201016822 六、發明說明： 【發明所屬之技術領域】 本發明係關於進行金屬板、化妝板、塑質板、玻璃板 等加工、運搬、貯藏等時，暫時性地保護其表面所使用之 表面保護薄膜、與貼著該表面保護薄膜的層合體。 【先前技術】 φ 一般作爲於金屬板、化妝板、塑質板、玻璃板等加工 、運搬、貯藏等時使用於暫時性地保護其表面之表面保護 薄膜，已知於塑質薄膜等基材上，設置以合成樹脂系黏著 劑作爲主成分，添加交聯劑而進行交聯處理所成之黏著層 者（參照專利文獻1 )。 專利文獻1 :特開昭63-225677號公報（實施例） 【發明內容】 〇 發明所要解決的課題 然而，如此表面保護薄膜雖貼附初期的黏著性良好， 但貼附後的經時黏著性會有上昇之傾向。因此使用後的表 面保護薄膜無法由被保護物容易地剝離’剝離作業繁雜’ 又依情況，於被保護物之表面上表面保護薄膜之黏著層的 一部分會殘留糊分、或表面保護薄膜會拉伸而有著斷裂等 問題。 特別爲，表面保護薄膜所貼附之被保護物，例如於熱 成型加工或塗裝後的乾燥步驟等中’於100〜i5〇°C程度之 201016822 高溫狀態，或於40〜60°C程度之中溫狀態下長期間保存時 ，經時性黏著性會顯著上昇。 又，藉由如此熱成型加工時或塗裝後的乾燥步驟中之 加熱處理（特別爲如上述之高溫狀態的情況）等，亦有著 產生浮起等剝離現象之問題。 因此，本發明係以提供對於金屬板、化妝板、塑質板 、玻璃板等被保護物表面具有優良初期黏著性，且使用於 伴隨加熱處理，特別爲高溫加熱之用途之情況，加熱處理 後的黏著力上昇亦較少，自被保護物進行剝離時對被保護 物表面的糊分難以殘留，且不會產生浮起等剝離現象的表 面保護薄膜、與貼著該表面保護薄膜的層合體爲目的。 解決課題之手段 本發明的表面保護薄膜爲於基材一面上具有黏著層之 表面保護薄膜，其特徵爲前述黏著層於150 °C中之貯藏彈 性率與於2(TC中之貯藏彈性率的差滿足（1)式，且ίαηδ 極大溫度爲-5 °C以下者。 〔數 1〕 G’（150) -G，（20) ^ 0 ... ( 1 ) 〔式中，G，（150)表示，於150°C中之貯藏彈性率，G’（ 20)表示於20°C中之貯藏彈性率。又，tan5爲將損失彈性 率除以貯藏彈性率的値〕。 又，較佳的前述黏著層之特徵爲，於l〇〇°C〜15〇°C中 201016822 之tanS爲〇· 1以下者。 又，較佳的本發明之表面保護薄膜之特徵爲，將前述 表面保護薄膜之具有黏著層的面、與不銹鋼板（JIS G43 05所規定之SUS 3 04鋼板）進行貼合，於150°C之環境 中’放置30分鐘後，表面保護薄膜之對於不銹鋼板的黏 著力（JIS Z0237 : 2000中之 180度剝開黏著力）爲 0.1N/50mm 〜lN/50mm 者。 φ 且’對於黏彈性體之正弦波狀變形的應力之應答以複 數表示時，定義爲如（2)式，G，表示貯藏彈性率，G’’表 示損失彈性率，表示複彈性率。 〔式中，G’表示G之彈性成分，G’’表示G之黏性成分〕 〇 〇 又，本發明所謂之貯藏彈性率爲，與於黏彈性體賦予 變形時之能量貯藏分有關，損失彈性率與該能量的熱等所 引起的損失分有關。所謂複彈性率爲，表示黏彈性體中之 應力與變形的關係之物性値。此可由測定動態黏彈性時求 得。且，此所謂動態黏彈性爲，賦予具有正弦變化之規則 性振動時所表現的黏彈性行爲。 又’所謂tan5爲，損失彈性率對於貯藏彈性率之比 ，以損失彈性率/貯藏彈性率所表示之値。又，所謂tan3 極大溫度爲tanS爲極大値時的溫度（°C )。 201016822 本發明的層合體的特徵爲，上述表面保護薄膜的具有 黏著層之面貼著於硬塗佈層上者。又，前述硬塗佈層的特 徵爲，對於水之接觸角爲110度以下，對於山茶油之接觸 角爲50度以下者。又，前述硬塗佈層的特徵爲，對於水 之接觸角爲50度以上，濕潤張力爲27〜45mN/m者。 發明效果 本發明爲，提供於基材的一面上具有顯示特定物性的 黏著層之表面保護薄膜，故，對於金屬板、化妝板、塑質 板、玻璃板等被保護物表面具有優良的初期黏著性，且使 用伴隨加熱處理，特別爲高溫加熱之用途時，加熱處理後 黏著力上昇亦較少，自被保護物進行剝離時對於被保護物 之表面難以產生糊分殘留，且不會產生浮起等剝離現象的 表面保護薄膜。特別爲可提供貼著於硬塗佈層，進一步貼 著於具有特定表面物性之硬塗佈層時，亦顯示優良初期黏 著性，於加熱處理後於硬塗佈層亦難產生糊分殘留之表面 保護薄膜。 〔實施發明之形態〕 以下對於各構成要素之實施形態作說明。 作爲本發明所使用的基材’特別不論透明·不透明， 可配合用途作適宜選擇，但作爲材質’僅爲透明者即可， 可舉出聚對苯二甲酸乙二酯、聚丁烯對苯二甲酸酯、聚萘 二甲酸乙二酯、聚碳酸酯、聚乙烯、聚丙烯、聚苯乙烯、 -8 - 201016822 三乙醯基纖維素、丙烯酸、聚氯化乙烯、原菠烯基化合物 等塑質薄膜。作爲不透明者，可舉出紙、合成紙等不透明 基材、於上述塑質薄膜内部含有顔料等使其不透明化者、 於上述塑質薄膜設有具隱蔽性著色層者。 基材之厚度依用途而相異，故無法一槪定論，但由考 慮到處理之容易性等，作爲下限以2 μιη以上爲佳，較佳爲 ΙΟμπι以上’作爲上限以300μηι以下爲佳，較佳爲125μιη φ 以下程度爲一般。 如此基材因提高與後述黏著層之接著性，故施予電漿 處理、電暈放電處理、遠紫外線照射處理、噴砂加工處理 等易接著處理、或設置底漆易接著處理層者亦佳。 其次’對於黏著層作說明。黏著層爲於15 0°C中之貯 藏彈性率與於20°C中之貯藏彈性率的差滿足上述（1 )式 ，且tanS極大溫度以-5°C以下爲佳，較佳爲-l〇°C以下，更 佳爲-20°C以下。 ❹ 如此黏著層爲，可成爲於150 °C中之貯藏彈性率與於 20 °C中之貯藏彈性率的差爲滿足上述（1)式，且tan5極 大溫度爲-5 °C以下時，使用於伴隨加熱處理，特別爲高溫 加熱的用途之情況，加熱處理後之黏著性上昇較少，自被 保護物進行剝離時，對於被保護物之表面難以產生糊分殘 留，且不會產生浮起等剝離現象的表面保護薄膜。 即，黏著層爲於150°C中之貯藏彈性率與於20°C中之 貯藏彈性率的差爲滿足上述（1)式時，可防止高溫時黏 著層過度軟代而與被保護物表面過度容易融合，使用於伴 -9- 201016822 隨加熱處理，特別爲100°C〜150°c程度之高溫加熱的用途 之情況，加熱處理後的黏著力上昇亦較少，自被保護物進 行剝離時對於被保護物表面難以產生糊分殘留。 且，黏著層爲將tans極大溫度設定爲-5t以下時，因 可得到適度黏性，故初期黏著性優良，即使處於1 〇〇°C〜 150°C程度之高溫狀態，亦難以產生浮起等剝離現象。 又，黏著層於1〇〇°C〜150°C中之tan5爲0.1以下者爲 佳。於100°C〜150°C中之tanS設定爲0.1以下時，黏著層 中之彈性成分的作用比黏性成分的作用更強烈出現，不會 過度與被保護物表面融合，自被保護物進行剝離時，可使 對被保護物表面之糊分殘留更難產生。又，依被保護物的 材料或形狀而相異，其有可防止初期黏著力過高的傾向。 又，黏著層於150 °C之環境中，放置30分鐘後對於不 銹鋼板之黏著力，以0.1 N/5 Omm〜1N/5 Omm爲佳。藉由於 15(TC之環境中，放置30分鐘後對於不銹鋼板之黏著力於 0.1N/50mm以上，於熱成型加工時或塗裝後之乾燥步驟中 之加熱處理等，可使其難產生浮起等剝離現象，藉由 1N/5Omm以下，剝離性爲良好，可提高作業性、處理性。 作爲構成如此黏著層之黏著劑，使用天然樹脂系黏著 劑、合成樹脂系黏著劑等，更佳爲使用丙烯酸系黏著劑、 聚矽氧系黏著劑、胺酯系黏著劑等合成樹脂系黏著劑。其 中以具有耐候性且不易引起凝集破壞，且容易進行黏著力 控制、可調整再剝離性、再貼著性之性能，以交聯性黏著 劑爲佳，由處理容易性來看以使用交聯性丙烯酸系黏著劑 -10- 201016822 爲特佳。對於使用於黏著層之交聯劑，並無特別限定，例 如可使用異氰酸酯系交聯劑、環氧系交聯劑、亞胺系交聯 劑、及金屬螯合劑等。 黏著層之厚度並無特別限定，考慮到初期及加熱後之 黏著性、黏著力、處理性、經濟性等時，以Ιμιη〜30μιη 爲佳，較佳爲2μηι〜ΙΟμιη。 黏著層中，除可添加黏著性劑及交聯劑以外，亦可添 # 加顏料、染料、著色劑、消光劑、防帶電劑、難燃劑、防 霉劑、防銹劑、抗菌劑、紫外線吸收劑、光安定劑、熱安 定劑、抗氧化劑、可塑劑、塗平劑、流動調整劑、消泡劑 、分散劑、螢光增白劑、貯藏安定劑、矽烷偶合劑等添加 劑。但這些添加劑之添加量以不妨礙黏著層效果的範圍爲 佳。 如以上之本發明的表面保護薄膜，可添加上述黏著性 劑、交聯劑、及視必要所添加之添加劑可於溶劑中溶解或 ® 分散後調製爲黏著層用塗佈液，藉由過去公知塗佈方法， 例如藉由棒塗佈器、染料塗佈器、葉片塗佈器、轉動塗佈 器、輥塗佈器、凹版塗佈器、淋塗佈器、噴霧器、絲網印 刷等’塗佈於上述基材上，藉由加熱進行乾燥、硬化形成 黏著層而得到。又，由處理性之觀點來看，於基材上經塗 佈、乾燥後’於露出之黏著層表面設置隔離物後，可經加 熱使其硬化而製作。 又’本發明的表面保護薄膜爲，亦可由將上述黏著層 用塗佈液與上述同樣地，於隔離物上進行塗佈、乾燥，與 -11 - 201016822 基材貼合後，經加熱使其硬化而得到。 作爲本發明之表面保護薄膜的使用方法之一例子，例 如可舉出偏光板等光學構件之製造時、印刷步驟時、電子 電路基板之製造時、如陶瓷電容器之電子零件製造時之保 護薄膜等。 如以上，本發明的表面保護薄膜爲，於基材一面上具 有黏著層之表面保護薄膜，前述黏著層於15 0°C中之貯藏 彈性率與於20°C中之貯藏彈性率的差爲滿足上述（1)式 ，且tan δ極大溫度爲-5 °C以下，故對於金屬板、化妝板、 塑質板、玻璃板等被保護物表面之初期黏著性優良，且使 用於伴隨加熱處理，特別爲高溫加熱之用途時，即使於加 熱處理後其黏著力上昇較少，自被保護物進行剝離時對於 被保護物之表面難以產生糊分殘留，且難產生浮起等剝離 現象。 本發明的層合體爲，上述表面保護薄膜之具有黏著層 的面貼合於貼著對象所成者。 以下，作爲貼著對象，舉出種種領域所使用之硬塗佈 層作說明。作爲其中一例之硬塗佈層可由，調製硬化性組 成物（塗料）將此塗佈於所望被塗佈對象，經硬化後得到 〇 可使用於本例之硬化性組成物含有樹脂成分。樹脂成 分含有熱硬化型樹脂或電離放射線硬化型樹脂之一方或雙 方。熱硬化型樹脂及電離放射線硬化型樹脂，例如由聚酯 系樹脂、丙烯酸系樹脂、丙烯酸胺酯系樹脂、聚酯丙烯酸 -12- 201016822 酯系樹脂、聚胺酯丙烯酸酯系樹脂、環氧丙烯酸酯系樹脂 、胺酯樹脂、環氧系樹脂、聚碳酸酯系樹脂、三聚氰胺系 樹脂、酚系樹脂、聚矽氧系樹脂、氟系樹脂等所構成。 特別由經硬化後之被膜硬度（硬塗佈性）優良的觀點 來看’樹脂成分至少含有電離放射線硬化型樹脂者爲佳。 作爲電離放射線硬化型樹脂，可使用藉由電離放射線（紫 外線或電子線）之照射進行交聯硬化的光聚合性預聚合物 Φ 。本例中，可單獨使用後述光聚合性預聚合物、或亦可組 合2種以上使用。 光聚合性預聚合物中有陽離子聚合型與自由基聚合型 。作爲陽離子聚合型光聚合性預聚合物，可舉出環氧系樹 脂或乙烯醚系樹脂等。作爲環氧系樹脂，例如可舉出雙酚 系環氧樹脂、酚醛清漆型環氧樹脂、脂環式環氧樹脂、脂 肪族環氧樹脂等。作爲自由基聚合型光聚合性預聚合物， 1分子中具有2個以上之丙烯醯基，藉由進行交聯硬化成 ® 爲3次元網目結構之丙烯酸系預聚合物（硬質預聚合物） 由硬塗佈性觀點來看特佳而使用。 作爲丙烯酸系預聚合物，可舉出胺酯丙烯酸酯、聚酯 丙烯酸酯、環氧丙烯酸酯、三聚氰胺丙烯酸酯、聚氟烷基 丙烯酸酯、聚矽氧丙烯酸酯等。胺酯丙烯酸酯系預聚合物 ，例如可由將藉由聚醚多元醇或聚酯多元醇與聚異氰酸酯 的反應所得之聚胺酯寡聚物以與（甲基）丙烯酸之反應進 行酯化而得。作爲聚酯丙烯酸酯系預聚合物，例如可由將 於藉由多元羧酸與多元醇之縮合所得之兩末端上具有羥基 -13- 201016822 的聚酯寡聚物之羥基以（甲基）丙烯酸進行酯化、或亦可 將於多元羧酸加成環氧化物所得之寡聚物末端的羥基以（ 甲基）丙烯酸進行酯化而得。環氧丙烯酸酯系預聚合物， 例如可由比較低分子量之雙酚型環氧樹脂或酚醛清漆環氧 樹脂之環氧乙烷環、與（甲基）丙烯酸之反應進行酯化而 得。 丙烯酸系預聚合物可配合被塗佈構件之種類或用途等 而適宜選擇。又，丙烯酸系預聚合物亦可單獨使用，但欲 @ 提高交聯硬化性、或硬化收縮之調整等賦予種種性能，加 入光聚合性單體爲佳。 作爲光聚合性單體，可舉出單官能丙烯酸單體（例如 2-乙基己基丙烯酸酯、2-羥基乙基丙烯酸酯、2-羥基丙基 丙烯酸酯、丁氧基乙基丙烯酸酯等）、2官能丙烯酸單體 (例如1,6·己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、二 乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、羥基三甲基乙 酸酯新戊二醇二丙烯酸酯等）、3官能以上之丙烯酸單體 @ (例如二季戊四醇六丙烯酸酯、三甲基丙烷三丙烯酸酯、 季戊四醇三丙烯酸酯等）。且，「丙烯酸酯」中如文字所 述除丙烯酸酯以外，亦含有甲基丙烯酸酯。這些光聚合性 單體可單獨使用、或組合2種以上使用。 硬化性組成物中之光聚合性預聚合物及光聚合性單體 之合計含有量（固體成分換算）對於全樹脂成分而言，以 40〜99重量％爲佳，較佳爲60〜95重量％，更佳爲80〜 9 0重量％。 -14 - 201016822 形成上述硬塗佈層時，藉由紫外線照射使其硬化而使 用時’於硬化性組成物中，添加光聚合啓始劑、光聚合促 進劑、紫外線增感劑等添加劑爲佳。這些添加劑之添加量 對於上述光聚合性預聚合物及光聚合性單體之合計100重 量份而言’一般選自0.2〜10重量份之範圍。 且’作爲樹脂成分，取代電離放射線硬化型樹脂、或 與此同時將熱硬化型樹脂含於樹脂成分亦可。於樹脂成分 ® 含有熱硬化型樹脂時’可單獨或倂用熱聚合性單體或預聚 合物’視所需可含有熱聚合啓始劑，即藉由加熱產生活性 自由基種的化合物等。 又’作爲樹脂成分，上述熱硬化型樹脂或電離放射線 硬化型樹脂以外，僅不阻礙本發明之效果的範圍即可，亦 可含有熱可塑性樹脂等其他樹脂。 又’硬化性組成物中，僅不阻礙本發明之效果的範圍 即可’視必要可適宜添加添加成分。作爲添加成分，例如 ® 可舉出無機微粒子、樹脂微粒子、表面調整劑、滑劑、著 色劑、顏料、染料、螢光增白劑、難燃劑、抗菌劑、防霉 劑、紫外線吸收劑、光安定劑、熱安定劑、抗氧化劑、可 塑劑、塗平劑、流動調整劑、消泡劑、分散劑、貯藏安定 劑、交聯劑等。特別爲藉由添加所望尺寸的無機微粒子或 樹脂微粒子，可形成所望形狀之消光硬塗佈層。如此硬塗 佈層藉由例如殘留單體成分或上述種種添加成分之影響， 貼著表面保護薄膜施予加熱處理（例如，150。(：，90分鐘 )等時’比貼著於其他被保護物時，有著更容易殘留糊分 -15- 201016822 的傾向。 特別對於消光硬塗佈層，對消光硬塗佈層之凹凸，黏 著層之密著性較高時，消光硬塗佈層與接觸之黏著層之表 面積因變大，施予加熱處理等時，比透明硬塗佈（Clear Hard Coat)層有著更容易殘留糊分的傾向。又，對消光硬 塗佈層之凹凸，黏著層之密著性較低時，消光硬塗佈層與 接觸之黏著層的表面積因變小，比透明硬塗佈層具有更容 易產生浮起之傾向。然而，本發明的表面保護薄膜爲，因 _ 黏著層具有特定物性，即使爲貼著於消光硬塗佈層者，加 熱處理後亦難以殘留糊分，亦不容易產生浮起。 又，本發明的表面保護薄膜，即使作爲貼著對象之一 例的硬塗佈層表面特性爲特定者，可使其成爲加熱處理後 不容易產生糊分殘留者。具體而言作爲硬塗佈層，對於水 之接觸角調整爲比特定値小，對於山茶油之接觸角調整爲 比特定値小。 例如，於硬塗佈層表面附著指紋時，欲使該附著之指 φ 紋不容易醒目（指紋辨識困難度之提高），並非於被膜表 面加強賦予撥水性與撥油性，適度地賦予親水性與親油性 爲有效。而欲使對水之接觸角與對山茶油之接觸角調整爲 比各特定値小，藉由調整硬塗佈層之表面特性，可表現適 度親水性與親油性。於硬塗佈層的表面表現適度親水性與 親油性時，對被膜表面之指紋成分（由水性成分與油性成 分所成）的接觸面積不會變的過小，可將指紋成分於被膜 表面適度地濕潤而擴大。其結果，即使於硬塗佈層表面附 -16- 201016822 著指紋之情況，可使該附著之指紋不會過於醒目（指紋辨 識困難度的提高）。 又，除上述調整以外，將對水之接觸角調整至所定角 以上之同時，藉由將濕潤張力調整至所定範圍，除具備指 紋辨識困難度提高與硬塗佈性之降低防止作用以外，指紋 附著後之該指紋的拭擦性變的良好，且拭擦後的指紋成分 亦不會過於醒目。 本例中，硬塗佈層對水之接觸角調整爲110°以下者爲 佳。較佳爲調整至100°以下。對水之接觸角調整至110° 以下時，與水之接觸面積不會過小，可使附著之指紋不會 過於醒目（指紋辨識困難度提高）。 本例中，硬塗佈層對山茶油之接觸角調整爲50°以下 者爲佳。較佳爲調整至40。以下。對山茶油之接觸角調整 至50°以下時，指紋中之油性成分會濕潤擴大。因此，附 著之指紋不會過於醒目（指紋辨識困難度提高），且拭擦 6 後的指紋成分亦不會過於醒目。 本例中，硬塗佈層對水之接觸角調整爲50°以上者爲 佳。較佳爲調整至60°以上，更佳爲70°以上，特佳爲80° 以上。藉由調整對水之接觸角至5 0。以上，與水之接觸面 積不會變的過大。其結果，指紋中之水性成分容易分離， 可提高指紋之擦拭性。即，本例中，將硬塗佈層對水之接 觸角調整至所定範圔時，除指紋辨識困難度提高以外，指 紋之擦拭性亦提高。 且，對水之接觸角及對山茶油之接觸角的値皆爲依據 -17- 201016822 JIS-R3257 ( 1 999 )之方法所測定之値。 本例中，將硬塗佈層之濕潤張力調整至27mN/m以上 時爲佳。較佳爲30mN/m以上。又，將硬塗佈層之濕潤張 力調整至45mN/m以下時爲佳。較佳爲40mN/m以下，更 佳爲38mN/m以下。將硬塗佈層之濕潤張力調整至所定範 圍時，可提高指紋之擦拭性。 且，濕潤張力値爲依據JIS-K6 768 ( 1999)之方法所 測定的値。 n 具有如此表面物性的硬塗佈層係可由，於上述硬塗佈 層之硬化性組成物，添加藉由Griffin’s法之HLB値爲指 定範圍的化合物（非離子系化合物）作爲添加成分而得到 。作爲如此化合物，可舉出藉由Griffin’s法之HLB値爲 例如2以上，較佳爲5以上，更佳爲10以上，例如1 8以 下，較佳爲15以下之非離子系化合物等。藉由添加H LB 値被調整至適切的非離子系化合物時，硬塗佈層對水之接 觸角、對山茶油之接觸角及濕潤張力可容易被調整至上述 ® 所定範圍。 非離子系化合物爲溶解於水而不顯示離子性之化合物 的總稱，但係由疏水基（親油基）與親水基之組合經結合 所構成。 作爲如此化合物，爲至少具有一種以上的親水基（例 如聚環氧化物、羥基、羧基、磺醯基、燐酸鹽、胺基、異 氰酸酯基、環氧丙基、烷氧基甲矽烷基、銨鹽、各種金屬 鹽等）之化合物，例如可舉出乙氧基化甘油三丙烯酸酯、 18 - 201016822 乙氧基化雙酚A二丙烯酸酯、聚乙二醇二丙烯酸酯、聚醚 變性丙烯酸酯及聚羥基變性丙烯酸酯等。其中亦由對溶劑 之溶解性或處理性之觀點來看，使用聚乙二醇二丙烯酸酯 爲佳。 又，作爲非離子系化合物，可使用脂肪酸酯或聚醚等 〇 作爲脂肪酸酯，可舉出藉由1元醇或2價以上之多元 春 醇與脂肪酸經縮合的脂肪酸酯，例如可舉出丙二醇單硬脂 酸酯、丙二醇單月桂酸酯、二乙二醇單硬脂酸酯、二乙二 醇單月桂酸酯、甘油單硬脂酸酯、山梨糖醇酐倍半油酸酯 、山梨糖醇酐單油酸酯、山梨糖醇酐單硬脂酸酯、山梨糖 醇酐單棕櫚酸酯、山梨糖醇酐單月桂酸酯等。又，作爲脂 肪酸酯，亦可舉出聚氧化烯加成脂肪酸酯。 且，亦可添加於脂肪酸酯使氧化伸烷基進行加成聚合 的非離子系化合物。作爲經加成聚合之氧化烯，以氧化乙 Φ 烯或氧化丙烯爲佳。氧化乙烯或氧化丙烯各可單獨下進行 加成聚合、或亦可進行共聚合加成者。 作爲聚氧化烯加成脂肪酸酯，例如可舉出聚環氧乙烷 硬化蓖麻油、單硬脂酸聚環氧乙烷甘油、聚環氧乙烷（4 )山梨糖醇酐單硬脂酸酯、聚環氧乙烷（20)山梨糖醇酐 單硬脂酸酯、聚環氧乙烷（4)山梨糖醇酐三硬脂酸酯、 聚環氧乙烷（5)山梨糖醇酐單油酸酯、聚環氧乙烷（5) 山梨糖醇酐單油酸酯、聚環氧乙烷（20)山梨糖醇酐三油 酸酯、聚環氧乙烷（4)山梨糖醇酐單月桂酸酯、聚氧乙 -19- 201016822 二醇400單油酸酯、聚氧乙二醇400單硬脂酸酯、聚乙二 醇400單月桂酸酯、聚環氧乙烷（4)山梨糖醇酐單月桂 酸酯等。 且，本例中，作爲脂肪酸酯或聚醚以外之化合物，亦 可使用聚環氧乙烷膽巢基醚或聚環氧乙烷癸基十四烷基醚 等。 藉由Griffin’s法之HLB値爲所定範圍的化合物之含 有量，對於樹脂成分100重量份而言，較佳爲0.05重量 _ 份以上，更佳爲0.1重量份以上，特佳爲1重量份以上， 較佳爲60重量份以下，更佳爲15重量份以下，特佳爲10 重量份以下。將該化合物之含有量下限設定爲0」重量份 時，硬塗佈層對水之接觸角、對山茶油之接觸角及濕潤張 力可容易被調整至上述所定範圍。又，將該化合物之含有 量上限調整至60重量份時，可防止硬塗佈層表面之硬度 (硬塗佈性）的降低。藉由添加適量，可期待進一步提高 硬塗佈層之指紋擦拭性。 @ 硬塗佈層爲進一步將鉛筆硬度測定値調整至Η以上時 爲佳。更佳爲2Η以上。藉由調整鉛筆硬度測定値至所定 値以上時，指紋辨識困難度可提高或不會降低指紋擦拭性 下，可有效地防止硬塗佈層表面之刮傷。且，鉛筆硬度測 定値爲依據JIS-Κ5 6 00-5-4 ( 1 999 )的方法所測定之値。 硬塗佈層爲，進一步折射率値被調整至1.45〜1.65時 爲佳。較佳爲1.46〜1.52。藉由調整折射率値至所定範圍 時，可使硬塗佈層之折射率與指紋成分之折射率的差變小 -20- 201016822 。其結果，於硬塗佈層附著指紋時，該附著之指紋可進一 步不容易醒目（指紋辨識困難度進一步提高），且擦拭後 之指紋成分亦不容易醒目。 硬塗佈層之厚度以0.1 μιη以上30μιη以下程度者爲佳 。藉由將硬塗佈層之厚度爲Ο.ίμιη以上時，可使其成爲具 有充分硬度之被膜。另一方面，即使硬塗佈層之厚度超過 3 Ομηι，並非使被膜硬度進一步提高。又，硬塗佈層之厚度 φ 變厚時，藉由被膜收縮有著容易產生彎曲之傾向。因此， 由經濟性或彎曲防止性的觀點來看，以30μπι以下之厚度 者爲佳。且，本例中，可成爲硬塗佈層之厚度爲ΙΟμιη以 下，進一步爲5μιη以下程度之薄膜。即使作爲薄膜，其必 要之充分性能亦可確保。 且，欲得到上述表面特性，亦可於硬塗佈層表面上施 予電漿處理、電暈放電處理、遠紫外線照射處理等表面處 理。 Φ 具有如此表面物性之硬塗佈層，比上述硬塗佈層更容 易受到添加成分、或表面處理等影響，故施予加熱處理等 後與上述硬塗佈層相比，具有容易殘留糊分的傾向。然而 ，本發明之表面保護薄膜因黏著層具有特定物性，即使爲 貼著於具有如此特定之表面物性的硬塗佈層者，加熱處理 後亦可不容易殘留糊分。 硬化性組成物一般以塗料形態下實現。作爲有機溶劑 系塗料時，可依據樹脂成分種類而作適宜選擇即可，將上 述樹脂成分（視必要之進一步添加成分）以有機溶劑等稀 -21 - 201016822 釋溶劑進行溶解或分散後，視必要加入添加劑後，可製造 出硬化性組成物。 作爲被塗佈對象，其爲作爲期待賦予硬塗佈性（耐擦 傷性）與ί曰紋辨識困難度提局效果之基材。可使用於本例 中的基材型態並無特別限定，亦可爲薄膜狀、薄片狀或板 狀等具有任意厚度者。又’基材之表面，例如可爲凸凹形 狀、或亦可爲具有三次元曲面之立體形狀。 對於基材的材質亦無特別限制，雖可爲玻璃板等硬質 基材，但本例中，具有可撓性之樹脂基材爲佳。構成樹脂 基材之樹脂種類並無特別限定。例如作爲以薄膜狀或薄片 狀形成樹脂基材時的樹脂，例如可舉出丙嫌酸、聚碳酸酯 、聚氯化乙烯、聚酯、聚丙烯、聚乙烯、乙醯基纖維素、 環烯烴等。其一方面’例如作爲以板狀形成樹脂基材時的 樹脂，例如可舉出丙烯酸'聚碳酸酯、聚氯化乙烯等。 且，以提高硬化性組成物之硬化物所構成之硬塗佈層 的接著性爲目的下，，可於基材表面施予易接著處理。作 爲易接著處理，例如可舉出電漿處理、電暈放電處理、遠 紫外線照射處理、下引易接著層之形成等。 對於被塗佈對象之硬化性組成物的塗佈（塗佈），可 依據常法進行，例如可舉出棒塗佈、染色塗佈、葉片塗佈 、轉動塗佈、輥塗佈、凹版塗佈、淋塗佈、含浸塗佈、噴 霧塗佈、絲網印刷、刷毛塗佈等。塗佈後之塗膜厚度爲， 後述乾燥、硬化後，較佳成爲Ο.ίμιη以上30μπι以下程度 。將硬化性組成物塗佈於被塗佈對象後，將塗佈後塗膜以 -22- 201016822 50〜120°C程度進行乾燥爲佳。 硬化性組成物之硬化對於塗佈後之塗膜而言，可藉由 經熱的熟成及/或照射電離放射線（光）而進行。 經由熱之情況，作爲該熱源，例如可使用電熱器、紅 外線燈、熱風等。藉由電離放射線（光）進行時，作爲該 光線源，僅爲塗佈於基材的硬化性組成物可於短時間硬化 者即可’並無特別限定。例如作爲紅外線之光線源，可舉 φ 出燈、電阻加熱板、雷射等。作爲可見光線之光線源，可 舉出日光、燈、螢光燈、雷射等。作爲紫外線（電離放射 線）之光線源，可舉出超高壓水銀燈、高壓水銀燈、低壓 水銀燈、碳極電弧、金屬鹵素燈等。由如此紫外線的光線 源所發的 l〇〇nm〜400nm，較佳爲 200nm〜400nm之波長 區域的紫外線進行照射。作爲電子線（電離放射線）之光 線源，可舉出掃描型或簾幕型之電子線加速器等。由如此 電子線加速器所發之lOOnm以下的波長區域的電子線進行 ⑩照射。 電離放射線之照射量，依電離放射線的種類而相異， 例如以紫外線之情況爲，光量以100〜500mJ/cm2程度爲 佳，電子線時以10〜lOOOkrad程度爲佳。 如以上所製造之硬塗佈層可使用於必須賦予硬塗佈性 (耐擦傷性）與指紋辨識困難度提高效果的用途，特別爲 可使用於各種顯示器（例如電漿顯示板PDP、陰極射線管 CRT、液晶顯示器LCD、電致發光顯示器ELD等）用；展 示櫃、時鐘或計測器的蓋玻璃用；銀行的ATM或車票的 -23- 201016822 販賣機等作爲代表之觸控面板方式的電子機器接觸面用； 等硬塗佈爲佳。 且，電子機器當然含有具有上述各種顯示器之行動電 話（例如，附含 PDA (Personal Digital Assistants)功能 之個人用行動情報終端機）或個人電腦等情報處理裝置。 【實施方式】 〔實施例〕 以下，藉由實施例對本發明作進一步說明。且「份」 、「％」若無特別標示時，其以重量爲基準。 〔實施例1〜3及比較例1〜4〕 作爲基材，於厚度25μιη之聚對苯二甲酸乙二酯薄膜 (lumirrorS28 : Toray公司）的一面上，將表 1處方之 黏著層用塗佈液（實施例1〜3、比較例1〜4 )藉由棒塗 佈器法進行各塗佈，經90°C的1.5分鐘乾燥後，形成乾燥 膜厚2.5 μιη之黏著層，因處理性良好，故與隔離物（MRF :三菱化學聚酯薄膜公司）貼合。其次於60。(：之環境下進 行4 8小時熟成，製作出實施例丨〜3及比較例1〜4之表 面保護薄膜。 -24- 201016822 〔表1〕 製品名 公司名 固體成 分(％) 實施例(份） 比較1 mm 1 2 3 1 2 3 4 SKDyne 1439U 綜硏化學公司 30 22.75 Finetac CT-3020 DIC公司 30 24.78 OlibainBPS6078TF 東洋油墨公司 42 15.06 01ibainBPS5977 東洋油墨公司 28 17.86 Quickmaster SPS-1068 DIC公司 40 16.50 corponeal N-4900 曰本合成化學公司 38 20.71 SKDyne 1491H 綜硏化學公司 30 10.63 E-50C 綜硏化學公司 45 0.34 DN-980 DIC公司 75 0.74 BXX6105 東洋油墨公司 37.5 1.51 BXX 5983 東洋油墨公司 5 0.05 D-45 DIC公司 45 0.13 Tetrad C 三菱瓦斯化學公司 100 0.83 L-45 綜硏化學公司 45 0.10 乙酸乙酯 31.97 38.18 69.25 22.46 33.14 43.77 甲苯 31.90 36.10 22.18 33.04 44.36 10.63 甲基乙基酮 10.63 合計（份） 86.96 99.80 85.82 62.55 66.31 109.67 31.99 NV (%) 8.02 8.01 8.03 8.00 8.04 7.93 10.10201016822 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to surface protection for temporarily protecting a surface of a metal plate, a cosmetic board, a plastic plate, a glass plate, etc. during processing, transportation, storage, and the like. A film and a laminate attached to the surface protective film. [Prior Art] φ is generally used as a surface protection film for temporarily protecting a surface of a metal plate, a cosmetic board, a plastic plate, a glass plate, etc., for processing, transporting, storing, etc., and is known as a substrate such as a plastic film. In the above, an adhesive layer formed by a crosslinking treatment and a crosslinking agent is added as a main component, and a synthetic resin-based adhesive is used as a main component (see Patent Document 1). [Problem to be Solved by the Invention] However, the surface protective film has good adhesion at the initial stage of adhesion, but the adhesion with time after attachment is good. There will be a tendency to rise. Therefore, the surface protective film after use cannot be easily peeled off by the protected object, and the peeling operation is complicated. Depending on the case, a part of the adhesive layer of the surface protective film may remain on the surface of the protected object, or the surface protective film may be pulled. Stretching and having problems such as breakage. In particular, the protected material to which the surface protective film is attached, for example, in the hot forming process or the drying step after coating, etc., is in the high temperature state of 201016822 at a level of 100 to i5 ° C, or at a temperature of 40 to 60 ° C. When stored in a medium temperature state for a long period of time, the temporal adhesiveness increases remarkably. Further, by such heat treatment during the hot forming process or in the drying step after the coating (especially in the case of the high temperature state as described above), there is a problem that peeling phenomenon such as floating occurs. Therefore, the present invention provides an excellent initial adhesion to a surface of a protected object such as a metal plate, a cosmetic board, a plastic plate, or a glass plate, and is used in the case of heat treatment, particularly high-temperature heating, after heat treatment. The adhesion is also less, and the surface protective film which is hard to remain on the surface of the object to be protected from peeling off when the object to be protected is peeled off, and which does not cause peeling phenomenon such as floating, and the laminate attached to the surface protective film for purpose. Means for Solving the Problem A surface protective film of the present invention is a surface protective film having an adhesive layer on one side of a substrate, which is characterized by a storage elastic modulus of the adhesive layer at 150 ° C and a storage elastic modulus of 2 (TC). The difference satisfies the formula (1), and the maximum temperature of ίαηδ is -5 ° C or less. [Number 1] G'(150) -G, (20) ^ 0 . . . (1) wherein G, (150) represents the storage modulus at 150 ° C, and G' (20) represents the storage modulus at 20 °C. Further, tan5 is a enthalpy of dividing the loss elastic modulus by the storage modulus. Further, it is preferable that the adhesive layer is characterized in that tanS of 201016822 is 〇·1 or less in l〇〇°C to 15〇°C. Further, a preferred surface protection film of the present invention is characterized in that the surface of the surface protective film having an adhesive layer is bonded to a stainless steel plate (SUS 3 04 steel plate defined by JIS G43 05) at 150 ° C. In the environment, after 30 minutes of standing, the adhesion of the surface protective film to the stainless steel plate (JIS Z0237: 180 degree peeling adhesion in 2000) is 0. 1N/50mm ~ lN/50mm. When φ and 'the response to the stress of the sinusoidal deformation of the viscoelastic body is expressed by a complex number, it is defined as the formula (2), G represents the storage elastic modulus, and G'' represents the loss elastic modulus, and represents the complex elastic modulus. [wherein G' represents the elastic component of G, and G'' represents the viscous component of G.] Further, the so-called storage modulus of the present invention is related to the energy storage component when the viscoelastic body imparts deformation, and the loss The modulus of elasticity is related to the loss caused by the heat of the energy and the like. The complex elastic modulus is a physical property 表示 indicating the relationship between stress and deformation in a viscoelastic body. This can be obtained by measuring the dynamic viscoelasticity. Moreover, the so-called dynamic viscoelasticity is a viscoelastic behavior expressed when a regular vibration having a sinusoidal variation is imparted. Further, tan5 is the ratio of the loss elastic modulus to the storage elastic modulus, which is expressed by the loss elastic modulus/storage modulus. Further, the maximum temperature of tan3 is a temperature (°C) at which tanS is a maximum enthalpy. 201016822 The laminate of the present invention is characterized in that the surface of the surface protective film having the adhesive layer is applied to the hard coat layer. Further, the hard coat layer is characterized in that the contact angle with respect to water is 110 degrees or less, and the contact angle with respect to camellia oil is 50 degrees or less. Further, the hard coat layer is characterized in that the contact angle with respect to water is 50 degrees or more and the wet tension is 27 to 45 mN/m. Advantageous Effects of Invention The present invention provides a surface protective film having an adhesive layer exhibiting specific physical properties on one surface of a substrate, and therefore has excellent initial adhesion to a surface of a protected object such as a metal plate, a cosmetic board, a plastic plate, or a glass plate. When the use is accompanied by heat treatment, especially for high-temperature heating, the adhesion is less after the heat treatment, and it is difficult for the surface of the object to be protected to have a residual residue when peeled off from the object to be protected, and no floating occurs. A surface protective film that acts as a peeling phenomenon. In particular, it is also possible to provide a hard coat layer which is adhered to the hard coat layer and further adheres to a hard coat layer having a specific surface property, and also exhibits excellent initial adhesion, and it is difficult to cause a paste residue in the hard coat layer after the heat treatment. Surface protection film. [Mode for Carrying Out the Invention] Hereinafter, embodiments of each component will be described. The base material used in the present invention can be appropriately selected depending on the application, in particular, whether it is transparent or opaque, but the material 'only needs to be transparent, and polyethylene terephthalate and polybutylene to benzene are mentioned. Dicarboxylate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, -8 - 201016822 triacetyl cellulose, acrylic acid, polyvinyl chloride, raw spintenyl compound Plastic film. The opaque one may include an opaque substrate such as paper or synthetic paper, or a viscous film containing a pigment or the like inside the plastic film, and a viscous colored layer in the plastic film. The thickness of the substrate varies depending on the application, and therefore cannot be determined. However, the lower limit is preferably 2 μm or more, and preferably ΙΟμπι or more as the upper limit is preferably 300 μηι or less, in consideration of easiness of handling, and the like. The optimum degree is 125 μιη φ or less. Since the substrate is improved in adhesion to an adhesive layer to be described later, it is also preferable to apply a plasma treatment, a corona discharge treatment, a far ultraviolet irradiation treatment, a sandblasting treatment, or the like, or to provide a primer to be easily treated. Second, let's explain the adhesive layer. The difference between the storage modulus of the adhesive layer at 150 ° C and the storage modulus at 20 ° C satisfies the above formula (1), and the maximum temperature of tanS is preferably -5 ° C or less, preferably -1 Below 〇 ° C, more preferably below -20 ° C.如此 Such an adhesive layer is such that the difference between the storage modulus at 150 ° C and the storage modulus at 20 ° C satisfies the above formula (1), and when the maximum temperature of tan 5 is -5 ° C or less, In the case of heat treatment, particularly in the case of high-temperature heating, the adhesion after heat treatment is less increased, and when the object to be protected is peeled off, it is difficult for the surface of the object to be protected to have a residual residue, and no floating occurs. A surface protective film that is peeled off. That is, the adhesive layer has a difference in the storage modulus at 150 ° C and the storage modulus at 20 ° C to satisfy the above formula (1), thereby preventing excessive adhesion of the adhesive layer to the surface of the protected object at a high temperature. Excessively easy to fuse, used in conjunction with -9- 201016822 with heat treatment, especially for high temperature heating of 100 ° C ~ 150 ° c, the adhesion after heat treatment is also less, peeling off from the protected material When it is difficult to produce a paste residue on the surface of the object to be protected. Further, when the adhesive layer has a maximum tans temperature of -5 t or less, since the viscosity is moderately obtained, the initial adhesion is excellent, and even if it is at a high temperature of about 1 〇〇 ° C to 150 ° C, it is difficult to cause floating. Peeling phenomenon. Moreover, the adhesion layer is tan0 of 0 ° ° C ~ 150 ° C is 0. 1 or less is preferred. The tanS in 100 ° C ~ 150 ° C is set to 0. When 1 or less, the effect of the elastic component in the adhesive layer is more strongly than that of the adhesive component, and does not excessively fuse with the surface of the protected object, and the surface of the protected object can be pasted when peeled off from the protected object. Residues are more difficult to produce. Further, depending on the material or shape of the object to be protected, it tends to prevent the initial adhesion from being excessively high. Moreover, the adhesive layer is placed in an environment of 150 ° C, and after 30 minutes of standing, the adhesion to the stainless steel plate is 0. 1 N/5 Omm ~ 1N/5 Omm is preferred. By the 15 (TC environment, after 30 minutes of placement, the adhesion to the stainless steel plate is 0. 1N/50mm or more, in the heat treatment processing or the heat treatment in the drying step after coating, it is difficult to cause peeling phenomenon such as floating, and the peelability is good by 1N/5Omm or less, and workability can be improved. Processing. As the adhesive constituting the adhesive layer, a natural resin-based adhesive, a synthetic resin-based adhesive, or the like is used, and a synthetic resin-based adhesive such as an acrylic adhesive, a polyoxygen-based adhesive, or an amine-ester adhesive is more preferably used. . Among them, a cross-linking adhesive is preferred because it has weather resistance and is less likely to cause aggregation damage, and is easy to perform adhesion control, adjustable re-peelability, and re-adhesiveness, and cross-linking is used from the viewpoint of ease of handling. Acrylic adhesive -10- 201016822 is especially good. The crosslinking agent to be used for the adhesive layer is not particularly limited, and examples thereof include an isocyanate crosslinking agent, an epoxy crosslinking agent, an imide crosslinking agent, and a metal chelating agent. The thickness of the adhesive layer is not particularly limited, and is preferably Ιμηη~30μηη, preferably 2μηι〜ΙΟμιη, in consideration of adhesion at the initial stage and after heating, adhesion, handleability, economy, and the like. In the adhesive layer, besides adding an adhesive and a crosslinking agent, it is also possible to add a pigment, a dye, a coloring agent, a matting agent, an antistatic agent, a flame retardant, an antifungal agent, a rust preventive agent, an antibacterial agent, Additives such as ultraviolet absorbers, photosensitizers, heat stabilizers, antioxidants, plasticizers, leveling agents, flow regulators, defoamers, dispersants, fluorescent whitening agents, storage stabilizers, and decane coupling agents. However, the addition amount of these additives is preferably in a range which does not hinder the effect of the adhesive layer. The surface protective film of the present invention can be prepared by dissolving or dispersing the above-mentioned adhesive agent, a crosslinking agent, and, if necessary, an additive, in a solvent to prepare a coating liquid for an adhesive layer, which is known in the past. Coating method, for example, by a bar coater, a dye applicator, a blade coater, a rotary coater, a roll coater, a gravure coater, a shower coater, a sprayer, a screen printing, etc. It is obtained by coating on the above substrate, drying and hardening by heating to form an adhesive layer. Further, from the viewpoint of handleability, after the substrate is coated and dried, a spacer is provided on the surface of the exposed adhesive layer, and then it can be formed by curing by heating. In the surface protective film of the present invention, the coating liquid for an adhesive layer may be applied and dried on a separator in the same manner as described above, and bonded to a substrate of -11 to 201016822, and then heated. Hardened and obtained. An example of the method of using the surface protective film of the present invention is, for example, a production process of an optical member such as a polarizing plate, a printing step, a production of an electronic circuit board, a protective film such as a ceramic capacitor, and the like. . As described above, the surface protective film of the present invention is a surface protective film having an adhesive layer on one side of the substrate, and the difference between the storage modulus of the adhesive layer at 150 ° C and the storage modulus at 20 ° C is When the above formula (1) is satisfied and the maximum temperature of tan δ is -5 ° C or lower, the initial adhesion to the surface of the object to be protected such as a metal plate, a cosmetic board, a plastic plate, or a glass plate is excellent, and it is used for heat treatment. In particular, when it is used for high-temperature heating, even if the adhesive force is less increased after the heat treatment, peeling of the surface of the object to be protected is less likely to occur when the object to be protected is peeled off, and peeling such as lifting is less likely to occur. In the laminate of the present invention, the surface of the surface protective film having the adhesive layer is bonded to the object to be adhered. Hereinafter, as a sticking object, a hard coat layer used in various fields will be described. The hard coat layer which is one of the examples can be applied to a target to be coated by a preparation of a hardenable composition (coating material), and cured to obtain a resin component which can be used in the curable composition of this example. The resin component contains one or both of a thermosetting resin or an ionizing radiation curable resin. The thermosetting resin and the ionizing radiation curable resin are, for example, a polyester resin, an acrylic resin, an urethane acrylate resin, a polyester acrylate-12-201016822 ester resin, a polyurethane acrylate resin, or an epoxy acrylate resin. A resin, an amine ester resin, an epoxy resin, a polycarbonate resin, a melamine resin, a phenol resin, a polyoxyn resin, a fluorine resin, or the like. In particular, it is preferable that the resin component contains at least an ionizing radiation curable resin from the viewpoint of excellent hardness (hard coating property) of the film after curing. As the ionizing radiation-curable resin, a photopolymerizable prepolymer Φ which is cross-linked and hardened by irradiation with ionizing radiation (ultraviolet rays or electron beams) can be used. In the present embodiment, the photopolymerizable prepolymer described later may be used alone or in combination of two or more kinds. The photopolymerizable prepolymer has a cationic polymerization type and a radical polymerization type. The cationic polymerization type photopolymerizable prepolymer may, for example, be an epoxy resin or a vinyl ether resin. Examples of the epoxy resin include a bisphenol epoxy resin, a novolak epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin. As the radical polymerization type photopolymerizable prepolymer, an acrylic prepolymer (hard prepolymer) having two or more acrylonitrile groups in one molecule and being crosslinked and cured into a three-dimensional mesh structure is used. It is particularly useful for the viewpoint of hard coatability. Examples of the acrylic prepolymer include an amine ester acrylate, a polyester acrylate, an epoxy acrylate, a melamine acrylate, a polyfluoroalkyl acrylate, and a polyoxy acrylate. The urethane acrylate-based prepolymer can be obtained, for example, by esterification of a polyurethane oligopolymer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate in a reaction with (meth)acrylic acid. As the polyester acrylate-based prepolymer, for example, the hydroxyl group of the polyester oligomer having hydroxy-13-201016822 at both ends thereof obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol can be carried out with (meth)acrylic acid. The esterification may be carried out by esterification of a hydroxyl group at the terminal of the oligomer obtained by adding a polyvalent carboxylic acid to an epoxide with (meth)acrylic acid. The epoxy acrylate-based prepolymer can be obtained, for example, by esterification of a relatively low molecular weight bisphenol type epoxy resin or an oxirane ring of a novolak epoxy resin with a reaction of (meth)acrylic acid. The acrylic prepolymer can be suitably selected in accordance with the type, use, and the like of the member to be coated. Further, the acrylic prepolymer may be used alone, but it is preferable to add a photopolymerizable monomer to impart various properties such as improvement of crosslinking hardenability or adjustment of curing shrinkage. Examples of the photopolymerizable monomer include monofunctional acrylic monomers (for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butoxyethyl acrylate, etc.). , a bifunctional acrylic monomer (eg 1,6·hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, hydroxytrimethyl acetate) A neopentyl glycol diacrylate or the like, a trifunctional or higher acrylic monomer @ (for example, dipentaerythritol hexaacrylate, trimethylpropane triacrylate, pentaerythritol triacrylate, etc.). Further, in the "acrylate", as described in the text, methacrylate is contained in addition to the acrylate. These photopolymerizable monomers may be used singly or in combination of two or more. The total content of the photopolymerizable prepolymer and the photopolymerizable monomer in the curable composition (in terms of solid content) is preferably 40 to 99% by weight, preferably 60 to 95% by weight based on the total resin component. %, more preferably 80 to 90% by weight. -14 - 201016822 When the hard coat layer is formed, it is cured by ultraviolet irradiation, and it is preferable to add an additive such as a photopolymerization initiator, a photopolymerization accelerator, or a UV sensitizer to the curable composition. . The amount of these additives added is generally selected from the range of 100 parts by weight of the photopolymerizable prepolymer and the photopolymerizable monomer. 2 to 10 parts by weight. Further, the resin component may be substituted for the ionizing radiation-curable resin or the thermosetting resin may be contained in the resin component. When the resin component is contained in the thermosetting resin, the thermally polymerizable monomer or prepolymer may be contained alone or in the form of a thermal polymerization initiator, that is, a compound which generates an active radical species by heating. In addition to the above-mentioned thermosetting resin or ionizing radiation-curable resin, the resin may be contained in the range of not only the effect of the present invention but also other resins such as a thermoplastic resin. Further, the curable composition may be a range in which the effect of the present invention is not inhibited. The additive component may be added as appropriate. Examples of the additive component include inorganic fine particles, resin fine particles, surface conditioners, slip agents, colorants, pigments, dyes, fluorescent whitening agents, flame retardants, antibacterial agents, antifungal agents, and ultraviolet absorbers. Light stabilizer, heat stabilizer, antioxidant, plasticizer, coating agent, flow regulator, defoamer, dispersant, storage stabilizer, crosslinker, etc. In particular, by adding inorganic fine particles or resin fine particles of a desired size, a matte hard coat layer having a desired shape can be formed. Such a hard coating layer is applied to the surface protective film by heat treatment (for example, 150 ((:, 90 minutes), etc.) by being affected by, for example, a residual monomer component or the above-described various additive components. When there is a substance, there is a tendency to more easily leave the paste -15- 201016822. Especially for the matte hard coating layer, when the adhesion of the matte hard coating layer is high, the adhesion of the adhesive layer is high, the matte hard coating layer is in contact with When the surface area of the adhesive layer is increased, when the heat treatment or the like is applied, the Clear Hard Coat layer tends to have a more residual odor. Further, the unevenness of the matte hard coat layer, the adhesive layer When the adhesion is low, the surface area of the matte hard coat layer and the contact adhesive layer becomes smaller, and the flat hard coating layer tends to float more easily. However, the surface protective film of the present invention is The adhesive layer has a specific physical property, and even if it is adhered to the matte hard coat layer, it is difficult to cause a paste after heat treatment, and it is less likely to cause floating. Further, the surface protective film of the present invention is an example of a sticking object. The surface characteristics of the hard coat layer are specific, and it is not likely to cause a residue after the heat treatment. Specifically, as a hard coat layer, the contact angle with respect to water is adjusted to be smaller than a specific enthalpy, and for the camellia oil The contact angle is adjusted to be smaller than a specific 。. For example, when a fingerprint is attached to the surface of the hard coating layer, the φ pattern of the attached finger is not easily conspicuous (increased difficulty in fingerprint identification), and the water repellency is not enhanced by the surface of the film. It is effective in imparting oiliness and moderately imparting hydrophilicity and lipophilicity, and it is desirable to adjust the contact angle of water to the contact angle of camellia oil to be smaller than each specific one, and to adjust the surface characteristics of the hard coating layer. Moderate hydrophilicity and lipophilicity. When the surface of the hard coating layer exhibits moderate hydrophilicity and lipophilicity, the contact area of the fingerprint component (formed by the aqueous component and the oil component) on the surface of the coating layer does not become too small. The fingerprint component is moderately wetted and enlarged on the surface of the film. As a result, even if the surface of the hard coating layer is attached with a fingerprint of -16,168,822, the attached fingerprint can be prevented from being too awake. (Improved difficulty in fingerprint identification.) In addition to the above adjustment, the contact angle of water is adjusted to a predetermined angle or more, and the wet tension is adjusted to a predetermined range, in addition to the difficulty in fingerprint identification and hard coating. In addition to the effect of preventing the decrease in the cloth property, the rubbing property of the fingerprint after the fingerprint is attached becomes good, and the fingerprint component after the wiping is not too conspicuous. In this example, the contact angle of the hard coating layer to water is adjusted to 110° or less is preferred. It is preferably adjusted to 100° or less. When the contact angle of water is adjusted to 110° or less, the contact area with water is not too small, so that the attached fingerprint is not too conspicuous (fingerprint identification is difficult. In this example, the hard coating layer is preferably adjusted to a contact angle of 50° or less for the camellia oil. It is preferably adjusted to 40 or less. When the contact angle of the camellia oil is adjusted to 50° or less, the fingerprint is used. The oily ingredients in the oil will expand and expand. Therefore, the attached fingerprint will not be too eye-catching (the difficulty of fingerprint recognition is improved), and the fingerprint component after wiping 6 will not be too conspicuous. In this embodiment, it is preferred that the contact angle of the hard coat layer to water is adjusted to 50 or more. It is preferably adjusted to 60 or more, more preferably 70 or more, and particularly preferably 80 or more. By adjusting the contact angle to water to 50. Above, the contact area with water does not become too large. As a result, the aqueous component in the fingerprint is easily separated, and the wiping property of the fingerprint can be improved. That is, in this example, when the contact angle of the hard coating layer with respect to water is adjusted to a predetermined range, the degree of difficulty in fingerprint recognition is improved, and the wiping property of the fingerprint is also improved. Moreover, the contact angles of water and the contact angles of camellia oil are determined according to the method of -17-201016822 JIS-R3257 (1 999). In this embodiment, it is preferred to adjust the wetting tension of the hard coat layer to 27 mN/m or more. It is preferably 30 mN/m or more. Further, it is preferred to adjust the wet tension of the hard coat layer to 45 mN/m or less. It is preferably 40 mN/m or less, more preferably 38 mN/m or less. When the wet tension of the hard coat layer is adjusted to a predetermined range, the wiping property of the fingerprint can be improved. Further, the wetting tension 値 is 値 measured according to the method of JIS-K6 768 (1999). n The hard coat layer having such a surface physical property may be obtained by adding a compound (nonionic compound) having a specified range of HLB G of the Griffin's method to the curable composition of the hard coat layer as an additive component. The HLB of the Griffin's method is, for example, 2 or more, preferably 5 or more, more preferably 10 or more, for example, 18 or less, and preferably 15 or less nonionic compounds. When the H LB is added to the appropriate nonionic compound, the contact angle of the hard coating layer to water, the contact angle to the camellia oil, and the wetting tension can be easily adjusted to the range specified by the above ® . The nonionic compound is a general term for a compound which is dissolved in water and does not exhibit ionicity, but is composed of a combination of a hydrophobic group (lipophilic group) and a hydrophilic group. As such a compound, it has at least one or more hydrophilic groups (for example, polyepoxide, hydroxyl group, carboxyl group, sulfonyl group, decanoate, amine group, isocyanate group, epoxypropyl group, alkoxymethyl sulfonyl group, ammonium salt) Examples of the compound of the various metal salts and the like include ethoxylated glycerin triacrylate, 18 - 201016822 ethoxylated bisphenol A diacrylate, polyethylene glycol diacrylate, polyether modified acrylate, and Polyhydroxy modified acrylate and the like. Among them, polyethylene glycol diacrylate is preferably used from the viewpoint of solubility or handleability of the solvent. Further, as the nonionic compound, hydrazine such as a fatty acid ester or a polyether may be used as the fatty acid ester, and a fatty acid ester which is condensed with a fatty acid by a monohydric alcohol or a divalent or higher valence alcohol may be mentioned, for example, Examples of propylene glycol monostearate, propylene glycol monolaurate, diethylene glycol monostearate, diethylene glycol monolaurate, glyceryl monostearate, sorbitan sesquioleate , sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monolaurate, and the like. Further, examples of the fatty acid ester include polyoxyalkylene addition fatty acid esters. Further, it may be added to a nonionic compound in which a fatty acid ester is subjected to addition polymerization of an alkylene oxide group. As the alkylene oxide to be subjected to addition polymerization, it is preferred to oxidize ethylene propylene or propylene oxide. Each of ethylene oxide or propylene oxide may be subjected to addition polymerization alone or may be subjected to copolymerization addition. Examples of the polyoxyalkylene addition fatty acid ester include polyethylene oxide hardened castor oil, monostearic acid polyethylene oxide glycerin, and polyethylene oxide (4) sorbitan monostearic acid. Ester, polyethylene oxide (20) sorbitan monostearate, polyethylene oxide (4) sorbitan tristearate, polyethylene oxide (5) sorbitan Monooleate, polyethylene oxide (5) sorbitan monooleate, polyethylene oxide (20) sorbitan trioleate, polyethylene oxide (4) sorbitol Anhydride monolaurate, polyoxyethylene-19- 201016822 diol 400 monooleate, polyoxyethylene glycol 400 monostearate, polyethylene glycol 400 monolaurate, polyethylene oxide (4 ) sorbitan monolaurate or the like. Further, in the present embodiment, as the compound other than the fatty acid ester or the polyether, polyethylene oxide cholesteryl ether or polyethylene oxide decyltetradecyl ether may be used. The HLB of the Griffin's method is the content of the compound of the predetermined range, and is preferably 0. by weight of the resin component: 100 parts by weight. 05 weight _ or more, more preferably 0. 1 part by weight or more, particularly preferably 1 part by weight or more, preferably 60 parts by weight or less, more preferably 15 parts by weight or less, and particularly preferably 10 parts by weight or less. When the lower limit of the content of the compound is set to 0" by weight, the contact angle of the hard coating layer with water, the contact angle with the camellia oil, and the wet tension can be easily adjusted to the above-defined range. Further, when the upper limit of the content of the compound is adjusted to 60 parts by weight, the hardness (hard coatability) of the surface of the hard coat layer can be prevented from being lowered. By adding an appropriate amount, it is expected to further improve the fingerprint wiping property of the hard coat layer. @ Hard coating layer is better when the pencil hardness measurement 値 is further adjusted to Η or more. More preferably 2 Η or more. By adjusting the pencil hardness to a predetermined value or more, the difficulty of fingerprint recognition can be improved or not reduced under the fingerprint wiping property, and the surface of the hard coating layer can be effectively prevented from being scratched. Further, the pencil hardness measurement 値 is measured in accordance with the method of JIS-Κ5 6 00-5-4 (1 999 ). The hard coat layer is such that the further refractive index 値 is adjusted to 1. 45~1. 65 o'clock is better. Preferably 1. 46~1. 52. By adjusting the refractive index 値 to a predetermined range, the difference between the refractive index of the hard coat layer and the refractive index of the fingerprint component can be made small -20- 201016822. As a result, when the hard coating layer is attached with a fingerprint, the attached fingerprint can be further difficult to be conspicuous (the difficulty in fingerprint identification is further improved), and the fingerprint component after wiping is not easily noticeable. The thickness of the hard coating layer is 0. It is preferably 1 μm or more and 30 μm or less. By the thickness of the hard coating layer is Ο. When ίμιη or more, it can be made into a film with sufficient hardness. On the other hand, even if the thickness of the hard coat layer exceeds 3 Ομηι, the film hardness is not further improved. Further, when the thickness φ of the hard coat layer is increased, the film tends to be warped due to shrinkage of the film. Therefore, it is preferable that the thickness is 30 μm or less from the viewpoint of economy or bending prevention. Further, in this example, the thickness of the hard coat layer may be ΙΟμηη or less, and may further be 5 μm or less. Even as a film, the necessary performance is ensured. Further, in order to obtain the above surface characteristics, surface treatment such as plasma treatment, corona discharge treatment, or far ultraviolet irradiation treatment may be applied to the surface of the hard coat layer. Φ The hard coat layer having such a surface physical property is more susceptible to the addition of components or surface treatment than the hard coat layer. Therefore, it is easy to leave a paste compared with the hard coat layer after heat treatment or the like. Propensity. However, since the surface protective film of the present invention has specific physical properties due to the adhesive layer, even if it is applied to a hard coat layer having such specific surface physical properties, the paste may not easily remain after heat treatment. The hardenable composition is generally achieved in the form of a coating. In the case of the organic solvent-based coating material, the resin component may be appropriately selected depending on the type of the resin component, and the resin component (additional component if necessary) may be dissolved or dispersed in a solvent such as an organic solvent or the like, and may be dissolved or dispersed as necessary. After the addition of the additive, a hardenable composition can be produced. As a target to be coated, it is a substrate which is expected to provide a hard coating property (scratch resistance) and a difficulty in identifying the texture. The type of the substrate to be used in the present embodiment is not particularly limited, and may be any thickness such as a film, a sheet or a plate. Further, the surface of the substrate may be, for example, a convex-concave shape or a three-dimensional shape having a three-dimensional curved surface. The material of the substrate is not particularly limited, and may be a hard substrate such as a glass plate. However, in this embodiment, a flexible resin substrate is preferred. The type of the resin constituting the resin substrate is not particularly limited. For example, examples of the resin in the case of forming a resin substrate in the form of a film or a sheet include acrylic acid, polycarbonate, polyvinyl chloride, polyester, polypropylene, polyethylene, acetyl cellulose, and cycloolefin. Wait. On the other hand, for example, as the resin when the resin substrate is formed in a plate shape, for example, acrylic acid polycarbonate, polyvinyl chloride or the like can be given. Further, for the purpose of improving the adhesion of the hard coat layer composed of the cured product of the curable composition, the surface of the substrate can be easily treated. As the easy-to-treat treatment, for example, a plasma treatment, a corona discharge treatment, a far ultraviolet irradiation treatment, a formation of a lower adhesion layer, and the like can be given. The coating (coating) of the curable composition to be coated can be carried out according to a usual method, and examples thereof include bar coating, dye coating, blade coating, spin coating, roll coating, and gravure coating. Cloth, shower coating, impregnation coating, spray coating, screen printing, brush coating, and the like. The thickness of the coating film after coating is preferably Ο after drying and hardening as described later. Ίμιη above 30μπι below the degree. After applying the curable composition to the object to be coated, it is preferred to dry the coated film at a temperature of from -22 to 201016822 at 50 to 120 °C. The hardening of the curable composition can be carried out by coating the coated film by heat aging and/or irradiation with ionizing radiation (light). As the heat source, for example, an electric heater, an infrared lamp, hot air or the like can be used. When it is carried out by ionizing radiation (light), only the curable composition applied to the substrate can be cured in a short period of time as the light source, and is not particularly limited. For example, as a light source of infrared rays, a φ lamp, a resistance heating plate, a laser, or the like can be cited. As the light source of visible light, sunlight, a lamp, a fluorescent lamp, a laser, and the like can be cited. Examples of the light source of ultraviolet rays (ionizing radiation) include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, and a metal halide lamp. Ultraviolet rays are emitted from the ultraviolet light source at a wavelength of from 1 nm to 400 nm, preferably from 200 nm to 400 nm. As the light source of the electron beam (ionizing radiation), a scanning type or a curtain type electron beam accelerator or the like can be given. The electron beam of the wavelength region of 100 nm or less which is emitted by the electron beam accelerator is irradiated with 10 electrons. The amount of irradiation of the ionizing radiation varies depending on the type of the ionizing radiation. For example, in the case of ultraviolet rays, the amount of light is preferably about 100 to 500 mJ/cm2, and the electron beam is preferably from 10 to 100 krad. The hard coat layer produced as described above can be used for applications in which it is necessary to impart hard coatability (scratch resistance) and difficulty in fingerprint recognition, and is particularly useful for various displays (for example, plasma display panel PDP, cathode ray). Tube CRT, liquid crystal display (LCD), electroluminescent display (ELD, etc.); display cabinet, clock or meter cover glass; bank ATM or ticket -23- 201016822 vending machine, etc. as representative of touch panel electronic For machine contact surfaces; hard coating is preferred. Further, the electronic device naturally includes a mobile phone having the above various displays (for example, a personal mobile information terminal equipped with a PDA (Personal Digital Assistants) function) or an information processing device such as a personal computer. [Embodiment] [Examples] Hereinafter, the present invention will be further described by way of examples. And "parts" and "%" are based on weight unless otherwise specified. [Examples 1 to 3 and Comparative Examples 1 to 4] As a substrate, the adhesive layer of the formulation of Table 1 was coated on one side of a polyethylene terephthalate film (lumirror S28: Toray) having a thickness of 25 μm. The liquids (Examples 1 to 3 and Comparative Examples 1 to 4) were each coated by a bar coater method and passed through a temperature of 90 ° C. After drying for 5 minutes, a dry film thickness of 2. The adhesive layer of 5 μm is bonded to the separator (MRF: Mitsubishi Chemical Polyester Film Co., Ltd.) because of its good handleability. Followed by 60. The surface protective film of Example 丨~3 and Comparative Examples 1-4 was produced in the environment of (:). -24- 201016822 [Table 1] Product name Company name solid content (%) Example (part) ) Compare 1 mm 1 2 3 1 2 3 4 SKDyne 1439U Comprehensive Chemical Company 30 22. 75 Finetac CT-3020 DIC Corporation 30 24. 78 OlibainBPS6078TF Toyo Ink Company 42 15. 06 01ibainBPS5977 Toyo Ink Company 28 17. 86 Quickmaster SPS-1068 DIC 40 16. 50 corponeal N-4900 Sakamoto Synthetic Chemical Company 38 20. 71 SKDyne 1491H Integrated Chemical Company 30 10. 63 E-50C Comprehensive Chemical Company 45 0. 34 DN-980 DIC Company 75 0. 74 BXX6105 Toyo Ink Company 37. 5 1. 51 BXX 5983 Toyo Ink Company 5 0. 05 D-45 DIC Corporation 45 0. 13 Tetrad C Mitsubishi Gas Chemical Company 100 0. 83 L-45 Integrated Chemical Company 45 0. 10 ethyl acetate 31. 97 38. 18 69. 25 22. 46 33. 14 43. 77 toluene 31. 90 36. 10 22. 18 33. 04 44. 36 10. 63 methyl ethyl ketone 10. 63 total (parts) 86. 96 99. 80 85. 82 62. 55 66. 31 109. 67 31. 99 NV (%) 8. 02 8. 01 8. 03 8. 00 8. 04 7. 93 10. 10
對於表1的實施例及比較例所得之黏著層，（1 )對 於 1 50°c、20°c之貯藏彈性率、tans極大溫度、loot〜 1 50°C中之tanS進行測定。又，對於實施例及比較例所得 之表面保護薄膜，（2)對於初期黏著力、（3)對於加熱 後之黏著力、（4)對於糊分殘留、（5)對於浮起進行評 估。結果如表2所示。 -25- 201016822 (1) 150°c、20°c之貯藏彈性率、tans極大溫度、100°c〜 1 50°C 中之 tan6 將表1處方之黏著劑、硬化劑及溶劑秤出所定量後， 經混合並充分攪拌。欲使乾燥後的塗膜厚度成爲1mm程 度，移至其他容器中，並進行40 °C下4天的乾燥·熟成。 其後自容器僅取出塗膜，製作出測定試料。 使用黏彈性測定裝置（PhysicaMCR301 : Anton Paar 公司），藉由進行測定試料之動態黏彈性，求得1 50°C、 2〇°C之貯藏彈性率、tanS極大溫度、100°C〜1 50°C中之 tanS。測定條件爲變形0.1%、周波數1Hz、溫度範圍-30°C 〜160〇C。 (2 )初期之黏著力 欲使實施例、及比較例的表面保護薄膜的長度方向成 爲塗佈方向，切出寬爲50mmx長度約200mm之尺寸的試 驗片。其次，將試驗片貼附於不銹鋼板（JIS G43 05所規 定之SUS304鋼板），於23°C，50%RH之環境下放置1小 時後，以JIS Z0237 : 2000爲準，使用萬能拉力測試機（ TensilonHTM-100 ： Orientec 公司），測定 180 度拉引剝 離之黏著力。 (3 )加熱後之黏著力 與（2)同樣地，製作出試驗片，貼附於不銹鋼板， 於23t，50%RH之環境下放置30分鐘後，於150°C之環 201016822 境下放置30分鐘，再於23°C，50%RH之環境下放置30 分鐘後，與（2)同樣地測定180度拉引剝離之黏著力。 (4)糊分殘留 測定（3 )之加熱後的黏著力後，將不銹鋼板狀態以 目視方式觀察·，進行糊分殘留之評估。評估爲，將完全未 於不銹鋼板上糊分殘留者爲「〇」，於不銹鋼板之一部分 ❹ 有糊分殘留者爲「△」，於不銹鋼板與基材之間引起凝集 破壞而於不銹鋼板的幾乎全面上有糊分殘留者爲「X」。 (5 )浮起 測定（3)之加熱後的黏著力中，將貼著試驗片之不 銹鋼板以150°C的環境下放置30分鐘後，於23°C，50%RH 的環境下放置30分鐘時’由不銹鋼板是否產生浮起，由 目視進行評估。將試驗片與不銹鋼板貼合且幾乎無浮起產 Φ 生者爲「〇」，試驗片於不銹鋼板密著的面積比剝落面積 大時爲「△」，試驗片自不銹鋼板剝落的面積比密著之面 積還大者爲「X」。 -27- 201016822 〔表2〕 貯藏彈ΰ Ξ率 tana 極 100t>150°C 中 黏著力(N/5〇mm) 糊分 浮起 製品名 G，(150) G’(20) G’(150)-G’(20) 大溫度 之ΐβηδ値 初期 加熱後 殘留 實施例1 3·11χ103 1_78χ103 1.33χ103 -22.0 0.1以下 0.14 0.19 〇 〇 實施例2 8_97χ102 1_25χ102 7.72χ102 -23.6 0.1以下 0.07 0.18 〇 〇 實施例3 1.05χ104 8.15χ103 2.35χ103 -10.8 0.1以下 0.05 0.06 〇 Δ 比較例1 6·41χ102 5_45χ103 -4.81χ103 -23.9 0.27-0.33 8.09 14.31 X 〇 比較例2 5.25χ102 3.40χ103 -2.88χ103 -20.0 0.55-0.58 10.05 13.61 X 〇 比較例3 5.36χ103 1.55χ105 -1.50χ105 -4.4 0.1以下 0.06 0.06 一 X 比較例4 7·19χ104 8_35χ104 -1.16χ104 -21.2 0.1以下 0.64 14.14 X 〇 由表2得知，實施例之表面保護薄膜爲，黏著層於 15(TC中之貯藏彈性率與於20°C中之貯藏彈性率的差比〇 大，滿足上述（1)式，且tanS極大溫度爲-5 °C以下。因 此，具有優良初期黏著性，150°C，30分鐘之加熱處理後 黏著力之上昇亦較少，自不銹鋼板進行剝離時亦無對於表 面之糊分殘留，且浮起亦難產生。又，加熱後之黏著力（ JIS Z0237 : 2000中之 180度拉引剝離黏著力）爲 0.1N/50mm〜lN/50mm，故剝離性爲良好。 比較例1、2之表面保護薄膜爲，黏著層之tanS極大 溫度爲- 5°C以下，但於l〇〇°C〜150°C中之tanS比0.1大， 且於150°C中之貯藏彈性率與於20°C中之貯藏彈性率的差 比〇小，其爲未能滿足上述（1)式者，故雖不會產生浮 起，但初期黏著性高，於15(TC，30分鐘之加熱處理後其 黏著力亦提高，成爲自不銹鋼板進行剝離時對於表面有糊 分殘留者。又，加熱後之黏著力（JIS Z0237 : 2000中之 180度拉引剝離黏著力）爲IN/5 0mm以上，故其爲剝離性 201016822 較差者。 比較例3之表面保護薄膜爲，雖定 性率與於20°C中之貯藏彈性率的差比 tanS極大溫度比-5°C高，故產生浮起。 殘留者。 比較例4的表面保護薄膜爲，黏毫 度爲-5°C以下，且於1〇〇°C〜150°C中之 φ 故未產生浮起，初期黏著性不過高而得 ，於150°C中之貯藏彈性率與於20°C中 比0小，並非滿足上述（1 )式，故加 提高，成爲自不銹鋼板進行剝離時對於 〔實施例4〕 準備於基材的一面具有由電離放射 ® 之透明硬塗佈層、與另一面上具有由二 離放射線硬化型樹脂所成之消光硬塗佈 KB薄膜GN7B : Kimoto公司）。其次 薄膜的透明硬塗佈層上，貼著具有實施 膜的·黏著層之面，製作出實施例4之層 塗佈層對水之接觸角爲62度，對山茶汗 ，濕潤張力爲23mN/m以下。 〔實施例5〕 f 1 5 0 °C中之貯藏彈 0小，但黏著層之 因此成爲未有糊分 ^層之tanS極大溫 tan5爲0.1以下， 到良好結果。然而 之貯藏彈性率的差 熱處理後之黏著力 表面有糊分殘留者 線硬化型樹脂所成 氧化矽微粒子與電 層的硬塗佈薄膜（ ，於準備之硬塗佈 例1之表面保護薄 合體。且，透明硬 1之接觸角爲31度 -29- 201016822 於實施例4的硬塗佈薄膜的消光硬塗佈層上，貼著具 有實施例1之表面保護薄膜的黏著層之面，製作出實施例 5之層合體。且，消光硬塗佈層對水之接觸角爲79度，對 山茶油之接觸角爲34度，濕潤張力爲23mN/m以下，由 JIS B0601 : 2 001所算出的算術平均粗度爲〇.12±0.04μπι。 〔實施例6〕 準備於基材一面上具有對水之接觸角爲76度、對山 茶油之接觸角爲36度、濕潤張力爲3 2 mN/m之硬塗佈層 的硬塗佈薄膜（KB薄膜AFP : Kimonto公司）。其次，於 準備之硬塗佈薄膜的硬塗佈層上，貼著具有實施例1的表 面保護薄膜之黏著層的面，製作出實施例6之層合體。 〔比較例5〜7〕 實施例4〜6之層合體中，取代實施例1之表面保護 薄膜，變更爲比較例4之表面保護薄膜以外，與實施例4 〜6同樣地，製作出比較例5〜7之層合體。 對於實施例4〜6及比較例5〜7所得之層合體，對於 自硬塗佈層剝離表面保護薄膜時的（6)初期之黏著力、 (7)加熱後之黏著力、（8)糊分殘留、（9)浮起進行 評估。結果如表3所示。 (6 )初期之黏著力 對於實施例4〜6及比較例5〜7所得之層合體，製作 -30- 201016822 寬 50mmx長度約 200mm之尺寸的試驗片，於 23 °C， 5 0%RH之環境下放置1小時後，依據JIS Z0237 : 2000， 使用萬能拉力測試機（TensilonHTM-100: Orientec公司 )，自硬塗佈層剝開表面保護薄膜，測定1 8 0度拉引剝離 之黏著力。 (7 )加熱後之黏著力 φ 與（6)同樣地製作出試驗片，於23°C，50%RH之環 境下放置30分鐘後，於150°C之環境下放置30分鐘，再 於2 3°C，5 0%RH之環境下放置30分鐘後，與（6)同樣 地，測定180度拉引剝離之黏著力。 (8 )糊分殘留 對於實施例4〜6及比較例5〜7之層合體，製作出切 成A-4尺寸的試驗片，於23°C，50%RH之環境下放置30 φ 分鐘後，於150 °C之環境下放置90分鐘，再於23 °C， 50%RH之環境下放置30分鐘後，以手自硬塗佈層剝開表 面保護薄膜。評估以目視方式觀察，於硬塗佈層上之全面 有糊分殘留者爲「XX」，於硬塗佈層上處處有糊分殘留者 爲「X」，以目視下雖難以辨識，但由放大鏡（25 x25倍 )觀察時，於硬塗佈層上有點狀（約1〇μιηχ20μιη程度之 尺寸）微細糊分殘留者爲「△」，點狀微細之糊分殘留幾 乎無者爲「〇」。 -31 - 201016822 (9 )浮起 對於（7)之加熱後黏著力的測定，將試驗片以15(TC 的環境下放置30分鐘後，於23 °C，5 0%RH之環境下放置 30分鐘時，自硬塗佈層是否產生浮起以目視進行評估。將 試驗片與硬塗佈層貼合幾乎無產生浮起者爲「〇」，試驗 片密著於硬塗佈層之面積比剝落面積還大者爲「△」，試 驗片自硬塗佈層剝落的面積比密著之面積還大者爲「X」 〔表3〕 製品名 黏著力（N/50mm) 糊分殘留 浮起 初期 加熱後 實施例4 0.11 0.27 〇 〇 實施例5 0.07 0.20 〇 〇 實施例ό 0.10 0.26 Δ 〇 比較例5 0.48 3.88 X 〇 比較例ό 0.44 3.86 X 〇 比較例7 0.55 3.79 XX 〇 由表3得知，實施例之層合體皆對於硬塗佈層顯示優 良初期黏著性，於150°C，30分鐘的加熱處理後亦少有黏 著力上昇，且成爲不會產生浮起者。 又，實施例4、5之層合體爲，於150°C，90分鐘的 加熱處理後自硬塗佈層剝離表面保護薄膜時，硬塗佈層以 目視下無法辨識糊分殘留，且以放大鏡觀察時亦幾乎無微 細糊分殘留。 又，實施例6之層合體爲，於150°C，90分鐘的加熱 -32- 201016822 處理自硬塗佈層剝離表面保護薄膜時’硬塗佈層爲具有特 定物性者，故與實施例4、5之層合體的硬塗佈層相比較 時，糊分殘留的評估爲較差者，由目視無法辨識糊分殘留 ，亦非由放大鏡觀察時可確認到微細糊分殘留之程度者。 另一方面，比較例之層合體爲，黏著層之tanS極大 溫度爲-5°C以下，且100T：〜150°C中之tan5爲〇.1以下， 故不會產生浮起，初期黏著性亦不會過高，得到良好結果 φ 。然而，表面保護薄膜之黏著層於150 °C中之貯藏彈性率 與於20 °C中之貯藏彈性率的差比〇小，其爲非滿足上述（ 1)式者，比較例5、6之層合體於l5〇°C，90分鐘的加熱 處理後自硬塗佈層剝離表面保護薄膜時，成爲由目視可明 顯觀察到糊分殘留於硬塗佈層上處處產生者。 又，比較例7之層合體因其爲硬塗佈層爲具有特定物 性者，於150°C，90分之加熱處理後自硬塗佈層剝離表面 保護薄膜時，成爲由目視可明顯觀察到糊分殘留於硬塗佈 ® 層上爲全面產生者。 使用於如此實施例之層合體的表面保護薄膜，與使用 於比較例之層合體的表面保護薄膜相比較，即使被保護物 爲種種硬塗佈層之情況，顯示適度初期黏著性、加熱處理 後之黏著力上昇抑制、浮起防止性、糊分殘留防止性等極 優良之性能。 -33-For the adhesive layers obtained in the examples and comparative examples of Table 1, (1) the tans in the storage elastic modulus at 1 50 ° C, 20 ° c, the tans maximum temperature, and the loot to 150 ° C were measured. Further, with respect to the surface protective films obtained in the examples and the comparative examples, (2) the initial adhesion, (3) the adhesion after heating, (4) the residual of the paste, and (5) the evaluation of the floating. The results are shown in Table 2. -25- 201016822 (1) Storage elastic modulus at 150°c, 20°c, tans maximum temperature, tan6 in 100°c~1 50°C After weighing the adhesives, hardeners and solvents prescribed in Table 1, , mix and stir well. The thickness of the coating film after drying was adjusted to 1 mm, and it was transferred to another container, and dried and cooked at 40 ° C for 4 days. Thereafter, only the coating film was taken out from the container to prepare a measurement sample. Using a viscoelasticity measuring device (Physica MCR301: Anton Paar), by measuring the dynamic viscoelasticity of the sample, the storage elastic modulus at 150 ° C, 2 ° C, the maximum temperature of tanS, and 100 ° C to 1 50 ° were obtained. tanS in C. The measurement conditions were a deformation of 0.1%, a cycle number of 1 Hz, and a temperature range of -30 ° C to 160 ° C. (2) Adhesive strength at the initial stage The longitudinal direction of the surface protective film of the examples and the comparative examples was set to the coating direction, and a test piece having a width of 50 mm x and a length of about 200 mm was cut out. Next, the test piece was attached to a stainless steel plate (SUS304 steel plate specified in JIS G43 05), and placed in an environment of 23 ° C, 50% RH for 1 hour, and then the universal tensile tester was used in accordance with JIS Z0237:2000. (Tensilon HTM-100: Orientec), measuring the adhesion of 180 degree pull-off peeling. (3) Adhesive force after heating, in the same manner as (2), a test piece was prepared, attached to a stainless steel plate, placed in an environment of 23t, 50% RH for 30 minutes, and then placed under the ring of 201016822 at 150 °C. After 30 minutes, the mixture was allowed to stand in an environment of 23 ° C and 50% RH for 30 minutes, and the adhesion of the 180-degree peeling peeling was measured in the same manner as in (2). (4) Paste residue After the adhesion after heating (3) was measured, the state of the stainless steel plate was visually observed, and the evaluation of the residue remained. The evaluation is that the residue remaining on the stainless steel plate is “〇”, and the residue in the stainless steel plate is “△”, causing agglomeration damage between the stainless steel plate and the substrate. Almost all of the remaining people have "X". (5) In the adhesion after heating of the floating measurement (3), the stainless steel plate attached to the test piece was allowed to stand in an environment of 150 ° C for 30 minutes, and then placed in an environment of 23 ° C and 50% RH. At the minute, 'whether the stainless steel plate is floated or not, it is evaluated visually. When the test piece is bonded to the stainless steel plate and there is almost no floating production, the amount of the test piece is "△" when the area of the stainless steel plate is larger than the peeling area, and the area ratio of the test piece peeled off from the stainless steel plate. The larger area of the close is "X". -27- 201016822 [Table 2] Storage magazine Ξ rate tana pole 100t> 150 °C adhesion (N/5〇mm) paste float product name G, (150) G'(20) G' (150 )-G'(20) 温度βηδ値 at a large temperature remains after initial heating. Example 1 3·11χ103 1_78χ103 1.33χ103 -22.0 0.1 or less 0.14 0.19 〇〇Example 2 8_97χ102 1_25χ102 7.72χ102 -23.6 0.1 or less 0.07 0.18 〇〇Example 3 1.05χ104 8.15χ103 2.35χ103 -10.8 0.1 or less 0.05 0.06 〇Δ Comparative Example 1 6·41χ102 5_45χ103 -4.81χ103 -23.9 0.27-0.33 8.09 14.31 X 〇Comparative Example 2 5.25χ102 3.40χ103 -2.88χ103 -20.0 0.55-0.58 10.05 13.61 X 〇Comparative Example 3 5.36χ103 1.55χ105 -1.50χ105 -4.4 0.1 or less 0.06 0.06 -X Comparative Example 4 7·19χ104 8_35χ104 -1.16χ104 -21.2 0.1 or less 0.64 14.14 X 〇 Obtained from Table 2, the surface protection of the example In the film, the difference between the storage elastic modulus of the adhesive layer at 15 (TC) and the storage elastic modulus at 20 ° C is large, satisfying the above formula (1), and the maximum temperature of tanS is -5 ° C or lower. Has excellent initial adhesion, 150 ° C, 30 minutes After the heat treatment, the adhesion is also less increased. When the stainless steel sheet is peeled off, there is no residue on the surface, and floating is difficult to produce. Moreover, the adhesion after heating (JIS Z0237: 180 degree pull in 2000) The peeling adhesion is 0.1 N/50 mm to 1 N/50 mm, so the peeling property is good. The surface protective films of Comparative Examples 1 and 2 have a tanS maximum temperature of the adhesive layer of -5 ° C or less, but at 10 ° ° The tanS in C~150 °C is larger than 0.1, and the difference between the storage elastic modulus at 150 ° C and the storage elastic modulus at 20 ° C is smaller than that of the above formula (1). Therefore, although there is no floating, the initial adhesion is high, and the adhesion is improved after 15 (TC, 30 minutes of heat treatment, and it becomes a residue on the surface when peeling off from the stainless steel plate. Also, after heating The adhesion (JIS Z0237: 2000 degree pull adhesion) is IN/5 0mm or more, so it is poor in peelability 201016822. In the surface protective film of Comparative Example 3, although the difference between the qualitative rate and the storage modulus at 20 ° C was higher than the tanS maximum temperature of -5 ° C, floating occurred. Remaining. The surface protective film of Comparative Example 4 has a viscosity of -5 ° C or less and φ at 1 ° C to 150 ° C, so that no floating occurs, and the initial adhesiveness is not too high, and is 150 °. The storage modulus in C is smaller than 0 at 20 ° C, and does not satisfy the above formula (1). Therefore, when it is peeled off from a stainless steel sheet, it is ionized on the side prepared on the substrate of [Example 4]. A transparent hard coat layer of Radiation® and a matte hard-coated KB film GN7B made of a diastereze-curable resin on the other side: Kimoto Co., Ltd.). Next, on the transparent hard coat layer of the film, the surface of the adhesive layer having the film was applied, and the contact angle of the layer coating layer of Example 4 to water was 62 degrees. For the camellia sweat, the wet tension was 23 mN/ m or less. [Example 5] The storage bomb at f 1 50 °C was small, but the adhesive layer was not etched. The tanS maximum temperature of the layer was less than 0.1, which was a good result. However, the difference in storage modulus is the surface of the adhesive layer after the heat treatment, and the hard coat film of the ruthenium oxide microparticles and the electric layer formed by the line-hardening resin is prepared. Further, the contact angle of the transparent hard 1 was 31 degrees -29 to 201016822. On the matte hard coat layer of the hard coat film of Example 4, the surface of the adhesive layer having the surface protective film of Example 1 was applied thereto. The laminate of Example 5 was obtained, and the contact angle of the matte hard coat layer to water was 79 degrees, the contact angle to camellia oil was 34 degrees, and the wet tension was 23 mN/m or less, which was calculated by JIS B0601: 2 001. The arithmetic mean roughness is 12.12±0.04μπι. [Example 6] It is prepared to have a contact angle with water of 76 degrees on one side of the substrate, a contact angle of 36 degrees to camellia oil, and a wetting tension of 3 2 mN. a hard coating film of a hard coating layer of /m (KB film AFP: Kimonto Co.). Next, an adhesive layer having the surface protective film of Example 1 was attached to the hard coat layer of the prepared hard coat film. The laminate of Example 6 was produced on the surface. [Comparative Examples 5 to 7 In the laminates of Examples 4 to 6, the laminates of Comparative Examples 5 to 7 were produced in the same manner as in Examples 4 to 6 except that the surface protective film of Example 1 was changed to the surface protective film of Comparative Example 4. In the laminates obtained in Examples 4 to 6 and Comparative Examples 5 to 7, (6) initial adhesion to the self-hard coating layer, and (7) adhesion after heating, (8) The residue was evaluated and (9) floated and evaluated. The results are shown in Table 3. (6) Initial adhesion The laminates obtained in Examples 4 to 6 and Comparative Examples 5 to 7 were produced in the range of -30 to 201016822 and 50 mm wide. A test piece having a length of about 200 mm was placed in an environment of 23 ° C, 50% RH for 1 hour, and then subjected to a self-hard coating using a universal tensile tester (Tensilon HTM-100: Orientec) in accordance with JIS Z0237:2000. The surface protective film was peeled off, and the adhesion of the 180-degree peeling peel was measured. (7) Adhesive force φ after heating A test piece was produced in the same manner as (6) at 23 ° C, 50% RH. After standing for 30 minutes, it was placed in an environment of 150 ° C for 30 minutes, and then placed at 23 ° C, 50% RH. After 30 minutes, the adhesion of the 180-degree peeling peeling was measured in the same manner as in (6). (8) The paste remained. The laminates of Examples 4 to 6 and Comparative Examples 5 to 7 were cut into A-4. The test piece of the size was placed in an environment of 23 ° C, 50% RH for 30 φ minutes, placed in an environment of 150 ° C for 90 minutes, and then placed in an environment of 23 ° C, 50% RH for 30 minutes. The surface protective film is peeled off by a self-hard coating layer. The evaluation was visually observed. The overall rug residue on the hard coat layer was “XX”, and the residue on the hard coat layer was “X”, which was difficult to identify by visual observation. When the magnifying glass (25 x 25 times) is observed, it is a little bit on the hard coating layer (about 1 〇μηηχ20μηη). The fine paste remains as "△", and the minute fine residue remains almost nothing. . -31 - 201016822 (9) Floatation For the measurement of the adhesion after heating (7), place the test piece in an environment of 15 (TC environment for 30 minutes, and place it at 23 ° C, 50% RH). In the minute, whether the self-hard coating layer is floated or not is visually evaluated. The test piece and the hard coating layer are bonded together with almost no floating, and the area ratio of the test piece to the hard coating layer is The larger the peeling area is "△", and the area where the test piece peels off from the hard coating layer is larger than the area of the dense one is "X" [Table 3] Product name adhesion (N/50mm) Paste residue floating After initial heating Example 4 0.11 0.27 〇〇 Example 5 0.07 0.20 〇〇 Example ό 0.10 0.26 Δ 〇 Comparative Example 5 0.48 3.88 X 〇 Comparative Example ό 0.44 3.86 X 〇 Comparative Example 7 0.55 3.79 XX 〇 The laminate of the examples showed excellent initial adhesion to the hard coat layer, and the adhesion was less likely to increase after heat treatment at 150 ° C for 30 minutes, and the float was not generated. The laminate of 5 is a self-hard coating layer after heat treatment at 150 ° C for 90 minutes. When the surface protective film was removed, the hard coating layer could not be discerned by visual observation, and almost no fine residue remained when observed by a magnifying glass. Further, the laminate of Example 6 was at 150 ° C for 90 minutes. Heating-32-201016822 When the surface coating film is peeled off from the hard coating layer, the hard coating layer has specific physical properties, so when it is compared with the hard coating layer of the laminate of Examples 4 and 5, the paste remains. If the evaluation is poor, the residual residue cannot be recognized by visual observation, and the degree of residual fine residue can be confirmed when not observed by a magnifying glass. On the other hand, the laminate of the comparative example has a tanS maximum temperature of the adhesive layer of -5. Below °C, and at 100T: ~150 °C, tan5 is less than or equal to 1.1, so floating does not occur, the initial adhesion is not too high, and good results are obtained. However, the adhesion layer of the surface protective film is The difference between the storage modulus at 150 °C and the storage modulus at 20 °C is smaller than that of the above formula (1), and the laminate of Comparative Examples 5 and 6 is at 15 °C, 90. Peeling the surface protective film from the hard coating layer after a minute of heat treatment The result is that the paste remains apparent on the hard coat layer by visual observation. Further, the laminate of Comparative Example 7 has a specific physical property because it is a hard coat layer, and is at 150 ° C, 90 ° C. When the surface protective film is peeled off from the hard coating layer after the heat treatment, it is apparent that the paste remains on the hard coat layer by visual observation. The surface protective film used in the laminate of the embodiment, In comparison with the surface protective film of the laminate of the comparative example, even if the protected material is a hard coating layer, it exhibits moderate initial adhesion, adhesion improvement after heat treatment, floating prevention, and paste residue. Excellent performance such as prevention. -33-