200530363 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關具有脫模性之表面保護膜及表面保護材 料’特別是有關適用於印刷基板製作步驟等中具有黏合性 光阻之曝光時原稿（光罩）表面上之表面保護膜及表面保 護材料。 【先前技術】 通常印刷電路板、樹脂凸板係於液狀光阻等具有黏合 性之光阻中使光罩（曝光用原稿）進行密合曝光後製作之 。曝光結束後使光罩由光阻剝離時，爲防止部份光阻附著 於光罩表面，先行技術中，於光罩上之光阻對面進行設置 具有脫模性之表面保護材料（表面保護薄片）。 做爲此光罩用之奏面保護材料者，被揭示有塑膠薄膜 單面上具有具脫模性之表面保護膜，另一面具有黏合層者 (日本專利公開公報；特開平i丨_ 7丨2 1號公報）。惟，此 表面保護材料中對於表面保護膜無法有效防止光阻之附著 ’爲去除殘留於此等表面保護膜之光阻、其他灰塵等。藉 由洗淨溶劑進行表面保護膜表面之定期淸潔（擦拭操作） 。因此’此表面保護材料中即使淸潔後仍被要求持續防止 光阻附著之脫模性。 針對此，被揭示藉由洗淨溶劑之淸潔後仍持續進行對 於光阻之脫模性的表面保護材料（日本專利公開公報：特 開2000 -2 7 3 4 1 2號公報）。此表面保護材料中針對藉由低 -5- 200530363 (2) 級醇等之洗淨溶劑淸潔後，可持續進行有效的脫膜性。惟 ，做爲最近之光阻塗佈方法者，爲提昇量產性被採用先行 網版印刷至噴霧塗層、簾塗層之方法。因此，變更含於光 阻中之溶劑成份、含量’藉由含於光阻中之多元醇，其衍 生物等所成之溶劑後’漸漸侵触表面保護膜，對於光阻無 法維持有效脫模性。 另外’用於光罩表面之表面保護材料於印刷電路板等 基之基板中藉由穿孔’等出現凹凸，因此，密合曝光時其 · 凸部不僅尚於平滑部之壓力’每次曝光即剝削表面保護膜 造成問題點。 【發明內容】 本發明之目的爲提供一種表面保護膜不受洗淨溶劑之 淸潔而侵蝕，且，不被含於光阻之多元醇，其衍生物等所 成之溶劑所侵蝕’對於光阻可維持極高度脫模性之表面保 護膜，及使用其之表面保護材料。 肇 本發明另一目的係提供一種重覆使用後，不僅可防止 降低表面保護膜受物理性剝削後之表面保護膜脫模性，同 時可抑制濁度上昇，防止降低解像力之困擾。 爲達成該目的，本發明表面保護膜之特徵爲具有脫模 性之表面保護膜者，由電離放射線硬化型樹脂組成物，及 異氰酸酯預聚物所形成者。 又，本發明表面保護膜之特徵係由電離放射線硬化型 樹脂組成物、異氰酸酯預聚物、及脫模劑所形成者。 -6 - 200530363 (3) 本發明表面保護膜中，異氰酸酯預聚物之含量並未特 別限定，通常理想之構成表面保護膜總樹脂固形份爲1重 量％以上、50重量％以下者。 本發明表面保護膜中，脫模性可藉由含於電離放射線 硬化型樹脂.組成物之脫模性成份或脫模劑附與之。 理想之脫模劑爲聚矽氧系化合物者。又，較佳之聚矽 氧系化合物爲聚矽氧丙烯酸酯者。理想之聚矽氧丙烯酸酯 之含聚矽氧率爲50重量％以上、90重量％以下、數平均分 Φ 子量爲5 0 0 0〜20000、丙烯酸酯官能基數爲3以上者。本發 明之含聚矽氧率係指聚矽氧丙烯酸酯中佔有聚烷基矽氧烷 骨架之比例者。 本發明表面保護材料之特徵係於塑膠薄膜單面具有上 述表面保護膜，另一面具有黏合層者。 本發明表面保護膜及表面保護材料係含電離放射線硬 化型樹脂組成物同時含有異氰酸酯預聚物，其表面保護膜 不會受洗淨溶劑淸潔後之侵蝕，更不受含於光阻之多元醇 ® ’其衍生物等所成溶劑之侵蝕，對於光阻可維持極高脫模 性者。 本發明中以電離放射線硬化型樹脂組成物做爲構成表 面保護膜之樹脂成份使用後，重覆進行曝光仍不易剝離表 面保護膜。藉由此，不僅可防止降低脫模性，同時抑制濁 度上昇，可防止降低解像力。且，表面保護膜不易受損， 因此可大幅提昇表面保護膜之耐久性，增加可曝光之次數 -7- 200530363 (4) 【實施方式】 〔發明實施之最佳形態〕 以下針對本發明表面保護膜，各構成要素之實施形態 進行說明。 構成本發明表面保護膜之電離放射線硬化型樹脂組成 物係由可藉由電離放射線（紫外線或電子線）之照射進行 交聯硬化之材料所成者，防止硬化後表面保護膜之機械強 Φ 度、濁度之降低。表面保護膜之硬度依其被層合體而異， 一般JIS Κ 54〇0 : 1 990之錐度磨損硬度試驗中前後之濁度 差（亦即，錐度磨損硬度試驗後之濁度減掉錐度磨損硬度 試驗前之濁度的値，以下簡稱「△ Η」）爲未達2 5者宜， 更佳者爲未達20者。 做爲電離放射線硬化型樹脂組成物者可使用聚合性預 聚物者。做爲此光聚合性預聚物者特別以1分子中具有2 個以上之丙烯醯基，藉由交聯硬化後呈3元網目結構之丙 β 烯系預聚物者爲最佳使用者。此丙烯系預聚物例者可使用 尿烷丙烯酸酯、聚酯丙烯酸酯、環氧基丙烯酸酯、蜜胺丙 烯酸酯、聚氟烷基丙烯酸酯、聚矽氧丙烯酸酯等。此等丙 烯系預聚物更可單獨使用，惟，爲更提昇交聯硬化性、表 面保護膜之硬度，加入光聚合性單體者更理想。 做爲光聚合性單體者可使用1種或2種以上之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單官能丙烯基單體、1，6-己烷 200530363 (5) 二醇二丙烯酸酯、新戊二醇二丙烯酸酯、二乙二醇二烯酸 醒、聚乙二醇二丙烯酸酯、羥基三甲基乙酸酯新戊二醇二 丙_酸酯等2官能丙烯基單體、二季戊四醇六丙烯酸酯、 三甲基丙院三丙烯酸酯、季戊四醇三丙烯酸酯等多官能丙 烯基單體等者。 表面保護膜係於藉由上述光聚合性預聚體及光聚合性 單體以外’紫外線照射後硬化時使用光聚合啓發劑、光聚 合促進劑等之添加劑者宜。 做爲光聚合啓發劑例者如：苯乙酮、二苯甲酮、米希 勒醒、苯偶因、苄甲基縮酮、苯甲醯苯甲酸酯、α-醯肟 酯、噻噸酮、類等例。 又’光聚合促進劑係於硬化時可藉由空氣減少聚合障 礙、增加硬化速度者’如：Ρ-二甲胺苯甲酸異戊酯、Ρ-二 甲胺苯甲酸乙酯等例。 以下’針對上述之電離放射線硬化型樹脂組成物與同 曰寸構成本發明表面保護膜異氰酸酯預聚物進行說明。其中 · 異氯酸酯預聚物係指與聚醇樹脂同時於常溫硬化系所使用 之異氯酸酯預聚物者。異氰酸酯預聚物係藉由原料異氰酸 酉曰之甲苯基二異氰酸酯系、二苯基甲烷二異氰酸酯系、二 甲本基二異氰酸酯系、異氟爾酮二異氰酸酯系、六亞甲基 一異氯酸酯系等者’特別由無黃變性、耐氣候性之觀點視 之’又以二甲苯基二異氰酸酯系、異氟爾酮二異氰酸酯系 、六亞甲基二異氰酸酯系爲更佳使用者。 將此異氰酸酯預聚物與電離放射線硬化型樹脂組成物 -9- 200530363 (6) 同時進行交聯硬化後，可於表面保護膜維持脫模性。與此 電離放射線硬化型樹脂組成物同時含有異氰酸酯預聚物後 ，具維持脫模性之理由雖未明朗，卻可由下述推測。亦即 ，被膜表面因空氣中之氧藉由硬化障礙、脫模劑造成不少 硬化障礙，更降低耐溶劑性，若表面保護膜中含有異氰酸 酯預聚物則於被膜表面進行異氰酸酯預聚物之交聯反應後 可補足硬化障礙後稍有交聯不足之虞者。藉此表面保護膜 相較於未含異氰酸酯者，其較可提昇耐溶劑性，較可維持 φ 脫模性者。另外’於不活性氣體等氣氛下照射電離放射線 後，雖可防止藉由此空氣中氧產生之硬化障礙，惟，此法 之設備費用太高，且無法藉由脫模劑防止硬化障礙。 異氰酸酯預聚物僅少量含有後可取得上述效果，其含 量未特別限定。又，異氰酸酯基之含有率依其表面保護膜 之厚度，脫模劑之添加量而異，因此無法一槪而論，一般 ，於構成表面保護膜之總樹脂固形份中做爲下限者以1重 量％以上者宜，較佳者爲5重量％以上，更佳者爲1〇重量 魯 %以上，上限以50重量％以下，較佳者爲30重量％以下。 做成1重量％以上後’於表面保護膜之表面進行異氰酸酯 預聚物之交聯反應後’可補足藉由硬化障礙產生稍嫌不足 之交聯者，做成50重量Y。以下，使用電離放射線硬化型樹 脂組成物後，可使取得之被膜硬度等物性不受損。 以下，針對本發明附與脫模性於表面保護膜之成份， 進行說明。 做爲脫模劑者’未特別限定，可使用利用氟系化合物 -10- (7) (7)200530363 、聚矽氧系化合物之脫模劑者，考量光阻初期之脫模性則 以聚矽氧系化合物者佳。做爲此聚矽氧系化合物例者如： 聚矽氧油、聚矽氧樹脂、有機矽倍半噁烷之梯形聚合物、 聚矽氧系梳形接枝聚合物、聚矽氧丙酸酯等例，其中又以 使用聚矽氧丙烯酸酯者可與上述電離放射線硬化型樹脂組 成物同時進行交聯爲較佳者。 又，做爲光聚合性預聚物者，單獨用上述聚氟烷基丙 烯酸酯、及聚矽氧丙烯酸酯時，未使用後述脫模劑即可附 與脫模性於表面保護膜，而，此等光聚合成預聚物其做爲 脫模劑者除上述外，與其他電離放射線硬化型樹脂組成物 同時使用較單獨使用者佳。 由做爲表面保護膜時與被層合體之黏合性、重覆進行 表面硬度、初期脫模性、及曝光，淸潔後之脫模性的維持 觀點視之，特別以聚矽氧丙烯酸酯爲最佳做爲脫模劑之使 用。以聚矽氧丙烯酸酯做爲脫模劑使用時，藉由其他電離 放射線硬化型樹脂組成物提高表面硬度，僅少量添加聚矽 氧丙烯酸酯即可出現充份之脫模性，使聚矽氧含有率做成 時定者，由重覆進行曝光、淸潔後之維持脫模性觀點視之 ，使數平均分子量、丙烯酸酯官能基數做成特定者較佳。 亦即，此聚矽丙烯酸酯其聚矽氧含有率之下限以50 重量％以上者宜，較佳者爲60重量％以上，上限爲90重 量％以下者宜，較佳者爲80重量％以下。聚矽氧含有率做 成5 0重量％以上後，可附與良好之脫模性，90重量％以下 可附與有效之丙烯酸酯官能基數後，維持良好脫模性。 -11 - 200530363 (8) 又，數平均分子量爲 5 0 0 0〜20000者宜，更佳者爲 10000〜15000。數平均分子量做成5 000以上於曝光時可防 止脫模劑複印於光阻側，做爲20000以下則可防止降低與 上述電離放射線硬化型樹脂組成物之互溶性，維持被膜之 透明性，同時，可維持表面保護膜之脫模性。 又，丙烯酸酯官能基數爲3以上者宜，更佳者爲3以 上，8以下者。將丙烯酸酯官能基數做爲3以上後，可充 份取得與該電離放射線硬化型樹脂組成物之反應性，維持 良好脫模性。另外，若丙烯酸酯官能基數做成8以上，則 即使提昇與該電離放射線硬化型樹脂組成物之反應性，卻 無法維持脫模性，因此，於該範圍者宜。 該脫模性之添加量依其使用之氟系化合物，或聚矽氧 系化合物等之脫模劑種類而異，通常，聚氧系化合物時， 爲構成表面保護膜總樹脂固形份中之0.1重量％〜20重量％ 者。使用聚矽氧丙烯酸酯時，更依其含有聚矽氧率異，以 0.5重量％〜10重量％者宜，更佳者爲〇.5重量％〜5重量％ 者。 本發明表面保護膜除該電離放射線硬化型樹脂組成物 、異氰酸酯預聚物、及必要時所添加之脫模劑外，在不妨 礙此等效果之範圍下亦可摻混其他樹脂。惟，聚醇樹脂等 類與異氰酸酯預聚物反應之樹脂時，務必多量添加被反應 份之異氰酸酯預聚物。又，表面保護膜中只要不阻礙此等 效果，亦可含有潤滑劑、微粒子、螢光增白劑、顏料、靜 電防止劑、難燃劑、抗菌劑、防黴菌、抗氧化劑、可塑劑 -12- (9) 200530363 、矯正劑、流動調整劑、消泡劑、分散劑等 特別是做爲光罩用表面保護膜者，由密 真空塗敷之觀點視之，以表面保護膜中含 脂粒等微粒子後，於表面保護膜之表面形成 宜。做爲此微粒子者可使用碳酸鈣、碳酸鎂 氧化矽、氫氧化鋁、陶土、黏土、滑石等無 樹脂粒子、聚苯乙烯樹脂粒子、聚胺基甲酸 、聚乙烯樹脂粒子、苯並鳥糞胺樹脂粒子、 等樹脂粒等者。此微粒子之添加量衣其微粒 保護膜之厚度而異，因此未能一槪而論，一 表面保護膜之總樹脂固形份時，爲0. 1重量 宜。又，此微粒子之平均粒徑依其表面保護 不能一槪而論，一般以 Ιμηι〜ΙΟμιη者：1 0..5μηι〜5μπι被使用之。 表面保護膜之厚度並未特別限定，通常 時不降低光阻之解像度愈薄者宜。又，重覆 膜之表面硬度、密合曝光後，爲防止表面保 維初期之脫模性及淸潔後之脫模性務必呈某 者宜。具體而言以〇·5μηι〜5μηι’較理想者爲 〇 此表面保護膜除電離放射線硬化型樹脂 酸酯預聚物、及必要時所添加之脫模劑、混 其他添加劑、及稀釋溶媒等後，進行調整表 佈液之後，藉由先行技術公知之塗層方法， 各種添加劑。 合曝光時易於 無機顏料、樹 微細之凹凸者 、硫酸鋇、二 機頻料、丙;(¾ 乙酯樹脂粒子 環氧樹脂粒子 子種類、表面 般，針對構成 %〜1 0重量％者 膜之厚度而異 :，較佳者爲 ，爲使於曝光 進行表面保護 護膜之剝削， 種程度之厚度 1 μ m〜3 μ m 者 組成物、異氰 合其他樹脂、 面保護膜用塗 如：棒塗層、 -13- 200530363 (10) 塑模塗層、混合塗層、旋轉塗層、滾輥塗層、影寫版塗層 '流動塗層、噴塗、網版印刷等做爲保護光罩等進行直接 塗佈後’必要時藉由乾燥、電離放射線之照射後進行硬化 ’更:於必要時藉由加熱進行固化後可製作之。 《故爲照射電離放射線之方法者，可採用照射由超高壓 水銀燈、高壓水銀燈、低壓水銀燈、碳弧、金屬鹵素燈等 所發射之 l〇〇nm〜400nm、較佳者爲 200nm〜400nm之波長 域之紫外線、或照射由掃描型、簾型電子線加速器所發射 之lOOnm以下之波長域電子線等方法者。 本發明表面保護膜除上述之直接形成於光罩後使用之 外，亦可如：設置黏合層於單面之塑膠薄膜之另一面上與 上述同法形成表面保護膜後製成表面保護材料後，黏合具 有此表面保護薄膜之黏合層面與光罩表面後使用之。 做爲此塑膠薄膜者並未特別限定，惟，透明性高者宜 ，特別於曝光時使用之紫外線透光率高者更爲理想。做爲 此塑膠薄膜者可使用如：聚對苯二甲酸乙二醇酯、聚對苯 二甲酸丁二醇酯、聚乙烯萘二甲酸酯、聚碳酸酯、聚乙烯 、聚丙烯、聚苯乙烯、三乙醯纖維素、丙烯、聚氯化乙烯 等透明性良好之塑膠薄膜。特別以雙軸延伸之聚對苯二甲 酸乙二醇酯薄膜之機械性強度、尺寸安定性較理想爲最理 想使用者。又以於表面易於進黏合處理者爲較佳使用者。 做爲易黏合處理者如：電漿處理、電暈放電處理、遠紫外 線照射處理、底塗易黏合處理層之形成等例。 塑膠薄膜之厚度由曝光時不降低光罩之解像度觀點視 -14- (11) (11)200530363 之以愈薄者宜’而考量其使用性、機械性強度等，以 Ιμπι〜ΙΟΟμπι爲宜，較佳者爲 2μιη〜25μιη，更佳者爲 4μηι 〜15μηι 者。 黏合層至少由黏合性成份所形成者。做爲黏合性成份 者並未特別限定，一般使用天然樹脂系黏合劑，合成樹脂 系黏合劑等者’更佳者爲使用丙烯系黏合劑、聚矽氧系黏 合劑、尿院系黏合劑寺之合成樹脂系黏合劑者。又，在不 阻礙黏合性之範圍下，可含有與交聯劑、表面保護膜同類 ® 之添加劑於黏合層中。 黏合層之厚度並未特別限定，一般只要不阻礙透明性 (解像度）下可取得適當之黏合性者，以〇.5μηι〜20μιη者 宜，較佳者爲Ιμηι〜ΙΟμιη，更佳者爲2μπι〜4μιη。又，於黏 合層中爲使不因其黏合性降表面保護材料之使用性，預先 於塑膠薄膜、紙等表面黏合脫模處理之分離器即可。 黏合層係使黏合性成份、及必要時所添加之交聯劑、 m 其他添加劑於溶劑中溶解或分散後，調製黏合層用塗佈液 胃 後’藉由相同於上述表面保護膜之先行技術公知之塗層方 法塗佈於該塑膠薄膜表面保護膜所形成面之背面後，乾燥 之後可製作之。又，將該黏合層用塗佈液塗佈於分離器等 ’乾燥後，於塑膠薄膜表面保護膜所形成之面之背面藉由 層壓塑料後亦可製作之。 〔實施例〕 以下，以實施例爲基準進行本發明更詳細之說明。又 •15- (12) (12)200530363 ，本實施例中「份」、「％」未特定限定下代表重量基準 者0 〔實施例1〕 將厚度6μπι之聚對苯二甲酸乙二醇酯薄膜（lumira : 東菱公司）之單面以下記處方之表面保護膜用塗佈液，另 一面以下記處方之黏合層用塗佈液分別依序進行塗佈、乾 燥後，於表面保護膜所形成之面於高壓水銀燈進行照射紫 I 外線後，形成厚度2 μιη之表面保護膜。另外，考量具黏合 層面之使用性，黏合厚度25μιη之分離器（MRB :三菱化 學聚酯薄膜公司），6 0 °C下進行2天固化之後，製作實施 例1之表面保護材料。又，做爲脫模劑使用之聚矽氧丙烯 酸酯a其聚矽氧含有率爲7〇%、數平均分子量約爲12000 、丙烯酸酯官能基數爲6者。 〈實施例1之表面保護膜用塗佈液之處方〉 _ •電離放射線硬化型樹脂組成物 1 6份 (聚酯丙烯酸酯）（固形分100% ) (Alonix M7100 :東亞合成公司） •異氰酸酯預聚物（固形分7 5 % ) 5 · 5份 (Banock D7 50 :大日本油墨化學工業公司） •脫模劑 0.2份 (聚矽氧丙烯酸酯a )(固形分100% ) •光聚合啓發劑 1份 -16- (13) 200530363 (Irgaquia 184 : chiba speciality chemicals 公司） •丁酮 7 7份 〈黏著層用塗佈液之處方〉 •丙烯系黏著劑（固形分4〇% ) 1〇份 (Alontack SCL-200 :東亞合成化學公司） •甲苯 1 0份200530363 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a surface protective film and a surface protective material having a mold release property, and particularly to an exposure with an adhesive photoresist suitable for use in a printing substrate manufacturing process, etc. Surface protection film and surface protection material on the surface of the original (mask). [Prior art] Generally, a printed circuit board and a resin convex plate are produced by closely exposing a photomask (original document for exposure) in an adhesive photoresist such as a liquid photoresist. When the photomask is peeled from the photoresist after the exposure, in order to prevent part of the photoresist from adhering to the photomask surface, in the prior art, a surface-protective material (surface protection sheet) having a mold release property is provided on the surface of the photoresist on the photomask ). As the surface protection material for this photomask, it has been revealed that a plastic film has a surface protective film with releasability on one side and an adhesive layer on the other side (Japanese Patent Laid-Open Publication; JP-A-Hei i 7 2 Bulletin No. 1). However, the surface protection material cannot effectively prevent the adhesion of the photoresist to the surface protection film ′ is to remove the photoresist and other dust remaining on the surface protection film. Periodically clean the surface of the surface protective film (cleaning operation) by washing the solvent. Therefore, 'this surface protection material is required to continuously prevent the release property of photoresist adhesion even after cleaning. In view of this, it has been disclosed that a surface protection material for releasing the photoresist is continued after cleaning with a cleaning solvent (Japanese Patent Laid-Open Publication: JP 2000-2 7 3 4 1 2). In this surface protection material, after being cleaned with a cleaning solvent such as low -5- 200530363 (2) grade alcohol, the film can be continuously and effectively released. However, as a recent photoresist coating method, in order to improve mass productivity, the method of first screen printing to spray coating and curtain coating is adopted. Therefore, after changing the composition and content of the solvent contained in the photoresist, 'the solvent formed by the polyhydric alcohol, its derivative, etc. contained in the photoresist' gradually invaded the surface protection film, and the effective release property for the photoresist could not be maintained. . In addition, the "surface protection material for the photomask surface is perforated in a substrate such as a printed circuit board by perforation", so when the exposure is close, the convex part is not only the pressure of the smooth part. " Exploiting the surface protection film causes problems. [Summary of the Invention] The object of the present invention is to provide a surface protection film which is not corroded by the cleaning solvent and is not corroded by the cleaning solvent, and is not corroded by the solvents formed by the photoresist-containing polyols, their derivatives, etc. The surface protection film which can maintain extremely high mold release property, and the surface protection material using the same. Another object of the present invention is to provide a surface protection film which can not only reduce the release property of the surface protection film after being physically peeled after repeated use, but also can suppress the increase in turbidity and prevent the trouble of reducing the resolution. In order to achieve this object, the surface protection film of the present invention is characterized by a surface protection film having releasability, an ionizing radiation-curable resin composition, and an isocyanate prepolymer. The surface protective film of the present invention is characterized by being formed of an ionizing radiation-curable resin composition, an isocyanate prepolymer, and a release agent. -6-200530363 (3) The content of the isocyanate prepolymer in the surface protective film of the present invention is not particularly limited, and generally the ideal solid resin content of the surface protective film is 1% by weight or more and 50% by weight or less. In the surface protective film of the present invention, the releasability can be attached by a releasable component or a release agent contained in the ionizing radiation-curable resin. Composition. The ideal release agent is a silicone compound. Further, the preferred silicone compound is a silicone acrylate. The ideal polysiloxane contains 50% by weight or more and 90% by weight or less of the polysiloxane, and the number average molecular weight is 50,000 to 20000, and the number of acrylate functional groups is 3 or more. The polysiloxane-containing oxygen content of the present invention refers to the proportion of the polyalkylsiloxane group in the polysiloxane group. The surface protection material of the present invention is characterized in that the plastic film has the surface protection film on one side and an adhesive layer on the other side. The surface protection film and the surface protection material of the present invention contain an ionizing radiation-curable resin composition and also contain an isocyanate prepolymer. The surface protection film will not be attacked by the cleaning solvent, and it will not be affected by the multiples contained in the photoresist. Erosion of solvents formed by alcohols and their derivatives, etc., which can maintain extremely high release properties for photoresist. In the present invention, after the ionizing radiation-curable resin composition is used as the resin component constituting the surface protective film, it is not easy to peel off the surface protective film after repeated exposure. By this, it is possible to prevent not only lowering of mold release property but also turbidity increase and lowering of resolution. In addition, the surface protection film is not easy to be damaged, so the durability of the surface protection film can be greatly improved, and the number of exposure times can be increased. 7- 200530363 (4) [Embodiment] [The best form of the invention] The following is the surface protection of the present invention A film and an embodiment of each component will be described. The ionizing radiation hardening resin composition constituting the surface protective film of the present invention is made of a material that can be cross-linked and hardened by irradiation of ionizing radiation (ultraviolet rays or electron rays) to prevent the mechanical strength of the surface protective film from being hardened. , Decrease in turbidity. The hardness of the surface protective film varies depending on the laminated body. Generally, the turbidity difference in the taper abrasion hardness test before and after JIS KK 5400: 1 990 (that is, the turbidity after the taper abrasion hardness test minus the taper abrasion hardness The turbidity 値 before the test (hereinafter referred to as "△ Η") is preferably less than 25, and more preferably less than 20. As the ionizing radiation-curable resin composition, a polymerizable prepolymer can be used. As the photopolymerizable prepolymer, those who have two or more acryl fluorene groups in one molecule and cross-linking and hardening to form a ternary net-like prepolymer are the best users. Examples of the propylene-based prepolymer include urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate, polyfluoroalkyl acrylate, and polysiloxane. These propylene-based prepolymers can be used alone, but it is more desirable to add a photopolymerizable monomer in order to improve the cross-linking hardenability and the hardness of the surface protective film. As the photopolymerizable monomer, one kind or two or more kinds of 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butoxyethyl acrylate, etc. can be used. Functional propylene-based monomer, 1,6-hexane 200530363 (5) Glycol diacrylate, neopentyl glycol diacrylate, diethylene glycol dienoate, polyethylene glycol diacrylate, hydroxytrimethyl Bifunctional propylene-based monomers such as diacetic acid neopentyl glycol dipropionate; polyfunctional propylene-based monomers such as dipentaerythritol hexaacrylate, trimethylpropylene triacrylate, pentaerythritol triacrylate, and the like. The surface protective film is preferably one that uses additives such as a photopolymerization initiator and a photopolymerization accelerator at the time of curing after ultraviolet radiation by using a photopolymerizable prepolymer and a photopolymerizable monomer other than the aforementioned photopolymerizable monomers. Examples of photopolymerization heuristics are: acetophenone, benzophenone, Michler wake, benzoin, benzyl methyl ketal, benzamidine benzoate, α-amoxime ester, thioxanthine Examples of ketones and classes. Also, "photopolymerization accelerators are those which can reduce the polymerization barrier and increase the hardening speed by air during hardening", such as P-dimethylamine benzoate isoamyl, P-dimethylamine benzoate and the like. Hereinafter, the above-mentioned ionizing radiation-curable resin composition and the isocyanate prepolymer constituting the surface protective film of the present invention are described. Among them, isochlorate prepolymer refers to the isochlorate prepolymer used at the same time as room temperature curing system of polyalcohol resin. The isocyanate prepolymer is based on the raw materials of isocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dimethylbenzyl diisocyanate, isoflurone diisocyanate, and hexamethylene monoisocyanate. Chlorate-based and the like are "especially viewed from the viewpoint of non-yellowing and weather resistance", and xylyl diisocyanate, isoflurone diisocyanate, and hexamethylene diisocyanate are preferred users. . This isocyanate prepolymer and an ionizing radiation-curable resin composition -9- 200530363 (6) The cross-linking and curing can be performed simultaneously, and the release property can be maintained on the surface protective film. The reason why the ionizing radiation-curable resin composition contains an isocyanate prepolymer at the same time is that the reason for maintaining the mold release property is not clear, but it can be estimated as follows. That is, the surface of the film is hardened by oxygen in the air due to hardening obstacles and mold release agents, and the solvent resistance is further reduced. If the surface protective film contains an isocyanate prepolymer, the isocyanate prepolymer is formed on the surface of the film. After the crosslinking reaction can make up for those who are slightly insufficient after sclerosis. This allows the surface protection film to improve solvent resistance and maintain φ releasability compared to those without isocyanate. In addition, after irradiating ionizing radiation in an atmosphere such as an inert gas, although the hardening obstacle caused by oxygen in the air can be prevented, the equipment cost of this method is too high, and the hardening obstacle cannot be prevented by the release agent. The above-mentioned effect can be obtained when the isocyanate prepolymer is contained in a small amount, and its content is not particularly limited. In addition, the content of isocyanate groups varies depending on the thickness of the surface protective film and the amount of release agent added, so it cannot be said in a nutshell. Generally, the lower limit of the total resin solid content constituting the surface protective film is 1 It is preferably at least 5% by weight, more preferably at least 5% by weight, more preferably at least 10% by weight, and the upper limit is at most 50% by weight, and more preferably at most 30% by weight. When it is 1% by weight or more, ‘after the cross-linking reaction of the isocyanate prepolymer on the surface of the surface protective film’, it is possible to make up 50% by weight, which may cause insufficient crosslinking due to the hardening barrier. Hereinafter, after using an ionizing radiation-curable resin composition, physical properties such as hardness of the obtained film are not impaired. Hereinafter, the components of the present invention which are provided with a mold release property to the surface protective film will be described. As the release agent, there is no particular limitation, and a release agent using a fluorine compound -10- (7) (7) 200530363 and a polysiloxane compound can be used. In consideration of the release property in the early stage of the photoresist, the polymer is Silicone compounds are preferred. Examples of polysiloxane compounds are: polysiloxane oil, polysiloxane resin, organosilicon ladder polymer, polysiloxane comb graft polymer, polysiloxane For example, it is more preferable that a polysiloxane may be crosslinked with the ionizing radiation-curable resin composition at the same time. In addition, as the photopolymerizable prepolymer, when the above-mentioned polyfluoroalkyl acrylate and polysiloxane are used alone, the release property can be attached to the surface protective film without using a release agent described later. In addition to the above, these photopolymerized prepolymers are used as release agents, and it is better to use them together with other ionizing radiation-curable resin compositions than individual users. From the standpoint of adhesion to the laminated body when used as a surface protection film, repeated surface hardness, initial mold release, and exposure, and maintenance of the mold release after cleaning, the polysiloxane is particularly used as Best used as a release agent. When polysiloxane is used as a release agent, the surface hardness is improved by other ionizing radiation-curable resin composition. Only a small amount of polysiloxane is used to release sufficient moldability, making polysiloxane When the content rate is set to be constant, it is preferable to make the number average molecular weight and the number of acrylate functional groups specific from the viewpoint of repeating exposure and maintaining the releasability after cleaning. That is, the lower limit of the content of the polysiloxane of the polysiloxane is preferably 50% by weight or more, preferably 60% by weight or more, and the upper limit of 90% by weight or less, and more preferably 80% by weight or less. . When the polysiloxane content is 50% by weight or more, good mold release properties can be attached, and 90% by weight or less can be added with effective acrylate functional groups to maintain good mold release properties. -11-200530363 (8) The number average molecular weight is preferably from 5 0 0 to 20,000, and more preferably from 10,000 to 15,000. When the number average molecular weight is over 5,000, it is possible to prevent the release agent from being copied on the photoresist side when exposed. When it is less than 20,000, it can prevent the mutual solubility with the ionizing radiation-curable resin composition from being lowered and maintain the transparency of the film. , Can maintain the release of the surface protective film. The number of acrylate functional groups is preferably 3 or more, more preferably 3 or more and 8 or less. When the number of acrylate functional groups is 3 or more, the reactivity with the ionizing radiation-curable resin composition can be sufficiently obtained, and a good mold release property can be maintained. Further, when the number of acrylate functional groups is 8 or more, the releasability with the ionizing radiation-curable resin composition cannot be maintained, and therefore, it is preferable to be in this range. The amount of the release property varies depending on the type of the release agent such as a fluorine-based compound or a polysiloxane compound. In general, in the case of a polyoxy compound, it is 0.1% of the total solid content of the surface protective film. Weight% ~ 20% by weight. When polysiloxane is used, the polysiloxane content may vary depending on the polysiloxane content, and it is preferably 0.5% to 10% by weight, and more preferably 0.5% to 5% by weight. In addition to the ionizing radiation-curable resin composition, the isocyanate prepolymer, and the release agent added when necessary, the surface protective film of the present invention may be blended with other resins as long as these effects are not hindered. However, in the case of a resin that reacts with an isocyanate prepolymer such as a polyol resin, it is necessary to add a large amount of the isocyanate prepolymer to be reacted. The surface protective film may contain lubricants, fine particles, fluorescent whitening agents, pigments, antistatic agents, flame retardants, antibacterial agents, anti-molds, antioxidants, and plasticizers, as long as these effects are not hindered. -(9) 200530363, correction agent, flow regulator, defoaming agent, dispersant, etc. Especially as surface protective film for photomask, from the viewpoint of dense vacuum coating, the fat particles in the surface protective film are considered After waiting for the fine particles, it is preferable to form on the surface of the surface protective film. For this microparticle, you can use calcium carbonate, magnesium carbonate silica, aluminum hydroxide, clay, clay, talc and other resin-free particles, polystyrene resin particles, polyurethane, polyethylene resin particles, benzoguanamine Resin particles, resin particles, etc. 1 重量 宜。 The added amount of this microparticles varies in the thickness of the microparticle protective film, so it cannot be said that the total resin solid content of a surface protective film is 0.1 weight appropriate. In addition, the average particle size of the microparticles cannot be considered in terms of its surface protection. Generally, 1 μm to 10 μm is used: 1 0..5 μm to 5 μm. The thickness of the surface protective film is not particularly limited, and generally, the thinner the resolution without reducing the photoresist is, the better. In addition, after the surface hardness of the repeated film and the adhesion exposure, it is necessary to show some of the mold release property at the initial stage of surface maintenance and the mold release property after cleaning. Specifically, 0.5 μm to 5 μm ′ is the ideal. The surface protective film is made of ionizing radiation-curable resin ester prepolymer, and if necessary, a release agent, other additives, and a diluted solvent are added. After adjusting the surface cloth liquid, various additives are applied by a coating method known in the prior art. It is easy to inorganic pigments, fine unevenness of the tree, barium sulfate, two-frequency materials, and acrylic resins when exposed to light; (¾ ethyl ester resin particles, epoxy resin particles, types and surface, for the composition of% to 10% by weight of the film Thickness varies: Preferably, in order to peel the surface protective film for exposure, a thickness of 1 μm to 3 μm is used for the composition, other isocyanide resins, and the surface protective film, such as: Rod coating, -13- 200530363 (10) Mould coating, hybrid coating, spin coating, roller coating, photocopy coating 'flow coating, spray coating, screen printing, etc. as protective masks After direct coating, 'curing by drying and irradiation with ionizing radiation if necessary' and more: can be produced after curing by heating if necessary. "Therefore, for the method of irradiating ionizing radiation, you can use irradiation Ultra-high-pressure mercury lamp, high-pressure mercury lamp, low-pressure mercury lamp, carbon arc, metal halide lamp, etc. emit 100nm ~ 400nm, preferably 200nm ~ 400nm in the wavelength range of ultraviolet rays, or irradiate by scanning type, curtain type electronic wire From the accelerator Those with wavelengths below 100 nm, such as electron beams. In addition to the surface protection film of the present invention, which can be used directly after being formed on a photomask, it can also be provided with an adhesive layer on the other side of the plastic film on one side, which is the same as the above. After forming the surface protective film, the surface protective material is formed, and then the adhesive layer with the surface protective film is bonded to the surface of the photomask. The plastic film is not particularly limited, but it is suitable for high transparency, especially Those with high UV transmittance are more ideal for exposure. Those who use this plastic film can use: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate Esters, polycarbonates, polyethylene, polypropylene, polystyrene, triethyl cellulose, propylene, polyvinyl chloride and other transparent plastic films. Especially biaxially stretched polyethylene terephthalate Alcohol ester film is more ideal for its mechanical strength and dimensional stability. It is also better for those who are easy to enter the surface for adhesive treatment. For those who are easy to adhere, such as plasma treatment and corona Examples of electrical treatment, far-ultraviolet irradiation treatment, formation of primer-adhesive treatment layer, etc. The thickness of the plastic film is determined from the viewpoint of not reducing the resolution of the photomask during exposure. -14- (11) (11) 200530363 'In consideration of its usability, mechanical strength, etc., it is preferably 1 μm to 100 μm, more preferably 2 μm to 25 μm, and more preferably 4 μm to 15 μm. The adhesive layer is formed of at least an adhesive component. As an adhesive Sexual ingredients are not particularly limited. Natural resin-based adhesives, synthetic resin-based adhesives, etc. are generally used. 'Better ones are acrylic resins, silicone adhesives, and urine-based adhesives. For adhesives, as long as it does not impede the adhesion, it may contain additives similar to cross-linking agents and surface protection films in the adhesive layer. The thickness of the adhesive layer is not particularly limited. Generally, as long as appropriate adhesion can be obtained without impeding transparency (resolution), 0.5 μm to 20 μm is preferred, 1 μm to 10 μm is more preferred, and 2 μm is more preferred. 4μιη. In addition, in order to prevent the usability of the surface protection material from being reduced due to its adhesiveness, a separator may be adhered and demoulded in advance to the surface of the plastic film, paper, or the like. The adhesive layer is made by dissolving or dispersing the adhesive component, and the cross-linking agent, m and other additives, if necessary, in the solvent, and then preparing the coating liquid for the adhesive layer after the stomach. A known coating method is applied to the back surface of the surface on which the plastic film surface protection film is formed, and then it can be manufactured after drying. Alternatively, the coating solution for an adhesive layer may be coated on a separator or the like and dried, and then it may be produced by laminating a plastic on the back surface of the surface formed by the protective film of the plastic film. [Examples] Hereinafter, the present invention will be described in more detail with reference to examples. 15- (12) (12) 200530363, in this example, "parts" and "%" represent weight basis without specific limitation. 0 [Example 1] Polyethylene terephthalate with a thickness of 6 μm Film (lumira: Toyo Co., Ltd.) The coating solution for the surface protection film is described below on one side, and the coating solution for the adhesive layer is written on the other side. After the formed surface was irradiated with a purple I outer line in a high-pressure mercury lamp, a surface protective film having a thickness of 2 μm was formed. In addition, considering the usability of the adhesive layer, a separator with a thickness of 25 μm (MRB: Mitsubishi Chemical Polyester Film Co., Ltd.) was cured at 60 ° C for 2 days, and then the surface protection material of Example 1 was produced. The polysiloxane acrylate a used as a release agent has a polysiloxane content of 70%, a number average molecular weight of about 12,000, and a number of acrylate functional groups of six. <Prescription of coating solution for surface protective film of Example 1> _ • 16 parts of ionizing radiation-curable resin composition (polyester acrylate) (solid content: 100%) (Alonix M7100: Toa Synthetic Co., Ltd.) Polymer (75% of solid content) 5 · 5 parts (Banock D7 50: Dainippon Ink Chemical Industry Co., Ltd.) • 0.2 parts of release agent (polysiloxane a) (100% of solid content) • Photopolymerization initiator 1 part -16- (13) 200530363 (Irgaquia 184: chiba speciality chemicals company) • Butanone 7 7 parts <application solution for adhesive layer> • Acrylic adhesive (solid content 40%) 10 parts ( Alontack SCL-200: Toa Synthetic Chemical Co., Ltd. • 10 parts of toluene
•醋酸乙酯 1 〇份 〔實施例2〕 除變更實施例1之表面保護膜用塗佈液爲下記處方之 表面保護膜用塗佈液之外，與實施例1同法，製作實施例 2之表面保護材料。又，做爲脫模劑使用之聚矽氧丙烯酸 酯b其聚矽氧含有率爲20%、數平均分子量約爲3〇〇〇、丙 烯酸酯官能基數爲2者。 • 〈實施例2之表面保護膜用塗佈液之處方〉 •電離放射線硬化型樹脂組成物 1 6份 (環氧丙烯酸酯）（固形分1 〇 〇 % ) (KAYARAD R1 30 ：日本化藥公司） •異氰酸酯預聚物（固形分7 5 % ) 5 · 5份 (banock D750 :大臼本油墨化學工業公司） •脫模劑 〇 · 2份 (聚矽氧丙烯酸酯b )(固形分100% ) -17- 200530363 (14) •光聚合啓發劑 1份 (Irgaquia 184 : chiba speciality chemicals 公司） •丁酮 77份 〔實施例3〕 除變更實施例1之表面保護膜用塗佈液爲下記處方之 表面保護膜用塗佈液之外，與實施例1同法，製作實施例 3之表面保護材料。又，做爲脫模劑使用之聚矽氧油係使 聚矽氧烷之單末端進行改性爲有機基者。 〈實施例3之表面保護膜用塗佈液之處方〉 •電離放射線硬化型樹脂組成物 1 6份 (尿烷丙烯酸酯）（固形分1 0 0 % ) (NKoligo U15HA :新中村化學工業公司） •異氰酸酯預聚物（固形分7 5 % ) 5 . 5份 (banock D750 :大日本油墨化學工業公司） •脫模劑 〇 · 2份 (聚矽氧油）（固形分100% ) (X22-170DX:信越化學工業公司） •光聚合啓發劑 1份 (Irgaquia 184 : chiba speciality chemicals 公司) •丁酮 77份 〔比較例1〕 -18- 200530363 (15) 將實施例1之表面保護膜用塗佈液變更爲下記處方之 表面保護膜用塗佈液（未添加異氰酸酯預聚物者）之外， 與實施例1同法，製作比較例1之表面保護材料。 〈比較例1之表面保護膜用塗佈液之處方〉 •電離放射線硬化型樹脂組成物 2 0份 (聚酯丙烯酸酯）（固形分100%) (Alonixm 7100:東亞合成公司） 馨 •脫模劑 〇 · 2份 (聚矽氧丙烯酸酯a)(固形分100%) •光聚合啓發劑 1份 (Irgaquia 184 : chiba speciality chemicals 公司) •丁酮 7 9份 〔比較例2〕 將實施例2之表面保護膜用塗佈液變更爲下記處方之 ® 表面保護膜用塗佈液（未添加異氰酸酯預聚物者）之外， 與實施例2同法製作比較例2之表面保護材料。 〈比較例2之表面保護膜用塗佈液之處方〉 •電離放射線硬化型樹脂組成物 20份 (環氧丙烯酸酯）（固形分1〇〇% ) (KAYARAD R130 ：日本化藥公司） 〇.2份 •脫模劑 -19- 200530363 (16) (聚矽氧丙烯酸酯b )(固形分1 0 0 % ) •光聚合啓發劑 1份 (Irgaquia 184 : chiba speciality chemicals 公司） •丁酮 7 9份 〔比較例3〕• 10 parts of ethyl acetate [Example 2] Example 2 was prepared in the same manner as in Example 1 except that the coating solution for the surface protective film of Example 1 was changed to the coating solution for the surface protective film described below. Surface protection material. The polysiloxane acrylate b used as a release agent has a polysiloxane content of 20%, a number average molecular weight of about 3,000, and a number of acrylate functional groups of two. • <Preparation of coating solution for surface protective film of Example 2> • 16 parts of ionizing radiation-curable resin composition (epoxy acrylate) (solid content: 100%) (KAYARAD R1 30: Nippon Kayaku Co., Ltd. ) • Isocyanate prepolymer (75% solid content) 5 · 5 parts (banock D750: Oisomoto Ink Chemical Industry Co., Ltd.) • Release agent 0.2 parts (polysiloxane b) (solid content 100% ) -17- 200530363 (14) • 1 part of photopolymerization heuristic (Irgaquia 184: chiba speciality chemicals company) • 77 parts of methyl ethyl ketone [Example 3] Except that the coating solution for the surface protective film of Example 1 was changed to the following prescription A surface protection material of Example 3 was prepared in the same manner as in Example 1 except for the coating solution for a surface protection film. In addition, the polysiloxane oil used as a release agent is one in which one end of the polysiloxane is modified into an organic group. <Preparation of coating solution for surface protection film of Example 3> 16 parts of ionizing radiation hardening resin composition (urethane acrylate) (solid content 100%) (NKoligo U15HA: Shin Nakamura Chemical Industry Co., Ltd.) • Isocyanate prepolymer (75% solids content) 5.5 parts (banock D750: Dainippon Ink Chemical Industry Co., Ltd.) • Release agent 0.2 parts (polysiloxane) (solid content 100%) (X22- 170DX: Shin-Etsu Chemical Industry Co., Ltd. • 1 part photoinitiator (Irgaquia 184: chiba speciality chemicals company) • 77 parts of methyl ethyl ketone [Comparative Example 1] -18- 200530363 (15) Apply the surface protective film of Example 1 A surface protection material of Comparative Example 1 was prepared in the same manner as in Example 1 except that the cloth liquid was changed to a coating solution for a surface protection film (not added with an isocyanate prepolymer) as described below. <Prescription of coating solution for surface protection film of Comparative Example 1> • 20 parts of ionizing radiation-curable resin composition (polyester acrylate) (solid content 100%) (Alonixm 7100: Toa Kosei Co., Ltd.) 0.2 parts (polysiloxane a) (solid content 100%) • 1 part photoinitiator (Irgaquia 184: chiba speciality chemicals) • 7 parts of methyl ethyl ketone [Comparative Example 2] Example 2 The coating solution for the surface protection film was changed to the ® coating solution for the surface protection film (without an isocyanate prepolymer added) described below, and the surface protection material of Comparative Example 2 was produced in the same manner as in Example 2. <Prescription of coating liquid for surface protection film of Comparative Example 2> • 20 parts of ionizing radiation-curable resin composition (epoxy acrylate) (solid content: 100%) (KAYARAD R130: Nippon Kayaku Co., Ltd.) 2 parts • Releasing agent-19- 200530363 (16) (polysiloxane b) (solid content 100%) • 1 part of photopolymerization initiator (Irgaquia 184: chiba speciality chemicals company) • Butanone 7 9 [Comparative Example 3]
將實施例3之表面保護膜用塗佈液變更爲下記處方之 表面保護膜用塗佈液（未添加異氰酸酯預聚物者）之外， 與實施例3同法，製作比較例3之表面保護材料。 〈比較例3之表面保護膜用塗佈液之處方〉 •電離放射線硬化型樹脂組成物 20份 (尿烷丙烯酸酯）（固形分100%) (NKoligo U15HA:新中村化學工業公司） •脫模劑 0 · 2份 (聚矽氧油）（固形分100%) (X22-170DX:信越化學工業公司） •光聚合啓發劑 1份 (Irgaquia 184 ·· chiba speciality chemicals 公司) •丁酮 79份 針對實施例、及比較例所取得之表面保護材料，^ @ 如下試驗評定表面保護膜是否不受洗淨溶劑之淸潔，^ + 受含於光阻中之多元醇等溶劑之侵蝕，對於光阻是否，維_ -20- 200530363 (17) 高度脫模性者。又，針對進行重覆曝光之表面保護膜之耐 磨損性進行評定。其評定結果示於表1。 (1 )初期脫模性之評定 於具有實施例1〜3、及比較例1〜3之表面保護材料之 表面保護膜之面貼合黏著膠帶（nit聚酯3 lb :日東電工公 司），利用張力試驗機（Tensilon HTM-100:東洋Boldw-in公司），測定剝離速度3 00mm/min中1 80°C剝離力，進 行評定之。評定做成「◎」：剝離力爲未達20g/50mm者 ，「〇」：20g/50mm〜30g/50mm者，「X」：未硬化、黏 腻感者。 (2 )擦拭試驗後之脫模性評定 做爲擦拭試驗者係使具有實施例1〜3、及比較例1、2 表面保護材料之表面保護0吴之面以紗布含浸洗淨溶齊彳之& 醇（EtOH)，將進行50次擦拭操作後之脫模性與上記初 期脫模性同法進行測定之。又，爲針對含於光阻之多元醇 之耐溶劑性進行評定，使用丙二醇單甲醚（p G Μ )取代乙 醇（EtOH )後’與上記同法進行擦拭試驗。評定做成「◎ 」：剝離力低於初期測定値之2倍者，r〇」·· 2倍以上 、1 〇以下者，「X」：1 〇倍以上者。 (3 )耐磨損性之評定 剝取實施例1〜3、及比較例1、2之表面保護材料之分 -21 - 200530363 (18) 離器後，黏於透明聚對苯二甲酸乙二醇酯薄膜（厚度 1 8 8 μ m )後’依Π S K 5 4 0 〇 : 1 9 9 0爲基準，以磨損輪C S -10F、荷重500g、旋轉速度70rpm、旋轉數100次進行錐 度磨ί貝5式驗’由5式驗後之濁度減去試驗前之濁度（初期濁 度）之値做爲錐度磨損硬度△ Η。.又，濁度係依j! s κ 7136: 2000爲基準，利用濁度計（NDH 2000:臼本電飾 公司）進行測定之。評估做成「〇」：△ Η爲未達2 〇者 〔表1〕 初期之脫 模性 擦拭試驗後之脫模性 耐磨損性 EtOH PGM 實施例1 ◎ ◎ ◎ 〇 比較例1 ◎ 〇 〇 實施例2 ◎ 〇 〇 〇 比較例2 ◎ X X 一〇 實施例3 〇 〇 〇 〇 比較例3 X — 一 —The coating solution for the surface protection film of Example 3 was changed to the coating solution for the surface protection film (not added with the isocyanate prepolymer) described below, and the same method as in Example 3 was used to prepare the surface protection of Comparative Example 3. material. <Prescription of coating solution for surface protection film of Comparative Example 3> • 20 parts of ionizing radiation curable resin composition (urethane acrylate) (solid content 100%) (NKoligo U15HA: Shin Nakamura Chemical Industry Co., Ltd.) • Demolding Agent 0 · 2 parts (polysiloxane) (solid content 100%) (X22-170DX: Shin-Etsu Chemical Industry Co., Ltd.) • 1 part of photopolymerization initiator (Irgaquia 184 · · chiba speciality chemicals company) • 79 parts of methyl ethyl ketone For the surface protection materials obtained in the examples and comparative examples, ^ @ The following test is used to evaluate whether the surface protection film is not damaged by the cleaning solvent, ^ + is attacked by the solvents such as polyhydric alcohol contained in the photoresist, and for the photoresist No, dimension_ -20- 200530363 (17) Highly mold-releasing person. The abrasion resistance of the surface protective film subjected to repeated exposure was evaluated. The evaluation results are shown in Table 1. (1) Evaluation of the initial release property Adhesive tape (nit polyester 3 lb: Nitto Denko Corporation) was attached to the surface having the surface protective film of the surface protective material of Examples 1 to 3 and Comparative Examples 1 to 3, and was used Tensile testing machine (Tensilon HTM-100: Toyo Boldw-in Co., Ltd.) measured peeling force at 180 ° C at a peeling speed of 300 mm / min, and evaluated it. The evaluation was made "◎": the peeling force was less than 20g / 50mm, "0": 20g / 50mm to 30g / 50mm, and "X": unhardened and sticky. (2) Evaluation of releasability after wiping test. As a wiping tester, the surface protection of the surface protection materials of Examples 1 to 3 and Comparative Examples 1 and 2 was applied. The surface of Wu was impregnated with gauze and dissolved. & Alcohol (EtOH) was measured in the same manner as the above-mentioned initial mold release after 50 wiping operations. In order to evaluate the solvent resistance of the photoresist-containing polyhydric alcohol, propylene glycol monomethyl ether (p G M) was used instead of ethanol (EtOH) 'and the wiping test was performed in the same manner as described above. The evaluation was made "◎": the peeling force was lower than twice the initial measurement value, r0 "... 2 times or more and 10 or less, and" X ": 10 times or more. (3) Evaluation of abrasion resistance The surface protection materials of Examples 1 to 3 and Comparative Examples 1 and 2 were stripped -21-200530363 (18) After being separated, they were adhered to transparent polyethylene terephthalate Alcohol ester film (thickness 18.8 μm) after taper grinding according to SK 5 4 0 0: 1 9 0, based on wear wheel CS -10F, load 500 g, rotation speed 70 rpm, rotation 100 times The “Bai Type 5 test” is obtained by subtracting the turbidity (the initial turbidity) before the test from the turbidity after the 5 test as the taper abrasion hardness △ Η. In addition, the turbidity is measured with a turbidimeter (NDH 2000: Usmoto Electric Co., Ltd.) based on j! S κ 7136: 2000. The evaluation was "0": △ Η is less than 200 [Table 1] EtOH PGM, mold release and abrasion resistance after the initial mold release wipe test Example 1 ◎ ◎ ◎ Comparative Example 1 ◎ 〇〇 Example 2 ◎ 〇〇〇Comparative Example 2 XX XX Example 3 30,000 Comparative Example 3 X — 一 —
由表1結果證明，實施例1〜3之表面保護材料其表面 保護膜係由電離放射線硬化型樹脂組成物、異氰酸_胃 物、及脫模劑所形成者，因此，表面保護膜對於爲洗淨所 使用洗淨溶劑之乙醇不僅具有良好耐溶劑性，對於含於光 阻中之多元醇的丙二醇單甲醚亦具有良好耐溶劑性者。 -22- 200530363 (19) 特別是實施例1之表面保護材料其表面保護膜使用含 脫模劑之聚矽氧率爲7 0重量％、數平均分子量約爲丨2 〇 〇 〇 、丙儲酸酯官能基數爲6之聚砂氧丙烯酸酯。因此，擦拭 試驗後仍維持極佳之脫模性。 另外’比較例1之表面保護材料其表面保護膜係未含 異氰酸酯預聚物所形成者，因此，相較於實施例1其擦拭 試驗後之脫模性維持不理想者。 又，實施例2之表面保護材料其表面保護膜係使用含 φ 有脫模劑之聚砂氧率爲20重量。/。、數平均分子量約爲 3000、丙烯酸酯官能基數爲2之聚矽氧丙烯酸酯者，因此 ’擦拭驗驗後仍維持良好脫模性。反之，比較例2之表面 保護材料其表面保護膜爲未含異氰酸酷預聚物所形成者， 因此’相較於實施例2其擦拭試驗後其脫模性之維持不良 者。 又’實施例3之表面保護材料其表面保護膜係使用脫 模劑之聚矽氧油者’且含異氰酸酯預聚物所形成者，因此 ® ’初期脫模性良好、擦拭試驗後亦維持良好脫模性者。反 之，比較例3之表面保護材料則未含異氰酸酯預聚物所形 成者’因此’表面保護膜藉由聚砂氧油造成硬化障礙，未 硬化下出現黏著感。 〔產業上可利用性〕 本發明之表面保護膜係由電離放射線硬化型樹脂組成 物，及異氰酸酯預聚物所形成後具脫模性者，不受洗淨溶 -23- 200530363 (20) 劑淸潔，含於光阻之溶劑所侵蝕，重覆進行曝光、淸潔仍 可取得維持高度脫模性之表面保護膜、及表面保護薄膜者From the results in Table 1, it is proved that the surface protective films of the surface protective materials of Examples 1 to 3 are formed of an ionizing radiation-curable resin composition, an isocyanate, and a release agent. Therefore, the surface protective film is suitable for The ethanol used as a washing solvent for washing not only has good solvent resistance, but also has good solvent resistance to propylene glycol monomethyl ether of a polyhydric alcohol contained in a photoresist. -22- 200530363 (19) Especially the surface protection material of Example 1 whose surface protection film uses a release agent-containing polysiloxane with an oxygen content of 70% by weight, a number average molecular weight of about 2,000, and propionic acid Poly sand oxyacrylate with 6 ester functional groups. Therefore, excellent releasability was maintained after the wiping test. In addition, the surface protection material of 'Comparative Example 1' did not contain an isocyanate prepolymer because its surface protection film was formed. Therefore, compared with Example 1, the release property after the wiping test was not satisfactory. In addition, the surface protection film of Example 2 uses a polysand containing a mold release agent with a surface protection film having an oxygen ratio of 20% by weight. /. Polysiloxane having a number average molecular weight of about 3,000 and a number of acrylate functional groups of 2, therefore, the mold release property is maintained after the wiping test. In contrast, the surface protective material of Comparative Example 2 had a surface protective film formed of an isocyanate-free prepolymer, and therefore, compared with Example 2, the surface-protective material had a poor release property after the wiping test. Also, the surface protection material of Example 3 has a surface protective film made of a silicone oil using a release agent and is formed of an isocyanate-containing prepolymer. Therefore, it has a good initial release property and maintains a good after wiping test. Demons. On the other hand, the surface protection material of Comparative Example 3 did not contain an isocyanate prepolymer formed. Therefore, the surface protection film was hardened by polysynthetic oil, and a sticky feeling appeared when it was not hardened. [Industrial Applicability] The surface protective film of the present invention is made of an ionizing radiation-curable resin composition and an isocyanate prepolymer, and is mold-releasing, and is not subject to washing. 23- 200530363 (20)淸 clean, eroded by the solvent contained in the photoresist, repeated exposure, 淸 clean can still obtain a surface protection film and surface protection film to maintain high release
-24--twenty four-