之隱蔽性將變得良 好，藉由設爲20質量份以內，起因於母煉膠之基材破裂， 或魚眼等之異物將變得不容易發生。 此等基材片之厚度最好因應於使用目的或狀況而予以 適當決定，單面黏著片之情形，基於貼銅積層物作業性或 ^ 抗排斥性之觀點，適宜爲1 5〜2 5 0 μιη，更佳爲2 5〜1 1 5 μιη， 更理想爲50〜95 μιη。另一方面，雙面黏著片之情形，適宜 爲3〇〜2〇〇0111，更佳爲5〇〜15〇0111，再者，坪量（卩&口€]：\^丨邑111 ingsm)適宜爲 10 〜100g/m2，更佳爲 15 〜50g/m2。 (基材片之表面處理） 另外，基於與積層於基材片上之層（黏著劑層或印刷 層等）的緊貼性得以提高之目的下，亦可對基材片之單面 或雙面實施電暈處理、電漿處理、粗糙面化處理、火焰處 φ 理、鉻酸處理、熱風處理、臭氧照射處理，紫外線照射處 理或是也可以塗布增黏塗劑。尤其，於積層黏著劑側之基 材表面，藉由實施電暈處理或增黏塗劑處理，於是黏著劑 層不容易從基材之表面剝離，將本發明之再剝離用黏著片 黏貼於黏附物後之再剝離性將提高，能夠進一步防止黏著 劑層殘留於黏附物。 增黏塗劑層（anchor coat)係藉由將由吸附墨水之顏 料、黏結樹脂與分散劑所構成的增黏塗劑塗布於基材片上 -21- 200846439 而予以形成。顏料能夠使用習知之碳酸鈣、氧化鈦、合成 二氧化矽等。其中，將基材片捲成圓筒狀之際，也考量防 止基材片背面與增黏塗劑層之結塊，較宜爲使粒徑得以自 由變化之合成二氧化矽。黏結樹脂能夠使用丙烯酸樹脂、 胺甲酸酯樹脂、聚乙烯醇樹脂、氯乙烯·醋酸乙烯酯共聚合 樹脂、聚酯樹脂等。其中，較宜爲大多紫外線硬化型墨水 (UV墨水）之黏結樹脂所使用之丙烯酸樹脂。分散劑並未 予以特別限定，塗布於利用溶劑容易膨潤或溶解之聚苯乙 烯或AB S等基材片上之情形，選擇不使基材片予以溶解之 分散劑，較宜爲異丙醇、乙醇等之以醇爲主體之物。增黏 塗劑之摻合較宜爲顏料5〜10質量份、黏結樹脂20〜30質 量份、分散劑60〜70質量份之範圍內。塗布劑之塗布量適 宜爲 0.5 〜4.0g/m2，更佳爲 1.0 〜2.0g/m2。 增黏塗劑之對基材片的塗布法能夠使用照相凹版塗布 機、刮刀塗布機、滾筒塗布機等。其中，較宜爲照相凹版 塗布機。 (黏著劑之調製） 使用於本發明之再剝離用黏著片的黏著劑能夠使用習 知之丙烯酸系、橡膠系、乙烯醚系、矽氧烷系之黏著劑。 此等黏著劑之中，較宜爲丙烯酸系黏著劑。尤其，單體成 分較宜爲含有具備碳數1〜1 4烷基之（甲基）丙烯酸酯的 丙烯酸系共聚物。例如爲：（甲基）丙烯酸甲酯、（甲基） 丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸異 -22- 200846439 丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、 (甲基）丙烯酸正戊酯、（甲基）丙烯酸正己酯、（甲基） 丙烯酸正辛酯、（甲基）丙烯酸異辛酯、（甲基）丙烯酸 -2-乙基己酯、（甲基）丙烯酸正壬酯、（甲基）丙烯酸異 壬酯、（甲基）丙烯酸正癸酯、（甲基）丙烯酸正月桂酯 等，能夠單獨使用或倂用二種以上後而使用。其中，較宜 爲以丙烯酸正丁酯、丙烯酸-2-乙基己酯，或倂用此等之單 0 體爲主要成分，其用量適宜爲黏著劑組成中之50〜99質量 %，更佳爲95〜99質量％。再者，以（丙烯酸正丁酯/丙 烯酸-2-乙基己酯）所示之質量比適宜爲70/3 0〜0/100，更 佳爲45/55〜5/95，更理想爲35/65〜15/85。本發明人等發 現：主要單體係藉由設定上述之種類、用量，容易控制於 上述動態黏彈性光譜中之低溫區域的損失正切之外，並容 易將凸的波峰値控制於目的之範圍。 再者，較宜於〇 · 〇 1〜1 5質量％之範圍添加側鏈上具有 • 羥基、羧基、胺基等官能基之乙烯系單體。例如爲：（甲 基）丙烯酸-2-羥乙酯、（甲基）丙烯酸-2-羥丙酯、（甲基） 丙烯酸-4-羥丁酯、丙烯酸、甲基丙烯酸、馬來酸、馬來酸 酐、衣康酸、巴豆酸、富馬酸、丙烯酸馬來酸酐羧丙酯、 二甲胺乙基丙烯醯胺、N-乙烯基吡咯烷酮、丙烯腈、N-乙 烯基己內醯胺、丙烯醯胺、苯乙烯、醋酸乙酯、N-羥甲基 丙烯醯胺、甲基丙烯酸環氧丙酯等，此等乙烯系單體能夠 單獨使用或倂用二種以上後而使用。其中，較宜爲使用含 -23- 200846439 有羧基之乙烯系單體，更佳爲使用丙烯酸、甲基丙烯酸或 ^ 倂用此等之單體义再者，其用量較宜爲0.5〜4.0質量％。 尤其，爲了使再剝離性與對彎曲面之黏接性得以提高，較 宜倂用丙烯酸與甲基丙烯酸後而使用。尤其，使用將丙烯 酸與甲基丙烯酸之總量成爲黏著劑組成中之1 · 5〜2 · 5質量 %的量，甲基丙烯酸與丙烯酸之比例適宜設爲質量比〇.5 〜2.0’更佳爲1.0〜1.5。本發明人等發現：含有羧基之單 I 體係藉由設定上述之種類、用量，便容易將上述動態黏彈 性光譜中之損失正切値控制於目的之範圍內，再剝離性將 進一步提高。 丙烯酸系共聚物能夠藉由依照溶液聚合法、塊狀聚合 法、懸浮聚合法、乳化聚合法、紫外線照射法、電子線照 射法予以共聚合後而得到。其中，較宜爲乳化聚合法。 爲了進一步提高黏著劑之凝聚力，使黏著力或再剝離 性得以提高，較宜添加交聯劑。例如，交聯劑可列舉：異 # 氰酸酯系交聯劑、環氧系交聯劑、螯合物系交聯劑、噁唑 啉系交聯劑等。其中，較宜爲噁唑啉系交聯劑。尤其，使 用噁唑啉系交聯劑之情形，藉由提高與基材片之緊貼性， 因而再剝離性將提高而較佳。再者，與噁唑啉基進行反應 之單體，較宜使用丙烯酸與甲基丙烯酸，噁唑啉基相對於 羧基之官能基數目比將成爲0.05〜0·25。另外，爲了使 黏著力得以提高，也能夠使用習知之賦與黏著的樹脂。 本發明之動態黏彈性光譜中之50°C〜120°C的損失正 -24- 200846439 切能夠根據交聯劑之添加量、Tg而加以調整。欲使損失正 切予以上升之情形，藉由減少交聯劑之添加量、使用Tg 低的交聯劑而予以達成；欲予以降低之情形，藉由增加交 聯劑之添加量、使用高Tg的交聯劑而予以達成。 另外，於黏著劑中，例如能夠添加光安定化劑、紫外 線吸收劑、可塑劑、軟化劑、塡充劑、顏料、難燃劑等習 用之添加劑。光安定化可列舉：鏈抑制劑、過氧化氫分解 Φ 劑、金屬惰性劑及紫外線吸收劑等。藉由使用如此之添加 劑，能夠使上述之耐黃變性得以提高。 (黏著劑之型式） 黏著劑之型式能夠使用乳液型、溶劑型、無溶劑型等 之黏著劑，用於本發明之再剝離用黏著片的黏著劑較宜爲 乳液型黏著劑。本發明人等發現：因爲乳液型黏著劑不使 用溶劑，就環境面而言，爲優越之同時，也容易將上述動 態黏彈性光譜中之高溫領域的損失正切控制於目的之範圍 _ 內。 (丙烯酸系乳液型黏著劑之調製） 本發明中之丙烯酸系乳液型黏著劑之製法並未予以特 別限定，能夠使用習知方法。聚合方法能夠採用分批聚合、 連續滴下聚合、分開滴下聚合等，例如，聚合溫度約爲20 〜100〇C 〇 於爲了得到乳液型黏著劑之乳化聚合之際，爲了確保 聚合安定性，能夠適量使用陰離子系或非離子系之乳化 -25- 200846439 劑。尤其乳化劑並未予以特別限定，能夠使用習知之乳化 劑。陰離子系乳化劑可列舉：月桂基硫酸鈉、月桂基硫酸 銨、十二烷基苯磺酸鈉、聚環氧乙烷烷基醚硫酸鈉、聚環 氧乙烷烷基苯基醚硫酸鈉等；非離子系乳化劑可列舉：聚 環氧乙烷烷基醚、聚環氧乙烷烷基苯基醚等。以上之乳化 劑能夠單獨使用或倂用數種後而使用。另外，陰離子系或 非離子系中任一種也可以使用例如已導入丙烯基之自由基 聚合性乳化劑。 ^ 於爲了得到乳液型黏著劑之乳化聚合時，可使用聚合 起始劑。聚合起始劑並未予以特別限定，能夠使用習知之 聚合起始劑。具體而言，可以使用由二氫氯化-2,2 5-偶氮二 (、2-甲基二乙基甲酮脒）鹽、4,4’-偶氮二（4-氰基）戊酸、 二氫氯化-2,2’-偶氮二（2-脒基丙烷）等之偶氮系；過氧化 苯甲醯、第三丁基過氧化氫、過氧化氫等之過氧化物；由 過硫酸鹽與亞硫酸氫鈉之組合或過氧化物與抗壞血酸鈉之 φ 組合等所構成的氧化還原起始劑。通常，此等之起始劑最 好將既定量添加於乳化聚合之各階段，使聚合反應得以進 行。 其中，期望使用生成碳自由基之起始劑，較宜使用偶 氮系起始劑。碳自由基缺乏脫氫能力，聚合物之接枝化將 變得不容易進行，變得能夠容易得到直鏈狀之聚合物。其 結果，本發明人等發現：容易將上述動態黏彈性光譜中之 高溫領域的損失正切、中溫領域的損失正切之下方的凸波 -26- 200846439 峰値控制於目的之範圍內。 於爲了得到乳液型黏著劑之際，可使用還原劑。還原 劑可列舉：抗壞血酸、酒石酸、檸檬酸、葡萄糖、甲醛亞 硫酸金屬鹽等之還原性有機化合物；硫代硫酸鈉、亞硫酸 鈉、重亞硫酸鈉、偏重亞硫酸鈉等之還原性無機化合物。 於爲了得到乳液型黏著劑之乳化聚合時，爲了調整聚 合度，能夠使用鏈轉移劑。如此之鏈轉移劑可列舉：十二 烷基锍、丁基锍、2 -锍基乙醇、三氯溴甲烷等，能夠使用 ^ 由此等鏈轉移劑之族群所選出之至少一種以上。其中，將 丙烯酸系單體作爲單體成分使用之情形下，相對於1 00質 量份之丙烯酸系單體，適宜摻合〇. 0 1〜〇 · 2質量份之十二烷 基锍，更佳摻合0.01〜0.04質量份，最好摻合0.01 5〜0.025 質量份。 於爲了得到乳液型黏著劑之乳化聚合時，乳化聚合 後，通常藉由使用氨等之中和劑以進行中和處理，調整成 φ 既定之pH，可以得到安定之乳液型黏著劑，其中，較宜爲 p Η 8 . 5〜9.5之範圍。 (黏著劑層之厚度） 單面黏著片之情形，使用於本發明之再剝離用黏著片 之黏著劑層的厚度’其乾燥後之厚度適宜爲3〜200 μιη ’更 佳爲5〜50μιη，尤以1〇〜25μιη特別理想。另外，雙面黏著 片之情形，適宜爲30〜3 00 μιη，更佳爲50〜200 μπι。在上 述下限値之下的情形’所得的再剝離用黏著片之黏接性將 -27- 200846439 變得不足，超過上限値之情形’於印刷或模切加工時’黏 著劑之溢出將變得容易發生。 (剝離片） 於本發明之再剝離用黏著片中，必要時’於黏著劑層 上設置剝離片。此剝離片可列舉··牛皮紙、玻璃紙及高級 紙等之紙；於此等紙上，單面或雙面塗布聚乙烯醇等之合 成樹脂或黏土的紙；或是於此等紙上，單面或雙面積層聚 I 乙烯樹脂等的紙；或是於聚對苯二甲酸乙二酯、聚萘二甲 酸乙二酯及聚丙烯等之塑膠薄膜上，單面或雙面塗布氟樹 脂或矽樹脂等剝離劑之物。針對此剝離片之厚度’雖然並 未予以特別限定，一般於20〜3 Ομιη之範圍。 (再剝離用黏著片之製法） 本發明之再剝離用黏著片之製法並未予以特別限定’ 能夠依照習知之製法加以製造。例如，單面黏著片之情形， 可以利用下列方法而得到：於剝離片上，進行黏著劑溶液 # 之塗布、乾燥、熱硬化，或依照電磁放射線效果等之處理 後，使黏著片予以貼合。另外，雙面黏著片之情形，可以 利用下列方法而得到：將黏著劑溶液塗布於剝離片上，將 該處理後之剝離片貼合於基材片雙面。或是，也能夠利用 下列方法而得到：於直接將黏著劑溶液塗布於基材片之 後，進行該處理以貼合剝離片。再者，爲了使基材片與黏 著劑層之緊貼性得以提高，也可以於40〜1 〇〇 °C等之高溫 下進行貼合。本發明之再剝離用黏著片係藉由選擇製程， - 28- 200846439 能夠作成捲狀、帶狀或片狀而加以製造。 (使用例） 使用進行如此方式所製造之再剝離用黏著片情形的形 狀或尺寸並未予以特別限定，能夠因應於用途或目的而加 以適當設定，從捲狀、帶狀或片狀之黏著片切割後而使用。 尤其，單面黏著片之情形，於要求切割成的形狀或尺寸之 前，或切割之後，在未設置基材片的黏著劑層之表面側， $ 進行爲了表示商品名、服務或廣告宣傳內容等之各種圖案 或文字等之印刷。印刷方式並未予以特別限定，能夠採用 膠版印刷方式等之平版印刷法；照相凹版印刷方式等之凹 版印刷法、撓性版印刷方式等之凸版印刷法；或網板印刷 方式等之孔版印刷法等之各種印刷方式。 再者，以保護其印刷面或提高創意性或美觀性爲目 的，也可以透過黏著劑層或黏接劑層，將透明薄膜或消光 色調之半透明薄膜積層於印刷面。已實施印刷、剪裁成各 φ 種形狀、尺寸之再剝離用黏著片的片材、貼紙或標籤係作 爲黏貼於化妝品、化妝用品、家事用品、醫藥品、食品、 飲品、電化製品或文具等之商店所零售之商品等，對 消費者促銷的醒目標麵寺之促銷資材所使用。另外，_占貝占 在電車、汽車或計程車等之車輛、香煙或飲料等之自動，販 賣機、自動剪票機、櫥窗等之公共面前所利用的設備等， 作爲對消費者進行商品或服務之廣告宣傳的促銷資材所& 用。再者，黏貼在複印機、印表機、傳真機、個人電腦、 -29- 200846439 電視、空氣調節器、冰箱及洗衣機等之各種電器製品；碳 粉匣或墨水匣等大多採行再使用的各種關聯性製品·，或構 成汽車、機車及建築材料等之各種內外裝飾零件等之上， 表示商品及零件之品名，或是表示爲了使用者或修理員等 之操作說明書或零件交換程序之文字及圖示等各種影像資 訊。例如，將消耗品之訂購地址或修理之連絡地址予以記 入。或是’也能夠將既定之資訊記入黏著片表面之方式來 予以構成。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive sheet for re-peeling which can be peeled off after being adhered to an adhesive. [Prior Art] For the purpose of advertising products or services, packaging containers for cosmetics, cosmetics, beverages, foods, etc., equipment installed in public places such as vending machines and automatic ticket machines, or trams and automobiles. Adhesive sheets for printed characters or images are attached to vehicles used in public places. For these adhesive sheets, it is sought that after the adhesive is applied for a certain period of time, the adhesive does not remain on the adhesive, and the substrate sheet is not cut, and the peeling property is perfectly peeled off. However, in order to exhibit re-peelability, in general, it is necessary to design a weak adhesive force, and if it adheres to an adhesive or a curved surface having irregularities, there is a problem that peeling occurs over time. On the other hand, in the name of the product, or for the purpose of the user or the repairer's operating instructions or parts replacement procedures, in copiers, printers, fax machines, personal computers, televisions, air conditioners, refrigerators and Various electrical appliances such as washing machines; most of them are used in various related products such as toner cartridges or ink cartridges; or on various interior and exterior decorative parts such as automobiles, locomotives and building materials, and adhered to adhesive sheets. Since these adhesive sheets are used after being adhered for a long time, it is particularly required that during the adhesion to the adhesive, there is no floating occurrence or peeling between the adhesive sheet and the adhesive (hereinafter, there will be called floating peeling). In the case of the adhesion, it is generally practiced to remove the adhesive sheet. 200846439 However, in recent years, based on the care for the natural environment, it is strongly desired to recycle the products or parts or parts of the parts constituting the products. For example, parts or members of various electrical products, parts or members of these various related products, and the like are formed by a thermoplastic resin to perform circulation or the like. Specifically, a disintegrator is used to disassemble used parts or components or parts or components that exceed the number of years of durability into nine-grain shapes, heat-melt them, and then form them into certain parts or components. Reuse such recycled molded articles again. When the parts or the like are pulverized, the adhesive sheet is attached to the parts and the like, and the parts to which the adhesive sheet is pasted and the adhesive sheet are not melted, and the parts to be recycled by the impurities which are melted without being melted by heating are melted. The strength is not reduced and there is a need to remove the adhesive sheet. Therefore, it is conventionally known that the adhesive sheet is heated by a hair dryer, peeled off, or scraped off by a honing machine, and then the part or the like is broken into nine particles, which are then melted to obtain a recycled molded article. However, the operation of peeling the adhesive sheet from a part or the like is a troublesome and time-consuming operation which is extremely troublesome, whereby the recycling cost of the zero Φ piece is inevitably increased, and therefore, when the adhesive sheet is peeled off, it is required The adhesive does not remain on the adhesive, and the base material sheet is not cut, and can be easily peeled off again. However, if only the re-peelability is emphasized, there will be an adhesive sheet in the case where various electrical products or the like are adhered to the surface having the uneven surface on which the observed embossing has been performed, or in the case of sticking to the curved adhesive. A problem with floating stripping occurred. Further, since the gas generated from the thermoplastic resin constituting various electric products and the like is released, there is a problem that air bubbles are temporarily accumulated and a bubble is accumulated between the one piece of 200846439 and the thermoplastic resin. In order to solve the problem of the above-mentioned problem, Patent Document 1 discloses an acrylic adhesive composition characterized in that it is 74.999 to 99.9% by mass based on the (meth)acrylic acid alkyl ester monomer component, and (meth)propene. The acid alkyl ester monomer component can be copolymerized with a carboxyl group-containing monomer 〇~〇〇〇1% by mass, and the (meth)acrylic acid alkyl ester monomer component can be copolymerized with a hydroxyl group-containing monomer 0.1 to 5 mass. %, and 100 parts by weight of the acrylic copolymer obtained by radical copolymerization with other monomer components of copolymerization - 20% by mass of the copolymerizable monomer, containing an isocyanate crosslinking agent 〇. i ~ 5 The acrylic adhesive composition in the form of a weight, the storage elastic modulus at 1 20 ° C in the dynamic viscoelastic spectrum measurement of the dried film of the adhesive composition is 2 x 105 - 7 x 105 dyn / cm 2 and the loss tangent (tan S) is 〇 〇5 〜 0.4, and the storage modulus at 0 ° C is lxlO5 ~ 4xl06dyn / cm2. However, in the case of the adhesive-processed product disclosed in the above-mentioned Patent Document 1, the re-peelability is excellent, but it is an image forming apparatus such as a copying machine, a printer, a transmission machine, or a multi-functional machine or the like. An electronic device such as an electric appliance has an uneven surface on which embossing is performed, and the adhesive force is insufficient, and once it has been pasted for a long period of time, there is a problem of being peeled off. Further, an adhesive film for re-peeling (refer to Patent Document 2) is known, which is characterized in that the peeling adhesion force of 1 to 80 degrees with respect to the polymethyl methacrylate sheet is 〇.2N/25 mm to 5.0 N/25 mm, The peeling length after 3 minutes in the fixed load peeling measurement method was 50 mm or less, and the adhesive film was attached to a polymethyl methacrylate plate, and after being allowed to stand at room temperature for 1 hour, the peeling speed was 200846439 1 m/min, When the peeling angle is 180 degrees, the adhesive force when peeling is set to p1, and after standing at 60 °C for 24 hours, the peeling speed is lm/min, the peeling angle is 180 degrees, and the adhesive force is set to P2. The ratio of P1 to P2 (P1/P2) is 1.4 to 〇·7. This technique relates to an adhesive film for re-peeling which has excellent adhesiveness, does not cause floating peeling, and the like, and the adhesive does not contaminate the adhesive at the time of peeling, and has excellent removability. Further, a re-peelable adhesive film (refer to Patent Document 3) is known, which is based on an adhesive film in which a polystyrene film substrate, an adhesive layer, and a release sheet are laminated, and is different from polystyrene. Adhesion of the adhesive over time 'peeling speed is 2·0~4.0N/25mm at 5mm/min, and peeling speed is 8.0~12.0 N/25mm at 300mm/min; and a re-peelable type of water-based adhesive The object (refer to Patent Document 4) is an aqueous adhesive composition comprising a polymer particle [X] and an anthracene derivative [Y], wherein the polymer particle [X] is composed of a carbonyl group. The polymer having an acid value of 3 to 30 with a carboxyl group has an average particle diameter of 300 nm. The anthracene derivative [Y] has at least two mercapto groups in the molecule, and the re-peelable type is adhered to the water. The film formed by the agent composition has a glass transition temperature of -25 ° C or lower, a gel fraction of 80% by mass or more, and an amount of water extract of 2% by mass or less. These techniques are related to a technique that is excellent in adhesion and adheres to the adherent and can be easily peeled off from the surface of the adhesive even after standing for a long period of time, especially the latter technique for using an emulsion type adhesive. . However, in the above-mentioned Patent Documents 2 to 4, there is no description about the problem that the rough sugar surface on which the unevenness has been applied is adhered to the surface of 200846439 such as embossing, and in fact, it is adhered to the embossed surface or the like. Rough surface, the adhesive film is easily peeled off after a long period of time. Further, Patent Document 5 discloses a method of easily removing an adhesive sheet from a component of an image forming apparatus such as a copying machine or a printer or various electronic devices, and forming a recess in which a groove and a groove intersect in a region where the adhesive sheet is adhered. When recycling, the adhesive sheet is cut along the groove by means of a tool for decomposition, and the concave portion is used as a mark to peel off the adhesive sheet. However, in the method of the above-mentioned Patent Document 5, it is necessary to perform the processing for forming the concave portion in the pasted part, and in order to cut the adhesive sheet, if the adhesive sheet having a strong adhesive force is used, it is feared that the base is peeled off. The material will break, or the adhesive will remain on the adhesive, which will result in poor peeling efficiency. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. 20-4-1775. Patent Document 4: Japanese Patent Laid-Open No. Hei 2 0 0 - 2 7 7 7 1 1 * Patent Document 5: Japanese Patent Laid-Open Publication No. 2003-308020 A SUMMARY OF INVENTION Technical Problem In view of the above, the present invention provides an adhesive sheet for re-peeling, which is not only a smooth surface of an adhesive, but also has a superior adhesiveness to a rough surface having irregularities such as embossing, and once the attachment of the adhesive sheet is completed. The floating peeling of the adhesive sheet 200846439 will not easily occur for a long period of time, and the superior re-peelability at the time of peeling off the adhesive sheet is less likely to cause adhesion of the adhesive due to the adhesive. In particular, the other object of the present invention is to provide an adhesive sheet for re-peeling by using polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyphenylene ether, AB S, polycarbonate. The smooth surface and rough surface of the thermoplastic resin with the ester and these composite materials as the main component show excellent adhesion and re-peelability, and floating peeling will not occur for a long time. Further, the other object of the present invention is to provide an adhesive sheet for re-peeling which exhibits superior adhesion and re-peelability to a smooth surface and a rough surface having a surface layer containing an acrylic resin as a main component, and will not be long-term. Floating peeling will occur. Further, another object of the present invention is to provide an adhesive sheet for re-peeling, which solves the above problems, and which exhibits excellent adhesion and removability to the curved surface of each of the above-mentioned adherends, and long-term floating peeling will not occur. occur. Further, another object of the present invention is to provide an adhesive sheet which does not cause bubbles to accumulate between the adhesive sheet and the thermoplastic resin even if the gas generated from the thermoplastic resin to be adhered is released. In order to solve the above problems, it has been found that the use of an adhesive sheet which maintains a moderately elastic and viscous adhesive can achieve the object of the present invention. Moreover, it has been found that the floating peeling and re-peelability after long-term adhesion can be achieved by measuring the loss tangent of the high temperature region in the dynamic viscoelastic spectrum. -200846439 It is foreseen that the present invention can be completed. That is, the present invention provides an adhesive sheet for re-peeling, which is a re-peelable adhesive sheet having an adhesive layer on at least one side of a substrate, and is characterized by a frequency of the adhesive layer of 1 Η z, - 5 0 The loss tangent of the dynamic viscoelastic spectrum at ~150 °C is: (a) in the low temperature region below -2 0 C, with a convex peak above; (b) in the medium temperature region of 10 to 40 °C, There is a convex peak below; I (c) at 70C, the loss tangent is 〇_38~0.57. EFFECTS OF THE INVENTION The adhesive sheet of the present invention is not only a smooth surface for an adhesive, but also has a superior adhesion to a rough surface having a concave or convex surface or a curved surface, and the floating of the adhesive sheet once the attachment of the adhesive sheet is completed. Peeling or the like will not occur for a long period of time, and when the adhesive sheet is peeled off, the adhesive or the substrate sheet is not broken by the adhesive. Therefore, it is suitable for the following premise: for the purpose of advertising for goods or services, in public places such as packaging containers, vending machines, and automatic ticket machines for cosmetics, cosmetics, cosmetics, foods, and the like. The equipment to be installed, or the vehicle used in public places such as electric cars and automobiles, or the various types of image information such as the instructions and parts replacement procedures for the user or the repairer, etc., are attached to the copying machine and the printer. Various electrical appliances such as computers, fax machines, personal computers, televisions, air conditioners, refrigerators, and washing machines; most of them are used in various related products such as toner cartridges or ink cartridges, or constitute automobiles, locomotives, and buildings. Various internal and external decorative parts such as materials are peeled off after being adhered to a regular period of -11-200846439. In particular, since the adhesive sheet of the present invention is made of a composite material of polyethylene, polypropylene, polyethylene terephthalate, polystyrene, modified polyphenylene ether, ABS, polycarbonate, and the like, The smooth surface and the rough surface or the curved surface composed of the thermoplastic resin of the main component have excellent adhesiveness and excellent releasability, and in the case of recycling the electrical product to which the adhesive sheet of the present invention is attached, When the adhesive sheet is peeled off, the adhesive is not contaminated by the adhesive, or the substrate sheet is cut, and since the peeling operation is also easy, it is adhered as a superior adhesive sheet to be recycled. The purpose of electrical appliances and other components. Further, in the adhesive sheet of the present invention, even if gas is released from the thermoplastic resin, bubble accumulation between the adhesive sheet and the thermoplastic resin can be prevented. In particular, in various home electric appliances such as copiers, printers, televisions, etc., in the case where the label is attached by hand after completion of the product, it is preferably a thick label, if the adhesive sheet according to the present invention, Since the φ repulsive force is strong on a thick substrate, even if the thickness of the bubble is not easily discharged, a label having good removability and peeling resistance and which is less likely to accumulate bubbles can be produced. Further, in the case of a smooth surface and a rough surface or a curved surface having a surface layer containing an acrylic resin as a main component, the adhesive sheet of the present invention exhibits excellent adhesion and removability, and is used as a cosmetic or cosmetic product. The tube used for the packaging container or the adhesive sheet for re-peeling adhered to the curved surface of the vending machine is also excellent. -12-200846439 [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the adhesive sheet for re-peeling of the present invention will be described in more detail based on the structural requirements thereof. Further, in the present specification, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the same is true for derivatives of acrylic acid or methacrylic acid. In addition, the term "circulation" refers to the case where the used product is reused as a raw material of the same kind or another kind of product, and the two used cases are used in the original state or after being partially trimmed and then used (rouse). . (Structure for Re-peeling Adhesive Sheet) The adhesive sheet for re-peeling of the present invention is formed by laminating an adhesive on at least one side of a substrate sheet as a basic structure, and is formed in the form of a single-sided adhesive sheet or a double-sided adhesive sheet. If necessary, the release sheet is placed on the adhesive layer. In either case, the adhesive layer laminated on the substrate sheet may be laminated on the entire surface of at least one side of the substrate sheet, or may be a part. • In the case of the 'single-sided adhesive sheet, it is also possible to print on the surface of the adhesive sheet and the substrate sheet on the opposite side. Further, for the purpose of protecting the printed surface, or for improving creativity or aesthetics, a transparent film or a matte-tone translucent film may be laminated on the printing surface through an adhesive layer or an adhesive layer. (Method for specifying the dynamic viscoelastic property of the adhesive layer) The dynamic viscoelastic property of the adhesive layer constituting the adhesive sheet for re-peeling of the present invention, which is a loss tangent of a dynamic viscoelastic spectrum at a specific frequency and a specific temperature, or According to the loss tangent and storage elastic modulus, -13- 200846439 In addition, the temperature of the dynamic viscoelastic spectrum at a specific frequency is shown as the temperature of the loss tangent peak, or the peak of the loss tangent is specified. In the measurement of dynamic viscoelasticity, a test piece was sandwiched between parallel disks of the measurement site of the same test machine using a viscoelasticity tester (trade name: Ares 2KSTD, manufactured by Rheometrics Co., Ltd.), and the measurement was performed at a frequency of 1 Hz. Storage elastic modulus (G') and loss elastic modulus (G") from -50 ° C to 150 ° C. The test piece can also be used to sandwich the adhesive of thickness 〇·5~2.5 mm in parallel circles. In the case of the latter, the thickness of the adhesive is adjusted to the above range, and the present inventors have confirmed that even if the thickness of the adhesive is adjusted to the above range, even if the substrate is Clamping in the middle does not affect the dynamic viscoelastic spectrum of the adhesive. The adhesive layer constituting the adhesive sheet for re-peeling of the present invention has a loss in the range of -50 ° C to 150 ° C at a frequency of 1 Hz. Tangent, in the low temperature region below -20 °C, there is a convex peak on the upper, decreasing from the low temperature region to the medium temperature region, in the middle temperature region of 10 to 40 °C, the convex peak below, from the middle temperature# The area rises to a high temperature area and is taken at 7 0 特定 within a specific range. By setting the loss tangent to each of the above ranges, moderate fluidity is imparted to the adhesive. Specifically, permeable liquidity is found even in minute irregularities on the surface of the adherend. At the same time, since it is not excessively flowing, the excessive increase in the adhesive force can be suppressed. Furthermore, the stress applied to the adhesive can be alleviated by the moderate flow of the adhesive. As a result, after exposure to time or in a high temperature environment, exposure is performed. And peeling off the adhesive sheet adhered to the adhesive, the substrate which is to be peeled off does not easily break, and the adhesive becomes easy to remain in the adhesive. In addition, even if it passes over time or high temperature In the environment, when the adhesive sheet attached to the adhesive is exposed, it is not easy to cause floating peeling of the adhesive sheet. Further, in the case where the adhesive sheet is adhered to the thermoplastic resin, even if gas is released from the thermoplastic resin, Between the adhesive sheet and the thermoplastic resin, bubble accumulation will also become less likely to occur. (The loss of the adhesive layer in the high temperature region is tangent) In the high temperature region of 50 to 120 ° C, the adhesive layer constituting the I-adhesive sheet for re-peeling of the present invention has a loss tangent of 0.38 to 0.57 at a frequency of 1 Hz and 70 ° C. The loss tangent at 70 ° C Suitably it is 0·43~0.55, more preferably 0.46~〇·5 4. In addition, the loss tangent at 50 °C is suitably 0 · 3 8~0 · 5 3 , more preferably 0.40~0.51. The loss tangent at 100 °C is suitably 0.40 to 0.65, more preferably 0.44 to 0.65, and particularly preferably 0.50 to 0.60. Further, the loss tangent at 120 ° C is suitably 0.40 to 0.66, more preferably 0.45 to 0. 66. Among them, especially 0.51 to 0.62 is particularly desirable. (The loss tangent of the adhesive layer in the intermediate temperature region) # Between the frequencies 1 Hz and 10 ° C to 60 ° C, the loss tangent of the adhesive layer constituting the adhesive sheet for re-peeling of the present invention is a convex peak below . Further, the peak 値 is suitably 〇 35 to 0.51, more preferably 0.4 to 0.51. (The temperature of the convex peak showing the loss tangent curve in the low temperature region) At the frequency of 1 Hz, the adhesive layer of the adhesive sheet for re-peeling of the present invention is formed, and the temperature of the convex peak showing the loss tangent curve is suitably _ 2 〇t Hereinafter, it is more preferably -25 ° C or less, particularly preferably -30 ° C or less. If it is adhered to the inside of the lane, the adhesive layer will be easy to flow on the embossed surface, such as the embossed surface -15-200846439. As a result, the adhesion to the adhesive becomes sufficient, and it floats over time. Peeling is not easy to occur. In addition, when re-peeling is performed, it is not easy to show a feeling of intermittent resistance, or a peeling sound of smashing, and a smooth peeling operation can be performed. (The peak of the loss tangent in the low temperature region) The adhesive layer constituting the adhesive sheet for re-peeling of the present invention preferably has a peak of loss tangential 値 of 1. 3 to 1. 0 or less. (Storage modulus of the adhesive layer) The adhesive layer constituting the adhesive sheet for re-peeling of the present invention at a frequency of 1 Hz preferably has a storage modulus at 70 ° C of 6.0 x 1 04 to 2.1 x 105 (Pa). Further, the storage modulus at 50 ° C is preferably 7.0 χ 104 to 2.4 x 105 (Pa). Further, the storage modulus at 100 ° C is preferably 3.0 X 1 0 4 to 1.6 X 1 0 5 (Pa). In addition, the storage modulus at 120 ° C is preferably 2. ΟχΙΟ 4 to 1.4 x lO5 ( Pa). Further, the storage elastic modulus at -40 ° C is preferably 5.0 x 1 〇 6 〜 5. 〇 xl 〇 7 (Pa) 〇 φ (initial adhesion) initial adhesion of the adhesive sheet for re-peeling of the present invention F a is preferably 3.0 to 9.0 (N/25 mm). Further, the initial adhesion force Fa is preferably 3.0 to 8.0 (N/25 mm), and more preferably 3.0 to 7.0 (N/25 mm). Further, the initial adhesion force Fa is a polyphenylene bromide plate having an arithmetic mean height R a ( 3 ) of 轮廓 〇 〇 1 μ m with respect to a profile curve defined in accordance with JIS B 〇 6012()()1. 9 After the definition of the peeling and peeling adhesion, the 90 degree peeling and peeling force is based on JIS Z 023 7, the pressure-adhesive speed is 5mm/s, the pressure-adhesive frequency is repeated once, and -16-200846439 will be affixed to the test. The test piece of the sheet was placed in a gas atmosphere at a temperature of 23 ± 2 ° C and a relative humidity of 50 Å for 24 hours, and the enthalpy measured under the conditions of a tensile speed of 50 m m / min. When the initial adhesive force Fa is in the above range, peeling does not easily occur during the adhesion of the adhesive sheet. Further, at the time of peeling off, the adhesive remains on the adherend, or the peeling of the base sheet from the broken adhesive does not easily occur. In the adhesive sheet for re-peeling of the present invention, when the initial adhesive force of the polystyrene sheet having a Ra (3) of 6.8 to 7·2 μm is Fb (N/25 mm), the Fa and The relationship of Fb should be in accordance with formula (1): 0.30 <Fb/Fa <l.00 (1) The initial adhesion force Fb is defined by the 90 degree peeling adhesion force of the polystyrene sheet of 6.8 to 7.2 卞111 with respect to the Ra(3), and the 90 degree peeling adhesion system is According to JIS Z 02 3 7, at a pressure-adhesive speed of 5 mm/s and a number of times of pressure-bonding, the test piece of the test piece is attached to a gas atmosphere at a temperature of 23 ± 2 ° C and a relative humidity of 50 ± 5%. After 24 hours of standing, the crucible was measured under the conditions of a stretching speed of 50 mm/min. Further, it is preferable that the Fb/Fa is in accordance with the following formula (2), and it is preferable to conform to the following formula (3). The relationship between the Fb and the Fa is in this range, which means that the adhesive sheet not only has a smooth surface to the adherend, but also has excellent adhesion even to a rough surface having irregularities. If the Fb/Fa is in the range of this, a good adhesion to a rough surface having a concave-convex surface can be obtained, and the floating peeling does not easily occur. 0.40 <Fb/Fa <l .00 ( 2 ) -17- 200846439 0.50 <Fb/Fa <l.00 (3) (Substrate sheet) The substrate sheet to be used for the adhesive sheet for re-peeling of the present invention is not particularly limited, and examples thereof include a plastic film and a cellulose film. , non-woven, paper, cloth or metal foil. Examples of the plastic film include polyolefin (for example, polypropylene, polyethylene), polyester (for example, polyethylene terephthalate, polyethylene naphthalate), polystyrene, ABS, and polycarbonate. , polyimine film, polyvinyl chloride, nylon, polyvinyl alcohol, etc.; cellulose film can be listed as: cellophane (cellophane), cellulose diacetate, cellulose triacetate and the like. Further, examples of the non-woven fabric include pulp, snail, manila hemp, acrylonitrile, nylon, polyester, and the like; and papers include high-grade paper and resin-coated paper. In particular, in the case of a single-sided adhesive sheet, in order to prevent the substrate sheet from being cut at the time of re-peeling, it is preferable to use the plastic-based film as a substrate sheet. Further, regarding the above materials, the m II component alone can be used as a main component, and such a composite material can also be used. In the case of modifying the substrate sheet, other components may be added in a small amount. For example, in the case where polystyrene is used for the substrate sheet, it is preferred to use high-impact polystyrene (HIPS) which is improved in softness by blending polybutene = a small amount of polystyrene into the main component. It is necessary to use light resistance as a green MT'. It is preferable to use methyl methacrylate-styrene copolymer resin (MS resin) or acrylonitrile-styrene-acrylic copolymer resin (ASA resin). A monomeric copolymer resin or a substrate sheet blended with an acrylic resin. -18- 200846439 In addition, in the case where the adhesive sheet for re-peeling is used for a label or the like of a recycling member, it is preferable to use the main component of the base material for the re-peeling adhesive sheet as a main component of the recycling member of the adhering object. A substrate which can be subjected to the same recycling treatment is particularly preferable as a substrate which is the same as the recycling member to be adhered. For example, it is suitable for bonding to a component made of a thermoplastic resin containing polypropylene, polyethylene, polystyrene, polyphenylene ether, AB S, polycarbonate, and the like as a main component of the thermoplastic resin. In the case of the use of the member such as a product, polypropylene, polyethylene, polystyrene, polyphenylene ether, AB S or polycarbonate having the same properties as the main component of the member is used as a main component of the substrate sheet, The compatibility with the member is improved, and if it is not peeled off as necessary, it is possible to directly recycle the material together with the member in the state of adhering the adhesive sheet, and the recycling suitability can be further improved. For example, in the case where the main component of the member is polypropylene, it is desirable to use polypropylene as a main component of the substrate sheet; in the case where the main component of the member is polyethylene, it is desirable to use polyethylene as a main component of the substrate sheet; In the case where the main component of the member is polystyrene, it is desirable to use polystyrene as a main component of the substrate sheet; in the case where the main component of the member is polyphenylene ether, it is desirable to use polyphenylene ether as a main component of the substrate sheet; In the case where the main component of the member is ABS, it is desirable to use ABS as a main component of the substrate sheet; in the case where the main component of the member is polycarbonate, it is desirable to use polycarbonate as a main component of the substrate sheet; In the case where the composition is a composite material of polycarbonate and AB S, it is desirable to use a substrate composed of a thermoplastic resin containing polycarbonate, A b S, or -19-200846439 polycarbonate and abs composite as a main component. sheet. Further, in order to suppress the accumulation of bubbles between the adhesive sheet and the thermoplastic resin caused by the release of the gas from the thermoplastic resin, it is desirable to use a substrate excellent in gas permeability. For example, polypropylene, polyethylene, polystyrene, etc. are mentioned. In the case of the HIPS substrate sheet, the tensile strength at break MD is preferably 20 MPa 0 or more, and TD is preferably 15 MPa or more. When it is in the above range, it is possible to peel off the substrate without being cut and peeling off. Further, the tensile elongation at break is preferably 30 to 60% both in MD and TD. In the above range, in order to impart moderate rigidity and flexibility, the film does not easily break, and it becomes less likely to be stretched, and the releasability is further improved. The tensile strength and tensile elongation at break of the substrate sheet are in a gas environment of temperature 23 ° 2 ° C and relative humidity 50 ± 5%, and the substrate is stretched at a tensile speed of 200 mm/min # The sheet is defined by the strength and elongation at which the substrate breaks. In the case of the regulation, it is defined in accordance with the flow direction (MD) and the width direction (TD) of the substrate sheet. At the time of the measurement, the present inventors have confirmed that the base material sheet is not affected by the tensile strength at break and the tensile elongation at break even when the pressure-sensitive adhesive layer is laminated. In the case of coloring the substrate, a coloring agent (masterbatch) in which an inorganic pigment such as titanium oxide is stirred by using the same resin as the substrate sheet can be added. The amount of the masterbatch containing 50% by mass of the titanium oxide is preferably 5 to 20 parts by mass, more preferably 10 to 15 parts by mass, based on 100 parts by mass of the resin of the film base. When the amount is 5 parts by mass or more, the concealing property of the substrate is improved, and if it is within 20 parts by mass, the substrate caused by the master batch is broken, or foreign matter such as fish eyes becomes less likely to occur. . The thickness of the substrate sheets is preferably determined in accordance with the purpose or condition of use, and the case of the single-sided adhesive sheet is preferably 1 5 to 2 5 0 based on the workability of the copper-clad laminate or the resistance to repellency. Μιη, more preferably 2 5 to 1 1 5 μιη, more preferably 50 to 95 μιη. On the other hand, in the case of double-sided adhesive sheets, it is suitable for 3〇~2〇〇0111, more preferably 5〇~15〇0111, and further, the amount of flat (卩&口€]:\^丨邑111 ingsm It is suitably 10 to 100 g/m2, more preferably 15 to 50 g/m2. (Surface Treatment of Substrate Sheet) Further, one or both sides of the substrate sheet may be used for the purpose of improving the adhesion to the layer (adhesive layer or printing layer) laminated on the substrate sheet. Corona treatment, plasma treatment, roughening treatment, flame treatment, chromic acid treatment, hot air treatment, ozone irradiation treatment, ultraviolet irradiation treatment or coating with a tackifier may also be applied. In particular, the surface of the substrate on the side of the adhesive layer is subjected to a corona treatment or an adhesion-promoting treatment, so that the adhesive layer is not easily peeled off from the surface of the substrate, and the adhesive sheet for re-peeling of the present invention is adhered to the adhesive. The removability after the article is improved, and the adhesive layer can be further prevented from remaining on the adherend. The anchor coat is formed by applying an adhesion-promoting agent composed of a pigment for adsorbing ink, a binder resin and a dispersant to a substrate sheet - 21 - 200846439. As the pigment, conventional calcium carbonate, titanium oxide, synthetic cerium oxide or the like can be used. Among them, when the base material sheet is wound into a cylindrical shape, it is also considered to prevent agglomeration of the back surface of the base material sheet and the adhesion-promoting coating layer, and it is preferable to synthesize cerium oxide which allows the particle diameter to be freely changed. As the binder resin, an acrylic resin, a urethane resin, a polyvinyl alcohol resin, a vinyl chloride-vinyl acetate copolymer resin, a polyester resin or the like can be used. Among them, an acrylic resin used for a binder resin of a large ultraviolet curable ink (UV ink) is preferred. The dispersing agent is not particularly limited, and it is applied to a substrate sheet such as polystyrene or AB S which is easily swollen or dissolved by a solvent, and a dispersing agent which does not dissolve the substrate sheet is preferably used, and is preferably isopropanol or ethanol. Wait for the alcohol as the main thing. The blending of the tackifier is preferably in the range of 5 to 10 parts by mass of the pigment, 20 to 30 parts by mass of the binder resin, and 60 to 70 parts by mass of the dispersant. The coating amount of the coating agent is suitably from 0.5 to 4.0 g/m2, more preferably from 1.0 to 2.0 g/m2. As the coating method of the adhesion-promoting agent to the substrate sheet, a gravure coater, a knife coater, a roll coater or the like can be used. Among them, a gravure coater is preferred. (Preparation of Adhesive) A conventional acrylic, rubber-based, vinyl ether-based or decane-based adhesive can be used as the adhesive for the adhesive sheet for re-peeling of the present invention. Among these adhesives, an acrylic adhesive is preferred. In particular, the monomer component is preferably an acrylic copolymer containing a (meth) acrylate having a carbon number of 1 to 14 alkyl groups. For example: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-22-200846439 propyl (meth)acrylate, n-butyl (meth)acrylate, Isobutyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylic acid- 2-ethylhexyl ester, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, n-lauryl (meth)acrylate, etc., can be used alone or in combination. Use more than two kinds. Among them, it is preferred to use n-butyl acrylate, 2-ethylhexyl acrylate, or ruthenium as the main component, and the amount thereof is preferably 50 to 99% by mass in the adhesive composition, more preferably It is 95 to 99% by mass. Further, the mass ratio of (n-butyl acrylate/2-ethylhexyl acrylate) is suitably 70/30 to 0/100, more preferably 45/55 to 5/95, more preferably 35. /65~15/85. The inventors of the present invention have found that the main single system can easily control the loss tangent of the low temperature region in the dynamic viscoelastic spectrum by setting the above-mentioned type and amount, and it is easy to control the peak of the convex peak to the target range. Further, it is preferred to add a vinyl monomer having a functional group such as a hydroxyl group, a carboxyl group or an amine group in the side chain in the range of from 1 to 15% by mass. For example: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acrylic acid, methacrylic acid, maleic acid, horse Anhydride, itaconic acid, crotonic acid, fumaric acid, acrylic acid maleic anhydride carboxypropyl ester, dimethylamine ethyl acrylamide, N-vinyl pyrrolidone, acrylonitrile, N-vinyl caprolactam, propylene Amidoxime, styrene, ethyl acetate, N-methylol acrylamide, glycidyl methacrylate, etc. These vinyl monomers can be used singly or in combination of two or more. Among them, it is preferred to use a vinyl monomer having a carboxyl group of -23-200846439, more preferably using acrylic acid, methacrylic acid or the like, and the amount thereof is preferably 0.5 to 4.0 mass. %. In particular, in order to improve the adhesion between the re-peelability and the curved surface, it is preferred to use acrylic acid and methacrylic acid. In particular, the total amount of acrylic acid and methacrylic acid is used as an amount of 1 · 5 to 2 · 5 mass % of the adhesive composition, and the ratio of methacrylic acid to acrylic acid is suitably set to a mass ratio of 〇.5 to 2.0'. It is 1.0 to 1.5. The present inventors have found that the mono-I system containing a carboxyl group can easily control the loss tangent in the dynamic viscoelastic spectrum within the intended range by setting the above-mentioned type and amount, and the releasability is further improved. The acrylic copolymer can be obtained by copolymerization according to a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, an ultraviolet irradiation method, or an electron beam irradiation method. Among them, an emulsion polymerization method is preferred. In order to further improve the cohesive force of the adhesive and improve the adhesion or re-peelability, it is preferred to add a crosslinking agent. For example, the crosslinking agent may, for example, be an isocyanate crosslinking agent, an epoxy crosslinking agent, a chelate crosslinking agent, or an oxazoline crosslinking agent. Among them, an oxazoline crosslinking agent is preferred. In particular, when an oxazoline-based crosslinking agent is used, the removability is improved by improving the adhesion to the substrate sheet. Further, as the monomer which is reacted with the oxazoline group, acrylic acid and methacrylic acid are preferably used, and the ratio of the number of functional groups of the oxazoline group to the carboxyl group is 0.05 to 0.25. Further, in order to improve the adhesion, it is also possible to use a conventionally bonded resin. The loss of 50 ° C to 120 ° C in the dynamic viscoelastic spectrum of the present invention is -24-200846439. The cut can be adjusted according to the amount of crosslinking agent added and Tg. In order to increase the loss tangentially, it is achieved by reducing the amount of crosslinking agent added and using a crosslinking agent having a low Tg; if it is to be reduced, by increasing the amount of crosslinking agent added, using a high Tg It is achieved by a crosslinking agent. Further, as the adhesive, for example, a conventional additive such as a light stabilizer, an ultraviolet absorber, a plasticizer, a softener, a chelating agent, a pigment, or a flame retardant can be added. Examples of the light stabilizer include a chain inhibitor, a hydrogen peroxide decomposition Φ agent, a metal inert agent, and a UV absorber. By using such an additive, the above-described yellowing resistance can be improved. (Type of Adhesive) The adhesive type may be an emulsion type, a solvent type, or a solventless type. The adhesive for the re-peelable adhesive sheet of the present invention is preferably an emulsion type adhesive. The present inventors have found that since the emulsion type adhesive does not use a solvent, it is advantageous in terms of the environmental surface, and it is also easy to control the loss in the high temperature field in the above dynamic viscoelastic spectrum to the range of the purpose. (Preparation of Acrylic Emulsion Type Adhesive) The method for producing the acrylic emulsion type adhesive of the present invention is not particularly limited, and a conventional method can be used. The polymerization method can be a batch polymerization, a continuous dropping polymerization, a separate dropping polymerization, etc., for example, a polymerization temperature of about 20 to 100 〇C. In order to obtain an emulsion polymerization of an emulsion type adhesive, in order to ensure polymerization stability, it is possible to appropriately Anionic or nonionic emulsifier-25-200846439 is used. Particularly, the emulsifier is not particularly limited, and a conventional emulsifier can be used. Examples of the anionic emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, and the like. Examples of the nonionic emulsifier include polyethylene oxide alkyl ether and polyethylene oxide alkylphenyl ether. The above emulsifiers can be used singly or in combination of several kinds. Further, for example, any of an anionic or nonionic surfactant may be used, for example, a radical polymerizable emulsifier having a propylene group introduced therein. ^ In order to obtain an emulsion polymerization of an emulsion type adhesive, a polymerization initiator can be used. The polymerization initiator is not particularly limited, and a conventional polymerization initiator can be used. Specifically, a salt of dihydrochloride-2,2 5-azobis(,2-methyldiethylformone), 4,4'-azobis(4-cyano)pentane can be used. An azo type such as acid or dihydrochloride-2,2'-azobis(2-amidinopropane); a peroxide such as benzamidine peroxide, t-butyl hydroperoxide or hydrogen peroxide a redox initiator composed of a combination of persulfate and sodium hydrogen sulfite or a combination of a peroxide and φ ascorbate. In general, it is preferred that such initiators be added to the various stages of the emulsion polymerization to allow the polymerization to proceed. Among them, it is desirable to use an initiator which generates a carbon radical, and an azo initiator is preferably used. The carbon radical lacks the dehydrogenation ability, and the grafting of the polymer becomes difficult to proceed, and the linear polymer can be easily obtained. As a result, the inventors of the present invention found that it is easy to control the loss of the high-temperature field in the dynamic viscoelastic spectrum and the loss of the convex wave in the middle-temperature field to the target range of -26-200846439. In order to obtain an emulsion type adhesive, a reducing agent can be used. The reducing agent may, for example, be a reducing organic compound such as ascorbic acid, tartaric acid, citric acid, glucose or formaldehyde sulfite metal salt; or a reducing inorganic compound such as sodium thiosulfate, sodium sulfite, sodium metabisulfite or sodium metabisulfite. In order to obtain an emulsion polymerization of an emulsion type adhesive, a chain transfer agent can be used in order to adjust the degree of polymerization. Examples of such a chain transfer agent include dodecyl hydrazine, butyl hydrazine, 2-mercaptoethanol, and trichlorobromomethane. At least one or more selected from the group of chain transfer agents can be used. In the case where the acrylic monomer is used as the monomer component, it is preferable to blend 〇. 0 1 to 〇· 2 parts by mass of dodecyl hydrazine with respect to 100 parts by mass of the acrylic monomer. The blending is carried out in an amount of 0.01 to 0.04 parts by mass, preferably 0.01 to 0.025 parts by mass. In order to obtain an emulsion polymerization of an emulsion type adhesive, after the emulsion polymerization, a neutralization treatment is usually carried out by using a neutralizing agent such as ammonia, and the pH is adjusted to a predetermined pH to obtain a stable emulsion type adhesive. It is more suitable for the range of p Η 8 . 5~9.5. (Thickness of Adhesive Layer) In the case of a single-sided adhesive sheet, the thickness of the adhesive layer used in the adhesive sheet for re-peeling of the present invention is preferably 3 to 200 μm, more preferably 5 to 50 μm, after drying. Especially ideal for 1〇~25μιη. Further, in the case of the double-sided adhesive sheet, it is preferably 30 to 300 μm, more preferably 50 to 200 μm. In the case of the lower limit 値, the adhesion of the obtained adhesive sheet for re-peeling will become insufficient for -27-200846439, and the case of exceeding the upper limit ' 'in the case of printing or die-cutting processing' will become an overflow of the adhesive. It is easy to happen. (Peeling sheet) In the adhesive sheet for re-peeling of the present invention, if necessary, a release sheet is provided on the adhesive layer. Examples of the release sheet include papers such as kraft paper, cellophane, and fine paper; on the paper, a synthetic resin such as polyvinyl alcohol or a clay paper is coated on one side or both sides; or on such paper, single-sided or Double-layered poly(ethylene) resin or other paper; or plastic film of polyethylene terephthalate, polyethylene naphthalate, and polypropylene, coated with fluororesin or enamel resin on one or both sides Etc. The thickness of the release sheet is not particularly limited, but is generally in the range of 20 to 3 Ο μηη. (Manufacturing method of the adhesive sheet for re-peeling) The method for producing the adhesive sheet for re-peeling of the present invention is not particularly limited, and can be produced according to a conventional production method. For example, in the case of a single-sided adhesive sheet, it can be obtained by coating, drying, thermally curing the adhesive solution # on the release sheet, or adhering the adhesive sheet in accordance with the electromagnetic radiation effect or the like. Further, the case of the double-sided adhesive sheet can be obtained by applying an adhesive solution onto the release sheet, and attaching the treated release sheet to both sides of the substrate sheet. Alternatively, it can be obtained by directly applying the adhesive solution to the substrate sheet, and then performing the treatment to adhere the release sheet. Further, in order to improve the adhesion between the substrate sheet and the adhesive layer, it is also possible to bond at a high temperature of 40 to 1 °C or the like. The adhesive sheet for re-peeling of the present invention can be produced by a selective process, - 28-200846439, in the form of a roll, a belt or a sheet. (Use Example) The shape or size of the adhesive sheet for re-peeling produced in this manner is not particularly limited, and can be appropriately set depending on the use or purpose, from a roll, a belt or a sheet-like adhesive sheet. Used after cutting. In particular, in the case of a single-sided adhesive sheet, before the shape or size required to be cut, or after the cutting, on the surface side of the adhesive layer on which the substrate sheet is not provided, $ is performed to indicate the trade name, service, advertisement content, etc. Printing of various patterns or characters. The printing method is not particularly limited, and a lithographic printing method such as an offset printing method, a gravure printing method such as a gravure printing method, a flexographic printing method such as a flexographic printing method, or a stencil printing method such as a screen printing method can be used. Various printing methods. Further, for the purpose of protecting the printed surface or improving the creativity or the appearance, a transparent film or a matte-tone translucent film may be laminated on the printing surface through the adhesive layer or the adhesive layer. Sheets, stickers, or labels that have been printed and cut into various φ shapes and sizes of adhesive sheets for re-peeling are attached to cosmetics, cosmetics, household goods, pharmaceuticals, foods, drinks, electrochemical products, stationery, etc. The goods that are retailed in the store are used for the promotional materials of the consumer's promotional target. In addition, _ occupies a car, a car or a taxi, etc., a vehicle, a cigarette or a beverage, etc. Advertising materials for promotion and use. In addition, it is attached to various electrical appliances such as copiers, printers, fax machines, personal computers, -29-200846439 TVs, air conditioners, refrigerators, and washing machines; most of the toner cartridges or ink cartridges are used. Related products, or various internal and external decorative parts, such as automobiles, locomotives, and building materials, indicate the names of products and parts, or the texts of the operating instructions or parts exchange programs for users or repairers. Various image information such as illustrations. For example, the order address of the consumable or the contact address of the repair is entered. Or ' can also be constructed by recording the established information on the surface of the adhesive sheet.
本發明之再剝離用黏著片係使用於上述用途之情形， 爲了對黏附物顯示良好之黏接性，不僅於各種電器製品等 之平滑面，即使黏貼於具有凹凸之粗糙面的情形，也不會 發生浮動剝離，以及因爲具優越之再剝離性，即使從長期 被黏貼之黏附物，撕剝本發明之再剝離用黏著片的情形， 黏著劑也將殘留於黏附物之表面，基材片也不會被切斷。 亦即，本實施形態之再剝離用黏著片係適合於製造作爲宣 傳與廣告媒體、資訊顯示用所使用之片材、貼紙或標籤。 更具體而言，於使用本發明之黏著片或該黏著片之標 籤係包含進行再循環之際剝離黏著片或黏著標籤之步驟， 並且適用黏貼於具備由以表面輪廓曲線之算術平均高度 Ra(3)爲〇〜1〇·〇 μπι之聚乙烯、聚丙烯、聚對苯二甲酸乙 二酯、聚苯乙烯、聚苯醚、ABS、聚碳酸酯及此等之複合 材料爲主要成分之熱可塑性樹脂所形成的構件之電器製品 的該構件之用途。其中，適合於黏貼於依照以（長期貼附 -30- 200846439 後之黏接力容易變高）聚苯乙烯、聚苯醚、AB S、聚碳酸 酯及此等之複合材料爲主要成分之熱可塑性樹脂所形成的 構件之用途。另外，藉由使用以與該構件主要成分之同種 類的熱可塑性樹脂爲主要成分之基材片使用，與該構件之 相溶性將提高’必要時不予以再剝離，直接黏貼黏著片之 狀態下’該每個構件進行物質再循環也變得可能，能夠進 一步提高再循環適合性。還有，作爲黏貼本發明之黏著片 或使用該黏著片之標籤，使用於再循環用途之構件的材 質’不僅爲如上述之樹脂製品，也可以爲玻璃或金屬等之 無機材料所構成的構件。另外，本發明之黏著片係適合黏 貼於表面更粗糙的構件之用途，黏貼於Ra ( 3 )爲3 . 〇〜 ΙΟ.Ομιη之上述構件後而使用更爲有效，尤其，黏貼於Ra (3 )爲5 · 0〜1 〇 · 〇 μΓη之上述構件後而使用特別有效。 再者’即使從上述熱可塑性樹脂，氣體釋出爲容易發 生之狀況（例如，成型後隨即或高溫環境下），黏貼本發 明黏著片之情形，也能;夠抑制於黏著片與熱可塑性樹脂之 間發生氣泡之積存。 再者’貼附於具有以丙烯酸系樹脂、或是以上述熱可 塑性樹脂爲主要成分之表面層的彎曲面，適用必須於一定 期間貼附後剝離之用途。尤其，適合於作爲黏貼於具有以 丙嫌酸系樹脂爲主要成分之表面層的聚丙烯、聚乙烯、及 以其複合材料爲主要材料之包裝容器（於化妝品或化妝用 品所使用之管容器）的標籤材料而使用。或是，適合黏貼 -31- 200846439 於藉由塗布以丙烯酸系樹脂爲主要成分之塗料的金屬、或 以聚甲基丙烯酸甲酯或上述熱可塑性樹脂爲主要成分之塑 膠所形成，其彎曲部分之曲率半徑爲200mm以內之彎曲凸 面（自動販賣機之彎曲部、電器製品之轉角部分）。另外， 本發明之黏著片適合黏貼於較彎曲部分之曲率半徑爲小之 構件的用途，黏貼於曲率半徑爲5 0mm以內之該構件後而 使用更爲有效。尤其，黏貼於曲率半徑爲1 0mm以內之該 I 構件後而使用特別有效。 [實施例] 接著，根據本發明之實施例與比較例以詳加說明。以 下之實施例與比較例中，「份」係表示質量份。 (實施例1 ) 於具備攪拌機、回流冷卻管、氮氣導入管、溫度計、 滴定漏斗之反應容器中，加入Latemul S-180(花王公司 製：有效成分5 0 % ) 3份、去離子水40份，一面注入氮氣， φ 並一面升溫至60°C。於攪拌中，添加已使二氫氯化-2,2’-偶氮二（2-甲基丙脒）0.05份溶解於去離子水4.95份中之 水溶液，接著，於由作爲丙烯酸單體之丙烯酸-2-乙基己酯 7 2.3份、丙烯酸丁酯25份、甲基丙烯酸甲酯0.5份、丙烯 酸1 . 〇份、甲基丙烯酸1.2份、作爲鏈轉移劑之十二烷基锍 0.02份所構成的單體混合物中，添加已加入Latemul S-l 80 (2份）、去離子水20份予以乳化後之單體預乳化液之一 部分（4份），使反應容器內溫度保持於6〇°C的同時，予 -32- 200846439 以聚合60分鐘。接著，使反應容器內溫度保持於60t：的 同時’使用各自之滴定漏斗，分別將剩餘之單體預乳化液 與二氫氯化-2,2'偶氮二（2-甲基丙脒）0.2份溶解於去離 子水19.8份中之水溶液，使反應容器內溫度保持於6〇 π的 同時’耗時240分鐘滴入而予以聚合。於滴入結束後，於 相同溫度下攪拌1 8 0分鐘，冷卻內容物之後，使ΡΗ成爲 8.5之方式來利用氨水（有效成分1 〇 % )加以調整。相對 φ 於此所得的水分散液100份，添加作爲平坦劑之Surflynol 42 0 ( Air Products Japan公司製）0.8份。進一步添加作爲 交聯劑之噁唑啉系交聯劑Epocross K-2020E (日本觸媒公 司製），以使噁唑啉基與含有羧基之單體（丙烯酸及甲基 丙烯酸）之羧基的莫耳比成爲0.15倍之方式來進行添加之 後，利用1 0 0篩孔金屬網以進行過濾而調製乳液型黏著劑。 接著，於將聚矽烷化合物塗布於聚乙烯積層紙的剝離 片（王子製紙公司製之「OKB-150NC」）上，塗布黏著劑 # 後，於80°C予以乾燥90秒鐘，得到乾燥後之厚度20μιη的 黏著劑層。接著，於此黏著劑層面上貼合Yupo SGS80( Yupo Corporation公司製），於40°C之氣體環境中放置3天後， 得到再剝離用黏著片（1 )。 (實施例2 ) (增黏塗劑之調製） 墨水接受性樹脂係添加丙烯酸樹脂溶液（綜硏化學製 之「Thermolac FE-3 2-3」、固形成分45% ) 50份、作爲稀 -33- 200846439 釋溶劑之乙醇與異丙醇之4 : 1混合溶劑4 5份、作爲抗結 塊劑之合成二氧化砍（富士 Silicea化學製之「Sylysia 3:50」）5份，調整合計100份之摻合液。使用塗料調節機， 將摻合液分散20分鐘，得到固形成分27.5 %之增黏塗劑。 (聚苯乙烯薄膜基材片之製膜） 將含有5 0 %之氧化鈦的母煉膠分批1 5份添加於分別 使60份之苯乙烯與40份之SBR予以接枝聚合的HIPS樹 • 脂100份中而成之摻合物，於20(TC，使用T模頭擠出製 膜機，予以熔融擠出，得到厚度100 μιη之未拉伸薄膜。接 著，於該薄膜之兩面，成爲5 0 mN/m濕潤指數之方式來進 行電暈處理。再者，於積層增黏塗劑層之表面，使用照相 凹版塗布機以塗布該塗布劑，藉由設置塗布量1.5g/m2之 增黏塗劑層以調製聚苯乙烯薄膜基材片。 除了使用該聚苯乙烯薄膜作爲基材片以外，進行相同 φ 於實施例1之方式後而得到黏著片（2 )。 進行所得的黏著片（2 )之評估後，對於HIPS樹脂九 粒（東洋苯乙烯公司製之HIPS樹脂），添加20%之黏著 片（2 )，予以均勻混合後，於擠出溫度2 2 0。(：進行1次 再九粒化。同樣的’未添加黏著片之情形，也進行1次再 九粒化（空白）。接著，將經再九粒化之九粒於模具溫度 5 0°C、於熔融溫度220 °C以成形成試驗片。遵照JIS K 7113，於溫度23 °C、相對濕度50%之氣體環境中，測定拉 •34· 200846439 伸斷裂強度與拉伸斷裂伸度。（拉伸速度：50mm/min、試 驗片之形狀：1號型試驗片）。測定機器係使用A and D 公司製之Tensilon萬能試驗機「RTA-100」，設定試驗片 之標線間距離50mm、抓握具間距離1 15mm、抓握部分長 度各30mm、平行部分之寬度l〇mm、厚度5mm。同樣的， 取代PS樹脂九粒，將20%之黏著片添加於利用苯乙烯系 樹脂所改性之 PPE樹脂九粒（GE Plastics公司製之 φ 「Noryl」）中之情形，也同樣地於240°C進行再九粒化及 試料片作成。使黏著片（2 )與再循環構件予以一體化，評 估再循環情形的拉伸物性之變化，相較於未添加黏著片之 情形，確認了添加於任一種樹脂中之情形，拉伸斷裂強度 之降低均爲9 %，拉伸斷裂伸度之增加均爲1 3 %，任一種 特性變化均具有±20%以下之適合再循環特性。 (實施例3 ) 除了基材片使用厚度65 μηι聚苯乙烯基材片以外，進 # 行相同於實施例2之方式，得到黏著片（3 )。所得的黏著 片（3 )也進行相同於實施例2之方式，將20 %之黏著片 (3 )添加於HIPS樹脂九粒與改性ΡΡΕ樹脂九粒後，評估 再循環情形的拉伸物性變化，確認了添加於任一種樹脂中 之情形，拉伸斷裂強度之降低均爲1 2 %，拉伸斷裂伸度之 增加均爲 1 5 %，任一種特性變化均具有土20 %以下之適合 再循環特性。 (實施例4 ) -35- 200846439 除了於乳液型黏著劑之調整中，將使用於實施例1之 交聯劑設爲噁唑啉系交聯劑Epocross K_201〇 (日本觸媒公 司製）’使D惡嗤啉基與羧基的莫耳比成爲0.03倍之方式來 添加之外，進行相同於實施例1之方式後而得到黏著片 (4 ) ° (實施例5 ) 除了於乳液型黏著劑之調整中，使揭示於實施例1之 U惡嗤啉基與羧基的莫耳比成爲倍之方式來添加之外， 進行相同於實施例1之方式後而得到黏著片（5 )。 (實施例6 ) 除了於乳液型黏著劑之調整中，使揭示於實施例1之 噁唑啉基與羧基的莫耳比成爲0.25倍之方式來添加之外， 進行相同於實施例1之方式後而得到黏著片（6 )。 (實施例7 ) 除了於乳液型黏著劑之調整中，將倂用實施例1之丙 烯酸1 . 〇份、甲基丙烯酸1.2份使用之摻合，變更爲單獨之 丙烯酸2.2份之外，進行相同於實施例1之方式後而得到 黏著片（7 )。 (實施例8 ) 除了於乳液型黏著劑之調整中，將倂用實施例1之丙 烯酸1.0份、甲基丙烯酸1.2份使用之摻合，變更爲單獨之 甲基丙烯酸2.2份之外，進行相同於實施例1之方式後而 得到黏著片（8 )。 -36- 200846439 (比較例1 ) 於具備攪拌機、回流冷卻管、氮氣導入管、溫度計、 滴定漏斗之反應容器中，加入丙烯酸-2 ·乙基己酯7 9份、 甲基丙烯酸甲酯20份、丙烯酸0.8份、丙烯酸-2-羥乙酯 〇·2份與作爲聚合觸媒之偶氮雙異丁二腈0.2份溶解於醋酸 乙酯1〇〇份中，於80 °C聚合8小時後冷卻，使固形成分成 爲3 0 %之方式來添加醋酸乙酯後而得到丙烯酸共聚物溶 φ 液。接著，相對於該丙烯酸共聚物溶液1 0 0份，添加異氰 酸酯系交聯劑（大日本油墨化學工業公司製之「Burnock NC-40」）0.7份，進行15分鐘之攪拌後而調製溶劑型黏 著劑。除了黏著劑之調製之外，進行相同於實施例1之方 式後而得到黏著片（Η 1 )。 (比較例2 ) 於具備攪拌機、回流冷卻管、氮氣導入管、溫度計、 滴定漏斗之反應容器中，加入丙烯酸丁酯90.3份、醋酸乙 • 烯酸酯8份、丙烯酸1 .5份、丙烯酸-2-羥乙酯0.2份與作 爲聚合觸媒之偶氮雙異丁二腈0.2份溶解於醋酸乙酯100 份中’於8 0 °C聚合8小時後而得到丙烯酸共聚物溶液。接 著’相對於該丙烯酸共聚物溶液之固形成分1 00份，添加 不均化松香酯（荒川化學公司製之「Super Ester A100」） 1〇份及聚合松香季戊四醇酯（荒川化學公司製之「Pens el D135」）l〇份，使固形成分成爲45 %之方式來添加醋酸乙 酯’均勻混合後而得到丙烯酸共聚物混合溶液。其後，相 -37- 200846439 對於該丙烯酸共聚物溶液1 ο 0份，添加異氰酸酯系交聯劑 (大日本油墨化學工業公司製之「Burnock NC-40」）1,2 份，進行1 5分鐘之攪拌後而調製溶劑型黏著劑。除了黏著 劑之調製之外，進行相同於實施例1之方式後而得到黏著 片（H2) 〇 (參考例1 ) 於具備攪拌機、回流冷卻管、氮氣導入管、溫度計、 滴定漏斗之反應容器中，加入去離子水40份，一面注入氮 ® 氣，並一面升溫至75 °C。於攪拌下，添加第三丁基氫過氧 化物〇·〇3份、L-抗壞血酸0.015份，接著，於由作爲丙烯 酸單體之丙烯酸-2-乙基己酯75份、丙烯酸丁酯19份、甲 基丙烯酸甲酯2份、醋酸乙烯酯1份、丙烯酸1 .5份、甲 基丙烯酸1.5份、作爲鏈轉移劑之十二烷基锍0.02份所構 成的單體混合物中，添加Latemul E-118B (花王公司製、 有效成分25% ) 1.6份與去離子水15份予以乳化後之單體 φ 預乳化液之一部分（4份），使反應容器內溫度保持於75 °C的同時，予以聚合60分鐘。接著，使反應容器內溫度保 持於75T：的同時，使用各自之滴定漏斗，分別將剩餘之單 體預乳化液、第三丁基氫過氧化物之水溶液（有效成分1 % ) 15份、L-抗壞血酸之水溶液（有效成分0.5% ) 15份， 使反應容器內溫度保持於75 °C的同時，耗時240分鐘滴入 而予以聚合。於滴入結束後，於相同溫度下攪拌1 8 0分鐘， 冷卻內容物之後，使pH成爲8.5之方式來利甩氨水（有效 -38- 200846439 成分1 〇 % )加以調整。相對於此所得的水分散液1 〇 〇份， 添加作爲平坦劑之Surflynol 420( Air Products Japan公司 製）0.8份。進一步添加作爲交聯劑之噁唑啉系交聯劑 Epocross K-20 2 0E (日本觸媒公司製），以使噁唑啉基與 含有羧基之單體（丙烯酸及申基丙烯酸）之羧基的莫耳比 成爲〇 · 2倍之方式來進行添加之後，利用1 〇 〇篩孔金屬網 以進行過濾而調製乳液型黏著劑。 g 除了乳液型黏著劑之調製以外，進行相同於實施例1 之方式後而得到再剝離用黏著片（H3 )。 (實施例9) (ABS基材片之製膜） 將含有5 0 %氧化鈦之母煉膠2 0份添加於A B S樹脂1 0 〇 份中，利用壓延法以進行製膜後而得到厚度80μπι之未拉 伸薄膜。接著，於該薄膜之兩面，成爲4 6 mN/m之濕潤指 數之方式來進行電暈處理。進一步藉由使用照相凹版塗布 ^ 機，將實施例2使用之增黏塗劑塗布於該薄膜上，設置塗 布量1.5g/m2之增黏塗劑層以調製ABS薄膜基材片。 除了基材片使用該A B s薄膜之外’進行相同於實施例 1之方式後而得到再剝離用黏著片（9 ) ° 進行所得的黏著片（9 )之評估後，相對於ABS樹脂 九粒（UMG ABS公司製之難燃ABS樹脂），添加1%之黏 著片（9 )均勻混合後，於擠出溫度240 °C進行1次再九粒 化。同樣的，未添加黏著片之情形’也進行1次再九粒化 -39- 200846439 (空白）。接著，將經再九粒化之九粒，於模具溫度50°C 於熔融溫度20 0它成形成試驗片。遵照JIS K 71 13，於溫度 2 3 °C、相對濕度50%之氣體環境中，測定拉伸斷裂強度與 拉伸斷裂伸度。（拉伸速度：50mm/min、試驗片之形狀： 1號型試驗片）。測定機器係使用A and D公司製之Tensilon 萬能試驗機「R T A _ 1 0 0」，設定試驗片之標線間距離5 0 m m、 抓握具間距離1 15mm、抓握部分長度各30mm、平行部分 之寬度10mm、厚度5mm。使黏著片（9 )與再循環構件予 以一體化，評估再循環情形的拉伸物性之變化，相較於未 添加黏著片之情形，確認了添加於任一種樹脂中之情形， 拉伸斷裂強度之降低均爲0%，拉伸斷裂伸度之增加均爲〇 %，任一種特性變化均具有±20%以下之適合再循環特性。 (實施例10 ) . 除了基材片使用厚度120 pmABS基材片之外，進行相 同於實施例4之方式後而得到黏著片（1 0 )。所得的黏著 φ 片（1 〇 )也進行相同於實施例4之方式，將1 %之黏著片 (1 〇 )添加於ABS樹脂九粒後，評估再循環情形的拉伸物 性之變化，確認了添加於任一種樹脂中之情形，拉伸斷裂 強度之降低均爲1%，拉伸斷裂伸度之增加均爲〇%，任一 種特性變化均具有±20%以下之適合再循環特性。 (實施例1 1 ) (聚碳酸酯基材片之製膜） 將含有50%氧化鈦之母煉膠20份添加於聚碳酸酯樹 -40-The adhesive sheet for re-peeling of the present invention is used in the above-mentioned use, and in order to exhibit good adhesion to the adhesive, it is not only a smooth surface of various electrical products or the like, even if it is adhered to a rough surface having irregularities, The floating peeling may occur, and the adhesive may remain on the surface of the adhesive even if the adhesive sheet for re-peeling of the present invention is peeled off from the adhesive which has been adhered for a long period of time due to the superior re-peelability. It will not be cut off. That is, the adhesive sheet for re-peeling of the present embodiment is suitable for producing sheets, stickers or labels used for publicity, advertising, and information display. More specifically, the label for using the adhesive sheet or the adhesive sheet of the present invention includes a step of peeling off the adhesive sheet or the adhesive label when recycling, and is suitable for sticking with an arithmetic mean height Ra of the surface contour curve ( 3) The heat of the main component of polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyphenylene ether, ABS, polycarbonate and these composite materials of 〇~1〇·〇μπι Use of the member of an electrical article of a member formed of a plastic resin. Among them, it is suitable for sticking to thermoplastics based on polystyrene, polyphenylene ether, AB S, polycarbonate and the like which are mainly composed of (the adhesion after long-term attachment -30-200846439) is high. The use of components formed by resins. In addition, by using a base material sheet containing a thermoplastic resin of the same type as the main component of the member as a main component, the compatibility with the member is improved, and when it is not peeled off as necessary, the adhesive sheet is directly adhered. It is also possible to carry out material recycling for each member, which can further improve the recycling suitability. Further, as the adhesive sheet of the present invention or the label using the adhesive sheet, the material used for the member for recycling is not only a resin product as described above, but also a member composed of an inorganic material such as glass or metal. . In addition, the adhesive sheet of the present invention is suitable for sticking to a member having a rougher surface, and is more effective after being applied to the above-mentioned member of Ra(3) of 3.(〇)Ο.Ομιη, especially, sticking to Ra (3) It is particularly effective after being used for the above components of 5 · 0~1 〇·〇μΓη. Furthermore, even in the case where the gas is released from the above-mentioned thermoplastic resin in a state where it is easy to occur (for example, immediately after molding or in a high-temperature environment), the adhesive sheet of the present invention can be adhered to, and the adhesive sheet and the thermoplastic resin can be suppressed. The accumulation of bubbles occurs between them. Further, it is attached to a curved surface having a surface layer containing an acrylic resin or a thermoplastic resin as a main component, and is applied to a film which must be attached and peeled off after a certain period of time. In particular, it is suitable as a packaging container (a tube container used for cosmetics or cosmetics) which is adhered to a surface layer having a surface material containing a acrylic acid resin as a main component, and a composite material thereof as a main material. Use of the label material. Or, it is suitable for sticking -31- 200846439 by forming a metal coated with an acrylic resin as a main component or a plastic containing polymethyl methacrylate or the above thermoplastic resin as a main component, and the bent portion thereof A curved convex surface having a radius of curvature of 200 mm (the curved portion of the vending machine, the corner portion of the electrical product). Further, the adhesive sheet of the present invention is suitable for use in a member having a small radius of curvature of a relatively curved portion, and is more effective after being applied to the member having a radius of curvature of 50 mm or less. In particular, it is particularly effective to adhere to the I member having a radius of curvature of 10 mm or less. [Examples] Next, the examples and comparative examples of the present invention will be described in detail. In the following examples and comparative examples, "parts" means parts by mass. (Example 1) In a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, and a titration funnel, 3 parts of Latemul S-180 (manufactured by Kao Corporation: 50% active ingredient) and 40 parts of deionized water were added. Nitrogen gas was injected into the surface while φ was raised to 60 °C. While stirring, an aqueous solution in which 0.05 part of dihydrochloride-2,2'-azobis(2-methylpropionamidine) was dissolved in 4.95 parts of deionized water was added, followed by being used as an acrylic monomer. 7 2.3 parts of 2-ethylhexyl acrylate, 25 parts of butyl acrylate, 0.5 parts of methyl methacrylate, 1 part of acrylic acid, 1.2 parts of methacrylic acid, and 0.02 parts of dodecyl fluorene as a chain transfer agent Add a part (4 parts) of the monomer pre-emulsion which has been added with the addition of Latemul Sl 80 (2 parts) and 20 parts of deionized water to the monomer mixture, and keep the temperature inside the reaction vessel at 6 °. At the same time as C, give -32-200846439 to polymerize for 60 minutes. Next, while maintaining the temperature in the reaction vessel at 60t:, using the respective titration funnels, respectively, the remaining monomer pre-emulsion and dihydrochloride-2,2' azobis(2-methylpropionamidine) 0.2 part of an aqueous solution dissolved in 19.8 parts of deionized water was allowed to be polymerized by dropwise addition for 240 minutes while maintaining the temperature inside the reaction vessel at 6 〇π. After the completion of the dropwise addition, the mixture was stirred at the same temperature for 180 minutes, and after cooling the contents, the hydrazine was adjusted to 8.5 to adjust the aqueous ammonia (active ingredient 1 〇 %). With respect to φ of 100 parts of the aqueous dispersion obtained in the above, 0.8 parts of Surflynol 42 0 (manufactured by Air Products Japan Co., Ltd.) as a flat agent was added. Further, an oxazoline-based crosslinking agent Epocross K-2020E (manufactured by Nippon Shokubai Co., Ltd.) as a crosslinking agent is further added to give a molar group of a oxazoline group and a carboxyl group-containing monomer (acrylic acid and methacrylic acid). After the addition was carried out in a manner of 0.15 times, the emulsion type adhesive was prepared by filtration using a 100 mesh metal mesh. Next, the polydecane compound was applied onto a release sheet of polyethylene laminated paper ("OKB-150NC" manufactured by Oji Paper Co., Ltd.), and the adhesive # was applied, and then dried at 80 ° C for 90 seconds to obtain a dried product. An adhesive layer having a thickness of 20 μm. Next, Yupo SGS80 (manufactured by Yupo Corporation) was attached to the adhesive layer, and after standing for 3 days in a gas atmosphere of 40 ° C, an adhesive sheet (1 ) for re-peeling was obtained. (Example 2) (Preparation of adhesion-increasing agent) The ink-receiving resin was added with an acrylic resin solution ("Thermolac FE-3 2-3" manufactured by Kokusai Chemical Co., Ltd., solid content 45%) 50 parts, as a thin-33 - 200846439 5 parts of 4:1 mixed solvent of ethanol and isopropanol, 5 parts of synthetic dioxide (antibiotics, "Sylysia 3:50" by Fuji Silica Chemical Co., Ltd.) as an anti-caking agent, adjusted to a total of 100 parts Blending solution. The blending solution was dispersed for 20 minutes using a paint conditioner to obtain a tackifying coating agent having a solid content of 27.5 %. (Formation of Polystyrene Film Substrate Sheet) A batch of 15 parts of a master batch containing 50% of titanium oxide was added to a HIPS tree in which 60 parts of styrene and 40 parts of SBR were graft-polymerized, respectively. • A blend of 100 parts of fat, melt-extruded at 20 (TC, using a T-die extrusion film-forming machine to obtain an unstretched film having a thickness of 100 μm. Then, on both sides of the film, Corona treatment was carried out in a manner of a moisture index of 50 mN/m. Further, on the surface of the layer of the adhesion-promoting coating layer, a gravure coater was used to coat the coating agent by setting a coating amount of 1.5 g/m2. The adhesive layer was prepared to prepare a polystyrene film substrate sheet. The adhesive sheet (2) was obtained by the same method as in Example 1 except that the polystyrene film was used as the substrate sheet. After the evaluation of the sheet (2), 20 parts of the HIPS resin (HIPS resin manufactured by Toyo Styrene Co., Ltd.) was added with 20% of the adhesive sheet (2), and uniformly mixed, and then extruded at a temperature of 2 2 0. 1 time and then 9 granulations. The same 'without the addition of adhesive sheets, also carried out 1 time Granulation (blank). Next, nine pieces of the ninth granules were formed at a mold temperature of 50 ° C and a melting temperature of 220 ° C to form test pieces. According to JIS K 7113, at a temperature of 23 ° C, relative humidity In the 50% gas environment, the tensile strength at break and tensile elongation at break were measured. (Tensile speed: 50 mm/min, shape of test piece: test piece No. 1). The Tensilon universal testing machine "RTA-100" manufactured by D Company sets the distance between the marking lines of the test piece to 50 mm, the distance between the gripping tools to be 15 mm, the length of the grip portion to 30 mm, the width of the parallel portion to l mm, and the thickness to 5 mm. Similarly, in place of the resin of the PS resin, 20% of the adhesive sheet was added to nine pieces of the PPE resin modified by the styrene resin (φ "Noryl" manufactured by GE Plastics Co., Ltd.), and similarly to 240. The ninth granulation and the preparation of the test piece were carried out at ° C. The adhesive sheet (2) was integrated with the recirculating member, and the change in the tensile physical properties in the case of recycling was evaluated, and the addition was confirmed as compared with the case where the adhesive sheet was not added. In the case of any kind of resin, stretching The reduction in strength was 9%, the increase in tensile elongation at break was 13%, and any change in characteristics had a suitable recycling property of ±20% or less. (Example 3) In addition to the thickness of the substrate sheet, 65 μηι The adhesive sheet (3) was obtained in the same manner as in Example 2 except for the polystyrene substrate sheet. The obtained adhesive sheet (3) was also subjected to the same manner as in Example 2, and 20% of the adhesive sheet ( 3) After adding nine particles of HIPS resin and nine modified resin, the tensile property change in the case of recycling was evaluated, and it was confirmed that the addition of the resin was in any of the resins, and the reduction in tensile breaking strength was 12%. The increase in tensile elongation at break is 15%, and any change in characteristics has a suitable recycling characteristic of less than 20% of soil. (Example 4) -35- 200846439 In addition to the adjustment of the emulsion type adhesive, the crosslinking agent used in Example 1 was used as an oxazoline crosslinking agent Epocross K_201 (manufactured by Nippon Shokubai Co., Ltd.). The adhesive sheet (4) was obtained in the same manner as in Example 1 except that the molar ratio of the D-oxalinyl group to the carboxyl group was 0.03 times. (Example 5) Except for the emulsion type adhesive In the adjustment, the adhesive sheet (5) was obtained in the same manner as in Example 1 except that the molar ratio of the U oxalinyl group and the carboxyl group disclosed in Example 1 was doubled. (Example 6) The same procedure as in Example 1 was carried out except that the molar ratio of the oxazoline group and the carboxyl group disclosed in Example 1 was 0.25 times in the adjustment of the emulsion type adhesive. Then, an adhesive sheet (6) is obtained. (Example 7) In addition to the adjustment of the emulsion type adhesive, the blending of the acrylic acid of Example 1 and the use of 1.2 parts of methacrylic acid was changed to 2.2 parts of the acrylic acid alone, and the same was carried out. The adhesive sheet (7) was obtained in the same manner as in Example 1. (Example 8) In addition to the adjustment of the emulsion type adhesive, 1.0 part of the acrylic acid of Example 1 and 1.2 parts of methacrylic acid were blended and changed to 2.2 parts of methacrylic acid alone, and the same was carried out. The adhesive sheet (8) was obtained in the manner of Example 1. -36- 200846439 (Comparative Example 1) In a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen inlet tube, a thermometer, and a titration funnel, 7 parts of 2-ethylhexyl acrylate and 20 parts of methyl methacrylate were added. 0.8 parts of acrylic acid, 2 parts of 2-hydroxyethyl acrylate and 2 parts of azobisisosuccinonitrile as a polymerization catalyst were dissolved in 1 part of ethyl acetate, and polymerized at 80 ° C for 8 hours. After cooling, the ethyl acetate was added in such a manner that the solid content became 30%, and an acrylic copolymer dissolved φ liquid was obtained. Then, 0.7 parts of an isocyanate-based crosslinking agent ("Burnock NC-40" manufactured by Dainippon Ink and Chemicals, Inc.) was added to 100 parts of the acrylic copolymer solution, and the mixture was stirred for 15 minutes to prepare a solvent-type adhesive. Agent. The adhesive sheet (Η 1 ) was obtained in the same manner as in Example 1 except that the preparation of the adhesive was carried out. (Comparative Example 2) 90.3 parts of butyl acrylate, 8 parts of ethyl acetate, 1.5 parts of acrylic acid, and acrylic acid were added to a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, and a titration funnel. 0.2 part of 2-hydroxyethyl ester and 0.2 part of azobisisosuccinonitrile as a polymerization catalyst were dissolved in 100 parts of ethyl acetate to be polymerized at 80 ° C for 8 hours to obtain an acrylic copolymer solution. Then, '100 parts of the solid content of the acrylic copolymer solution was added, and a heterogeneous rosin ester ("Super Ester A100" manufactured by Arakawa Chemical Co., Ltd.) and a polymerized rosin pentaerythritol ester ("Pens of Arakawa Chemical Co., Ltd." were added. El D135") is a mixture of acrylic acid copolymers obtained by uniformly adding ethyl acetate in such a manner that the solid content is 45%. Then, phase-37-200846439, 1 part of the acrylic copolymer solution was added, and 1, 2 parts of an isocyanate-based crosslinking agent ("Burnock NC-40" manufactured by Dainippon Ink and Chemicals Co., Ltd.) was added for 15 minutes. After stirring, a solvent-based adhesive is prepared. In addition to the preparation of the adhesive, the adhesive sheet (H2) 〇 (Reference Example 1) was obtained in the same manner as in Example 1 in a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a titration funnel. Add 40 parts of deionized water, and add nitrogen® gas to the side while heating to 75 °C. 3 parts of a third butyl hydroperoxide ruthenium ruthenium and 0.015 parts of L-ascorbic acid were added under stirring, followed by 75 parts of 2-ethylhexyl acrylate as an acrylic monomer, and 19 parts of butyl acrylate. Addition of Latemul E to a monomer mixture consisting of 2 parts of methyl methacrylate, 1 part of vinyl acetate, 1.5 parts of acrylic acid, 1.5 parts of methacrylic acid, and 0.02 parts of dodecyl hydrazine as a chain transfer agent -118B (manufactured by Kao Corporation, 25% active ingredient) 1.6 part of a monomer φ pre-emulsion (4 parts) emulsified with 15 parts of deionized water, keeping the temperature inside the reaction vessel at 75 °C It was polymerized for 60 minutes. Next, while maintaining the temperature in the reaction vessel at 75T:, using the respective titration funnels, the remaining monomer pre-emulsion and the third butyl hydroperoxide solution (active ingredient 1%) were respectively 15 parts, L - 15 parts of an aqueous solution of ascorbic acid (0.5% of active ingredient), and the temperature in the reaction vessel was maintained at 75 ° C while being dropwise added for 240 minutes to be polymerized. After the completion of the dropwise addition, the mixture was stirred at the same temperature for 180 minutes, and after cooling the contents, the pH was adjusted to 8.5 to adjust the ammonia water (effective -38 - 200846439 component 1 〇 %). To the obtained aqueous dispersion, 0.8 parts of Surflynol 420 (manufactured by Air Products Japan Co., Ltd.) as a flattening agent was added to the obtained aqueous dispersion. Further, an oxazoline-based crosslinking agent Epocross K-20 2 0E (manufactured by Nippon Shokubai Co., Ltd.) as a crosslinking agent is added to make a carboxyl group of a oxazoline group and a carboxyl group-containing monomer (acrylic acid and acrylic acid) After the molar ratio was added in a manner of 2 times, the emulsion type adhesive was prepared by filtration using a 1 mesh mesh metal mesh. g The adhesive sheet (H3) for re-peeling was obtained in the same manner as in Example 1 except that the emulsion type adhesive was prepared. (Example 9) (Formation of ABS substrate sheet) 20 parts of a master batch containing 50% of titanium oxide was added to 10 parts of ABS resin, and a film was formed by a calendering method to obtain a thickness of 80 μm. Unstretched film. Then, corona treatment was carried out so as to have a wetness index of 4 6 mN/m on both sides of the film. Further, an adhesion-promoting agent used in Example 2 was applied onto the film by using a gravure coater, and an adhesion-promoting coating layer of 1.5 g/m2 was set to prepare an ABS film substrate sheet. The evaluation of the obtained adhesive sheet (9) after the same method as in Example 1 was carried out except that the substrate sheet was used in the same manner as in Example 1, and the ABS resin was obtained. (Flameable ABS resin manufactured by UMG ABS Co., Ltd.), 1% of the adhesive sheet (9) was uniformly mixed, and then subjected to an extrusion temperature of 240 ° C for one time and then nine granulations. Similarly, the case where no adhesive sheet was added was also carried out once again and then nine-granulated -39-200846439 (blank). Next, nine pieces which were further granulated were formed into a test piece at a mold temperature of 50 ° C at a melting temperature of 20 0. The tensile breaking strength and the tensile elongation at break were measured in a gas atmosphere at a temperature of 2 3 ° C and a relative humidity of 50% in accordance with JIS K 71 13. (Tensile speed: 50 mm/min, shape of test piece: No. 1 test piece). For the measuring machine, the Tensilon universal testing machine "RTA _ 1 0 0" manufactured by A and D company was used, and the distance between the marking lines of the test piece was set to 50 mm, the distance between the gripping tools was 1 15 mm, and the length of the gripping portion was 30 mm each. The width of the part is 10 mm and the thickness is 5 mm. The adhesive sheet (9) was integrated with the recirculating member to evaluate the change in the tensile physical properties in the case of recycling, and the case where it was added to any of the resins was confirmed as compared with the case where the adhesive sheet was not added, tensile breaking strength The decrease is 0%, the increase in tensile elongation at break is 〇%, and any characteristic change has a suitable recycling characteristic of ±20% or less. (Example 10) An adhesive sheet (10) was obtained in the same manner as in Example 4 except that a thickness of 120 pmA of the BS substrate sheet was used for the substrate sheet. The obtained adhesive φ sheet (1 〇) was also subjected to the same manner as in Example 4, and after adding 1% of the adhesive sheet (1 〇) to the ABS resin, the change in the tensile physical properties in the case of recycling was confirmed. In the case of being added to any of the resins, the reduction in tensile breaking strength is 1%, the increase in tensile elongation at break is 〇%, and any change in characteristics has a suitable recycling property of ±20% or less. (Example 1 1 ) (film formation of polycarbonate substrate sheet) 20 parts of a master batch containing 50% of titanium oxide was added to a polycarbonate tree -40-
.200846439 脂1 〇〇份中而成的摻合物，利用壓延法以進行製膜後 到厚度100 μπι之未拉伸薄膜。接著，於該薄膜之兩面 爲50mN/m之濕潤指數之方式來進行電暈處理。進一 由使用照相凹版塗布機，將實施例2使用之增黏塗劑 於該薄膜上，設置塗布量1.5g/m2之增黏塗劑層以調 碳酸酯薄膜基材片。 除了使用該聚碳酸酯薄膜作爲基材片之外，進行 於實施例1之方式後而得到黏著片（1 1 )。 進行所得的黏著片（1 1 )之評估後，對於聚碳酸 HIPS之合金樹脂九粒（Dai cel Polymer公司製之難燃 酸酯-HIPS合金樹脂），添加2.5%之黏著片（1 1 )， 混合後，於擠出溫度24(TC進行1次再九粒化。同樣的 添加黏著片之情形，也進行1次再九粒化（空白）。接 將經成再丸粒化之九粒，於模具溫度50°C、於熔融溫g °C，成形成試驗片。遵照JIS，K 71 13，於溫度23°C、 濕度50%之氣體環境中，測定拉伸斷裂強度與拉伸斷 度。（拉伸速度·· 50mm/min、試驗片之形狀：1號型 片）。測定機器係使用A and D公司製之Tensilon萬 驗機「RTA-100」，設定試驗片之標線間距離50mm、 具間距離1 15mm、抓握部分長度各30mm、平行部分之 10mm、厚度5mm。使黏著片（11)與再循環構件予乜 化，評估再循環情形的拉伸物性之變化，相較於未裙 著片之情形，確認了添加於任一種樹脂中之情形，g ίΐί得 ，成 步藉 塗布 製聚 相同 酯與 聚碳 均勻 ，未 ^著， f 220 相對 裂伸 試驗 能試 抓握 .寬度 、一體 ;加黏 :伸斷 -41- 200846439 裂強度之降低均爲3 %，拉伸斷裂伸度之降低均爲4 %，任 一種特性變化均具有±2 0 %以下之適合再循環特性。 針對於上述實施例、比較例及參考例所得的黏著片， 進行以下之評估，將所得的結果顯示於表1〜3。另外，將 利用實施例1測出的損失正切曲線作成第1圖後而顯示。 (動態黏彈性之測定） 使用黏彈性試驗機（Rheometrics公司製之商品名： | Ares 2K STD)，將上述所得的試驗片夾入平行圓盤狀之測 定部中，測定於頻率1Hz、從- 50°C至150°C爲止之貯藏彈 性率（G’）與損失彈性率（G”）。損失正切tariS係依照下 列計算式而算出。試驗片係重疊複數片各實施例及比較例 的黏著片，使除去基材厚度之實質黏著劑的厚度成爲 0.64mm之方式來予以積層後而製得。 損失正切tar^= G”/ G’ 但是，於黏著片（2)〜（3)及（9)〜（11)中，由 φ 於因加熱而造成聚苯乙烯基材片、ABS基材片、聚碳酸酯 基材片之軟化，測定將變得困難，黏著片（2 )〜（3 )及 (9 )〜（1 1 )之動態黏彈性的測定値係挪用將yup〇 SGS80 使用於基材片之黏著片（1 )的測定値。 (初期黏著力Fa之測定） 遵照JIS Z 0237，於溫度23。(：、相對濕度50%之氣體 環境中，將黏著片切斷成寬25mm、長100mm，依照JIS B 0 60 1 2QQ1所定義之輪廓曲線的算術平均高度Ra( 3 )爲Ο.ΐμπι -42- 200846439 之聚苯乙烯板，利用2kg之滾筒，以壓黏速度5mm/s、壓 黏次數1次來回黏貼後，放置24小時。接著，使用拉伸試 驗機（A and D股份公司製之RTA100 )，利用50mm/min 之速度、90度撕剝，測定黏接力。 (初期黏著力Fb之測定） 遵照JIS Z 02 3 7，於溫度23°C、相對濕度50%之氣體 環境中，將黏著片切斷成寬25mm、長100mm，依照JIS B 060 1 2G()1所定義之輪廓曲線的算術平均高度Ra( 3 )爲7·0μιη 之聚苯乙烯板，利用2kg之滾筒，以壓黏速度5mm/s、壓 黏次數1次來回黏貼後，放置24小時。接著，使用拉伸試 驗機（A and D股份公司製之RTA100 )，利用50mm/min 之速度、90度撕剝，測定黏接力。 (輪廓曲線之算術平均高度Ra ( 3 )之測定） 使用於上述黏著力測定時之聚苯乙烯板’依照JIS B 060 1 2()()1所定義之輪廓曲線的算術平均高度Ra ( 3 ) ( μιη) φ 係遵照下列測定方法所測定的。使用表面形狀測定裝置 Surfcom 5 7 5 Α (東京精密股份公司製），利用接觸尖端 5μπιΙΙ、鑽石、測定力4mN以下、測定基準長度之條 件，測定聚苯乙烯板每一試料1 〇處之表面粗糙度’求出輪 廓曲線的算術平均高度（Ra ( 3) ; μιη) ° (耐剝離性之評估） 於溫度2 3 Τ：、相對濕度5 0 %之氣體環境中’將黏著片 切斷成寬25mm、長100mm，於具有依照JIS Β 060 1 2ί)()1所 -43- 200846439 定義之輪廓曲線的算術平均高度Ra ( 3 )爲0.1 μπι及7.0 μιη 之表面的聚苯乙烯扳、聚苯醚板、ABS板及聚碳酸酯板上， 利用2kg之滾筒，1次來回壓黏後’放置1小時。接著， 於溫度60 °C、相對濕度〇〜5%之環境中，放置60天後， 根據目視以判定黏著片的浮動剝離狀態。 〇：對於所有的黏附物，無浮動剝離，爲沒有問題之 狀態。 △:對於一部分的黏附物，無浮動剝離。 ® X :對於所有的黏附物，發生浮動剝離。 (再剝離性之評估） 於溫度23 °C、相對濕度50%之氣體環境中，將黏著片 切斷成寬25mm、長i〇0mm，於具有依照jIS b 060 1 2〇(h所 定義之輪廓曲線的算術平均高度Ra ( 3 )爲Ο.ΐμπι及7.0μιη 之表面的聚苯乙烯板、聚苯醚板、ΑΒ S板及聚碳酸酯板上， 利用2kg之滾筒，1次來回壓黏後，放置1小時。進一步 φ 於溫度60°C、相對濕度〇〜5%之環境中，放置60天，接 著，於溫度2 3 °C、相對濕度5 0 %之氣體環境中放置1小時 後，沿著撕剝角度135度方向、以lm/分鐘之速度，根據 目視以判定撕剝後之狀態。 〇：對於所有的黏附物，無糊殘留，容易剝離。 △:對於一部分的黏附物，無糊殘留，能夠剝離。 X :對於黏附物之糊殘留顯著，再剝離爲困難的。 (再循環適合性之評估：再循環再使用性） -44- 200846439 於溫度23 °C、相對濕度50%之氣體環境中，將黏著片 切斷成寬25mm、長l〇〇mm，於具有依照JIS B 060 1 2Q()1所 定義之輪廓曲線的算術平均高度Ra(3)爲Ο.ΐμπι及7.0μπι 之表面的聚苯乙烯板、聚苯醚板、AB S板及聚碳酸酯板上， 利用2kg之滾筒，1次來回壓黏後，放置1小時。進一步 於溫度60 °C、相對濕度0〜5%之環境中，放置60天，接 著，於溫度2 3 °C、相對濕度5 0 %之氣體環境中放置1小時。 | 其後，黏著劑殘留於黏附物，使基材片不會破裂之方式， 一面留意，並一面剝離黏著片，評估其剝離作業之進行容 易性。 〇：對於所有的黏附物，即使不刻意設計，黏著劑之 殘留或基材片之破裂也不會發生，能夠再剝離，剝離作業 性優異。 △:對於一部分的黏附物，即使不刻意設計，黏著劑 之殘留或基材片之破裂也不會發生，能夠進行剝離作業性。 • X :藉由用吹風機加熱，且非常慢地予以剝離，雖然 再剝離成爲可能的，但是剝離作業性爲差的。 X X ··藉由用吹風機加熱，且即使非常慢地加以剝離， 黏著劑將殘留於黏附物，且基材片之破裂將發生’剝離作 業性極爲困難。 (對於彎曲面之耐剝離性及再剝離性之評估1) 利用UV墨水印刷於黏著片後，於其表面，透過1 5 μιη 之黏著劑層而積層20 μιη之聚丙烯薄膜，製作寬50mm、長 -45- 200846439 5 0mm之顯目標籤。接著，於表面已塗布丙烯酸系樹脂之聚 乙烯製擠出管容器之（彎曲面的）該丙烯酸樹脂塗層上， 黏貼顯目標籤，於溫度23 °C、相對濕度50%之環境中放置 3個月，藉由目視以判定顯目標籤之浮動剝離狀態及再剝 離性。 ◎:無標籤之浮動剝離，並且爲再剝離性也無問題之 狀態。 ¥ 〇：雖然觀察到無實用上問題程度之僅極少數標籤之 浮動，再剝離性爲無問題之狀態。 〇〜△:雖然觀察到僅極少數標籤之浮動及極少量黏 著劑殘存於黏附物，均爲無實用上問題程度之浮動、黏著 劑殘存。 △:雖然無標籤之浮動剝離，但是一旦剝離標籤時， 發生黏著劑殘存於容器表面，或基材片之破裂。 X :雖然再剝離性無問題，但是標籤之浮動剝離顯著 • 發生。 X X :標籤之浮動剝離顯著發生，並且一旦剝離標籤 時’發生黏著劑殘存於容器表面，或基材片之破裂。 (對於彎曲面之耐剝離性及再剝離性之評估2 ) 利用膠版印刷於黏著片後，於其表面，透過黏著劑層 而積層20μιη之聚丙烯薄膜，製作寬5〇mm、長5〇min之標 籤。接著，黏貼於曲率半徑25mm之聚甲基丙烯酸甲酯的 表面上’於溫度23。(：、相對濕度50%之環境中放置3個月， -46· 200846439 藉由目視以判定標籤之浮動剝離狀態及再剝離性。 ◎:無標籤之浮動剝離，並且爲再剝離性也無問題之 狀態。 〇：雖然觀察到無實用上問題程度之僅極少數標籤之 浮動，再剝離性爲無問題之狀態。 〇〜△:雖然觀察到僅極少數標籤之浮動及極少量黏 著劑殘存於黏附物，均爲無實用上問題程度之浮動、黏著 劑殘存。 △:雖然無標籤之浮動剝離，但是一旦剝離標籤時， 發生黏著劑殘存於容器表面，或基材片之破裂。 X :雖然再剝離性無問題，但是標籤之浮動剝離顯著 發生。 X X :標籤之浮動剝離顯著發生，並且一旦剝離標籤 時，發生黏著劑殘存於容器表面，或基材片之破裂。 (膨脹之評估） # 針對在黏著片上進行網板印刷之後，將Yupo SGS80 用於基材片的黏著片（1)及（HI)〜（H3)，於其表面， 透過1 5 μπι之黏著劑層而積層20 μπι之聚丙烯薄膜，使用聚 苯乙烯薄膜基材之黏著片（2 )〜（3 )之情形，於其表面， 透過20μπι之黏著劑層而積層25μπι之聚苯乙嫌薄膜，製作 寬70mm、長70mm之標籤。接著，黏貼於HIPS板之表面， 於溫度6 0 °C、相對濕度9 0 %之環境中放置1天’藉由目視 以判定標籤之膨脹狀態。 -47- 200846439 〇：爲膨脹未被觀察到之狀態。 〇〜△:注視時，觀察到不影響外觀程度之極些微膨 脹。 △:觀察到些微膨脹。 X:明顯發生膨脹，爲有問題之標籤。.200846439 A blend of a 1 part of a fat, which was subjected to calendering to an unstretched film having a thickness of 100 μm. Next, corona treatment was carried out so that the both sides of the film had a wetness index of 50 mN/m. Further, by using a gravure coater, the tackifying agent used in Example 2 was applied to the film, and an adhesion-promoting coating layer having a coating amount of 1.5 g/m2 was set to adjust the carbonate film substrate sheet. An adhesive sheet (1 1 ) was obtained in the same manner as in Example 1 except that the polycarbonate film was used as the substrate sheet. After the evaluation of the obtained adhesive sheet (1 1 ), a 2.5% adhesive sheet (1 1 ) was added to the polyurethane resin of HIPS (non-flammable acid ester-HIPS alloy resin manufactured by Daicel Polymer Co., Ltd.). After mixing, at the extrusion temperature of 24 (TC is carried out once and then nine granulations. In the case of the same addition of the adhesive sheet, it is also carried out once and then nine granulations (blank). The test piece was formed at a mold temperature of 50 ° C and a melting temperature of g ° C. The tensile breaking strength and tensile fracture were measured in accordance with JIS, K 71 13, in a gas atmosphere at a temperature of 23 ° C and a humidity of 50%. (Tensile speed··50mm/min, shape of test piece: No.1 type). The measuring machine uses the Tensilon universal inspection machine "RTA-100" manufactured by A and D Co., Ltd. to set the distance between the marking lines of the test piece. 50mm, with a distance of 1 15mm, a grip length of 30mm, a parallel part of 10mm, and a thickness of 5mm. The adhesive sheet (11) and the recirculation member are preliminarily evaluated to evaluate the change in tensile properties of the recirculating case. In the case where the film was not skirted, it was confirmed that it was added to any of the resins, g ίΐί, Step by coating to make the same ester and polycarbon uniform, not ^, f 220 relative crack test can be gripped. Width, one; Adding: Stretch -41- 200846439 The crack strength is reduced by 3%, pull The reduction in elongation at break is 4%, and any characteristic change has a suitable recycling property of ±20% or less. For the adhesive sheets obtained in the above examples, comparative examples and reference examples, the following evaluation will be performed. The results obtained are shown in Tables 1 to 3. The loss tangent curves measured in Example 1 were shown in Fig. 1. (Measurement of dynamic viscoelasticity) A viscoelasticity tester (trade name manufactured by Rheometrics Co., Ltd.) was used. : | Ares 2K STD), the test piece obtained above was sandwiched in a parallel disk-shaped measuring section, and the storage elastic modulus (G') and loss elasticity at a frequency of 1 Hz and from -50 ° C to 150 ° C were measured. Rate (G"). The loss tangent tariS was calculated according to the following calculation formula. The test piece was obtained by laminating a plurality of sheets of the adhesive sheets of the respective examples and the comparative examples so that the thickness of the substantial adhesive which removed the thickness of the substrate was 0.64 mm. Accumulate Then, the loss tangent tar^= G"/ G' However, in the adhesive sheets (2) to (3) and (9) to (11), the polystyrene substrate sheet is caused by heating due to φ , ABS substrate sheet, polycarbonate substrate sheet softening, measurement will become difficult, the measurement of dynamic viscoelasticity of the adhesive sheets (2) ~ (3) and (9) ~ (1 1) will be used yup 〇SGS80 is used for the measurement of the adhesive sheet (1) of the substrate sheet. (Measurement of Initial Adhesion Fa) According to JIS Z 0237, at a temperature of 23. (: In a gas environment with a relative humidity of 50%, the adhesive sheet is cut into a width of 25 mm and a length of 100 mm, and the arithmetic mean height Ra(3) of the contour curve defined in JIS B 0 60 1 2QQ1 is Ο.ΐμπι -42 - Polystyrene board of 200846439, using a 2kg roller, pasting at a pressure-adhesive speed of 5mm/s and pressure-adhesive times, and then placing it for 24 hours. Then, using a tensile testing machine (RTA100 manufactured by A and D Co., Ltd.) The adhesive force is measured by a speed of 50 mm/min and a peeling of 90 degrees. (Measurement of initial adhesive force Fb) Adhere to JIS Z 02 3 7, in a gas atmosphere at a temperature of 23 ° C and a relative humidity of 50%. The sheet was cut into a polystyrene sheet having a width of 25 mm and a length of 100 mm and an arithmetic mean height Ra (3) of a contour curve defined by JIS B 060 1 2G() 1 as 7·0 μιη, using a 2 kg roller to press-adhesive The speed was 5 mm/s, and the pressure-adhesive times were applied back and forth for 24 hours. Then, using a tensile tester (RTA100 manufactured by A and D Co., Ltd.), the peel was measured by a speed of 50 mm/min and a peeling of 90 degrees. Relay (measurement of the arithmetic mean height Ra ( 3 ) of the contour curve) used for the above adhesion The arithmetic mean height Ra ( 3 ) ( μιη) φ of the profile curve defined in accordance with JIS B 060 1 2()() 1 was measured in accordance with the following measurement method. The surface shape measuring device was used. Surfcom 5 7 5 Α (manufactured by Tokyo Seimi Co., Ltd.), using the contact tip 5 μπιΙΙ, diamond, measuring force 4 mN or less, and measuring the reference length, measuring the surface roughness of each sample of the polystyrene plate at 1 ' The arithmetic mean height of the curve (Ra ( 3) ; μιη) ° (Evaluation of peel resistance) In a gas environment with a temperature of 2 3 Τ: and a relative humidity of 50%, the adhesive sheet is cut into a width of 25 mm and a length of 100 mm. Polystyrene board, polyphenylene ether board, ABS board having a surface having an arithmetic mean height Ra ( 3 ) of 0.1 μm and 7.0 μη according to a profile curve defined in JIS 060 060 1 2ί) () 1 - 43- 200846439 And on a polycarbonate plate, use a 2 kg roller and press it back and forth once and then 'place for 1 hour. Next, after leaving it for 60 days in an environment of a temperature of 60 ° C and a relative humidity of 5% to 5%, the floating peeling state of the adhesive sheet was judged by visual observation. 〇: For all the adhesives, there is no floating peeling, which is no problem. △: No floating peeling was observed for a part of the adherend. ® X : Floating peeling occurs for all adherents. (Evaluation of re-peelability) The adhesive sheet was cut into a width of 25 mm and a length of i 〇 0 mm in a gas atmosphere at a temperature of 23 ° C and a relative humidity of 50%, as defined in jIS b 060 1 2 (h) The arithmetic mean height Ra ( 3 ) of the profile curve is a polystyrene plate, a polyphenylene ether plate, a ΑΒ S plate and a polycarbonate plate on the surface of Ο.ΐμπι and 7.0 μιη, using a 2 kg roller, one time back and forth After that, it was allowed to stand for 1 hour. Further φ was placed in an environment of temperature 60 ° C and relative humidity 〇 5% for 60 days, and then placed in a gas atmosphere at a temperature of 23 ° C and a relative humidity of 50% for 1 hour. According to the peeling angle of 135 degrees, at a speed of lm/min, the state after peeling is determined according to the visual observation. 〇: For all the adherends, no paste remains, and it is easy to peel off. △: For a part of the adherend, It has no paste residue and can be peeled off. X: It is difficult for the paste residue of the adhesive to be re-peeled. (Recyclability evaluation: recycling reusability) -44- 200846439 At a temperature of 23 ° C, relative humidity 50 In the gas environment of %, the adhesive sheet is cut into a width of 25 mm and a length of l〇 Mm, a polystyrene board, a polyphenylene ether board, an AB S board having a surface having an arithmetic mean height Ra (3) according to a profile curve defined in JIS B 060 1 2Q() 1 and having a surface of Ο.ΐμπι and 7.0 μm On a polycarbonate plate, use a 2kg roller and press it back and forth for 1 hour. It is further placed in an environment of 60 ° C and a relative humidity of 0 to 5% for 60 days, then at a temperature of 2 3 °. C. Place in a gas atmosphere with a relative humidity of 50% for 1 hour. | Thereafter, the adhesive remains on the adherend so that the substrate sheet does not break, and the adhesive sheet is peeled off and the peeling operation is evaluated. 〇: For all the adhesives, even if the adhesive is not intentionally designed, the adhesive residue or the substrate sheet is not broken, and it can be peeled off again, and the peeling workability is excellent. △: For a part of the adherend, even Unintentional design, the adhesive residue or the rupture of the substrate sheet does not occur, and the peeling workability can be performed. • X: It is heated by a hair dryer and peeled off very slowly, although peeling is possible, but peeling off Workability is XX ·· By heating with a hair dryer, and even if it is peeled off very slowly, the adhesive will remain on the adhesive, and the rupture of the substrate sheet will be extremely difficult to peel off. (For peeling of the curved surface) Evaluation of the properties and re-peelability 1) After printing on the adhesive sheet with UV ink, a 20 μm polypropylene film was laminated on the surface through a 15 μm adhesive layer to make a width of 50 mm and a length of -45 to 200846439 50 mm. Then, on the acrylic coating of the (extruded surface) of the extruded polyethylene tube coated with acrylic resin on the surface, the visible label is adhered at a temperature of 23 ° C and a relative humidity of 50%. The environment was allowed to stand for 3 months, and the floating peeling state and re-peelability of the visible label were determined by visual observation. ◎: There is no label floating peeling, and there is no problem in re-peelability. ¥ 〇: Although only a few labels have been floated without any practical problems, the removability is no problem. 〇~△: Although it was observed that only a very small number of labels floated and a very small amount of adhesive remained in the adherend, there was no practical problem of floating and the adhesive remained. △: Although there is no floating peeling of the label, when the label is peeled off, the adhesive remains on the surface of the container or the substrate sheet is broken. X: Although there is no problem with re-peelability, the floating peeling of the label is significant. X X : Floating peeling of the label occurs remarkably, and once the label is peeled off, the adhesive remains on the surface of the container, or the substrate sheet is broken. (Evaluation of peeling resistance and removability of curved surface 2) After printing on an adhesive sheet by offset printing, a 20 μm polypropylene film was laminated on the surface thereof through an adhesive layer to prepare a width of 5 mm and a length of 5 μm. The label. Next, it was adhered to the surface of polymethyl methacrylate having a radius of curvature of 25 mm at a temperature of 23. (:, placed in an environment with a relative humidity of 50% for 3 months, -46· 200846439 By visual inspection to determine the floating peeling state and re-peelability of the label. ◎: No label floating peeling, and no problem with re-peelability State: 虽然: Although only a few of the labels of the degree of practical problems are observed to float, the removability is no problem. 〇~△: Although only a very small number of labels are observed floating and a very small amount of adhesive remains in Adhesives are floating without any practical problems, and the adhesive remains. △: Although there is no floating peeling of the label, once the label is peeled off, the adhesive remains on the surface of the container, or the substrate sheet is broken. X: Although There is no problem with the removability, but the floating peeling of the label remarkably occurs. XX: The floating peeling of the label remarkably occurs, and once the label is peeled off, the adhesive remains on the surface of the container, or the substrate sheet is broken. (Evaluation of expansion) # For the stencil printing on the adhesive sheet, the Yupo SGS80 is used for the adhesive sheets (1) and (HI)~(H3) of the substrate sheet, on the surface, through the 1 5 μπι Adhesive layer and 20 μπι polypropylene film, using the polystyrene film substrate adhesive sheet (2) ~ (3), on the surface, through the 20μπι adhesive layer and 25μπι polystyrene The film is made into a label having a width of 70 mm and a length of 70 mm. Then, it is adhered to the surface of the HIPS plate, and placed in an environment of a temperature of 60 ° C and a relative humidity of 90% for one day 'by visual inspection to determine the expansion state of the label. 47- 200846439 〇: The state that was not observed for expansion. 〇~△: When watching, it was observed that it did not affect the slight expansion of the appearance. △: Some slight expansion was observed. X: Significant expansion, the problematic label .
-48· 200846439 【表1】 實施例1 實施例2 實施例3 比較例1 比較例2 參考例1 • 損失正切 70°C 0.51 0.51 0.51 0.11 0.62 0.41 50°C 0.46 0.46 0.46 0.15 0.61 0.42 100°C 0.54 0.54 0.54 0.06 0.7 0.37 120°C 0.56 0.56 0.56 0.05 0.79 0.35 訪態黏彈性光譜 揖失正切之波峰（上方凸） 溫度rc) •35 -35 -35 -27 •12 -35 損失正切之波峰（上方凸） 1.14 1.14 1.14 1.37 1.43 U3 損失正切之波峰（下方凸） fig(°C) 26 26 26 無 無 無 黏著劑之構造 黏著劑型式 乳液型 乳液型 乳液型 溶劑型 溶劑型 乳液型 酸單體 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 甲基丙烯酸 甲基丙讎 甲基丙烯酸 甲基丙烯酸 基材片 YUPO SGS80 白色聚苯乙烯 lOO^m 白色聚苯乙烯 65 μ m YUPO SGS80 YUPO SGS80 YUPO SGS80 黏著力 初期黏著力Fa 6.5 6.6 6.8 4.9 10.1 5.6 Fb/Fa 0.64 0.61 0.58 0.08 0.45 0.57 評估結果 耐剝離性 Ra ： 0.1 μ m 〇 〇 〇 〇 〇 〇 Ra * 7.0 μ m 〇 〇 〇 X 〇 〇 再剝離性 Ra ： 0.1 /zm 〇 〇 〇 〇 X 〇 Ra · 7.0//m 〇 〇 〇 〇 X 〇 再循環再使用性 Ra : 0.1 jtzm 〇 〇 〇 〇 XX 〇 Ra ： 7.0 μ m 〇 〇 〇 〇 XX 〇 在彎曲面之耐剝離性1 ◎ 〇 ◎ X ◎ ◎ 在彎曲面之耐剝離性2 ◎ ◎ ◎ X ◎ ◎ 膨脹 〇 〇 〇 X 〇 Δ -49 - 200846439 【表2】 實施例4 實施例5 實施例6 實施例7 實線例8 動態黏彈 70°C 0.57 0.55 0.44 0.52 0.48 50°C 0.52 0.51 0.42 0.47 0.46 損失正切 100°C 0.69 0.59 0.46 0.57 0.50 120°C 0.73 0.62 0.47 0.60 0.53 性光譜 損失正切之波峰（上方凸）溫度rc) -35 -35 -35 -36 -34 損失正切之波峰（上方凸） 1.14 1.14 1.14 1.2 1.1 損失正切之波峰（下方凸）溫度（°c) 26 26 26 27 27 黏著劑之構造 黏著劑型式 乳液型 乳液型 乳液型 乳液型 乳液型 酸單體 丙烯酸 丙烯酸 丙烯酸 丙烯酸 甲基丙烯酸 甲基丙烯酸 甲基丙烯酸 甲基丙烯酸 基材片 YUPO SGS80 YUPO SGS80 YUPO SGS80 YUPO SGS80 YUPO SGS80 黏著力 初期黏著力Fa 6.1 6.2 6.5 6.8 6.1 Fb/Fa 0.70 0.68 0.60 0.65 0.58 |評估結果 耐剝離性 Ra * 0.1 μτη 〇 〇 〇 〇 〇 Ra · 7.0 /z m 〇 〇 〇 〇 〇 再剝離性 Ra : 0.1 //m 〇〜△ 〇 〇 〇 〇 Ra : 7.0 从 m 〇 〇 〇 〇 〇 再循環再使用性 Ra · 0.1 /zm 〇〜△ 〇 〇 〇 〇 Ra ： 7.0 μ m 〇 〇 〇 〇 〇 在彎曲面之耐剝離性1 ◎ ◎ ◎ 〇 ◎ 在彎曲面之耐剝離性2 ◎ ◎ ◎ 〇 ◎ 膨脹 〇 〇 〇 〇 〇〜△ -50- 200846439 【表3】-48· 200846439 [Table 1] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Reference Example 1 • Loss tangent 70 ° C 0.51 0.51 0.51 0.11 0.62 0.41 50 ° C 0.46 0.46 0.46 0.15 0.61 0.42 100 ° C 0.54 0.54 0.54 0.06 0.7 0.37 120°C 0.56 0.56 0.56 0.05 0.79 0.35 Interview viscoelastic spectrum loss tangent peak (upper convex) Temperature rc) •35 -35 -35 -27 •12 -35 Loss tangent peak (above Convex) 1.14 1.14 1.14 1.37 1.43 U3 Loss tangent peak (under convex) fig(°C) 26 26 26 No adhesive-free construction adhesive type emulsion type emulsion type solvent-based solvent type emulsion type acid monomer acrylic Acrylic Acrylic Acrylic Acrylic Acrylic Methyl Acrylate Methyl Acrylate Methyl Acrylate Methyl Acrylate Substrate YUPO SGS80 White Polystyrene lOO^m White Polystyrene 65 μm YUPO SGS80 YUPO SGS80 YUPO SGS80 Adhesive Initial Adhesion Fa 6.5 6.6 6.8 4.9 10.1 5.6 Fb/Fa 0.64 0.61 0.58 0.08 0.45 0.57 Evaluation result Peel resistance Ra : 0.1 μ m 〇〇〇〇〇〇Ra * 7.0 μ m 〇〇〇X 〇〇Re-peelability Ra : 0.1 /zm 〇〇〇〇X 〇Ra · 7.0//m 〇〇〇〇X 〇Recycling reusability Ra : 0.1 jtzm 〇〇〇〇XX 〇Ra : 7.0 μ m 〇〇〇〇 XX 耐 Resistant peeling resistance on curved surface 1 ◎ 〇 ◎ X ◎ ◎ Peel resistance on curved surface 2 ◎ ◎ ◎ X ◎ ◎ Expansion 〇〇〇 X 〇 Δ -49 - 200846439 [ Table 2] Example 4 Example 5 Example 6 Example 7 Example of solid line 8 Dynamic viscoelasticity 70 ° C 0.57 0.55 0.44 0.52 0.48 50 ° C 0.52 0.51 0.42 0.47 0.46 Loss tangent 100 ° C 0.69 0.59 0.46 0.57 0.50 120 ° C 0.73 0.62 0.47 0.60 0.53 Sex spectral loss tangent peak (upper convex) temperature rc) -35 -35 -35 -36 -34 Loss tangent peak (upper convex) 1.14 1.14 1.14 1.2 1.1 Loss tangent peak (lower convex) Temperature (°c) 26 26 26 27 27 Adhesive construction adhesive type emulsion type emulsion type emulsion type emulsion type acid monomer acrylic acid acrylic acid acrylic acid methacrylic acid methacrylic acid methacrylic acid methacrylic acid Material YUPO SGS80 YUPO SGS80 YUPO SGS80 YUPO SGS80 YUPO SGS80 Adhesive initial adhesion Fa 6.1 6.2 6.5 6.8 6.1 Fb/Fa 0.70 0.68 0.60 0.65 0.58 | Evaluation results Removability Ra * 0.1 μτη 〇〇〇〇〇Ra · 7.0 / Zm 〇〇〇〇〇 Re-peelability Ra : 0.1 //m 〇~△ 〇〇〇〇Ra : 7.0 Recycling from m 〇〇〇〇〇 Reusability Ra · 0.1 /zm 〇~△ 〇〇〇〇Ra : 7.0 μ m 耐 耐 〇〇〇〇〇 弯曲 弯曲 弯曲 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇〇〇〇 〇〇〇〇〇 △ △ ~ △ -50- 200846439 [Table 3 】
實施例9 實施例10 實施例11 動態黏彈 70°C 0.51 0.51 0.51 50°C 0.46 0.46 0.46 損失正切 100°C 0.54 0.54 0.54 120°C 0.56 0.56 0.56 性光譜 損失正切之波峰（上方凸）溫度（°c) -35 -35 -35 損失正切之波峰（上方凸） 1.14 1.14 1.14 損失正切之波峰（下方凸）溫度（°c) 26 26 26 黏著劑之構造 黏著劑型式 乳液型 乳液型 乳液型 酸單體 丙烯酸 丙烯酸 丙烯酸 甲基丙烯酸 甲基丙烯酸 甲基丙烯酸 基材片 白色ABS 80/zm 白色ABS 120 μ m 白色聚碳酸酯 100 μ m 黏著力 初期黏著力Fa 7.5 8.5 7.0 Fb/Fa 0.52 0.5 0.54 評估結果 耐剝離性 Ra ： 0.1 μ m 〇 〇 〇 Ra : 7.0/zm 〇 〇 〇 再剝離性 Ra ： 0.1 〇 〇 〇 Ra ： 7.0μπι 〇 〇 〇 再循環再使用性 Ra ： 0.1 /zm 〇 〇 〇 Ra ： 7.0//m 〇 〇 〇 在彎曲面之耐剝離性1 ◎ 〇 〇 在彎曲面之耐剝離性2 ◎ 〇 〇 -51- 200846439 由表1〜3可明確得知，根據本發明所得的再剝離用黏 著片，不僅是對於黏附物之平滑面，即使對於具有凹凸之 粗糙面，也具有優越之黏接性的同時，一旦結束黏著片之 黏貼時，黏著片之浮動剝離等將不會長期發生，另外，於 剝離黏著片之際，也不會因黏著劑而污染黏附物。 再者，實施例1〜8之黏著片，確認了即使黏貼於氣體 釋出容易發生之黏附物，也能夠抑制氣泡積存之發生。 [產業上利用之可能性] 若根據本發明之再剝離用黏著片，適合於下列用途： 以進行商品或服務之廣告宣傳爲目的，在化妝品、化妝用 品、飮料及食品等之包裝容器、自動販賣機及自動剪票機 等公共場所所設置之設備、或是電車及汽車等公共場所所 利用之車輛的黏貼，或是商品之品名表示，或者用以表示 爲了使用者或修理員等之操作說明書或零件替換程序之文 字及圖案等各種影像資訊，黏貼在複印機、印表機、傳真 • 機、個人電腦、電視、空氣調節器、冰箱及洗衣機等之各 種電器製品；大多採行再使用之碳粉匣、或墨水匣等各種 關聯性製品；或構成汽車、機車及建築材料等之各種內外 裝飾零件等，於一定之期間黏貼後而予以剝離。 尤其，本發明之黏著片，適合於下列用途：於進行再 循環之步驟，必須剝離黏著片，並且黏貼於具備由以表面 輪廓曲線之算術平均高度Ra ( 3 )爲〇〜1〇·〇μιη之聚苯乙 烯、聚苯醚、ΑΒ S、聚碳酸酯及此等之複合材料爲主要成 -52- 200846439 分之熱可塑性樹脂所形成的構件之電 外，本發明之黏著片，適合黏貼於表 途。黏貼於Ra( 3)爲3.0〜ΙΟ.Ομπι之 有效，尤其，黏貼於Ra ( 3 )爲5.0〜： 使用特別有效。 再者，適合黏貼於具有以丙烯酸 樹脂爲主要成分之表面層的彎曲面， 剝離之用途。尤其，適合作爲黏貼於 爲主要成分之表面層之聚丙烯、聚乙 爲主要成分之包裝容器（於化妝品或 容器）之標籤材料使用。或者，適合 系樹脂爲主要成分之塗料的金屬、或 酯或上述熱可塑性樹脂爲主要成分之 部分之曲率半徑爲200mm以內之彎由 彎曲部、電器製品之轉角部分）之用 【圖式簡單說明】 第1圖係本發明實施例1之黏著 【主要元件符號說明】 無0 益製品的該構件。另 面爲較粗糙構件之用 該構件後而使用更爲 I 0·0μιη之該構件後而 樹脂或上述熱可塑性 一定期間黏貼後必須 具有以丙烯酸系樹脂 烯，及以其複合材料 化妝用品所使用之管 黏貼於塗布以丙烯酸 是以聚甲基丙烯酸甲 塑膠所形成，其彎曲 &凸面（自動販賣機之 途。 劑的損失正切曲線。 -53-Example 9 Example 10 Example 11 Dynamic viscoelasticity 70 ° C 0.51 0.51 0.51 50 ° C 0.46 0.46 0.46 Loss tangent 100 ° C 0.54 0.54 0.54 120 ° C 0.56 0.56 0.56 Sex spectral loss tangent peak (upper convex) temperature ( °c) -35 -35 -35 Loss tangent peak (upper convex) 1.14 1.14 1.14 Loss tangent peak (lower convex) temperature (°c) 26 26 26 Adhesive construction adhesive type emulsion type emulsion type acid Monomer acrylic acid acrylic acid methacrylic acid methacrylic acid methacrylic acid substrate sheet white ABS 80/zm white ABS 120 μ m white polycarbonate 100 μ m adhesive initial adhesion Fa 7.5 8.5 7.0 Fb/Fa 0.52 0.5 0.54 evaluation As a result, the peeling resistance Ra: 0.1 μ m 〇〇〇Ra : 7.0 / zm 〇〇〇 re-peelability Ra : 0.1 〇〇〇 Ra : 7.0 μπι 〇〇〇 recycling reusability Ra : 0.1 /zm 〇〇〇Ra : 7.0 / / m 耐 resistance to peeling on the curved surface 1 ◎ 耐 resistance to peeling on the curved surface 2 ◎ 〇〇-51- 200846439 It can be clearly seen from Tables 1 to 3, according to the present invention The obtained adhesive sheet for re-peeling is not only a smooth surface for the adhesive, but also has excellent adhesiveness even for a rough surface having irregularities, and the floating peeling of the adhesive sheet once the adhesive sheet is pasted. It does not occur for a long time. In addition, when the adhesive sheet is peeled off, the adhesive is not contaminated by the adhesive. Further, in the adhesive sheets of Examples 1 to 8, it was confirmed that the occurrence of bubble accumulation can be suppressed even if the adhering substance which is likely to be released by gas release is adhered. [Possibility of Industrial Applicability] The adhesive sheet for re-peeling according to the present invention is suitable for the following purposes: for the purpose of advertising for goods or services, in packaging containers for cosmetics, cosmetics, beverages, foods, etc., automatically Equipment installed in public places such as vending machines and automatic ticket cutting machines, or stickers used in vehicles used in public places such as electric cars and automobiles, or product names, or instructions for users or repairers. Or various image information such as the text and pattern of the parts replacement program, and are attached to various electrical appliances such as copiers, printers, fax machines, personal computers, televisions, air conditioners, refrigerators, and washing machines; most of them use recycled carbon. Various related products such as white enamel or ink enamel; or various internal and external decorative parts constituting automobiles, locomotives, and building materials, etc., are peeled off after being adhered for a certain period of time. In particular, the adhesive sheet of the present invention is suitable for the following applications: in the step of recycling, the adhesive sheet must be peeled off and adhered to have an arithmetic mean height Ra (3) of a surface profile curve of 〇~1〇·〇μιη The polystyrene, the polyphenylene ether, the bismuth S, the polycarbonate and the composite materials thereof are the components of the thermoplastic resin formed mainly from -52-200846439, and the adhesive sheet of the invention is suitable for sticking to Table way. Adhesive to Ra(3) is 3.0~ΙΟ.Ομπι Effective, especially, pasted on Ra(3) is 5.0~: Use is particularly effective. Further, it is suitable for use in a curved surface having a surface layer containing an acrylic resin as a main component and peeling off. In particular, it is suitably used as a labeling material for packaging containers (in cosmetics or containers) in which polypropylene or polyethylene as a main component is adhered to the surface layer of the main component. Alternatively, a metal or an ester suitable for a coating material containing a resin as a main component or a portion having a radius of curvature of a portion having a radius of curvature of 200 mm or less as a main component of the thermoplastic resin as a main component is used for a curved portion or a corner portion of an electrical product. Fig. 1 is an adhesive of the first embodiment of the present invention. [Main component symbol description] This component of the product is not 0. On the other hand, after the member is used for a relatively rough member, the member having a more I 0·0 μm is used, and after the resin or the above-mentioned thermoplastic is adhered for a certain period of time, it is necessary to have an acrylic resin olefin and use it as a composite cosmetic. The tube is adhered to the coating with acrylic acid formed by polymethyl methacrylate plastic, and its curved & convex surface (the path of the vending machine. The loss tangent curve of the agent. -53-